PTQ Q2 2021 Digital Edition

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Q2 2021
ptq Q2 2021
PETROLEUM TECHNOLOGY QUARTERLY
REFINING
GAS PROCESSING
PETROCHEMICALS
SOx REDUCTION NEUTRALISING

ADDITIVES AMINE
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POWERING
A SUSTAINABL
FUTURE
axens spread dig.indd 2 17/03/2020 16:12

Through multi-specialist integrated
offers, we deliver ever more
inventive and sustainable solutions
to our industrial clients, always
aiming at preserving the planet.
www.axens.net
G
BLE
axens spread dig.indd 3 17/03/2020 16:12

THRIVE IN THE
NEW REALITY
Global economic challenges have prompted a dramatic fall in product demand and skewed product
slates. Recovery will probably be prolonged, and the repercussions will be long-lasting. At Shell
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SHELL_C&T_thrivenrewreality_PDQ.indd
shell.indd 1 1 12/1/20 11:35
12/03/2021 AM
13:03
ptq
3 As you were – almost
Chris Cunningham
5 ptq&a
21 A smart approach to tank dewatering

Fawaz Al Sahan, Omar Al Zayed and Fawaz Al Hadlaq
PETROLEUM TECHNOLOGY QUARTERLY Saudi Aramco
27 Delivering drop-in renewable fuels

Chuck Red and Ed Coppola Applied Research Associates
Q2 (Apr, May, Jun) 2021 Robert Valente, Christine Conway and Lin ZhoU Chevron Lummus Global
www.digitalrefining.com
33 Protecting your hydroprocessing reactor
Eric Lin and Richard Todd
Norton Engineering Consultants
39 Amine anomaly in a mild hydrocracker

Rajesh Mohan, Rohit Kumar, Himanshu Kumar Gupta and Basith Zohail N
Bharat Petroleum Corporation Limited
47 Dividing wall revamp boosts octane and throughput

Manish Bhargava and Anju Patil
DWC Innovations
55 Taking a holistic approach to a revamp

Joe Musumeci and John Estill Ascent Engineering
Gregory Mitchell Shell Norco
63 Selecting catalysts for marine fuels production

Abrar Hakeem Q8 Research
Ed Ouwerkerk Catalyst Intelligence
69 FCC SOx additives and security of supply

Tom Ventham, Cj Farley and Natalie Herring
UNICAT B.V. and G. W. Aru, LLC
75 Designing steam heat exchangers and tracing systems

Alex Chu
Swagelok
79 Neutralising amine selection for crude units

Eric Vetters
ProCorr Consulting Services
87 Energy network monitoring and optimisation

Elif Gül Göçer, Elif Melek Öztürk, GülşEn ŞAhin Andaş, Yahya Aktaş and Elif Mete
Tüpraş
93 Delayed coking as a sustainable refinery solution

Marcio Wagner Da Silva Petrobras
John Clark Coke Consulting Company
100 Boosting tube-side heat transfer

Nathan Hill
CALGAVIN
104 Crude logistics scheduling

Aurelio Ferrucci Prometheus SRL
Manoj Kumar HPCL - Mittal Energy Limited
Cover
Neste’s Porvoo refinery includes two NEXBTL units producing MY renewable diesel
Photo: Neste
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ed com copy 25.indd 1 15/03/2021 16:12

REFINERY
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you create your tomorrow today.
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© 2021 by Honeywell International Inc. All rights reserved.
honeywell uop.indd 1 12/03/2021 12:41

ptqPETROLEUM TECHNOLOGY QUARTERLY
As you were –
almost
Vol 26 No 3
Q2 (Apr, May, Jun) 2021
A
fter a full year of Covid, you might expect an impression of how the
world’s petroleum processing industry is developing to be confused.
Editor Although the pandemic slowed production everywhere except China,
Chris Cunningham and has accelerated closures that were anyway inevitable, the bigger emerging
editor@petroleumtechnology.com story appears to have changed little, with China and India quickly expanding
their roles in world markets while Europe’s refiners can barely make any money
Production Editor from their operations.
Rachel Storry
production@petroleumtechnology.com
India’s refineries have largely recovered their utilisation rates from pandemic
levels. The nation’s biggest site, Reliance’s Jamnagar complex, was reporting a
Graphics combined throughput for its domestic and export production of around 98%
Peter Harper early this year, still a little below the level it reached at the same point in 2020.
graphics@petroleumtechnology.com However, percentage rates in the high 90s and beyond are fairly typical of
Indian refining performance, a clear indicator of further expansions and new
Editorial refining capacity in the coming years. A forum organised by S&P Global in
tel +44 844 5888 773
fax +44 844 5888 667
February heard that India sees peak oil arriving much later there than else-
where in the world and that the scene is set to continue its refining industry as
Business Development Director the global epicentre of expansion. For instance, Bharat Petroleum is planning
Paul Mason to raise capacity at its Numaligarh refinery to 9 million t/y by 2025, from a cur-
sales@petroleumtechnology.com rent 3 million t/y.
The story of growing domination of global oil refining also continues in
Advertising Sales Office China where the industry is set to take over as the biggest producer, perhaps
tel +44 844 5888 771
fax +44 844 5888 662
within the coming year. This would be the first time ever that US refining has
not held the top spot.
Managing Director With increasing capacity, China’s refiners are, like India’s, becoming pre-
Richard Watts ferred customers for crude exporters and are, in turn, increasing their hold on
richard.watts@emap.com international markets for fuels.
A clearer picture of the status of US refineries should begin to emerge in
Circulation
the second quarter of the year. Percentage rates had been running in the low
Fran Havard
circulation@petroleumtechnology.com
80s before a winter storm battered the Gulf Coast region. In February, utili-
sation had hit a rock-bottom 56% before recovering to 63% in early March.
EMAP, 10th Floor, Southern House, Nonetheless, some major units were not expected to be fully on-line until later
Wellesley Grove, Croydon CR0 1XG in the spring. Logically, the resulting draw on stocks combined with refinery
tel +44 208 253 8695 closures should boost throughput, if not refining margins, as the year develops.
Oil refining in Europe declined throughout 2020 and seems unlikely to
change trajectory any time soon as the pandemic continues to bite. Projected
Register to receive your regular copy of
PTQ at www.eptq.com/register
refinery closures aside, the biofuels factor is also changing the shape of
European fuels production. Italian major Eni has so far converted two of its
PTQ (Petroleum Technology Quarterly) (ISSN refineries to produce biofuels and is considering conversion at Livorno in the
north west of the country. The company aims to be producing 5 million t/y of
No: 1632-363X, USPS No: 014-781) is published
quarterly plus annual Catalysis edition by EMAP and
is distributed in the US by SP/Asendia, 17B South biofuels by 2050.
Neste is shutting down its Naantali refinery in Finland with a switch to ter-
Middlesex Avenue, Monroe NJ 08831. Periodicals
postage paid at New Brunswick, NJ. Postmaster:
send address changes to PTQ (Petroleum Technology minal operations, while the company’s Porvoo refinery will be revamped
Quarterly), 17B South Middlesex Avenue, Monroe NJ
08831. Back numbers available from the Publisher to focus on co-processing renewable raw materials, continuing a policy that
at $30 per copy inc postage. began with production of renewable diesel at its Singapore and Rotterdam,
Netherlands sites.
In Portugal, Galp will finally shut down production at its 100 000 b/d refin-
ery at Matosinhos in response to the combined impact of the pandemic and the
need to upgrade operations. The company will confine operations to its other,
larger site at Sines.
CHRIS CUNNINGHAM
PTQ Q2 2021 3
ed com copy 25.indd 2 15/03/2021 16:12

Pr o ce ss Not e s
Heater coking is not inevitable
Avoid Fired Heater Coking HEAT FLUX CAN SURPRISE

For many refiners, heater coking in Crude and Vacuum Heat flux (BTU/hr/ft2 or kcal/hr/m2) measures the
Distillation Units (CDU/VDUs) is a common occurrence. amount of heat absorbed through a given outside
Many units around the world are shut down every two surface area of a heater tube. High heat flux raises tube
years, every year, or even every six months to deal metal temperature and causes high oil film temperature
with chronic heater coking. However, with the right inside the tube. Popular fired heater design programs
design features driven by a solid understanding of use a well-stirred firebox model and calculate peak
heater coking mechanisms, fired heater run length can heat flux by applying a simple multiplier to the average
be extended beyond five years, even with relatively heat flux. In reality, heater design parameters such as
challenging crudes. firebox height/width ratio, burner type, burner sizing,
burner placement, and air/flue gas flow patterns can
The two primary drivers of heater tube coking in CDU/
result in actual peak heat fluxes that are much higher
VDU services are oil film temperature and residence
than the “calculated” peak heat flux on the heater
time. Secondary factors such as crude coking tendency,
datasheet. Localized areas with very high heat flux will
solids content, and blend instability can further
coke and suffer from high tube metal temperature.
accelerate heater tube coking. So, which heater design
parameters will maximize heater run length and avoid Of course there are many other variables that must
shutdowns for high heater tube metal temperature or be considered, such as pass arrangement, vertical or
high heater pass pressure drop? horizontal tubes, cylindrical or box or cabin, coil steam,
etc. Problems stemming from blend instability are
MASS FLUX IS KING
becoming more common as refiners are increasingly
Mass flux (lb/s/ft2 or kg/s/m2) is found by dividing the mixing light shale crudes with heavy crudes. As the
mass flow through a heater tube by the tube’s cross- crude begins to vaporize, asphaltenes can precipitate
sectional area. High mass flux begets high velocity and out of unstable mixtures and coat the heater tubes,
suppresses coking in several important ways. First, forming coke and creating hot spots.
high mass flux means that the fluid moves through
the tube faster, minimizing residence time. Second, Even with challenging crudes, refiners have achieved
high velocity results in high heat transfer coefficient, Crude Heater and Vacuum Heater run length goals
which minimizes internal oil film temperature. Finally, through careful design and respect for the basics of
high mass flux creates high wall shear inside the tube, coking. Contact Process Consulting Services, Inc. to
minimizing build-up of solids or asphaltenes. learn more.
3400 Bissonnet St. +1 (713) 665-7046

Suite 130 info@revamps.com
Houston, TX 77005, USA www.revamps.com
pcs coking.indd 1 11/09/2020 15:55

ptq&a
Q We would like to explore oil to chemicals routes. Any References

process ideas for VGO/resid conversion? 1 For information about high olefin catalytic cracking including hardware
configuration, process conditions, and catalyst design for high olefin yields,
the reader is referred to Singh et al, Conventional FCC to maximum propylene
A Bani Cipriano, Segment Marketing Manager, Light Olefins, production, Hydrocarbon Processing, Sept 2020, and Dharia et al, Introducing
W. R. Grace & Co., Bani.Cipriano@Grace.com PropyleneMax Catalytic Cracking (PMcc®), Grace Catalagram, Vol 125, 2020.
The fluid catalytic cracking (FCC) unit provides an 2 For more information about refinery strategies in the aftermath of
excellent opportunity to increase the yield of petro- COVID-19, the reader is referred to Roundtable Session: Turbulent Markets
Getting the most out of the FCC during COVID-19, Hunt et al, AFPM 2020
chemical products from the refinery. Specifically, the Annual Meeting.
FCC is the unit that generates the highest yields of
propylene in the refinery. Propylene is a valuable pet-
rochemical feedstock, the majority being converted to A Mel Larson, Strategic Consulting Manager, Becht, mlarson@
polypropylene while the remaining finds use in produc- becht.com
tion of cumene and acrylonitrile among other end uses. The world is moving away from pure residua conver-
Under suitable conditions of hardware, operating con- sion; RFCCs are out of favour considering the demand
ditions, and catalytic system, FCCs can process VGO for low sulphur products. The shift has been to some ver-
and/or resid feeds. sion of hydrogen addition to bottom of the barrel. On
Conventional FCCs generate propylene yields in the the FCC front, east of Suez has focused on high conver-
range 4-5 wt%. FCCs can operate in max C3= mode and sion/propylene-making FCCs with recycling of a portion
can reach upwards of 12 wt%. Commercially proven of FCC naphtha to recrack as diesel. This trend will con-
high olefin yield catalytic cracking processes exist that tinue by maximising the cracking of VGO to petrochemi-
can achieve propylene yields of >20 wt%. One such cal feedstocks.
example is PMcc process technology available through a
joint effort of Technip Energies and Grace.1,2
The propylene yield depends in general on three key Q What is hydrogen embrittlement, where could it occur in
aspects1,2: our refinery, and how do we avoid it?
• Hardware configuration: as examples only, (i) regener-
ator design is different for resid vs VGO feeds, and (ii) A Collin Cross, Senior Product Analytics/Support Manager,
addition of a secondary, external riser for cracking naph- SUEZ – WTS, collin.cross@suez.com
tha can increase the yield of propylene. Hydrogen embrittlement (HE) is a type of damage suf-
• Process conditions: in general, higher ROT and lower fered in various high strength steels. It is caused by pen-
hydrocarbon partial pressures in the reactor will increase etration of monoatomic hydrogen into the metal which
the yield of propylene. then recombines to form molecular hydrogen leading to
• Catalyst for propylene maximisation: these catalysts internal pressures that weaken the intergranular struc-
in general (i) include the shape selective ZSM-5 zeolite ture. Various forms of specific damage occur from HE,
to crack gasoline olefins into propylene, (ii) are designed but generally all are versions of cracking. The differ-
to tolerate and retain their catalytic activity in the pres- ences in types of cracking are due to the specific impact
ence of harmful metals such as V, Ni, and Fe to name a on ductility, types of environments, and types of stresses
few, and (iii) have engineered macro and mesoporosity leading to the damage. The alloys most affected by this
to facilitate the upgrading of the largest feed molecules mechanism are certain carbon alloy steels, certain stain-
into valuable products. less steels, and some high strength nickel alloys.
It is also important to consider C3= and LPG ole- Units affected by HE in refineries are units that contain
fin recovery constraints (wet gas compressor, splitting environments with high concentrations of hot hydrogen,
capacity). In Q2 2020, during the COVID-19 pandemic, the proper chemical conditions, the right type of steel,
many FCCs were processing lower than customary rates and are subjected to various types of mechanical stress.
and this freed up C3= recovery capacity. Refiners turned There are also several special reasons HE can occur as
to strategies to maximise propylene (ZSM-5 usage and a result of welding practices, cleaning practices, metal
higher ROT). If operating at full rates, refiners may need manufacturing processes, and so on. While these are
to invest in additional recovery and splitting capacity if important mechanisms that can cause HE, for the dis-
operating in max C3= mode. cussion here we will focus on unit types that provide the
Finally, operating in max C3= mode can be very profit- correct hydrogen rich chemical environments and often-
able for refineries. We recently estimated that the PMcc times are the most at risk.
process can deliver approximately $2.60/bbl in uplift For HE to occur, generally three factors are necessary:
over an FCC processing a similar rate1, the uplift being high concentrations of hot (<300°F, 150°C) gaseous hydro-
the result of higher values for propylene over gasoline gen, alkaline conditions, and poisoning agents that slow
and fuels. the recombination of monoatomic hydrogen into molec-
www.digitalrefining.com PTQ Q2 2021 5
Q&A copy 37 (original) copy 9.indd 1 15/03/2021 18:09

ular hydrogen. Examples of common poisoning agents Hydrogen embrittlement can be avoided by using
are cyanide, arsenic and sulphides. The type of corrosion steels that are less susceptible and the use of proper
that favours the conditions above is called wet H2S cor- welding procedures for equipment in sour service.
rosion and most frequently occurs in cracking units such Monitoring the composition of sour water can help
as FCC and hydroprocessing units, cokers, amine units, determine the risk for hydrogen embrittlement for a cer-
sour water service units, and HF alkylation units. tain part of a unit while in operation. If conditions are
To avoid HE, there are many strategies that should such that there is an increased risk, actions can be taken
be employed. Routine inspection and monitoring help to reduce the risk. These can include reduction of corro-
the detection and mitigation of HE. Proper alloy usage sives by water wash or scavengers or the use of a corro-
is also an important factor. Post weld heat treating sion inhibitor. Failure of equipment by stress corrosion
(PWHT) of components, proper welding practices, and cracking due to hydrogen charging can be a very drastic
proper start-up/shutdown procedures of at-risk units event with severe consequences and all possible means
are all important. Protective linings can also be used in should be used to prevent this. Nalco Water can help
the proper circumstances to prevent hydrogen reactions manage the risk for hydrogen embrittlement with ana-
from occurring as favourably. Finally, chemical mitiga- lytical capabilities, monitoring, and the use of patented
tion can also be used to control HE to a large extent. Pathfinder corrosion inhibitors.
Chemical treatment generally falls into two categories,
which are scavenging and passivating. Traditionally, the A Andrew Layton, Principal Consultant, KBC (A Yokogawa
use of a scavenger was called for and many equipment Company), Andrew.Layton@KBC.global
OEMs still call for this method of mitigation. The most There are a number of embrittlement corrosion phenom-
common scavengers used are ammonium or sodium ena which are sometimes confused. A brief clarification
polysulphides. These chemicals are often called ‘cyanide of three of the most common is given here before talking
scavengers’ because they work to destroy the poisoning specifically about hydrogen embrittlement:
agent and thereby lower the concentration of monoat- • Temper embrittlement of steels, which is a high tem-
omic hydrogen to prevent its penetration. While polysul- perature long term phenomenon related to higher alloy
phide scavengers work well and are still in use today, materials especially when used in thick wall reactor
they have several negative side effects that have caused vessels.
their use to decline in recent decades considering the • H2 embrittlement of steels which is a low temperature
development of newer and less problematical chemical phenomenon usually related to absorption of H2 gen-
methods. The problematical side effects of polysulphides erated from cathodic corrosion reactions like Wet H2S
include downstream equipment fouling, toxicity, pump- corrosion
ability, and handleability. • High temperature H2 attack (HTHA) of steels is a rel-
Newer chemical mitigation methods surround the use atively high temperature phenomenon impacting more
of specialised high pH passivating inhibitors, or filmers, the low alloy materials like CS or C ½ Moly. This is often
somewhat like those commonly used in other fraction- discussed in recent years because it is related to signifi-
ator overhead corrosion services. While filmers do not cant incidents on hydrotreaters or naphtha reformers.
directly eliminate the cyanide (or other poisoning agents) This has resulted in the updating of the Nelson curves
as do polysulphides, they do effectively help to prevent which identify when HTHA is a concern as a function of
monoatomic hydrogen penetration and subsequent HE. temperature, H2 partial pressure, and material type.
HE is prevented in this case because the passivating film H2 embrittlement of steels is created by absorption of
fosters rapid recombination from monoatomic hydrogen H2 into the steel at low temperatures. It has several forms
back to molecular hydrogen outside the metal, thus pre- and there are many mechanisms proposed. Important
venting the penetration necessary for embrittlement to factors contributing to the phenomena include high
occur. Many refineries today prefer the use of filmers to hardness, the presence of stress, and water. Typical exam-
polysulphides due to their lack of negative side effects, ples are:
favorable economics, and strong ability to prevent HE. • Poor welding procedures where moisture may be
present
A Chris Claesen, Technical Director, Nalco Water, • Localised dissimilar metals, allowing a corrosion cell
Chris.Claesen@ecolab.com to be created in the presence of moisture; this will also
Hydrogen embrittlement is a complex process. A simple generate H2 at the cathode. This can happen in many
way to describe the cause is by the diffusion of atomic locations where there are dissimilar materials in the pres-
hydrogen into metal followed by recombination to ence of water. One example could be dissimilar bolt/
molecular hydrogen in voids or impurities in the metal, washer/structure materials on jetty or any external
causing local areas of high pressure inside the metal. supports.
It can occur during welding or in a sour wet environ- • Wet H2S corrosion, which is perhaps the most common
ment if conditions are such that atomic hydrogen can example of H2 embrittlement, especially if any cyanides
be generated and diffuse into the metal. The units with and high ammonia levels are present in the presence of
wet sour environments that can be most susceptible to H2S and water. Cyanides are a particular problem even at
embrittlement in a refinery are normally the FCC, ther- low ppm levels as they can remove the sulphidic protec-
mal cracking units such as cokers and visbreakers, and tive layer which helps prevent the corrosion cells being
downstream amine units. set up.
6 PTQ Q2 2021 www.digitalrefining.com

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Typical location examples for H2 embrittlement are: its polar group. The non-polar tail of the inhibitor is
• Poor welding and in hardness zones oriented vertical to the metal surface, then the atomic
• FCC/coker overheads and light ends systems where hydrogen reacts with the corrosion inhibitor forming a
H2S/cyanides and moisture are present barrier to the metal surface.
• Hydrotreater reactor effluent and stripper systems
where H2S/moisture/ammonia is present and some- A Henk Helle, Corrosion Engineer and Reliability Expert,
times cyanides, which is a particularly bad actor Petrogenium, henk.helle@petrogenium.com
• Gas treating systems such as amine systems Hydrogen embrittlement (HE) is the obstructing effect
• Alkylation units of dissolved atomic hydrogen on the plastic straining of
• Sour water systems metals. On elastic straining there is no such effect. Since
• Some crude and VDU systems dependent on crude refinery equipment is nominally designed to be stressed
type elastically, there is generally another factor at play: stress
Typical mitigations are: raisers, such as cracks or sharp notches, which induce
• Good welding practices local plastic zones.
• Improved steel fabrication standards and selection for This redefines the problem: HE is the cause, but hydro-
equipment going into wet H2S service gen stress cracking (HSC), or the propagation of cracks
• Dilution of corrosion precursors by water washing under the influence of dissolved atomic hydrogen, is the
with a focus on good mixing design as well as dilution consequence.
• Use of chemical additives such as polysulphides HSC can occur in a range of metals such as alloyed or
• Stress relieving of critical equipment after construction unalloyed ferritic steels and nickel-base alloys. Cracking
or mechanical/welding work occurs when atomic hydrogen diffuses through the metal
• Good inspection programme lattice to highly stressed points such as notches, inclu-
• Good positive materials identification to prevent dis- sions, weld defects or crack tips, and hinders the capac-
similar materials issues ity of the metal to deform plastically, causing it to crack
instead. This effect will be stronger at lower tempera-
A Berthold Otzisk, Senior Product Manager - Process tures where the diffusion of hydrogen is low enough to
Chemicals, Kurita Europe, berthold.otzisk@kurita-water.com become trapped in a stressed zone. The severity of HE
Hydrogen embrittlement is an insidious type of failure, depends first on the concentration of dissolved hydro-
often driven by bisulphide ions (HS-) as high pH corro- gen. HSC is a quick process: when the conditions are
sion. Refinery units with high pH operations are hydro- right, crack growth is a process of hours rather than
treaters, amine units, sour water strippers, and FCC light years, although cracking may stop when conditions
ends. Hydrocrackers, visbreakers, and coker fraction- change. In higher strength materials, the HSC rate tends
ators are occasionally affected, while H-Oil units (LC to be higher and potentially more catastrophic than in
Finers) or reformers are only infrequently affected. ductile metals.
Hydrogen embrittlement is a form of corrosion, where So, where in the refinery can HSC occur? It requires
high-strength steel becomes brittle and fractures fol- three ingredients: dissolved hydrogen, susceptible metal,
lowing exposure to hydrogen. Often this form of corro- and plastic strain. Hydrogen dissolves in metal when
sion is not recognised, which can lead to unexpected and in contact with hot hydrogen gas, such as in hydropro-
sometimes catastrophic damage. The complete mecha- cessing units, or when aqueous corrosion reactions
nism is not completely understood, because hydrogen form cathodic hydrogen in the presence of H2S, HCN,
embrittlement is not a permanent condition. It starts or HF. This form of hydrogen charging may cause HSC
with hydrogen atoms diffusing through the metal. When known by another name: sulphide stress cracking or SSC.
these atoms recombine to form hydrogen molecules, Aqueous H2S solutions are found in numerous locations
they can create extremely high pressure from inside the in a refinery from storage tanks to the sour water strip-
cavity they are in. When this occurs, the metal ductility per, basically all wet and ambient temperature locations.
is significantly reduced, leading to cracking and brittle This is pretty much everywhere in the refinery if the
failures. shutdown condition is considered as well. HF exposure
Hydrogen sulphide ions are known to promote hydro- is generally limited to HF alkylation units.
gen embrittlement by allowing more time for the atomic The stresses that produce local plasticity can have sev-
hydrogen to become absorbed. This inhibits the recom- eral causes: weld stresses and other fabrication stresses,
bination reaction of atomic hydrogen to molecular thermal stresses, internal pressure, and external forces.
hydrogen. Regarding design, installations are elastically strained,
The degree of embrittlement can be influenced by the but in practice they often are not.
amount of hydrogen and microstructure of the metal. Susceptible metals are ferritic materials or duplex
Ferritic steel is more susceptible to hydrogen embrittle- stainless, or Ni based alloys, and the critical property is
ment than high quality steels such as austenitic stain- hardness. The reason that hardness determines suscep-
less steels, aluminum, and nickel alloys with different tibility is that crack tip blunting in softer metals gives a
crystal structures. The best method of controlling hydro- lower stress intensity, whilst a sharper and more highly
gen damage is to limit the contact hydrogen has with stressed crack tip zone in harder metals is prone to brit-
the metal. Film forming inhibitors reduce the potential tle cleavage failure. An empirically derived hardness
for corrosion. They are absorbed to the metal through limit for ferritic steel is 22 HRC, below which HSC is

less likely (though not impossible). The finer points of cases lead to a sudden stop of the engine. Additionally,
HSC encompass an elaborate standard defining hard- all of the system upstream of the engine will suffer from
ness limits and other specifications of metallic materials fouling issues.
in relation to SSC in refineries. While lower sulphur in fuels will mean fewer harm-
Avoiding HSC requires the following main principles: ful emissions, the loss of lubricity that sulphur brings can
• When shutting down, slow-cool hot pressurised also make engine operations more challenging.
hydrogen-containing equipment in accordance with the Distillate ageing also contributes to increasing issues.
specifications. The percentage of distillate blend components in VLSFO
• Follow the materials specifications as given in NACE often come from complex secondary refinery streams
Standard MR0103. where much of the natural stability has been removed or
• Fastidiously adhere to MOC procedures. weakened.
Distillate ageing is a chemical process that produces
A Craig Harclerode, O&G Industry Principal, OSIsoft, sludge in the presence of elevated temperature, oxygen,
charclerode@osisoft.com or by a catalyst present in the fuel (for instance, a metal).
Hydrogen embrittlement, also referred to as high tem- These processes can be prevented by the use of propri-
perature hydrogen attack (HTHA) or methane reaction, etary additives.
is a widely documented corrosion phenomenon in petro- Unstable distillates oxidise (most commonly under
leum refining and petrochemical processes that can be elevated temperatures and pressures), forming sand-
best described by using intent search engines like Google like sediments which block injector nozzles, while gums
and articles like: AICHE Engage, Preventing HTHA, by become impregnated with inorganics (catalyst fines,
Lauren Grim (8/15/2016 post) or articles such as ASTM metals, sediments), creating a grinding paste on small
F519 and ASTM G142. In short, the Nelson Index cor- tolerance contact surfaces (fuel pumps, injectors, and so
relates the impact of hydrogen embrittlement on various on).
high strength material such as in the case of carbon steel Long chain paraffins present in many fractions of
alloys at high temperatures and high hydrogen partial VLSFO are also responsible for wax formation in fuels.
pressures. Injector blockages and separation failures indicate aged
An example of using advanced analytics can be distillate material.
found in the 2016 EMEA OSIsoft Users Conference in The major problem when blending VLSFO comes
a presentation by MOL’s Tibor Komróczki (Delivering however with asphaltene stability. It is well known in
Business Value from Digital Transformation) which the industry that, by blending different stocks, asphal-
describes how MOL developed HTHA advanced cor- tene stability will be impacted and finally asphaltene
rosion analytics by using PI Asset Framework (PI AF) will associate into larger molecules and precipitate.
to configure a HTHA template that was then rapidly Additionally, the paraffinic matrix of the VLSFO will
deployed to over 50 nodes across four refineries. make asphaltene naturally unstable as it will dilute the
Many companies like MOL are using advanced ana- resins that keep asphaltene in solution. These larger
lytics and methods to monitor for HTHA with asso- asphaltenic molecules require more time and oxygen
ciated operational alerts in addition to gathering than is available within one combustion cycle to burn.
intelligence to aid in the determination of preventive These unburnt residuals deposit on liners and pistons
measures such as the need to inspect or replace certain in the combustion chamber; or burn later and contrib-
nodes with different alloys or change operations. ute to poor ignition and airborne emissions.
An additional reference can be found in Leveraging Adding proprietary chemistries for chemically
the PI System in the Processing of Opportunity Crudes rebalancing the fuel and restoring stability is king for
by MOL’s Gábor Mucsina in the OSIsoft UC2017. This improving fuel performance and for avoiding all of the
presentation discusses the use of integrity operating operating issues, as asphaltenes can be kept in solution
windows (IOW) in areas including HTHA to aid in the and sustain inappropriate blending.
safe processing of opportunity crudes. Both ship owners and fuel suppliers have no chance
of controlling the blending in that a ship can bunker at
any place in the world and the fuel makers receive their
Q We have fuel performance issues when we blend low feeds from any place in the world.
sulphur marine fuels from different sources. How can we The problem can therefore be addressed only by
resolve this? enhancing asphaltene stability in situ, either while bun-
kering or at the fuel supplier tank.
A Marcello Ferrara, Chairman, ITW Technologies, mferrara@ ITW has a long track record in asphaltene stabilisa-
itwtechnologies.com; Domenico Ferrara, Process Engineer, ITW tion, ranging from blending incompatible stocks to get-
Technologies, dferrara@itwtechnologies.com ting out-of-range values of sediments back on-spec by
The difficulty for marine engines to keep up with the hot filtration, as well as dissolving precipitated asphal-
times has been severely tested by the new IMO 2020 tene and coke-like materials.
regulations which require the use of low sulphur fuels Additionally, ITW has a long track record in reduc-
which may create deposits and fouling inside the coming airborne emissions in engines and in power stations
bustion chamber and consequently cause severe damage firing any type of fuel oil, including the ones with very
to the pistons, liners and pistons rings, and in the worst high asphaltene content.

A Simon Calverley, Consulting Product Integration Director, reduced. Producing fuel oil from thermally cracked res-
KBC (A Yokogawa Company), Simon.Calverley@KBC.global idue still requires external diluent, but much less (-50%).
A known problem with fuel oils, including low sul- One effect of the thermal conversion is that the P0 of the
phur fuel oils, is instability. In an unstable fuel oil, non-asphalthene phase is reduced, while the FRMax of
asphaltenes precipitate so the fuel oil will have sol- the asphalthene phase is strongly increased.
ids present. Asphaltenes are a heavy (high molecular When blending to fuel oil viscosity specification, the
weight) component so are found in the heaviest hydro- residual stability of such a blend can be as low as 1.1
carbons on a refinery; lighter streams (cutters) are used with e.g. a P0=68 and a FRMax=62. Furthermore, these
to blend with the heavy streams so that the resultant fuel blends are high in asphalthene content. When blending
oil meets the specification. Some hydrocarbon species LSFOs from straight run origin with LSFO made with
have a tendency to precipitate asphaltenes whereas oth- thermally cracked material, the largely different FRMax
ers will keep them in solution; generally speaking, the of the individual components leads to instability.
more paraffinic cutters are the more likely they are to By contrast, the FRMax is dominated by the cracked
precipitate asphaltenes, whereas the more aromatic they material, and the P0 is an intermediate value between the
are the more likely that asphaltenes will stay in solu- straight run and cracked component. Even with minor
tion. Refiners will blend fuel oils such that they are sta- additions of cracked material, the blend becomes unsta-
ble, thus avoiding asphaltene deposition. However when ble and asphalthenes are rejected from the oil.
fuel oils are mixed they can become unstable; the fuel oils Fundamentally, there is no cure for this problem other
are said to be incompatible. than to identify the source and quality of different fuel
Low sulphur fuel oils may have a tendency to be oils and to keep them separate. Limiting the quantity of
incompatible with each other as they may have more cracked base material to low levels (10-15%) may help
light material in them than higher sulphur specification and result in stable blends. This depends on the respec-
marine fuel oils. This is because sulphur is more likely tive LSFOs properties. Dedicated blending tests or calcu-
to be a constraining property than it is in higher sulphur lation (pending availability of stream stability data) can
fuel oils. Thus it becomes necessary to blend for sulphur be conducted to determine stability limits and maximum
as well as other parameters such as viscosity. A higher allowed fraction of thermally cracked component.
mass or volume of cutters may be used to achieve the
sulphur specification than is the case in a higher sulphur A Chris Claesen, Technical Director, Nalco Water,
fuel oil. These lighter materials may have a relatively Chris.Claesen@ecolab.com
high paraffin content (this is not always the case, there Blending different fuels to make IMO 2020-compliant
are some aromatic cutters such as FCC LCO) and thus be VLSFO blends can create unstable mixtures that cause
more likely to precipitate asphaltenes. sedimentation and sludge. Sedimentation can occur in
There are numerous tests that can be performed and these blends because paraffins are an antisolvent (or
algorithms that can be used to predict whether a fuel oil non-solvent) for highly aromatic asphaltenes. Sometimes
blend, or mix of blended fuel oils are likely to produce a the sedimentation is immediate, particularly if the blend
stable or unstable fuel oil. components are highly incompatible, but often the sed-
imentation is much slower and may only be observed
A Jari Marci, Distillation and Thermal Conversion Expert, after a prolonged period of time or after exposure to
Petrogenium, jari.marci@petrogenium.com external stress such as elevated temperatures.
I assume that the performance issue is related to unstable These challenges can be addressed by treating with
blends of fuel oil, and thus to a total sediment potential Nalco Water additives that stabilise the asphaltenes in
exceeding the allowable limit of 0.1 wt%. the final blend.
A very common approach to producing residual low The principal function of the Nalco Water stability
sulphur fuel oil (LSFO), since the advent of IMO 2020, additives is to prevent flocculation and/or maintain the
is to blend low sulphur vacuum residue with desul- asphaltenes in a dispersed state in the fuel blend. By sta-
phurised gasoil. Such fuels are common on the market bilising the asphaltenes in the blend, the additives will
and are characterised by good stability (ASTM D7112) ultimately reduce the amount of sediment formed from
in terms of their P-value (P-value approx. 2.0-3.0). The otherwise incompatible or unstable VLSFO blends.
P-value is a measure of the blend stability and a ratio of The stability of a blend and the potential need for a sta-
two parameters: P0 and FRMax. bility additive can be predicted with a proprietary Nalco
P0 is the available aromaticity of the non-asphalthene Water blending model.
phase, and FRMax is the required aromaticity of the
asphalthene phase – so long as P0 > FRMax, the blend is A Mel Larson, Strategic Consulting Manager, Becht, mlarson@
stable and all asphalthenes are kept in solution. The indi- becht.com
vidual components of P0 and FRMax could be, for exam- This may be more of an issue of the engine than the fuel.
ple, 46 and 20 respectively. Furthermore, these oils have a The historical marine engine was built and tuned for
low asphalthene content. CCAI values of 850. In order to meet the lower sulphur
In the past and in some cases today, marine resid- VLSFO specification, less residua with less carbon con-
ual fuel is produced by processing of residue in a tent is being delivered as well as different viscosity. Each
visbreaker. Visbreaking is a mild thermal conversion pro- component in the bunker fuel blend should be assessed
cess by which the viscosity of a residue is substantially for compatibility as well. Globally, there has been an

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grace.indd 1 12/03/2021 12:54

increase in light sweet crude consumption to meet the Severe fouling in a vacuum unit’s preheat section is
VLSFO specification. Light sweet and unconventional generally linked to asphaltene precipitation and even
crudes tend to be more paraffinic in composition. The coking. This phenomenon is strongly governed by prod-
blending of highly paraffinic and conventional oils may uct temperature. Too high a wall temperature in a heat
result in precipitation either in the tank or throughout a exchanger of the preheat train will be prone to fouling
system lacking a homogenous fuel to the engine. development. This can later spread through the whole
train by reducing heat transfer. For instance, too cold a
desalter inlet temperature, resulting from a poor per-
Q What are the likely causes of and solutions for severe forming and fouled cold train part, will jeopardise the
fouling in a vacuum unit’s preheat section? desalter performance and result in a higher corrosion
risk in the hot train part. A similar performance cut in the
A Simon Calverley, Consulting Product Integration Director, hot train part will impact consumption of the fired heater
KBC (A Yokogawa Company), Simon.Calverley@KBC.global prior to the distillation column as well.
Fouling in vacuum unit preheat trains is often associated In the early 2010s, Technip Energies, in partnership
with the higher temperature section of the preheat train with Total and CEA, co-developed a dedicated test loop
though not exclusively so. There are numerous potential named BEECH (Fouling Exchanger Test Loop in French).
causes of fouling. Some of these are: Several measurement campaigns and studies have been
• Low velocities can lead to fouling. These are often performed showing the importance of wall temperature,
addressed by design changes to either the exchanger shear stress, and heat exchanger design on the fouling
internals or by changing the arrangement of the mechanisms in a preheat train. The main outcomes to
exchanger (e.g. from parallel to series). limit fouling development are:
• Corrosion deposits can cause fouling. • Reduce the wall temperatures as low as possible by
• Heavy cracked slop oil can end up in the vacuum unit, promoting a high heat transfer coefficient on the cold
particularly if there is a risk of oxygen contamination (for fluid side.
instance being stored in un-blanketed tanks). These are • Maximise shear stresses at the wall on both exchanger
often better processed in a unit that has cracked streams sides to limit deposits and improve heat transfer coeffi-
such as a visbreaker or FCC. Alternatively, blanketing the cients. This can be done by combining high regime flow
tanks they are stored in can reduce the risk of fouling. rates (for instance, above 2.0 m/s on the tube side) with
Some refiners have had success with oxygen scavengers. well-chosen and proven turbulence promoter heat trans-
• Asphaltene deposition can occur in the vacuum unit fer solutions (grooves or corrugations on walls, inserts).
preheat train. • Pressure drop should not be a ‘target’ but a ‘conse-
• Inadequate desalting can lead to fouling, often because quence’: Designs with higher energy consumption, using
solids are not effectively removed. If the vacuum units a more powerful pump will be paid back by a limited
are fed only with atmospheric residue from the refinery’s fouling development and hence a longer production
crude unit, this is more likely to be problematic in the lifetime.
crude unit. If the vacuum unit is fed with imported res- • Manage pressure drop on the whole train and not item
idue then either consider desalting it or, if it is desalted, by item; pressure drop must be expended where it is
then review the desalter operation. needed.
Analysis of the deposits helps in identifying the prob- • Avoid excess area applying standard fouling resistance
lem and the solutions to alleviate them. Antifoulants design method and prefer a margin based method where
and/or corrosion inhibitors may help and there are com- a limited heat transfer area is allocated to manage foul-
mercially available programmes, such as KBC’s HX mon- ing. When using resistance based design, up to 85% of
itor, for heat exchanger monitoring, advice on which the heat transfer area can be dedicated, from the design
exchangers to clean, and estimating the cost of the foul- phase, only to manage future fouling. In general, this
ing (such as increased energy consumption and CO2 results in very low velocities, leading to lower heat trans-
emissions, yield reduction, and throughput reduction). fer coefficients and higher tube wall temperatures, accel-
All these will help decide how much investigation is erating fouling development.
warranted and in justifying remedial action. • Whatever the selected heat exchanger technology
is, always take care of flow distribution in all the parts
A Jérémy Provost, Senior Technology Expert, Process & and avoid dead zone areas and bypass flows. These are
Technologies Division, Technip Energies, Jeremy.Provost@ starting points for fouling development. For instance,
technipenergies.com when designing a shell and tube heat exchanger, care-
There are few severe fouling root causes in a vacuum ful attention is given to the shell side to limit bypass and
unit’s preheat section. Their relative impacts depend dead zone areas with relevant baffle type selection and
mainly on the refinery’s strategy and objective (pro- arrangement.
cessing Middle East crude oils, heavy Canadian blend-
ings, capture opportunity crudes on the market, and A Berthold Otzisk, Senior Product Manager - Process
so on). These choices help determine the operation, Chemicals, Kurita Europe, berthold.otzisk@kurita-water.com
(required flexibility) of the preheat train and its design. The vacuum unit separates the heavier crude oil frac-
Nevertheless, the main causes which lead to severe foul- tions to decrease the boiling temperatures with a low-
ing are identified below. ering of the pressure. The boiling points are so high

that thermal cracking would occur under atmospheric heat system would be potential oxygen contamination
distillation. and interactions of compounds that result in precipita-
Many experienced specialists are working on vacuum tion either in a tank or as the solution is heated with an
heater designs and revamps to improve the efficiency increased propensity for precipitation. The challenge on
with less coke fouling. Vacuum heaters are typically cabin the passing effluent stream in preheat service is the tem-
or box type heaters with four or six passes in a single perature difference between the passing fluids and the
radiant cell. Maximising the convection section duty will resulting tube wall temperatures. On the bottoms side of
decrease the radiant section duty, which reduces the coke heat exchange, the tube wall engagement will be ‘cooler’
formation potential. The localised oil film temperature rising to a higher potential of ‘adherence’ to a surface
and oil residence time in the radiant section depend on and or cooling rapidly enough so as to enhance a precip-
the heat flux, tube mass flux rates, and bulk oil tempera- itate dropping out (some call this asphaltenes, however
ture. They are variables to minimise the rate of coking. it can be any maltene structure). The challenge in these
Some crude oils are less stable than others and have a services is to accurately identify the cause. Considering
poor thermal stability. Asphaltenes, maltenes, waxes, and this may be an interaction that causes some type of pre-
resins are components that change the behaviour and cipitate formation, find an appropriate solvent that can
structure with temperature, pressure, and the composi- keep the system flowing and in solution. In very severe
tion of crude oil. Asphaltenes are very sensitive to shear- services it is justifiable to install spare standby exchang-
ing forces and electrostatic interactions, which is why ers with rotation of cleaning and service to minimise the
vacuum units are often affected by asphaltene fouling lost revenue from outages. Others have found that some
and coking. Crude oils with poor thermal stability begin chemical additives work, but careful consideration is
to generate coke and gas at relatively low temperatures. required as to the impact on any downstream systems.
Crude unit heaters with a high outlet temperature and
high residence time in the crude column bottom decrease
the oil stability with rapid coke and gas formation. Q What is the optimum level of excess air in a natural draft
Minimising the oil film temperature and oil residence heater?
time will help to decrease the potential for coke forma-
tion, which improves the run length of the heater. A John Skelland, Senior Staff Consultant, KBC (A Yokogawa
Company), John.Skelland@KBC.global
A Chris Claesen, Technical Director, Nalco Water, Aim to operate the heater at its original design excess air
Chris.Claesen@ecolab.com level in the first instance. A good performance in mod-
There can be multiple reasons for this. If the preheat is ern heaters is 10% excess air (2% oxygen in the flue gas)
continuously fouling it may be a design issue related to for heaters fired with fuel gas. Fuel oil fired heaters usu-
exchanger design or configuration. The fouling can also ally require 15% excess air (about 3% stack oxygen). This
be related to crude blending, type of crudes processed, is often due to fuel oil burners being slightly more diffi-
impurities or contaminants content such as solids and cult to tune and operate. Operating at these low levels is
salts, desalter operation, and caustic addition. The use of made easier if automatic control is installed rather than
intermediate storage of atmospheric residue and blend- relying on frequent attention from the operators.
ing of other streams or imported materials can have a big It is sometimes possible to safely operate fired heat-
impact and needs to be evaluated. Key is to have a good ers at stack oxygen contents as low as 1% (~6% excess
model of the heat exchanger train that can track the per- air) if an advanced control system such as Yokogawa’s
formance of the whole train by NFIT and of each individ- Combustion One is installed. This system, incorporat-
ual exchanger such as Nalco Water’s Monitor. This can ing tunable diode laser spectroscopy (TDLS), gives fully
help to correlate fouling events with feed composition automatic control and optimisation of the combustion
and operational conditions. It is also important to have a process. It measures oxygen, carbon monoxide, and
good analytical programme in place to trend feed stabil- methane concentrations in the flue gas to prevent the risk
ity, composition and contaminant content. This, together of unstable combustion.
with analyses of fouling material, can help determine the
root cause and develop a mitigation strategy. The mitiga- A Edwin Voeten, Furnace & Combustion Expert, Petrogenium,
tion can be by elimination of problem crudes, improved Edwin.voeten@petrogenium.com
contaminant removal in the desalters, and controlled Optimal value excess air should be evaluated on a case-
blending for increased stability. This can be combined by-case basis. However, as a design case 3 vol% O2 in
with the use of a properly selected antifoulant, such as flue gas is typically used, which corresponds to some
Nalco Water’s Thermogain which deals with the identi- 15% excess air over the stoichiometric requirement.
fied fouling mechanism. The use of a forced draft fan is done for technical, eco-
nomic, and/or historical reasons.
A Mel Larson, Strategic Consulting Manager, Becht, mlarson@ The incentive to lower excess air is economics. As a
becht.com guideline, some 1% fuel efficiency can be gained for
This is a bit of an unusual question as most vacuum col- every 2 vol% of O2 reduction in flue gas. Excess air is
umns are fed directly from the atmospheric column. A easier to control by use of a forced draft fan (together
‘pre-heat’ section would indicate a standalone vacuum with other benefits from a forced draft arrange-
column before the furnace. On the feed side of a pre- ment). However, this requires additional capex.

Consequentially, a forced draft arrangement is typically designed to produce high purity hydrogen, methane
used in larger heaters. reacts with steam in a dedicated heater to produce a con-
In a natural draft heater, for every process change or verted syngas which, after CO shift, contains mainly
upset an operator may need to make changes to indi- hydrogen and CO2. The syngas is then purified through
vidual burner air registers in the field (and draft con- a PSA to produce hydrogen at 99.9% purity and a purge
trol/stack damper as well). Significantly, there may be gas that contains CO2, CO, and some hydrogen. This
an incentive to move towards forced draft where opera- purge gas is routed back as a fuel to the SMR furnace.
tion is expected to be less stable. Alternatively, in a nat- The SMR furnace produces a flue gas containing all of
ural draft unit a wider margin in excess air (a higher the CO2 emitted by the SMR unit.
value than the design value) can be used to minimise There are two main locations at which CO2 can be cap-
the risk of sub-stoichiometric firing from any operational tured: either the converted syngas identified as location
changes or upsets. This then has an economic penalty A or the flue gas identified as location B in Figure 1. CO2
(see the numbers above). absorption from syngas is much more favourable as it is
As a result, it is not uncommon to see a natural draft at high pressure and there is consequently a large driving
unit in the field operate in the 4-5 vol% O2 range, or force to absorb CO2. The syngas is quite pure and does
higher. Although I should mention that this often is a not contain any oxygen but it contains only part of the
consequence of operational staff having ‘other priorities’ CO2 emitted by the SMR unit (up to 60% depending on
and improvements are feasible. the scheme and operating conditions).
Note that this refers to gas fired natural draft units, Adversely, the flue gas contains all of the CO2 emit-
which is the standard. I know of less than a handful of ted by the SMR and up to 90% of the CO2 emitted can
oil fired natural draft units (in Turkey, Kazakhstan, and be absorbed there. But the flue gas conditions are harsh:
Russia). Such units should not have been designed with low pressure, high temperature, and a few per cent O2
the combination of fuel oil and natural draft, as this is a in the gas.
continuous source of trouble. Last thing I heard, the unit In terms of technology, a typical amine based acid
in Turkey was to be converted to forced draft. gas removal unit with activated MDEA can be used
to absorb all of the CO2 in syngas (up to 99%). Steam
A Grant Jacobson, Division Manager, Fired Heater Services, energy consumption can be reduced to about 1 GJ/t of
Becht, gjacobson@becht.com CO2 with an optimised process scheme which avoids
It depends on the heater design and operating objec- about 57% of the CO2 emissions of the SMR unit. The
tives. For most applications, optimised excess air (or avoided CO2 readily takes into consideration emissions
excess oxygen if discussing on just an O2 basis) can be of CO2 due to energy consumption in the carbon cap-
set between 15% and 25%. To confirm where this can be ture unit. This gives a better insight into the amount of
optimised safely it is important to conduct a CO break- CO2 that is effectively recovered in the overall process.
through test and then set the optimisation targets based CO2 emissions of a SMR unit can be significantly
on where CO breakthrough is observed. An example of reduced by installing mature technology such as
this would be if CO breakthrough occurs at 1.5% excess Advamine EnergizedMDEA technology which is
O2; the target to operate normally would be set at 3.0- licensed by Axens for syngas.
4.0% excess O2. It is critical to not lose sight of keeping On the other hand, solvent based post-combustion car-
fired equipment stable and safe, and optimising to rea- bon capture processes that are required to capture the CO2
sonable targets when able to do so. in flue gas are much more energy demanding. The steam
energy consumption of a first generation carbon capture
process such as a MEA solvent based process is up to 3.7
Q What options are there for CO2 capture from a SMR based GJ/t of CO2. The amount of CO2 avoided is, as a conse-
hydrogen unit? quence, only 67% considering the additional CO2 emitted
to regenerate the solvent. Post-combustion carbon capture
A Clément Salais, Associate Group Manager, Gas Business from flue gas enables further reduction of CO2 emissions
Group, Axens, clement.salais@axens.net from the SMR unit but requires the development of new
In a typical steam methane reforming (SMR) unit solvents and new processes to be more energy effective.
Flue gas B
A B
Syngas Flue gases
Inlet gas pressure 30 bar atm
Methane
Syngas Hydrogen Inlet gas CO2 content 17.3% 18%
Feed pretreat CO- A PSA
& reforming Shift Inlet gas CO2 partial 5.2 bar 0.18 bar
pressure
H2 recycle O2 in the inlet gas No -traces Few %
CO2 captured on SMR 60% 90%

Aux. Fuel Purge gas
Figure 1 Steam methane reforming: where to capture CO2?

Perfor
produced in low-carbon ways from electricity or with
Performance of post-combustion carbon capture processes
carbon capture and storage (CCS).
A B B Syngas, a mixture of hydrogen and carbon monox-
Syngas Flue gases Flue gases ide (H2 and CO), is produced on a large scale via steam
Technology for CO2 capture AdvAmine MEA process DMX process reforming of natural gas and water. In the steam reform-
Typical energy requirement 1.0-2.5 3.7 2.9
(GJ/t CO2) ing process, carbon dioxide (CO2) is produced as a
CO2 ‘avoided’ in SMR, % 57.01 67.0 72.0 by-product and emitted from two different sources: as
part of flue gas and as part of process gas.
1 Considering 1 GJ/t CO2 as the energy requirement
BASF’s OASE white is a proven amine scrubbing tech-
nology for deep CO2 removal from syngas and offers
Table 1 great energy efficiency and robust operation, achiev-
ing the minimum targeted process gas CO2 capture rate
Axens is currently developing, with IFP Energies of up to 99.97 mass%. The treated syngas can be further
nouvelles, a new process for post-combustion car- separated into H2 and CO to be used as a key raw mate-
bon capture called the DMX process that is much less rial for various products. OASE white technology has
energy intensive than first generation processes. It is a been successfully applied in many world scale ammonia
solvent based technology but with a new solvent that plants, syngas plants for petrochemicals, and others such
has specific demixing capabilities under certain con- as steel production (see Figure 1).
ditions of pressure and temperature. The energy con- Moving forward, the use of pure hydrogen (H2) can
sumption of the DMX process can be reduced to 2.3-2.9 support cleaner fuel for vehicles, whereas the high purity
GJ/t CO2 compared to the 3.7 GJ/t CO2 of the MEA CO2 captured by OASE white can support direct carbon
process, leading to further reduction of CO2 emissions capture and utilisation (CCU) to manufacture chemical
from the SMR unit as the CO2 avoided increases to 72% products on a commercial scale. CCS is also possible.
(see Table 1). For flue gas carbon capture, OASE blue technology
Its performance is proven at laboratory scale but was developed specifically as an optimised post-combus-
needs to be demonstrated industrially in order to tion capture technology with low energy consumption,
be ready for commercialisation. This demonstration low solvent losses, and a highly flexible operating range.
is in progress through the 3D Project funded by the A core task for the design of carbon capture technol-
European Union (H2020 - Grant Agreement N°838031). ogy is to reduce solvent loss by reason of economic effi-
It includes the construction of a demonstration unit at ciency and environmental friendliness. The development
the ArcelorMittal Steel Mill in Dunkirk, France which is programme of BASF with OASE blue for flue gas CO2
already in progress. Operation of the unit will begin in emissions capture and OASE white for process gas CO2
early 2022. emissions capture is demonstrating that, by combining
two effective technologies, the target of lowest CO2 foot-
A Elena Petriaeva, Technical Marketing Manager Middle East/ print overall is possible.
Central Asia, BASF OASE Gas Treatment Excellence, elena.
petriaeva@basf.com; Bernhard Geis, Industry Manager Europe/ A Ulrich Koss, Syngas & Syngas Conversion Expert,
Africa/Russia, BASF OASE Gas Treatment Excellence, bernhard. Petrogenium, ulrich.koss@petrogenium.com
geis@basf.com In a refinery, steam methane reforming (SMR) based
To meet the emission reduction targets required by 2050 hydrogen production represents one of the most promi-
under the Climate Change Act, energy sources will nent single-point sources of CO2 emissions. It consists of
need to shift to an almost entirely carbon-free energy. three consecutive process steps. In the steam reformer,
That points to a larger role for hydrogen, which can be a mixture of natural gas and steam is ‘reformed’, which
Raw material & process Chemical building blocks Present Future
OASE blue Carbon dioxide Liquid CO2 as food refrigerant

Natural (CO2) and other commercial uses Direct carbon capture
gas
Venting to atmosphere and utilisation (CCU) to
By-product
make chemical
products e.g. Methanol
Steam Flue gas CO2 Acid gas Supreme energy efficiency Carbon capture and
reforming removal unit Robust operation storage (CCS)
OASE white (AGRU) <20 ppm CO2 slip
Separation H2 as cleaner fuel for

Hydrogen
transportation
Syngas (H2)
Process gas
CO2 Carbon
monoxide Petrochemical products e.g. Ammonia, Methanol, Formaldehydes,
(CO) Acetic acid, Fischer-Tropsch conversion for added value chemicals.
Figure 1 Applications of OASE white amine scrubbing technology

means it is converted to syngas – a mixture of H2, CO, bustion temperature reasonably low, the amount of CO2
and CO2. The reforming reaction is strongly endothermic internally recirculated is 4-5 times larger than the amount
and consumes a lot of heat, which is provided by com- finally captured.
busting gas in the furnace of the SMR. Other (non-SMR):
In the downstream reactor, the water gas shift (WGS) If a new, large-scale blue H2 production is planned, a
reaction converts CO and steam contained in the syn- different concept can be applied: in such a case, an ATR-
gas to additional H2 and CO2. Third, a pressure swing solution is considered the optimum. Here, the SMR
adsorption (PSA) is used to separate a pure H2 prod- is replaced by a high pressure O2-driven autothermal
uct from the converted syngas. The PSA accumulates all reformer (HP ATR), which does not require external fir-
other components in an off-gas stream, consisting mainly ing. The converted syngas of this system offers a high
of CO2 but also containing unconverted CH4, CO, and CO2 concentration at a high pressure. CO2 extraction can
some H2. This gas is added to the fuel to the SMR burn- be accomplished very efficiently not only by the ‘work-
ers. Thus, all carbon contained ultimately ends up as CO2 ing horse’ amines but also using a simple cold methanol
in the SMR flue gas. The aim is to upgrade this ‘grey’ H2 absorption/flashing loop. ATR technology is available
production a to a ‘blue’ one, by adding carbon capture. from ThyssenKrupp Industrial Solutions, Air Liquide,
A first option is to add post-combustion CO2 capture Haldor Topsoe, and others. It requires an ASU to pro-
in the SMR flue gas path. This solution is successfully duce the O2 for the ATR.
applied to fertilizer production, where natural gas is con- A newcomer among the technologies for the CO2 emis-
verted into H2, then ammonia, and ultimately urea. For sion-free production of H2 from natural gas is the pro-
converting all ammonia into urea, more CO2 is needed duction of ‘turquoise’ H2 by means of methane pyrolysis.
and can be extracted from the syngas. To close this gap, a Here, the natural gas is directly de-composed to H2 and
handful of these plants source additional CO2, extracting carbon black solids, where the latter can be used as a
it from the flue gas of their SMRs using amine post-com- feedstock in tyre production or in any other industry
bustion capture technology. Oxygen and NOx pres- consuming carbon black. The technology is being devel-
ent in the flue gas require amine technology specifically oped by BASF, Linde, and ThyssenKrupp Industrial
adapted to such service, to keep emissions, corrosion, Solutions, but it is not yet fully commercial.
and amine degradation under control. Most references
use Mitsubishi’s KS-1 technology. Other technologies A Joris Mertens, Principal Consultant, KBC (A Yokogawa
available are BASF´s OASE blue, Aker’s CleanCarbon, Company), Joris.Mertens@KBC.global
DOW’s UCARSOL FGC3000, Fluor´s Econamine FG or CO2 can be captured from SMRs at different locations
Shell´s Cansolv. All consume considerable amounts of and using different technologies. Nearly all installations
steam. Amine degradation and emission control so far use amine solutions as the technology to capture CO2 and
have been a persistent problem and a relevant cost factor. we are aware of one large scale cryogenic CO2 capture
A second option is to add a compact amine wash plant.
between WGS and PSA. Such syngas amine wash selec- In SMRs most CO2 is generated at the process side,
tively extracts all CO2 upstream of the PSA, yielding not by burning fuel in the reformer furnace. Therefore,
a pure CO2 stream and a CO2-free PSA off-gas. Here, it is possible to capture most CO2 ‘pre-combustion’ after
the well-referenced ‘working horses’ of gas clean-up the shift reaction step, prior to the PSA and the furnace.
are applied, among them BASF´s aMDEA, Dow´s This has the advantage that pressure (and therefore driv-
UCARSOL, etc. This strategy is far more economical and ing force for amine capture ) is high, which considerably
easier to operate than the above post-combustion cap- reduces capital cost and plot space. However, it will not
ture. The downside is that only the ‘low hanging fruits’, allow one to capture all CO2 generated on the unit (even
the CO2 in the syngas, are captured. This is whilst the if capture would be 100% efficient) because CO2 gener-
CO2 generated in the SMR firing remains emitted, delim- ated by the fuel of the furnace is generated after capture.
iting the capture rate to 60%. Higher rates are possible if Pre-combustion capture will enable capturing 5-6 tonnes
the SMR is converted to H2-firing. However, such a strat- of CO2 per tonne of hydrogen produced while the total
egy will massively derate the SMR´s capacity, as it must CO2 emissions of the unit are at least 8 tonnes per tonne
produce the H2 fuel additionally to the H2 product. of hydrogen output.
Small-scale, electrically heated SMR (eSMR) tech- Post-combustion capture of the CO2 from the SMR fur-
nology exists, offering a hybrid between natural gas nace flue gas also has the advantage that it is a tail-end
and electricity. Future large-scale eSMRs, implemented solution which in many cases will be easier to fit in. But
together with the syngas amine wash, boost the capture it will be larger in size and require more capital invest-
rate but require an alternative outlet for the PSA off-gas. ment. In short, the choice between pre- and post-com-
A third option is to apply oxy-firing, which basically bustion is the result of a trade-off between a number of
means replacing N2 in the combustion air by recircu- advantages and disadvantages, the main ones being the
lated CO2. Doing so, the flue gas will largely consist of investment cost and the amount of carbon captured.
CO2 and water. After water condensing, the CO2 remain-
ing is purified and compressed. The principle is simple A Mel Larson, Strategic Consulting Manager, Becht, mlarson@
but requires an air separation unit (ASU), a quite sophis- becht.com
ticated tail gas treatment, and a substantial revision of Most modern SMRs have a means of hydrogen purifica-
the SMR firing and safety concepts. To keep the com- tion, commonly now it is either pressure swing absorp-

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tion and or a prism system. The effluent or reject stream percentage reduction in emissions based on any CO2
will be rich in CO2 (40-45 mol%). This stream is the can- credit (for EOR or as by-product), or regulatory require-
didate to be processed further either with cryogenic or ments and related credits or taxation going forward.
solvent systems to concentrate the CO2. The concen-
trated CO2 can be used for enhanced oil recovery. New Q Please explain the best approach to cutting NOx emissions
technologies are being developed to consider absorption from a gas turbine.
systems although not many have been taken to the com-
mercial scale yet. A Jan Zander, Energy Systems & Utilities Expert, Petrogenium,
jan.zander@petrogenium.com
A Sanjiv Ratan, Consulting Director, Zoneflow Reactor A new gas turbine should have proven low NOx burners
Technologies, SRatan@zoneflowtech.com (nothing new here). Some attention should be given to
For capture from a SMR based hydrogen unit, there are the low NOx technology if a partial load of the gas tur-
principally two CO2 containing streams - the shifted bine is required (such as in Oman LNG). For existing gas
process gas and the combustion flue gas. Typically, in a turbines it might be possible to retrofit low NOx burn-
hydrogen plant, the CO2 content of the shifted gas is sep- ers. In extreme cases, steam injection may be required
arated (along with other components) in the PSA unit in to reduce NOx. Water injection has been applied on gas
the form of its low-pressure purge gas. The purge gas is turbines in refineries, but may cause higher maintenance
usually utilised as primary fuel for SMR firing, which costs (burners and blades).
caters for the larger part of the SMR fired duty, and the
remaining heat release is provided by the make-up fuel A Paul den Held, Rotating Equipment expert, Petrogenium,
(also for firing control). paul.den.held@petrogenium.com
Accordingly, the flue gas ends up with the combined As an introduction, the NOx in the gas turbine combus-
CO2 from the hydrocarbon feed as well as make-up fuel. tion system is formed by the following three mechanisms:
Such a process configuration offers three options for 1. Thermal NOx: this is formed during fuel combustion
CO2 capture: by oxidation of molecular nitrogen (N2) in the combus-
1. From process gas upstream of the PSA unit tion air. The formation of thermal NOx is highly depen-
2. From PSA purge gas dent on the gas temperature.
3. From combustion flue gas 2. Prompt NOx: radicals like CH and CH3 can attack free
Options 1 and 2 are pre-combustion CO2 capture N2 in the air to form NOx.
alternatives but only offer partial capture (typically 3. Fuel NOx is produced by oxidation of nitrogen com-
around two thirds of the total load) whereas option 3 pounds contained in the fuel (up to 2% of the total NOx
can be combined with options 1 or 2 or just by itself as formed in the combustor).
post-combustion capture for higher CO2 removal. Each Two key parameters are normally used to character-
option has its pros and cons. ise the thermal NOx production during gas turbine com-
Option 1 is the simplest, most cost-effective, and most bustion: equivalence ratio (fuel to air ratio) and adiabatic
proven in terms of solvent based CO2 removal processes flame temperature. The relationship between the thermal
applied at process pressure on clean gas. It can be inte- NOx production and these two parameters is provided
grated in a new hydrogen plant as well as in a revamp in Figure 1.
project. The PSA purge gas volume reduces while its cal- Selection of the appropriate NOx abatement design
orific value increases, which increases NOx in the flue and the best approach for the gas turbine to reduce NOx
gas. The flue gas volume reduces on account of a lower depends on a number of factors:
volume of purge gas as well as some make-up fuel sav- 1. Type of combustion system available, refit or new
ings in lieu of avoiding heating up the removed CO2. design
Accordingly, the export steam quantity also goes down. 2. Type of fuel gas to be applied in the gas turbine
Option 2, though seldomly considered, may have more 3. Diluent available (steam, water or nitrogen)
relevance for CO2 removal retrofits in existing hydrogen 4. NOx limit requirements at the specific location
plants since it has no impact on the performance and/or 5. Manufacturers references on the typical fuel and fuel
adsorbent adaptation of the existing PSA unit. However, gas system
it needs pressure boosting to overcome the pressure There are different primary NOx abatement options.
drop and involves higher energy consumption for CO2
removal due to much lower CO2 partial pressures. In Conventional combustion systems
new plants, a PSA design can be optimised for higher For a gas turbine using mainly natural gas as the fuel
purge pressures versus reduced H2 recovery. The effect source and equipped with a conventional combustion
on the material and heat balance is similar to option 1 for system, the NOx abatement options are to apply a dilu-
the same CO2 removed. ent and select either water injection or steam injection.
Option 3, like any fired unit CO2 capture, suffers from Each of these options has its specific issues. These
limited available and/or well proven technologies, apart include the impact on the maintenance factor, the
from the capital and energy intensity of any post-com- reduced lifetime of the parts, and an obvious continu-
bustion capture. ous loss of water or steam. This technique is applied on
The choice and economics of CO2 capture in a SMR- many gas turbines in operation that are not equipped yet
based hydrogen plant are usually driven by the target with the dry low NOx systems. The diluent is applied

say, ammonia injection and a SCR catalyst
that converts NOx to molecular nitrogen.
No. 2 Oil, 10 atm
This system is only considered in the case of
Rate of production of themal NOx

Air preheat 590 k(600F)
Temperature
4000 2500 DLN combustion systems and the selection
300
High CO of a required diluent is not an option. The
d NO dt (ppv/ms)
Flame temperature
SCR has some distinct limitations.

emissions
3000 NO x
2000
200 In summary, the best approach to reducing
(k)
High smoke
NOx emissions from the gas turbine depends
(F)
emissions
2000
1500
on the NOx emission levels to be achieved,
100
the gas turbine hardware currently installed,
1000 the application of the gas turbine, diluents
0
available and the type of fuel gas used for
0.5 1.0
Equivalence ratio
1.5 the combustion.
Lean Rich
A John Skelland, Senior Staff Consultant, KBC (A
Figure 1 Equivalence (fuel to air) ratio and adiabatic flame temperature in Yokogawa Company), John.Skelland@KBC.global
thermal NOx production NOx emissions can be reduced by inject-
ing a small amount of water or steam into
to reduce the flame temperature and thereby reduce the the combustion zone, known as wet low emission tech-
NOx produced. nology (WLE). This reduces the temperature in the com-
The application of a diluent needs certainly to be con- bustion zone which reduces the rate of NOx production.
sidered for gas turbines operating on low-Btu type fuels, However, this water or steam injection is a thermody-
syngas types of fuel gases with a high content of hydro- namic loss and so reduces the energy efficiency of the gas
gen and CO2, and for coal gasification applications. For turbine. This technique also requires a supply of boiler
such fuel gas applications, the DLN systems may not feed water or steam to be provided. The technique has
be offered by the manufacturers. Petrogenium can offer historically been the most common retrofit to existing gas
experience in the evaluation of the designs offered by the turbines.
manufacturers. Alternatives to steam or water injection include:
• Dry low NOx combustion (DLN), a technology that
Dry low NOx combustion systems uses staged combustion and lean premixed fuel/air mix-
Dry low NOx (DLN) combustion systems are signifi- tures. This requires that the gas turbine has several com-
cantly more expensive (hardware costs are 30-40% more) bustors rather than a single combustor. It is very effective
than the standard combustor, and require a more com- in maintaining low NOx over the entire operating range.
plex staged fuel gas system and more intrinsically com- However, maintenance costs are generally higher than
plex fuel gas nozzles. Since NOx production increases for a standard gas turbine and the control system is more
exponentially with high adiabatic flame temperatures, complex. DLN upgrades are available as retrofits to some
the NOx abatement technologies focus on reducing the gas turbine models.
peak flame temperatures. This however conflicts with • Catalytic combustion: the turbine combines catalytic
the desire to have higher firing temperatures required combustion of fuel and air in a catalyst bed followed by
to achieve turbine efficiency. Modern DLN combustors normal fuel combustion at a low enough temperature to
manage this conflict by designing combustors that can prevent significant NOx formation. This technology is in
have lower peak flame temperatures whilst keeping the the early stages of commercialisation.
same firing temperatures. Combustion near stoichio- • Post-combustion exhaust gas clean-up systems includ-
metric conditions (equivalence ratio = 1) increases NOx ing selective catalytic reduction (SCR): this type of tech-
production. Therefore DLN combustors are designed nology requires the use of NOx reducing chemicals (such
around 0.5 equivalence ratio. This, however, brings chal- as ammonia) in the presence of a catalyst. The advan-
lenges, as combustors operating at this equivalence tages of this option include relatively low capital invest-
ratio often face risks of lean blow out (flame extinction). ment, a small footprint, and no need for modification to
Current gas turbine manufacturers each offer their spe- the gas turbine itself. However, operational expenses are
cific DLN combustion systems. high due to the cost of replacement catalyst. Also, the use
of hazardous chemicals such as ammonia is required.
Catalytic combustor (future systems) This technology can usually be installed as a retrofit to
The catalytic combustor is still in the ‘proof-of-concept’ existing gas turbines.
phase and requires substantial efforts before it is offered Of these, DLN is the most commonly used technology.
by manufacturers. Realistically speaking, it will be DLN and SCR can be combined where really low NOx
another 5-10 years or more before it would be commer- emissions are required.
cially available for heavy duty gas turbines.
A Greg Zoll, Manager, Power Generation Plant Services, Becht,
Secondary NOx abatement options gzoll@becht.com
Selective catalytic reduction works on the principle of The technology utilised for gas turbine NOx reduction is
removing NOx from the gas turbine exhaust utilising, well proven. It is almost universally achieved by use of

selective catalytic reduction (SCR) which utilises a vana- particle emissions (see Table 1). But, to properly answer
dium catalyst to reduce NOx to N2 and water. Ammonia the question of what is the “most effective”, requires an
is injected ahead of the catalyst as the reductant. For gas examination of other parameters such as:
turbines operating in combined cycle applications, the • What are the target emissions?
SCR is embedded in the heat recovery steam generator • What other contaminants need to be removed?
to achieve the correct exhaust gas temperature. In simple • What utilities are available?
cycle installations, cooling air is injected into the gas tur- • What is the available plot space?
bine exhaust ahead of the SCR. Alternatively, high tem- • What is the importance of capital cost versus operating
perature catalysts have been developed to eliminate or costs?
reduce the amount of cooing air required.
A Mel Larson, Strategic Consulting Manager, Becht, mlarson@
becht.com
Q What is the most effective way to capture particulates in The industry has two basic systems that maximise par-
FCC flue gas? ticulate removal from the FCC flue gas. In the US the
EPA expanded the definition of particulate from cata-
A Raj Singh, High Olefins FCC Technology Manager, Technip lyst by adding condensable particulates. This answer
Energies, Raj.singh@technipenergies.com; Steve Shimoda, will concentrate on the catalyst element. The systems
FCC Technology Director, Technip Energies, Steve.shimoda@ can be divided into wet and dry. A wet system is a flue
technipenergies.com gas scrubber where the flue is passed through a ven-
Today, refiners are taking a number of steps to reduce turi chamber that has a solution which will trap catalyst,
emissions across their operations to lower the environ- react with SOx, and make a slurry solution that can be
mental impact. FCC regenerators are the largest single used for other purposes. Scrubber systems often have a
source of particulate emissions in refineries. Capturing third stage catalyst separation system before the scrubber
catalyst particles from flue gas is accomplished through a to assist recovery of catalyst.
combination of equipment. The primary equipment uti- A dry system is most often but not always a two stage
lised are regenerator cyclones. The catalyst losses from a system of third stage multiple cyclone separation fol-
FCC regenerator are generally in a range of 250- 450 mg/ lowed by a electrostatic precipitator (ESP). The most
Nm3. effective system will be a function of location. In arid
The selection of equipment downstream of the regen- locations where water is a scare resource, using water
erator depends on additional objectives besides the cap- may not be desired, even if the mass of loss is lower
ture of catalyst fines. Typically, a third stage separator than in an ESP. ESPs have a narrower operating tem-
(TSS) provides a further reduction of catalyst in the flue perature range, allowing for some energy inefficiencies.
gas. This is critical for units that include a turboexpander Optimally, regardless of flue clean-up, always consider
for power recovery. Depending on the underflow capture the most efficient means to extra value from the FCC flue
device, the TSS system can bring the catalyst loading to gas, be it steam generation, power generation from pres-
less than 150 mg/Nm3 for a underflow cyclone, or 100 sure letdown, and or a combination of both to maximise
mg/Nm3 for an underflow filter. the energy recovery.
To get below 50 mg/Nm3, either an electrostatic pre-
cipitator (ESP) or a flue gas scrubber is used. A flue gas A King Yen Yung, Fluid Catalytic Cracking Expert, Petrogenium,
scrubber (FGS) can also reduce SOx emissions. However, kingyen.yung@petrogenium.com
scrubbers require water, which can be a challenge for cer- Before deciding on the most effective option, one should
tain locations, although they do alleviate the safety con- consider what the specifications are for the reduction of
cerns that have been associated with ESP use during particulates in the FCC flue gas being ultimately released
transient operation. to the atmosphere.
An alternative to the ESP and FGS is a full flow barrier Standard FCC units are equipped with two stage
filter. These are offered by a couple of suppliers and have cyclones in the regenerator. Nowadays many countries
demonstrated the capability to reduce particulates to less prescribe that dust emissions be reduced to a level below
than 5 mg/Nm3. There are not many installations, but at 50 mg/Nm3 which requires additional catalyst fines cap-
least one has been in operation for over 15 years. turing capacity. The most cost effective and simple way
The barrier filter has demonstrated to obtain the lowest to achieve this is the installation of third and fourth stage
separators (for instance, TSS and FSS from Shell licensed
through Dupont).
Summary of typical particulate emissions
The TSS/FSS system enables separation of virtually
Equipment Effluent particle loading, mg/Nm3 all erosive particles and hence protects the power recov-
Regenerator cyclones 250-450 ery expander and is fully contained in a single vessel of
TSS with underflow cyclone <150 proven mechanically sturdy construction.
TSS with underflow filter <100 Only when a TSS/FSS system is not able to meet the
ESP <50
Flue gas scrubber <50 dust emissions limit should someone consider the instal-
Barrier filter <5 lation of a far more expensive and operationally cum-
bersome electrostatic precipitator or wet gas scrubbing
Table 1 system.

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art.indd 1 12/03/2021 12:28

A smart approach to tank dewatering
A tank dewatering technology using smart sensors is designed to reduce hydrocarbon
losses and raise the quality of crude supplies to the refinery without process interruption
FAWAZ AL SAHAN, OMAR AL ZAYED and FAWAZ AL HADLAQ

Saudi Aramco
H
ydrocarbon tank dewatering is
a crucial process in the oil and Downstream transducer
gas industry. It impacts safety,
the environment, health, hydro- td
carbon losses, and crude quality. The sound velocity dewatering

Flow direction
L system was initially tested on crude tanks sinc
Flow direction
D
Improper tank dewatering can result
in incidents, process interruption, has a smaller difference in sound
tu
velocity
θ
than refined products like diesel an
tank corrosion, and customer claims.
Traditionally, there have been two when compared to water. Figure 2 shows how a sound velocity sensor can r
Upstream transducer
types of dewatering solutions: man- the difference between crude (with
1 sound ( td + tu ) Laround 1510 m/s) and wat
1 1 velocity
The speed of sound becomes c= L + =
ual and automatic. Common auto- 2 td tu td tu 2
matic dewatering solutions include sound velocity around 1260 m/s).
internally mounted microwave and Figure 1 Sound velocity sensor principle of operation Source: efunda
capacitance sensors and externally
mounted drain valves, microwave
and capacitance sensors on the Water
Water sound
sound velocity
drain pipes. velocity
For the first time in the oil and gas
industry, three disruptive solutions
for hydrocarbon tank dewatering
have been deployed: a sound veloc-
ity dewatering system, internally
mounted interface sensors, and Crude sound velocity
Crude sound
a combination of the two – smart velocity
dewatering.
Sound velocity dewatering system Figure

Figure 2 Sound
2 Sound velocity system
velocity dewatering dewatering system
– testing on crude – testing on crude
A sound velocity dewatering sys-
tem utilises a non-intrusive smart ments for the successful set-up of a The process parameters flow and
sensor, control system, and drain sound
Therevelocity dewatering
are a number system. sound for
of requirements velocity should be displayed
the successful set-up of a sound velo
control valve. The non-intrusive The sound velocity sensor requires remotely at the control system in
sensor has two transducers, which dewatering
correction system.
against The sound
the fluid’s oper- velocity sensor the
order to recognise requires
drainedcorrection
media against the
transmit and receive sound waves ating temperature as sound veloc- and calculate its volume, and also to
and recognise the media type based
operating temperature as sound velocity is temperature dependent. The sens
ity is temperature dependent. enable the detection of the drain con-
on its unique measured sound The sensor’s
location on location
the drain on pipe
the drain
shouldtrol
bevalve’s condition
correctly (stuck, as
selected passing,
the location will alw
velocity (see Figure 1). pipe should be correctly selected or healthy). A sound velocity value
The sound velocity dewatering of the
as fluidlocation
with awill
certain
alwaysmaximum
be full velocity,
should be to avoid for
estimated vortices inside the tank and
the drained
system was initially tested on crude of fluid with a certain maximum water and for the hydrocarbon at
tanks since crude has a smaller bubble to
velocity, formation in the
avoid vortices drain
inside thepipe. If the temperature.
operating current pipingThisdoes
can benot help in achie
difference in sound velocity than tank and to prevent bubble forma- found in the literature or calculated
some minor modifications to the drain pipe will be helpful, such as adding an
refined products like diesel and tion in the drain pipe. If the current by software.
naphtha when compared to water. piping
reducer does
withnota help
smallerin achieving
pipe size, orAfter installation
adding of the
a manual system,
valve downstream the s
Figure 2 shows how a sound velocity that, some minor modifications to field testing should be conducted
sensor can recognise the difference which
the draincan bewill
pipe partially closed.
be helpful, such during commissioning to ensure
between crude (with sound velocity as adding an elbow, a reducer with that the sound velocity sensor data
around 1510 m/s) and water (with aThe process
smaller parameters
pipe size, or adding a flow
man- and sound velocity
is healthy shouldsignal/
(signal strength, be displayed remote
sound velocity around 1260 m/s). ual valve system
control downstream of the to
in order sensors noise the
recognise ratio, no lossmedia
drained of signals). In
and calculate its volum
There are a number of require- which can be partially closed. addition, testing will enable selection
also to enable the detection of the drain control valve’s condition (stuck, pass
healthy). A sound velocity value should be estimated forPTQthe drained water an
Q2 2021 21
hydrocarbon at operating temperature. This can be found in the literature or c

by software.
Q2 Aramco.indd 1
After installation of the system, field testing should be conducted during comm
15/03/2021 10:55
Figure 4 shows the first sound velocity d
Saudi Aramco Riyadh refinery.
20.00
19.00 1540.00
18.00 1520.00
17.00 1500.00
16.00
1480.00
15.00
1460.00
14.00
VOLUME(OPER) (m3/h)
13.00 1440.00
Sound velocity (m/s)
12.00 1420.00
11.00
1400.00
10.00
1380.00
9.00
8.00 1360.00
7.00 1340.00
6.00
1320.00
5.00
1300.00
4.00
3.00
2.00
1280.00
1260.00
Figure 4 Sound velocity dewatering syst
Figure 4 Sound velocity dewatering
system set-up
1.00
1240.00
0.00
12:37 15:24 18:10 20:57 23:44 02:30 06:17 08:04

Figure 4 shows the first sound
velocity dewatering
Internally system, installed
mounted interface sensors
24.00 1540.00
for a crude tank at Saudi Aramco
23.00
22.00
1530.00 Riyadh
The refinery.velocity dewatering system h
sound
1520.00
21.00
20.00 1510.00
dewatering cycle some hydrocarbon will

1500.00
19.00
18.00 1490.00 Internally mounted interface sensors
17.00
16.00
1480.00
The sound velocity dewatering sys-
VOLUME(OPER) (m3/h)
1470.00
15.00
pipe.
tem hasBefore the start
one limitation of the
whereby at next drainag
Sound velocity (m/s)
1460.00
14.00
1450.00
the end of every dewatering cycle
13.00
12.00 1440.00
drained before will

some hydrocarbon water starts to flow in the
be trapped
11.00 1430.00
10.00 1420.00
along with water inside the drain

9.00
1410.00
8.00
addition ofthe
an start
internally mounted sensor
7.00 1400.00
6.00
5.00
1390.00 pipe. Before of the next
1380.00
4.00 1370.00 drainage cycle, this trapped hydro-
There are various types of internally mou
3.00
carbon should be drained before
1360.00
2.00
1.00 1350.00
0.00 1340.00
water starts to flow in the drain pipe.
include pressure
this issue,sensors,
the additionsound velocity
-1.00 1330.00
To overcome
15 09:24:25 09:24:45 09:25:05 09:25:25 09:25:45
09:24:35 09:24:55 09:25:15 09:25:35 of an internally mounted sensor was
these
explored.can be installed inside a hydrocarb
Figure 3 Sound velocity dewatering system – draining cycle operation (blue line is flow There are various types of inter-
measurement, red line is sound velocity measurement) water interface
nally mounted level. sensors.
interface
The best options include pressure
of the best cut-off point for the valve starts as water starts to be drained sensors, sound velocity sensors, or
to start closing at the end of every from the tank. guided wave radar (GWR). All of
drainage cycle. 3. If the sound velocity value drops these can be installed inside a hydro-
During commissioning, one must to a preset value (1400 m/s, for carbon tank and enable direct meas-
cross-check the drained media example), the valve will close auto- urement of the water interface level.
(water, hydrocarbon, or a mixture/ matically as the sensor starts to GWR has many advantages as it
emulsion) by hydrocarbon detec- detect traces of hydrocarbon in the indicates both the total and interface
tion paste throughout the test. This drain pipe. level, but this technology cannot
is to confirm that the sound velocity 4. In case of failure of the sound measure the water interface if the
sensor reading matches the media velocity sensor, the transmitter, or tank height exceeds a certain limit
inside the drain pipe. the signal during the drainage cycle, (10m normally) as the GWR signal
A sound velocity dewatering sys- an alarm is initiated and the drain energy will be lost once it reaches the
tem can be operated manually by valve will automatically close. water level. To overcome this limita-
opening the drain control valve to 5. If the dewatering cycle exceeds tion, side-mounting is a solution, but
trigger the drainage cycle, or auto- the expected pre-set duration (20 this requires the tank to be empty
matically based on a timer. The time minutes as an example, determined for it to be installed. A 4in nozzle
is based on historical data of how during commissioning), an alarm is with a purge mechanism will also be
much and how often water accu- initiated and the drain control valve required (see Figure 5).
mulates inside the hydrocarbon will automatically close. Another promising internally
tank. The sequence of operation of a 6. If the drain control valve is stuck mounted solution is pressure sensors
sound velocity dewatering system is: or internally leaking (passing) after which can be top or side mounted
1. Flush the drain pipe for, say, 30 receiving a command to close, an and can measure pressure, differ-
seconds to ensure that there is no alarm is initiated for operations per- ential pressure, water interface
trapped hydrocarbon in the drain sonnel to plan a corrective action. level, total hydrocarbon level, and
pipe. Figure 3 shows the sound velocity fluid temperature (see Figure 6). This
2. Sound velocity measurement dewatering system in operation. solution also has the capability to
Q2 Aramco.indd 2 15/03/2021 10:55

0.4 Echo curve
Positive probe end 1

0.2
2
3
0.0
False signal suppression

-0.2
Probe length
-0.4
100% 0%
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Figure 5 Internally mounted interface GWR sensor side mounted for empty tank echo testing
measure fluid density. The system Internally mounted interface (pressure)

are easy to install, maintain, and
utilises a pair of smart pressure sen- sensors: interface measurement accuracy replace while the tank is in operation
sors. Both sensors are of different and provide a cost effective solution
lengths and are installed from the for measuring water interface inside
Manual dipping, m DCS reading, m
top. One is immersed so that it is 0.215 0.202 hydrocarbon tanks.
close to the tank bottom where water 0.215 0.205
is present, and the other sensor is 0.24 0.221 Smart dewatering
inserted in the hydrocarbon (above 0.24 0.225 Smart dewatering is a digital
0.24 0.214
the maximum expected water level). 0.24 0.225 transformation technology which
The internally mounted pres- 0.24 0.227 provides a safe, simple, and econom-
sure sensors system was installed at 0.24 0.221 ical automatic dewatering system by
Saudi Aramco Riyadh refinery for 0.08 0.11 combining a sound velocity dewater-
0.06 0.11
testing. Manual gauging was used 0 0.07 ing system and internally mounted
to measure the actual water interface 0 0.08 interface sensors.
level inside the tank and to compare 0 0.08 The technology has two sets of
againt the smart sensors’ readings. smart sensors, one measuring the
Data was collected during different Table 1 water interface inside the tank and
days and times and revealed match- one measuring fluid in the drainpipe,
ing readings. Table 1 shows some of One set of smart sensors provides six in addition to a controller and a drain
the data collected and the difference measurements: pressure, differential control valve. The primary sensor, an
between the manual gauging and the pressure, total level, water interface internally mounted interface smart
internally mounted pressure sensor level, temperature measurement, sensor, measures the water interface
readings. Figure 7 shows continuous and tank overfill protection. They level and starts the dewatering cycle
measurement of the water interface provide a redundant or alternative when the water level reaches a set
level inside the same tank at Saudi level measurement for crude tanks point. The secondary sensor, a sound
Aramco Riyadh refinery. in addition to the existing tank gaug- velocity smart sensor, is mounted on
Internally mounted pressure sen- ing instrument. The sensors can be the drain pipe and used as a back-up
sors deliver numerous advantages. flush mounted with a self-cleaning sensor for stopping the dewatering
diaphragm and are small in size (1in operation if hydrocarbon is detected
threaded connection). The sensors in the drain pipe. The secondary sen-
0.350
0.300
0.250
Probe
length
12990 mm 0.200
Probe 0.150
length
17990 mm
Maximum interface 0.100
5000 mm
0.050 Z88CL4444.CPV1
Minimum interface 0.000

04-May 0:00 06-May 0:00 08-May 0:00
03-May 0:00 05-May 0:00 07-May 0:00 09-May 0:00
Figure 6 Internally mounted interface
(pressure) sensor set-up Figure 7 Internally mounted interface (pressure) sensors: water interface in crude tank
Q2 Aramco.indd 3 15/03/2021 10:55

Acknowledgment
The authors would like to acknowledge
inspiration and unprecedented support from
Saudi Aramco Riyadh refinery management,
primarily the Refinery Manager Abdulrahman
Sound-velocity sensor
(clamp-on or inserted) Al Fadhel, for supporting the team throughout
Hydrocarbon
tank proof of concept, piloting, filing of two patents,
Internally and acknowledging the authors’ efforts in this
mounted
sensors journey which started in 2010. The technology
has achieved multiple milestones and received
many recognitions, starting with The King
Sound-velocity Salman Award, then the The Gulf Engineering
transmitter
DCS Output to Union Award and Saudi Aramco company
Control drain-valve awards (ESARP and BOE).
system
Further reading
Figure 8 Smart dewatering set-up
1 Hadlaq F S, Sahan F A, Zayed O Z, Smart
Dewatering, US Patent Application Serial No.
sor calculates the volume of drained manually drain water from hydro- 16/806,091, 2020.
water in addition to providing ana- carbon tanks by providing a fully 2 Sahan F A, 2018, Multi-Layer Flow and Level
lytical information on the drain con- automatic solution. Visualizer, US Patent no. 10,126,155 B1.
trol valve’s condition (stuck, passing, • It eliminates water overflowing to 3 Sahan F A, Zayed O Z, Sound Velocity
or healthy). customers during shipment of crude Dewatering System, US Patent no. 9,086,354
Smart dewatering’s advantages and refined products. B2, 2015.
include the following: Figure 8 shows the complete smart 4 Sahan F A, Hadlaq F S, Saudi Aramco
• Smart dewatering is an IR 4.0 ena- dewatering set-up with both sets Engineering Report SAER- 8964: Water Interface
Continuous Measurement in Crude Tanks, 2018.
bler. It has smart sensors providing of sensors, control system, and the
5 Introduction to Transit Time Ultrasonic
multiple process parameters and drain control valve.
Flowmeters, efunda engineering fundamentals,
data analytics: www.efunda.com
■ Total level Conclusion
■ Overflow protection Smart dewatering is an example
■ Water interface measurement of digital transformation at Saudi

Fawaz Al Sahan is the Chairman of Saudi
■ Volume of drained water Aramco. This in-house developed

Aramco instrumentation standards with the
Process and Control Systems Department at
■ Temperature of fluid inside the solution is enabled by smart sensors
Saudi Aramco Company. He is a voting member
tank and of the drained fluid. and data analytics to serve a chal-
of ISO Technical Committees 185, 30 ,153, and
■ Drain control valve analytics lenging application in the oil and a voting member of SASO (Saudi Standards,
(passing, stuck, or healthy) gas industry. The technology serves Metrology and Quality Organization) Technical
■ Sound velocity measurement/ crude and refined product tank Committee of Electrical Metrology. With
drained media recognition. dewatering processes in refineries, more than 22 years of experience in the
• The technology improves safety terminals, and bulk plants, and can design, technical support, and maintenance
by ensuring zero hydrocarbon drain- be implemented while the tank is of instrumentation and automation systems,
age to the oily water sewer. in operation, without emptying the he is a certified engineering consultant (SCE)
• It eliminates exposure to fumes tank and without waiting for the and a certified automation professional (ISA).
during manual drainage, and elim- tank’s next scheduled inspection. He holds five patents, has published multiple
papers, and teaches on process measurement,
inates manual verification of the Smart dewatering has already
control valves and pressure relief valves.
water interface level and of the been deployed by Saudi Aramco,
Email: Fawaz.sahan@aramco.com.
drained fluid. pending commissioning. The two Omar Al Zayed is a Process Automation
• It addresses two important chal- key elements of the technology – the Supervisor at Saudi Aramco Riyadh refinery.
lenges for the oil and gas indus- internally mounted interface sen- With more than 22 years of experience in
try: crude quality and hydrocarbon sor and sound velocity dewatering instrumentation, he is a certified engineering
losses. system – have been fully tested and consultant (SCE), certified functional safety
• Smart dewatering technology been in operation for some years. engineer (TUV FS), and a senior ISA member.
offers multiple dewatering options Smart dewatering has the potential He holds several patents, has presented many
(sound velocity dewatering system, for implementation in all hydrocar- technical papers, holds a MBA, and is a certified
internally mounted interface sensors, bon tanks in the oil and gas indus- arbitrator in the Saudi Council of Engineers.
Email: omar.zayed@aramco.com.
and smart dewatering) for existing try. HSE has been the main driver of
Fawaz Al Hadlaq is an Instrument Engineer at
and new tanks inside a hydrocarbon this technology as it will ensure zero
Saudi Aramco Riyadh refinery. With 12 years
facility. hydrocarbon drainage to the oily of experience in instrumentation and project
• It eliminates operational upset by water sewer, and it protects employ- management, he is a certified engineering
preventing water overflowing with ees from exposure to fumes during professional of the Saudi Council of Engineers.
the crude to downstream processes manual drainage and while manu- He holds a master’s degree in renewable energy
inside a refinery. ally measuring the water interface from King Saud University.
• It eliminates the time and effort to level at the top of the tank. Email: Fawaz.hadlaq@aramco.com
Q2 Aramco.indd 4 15/03/2021 10:55

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Delivering drop-in renewable fuels
A series of pretreatment, hydrotreating, and distillation steps converts fresh or used
lipid based feedstocks to full range, drop-in renewable fuels
CHUCK RED and ED COPPOLA Applied Research Associates

ROBERT VALENTE, CHRISTINE CONWAY and LIN ZHOU Chevron Lummus Global
Hydrothermal Cleanup
Hydrothermal Cleanup (HCU) is Co-processing
a pretreatment step that uses tra-

ditional refinery components to Naphtha
remove inorganic materials from
waste fat, oil, and grease feed-
Jet
stocks. During HCU, water is com- Clean fats, CH crude Hydrocarbon
bined with feed oil and then fed oils and product
to the HCU reactor system at the greases CH reactor Diesel
temperature and pressure neces- Cracking and Hydrotreater
cyclisation
sary to maintain a hydrothermal/ Olefin saturation
Distillation
liquid-phase environment. Metals & deoxygenation
that are present in waste fats, oils,

and greases (FOG) are mostly in Figure 1 Simplified block flow diagram of the BIC process
the form of free salts and soaps.
Phosphorus is mostly in the form of fuels which do not require blending feed oil become one phase. Water
phospholipids. HCU relies on three with petroleum. Therefore, the BIC mediates the conversion of free
primary mechanisms to achieve process can be applied as an insert- fatty acids into CH crude, contain-
metals reduction: able unit to existing hydrotreating ing compounds such as normal and
1) Removal of soluble, free salts – units which enables co-processing, branched paraffins, high-density
similar to conventional desalting or built as a stand-alone unit for cycloparaffins, and aromatic mol-
2) Rapid acidulation of metal soaps renewable fuel production. ecules ideal for diesel and aviation
(Na, K, Mg, Ca, Fe, others) using a There are four main steps in the turbine fuels.
weak acid BIC process (see Figure 1): a cleanup Key reactions that occur during
3) Hydrolysis of phospholipids into step (HCU) where contaminants CH conversion include, but are not
phosphate salts and phosphate-free are chemically removed to make limited to:
lipids. Since oil and water are only suitable feed oil for the next step; • Hydrolysis of glycerides to pro-
partially soluble in each other at the conversion step, called catalytic duce free fatty acids
operating conditions, flow in the hydrothermolysis (CH), wherein • Cracking of fatty acids into
HCU reactor is maintained at a high the feed oil molecules are converted lower molecular weight acids and
Reynolds Number to achieve rapid to molecules that are nearly iden- hydrocarbons
mass transfer between each phase. tical to those found in petroleum; • Cyclisation of fatty acids into
Rapid mass transfer facilitates met- a hydrotreating step that is identi- alkyl cyclohexane compounds
als reduction by the mechanisms cal to the petroleum hydrotreating • Cyclisation of fatty acids into
identified above. processes that removes any remain- alkyl benzene compounds
ing heteroatoms (oxygen, sulphur, • Dehydrogenation of naph-
Biofuels Isoconversion nitrogen, and metals) down to thenic compounds into aromatic
The Biofuels Isoconversion (BIC) acceptable levels; and a final distil- compound
process converts freshly produced lation step that separates the hydro- • Decarboxylation of fatty acids
or used lipid based feedstocks, treated product into the naphtha, • Skeletal isomerisation of interme-
such as FOG into renewable fuels jet, and diesel fuels. diate and product compounds
including diesel, jet, and naphtha. Typical CH reactions of unsatu-
This process is unique because it Catalytic hydrothermolysis rated fatty acids, such as oleic acid
produces fuels that are molecularly In the CH process, water is com- and linolenic acid, are shown in
nearly identical to fuels produced bined with clean FOG products, Figure 2. Those reactions that occur
from petroleum. The nearly iden- pressurised, and heated in excess in the CH unit eliminate the need
tical chemistry results in jet and of supercritical water conditions. for further catalytic reforming,
diesel fuels that are true ‘drop-in’ At these conditions, water and the hydroisomerisation, or hydroc-
Q2 CLG.indd 1 15/03/2021 12:10

and potential hydroprocessing cata-
lyst foulants into the aqueous phase
product such that the downstream
HO
Oleic acid
n-butyl cyclohexane Isoconversion catalysts will sustain
relatively longer catalyst lives.
O
HO Unlike direct catalytic hydrogena-
O tion, which converts the glyceryl
Octanoic acid backbone of the triacylglycerides to
propane, and thereby results in con-
suming additional hydrogen, the
Linolenic acid BIC process converts the glyceryl
HO N-butyl Benzene backbone non-hydrogenatively into
O fuel gas for captive use in the CH
HO
reaction system.
O Chemical hydrogen consumption
Octanoic acid
in the BIC process is significantly
lower than that in direct hydro-
Figure 2 Characteristic CH conversion reactions genation processes due to the super-
critical water reforming of olefinic
racking, and also consume less isomers similar in concentration bonds in the unsaturated triglycer-
hydrogen than a route that uses all and type to petroleum derived ides via cyclisation and aromatisa-
hydroprocessing. fuels. Because cycloparaffin and tion reactions that produce lower
The process occurs in a single aromatic compounds are produced hydrogen content naphthenes and
step for less than two minutes of and retained in the products, the aromatic hydrocarbons. By way of
residence time. Product yields and BIC process uses less hydrogen than example, for a feedstock having a
product composition are controlled hydrotreated esters and fatty acids 13/1 unsaturates/saturates ratio,
by adjusting the process variables, (HEFA) type processes. such as that in conventional rape-
which include reaction temperature, seed oil, the chemical hydrogen
reaction pressure, residence time, Product distillation consumption for the direct hydro-
and water to oil ratio. The BIC process produces the entire genation route can be as high as
range of hydrocarbons from naph- 148% that of the BIC process.
Isoconversion tha through diesel boiling ranges. In the production of jet fuels,
The renewable CH crude contains To produce jet fuel, the whole aromatic content (ASTM D6379) is
oxygenated compounds, mainly hydrotreated product is distilled to required to be 8-20 vol%. BIC tech-
carboxylic acids. In order to meet meet several specification require- nology produces aromatic rings,
the fuel specifications, element oxy- ments that include distillation, which enable drop-in jet fuel pro-
gen must be removed from those distillation slope (T90-T50 and T90- duction independent of feedstock
oxygenates to produce pure hydro- T10), flash point, and freezing point. compositions.
carbons, and nearly all of the olefins BIC technology has features that A testing program carried out at
must be saturated to produce par- overcome deficiencies with technol- Chevron Energy Technology Center
affin compounds. For example, the ogies that practise direct catalytic in Richmond, California, has shown
total acid number (TAN, expressed hydrogenation of triacylglycer- that the ReadiNaphtha can be cata-
as mg KOH/g) of jet fuel or jet fuel ides-rich feedstocks using fixed bed lytically reformed to produce refor-
blending component under the CHJ hydroprocessing catalysts. They mate having a 98.8 RON and 87.3
Annex to D7566 must be less than include the following. MON (93 Anti-Knock Index) at a
0.015. Hydrotreating achieves deox- Unlike direct catalytic hydrogena- C5+ reforming yield of about 70
ygenation and reduces the TAN to tion, which essentially converts tria- vol%.
meet the jet fuel specification. This cylglycerides to their corresponding
results in jet fuel that has very good straight-chain n-alkanes (primarily ASTM certification
thermal and oxidative stability. high concentrations of n-hexade- ASTM D7566 Annex A6 has been
The BIC process uses commer- cane and n-octadecane), the BIC approved to add a new standard
cial hydrotreating catalyst that process incorporates cyclisation and for jet fuel (CHJ) produced by the
results in near-complete oxygen aromatisation reaction chemistry Biofuels Isoconversion process.
removal (TAN <0.01) without sat- to produce renewable jet and die- ASTM D7566 was developed by
urating aromatic rings to cyclopar- sel fuels containing n-alkanes, iso- ASTM International (formerly the
affins, opening cycloparaffin rings alkanes, naphthenes, and aromatics, American Society for Testing and
to form paraffins, or cracking of much more analogous to those in Materials) as an international stand-
jet and diesel range hydrocarbons petroleum derived distillate fuels. ard for renewable jet fuel. Renewable
into naphtha and gaseous hydro- The catalytic hydrothermolysis jet fuel produced in compliance
carbons. This results in fuels that reactor acts as a guard device to with the ASTM D7566 standard is
contain aromatic and naphthenic remove/transfer any inorganics deemed to meet the same require-
Q2 CLG.indd 2 15/03/2021 12:10

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ments as those for conventional characterised as hydrocarbonaceous types in the diesel precursor frac-
petroleum derived fuel, and thereby oils containing: tion that eliminates the requirement
only renewable jet fuel produced • Three long-chain fatty acid mol- for expensive downstream selective
and quality-controlled in compliance ecules in the 12-24 carbon number isomerisation.
with this standard can be carried in range each connected to a glyceryl • Since most renewable oils are not
commercial aircraft. The new annex backbone available at volumes nearing name-
allows the blending of up to 50% of • Some unsaturated double bonds plate capacities comparable to cur-
ARA and CLG’s ReadiJet with petro- as non-aromatic olefins rent petroleum hydroprocessing
leum derived jet fuel. • Some trace amounts of organic units, the co-hydroprocessing of
Details of the new ASTM D7566 sulphur and organic nitrogen blended petroleum/BIC partially
certification include: • Some trace levels of metals such treated crudes results in an advanta-
• Date of issue: January 30, 2020 as Na, K, Ca, P, Fe, Mg geous economy of scale.
• Standards developing organisa- In the conventional direct hydro- • Since hydrodeoxygenation of the
tion: ASTM International treating process, these feedstocks BIC partially treated crudes pro-
• Technology developing company: are converted into a saturated and duces water along with the hydro-
Applied Research Associates & hydrodeoxygenated, mostly diesel carbon products, a water phase will
Chevron Lummus Global range hydrocarbon mixture having be present in the recovery section to
• Standard Number: ASTM D7566 – essentially all straight-chain par- dissolve any ammonium sulphide
19b (Annex A6 catalytic hydrother- affins. Many literature references produced from the hydrotreatment
molysis jet (CHJ)) are showing that direct hydrotreat- of the petroleum hetero-compounds
ing of renewable oils fails to meet to avoid potential solids deposition
Renewable oils co-feedstock diesel cold flow properties unless problems and without having to
component an expensive downstream selec- inject water externally.
Many feedstocks have been tested tive isomerisation unit is installed.
successfully in the CH conversion Therefore, the direct hydrotreated Ebullated bed residue hydrocrackers
process since bench and pilot opera- mixtures need further downstream Recently, there has been interest in
tions began in 2006. The CH process catalytic hydrotreatment to signifi- co-processing renewable oils and
is tolerant of a wide range of renewa- cantly increase the isomer/normal waste oils in an ebullated bed res-
ble feedstock chemistries. Feedstocks paraffin to meet diesel fuel cold idue hydrocracker such as CLG’s
may be highly saturated, such as flow properties. LC-Fining process. This co-process-
tallow, or highly unsaturated, such The CH step of the BIC process ing option is generating much inter-
as tung oil; they may contain esters performs specific chemical reactions est among refiners in Europe. As
with short chains, such as coconut that generate not only iso olefins indicated above, the HCU process
oil (C12), or long chains, such as rape- and iso-paraffins but also naph- would be an excellent pretreatment
seed and carinata oil (C22); they may thenic and aromatic compounds in step to remove impurities such as
be clean triglycerides or clean fatty the CH crude oil derived co-feed- phosphorous and chlorides to a
acids. Feedstocks that have been suc- stock component. This renders it level that is acceptable to the cata-
cessfully tested include waste oils, much more like petroleum distil- lyst and metallurgy of the unit. For
such as used cooking oil, tallow, and lates than those of direct hydrogen- this process, the CH step would be
distillers corn oil, as well as virgin ated n-paraffinic rich renewable oils. by-passed since the HCU oil will
plant oils such as algae, camelina, Some of the features of co-hydro- go directly into a hydrocracking
canola, carinata, castor, coconut, processing renewable oils derived environment.
corn (from distiller’s grain), pea- from the BIC pretreatment process Recently, the Environmental
nut, pongamia, soybean, and tung with petroleum distillates include: Protection Agency (EPA) enacted
oil. More recently, work has been • HCU and CH reduce total met- 40 CFR 80.1126, which allows for
done that allows highly contami- als content to less than 5 ppm, even renewable oils to be co-processed
nated FOGs such as brown grease for feedstocks with metals content with fossil derived oils in a petro-
to be processed by pretreating with starting at over 1000 ppm. This will leum refinery, with the renewable
HCU. While feedstock chemistry allow co-processing of CH crude oil component qualifying for the
affects conversion rates and product from renewable waste feedstocks Renewable Identification Number
chemistry to a degree, the breadth without fouling the hydrotreating (RIN) programme.
of testing data enables CLG/ARA to catalyst.
provide sufficient process control to • Typical mid-distillate hydrotreat- Commercial development of the
enable the production of jet and die- ing reactors can operate at a severity BIC process
sel fuels with consistent chemistry to simultaneously reduce the oxygen ARA and CLG have advanced
and quality. content of the renewable CH crude the commercialisation of BIC at
oil to less than about 10 ppm and a steady pace since its invention
Hydrotreaters the sulphur content of the petroleum in 2006. ARA developed continu-
Renewable oils such as those from compounds to less than 5 ppm. ous flow bench and pilot systems
vegetable derived seed oils, non- • CH crude oil co-feedstock has a in 2008 and 2010 and built a 100
edible plant oils, and animal fats are very attractive mix of hydrocarbon b/d CH demonstration system in
Q2 CLG.indd 3 15/03/2021 12:10

2016, which was used to make over ties soon. Feedstock is 50% yellow co-inventor of the clean-up and conversion
160 000 gallons of 100% drop-in grease/50% brown grease. technologies employed in the Biofuels
renewable jet and diesel fuels for US • Confidential USA 2: a 5000 b/d ISOCONVERSION (BIC) process. He holds a
Navy MILSPEC certification testing commercial unit’s basic engi- BS in chemical engineering from West Virginia
University and MS in fuels engineering from
in the F/A-18 Hornet and Spruance neering activities are currently
the University of Utah.
Class Destroyer. on hold. Feedstock is 60% yellow Robert Valente is a Senior Principal Process
The following are ongoing com- grease/40% brown grease. Engineer with Chevron Lummus Global (CLG)
mercial activities for the BIC • Confidential USA 3: a 3130 b/d in Bloomfield, New Jersey. With over 30 years’
process: commercial unit is currently in basic experience, his expertise is in biofuels, slurry
• Euglena: a Japanese licensee engineering. Feedstock is 50% distill- hydrocracking, solid acid catalyst alkylation, LC-
recently completed the construc- er’s corn oil/50% used cooking oil. FINING, coking, visbreaking, styrene, selective
tion and start-up of an integrated Biofuels ISOCONVERSION, ReadiNaphtha,
CD-Hydro, and middle distillate hydrotreating.
demonstration system in Tokyo. The ReadiDiesel and ReadiJet are marks of Applied
He holds a BS in chemical engineering from
feedstock is a 30% algae (euglena) Research Associates and Chevron Lummus
Manhattan College, New York.
Christine Conway is a Senior Principal
lipids/waste 70% palm oil mixture. Global. LC-FINING is a mark of Chevron
Technology Specialist with CLG. With 20
The 5 b/d demonstration plant suc- Lummus Global.
years’ experience working with refining and
cessfully produced ReadiJet and Chuck Red is a Vice President with Applied petrochemical technology licensing companies,
ReadiDiesel in early 2020. Research Associates (ARA) and has led ARA’s she leads the development and design of the
• Confidential Europe: a commercial fuels programme since 2009. He has led BIC technology. She holds a bachelor’s degree
engineering study was completed to the development and commercialisation in chemical engineering from the University of
process 3900 b/d of rapeseed oil/ of hydrothermal clean-up and catalytic Minnesota.
animal tallow/used cooking oil. hydrothermolysis technologies that produce Lin Zhou is a Process Engineer with Lummus
• ReadiFuels-Iowa (RFI): a 2650 b/d 100% drop-in renewable jet and diesel fuel Technology in Bloomfield, New Jersey, where
from waste fats, oils, and greases. He is a she is responsible for the process design of
commercial unit is currently in the
United States Naval Academy graduate with CLG’s BIC technology. With over 10 years of
final phases of basic engineering
a BS in electrical engineering and holds MS in process engineering and R&D experience in
completion. Feedstock is 50% distill- Business Management from Troy University. biofuel production from bio-feedstocks, her
er’s corn oil/50% used cooking oil. Ed Coppola is a Principal Engineer with ARA research focuses on process intensification
• Confidential USA 1: a 5300 b/d where he directs research, development, and catalyst formulation. She holds a PhD in
commercial unit is scheduled to test and engineering in alternative energy chemical engineering from Stevens Institute of
resume basic engineering activi- and renewable fuels development. He is a Technology, Hoboken, New Jersey.
Q2 CLG.indd 4 16/03/2021 14:07

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2020 Sabin 1Expertise-PTQ.indd 1

sabin.indd 12/2/20 11:54
14/12/2020 AM
11:57
Protecting your hydroprocessing reactor
Owners and operators respect a hydroprocessing reactor’s minimum pressurisation
temperature but can fail to understand factors other than the temperature
ERIC LIN and RICHARD TODD

Norton Engineering Consultants
W
hen an owner or operator
in charge of a hydropro-
cessing unit is asked what
a reactor minimum pressurisation
temperature (MPT) is, they may
correctly respond that it is the low-
est temperature at which a reactor
can start pressurising above a pre-
determined limiting value after it
has already seen hydrogen service.
Some may even understand that the
purpose of respecting the MPT is Initial operation Long term operation
to protect the reactor against brittle
fracture caused by diffused hydro- Figure 1 Hydrogen embrittlement
gen. However, far fewer understand
MPT implications beyond those two embrittlement as “the reduction Hydrogen embrittlement
critical points. in toughness due to a metallurgi- The National Association of
Most hydroprocessing reactors are cal change that can occur in some Corrosion Engineers (NACE)
susceptible to failure mechanisms low-alloy steels as a result of long- describes hydrogen embrittlement
caused by temper embrittlement as term exposure in the temperature as “the ingress of hydrogen into
well as hydrogen embrittlement. range of about 650°F to 1070°F a component, an event that can
Whether it be concluding turna- (343°C to 577°C). This change seriously reduce the ductility and
round activities or overcoming an causes an upward shift in the duc- load-bearing capacity, cause crack-
upset condition, respecting the MPT tile-to-brittle transition temperature ing and catastrophic brittle failures
is important to ensure reliable and as measured by Charpy impact test- at stresses below the yield stress of
safe operation of the reactor vessel. ing. Although the loss of toughness susceptible materials.”4
This article provides insights and is not evident at operating temper- At elevated temperature and pres-
understanding around MPT that ature, equipment that is temper sure, molecular hydrogen partially
can impact hydroprocessing reactor embrittled may be susceptible to dissociates to form atomic hydro-
integrity along with other equip- brittle fracture during start-up and gen, H2 ↔ 2 H, which is a revers-
ment in the high pressure loop that shutdown.”3 ible, equilibrium-limited reaction.
is exposed to hydrogen. API 571 best practice recommends Atomic hydrogen is soluble in steel
Many papers and industry stand- limiting the amount of tramp ele- and will enter the lattice structure
ards have been published that ments such as manganese, silicon, of the walls. The inner surface of the
address concerns surrounding phosphorus, tin, antimony, and steel becomes saturated and atomic
MPT. A recent series of articles by arsenic in the base metal and weld- hydrogen starts diffusing towards
Pillot et al. focused on the effect of ing consumables to avoid the effects the outer surface. If a discontinu-
temper embrittlement and hydro- of temper embrittlement. When the ity or defect is present, then atomic
gen embrittlement on a material’s steel contains vanadium in the base hydrogen that is diffusing through
mechanical properties,1 along with a material, it is less sensitive to tem- the steel can reversibly form molec-
methodology to determine MPT for per embrittlement than when the ular hydrogen in the void, which
reactors that are already in service.2 steel does not contain vanadium.1 becomes trapped and starts to accu-
These two articles provide a frame- It has become standard practice in mulate. These trapped pockets of
work to further examine MPT for a recent years to use a low alloy steel hydrogen create fissures that lead
hydroprocessing unit. that contains vanadium with tight to intergranular cracking. Figure
control on the tramp elements to 1 depicts atomic hydrogen enter-
Temper embrittlement fabricate the steel walls of hydro- ing the wall and accumulating in
API RP 571 describes temper processing reactors. the grain boundaries, weakening
Q1 Norton.indd 1 15/03/2021 10:58

dition. Although hydrogen content
6 is higher in vanadium-enhanced
2 1/4 Cr-1Mo steady state steel, the more important feature
is that the difference between the
Local hydrogen content, ppm
5 2 1/4 Cr-1Mo-V steady state
2 1/4Cr-1Mo end of cooling hot and cold condition is small,
4 2 1/4 Cr-1Mo-V end of cooling
making this a desirable material of
construction to use. (There is much
3
less hydrogen diffusing in and out
2
of the wall during a cooldown and
heat-up cycle when vanadium is
1 present in the steel.)
Additionally, the base material
0 is usually followed by a stainless
0 50 100 150 200 steel weld overlay such as 347,
Position in base material, mm
which protects the low alloy steel
from corrosion and degradation.
Figure 2 Profiles of H2 content before and after cooling1 The addition of this overlay, though
necessary, increases the potential
the material and leading to a loss mechanisms that lead to brittle for premature failure of the reac-
of ductility and strength. A reactor failure in a hydroprocessing reactor due to a phenomenon known
wall that has become compromised tor, how is MPT determined? MPT as hydrogen induced disbonding
is not immediately obvious with- is a function of fracture mechanics (HID), which is characterised by
out the assistance of tests and scans. and/or Charpy V-Notch (CVN) a crack propagating at the inter-
Eventually, microfractures become toughness calculations. It will not face between the base material and
large cracks that can lead to com- be surprising then that the MPT is the austenitic stainless steel weld
plete loss of integrity and failure. normally calculated by the reac- overlay/cladding.5 The difference
As stated previously, MPT is a tor fabricator based on the base in hydrogen solubility between
minimum temperature that must material selected for the reactor the base material and the auste-
be obtained during start-up before wall. Common base materials for nitic stainless steel overlay creates
a reactor can be pressurised beyond hydroprocessing reactors include a region where hydrogen content
25% of its design pressure. Per API 2¼ Cr–1 Mo and 2¼ Cr–1 Mo–V. goes through a step change (see
RP 571, this 25% point is critical to The addition of vanadium allows Figure 3). During reactor cooldown,
prevent brittle fracture. The MPT a reactor of the same size to be the interface becomes a point where
tries to re-establish the equilib- lighter in weight. Another advan- hydrogen content increases, which
rium profile for atomic hydrogen tage with the addition of vanadium will accumulate if a defect is pres-
through the steel to minimise the to the base metal is the different. Coudreuse et al. provide more
potential for molecular hydrogen ence in atomic hydrogen content guidance that identifies how param-
being present at the grain bounda- between the cold start-up condition eters such as operating tempera-
ries that could result in rapid brittle and the hot, steady state condition ture, hydrogen partial pressure,
failure. During unit start-up, this is during normal operation. Figure cooldown rate, material thickness,
normally accomplished by heating 2 shows an example profile of the hydrogen diffusion coefficient and
up a recycle gas stream that passes hydrogen content through the steel time can influence hydrogen con-
through the heat transfer coil of a wall between the hot and cold content at the interface.5 Anecdotal evi-
heater before entering the reactor. dence from an API survey suggests
Once the minimum temperature that nearly 30% of reactors suffered
has been achieved, it is safe to start 1
Ct from HID. ASTM G146 - 01(2018)
increasing pressure in the system Profile before
cooling down
is the latest industry standard that
up to the normal operating point. Profile after evaluates disbonding in high tem-
C0
Factors such as climate, heater, perature, high pressure hydrogen
Hydrogen
cooling down
and compressor size in the hydro- 1

C0 service.
processing unit will also play an Fabricators can either roll and
important role in determining the weld plates or combine forged rings
time required to heat up the reactor. to create reactor shells. Due to the
It is far quicker to heat up the steel variability in quality and method
2
C0
2
Ct
walls of a reactor in a warm climate of supplied base material, it is rec-
during the summer months than it ommended to work with a list of
Overlay Base material
is to achieve the same MPT in a cold approved reactor vendors if one is

climate during the winter months. Figure 3 Profiles of hydrogen available. These vendors work with
concentration in material and overlay experienced suppliers that are more
Determining MPT before and after cooling down of a reactor likely to have uniform quality in the
With an understanding of the in a refining plant1 base material and thus are less sus-
Q1 Norton.indd 2 15/03/2021 10:58

ceptible to embrittlement. They will
also have competency and experi- 60
2,25Cr1Mo(690˚C - 8Hrs + SC)

ence in welding and post-weld heat
Shift of FATT under hydrogen, ˚C / ppm

treatment (PWHT) techniques. 50
C-0,5Mo (610˚C - 3Hrs20min)

To save time, fabricators may
5Cr0,5MoSi (710˚C - 1Hr40min)

2 1/4 Cr1Mo (690˚C - 8Hrs + SC)
be tempted to re-use exact reactor
2 1/4 Cr1Mo (690˚C - 8Hrs)

40
2 1/4 Cr1Mo (690˚C - 8Hrs + SC)

specifications for a ‘copy job’, espe-
cially if one reactor is already in ser-
2 1/4 Cr1MoV (705˚C - 8Hrs + SC)
2 1/4 Cr1MoV (705˚C - 8Hrs + SC)

30
vice and has experienced no issues
2 1/4 Cr1Mo (690˚C - 8Hrs)
2 1/4 Cr1Mo (690˚C - 8Hrs)

C-Mn (65ksi)
2 1/4 Cr1Mo (literature)
2 1/4 Cr1MoV (705˚C - 8Hrs)

2 1/4 Cr1MoV (705˚C - 8Hrs)
to date. Reputable fabricators will
C-Mn (70ksi)
20
always confirm the base and filler
materials received are specific to a
particular project. 10
Calculating the MPT 0

Base metal Martensitic HAZ Weld metal
The following example will out-
Localisation of Charpy V-Notched specimens
line the steps required to analyse a
reactor to determine the appropri-
ate MPT. A hydroprocessing reac- Figure 4 CVN transition curve shift as a function of H content (wtppm) in Cr-Mo(-V) and
tor with a 300 mm thick wall (base C-Mn steels1
material) that is made of 2¼ Cr–1
Mo with a normal operating tem- tin, and arsenic content in the weld gen content at 400°C and 150 kg/
perature of 400°C and pressure of metal expressed in ppm. cm2g for a 300 mm thick wall is 2.1
150 kg/cm2g will be examined. ppm. Figure 4 shows different val-
The first calculation step is to X = (10P + 5Sb + 4Sn + As)/100 ues for the shift in FATT due to the
determine the susceptibility of the presence of hydrogen in units of °C
base metal and weld metal to tem- Both JTE and X are parameters that per ppm of hydrogen content in the
per embrittlement through calcu- are controlled by the reactor fabrica- steel wall.
lation of the fracture appearance tor during manufacture of the reactor. The industry accepted temper-
transition temperature (FATT). The Upon shutdown of the reactor, ature shift for 2¼ Cr-1 Mo is 10°C
FATT at a 99% confidence level is residual hydrogen is present and per ppm of hydrogen content in the
given by:1 will therefore impact the integrity of steel. Based on this value, the over-
the reactor wall. This requires a cor- all temperature shift is calculated as:
FATT99% = -15.416 + 0.72670 JTE – 8.0043x10-4 rection to be added to the FATT99%
JTE2 to account for hydrogen embrit- ΔT = (residual H2 content, ppm) x (FATT99%
tlement. Correlations have been shift, °C / ppm)
JTE (Watanabe factor) is a parame- developed to estimate the expected
ter representative of the base metal residual hydrogen content in ppm For the current example, ΔT =
composition and the maximum rec- based on operating conditions.6 2.1 ppm x 10°C / ppm = 21°C. The
ommended value is 100 for 2¼ Cr-1 The corresponding residual hydro- final calculation for MPT is the sum-
Mo (per API RP 571). As established
earlier, temper embrittlement is a
function of the tramp elements in 1.4
the base metal so it is not surprising
that JTE is a function of the manga- 1.2
nese (Mn), phosphorus (P), silicon
(Si), and tin (Sn) compositions in the 1.0
50%
confidence
base metal, expressed in wt%. limit
0.8
K iC /KiC–US
JTE = (Si + Mn) x (P + Sn) x 104 95%

0.6
99%
Assuming a JTE of 100 and solving
for FATT99% gives a value of 49.2°C. 0.4
2 1/4 CR-1Mo steel
Rounding to the next largest inte-

ger, we get a value of 50°C.
1 1/4 CR-0,5Mo steel
0.2
The Bruscato factor, denoted X, Solid marks KiC test
is a parameter that represents the 0

-200 -100 0 100 200 300 400
weld material and the accepted
Excess temperature (T - FATT), ˚C
upper limit for 2¼ Cr-1 Mo is 15
(API RP 571). Similar to JTE, X is a
function of phosphorus, antimony, Figure 5 Relationship between Kic/Kic-US and excess temperature for ferritic steels7
Q1 Norton.indd 3 16/03/2021 13:38

subject it to de-embrittlement heat
treatment. Pillot et al. noted that
Master curve
with temper
Master curve with temper
embrittlement &
reactors built before 1975 with elec-
Reference
embrittlement hydrogen embrittlement tro-slag welds (ESW) have FATT
master curve values as high as 170°C.2
1 ppm 2 ppm 3 ppm
Start-up challenges
A Russian refiner started up its
K iC
unit during a time when the ambi-

FATT ∆T1ppm
∆T2ppm
∆T3ppm
ent temperature was -10°C. It took
some time for the unit to reach 0°C
let alone the MPT. After a couple
of days, the reactor finally reached
MPT but there was a problem.
Downstream of the reactor was a
T = To
T, ˚C hot high pressure separator (HHPS)
made of the same material as the
Figure 6 Cumulative effect of ageing and hydrogen embrittlement on quasistatic fracture reactor, which is typical in some
toughness hydroprocessing units. This HHPS
will have its own MPT but was hav-
mation of FATT99% and ΔT which is ering start-up time and MPT. For ing trouble warming up. An inspec-
71°C. the current example, a fair weather tion of the unit determined that a
locale in the middle of summer drain from the HHPS liquid line
Calculating the 25% pressurisation (southern USA for instance) would had been removed during ‘value
temperature have no trouble reaching 0°C for the engineering’. The original purpose
In the next calculation, the min- 25% pressurisation temperature, but of this drain was to allow warm
imum temperature necessary to it could prove difficult to achieve start-up gas to circulate throughout
safely pressure up the reactor to this temperature in a frigid climate the HHPS and then exit through the
25% of design pressure will be during the middle of winter (say in liquid outlet line. Without the drain,
determined. This sets the lower northern Canada or Russia). warm start-up gas simply entered
boundary for reactor start-up, even the HHPS and exited through the
before 25% of design pressure is Older reactors and ageing vapour outlet, completely bypass-
achieved. KIC is a measure of the Pillot et al. correctly point out that ing the lower half of the vessel.
plane strain fracture toughness of a the age of a reactor can have a large The client ended up using an elec-
given material. ‘Master Curves’ of impact on effective MPT.2 As a tric jacket to assist in the HHPS
these KIC values can easily be found reactor experiences multiple start- warm-up but this could have easily
in the literature for base materials ups and shutdowns, the MPT will been avoided had the drain been
such as 2¼ Cr-1 Mo. Figure 5 plots start to increase, possibly requiring present.
the KIC/KIC-US (‘upper shelf’) ratio longer start-up times. Oftentimes, Ask an operator what the reactor
against an excess temperature, a refiner will apply a healthy mar- MPT is and you may get a prompt
which is defined as the tempera- gin above the MPT so that every response. Ask them what their
ture under consideration minus the start-up will have a consistent HHPS MPT is and they will need
FATT.5 temperature to overcome in order to search their records for the infor-
In the current example, the FATT to compensate for such ageing. mation. The operating conditions
in consideration includes the hydro- Unfortunately, many older reactors in the HHPS are similar to the con-
gen shift (that is, MPT). 25% of the made of CS may also be dealing ditions in the reactor and as a result
design pressure is to be evaluated with the effects of high temperature the base material of the HHPS is
so the y-axis value of 0.25 for KIC/ hydrogen attack (HTHA) as their usually the same as the reactor. The
KIC-US becomes the starting point. curves fall well below those for low HHPS vessel also falls under ASME
Moving across to the right until the alloy on the Nelson Curves (API RP Sec. VIII Div. 2 of the pressure ves-
99% confidence limit is reached and 941). Figure 6 depicts the toughness sel code. Since it is located in the
then reading down in Figure 5 yields curves and shifting MPT of an age- same high pressure loop, the HHPS
an excess temperature of -80°C. ing reactor where the black master is exposed to hydrogen partial pres-
Subtracting 80°C from the MPT curve represents a virgin reactor sures that are similar to the reactor.
yields a minimum 25% pressuri- wall and the curves to the right rep- With the same material and com-
sation temperature of -9°C. Some resent the effects of temper embrit- parable residual hydrogen content,
fabricators have been known to con- tlement and increasing residual one can conclude the HHPS vessel
servatively round this temperature hydrogen. is also susceptible to the effects of
to 0°C. If initial MPT is not known, it is temper embrittlement and hydro-
Climate was identified earlier as possible to remove a test coupon gen embrittlement like the reactor.
an important factor when consid- from the reactor (if installed) and During start-up, the HHPS typically
Q1 Norton.indd 4 15/03/2021 10:58

lags the temperature wave increase not need to be at the mercy of the of MPT can be challenging in some
that is measured in the reactor. It MPT. A typical dewaxing unit may locations but there are solutions
can be expected that once the reac- have sized the reactor fired heater that can be implemented either dur-
tor reaches MPT, the HHPS most and recycle gas compressor appro- ing the design phase or even after
likely has not. For cold climates, it priately for the process but could the unit has been built, to achieve a
would be extremely tempting to make start-up of the unit challeng- fast, safe, and reliable start-up of the
start pressuring up beyond 25% of ing. Adequate over-design in the hydroprocessing unit.
design pressure once the reactor fired heater should be available
has reached MPT without waiting not just for the process but also for
for the HHPS MPT. It is better to start-up considerations. Promoting References
monitor HHPS skin temperatures as more heat circulation by running 1 Pillot S, Chauvy C, Corre S, Coudreuse L,
Gingell A, Héritier D, Toussaint P, Effect of
well to ensure integrity of the base a recycle gas compressor and its
temper and hydrogen embrittlement on
material for the entire high pressure standby is a strategy that is com-
mechanical properties of 2,25Cr-1Mo steel
circuit. monly used. If the compressor does grades - Application to Minimum Pressurizing
Another refiner had a naph- not have an installed standby, it is Temperature (MPT) issues. Part I: General
tha hydrotreater that was under- possible to use a temporary boost considerations & materials’ properties,
going start-up. The feed to a compressor solely for start-up pur- International Journal of Pressure Vessels and
naphtha hydrotreater does not Piping, 2013, Vol 110, 17-23.
require a large amount of heat The process engineer/ 2 Pillot S, Chauvy C, Corre S, Coudreuse L,
input to reach reactor operating Gingell A, Héritier D, Toussaint P, Effect of
temperature so instead of using operator should temper and hydrogen embrittlement on
a fired heater, a steam heater was mechanical properties of 2,25Cr-1Mo steel
installed. Temperatures were always consider grades - Application to Minimum Pressurizing
Temperature (MPT) issues. Part II: Vintage
ramped up at a steady rate and the
reactor eventually reached MPT.
MPT not only when reactors & MPT determination, International
Journal of Pressure Vessels and Piping, 2013,
After a few minutes of pressuring starting up but also Vol 110, 24-31.
up beyond 25% of design pressure, 3 American Petroleum Institute, Damage
reactor skin temperatures started when temperatures Mechanisms Affecting Fixed Equipment in the
to drop. When the question was Refining Industry, API RP 571, 2nd Ed, 2011,
asked about why skin tempera- start to fall, whether 4-10.
tures were dropping, the refiner 4 w w w. n a c e . o r g / r e s o u r c e s / g e n e r a l -
mentioned they were experiencing it is on purpose as re s o u rc e s / c o r r o s i o n - b a s i c s / g r o u p - 3 /
some hammering in the utility line hydrogen-embrittlement
and the steam supply to the heater in a shutdown or 5 Coudreuse L, Pillot S, Bourges P, Gingell
A, Hydrogen induced disbonding: from
had to be isolated. Understanding
the relationship between MPT and
otherwise laboratory to actual field conditions, NACE
Paper No. 05573, NACE, 2005.
pressurisation temperature, the 6 Sakai T, Takahashi T, Yamada M, Nose S,
refiner was warned that unless they poses. As illustrated by the example Katsumata M, Effect of Hydrogen on MPT
started depressurising, tempera- above, adding a drain valve to the and De-Hydrogenation during Shut Down in
tures would drop below MPT which HHPS liquid line should also pro- Hydroprocessing Reactors, PVP Vol 344, High
could lead to serious reactor dam- mote even heating of the vessel and Pressure Technology, ASME 1997.
age. Once the refiner’s engineers ensure the MPT is met here also. 7 Viswanathan R, Damage Mechanisms
heard “MPT” they understood the and Life Assessment of High-temperature
danger and immediately initiated Conclusion Components, ASM International, 1989.
a depressurisation of the unit. This The process engineer/operator
naphtha hydrotreater was an older should always consider MPT not
unit located in a cold region and its only when starting up but also Eric W Lin was until recently a Principal
MPT was well above 75°C. In com- when temperatures start to fall, Engineer with Norton Engineering Consultants,
parison, modern reactors will have whether it is on purpose as in a Inc. With over 23 years’ refining experience,
MPTs that fall in the range 40-70°C, shutdown or otherwise. There may he holds a bachelor’s degree in chemical
especially those that conform to be another vessel in the high pres- engineering from Columbia University, New
API RP 934-A. This example show- sure loop similar to the reactor that York. He has previously worked for Chevron
cases how important MPT is not also has its own MPT value and Lummus Global (CLG) on the design, start-up
only with increasing temperature that must be considered before any and troubleshooting of hydroprocessing units.
but also when temperatures start pressurisation above 25% of design
Richard S Todd is Process Engineering Manager
dropping and the reactor is already pressure is initiated. Not knowing
with Norton Engineering Consultants, Inc.
above 25% of design pressure. the MPT can result in a catastrophic
With 16 years of experience in the refining
failure so consult original records industry, he holds a bachelor’s degree and
MPT as a design consideration or have a coupon from the reactor PhD in chemical engineering from Monash
A unit that desires a quick start-up, tested (if available) to determine an University, Australia.
especially in a cold locale, does appropriate MPT. The attainment Email: rtodd@nortonengr.com
Q1 Norton.indd 5 15/03/2021 10:58

Reliability Issues In Your Vacuum Tower?
The Vacuum Tower wash bed is one of the most critical pieces of equipment in the Vacuum Distillation Unit
with good performance and long-term reliability necessary for unit profitability. The bed’s primary function is
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system that works in conjunction with the flash zone. A well-designed flash zone feed inlet device will significantly
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koch glitsch.indd 1 12/03/2021 12:56

Amine anomaly in a mild hydrocracker
Simulation and operational changes help to crack the riddle of frequent amine
carry-over from a high pressure amine absorber
RAJESH MOHAN, ROHIT KUMAR, HIMANSHU KUMAR GUPTA and BASITH ZOHAIL N
Bharat Petroleum Corporation Limited
A
vacuum gasoil mild hydro- are separated in separators/flash Cracks and blisters in the amine
cracker (VGO MHC) unit in drums into liquid and gas streams. absorber
a refinery treats VGO from The liquid streams then find their During unit turnaround in late 2017,
the vacuum distillation tower of way to the fractionation section, a number of internal cracks and
the crude distillation unit. Treated whereas the gas streams are further hydrogen blisters were identified
VGO serves as a feedstock for the purified in separators to remove in the HP amine absorber when the
FCC unit for (Bharat Stage) BS-IV/ heavier ends and in the high pres- vessel was offered for inspection.
VI grade gasoline production. The sure amine absorber to remove H2S. Phased array ultrasonic testing
VGO MHC unit at BPCL Kochi The purified recycle gas leaving the (PAUT) and wet florescent mag-
refinery (1.7 million t/y through- HP amine absorber is then fed to a netic particle inspection (WFMPI)
put) is operated to produce low recycle gas compressor knockout were carried out to analyse the
sulphur feedstock for the FCC unit, drum (RGC KOD) to remove any depth of the internal cracks. Major
together with conversion of excess amine droplets before being routed cracks were observed on the shell
VGO to low sulphur diesel. The to the suction of the RGC. The sys- internal surface below the trays.
design maximum feed sulphur in tem pressure of the VGO MHC is Some cracks were observed on the
VGO is 1.6 wt%. 105 kg/cm2 (g) and cracking and welds of ladder rungs on the shell.
The feed is charged to the reac- treating reactions are adjusted by Hydrogen blisters were observed
tor using charge pumps and is pre- varying the temperature between on the skim baffles, LT nozzles,
heated in the reactor effluent feed 340-400°C. The hydrogen con- and on the longitudinal seam of the
heat exchangers and the charge sumed in reactions is replenished absorber column. Multiple major
heater. The reactor needs hydrogen by make-up gas compressors. The and minor hairline cracks were also
supplied by the recycle gas com- unit process flow diagram is shown found at multiple circumferential
pressor (RGC) for hydrocracking in Figure 1. seam regions of the absorber col-
and hydrotreating reactions. The The HP amine absorber has a total umn (see Figure 2). Hydrogen blis-
effluents from the reactor consist of of nine single-pass fixed valve trays. ters with cracks were also observed
cracked products, desulphurised Recycle gas is scrubbed of H2S using near the 12in recycle gas inlet noz-
VGO, hydrogen sulphide, ammo- 35 wt% methanol diethanol amine zle, extending out towards the col-
nia, and excess hydrogen which (MDEA). umn shell and on the impingement
Recycle gas
HP steam compressor
Fresh H2
Suction
KOD Lean MDEA
Condensate
Recycle HP amine
gas bypass absorber Rich MDEA
Recycle gas to ARU
Long spillback To SWS
CWE RG KOD
Condensed HC
HP cold to cold flash drum
separator
HP hot
CFE separator Fuel gas
Cold Stripper
VGO feed Feed heater reflux drum De-ethaniser
HP flash feed
HT/HC drum
reactor Hot flash
drum
Stripper
To product fractionator
Figure 1 Process flow of VGO MHC at BPCL Kochi refinery
q2 bpcl.indd 1 15/03/2021 11:00

Comparison of old and new tray designs plans involved purchasing more
high sulphur crude, a level higher
Parameters New HC Old trays than the design flow rate of amine
trays would have to be pumped into the
Tray type Fixed valve Fixed valve column to maintain amine load-
Number of passes 1 1
Inner diameter, mm 2000 2000 ing at less than 0.4 mole H2S/mole
Tray spacing, mm 600 600 of MDEA. The original trays were
Tray thickness, mm 2 2 designed for a 105% amine flow
Tower area, m2 3.14 3.14 rate (115 t/h), but with process-
Active area, m2 2.43 2.47
Figure 2 Crack on the shell surface near Active area, % 78.6 78.6 ing of high sulphur VGO in mind
the circumferential seam Open area, m2 0.271 0.271 along with the existing problem of
Open area, % 11 11 amine carry-over it was decided
Downcomer Standard Standard to consult with the tray manufac-
data & type straight sloped
Top width, mm 340 400 turer for trays with liquid flow
Bottom width, mm 340 250 rates at 130% turn-up (150 t/h).
Clearance height, mm 40 65 The manufacturer hinted at down-
Outlet weir height, mm 50 65 comer velocity limitations at 130%
Outlet weir length, mm 1503 1600
Downcomer top 0.354 0.447 turn-up for the existing trays and
area, m² hence proposed mechanical modi-
Downcomer bottom 0.354 0.227 fications to the column relating to
area, m² downcomer design along with new
DC area, % 11.27 14.24
Figure 3 Hydrogen blistering on the trays with Type-I and Type-II fixed
impingement plate Table 1 valves. The downcomer design was
changed from the earlier segmental
plate (see Figure 3). Hardness tests This necessitated an increase in type to a sloped type. The down-
were carried out near the cracks lean amine flow to the HP amine comer top width from the column
and blisters; the result less than 180 absorber. But increased flow led to shell was increased to overcome the
BHN (Brinell hardness number). amine carry-over issues which were limitation in downcomer velocity
Cracks were eliminated by grind- as frequent as 10-12 instances dur- indicated in preliminary tray rating
ing the blistered surfaces and weld ing a shift. Amine carry-over from simulations. The high capacity tray
filling the internal cracks followed the absorber led to loss of amine dimensions are shown in Figure 4.
by post-weld heat treatment. Later, and required frequent replenish- A comparison of old and new trays
in 2019, an unplanned shutdown ment in the amine regenerating design details is provided in Table
was carried out for partial replace- unit. To reduce the carry-over 1. But ironically, after the change
ment of the bottom portion shell of events, the charge of the unit was to high capacity trays, amine car-
the amine absorber due to aggrava- reduced to maintain amine load- ry-over issues and an increase in
tion of cracks that developed on the ing at 0.4 mol/mol of MDEA. ∆P across the HP amine absorber
internal surface of the column shell. Management finally decided to were observed at both higher (80-
replace the existing trays of the 100 t/h) and lower (40-50 t/h)
Impact on unit operation absorber with high capacity trays, in amine flow rates. This aroused
The major reason identified for the hope of a solution to the prob- the curiosity of the operators who
hydrogen induced cracking and lem. But the issue became murkier were unable to comprehend the
hydrogen blisters was high rich with the change to high capacity phenomenon.
amine H2S loading of more than trays.
0.50 mol/mol of MDEA, against Amine carry-over at higher flow
the maximum acceptable industry Change to high capacity trays rates
limit of 0.40 mol/mol of MDEA. Because the company’s purchase After the trays in the original col-
umn were replaced with high
capacity trays, the operators main-
265 333 590 392 400 tained a H2S/amine ratio of 0.4
340
(EXISTING) mole/mole of MDEA during nor-
mal operation. But when process-
104
25
50
30
65
ing high sulphur VGO, the amine

110
180
100
2x110=220
requirement would increase in

(TYP)
30
60
017
T.S.=600
order to maintain the same mole

533
35
100
018
80 90
ratio. This necessitated an increase

120
205
100
in MDEA flow. However, beyond

65
178
an amine flow rate of 80 t/h, the

(EXISTING)
021
2
40
Section A–A 250

(FOR TRAYS #2 u/i #8)
operators observed liquid car-
ry-over from high pressure amine
Figure 4 Existing trays converted to high capacity trays absorber to the knockout drum
q2 bpcl.indd 2 15/03/2021 18:22

downstream. Because the amine ture, increasing strength of amine
flow rate could not be increased may lead to more foaming/liquid
beyond 80 t/h, the hydrocracker carry-over4
charge had to be reduced to main- 5. Replacement of charcoal in the
tain the safe H2S loading limit of charcoal filter with material with
0.4 moles H2S/mole MDEA for a high iodine number:9 this activ-
increased feed sulphur. ity also helped in reducing the fre-
The problem was acute with high quency of amine carry-over to the
sulphur VGO: the charge had to be recycle gas knockout drum
reduced to even turndown values 6. Amine washing of the amine
for longer periods of time. At times, absorber: each time amine washing
VGO was diluted with diesel to Figure 5 RMDEA at battery limit after was done, the amine sample from
meet the mole ratio. This resulted (left) and before (right) amine washing the RMDEA line was black in col-
in inventory build-up of high sul- our (see Figure 5), indicating that the
phur VGO, requiring export to sus- 5. Increasing system pressure from trays probably had some sludge on
tain refinery operations. Whenever 105 kg/cm2(g) to 106 kg/cm2(g) them
liquid carry-over occurred in the 6. Reducing the hot separator tem- Norman P Lieberman5 specifically
amine absorber, the following perature to 235℃ from 270℃ indicates the presence of erosion
changes in the process parameters 7. Reducing conversion from 45% corrosion products in the amine if
were observed: to 20% the colour of the amine is black, and
• Increased differential pressure None of these steps helped to our amine sample was black after
across the amine column from a resolve the issue. amine washing.
value of 0.07 kg/cm2 (g) to 0.14 kg/ This probably implied that the
cm2 (g) for nine trays Improving amine quality corrosion particles were stuck to
• Loss of liquid level in the absorber Before going into the details of steps trays and, because of vigorous
whenever the liquid carry-over taken to improve amine quality, it washing, became detached from the
problem was about to surface is imperative to know that during a trays and moved out of the column.
• A shift in temperature isotherm, refinery expansion, which included A technical paper2 mentions that
with the top vapour outlet tem- commissioning of a delayed coker high concentrations of suspended
perature from the amine absorber in 2016, a few changes were made in solids in the amine solvent, high
increasing rapidly from 45℃ to 55℃ the amine system. A common amine soluble iron in the lean amine, and
A literature survey was under- sharing network was established excess antifoam injection can be
taken to find out the root cause of across the refinery. It was later causative agents of foaming.
liquid carry-over. An article pin- noticed that the quality of amine Amine samples taken at the VGO
pointed the same effects of foam- degraded and the presence of par- MHC and amine regeneration unit
ing that our unit was experiencing ticles in the amine was observed as were surprisingly devoid of hydro-
which included an increase in ∆P amine suspended solids increased carbons. The main reason, which
across the column, loss of liquid to 300 ppm. It was this amine that was understood later, was that the
level, and shift of temperature iso- was in circulation through the hydrocarbons which became mixed
therm.1 Another article revealed VGO MHC. Also important to note with amine in the high pressure
some symptoms of foaming which is that the amine in the refinery absorber operating at 105 kg/cm2(g)
matched closely our unit’s experi- was changed from DEA to MDEA might have flashed in the flash
ences.2 In the process of analysing because of its better amine proper- drum of the amine regeneration
the root cause of the problem, a lot ties and lower steam requirement unit.
of measures were taken to mitigate for regeneration. To improve the
possible hydrocarbon condensa- amine conditions as part of the trou- Reducing gas flow to the amine
tion, to improve amine quality, bleshooting, the following actions absorber
and reduce gas load in the amine were taken: The gas/oil ratio was reduced
absorber: 1. Starting antifoam injection to the from 1288 Nm3/m3 to 700 Nm3/m3
1. Reducing cold separator temper- amine pump suction after clearance from the licensor.
ature3 to 45°C 2. Amine sharing with other units The mild hydrocracker was run on
2. Reduction of cooling water flow halted to reduce total suspended full diesel mode which resulted in
to the recycle gas cooler upstream of solids reduced amine carry-over as the
the HP amine absorber 3. Cartridge filter installation amine requirement reduced. The
3. Increasing the lean MDEA reduced visible particulate content gas bypass of the amine absorber
(LMDEA) temperature to 52℃ to 4. MDEA strength was increased to was opened partially, allowing
maintain a temperature differential 40%. The results were encouraging 30-40% of the gas flow to pass
of 10℃ between LMDEA and recy- at the early stages as lesser amine through the bypass and the rest to
cle gas flow was needed, but this could pass through the amine absorber.
4. Reducing the cold separator cause more corrosion problems These procedures brought about
hydrocarbon level in the long run. As per the litera- huge relief in the plant as the amine
q2 bpcl.indd 3 15/03/2021 18:23

F – Unit throughput, kg/hr
LMDEA to VH-V-10 V-10 O/L GAS
S – Feed sulphur, wt%
Temperature 43.00 C Temperature 44.84 C A – LMDEA flow rate to absorber,
Pressure
Mass Flow
107.0 kg/cm2_g
8.000e+004 kg/h
Pressure
Mass Flow
105.6 kg/cm2_g
4.116e+004 kg/h
kg/hr
w- Amine strength, wt%
VH-V-10 INLET GAS RDEA from V-10
Temperature 37.80 C Temperature 46.87 C Sensitivity analysis
Pressure 105.7 kg/cm2_g Pressure 105.7 kg/cm2_g A sensitivity analysis was carried
VH-V-10
out to capture the variation in recy-
Mass Flow 4.488e+004 kg/h Mass Flow 8.372e+004 kg/h
Number of Trays
VH-V-10
9.000
cle gas scrubber gas outlet tempera-
Rich Amine Results (RDEA from V-10-Acid Gas Loading) 0.4328 ture with the following parameters:
Rich Amine Results (RDEA from V-10-H2S Loading)
Rich Amine Results (RDEA from V-10-Amine Strength)
0.4328
33.45 wt %
1. HP cold separator inlet tempera-
VH-V-10 Inlet Gas-Nm3/hr 2.371e+005 STD_m3/h ture (hydrocarbon dewpoint)
VH-V-10 Outlet Gas-Nm3/hr 0.4328 STD_m3/h
2. Conversion at the outlet of the
reactor
Figure 6 Snapshot of simulation of amine absorber 3. Varying feed sulphur from 1.7-
3.3 wt%
carry-over issue subsided com- lier, a steady state simulation of the Simulation showed that the
pletely. However, this led to higher plant was done. hydrocarbon dewpoint varied lin-
H2S in the recycle gas, which neces- early with cold separator inlet
sitated opening of the purity vent Steady state simulation of VGO temperature, but as a temperature
to purge impure recycle gas from MHC difference of 10°C between LMDEA
the high pressure system to the Based on field observations, a and the cold separator was always
medium pressure system where the steady state model was devel- maintained, there was little chance
gas was amine treated and sent to oped using Aspen Hysys to under- of carry-over. It was also noted
fuel gas. Licensor confirmation on stand the operation of the amine from the simulation that the outlet
metallurgy compatibility was taken absorber. Various parameters gas temperature being higher than
These procedures brought about huge relief in the plant as the amine carry-over issue subsided
wherever high H2S concentration including hydrocarbon dew point, the LMDEA inlet temperature in
completely. However, this led to higher H2S in the recycle gas, which necessitated opening of the purity
was expected. A downside of this amine absorber temperature pro- the amine absorber was not due to
vent to purge impure recycle gas from the high pressure system to the medium pressure system where
measure was loss of H2 through the file, and the impact of varying feed increased conversion. Simulation
the gas was amine treated and sent to fuel gas. Licensor confirmation on metallurgy compatibility was
purity vent. sulphur content was studied by predicted a maximum tempera-
taken wherever high H2S concentration was expected. A downside of this measure was loss of H2
As a result of all these positive simulation. ture of 74℃ near the fourth and
through the purity vent.
changes, the charge of the plant Another goal of the simulation fifth trays inside the absorber on
As a result of all these positive changes, the charge of the plant was increased from 140 t/h to 245 t/h
was increased from 140 t/h to 245 was to vary gas and liquid flows increasing the feed sulphur from
with feed sulphur at 2.2 wt%. Amine flow was increased to 125 t/h, keeping a H2S loading of 0.4
t/h with feed sulphur at 2.2 wt%. in the column and to mimic the 1.7% to 3.2%, while during amine
moles/mole of MDEA with an amine strength of 40%. The continuous filtration of amine also helped
Amine flow was increased to 125 effect of fouling of trays. The Peng- carry-over incidents the top temper-
operators to slowly close the bypass over a period of time without any instance of amine carry-over.
t/h, keeping a H2S loading of 0.4 Robinson property package was ature was observed to increase to
Purging high H2S from the recycle gas through the purity vent and occasionally changing over to low
moles/mole of MDEA with an chosen as the thermodynamic prop- 52℃ (see Figures 10 and 11). A shift
sulphur VGO feed also helped to increase the hydrogen purity of the recycle gas.
amine strength of 40%. The contin- erty package for simulating the in temperature bulge upwards was
Although the gas bypass provided relief to the operators and helped to increase the charge, the riddle of
uous filtration of amine also helped hydrocarbon section, whereas the also observed when the feed sul-
amine carry-over was not completely solved. The presence of particulate matter in RDEA after amine
operators to slowly close the bypass amine section (HP amine absorber) phur was increased.
washing did provide a clue, but the possibility of abnormality in other parameters was not ruled out. In the
over a period of time without of the simulation was modelled
quest to find out the other reasons and to revalidate some of our field experiments outlined earlier, a
any instance of amine carry-over. using the Acid Gas property pack- Plugged recycle gas knockout drum
steady state simulation of the plant was done.
Purging high H2S from the recy- age. A snapshot of simulation in A recycle gas knockout drum is
cle gas through the purity vent and Hysys is shown in Figure 6. The placed upstream of the HP amine
occasionally changing over to low fidelity Steady state of the developed
simulation of VGOmodelMHC was absorber to prevent carry-over of
sulphur VGO feed also helped to confirmed with plant data andBased on field observations, a steady was wasany
state model condensed
developed using Aspen liquid hydrocar-
Hysys to understand the
increase the hydrogen purity of the found to be satisfactory. Rich amine bon to the amine absorber. It was
operation of the amine absorber. Various parameters including hydrocarbon dew point, amine absorber
recycle gas. H S loading

temperature
2
calculated
profile and the impactnormally by sulphur
of varying feed observed during
content was studiedthe operation that
by simulation.
Although the gas bypass pro- operators (using the following cal- the control valve oftothe
Another goal of the simulation was to vary gas and liquid flows in the column and mimicrecycle
the effectgas
of
vided relief to the operators and culation) and using empirical for- knockout drum drain was open
fouling of trays. The Peng-Robinson property package was chosen as the thermodynamic property
helped to increase the charge, the mulae package matched
for simulatingthe rich amine
the hydrocarbon H2Swhereas
section 100% throughout
the amine the absorber)
section (HP amine operation.
of the
riddle of amine carry-over was not loading output generated by the There was no gas blow-by to isthe
simulation was modelled using the Acid Gas property package. A snapshot of simulation in Hysys
completely solved. The presence simulation shown in Figure run:
6. The fidelity of the developed model cold flash drum
was confirmed with plantfrom
data andthewasrecycle
found to
of particulate matter in RDEA after be satisfactory. Rich amine H2S loading calculated normally gas knockout drum.
by operators (using theThis
followingindicated
calculation)
amine washing did provide a clue, Rich and usingamineempirical S loading
H2formulae matched (mol/mol
the rich amine that the output
H2S loading knockout
generateddrum bottoms
by the simulation run:
but the possibility of abnormality in of MDEA) was plugged. Deplugging during
other parameters was not ruled out. Rich amine H2S loading (mol/mol of MDEA) plant operation was risky at a pres-
In the quest to find out the other ($∗&∗'.''')*) sure of 105.0 Kg/cm2g (see Figure 8).
reasons and to revalidate some of = When the unit was shut down, the
(,∗-∗../∗0'12 )
our field experiments outlined ear- recycle gas knockout drum bottoms
F – Unit throughput, kg/hr.
S – Feed Sulphur, % (by wt.)
A – LMDEA flow rate to absorber, kg/hour
w- Amine Strength, % (by weight)
Sensitivity analysis
A sensitivity analysis was carried out to capture the variation in recycle gas scrubber gas outlet
q2 bpcl.indd 4 temperature with the following parameters: 15/03/2021 18:24
Absorber bypass line Treated recycle gas to RG compressor KOD
Lean MDEA
HP amine
absorber
Figure 7 Inspection after shutdown

Plugged during operation.
showed that the outlet piping of the Consensed HCs not removed.
knockout drum was plugged Recycle gas from
HP cold separator
RMDEA to ARU
was found to be heavily plugged
(see Figure 7) which confirmed our Control valve 100%
open throughout
suspicion. Liquid collected in the Plugged during operation. the operation
recycle gas knockout drum would Consensed HCs not removed.

To cold flash drum
then have to move out along with
the gas since the drain line was
plugged and this could be the cause Figure 8 HP amine absorber bypass and recycle gas knockout drum
of hydrocarbon carry-over and asso-
ciated foaming issues in the HP Aspen Hysys simulation which the foaming issues subsided with
amine absorber. served as input to the proprietary bypass. Thus the issue of foaming
tray design/rating tool. A propri- at higher amine flow rates could be
Symptoms of plugging etary tray design/rating tool with answered and gas bypass helped
LMDEA entering the HP amine built-in capability to rate such trays solve the problem. But operators
absorber carried particulate con- was used to rate the existing design faced a problem of amine carry-over
tamination, as amine washing of the high capacity trays and to at lower flow rates too. The next
demonstrated. This was also par- check various tray hydraulic param- section tells us the reason behind it.
tially responsible for the plugging eters on different liquid-vapour
of valves in the topmost trays of flow conditions which would indi- Carry-over at lower flow rates
the HP amine absorber. It was sus- cate the possibilities of liquid car- Even after changing over to higher
pected that particulate contami- ry-over from the tray. capacity trays, the problem of amine
nation had occurred over a period To evaluate the hydraulic robust- carry-over persisted. Amine carry-
of time when amine sharing with ness of the trays, it was essential to over was also observed at times as
other units was in practice and find out the quantity of recycle gas amine flow rate was reduced to con-
had settled on the top trays and bypassing the HP amine absorber. tain amine carry-over to the recy-
was washed off only during amine This was calculated using material cle gas knockout drum. This was
washing. On inspection of the trays balance equations. The recycle gas puzzling as amine carry-over was
during shutdown, at a later point of H2S composition at the exit of the expected only at higher flow rates
time, it was observed that the trays HP amine absorber had increased to of amine. This anomaly of amine
were relatively clean as they were 0.6 vol% and the inlet composition carry-over at both lower and higher
amine washed before shutdown. was close to 1 vol%. The amount amine flow rates brought the unit
But the stagnant areas of the trays of gas bypass was found to vary to its knees. To ascertain the cause
showed deposits which were rich in between 17 t/h and 25 t/h out of of this anomaly, tray details were
iron and could have been a contrib- a total 40-45 t/h of recycle gas. A studied and simulations performed.
utor of foaming. Dry sludge depos- hydraulic study of the HP amine An interesting observation in the
its formed in the seal pan area and absorber trays was performed for new tray installation was the pres-
inside the downcomer of one of the recycle gas flow with and without ence of only dynamic seal. In other
trays of the HP amine absorber. The bypass. The results suggested that words, the downcomer clearance
above mentioned theory prompted in the case of hydrocarbon+amine and exit weir height were the same.
us to use a proprietary tray design/ (depicted by a foaming factor of 0.6) Although most high capacity trays
rating tool to check the hydraulics and without gas bypass (gas flow have only dynamic seal to reduce
of the installed high capacity trays 45 t/h and amine flow 100 t/h), the the exit velocity losses,10 it is a cause
for partial plugging and hydrocar- froth height on a tray increased to of potential downcomer unseal-
bon condensation scenarios. 76% of tray spacing, suggesting the ing at lower flow rates where the
initial stages of foaming in the col- liquid enters spray regime. Spray
Hydraulic evaluation of trays umn. If gas bypass was practised regime occurs at low liquid flow
The thermophysical properties (gas flow 25 t/h, amine flow 100 rates, at weir loadings of < 2.5-3.3
of liquid and gas entering the HP t/h), the froth height fell to 48.3% g/m/in (20-30 m3/hr-m)7 when
amine absorber were obtained by of tray spacing, indicating why the crest height is less and at high
q2 bpcl.indd 5 15/03/2021 18:31

ing of downcomers. Simulation in
a proprietary tray design tool pro-
(a) (b) (c) (d)
vided an exit loss of 2.3 mm at an
amine flow rate of 40 m3/h.
The weir loading was also on the
lower side with a value of 24 m3/h
m. Table 2 summarises the results
of simulation. This suggests that
the trays may have been operating
in spray regime as the recycle gas
Figure 9 How downcomer unsealing bottlenecks a tower in the spray regime flow rate was high for the low flow
Reproduced with permission8,9 rate of amine. Downcomer unseal-
ing flood could have occurred.
Unfortunately, the supplier’s
51 software was unable to evaluate
whether the trays operated in the
50 spray regime and whether down-
49 comer unsealing flood actually
Temperature (˚C)
occurred. If it indeed occurred, the

48 amine was sprayed over to the recy-
47 cle gas compressor suction knockout
drum. Hence, operating at lower
46
than turndown flow was stopped.
45 The hydraulic analysis was una-
ble to provide complete answers.
44
0 1 2 3 4 5 6 7 8 9 At higher gas and amine flow rates,
Tray position (bottom-to-top) a foaming factor of 0.6 had to be
used, which is lower than the 0.7-
Figure 10 Stage-wise (bottom-to-top) temperature profile (conversion = 30 %, feed 0.75 usually used for these systems.
S = 1.7%, amine flow = 80 t/h) But even with a foaming factor of
0.6, froth height of only 76% of tray
spacing was achieved, which is still
75 a low number to explain flooding.
For the low liquid flow rates, the
70 hydraulic analysis established the
likelihood of downcomer unseal-
Temperature (˚C)
65
ing, but was unable to determine
60 whether the unsealing would lead
to flood. This remained unexplained
55 in the supplier’s proprietary tray
rating software. To gain better
50
understanding, a rigorous hydraulic
45
analysis was needed.
0 1 2 3 4 5 6 7 8 9 10
Tray position (bottom-to-top)
Replacement of amine absorber
The hydraulic calculations were
Figure 11 Stage-wise (bottom-to-top) temperature profile (conversion=30 %, feed done later. But replacement of the
S = 3.2%, amine flow = 100 t/h) amine absorber and its upstream
recycle gas knockout drum (whose
gas velocities. The gas atomises the trays. An article by H Z Kister6 pro- drain line was plugged) was car-
tray liquid, forming a dispersion. vided more evidence of potential ried out to solve the problem prior
There is no frothy pool, and the liq- downcomer unsealing problems at to the hydraulic calculations. The
uid resides as atomised drops in the low liquid flow rates. amine absorber was changed over
space between the trays. The contin- The concept of downcomer from a tray column to a packed col-
uous gas phase reaches the down- unsealing is encapsulated in this umn. Charcoal filters in the amine
comer outlet. There is no static seal article and reproduced with kind regeneration unit were replaced
to prevent gas from rising into the permission in Figure 9. Simulation and the unit was taken back online.
downcomer. Spray regime is evi- was done on the high pressure sec- The issue of amine foaming sub-
dent in simulations by low down- tion to ascertain the downcomer sided and the unit has been run-
comer exit loss and low height of exit loss. A lower exit loss indicates ning on full throughput ever since.
clear liquid below the froth zone on lower liquid flow rates and unseal- A conservative estimate of the sav-
q2 bpcl.indd 6 15/03/2021 11:00

ings due to charge increment for
Tray parameters at different liquid loads
just three months is shown in Table
3 as Rs 58 crore. It includes the sav-
ings accrued due to stoppage of Description Design No bypass Gas bypass
Gas flow rates, t/h 60 45 45 25
export of VGO at a discount of $9/ Amine flow rates, t/h 149 100 40 100
bbl when compared with crude and Downcomer loading (top), m3/hr-m2 324.8 218 87 218
stoppage of amine losses as part of Downcomer loading (bottom, m3/hr-m2 641.0 431 172 431
continuous draining during periods Weir loading, m3/hr-m 90.7 60 24 60
Downcomer exit loss, mm liquid 31.38 14 2.3 14.05
of continuous carry-over.
Conclusion Table 2
Amine columns in high pressure
systems have a higher foaming ten- Savings due to charge increase in VGO MHC
dency. Foaming most likely hap-
pens because of a combination of Average VGO MHC charge from Apr-Dec’19 175, t/h
factors. Corrosion particles includ- Average VGO MHC charge from Jan-Mar’20 225, t/h
ing iron sulphide9 carried by amine Charge increment 50 , t/h
HS VGO build-up @ VGO charge of 175 t/h 110.4, TMT
can stick to the trays of the column Discount for VGO parcel export ( w.r.t Dubai crude oil ) 9 ,$/bbl
and contribute partially to foaming. Barrelage factor 7.5, bbl/t
Inadequate draining of condensed Exchange rate 75, Rs/$
hydrocarbon from the knockout Savings by preventing VGO export 55.8, Rs Cr
Reduction in amine make in SRU 50, t/month
drum placed upstream of the amine Cost of amine 150, Rs/kg
absorber may result in carry-over Savings due to lower amine consumption 2.25, Rs Cr
and can aggravate foaming. Too Total savings 58.1, Rs Cr
much antifoam increases foam sta-
bility rather than reducing it.8 Foam Table 3
tests of amines obtained from high
pressure amine absorbers need not foam.9 In the case of an upset in the 9 Pauley C R, Hashemi R, Caothien S, Analysis
indicate the presence of hydrocar- HP amine absorber purging high of Foaming Mechanisms in Amine Plants,
bons. This is because most of the H2S gas through the purity vent and American Institute of Chemical Engineer’s
hydrocarbons may flash off by the treating this gas in a medium pres- Summer Meeting 22-24 Aug, 1988.
time the amine reaches the amine sure absorber is also possible as the 10 Pilling M, Design Considerations for High
Liquid Rate Tray Applications, AIChE Annual
regeneration unit from where amine lines are generally capable of han-
Meeting on Advances in Distillation Equipment
samples are taken for the foam test dling H2S rich gas.
and Applications, Nov 2006, San Francisco, CA.
and hydrocarbon analysis. Amine References
quality needs to be monitored reg- 1 Al Dhafeeri M A, Special Report: Identifying
ularly to ascertain efficient and sta- sources key to detailed troubleshooting of Rajesh Mohan is Shift Supervisor of mild
ble amine operation. High capacity amine foaming, Oil and Gas Journal, Vol 105, hydrocracker, CCR and sulphur recovery units
trays, if run at very low liquid flow Aug 2007, 1-12. at Bharat Petroleum Corporation Limited’s
rates, could move from the froth 2 Engel D, Amine Optimization Division, The Kochi Refinery. With more than 11 years of
regime to the spray regime and Woodlands, Texas; and S Northrop, ExxonMobil experience, he is an Accredited Energy Auditor,
could be a potential cause of amine Upstream Research, Spring, Texas, Manage recipient of a National Energy Conservation
carry-over. Many high capacity trays contaminants in amine treating units – Part 2: Award, and holds a chemical engineering
Rich amine filtration and foaming, Hydrocarbon degree from Anna University, Chennai, India.
rely only on dynamic seal and do
Processing, Jul 2018, 44. Rohit Kumar is Assistant Manager of the VGO
not have positive sealing. Positive
3 (Xin X) Zhu F, Hoehn R, Thakkar V, Yuh E, hydrocracker unit at Kochi Refinery. With over
sealing in trays is where the down- Hydroprocessing For Clean Energy Design, seven years of experience, he has led projects
comer clearance is less than the out- Operation, and Optimization, 2017, 98. in commissioning, troubleshooting and de-
let weir height. It is suspected that 4 von Phul S A, Cummings A L, Control of bottlenecking, and graduated in chemical
the absence of dynamic seal, espe- Foaming in Amine Systems, 2007, 5. engineering from Thapar Institute of Engineering
cially at low flow rates, can aggra- 5 Lieberman N P, Troubleshooting Process & Technology in Patiala (Punjab), India.
vate the liquid carry-over problem Operations, 4th ed, 2009, 93 Himanshu Kumar Gupta is Shift Supervisor of
and could be a potential cause of 6 Kister H Z, Mohamed N M, Troubleshoot mild hydrocracker, CCR and sulphur recovery
amine carry-over. Randomly packed and solve a gas treater downcomer unsealing units at Kochi Refinery. With six years of
columns are better in the case of problem, Part 1, Gas Processing, Jan/Feb 2015, experience, he holds a chemical engineering
39. degree from Motilal Nehru National Institute
high pressure amine absorbers
7 Kister H Z, Mohamed N M, Troubleshoot of Technology, Prayagraj, India.
because of their inherent low pres-
and solve a gas treater downcomer unsealing Basith Zohail is Shift Supervisor of mild
sure difference across the packing problem, Part 2, Gas Processing, Mar/Apr 2015, hydrocracker, CCR and sulphur recovery units
and their chances of foaming being 49. at Kochi Refinery. With five years’ experience
less. High iodine number in char- 8 Kister H Z, Practical Distillation Technology, in petroleum refining, he holds a chemical
coal can help in the removal of com- Course Manual, Copyright 2013, reprinted with engineering degree from Indian Institute of
pounds which promote and stabilise permission. Technology, Chennai, India.
q2 bpcl.indd 7 15/03/2021 11:00

With a retained, trained, and experienced workforce, we have
been improving our processes, facilities, and technology so
that when you are ready for your next project, we are too.
Rest assured, we will pick up the wrench when you need us
—Ariel Corporation; ready for anything.
www.arielcorp.com/weareready
ariel.indd 1 12/03/2021 13:08

Dividing wall revamp boosts octane
and throughput
Dividing wall column technology reduces energy and capex, but increasingly contributes to
higher revenues from better products, as in this application to light naphtha isomerisation
MANISH BHARGAVA and ANJU PATIL

DWC Innovations
E
conomic growth and envi-
ronmental awareness require
refineries to produce clean,
high-octane gasoline products. The n-Pentane i-Pentane
octane number or RON is primarily
the knock resistance measure of gas-
oline. It has a numerical value from or
0 to 100 and primarily describes the
n-Hexane 2-Methyl Pentane 3-Methyl Pentane
behaviour of the fuel in the engine
during combustion at lower tem-
peratures and speeds. To take RON or
values to higher levels, the reform-
ing and light naphtha isomerisation
n-Hexane 2,2-Dimethyl Butane 2,3-Dimethyl Butane
process became an integral part of
refineries. Light naphtha isomerisa-
tion not only produces high octane Figure 1 Primary reactions in a light naphtha isomerisation unit
isomerate products but it also takes
care of the latest stringent gasoline RON values of individual components evaluated on the basis of the prod-
specifications. Isomerisation units in a light naphtha isomerisation unit uct yields and the RON of the
can handle the benzene content of isomerate product. The liquid prod-
the gasoline pool and most ben- Component Boiling point, °C RON uct yield is determined principally
zene and its precursors are diverted i-Pentane 27.8 93.5 by the extent of hydrocracking
to the light naphtha fraction as the n-Pentane 36.1 61.7 which takes in the isomerisation
2,2-Dimethylbutane 48.7 93
feed to this unit. The isomerisation Cyclopentane 49.3 101.3
unit. Hydrocracking is an undesir-
unit saturates benzene to cyclohex- 2,3-Dimethylbutane 58 104 able side reaction which converts
ane. The configuration of an isomer- 2-Methylpentane 60.3 73.4 light naphtha into light hydrocar-
isation unit depends on the required 3-Methylpentane 63.3 74.5 bon gas molecules which are low
n-Hexane 68.7 30
RON value of the gasoline pool. Methylcyclopentane 71.8 95
RON components. There is an
Benzene 80 >100 inbuilt tendency in molecules with
Overview of a light naphtha Cyclohexane 80.7 83 higher molecular number such as
isomerisation unit the heptanes and above to crack and
Isomerisation and reforming are Table 1 produce undesirable components.
processes which help to improve C7+ molecules are diverted to the
the octane barrel of the end product The presence of other components CCR unit instead of the isomerisa-
by either converting straight chain in the feed such as benzene and tion unit, and benzene and benzene
paraffins to their branched isomers naphthenes tends to raise the reac- precursors help to manage this well.
or by changing linear hydrocarbons tion temperature as benzene satu- Figure 1 shows the primary light
into branched alkanes and cyclic ration and naphthene ring opening naphtha isomerisation reactions.
naphthenes which are then par- are highly exothermic, while low The isomerisation reaction
tially dehydrogenated to produce temperatures favour the conver- enhances the octane values of
high-octane aromatic hydrocarbons. sion of n-paraffins to iso-paraffins. straight chain alkanes by isom-
Isomerisation reactions are However, operating at low tem- erising the n-pentane (nC5, RON
reversible and mildly exothermic. peratures will decrease the reac- value 62) to iso-pentane (iC5, RON
Conversion to iso-paraffins does tion rate, so to overcome this a very 93.5). Other low RON components
not reach completion since the active catalyst is usually employed. like nC6 (RON 31) are isomerised
reaction is equilibrium governed. Light naphtha isomerisation is to 2-methylpentane (2MP, RON
Q2 DWC.indd 1 15/03/2021 11:36

capex involved in deploying var-
ious columns in the process of
Benzene < 4 wt%
Naphthenes < 2 wt% NHT-ISOM boosting octane makes the techno-
C 7 + < 3 wt% unit crats in the facility rethink other
D86 95 Vol% < 80
options. Also, with facilities that
stabiliser
Naphtha
have already invested in these col-
Naphtha splitting
umns, further enhancement of RON
Gasoline pool
Naphtha pool
Crude
is always on the table. In this article,
columns
Minimise flow
CDU
Stabilised Maximise benzene & we will be discussing the various
naphtha its precursosrs configurations of an isomerisation
unit. Figure 2 shows the typical loca-
tion of an isomerisation unit in a
Other cuts refinery. The top product from the
D86 5 Vol% > 98 NHT-CCR naphtha splitter with C7 less than
Unit
To VDU
3% is sent to the isomerisation unit.
Typical configurations of
Figure 2 Typical location of a light naphtha isomerisation unit in a refinery isomerisation units in a refinery
Once-through vs hexane recycle
74) and 3-methylpentane (3MP, erisation reactions are in equilib- The simplest isomerisation units are
RON 76). These 2MP and 3MP rium, the product octane number once-through units. Fresh feed is
molecules are then isomerised to is defined by the number of sep- sent to a feed pretreatment section
2,2-dimethylbutane (22DMB) with a aration units in the process. The and then passes through a series of
RON of 94 and 2,3-dimethylbutane sequence of columns used for sep- isomerisation reactors after mixing
(23DMB) with a RON of 104. Table aration of isopentanes or isohex- with hydrogen gas where it comes
1 shows the comparative RON val- anes clubbed with the isomerisation into contact with the catalyst. The
ues of individual components in an unit with recycle give benefits on reactor effluent is sent to a stabi-
isomerisation unit. account of managing the equilib- liser column where hydrogen and
rium of the reactions taking place in light hydrocarbons produced due
Unit configurations to meet RON the isomerisation unit to maximise to hydrocracking are removed from
requirements RON. As the benchmark for RON the top as off-gas and the isomerate
As isomerisation reactions are in is increased, there is an increase in is removed from the stabiliser bot-
equilibrium, various methods are reboiler duties which can be attrib- toms. The RON achievable through
used to push the reactions in the uted to the following factors: these once-through processes is
forward direction. The target RON • Increase in RON requires a about 85.
desired for the combined isomer- sharp separation between low and Refineries that want to achieve
ate product depends on two cri- high-octane molecules due to which RON beyond a value of 85 deploy
teria, the first being removal of the reboiler load of the column ways to recycle low octane mol-
products from the isomerate stream increases. ecules back to the isomerisation
and the other recycling low octane • RON can also be increased by reactor. Facilities which have an
molecules from the product back recycling low RON components isomerisation reactor followed by
to the isomerisation reactors. For back to the reactor, which increases a deisohexaniser (DIH) column can
this purpose, the depentaniser and the reboiler duties of the down- achieve a product RON of up to 88
deisopentaniser are installed. It can stream columns. by recycling a high percentage of
be concluded that, since the isom- Apart from increased opex, the the n-hexane, 2-methylpentane, and
3-methylpentane, which are low in
RON, back to the reactor.
ISOM reactors
This is achieved by drawing the
Reactor heater Off-gas
Light isomerate
mid-cut from the DIH column. The
DIH produces a light isomerate
distillate product consisting of C5
Dried H2 and branched C6 molecules (rich
Deisohexaniser
in DMBs), a C6 recycle side draw,

Stabiliser
and a C7+ bottoms product. For a

Product
Dried recycle stream at 60% of the fresh
naphtha
feed feed, an octane increase of several
points is achieved compared to the
once-through operation. Typically,
RON 87-88 Heavy isomerate one can expect a RON increase
from 83-84 to 87-88 with DIH col-
Figure 3 Typical configuration of a light naphtha isomerisation unit with hexane recycle umn hexane recycle to the isom-
Q2 DWC.indd 2 15/03/2021 11:36

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Isomerisation unit with hexane
recycle, deisopentanised feed, and
ISOM Reactors
Light
C5 recycle
Reactor
isomerate Unconverted n-pentanes with RON
heater Off-Gas values as low as 61 are sent to the
DIH distillate and thus become a
Deisopentaniser part of the final isomerate prod-
uct. For full conversion of all nor-
Deisohexaniser
Stabiliser
Dried
Naphtha mal paraffins, recycling is required
feed Product via a depentaniser (DP) installed
before the DIH column. This helps
to make a sharper separation
between the DMB-rich C6 isomer-
Dried H2
RON 89-90 Heavy isomerate ate product and the iC5/nC5 recycle
stream. The DP column removes
Figure 4 Typical light naphtha isomerisation unit with hexane recycle and iC5/nC5 as an overhead distillate
deisopentanised feed product upstream of the DIH and
recycles it back to the deisopen-
taniser column, which in turn sep-
arates iC5 as the high RON top
ISOM Reactors C5 Recycle
Light product, and nC5 is recycled back
Reactor
isomerate to the reactor via bottoms product.
heater Off-Gas This again helps in pushing the
equilibrium reactions in the for-
Deisopentaniser
ward direction. The configuration

Depentaniser
Deisohexaniser
(see Figure 5) improves RON up to

Stabiliser
Dried
Naphtha 93.
feed Product
Table 2 shows how the introduc-
tion of DP/DIP/DIH columns in
the isomerisation loop in various
combinations, clubbed with the type
Dried H2
RON 91-93 Heavy isomerate of process employed, impacts the
achievable RON.
Figure 5 Isomerisation unit with hexane recycle, deisopentanised feed, and C5 recycle
Developments in dividing wall
erisation reactor. Figure 3 shows ation section, it removes iC5 from column technology applied to
a typical configuration of a light the feed as overhead distillate prod- isomerisation
naphtha isomerisation unit with uct, which pushes the reaction in Advances in distillation play a key
hexane recycle. the forward direction. The balance role in minimising the costs of new
of the feed is sent to isomerisation and revamped projects in a refin-
Isomerisation unit with hexane reactors and the reactor effluent is ery. Dividing wall column (DWC)
recycle and deisopentanised feed sent to a DIH column to separate technology had limited acceptance
Some facilities, in addition to a DIH high octane C5/C6 isomerate prod- 20 years ago but is now reshaping
column with recycle, have a deiso- uct from low octane C6 molecules our distillation processes. DWC
pentaniser (DIP) column installed which are recycled to the isomeri- technology is increasingly used to
before the isomerisation reactor. sation reactor. Thus the addition of modernise conventional distillation
This helps in achieving an isomer- a DIP increases the RON over that sequences, especially in revamps of
ate product of RON up to 90. As of a ‘DIH only’ configuration (see existing units. Besides energy and
the DIP is placed in a feed fraction- Figure 4). throughput improvements, a DWC
revamp significantly improves the
Typical RON for various isomerisation unit configurations performance of downstream units.
The alignment of the dividing
wall inside the column plays a
Isomerisation unit process configuration No of column RON of isomerate
product dominant role in the selection of
Once-through Stabiliser 81-84 DWC for a particular separation.
Hexane recycle Stabiliser + deisohexaniser 87-88 The middle DWC is an ideal alter-
Deisopentanised feed and Deisopentaniser + stabiliser + deisohexaniser 89-90 native for side cut columns, which
hexane recycle
Pentane and hexane recycle Deisopentaniser + stabiliser + 91-93 helps to increase throughput and
Depentaniser + deisohexaniser gives better product specifications.
The top DWC provides an addi-
Table 2 tional source of heat integration
Q2 DWC.indd 3 15/03/2021 11:36

Vapour out Vapour out
Reflux in Reflux in
MAX L.L.
Partial Liquid draw Partial Liquid draw

Partial Liquid return Partial Liquid return
Dividing wall
Side product
Feed in
Feed in Dividing wall
Reboiler draw off Reboiler draw off Reboiler draw off
Reboiler return Reboiler return Reboiler return

MAX L.L. MAX L.L. MAX L.L.
MIN L.L. MIN L.L. MIN L.L.
T.L.
BTMS Liquid out BTMS Liquid 1 out BTMS Liquid 2 out
MIDDLE DIVIDING WALL COLUMN BOTTOM DIVIDING WALL COLUMN
Vapour out Vapour out Vapour out
T.L.
Reflux in Reflux in
MAX L.L.
Dividing wall No. 2
Sidecut product-2
Dividing wall
Dividing wall No. 1

Feed in
Feed in
Sidecut product-1
Reboiler draw off
Reboiler return Reboiler draw off

MAX L.L.
Reboiler return MAX L.L.
MIN L.L.
MIN L.L.
T.L.
BTMS Liquid out Bottoms product
TOP DIVIDING WALL COLUMN DUAL DIVIDING WALL COLUMN
Figure 6 Elevation of commonly used dividing wall columns Source: DWC Innovations
Q2 DWC.indd 4 15/03/2021 11:36

Isom Unit with DIH Recycle Light isomerate Revamp of DIH Column to DWC Prime Light isomerate
iC5 + NC5 + DMB iC5 + NC5 + DMB
Hydrogen Off gas Hydrogen Off gas
Deisohexaniser
Deisohexaniser
ISOMERISATION ISOMERISATION
Hydrotreated
Recycle MP + NC6
Hydrotreated C5 / C6
C5 / C6 Lt. Nap. feed Lt. Nap. feed
Recycle MP + NC6
C5 / C6
RON 87-88 Heavy isomerate MCP + CH + C7 RON 89-90 Heavy isomerate MCP + CH + C7
Figure 7 Revamp of a DIH column to DWC in an isomerisation unit with hexane recyle
with other process streams. On tionality of DIP or DP columns as RON value of the final isomerate.
the other hand, the bottom DWC the case may be. Besides enhanc- Although this configuration defi-
has the advantage of replacing a ing separation, DWC revamps pro- nitely gives a higher RON than a
two-column arrangement in an vide considerable energy savings once-through process, the RON can
indirect sequence. when compared to conventional be further increased by recirculating
The latest advance in DWC tech- distillation column flow schemes. methylpentanes back to the reac-
nology is dual wall dividing col- The use of DWC technology in an tor. Also, separation of isopentanes
umns which are known to have a isomerisation unit not only targets present in the fresh feed going to
higher thermodynamic efficiency improvement in RON but brings the isomerisation reactor contribute
than their counterparts. From the the added advantage of increased to higher RON values. The isopen-
outside, it is no different from a throughput which would other- tanes present in the fresh feed take
simple DWC but has the capability wise require installation of new a free ride in the isomerisation reac-
to deliver four or more high purity columns. The remaining part of tion process and restrict the forward
products from a single column. As this article focuses on the appli- reaction to produce more branched
dual wall columns are robust, flex- cations and outcomes of revamp- chain components. The conven-
ible, and easy to operate, this tech- ing the DIH column in various tional method for removing isopen-
nology has become viable. Figure 6 configurations. tanes from fresh feed is to install a
shows the elevations of commonly DIP column upstream of the isom-
used DWCs. Application of DWC in isomerisation erisation reactor.
units with hexane recycle The revamp of an existing DIH
Revamp of a deisohexaniser column The DIH column recirculates column to a DWC enables it to have
using DWC technology unbranched molecules, mainly the dual functionality of a deiso-
DWC technology plays a key role n-hexanes and methylpentanes, pentaniser. Hydrotreated naphtha
in enhancing the performance of after removal of branched, high- is first sent to the revamped DIH
isomerisation units. Facilities that RON molecules back to the isom- column which now produces four
want to improve the RON of the erisation reactor. The top product, sharp cuts. As Figure 7 shows, the
final isomerate find divided wall the light isomerate, contains mainly light/heavy isomerate and the recy-
column technology lucrative as this isopentanes, dimethylbutanes, cle are managed in a way similar to
involves only the deisohexaniser and methylpentanes. The less the that before the revamp, while the
(DIH) column being revamped, so amount of methylpentanes going fourth cut is the fresh feed to the
as to include the additional func- to the top product, the better the isomerisation reactor without iso-
Isom with DIP & DIH Recycle Light isomerate Revamp of DIH Column to DWC Prime
iC5 + NC5 + DMB
iC5 iC5 Recycle iC5 / NC5
Off gas
Hydrogen Off gas
Hydrogen
Deisopentaniser
Deisopentaniser
Deisohexaniser
Deisohexaniser
Light
isomerate
ISOMERISATION ISOMERISATION
iC5 + DMB
Hydrotreated Hydrotreated
C5 / C6 C5 / C6
Recycle MP + NC6 Recycle MP + NC6
Lt. Nap. feed Lt. Nap. feed
RON 89-90 Heavy isomerate MCP + CH + C7 RON 91-93 Heavy isomerate MCP + CH + C7
Figure 8 Revamp of a DIH column to DWC in an isomerisation unit with hexane recycle and deisopentanised feed
Q2 DWC.indd 5 15/03/2021 11:36

After this catalytic unit, the gas can be passed through streams (using basic carbon steels). However, the most
an amine unit before it is ready as feed for steam reform- obvious downside is the financial cost of burning valu-
ing. It will then be a very useful steam reforming feed, able hydrogen. Hydrogen sources in fuel gas can be
and in case it containsSummary some Hof , which
SOx additive it typically
performance does, from joint reformerprovides
venture or isom Conclusion units
on-site
Average where
support
values the oftomake
key gas or off- Low wear and m
manufacturing
parameters
performance Performance through reduced2 cat-
of an isomerisation unitreformingComparison
after revamp of apre-
of DIHand the next
post-revamp
column to DWC plant turnaround,
results typically upperiodto 10stream years,for so Sand acoustic m
the normal gas recycle within a steam unit can gases
plants are not separated
and serviceisoffices The benefitsoff as
in China.a hydrogen
duringof DWC technology
trial rich The design-rela
alyst activity, leading to increased 50 no maintenance required between turnarounds. Pulling too mu
be stopped. References for this type of unit do exist.Pre-revamp hydrotreating, Under increasingly selective
have hydrogenation,
stringentgrown global beyond or other
regulations hydro-
reductionon the such as shaft
catalyst
Parameter addition as well as the This
Post-revamp
simplicity of
Results/comments
installation Ideal
makes ultrasonic sen- structural integ

Average
Feed from values
FCC main column SOx, receiver Additivetorate, Performance
PUF t/h
HP separator,
of isomerisation
Feed S, Slurry gen
unit
147 sulphur,
after
reduction intensive
Excess
182
revamp O2, Feed
of processes.
pollutant in increased
rate energy More
emissions, commonly
consumption
byOriginal
124%
China concept has a the
or
limit main
capex.
of 10 the maintenanc
potential
ANo of columns
Pressure for afterburn.
in ppm RON Inof R2R
existing
lb/d units, o
f deisohexaniser
wt% column wt%to sors
dividing ideal
wall
vol% columnfor use in remote
Average value
locations which
Super
are
Super
only lapse of the fo
Joris drop 1.7 source of hydrogen incontent
refineryOptimisedfuel gas is from FCC dry service life. Th
across stripper, kg/cmConsultant, KBC (A Yokogawa
2
400.26 0.25
theisomerisation
first stage
Mertens, Principal
regenerator operatingRON ppm for 3.9theduring sulphur Refineries are
of diesel using fuels.
design
DeSOx DWC To
DeSOx tech-
comply
CV+
ity to produce
Competitor
Temperature atunit
stripper isomerisation
9 bottom, °C1153 8 0.7 Increase in125
accessible
Remarks
116 Reduction turnarounds.
in stripper bottom To protect
temperature the
reduced
0.83 H S,0.83 ultra-
C1, C2, technological p
Company), Joris.Mertens@kbc.global throughput 1.4 gas with which
the contains
4.2requirements, aduty
nology mixture foror hydrogen,
Feed sulphur, wt%
refineries maximising
aresensor
required 2 torevenue
1.2invest
configuration unit515
in Stabiliser
partial+ burn mode
Super DeSOx CV+ 4
removes the89-90
16 0.6
sonic electronics reboiler
from heat, the 1.1 uses stain- and fines mig
TheWater economics
from debutaniser of hydrogen
overhead 87-88 receiver recovery
to debutaniser depend feed, %on30
10-20% the Existing
0.132 and
in other
DIH
0.05column
technological non-condensables. from
Slurry sulphur, wt%
modernisation. newer orThe better dieselproducts.
desulphur- It is wear-free runn
majority of the hydrogen from the less steel waveguides to keep
Excess oxygen, vol% the electronics
1.2 1.3 safely of reservoir ro
supply
Temperature and at
deisohexaniser
demand
(DIH)
debutaniser side,bottom,on °C both the cost and the value
*% Ash is the total inorganics including iron and its compounds. 164 Many
performs
isation
170 refiners
dual
process
Fouledare choosing
reboiler
increasingly
includes to used
tubes limited
a capture
hydrogenation
temperature
in and purify
debottleneck-
process the prehensive
that axi
coke,
reducing theduty,potential for high away
9.2 functionality from
of hexanehot metal surfaces
% SOx reduction
up to 600˚C
47%
(1100˚F).
59%
the formation.
Catalyst flow, %
Debutaniser reboiler GCal 13.6 Reboiler duty debottlenecked
of
recovery. hydrogen
requires from fuel
system inggas
pressures streams
existing of more units by than using
in the 100a refinery.
pressure
bar and hydrodynamic
temperature hydrothermal deactiva- 20
recycle
Advanced
& deisopentaniser
processing software makes use of previous greater insight
after swing
temperatures
the revamp adsorption
to DWC of (PSA)
Light
more than unit.
naphtha
400°C.PSA units
isomerisation
Since are
even a thestraight-
issmall-
one nisms in theand co
tion
Table
Table in
1
1 the second stage. The impact recorded ultrasonic Table waveforms
2 to improve the resil- techniques
TheDeisopentaniser
value of recovery (DIP) + forward
est leaks and
can flexible
cause such option
fatal example,
fires, to plants
recover
in which
and hydrogen
the
components simpleat a position of the
of stabiliser
uneven coke burn-off in the first91-93 ience DIHof the The measurement when the sur- sand managem
If hydrogen
sation of is produced
+ deisohexaniser
diolefins in
89-90
from $2/MMBTU natural
5-10% 10
gas, Existing
high purity.
column
unit
revamp can of be sized
ofreliability
a DIH to internal
the
andfeed
column
metal
flowInrate
improves
Asthe presence of water at high tem- require the highest level safety. the rotating and sta
Reference
CV+)
stage
(DIH) in June
does 2018.greatly
not Table 2 shows,
influence face
performs morphology
dual is very rough, which is a situation The ability
then
perature the on hydrogenthe will be
reboiler worth side
process only(shell around side).$400/t.The it is processing,
1case
Kister of a
H reactor
Z, Componentand the theunit’s
circulation rangepump
trapping of
in contaminants
performance requiring
distillation by a
towers: typically
improv-
delivery
causes, ‘floating’ of the
average activity
catalyst
feed sulphur in two and stage slurry regen- sul- whereinnormal
functionality of hexane
ultrasonic wall
100 thickness measurements during well te
There
duty
ofarethe even refineriesreboiler
debutaniser that flare was excess
limited hydrogen,
due to inrecycle
this found
Uncontrolled
symptoms
rate of refinery
and
1000
& depentaniser
SOx cures,
m³/h fuel
normalised
ing
CEP,
and
Aug gas
RON
a
tostreams,
2004. along
delivery such
head
Actual
with as
ofan methane
SOx
65 increase
m, a and
well-in the pump is eq
phur
eration. levelsHowever,were very it similar
can result during in 0 break down. free rate (MSFR
which

fouling case hydrogen recovery has no value at all. The0 after CO , can
the5revamp tobe
10 DWC easily purified.
15 throughput. 20 After
25 recovery 30 of35hydrogen
the trial which affected thefirst
inoperation simi- of the debutan-
100
localised period,
afterburn resulting
in the a stage Jknown2
Rajesh isrefiner
Vice-Presidentin China Processrelieswithon theOil
Essar expertise
Limited India. andHe qual-has The
rate rotor
(MASR), posit
other
iser. extreme
The deposits is a site
on with
the a high
reboiler margin
were hydrocracker
cleaned in 90the Distancefor
ity use
of
along in
Hermetic. downstream
bathtub length, processes,
ft purge gas from the in the rotor m
lar level
and of uncontrolled
can impact the performance SOx as cal- of over 20 years
Fieldissignature of experience
method in refinery operations and process and holds ing your prod
being3 constrained by lack of hydrogen, which can make
shutdown.
Table PSA
a bachelor’s injecteddegree back
in into– the
Manish
chemical
areafuel monitoring
Bhargava gas
engineering is from
thesystem,
Founder
Annamalai minimising
andUniversity,
Director warning system
culated
the second usingstage a regenerator.
refinery correlation. In critical locations, getting a deeper insight intoHe cor- Operator insigh
80
the value of hydrogen reach $3000/t. any
India. losses and maximising
of DWC total
Innovations value. As
in Houston, theTexas.
process to ditions
has
and ex
InIn addition,
single stage excess full oxygen burn regener- levels Figure 5 CFD results 70 Leakage-free
rosion
– catalyst in
flow a pump
large
distribution area solution
can
comparison provide valuable insight into ing maximum
pentanes.
Results This is an attractive and lucrative scheme as purify
The
Pawan core theof
Gupta stream
isthe
Deputy using
19General
10-ton a PSA
years’
pump Manager is straightforward,
experience
system withwithEssar
is a
process
CNKfH+D the India.
optimisation
Oil Limited unit
300- power balance
(whichwhere
ators, can impact additive perfor-
the temperatures are understanding asset health. Fielddesign signature method the reservoir l
aPost-installation
DWC
The costrevamp
of hydrogen ofofaon DIH
recovery
the saves
Ky-Flex themedia installationin the of
HPa The
60
DIP
sep- flow can
He
500
hasrun
solutions over
canned with
and 12 minimal
distillation
years
motor
of outside
techniques
experience
pump.
in
Theand utilities
in process
refineries
water-cooled or
and requirement
chemical
and simulation
motor
plants, for
and
and
of pre-
the axial wear, thu
mance)
higher, were
the similar.
impact the catalyst is more severe. (FSM) in the
measures bathtub the is presented
metal loss as
trend density within distribu-
a reservoir and a
The costthe
column,
arator, of water
though hydrogenoffering
carry-over alsothe varies
samewas widely. Insignificantly
benefits.
reduced general, 50 it operator
played a pivotal
holds a bachelor’s
pump involvement.
according
role in the
degree in chemical
to API The
technology
685 plot
has space
engineering
a shaft needed
commercialisation
from MJP
power is
of compact
of dividing
Rohilkhand
185 kW. longer service l
SOx emissions
uneven coke burn-off dropped may result by 22% in excessively coked tion defined
wall (see
columns. area
Figure
He and
holds 4a) a and
quantifies
bachelor’s velocity
degreegeneralprofile
in and
chemical (see localised
Figure
engineering cor-
4b)
from ment principle
SOx emissions
will
toThe the beadvantage
much cheaper
debutaniser ofto this
overhead torevamp
avoid receiver.hydrogen
is a boost As aslippage
inresult,
RON 40the to and
to it is India.
University, an easy and straightforward option as a refin-
with
particles
fuel gas
the
than
switchto
flowing
to recover
the Super
riser
it after
DeSOx
and
it is
poor
lost
catalytic
to fuel gas.
perfor-
Valve RAll
along
ery
pressure
rosion.
MNIT, theThis
Jaipur,
upgrade.
Madhavan length
India containing
andof
allows
This
is General the
pipeline
aManager
MS
has
parts
arms.
degree
led many
were
The
operators
in chemical
Process refiners
with made
modelling and
engineering
Koch to
of forged
consider
Chemical results
refineries
from solid
ofto when it impac
Illinois
their
Technology
90,
mance, from
control
CV+. This 87
valve
poor previously,
in
translates the
yields and to analong
debutanisermore with
improve- a
overhead fresh
dry gas formation. Bed the feed
receiver increase boot
30 materials.
original
optimise
Institute
Group Thedesign
their
of Technology.
India Private housing
crude show
Email:
Limited is made
that
feedstock,
in the of
a large
Koch-Glitsch highly
chemical
mbhargava@dwcinnovations.com resistant
proportion
division. He hasof
inhibitor SS
over 316
cat-
pro-
20 Integrated
algorithm. mea
leaks
of 10-20%.
opened andless unintended
Figure frequently
7 control
compares with losses
a minimal of hydrogen
conventional and DIH to20
intermit- fuel
to a PSA
Ti system as
stainless steela ‘black
and box’been
has which they at
tested only 310 need
bar. toWith
think a To ensure respo high
mentdilute
and in SOx phase reduction
temperature levels variation from and afterburn alyst gramme,
years offrom (A)and
2experience the their
Gamma standpipe
scanintegrity
in mass transfer
results accumulates
assessment
technology
showing good and and overflows
programmes.
holds an M. Tech. due to uniform
gas can
post-revamp
tent water be withdrawal
avoided
version without
converted
(see significant
to a DWC The cost. Reducing Anju
configuration
correspond-
Figure
about once every 10-15 years to change outliquidthe distribution
adsorbent motor pump
47%impact
can to 59% (see the mechanical Figure
Figure 7). reliability of the internals 7). 10 atsystem
degree Patil
in
distribution pressure
themeasurement
The crotch
is Head
chemicalsincesection
of of
India112
engineering andno
thereprinciple, bar
Operations
was fromand
from an
which
for
Indian
uniform DWC operating
theresponse
initial
ispressure
Institutebased top
Innovations
of temperature
on section
inelectrical
Technology.
among Gurgaon, of
the scanlines A Oti
highwater
unit
ing pressure
with hexane
flow hydrogen
recycle.
rate was bleeds orfrom
reduced cascading
approximately hydro- India. layers
of 405°C, and inspect
the the
integrated, integrity
compact of the unit is designed vessels. for Aa and Berthold
control e
and may often require a capacity reduction to con- 0but the bathtub, withmeasures
a relatively small at amount of catalyst
She has 17 years’ experience in process design and simulation,
gen comes at al/h. costThe in terms of temperature
catalyst cycle length potential
Sandeep
poorly
Yadav
specifieddrop, is a
or
Senior
optimised
Manager voltagesProcess
PSA will multiple
Engineering
not sections Corrosion cou
with
beaKoch-Glitsch
maximis-
Koch
A
450
trol conventional
l/h to 108 configuration
bottom
the dilute phase temperatures. These issues have flowing of an isomerisation
of the strip- nominal
including
commonly pressure
dividing
through
wall
referred of 130
column
the slots. bar. In
technologies,
asThe addition
plana view
DeSOx and to
holds
of the
density rotor
bachelor’s lin- and
pro-of radiation bearing da
the DeSOx
on profitability
pipe or vessel, thetogenerating a grid scan.
topography When gamma
image (for instance, throu
Conclusion Chemical
Super Technology
DESOX Group India Private
Super Limited
DESOX CV+ in the
should
unit with be considered. ing for refinery. Unicat can independently
per could thehexane
be reduced recyclelongwith and DIP
a usedresulting column can attain
reduction in file ing, the motor housing serves asfixed
inamass
secondary contain- accumulations
degree inHechemical engineering offrom MNIT, Jaipur, India.
Many
driven refiners have
development since
of spent catalyst distributors division.
indicates
scanning
metal loss
has over
a that
tower,
phenomenon.
10 catalyst
years
I experience
remainscoverage is andtransfer
limited µ technology
is around
essen- remains
probes) a
are cons
ver
Directclose
areboiler
RON hydrogen to 90additives recovery from fuel gasDIP streams is Email:
assist refineries maximise the potential of their PSA Shivajiunit, from the pum
ofasregenerator
the
1). presence of Figure
the column o
induty (see apatil@dwcinnovations.com
SOx
for usereduction all types Table as part designs, especially for ment,
and
tially
holds
awhich
constant.
7 Increased SOx reduction using Super DeSOx CV+ provides
a bachelor’s
For
degreea leak-free,
a
in chemical
grid scan, safethe pump
engineering
multiple solution.
from
paths of tion
of is
the solved
equipm f
more
helps costly
remove due most to the
iC5low before pressurethe and
reactorthe lower which hydrogen
inofturnthe whetherUniversity, it is a new installation or an operating unit.
ofThe operation became stable and capacity tailored to the
India.
large their strategy
regenerators. for SOx emission On
occurs theto basis
fix t
contents,
affects
gas thewhich
concentration reaction inunitmost cases are
equilibrium
could toothe
in lowforwardto allow puri-
direc-
compliance. However, there be areincreased.
an increasing The results
num- of counterflow
multiple
pipe sockets sets in
ao
fication
tion. intoa achieve
membrane or PSA unit. Hydrogen inshown
lower
the
Compound ofBut
ber pre-revamp angleand
applications wye for RON
post-revamp
these
bathtub valuesadditives, beyond
distributoroperation partlythisare number,
due to A
scan level
Local could indicat
corrosion be s
purity
unreacted
in streamsnC can
needs potentially
to be be
recirculated recovered back by
to theprocess-
reac- indicates whet
more stringent
TechnipFMC’s
Table 1. SOx emission
5 compound angle legislation
wye bathtub in various spent Since
coupon all or scan
pro
ing The
tor. themDIH as feedcolumn on in a steam reformer where
the conventional the feed
regions, distributor
catalyst as well as has heightened
been interest to
developed inconfiguration
reducing
address cat- aing
theheatlengthbarrier
results orbec pp
hydrogen
is not
Conclusion able will
to unload
restrict the
nC furnace.
going to the light isomerate, the motor part
the costs
alyst of wet gas scrubber
maldistribution issues,5 caustic.
which areGrace oftenwas observedthe uniform
Another liquid disad
A more
hence
Component maximumexpensive
trapping option
conversion is cryogenic
by physical of nC hydrogen
toadditives
carry-over its regenerator.
high-octane
of andrecov-
water dissipation of
first
as
ery. In
company
non-uniform
most cases,
tobed commercialise
temperatures
thebottlenecks
investment
SOx 5in the
in a are cryogenic unit only four
equipmentscans mam
dete
isomer
can
continues
This cause is
distributornot achieved.
capacity
to deliver is now improved Also,
offered as because
that
performance some
a standard with not portion
easily
design pre-
thefor of temperature
typical
pipes. exampl m
is economic
nC
dicted becomes
by if athe
performing partfuelofprocess
gasthe stream
light contains other
isomerate
simulations andthis compo-
affects
hydrau- grated. Anoth
recent
the 5 first commercialisation
stage regeneratorofinSuper R2R DeSOx technology CV+.as Thiswell lines matching,
Non-intrusiv
nents
the
lic RON
rating with ainternals.
higher value
ofadversely. (for instance
By revamping
Koch-Glitsch worked the LPG, naphtha).
conventional
closely with the motor coo
improved
as for single additive provides
stage regenerators. increased The levels
compound of SOx angle However,
far higher wh
flex
This column
DIH mayOil change to in the their
dividing future
wall, as
more excess refinery fuelcuts gas
Essar
reduction
wye bathtub and
through utilised
distributor higherdesign, ceriumexperience andofvanadium
which the
to an
is sharper
troubleshoot dis-
improve- formance
ation
gies measurem
are and
availab
will be
can become more common due of to theincreased energy effi-
and
persion
ment toobtained
thoroughly
across
an original theand
review the
additive the
concept RON equipment
particle,
of slanted isomerate
in the
combined wyeunit, can
with
bathtubespe-be such
corrosion
seem as
to safety
poten
match
ciency
improved
cially and
those residue
further.
performing conversion physical levels. Sustained
separations, and
to real
iden- and inspection
an optimised
distributor spinel was
design, formation. optimised Several using refiners are
extensive pipe
would sockets
be diagn is
time
tify optimisation
potential8 shows ofthat,
problems. the fuel toBased and on
improve hydrogen the the networks
RON
symptoms of and can
the
Figure
now using
computational Super fluidDeSOx dynamics CV+, which
(CFD) ismodelling
delivering aand tion
fixed
scan tests,
outside
data, ando
lowe
be achieved
final product byfurther,
incorporating thethe DIH the hydrogen
column network
is revamped into
unsteady
higher
has been level operation
of SOx reduction,
validated of
through stripper
as demonstrated
commercial and debutaniser
experience. by to sive
without
cated document
more chang
liqu
atheDWC
under (digitalised)
so
increasedas to refinery
draw
loading, energy
four it cuts
was management
from
suspected the system.
column.
that The
water highly reliable
two case
CFD studieswas
modelling in this article. using Barracuda CPFD
conducted devices
cated lesscanliqu be
light
software, and the
accumulation which heavy
withinis wellisomerate
thesuitedsystem areforwas combined
the cause.
simulating and gassent solid to their
sensor safety
system, and
A Tom example of thi
theKoch-Glitsch
flow gasoline Ventham,
hydrodynamics pool, while
Sales
focused in theon third
& Technical,
fluidisedthe most cut
Europe
beds, isconvenient
recycled
such as to
and Africa Unicat the
way
com- eries worldwid
Hydrosteel
Figure 2b. ins
reactor
BV/G.
of removing in
W. a
mercial FCC regenerators.manner
Aru, water LLC similar to
tom.ventham@gwaru.com
prior to the the conventional
affected columns,andscheme. Xavier
lead- permeating thr
Super DESOX is a trademark of W. R. Grace and Co. This is a total
The
Llorente,
ing fourth
to
Compared the cut
Technical
to drawn
Sales Engineer
recommendation
the original from the to EMEA
slanted DIH
revamp column
& Asia,
wye theUnicat
HP primarily
bathtub,
Catalyst,
separa-the rosion. This is
open to
HERMETIC-Pum varyin
consists
optimised iC5 along
of design
xavier.llorente@unicatcatalyst.com
tor immediately upstream. with unreacted
is initially Once inclined the nC at5 which
problem a steep was isangle
recy-
fully induced crack
Operating from
For tower
more to
inform t
cled aidback
understood,
References
to towith
catalyst the
andflow
appreciable
DIPthe column.
into focusand was
amounts
Theput
down theon
of the
deisopentaniser hydrogen
arms, followed HP sep- col-in
refinery fuel Koch-Glitsch
gasisopentanes
has a number of particularly important method
ysis does
waidmann.alexa (FSM)
not g
umn
arator,
by removes
the
a shallower angle to reduce from
process
1 Yoo J S, Bhattacharyya A A, Radlowski C A, De-SOx catalyst: an theengineering
catalyst freshvelocityfeed along
group
and
drawbacks. Hydrogen has a low molecular weight giv- sensor
tity of pins
liquid arem
with
prevent the recycle
catalyst stream
from from
XRD study of magnesium aluminate spinel and its solid solutions,
evaluated the performance overflowing the
shortfalls revamped
the endof the
of DIH
the col-
existing
bath-
ing it The
aChem.
low calorific value per an electrical
conclusions cu
fro
umn. bottoms of the DIP a unit
column volume,
are to is
richremedy costly
inintostraight to
Ind. Eng. Res., 1991, 30, 1444-1448.
arrangement
tub arms. At and crotch
the prepared where solution
catalyst flows the
the Raising
possible
very to
ambiguou cata
dete
compress,
2 Reducing FCC
chain andincorporating
components introduces
SOx Emissions more to Verypressure Low Levels drop
UsinginDeSOx,
the fuel
problem.
distributor By arms, a and weirare routed
experience
is positioned to the toand isomerisation
proprietary
prevent cata- rosion
of insidem
any liquid o
gas headers. On top of this
UOP, 1992 NPRA Annual Meeting, New Orleans, Mar 1992.
reactor. there is a concern for ahydro-
lyst fromThe
separations revamp
software,
overflowing ofand aKoch-Glitsch
DIH column
to direct in flow
it provided
to this configura-
down solu-
the Stringent
In general, const n
gen provides
tion embrittlement the dualin piping sections, of avalving, Byand fit-
tion
two that would
branches. Themeet openfunctionality
Essar’s
slots incapacity the upper DPsection
goal. column of and
under-the fications
provide
Advanced have
theanalyad p
tings in
helps
standing that andare targeting
achieving not asuitableRON the of for91-93
source handling
in of the the hydrogen
final isomerate
problem, rich
the of their gasolin
arms are eliminated to prevent premature distribution.
Colin Baillie is the Manager of Grace’s FCC Environmental Additive operation.
An advanced If th
product.
solution
A comparison was implemented
a of CFD in thefrom
modelling HPresults separator fromvessel the number specifi
products. He holds PhD in chemistry the University of to another
data from pos
pac
which
original summarises
Table debottlenecked
3slanted wye the andbenefits
and improved
the optimised of DWC technology
the performance
compound emissions can
Liverpool, UK, as well as an MBA from the Open University, UK. system to analy
sistently that
for
of the
angle variousGCU.isomerisation
wye
bathtub is shown configurations.
in Figure 4. The catalyst technological cr
toring underres
conclusive co
www.eptq.com PTQ Q4 2019 73

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Q4 2021 53
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koch glitsch.indd 1 12/03/2021 12:42

Taking a holistic approach to a revamp
If all aspects of a system are carefully examined, even minor changes can lead to large
gains in unit performance and profitability
JOE MUSUMECI and JOHN ESTILL Ascent Engineering

GREGORY MITCHELL Shell Norco
E
ngineers frequently focus on later. Diameter limited, the column was fast tracked in order to meet the
one piece of the puzzle as a had been revamped in 1999 with already planned shutdown window.
cause for poor performance. high capacity trays and some addi- The project methodology Ascent
Blinkers on, fixing that one prob- tional condensing capacity. The used was not only to focus on the
lem becomes the project goal. A tower had under-performed since tower trays, as was previously
tray specialist will focus on the that revamp, leaving excess isobu- done, but to take a holistic approach
tray design, a hydraulic engineer tane in the bottom product. This to look at the entire system. This
will focus on hydraulics, and so required the refinery to purchase was particularly important since
on. While some improvement is additional isobutane for the alkyla- the tower had been designed
obtained, many opportunities to tion unit and limited the amount of for a different service, and some
yield major benefits can be missed. butane that could be blended into aspects of the equipment layout
Instead, a holistic review of the gasoline, both of which resulted in a may not have been ideally suited
entire plant operation by engineers considerable economic penalty. for butane splitter service. Ascent
familiar with all disciplines best A study was commissioned a started with a very detailed plant
identifies and captures the process- few years after the 1999 revamp match simulation and evaluation
ing opportunities. to determine the causes of poor of all major system components to
A recent review of a butane split- separation. Since the trays were identify deficiencies and opportu-
ter illustrates how analysing the changed from conventional valve nities. Verifying the reboiler, the
entire system – trays, reboiler, con- trays to high capacity trays during condenser, the controls, the operat-
denser, controls, and operation – the revamp, it was felt that the trays ing philosophy, and the other tower
uncovered multiple changes and were at fault, and the study focused internals in addition to the trays
modifications that, if implemented on the tray design and efficiency. was required if the project was to be
individually, would each improve The study presented several recom- a success.
isobutane recovery to varying mendations regarding tray design
degrees. details and proposed the tower be Butane splitter operation
Taken together, however, finding retrayed again. No action was taken As Figure 1 shows, a mixed C4
and implementing all these changes at that time. stream from the SGP is preheated
resulted in a predicted 50% increase Several years later, a short column by a set of feed/bottoms exchangers
in isobutane recovered at design outage was planned that would before entering the butane splitter
charge rates. A review of post- allow potential modifications to between trays 35 and 34. The tower
revamp operation has shown that improve tower performance. Ascent overhead vapour is condensed to
the modified tower has improved Engineering was asked to review bubble point in a bank of air coolers.
the refinery’s bottom line by at least the previous study and other, more There are eight parallel air cooler
$2.6 million/y through a combina- recent troubleshooting efforts and bays in this bank.
tion of improved operating guide- propose modifications that would The bottom tray is a chimney
lines and capital fixes to existing improve the tower performance. tray which collects liquid and
design issues. Based on the previous study, new gravity-feeds an elevated kettle
trays were an expected recommen- reboiler. The reboiler vapour return
Background dation. Reboiler performance was is distributed by a Schoepentoeter,
The butane splitter column pre- a known issue. The upcoming shut- located just above the chimney
sented here recovers isobutane from down was expected to be short, and tray. Schoepentoeter is a propri-
a mixed C4 stream originating in the time allotted would not allow for etary Shell vane type inlet device
the crude unit saturates gas plant the installation of new major equip- that is used to introduce gas/liquid
(SGP). The isobutane is used as ment such as a new reboiler. Tie-ins mixtures into a vessel or column.
make-up to the alkylation unit. for new equipment could be made The liquid from the reboiler gravity
The tower was originally built in if necessary. Because the shutdown flows to the tower sump.
1965 for a different service and was had already been scheduled prior to The butane splitter feed is frac-
converted to butane splitter service the project kick-off, the new study tionated into two products:
Q2 Ascent.indd 1 15/03/2021 11:52

Operating strategy and controls
n-Butane to storage The tower control scheme is
included in Figure 1. The distillate
product is on regulatory flow con-
PC NNF
Non-cond trol, as is the reboiler steam flow.
CWR
On-line analysers allow the console
LC
operator to monitor purity of both
CWS
products.
The operating strategy for the
A[
tower was reviewed. It was learned

that the console operator’s first pri-
ority was to adjust manually the
FC
iC4/nC4
Isobutane distillate rate to maintain approx-
to alky
imately 5% nC4 in the isobutane
Steam supply distillate. Secondly, the reboiler
steam condensate rate was set at a
FC conservative value that was stable
and kept the tower overhead fully
LC
A[ Condensate
return condensed. The console operator
tended to vary the reboiler conden-
Figure 1 Butane splitter flow scheme sate rate set point with tower charge
rate, and at lower charge rates the
• An isobutane distillate which pro- and tower drawings were closely reboiler steam flow was signifi-
vides part of the alkylation unit’s reviewed, and flooding calculations cantly lower than the observed
isobutane make-up requirements. were performed for the trays. The limit. Finally, the tower pressure
• Normal butane and heavier mate- tower control system and logic was was set as low as possible. Note
rial from the column bottom which reviewed. The reboiler and con- that this is a ‘non-material balance’
is pressurised out to a storage densers were rigorously rated. A type of control scheme, which does
sphere and eventually blended to nozzle elevation review revealed result in stable operation, but is not
gasoline. that there was little static head driv- recommended unless other con-
Column operation was reported ing the reboiler flow, so detailed trol schemes have been proven to
to be steady. Previous tower scans hydraulic calculations for the be unsuitable.1 This control scheme
showed no evidence of flooding. reboiler circuit were performed. may have been a holdover from the
The tower appeared to be reboiler The initial simulation results and previous service, before the tower
limited since increasing steam flow equipment calculations showed that was converted into a butane splitter.
beyond a certain point resulted in the tower’s performance with exist- With the distillate product rate
condensate flow meter instabil- ing equipment was much worse fixed, the tower suffered from poor
ity and control valve swings. The than calculated. The primary issues product purity control. To illus-
amount of isobutane in the bottoms identified were hydraulic limita- trate the problem, consider a tower
was significantly more than the 1999 tions with the reboiler piping and feed that is 5000 b/d of isobutane
design prediction, even at charge issues with the control scheme and and 5000 b/d of normal butane. If
rates well below design. Because the operating philosophy. Tray flooding the operator sets the distillate rate
tower pressure had to be set high was found to be unlikely, though at 4900 b/d, then the distillate will
enough to allow the bottom prod- low tray efficiency (which had been be nearly pure isobutane if there is
uct to be pressured out to storage previously identified by the client) adequate reflux, and the 5100 b/d
(approximately 100 psig), the tower was confirmed to be a problem. tower bottom product will have
seemed to have excess condensing A plant test was scheduled to some small percentage of isobutane.
capacity. determine whether changes in oper- If the tower feed rate drops to 4000
Ascent collected data sheets and ation could improve tower perfor- b/d of each component, and the
mechanical details for all equipment mance immediately. Gamma scans operator does not change the dis-
in the system. The client provided of the tower were also scheduled tillate rate set point, the 4900 b/d
operating data from the DCS sys- to see if the trays were prematurely distillate will become contaminated
tem and product analyses from the flooding and to help confirm the with 900 b/d of normal butane.
laboratory. conclusions made regarding the Similarly, if the tower feed jumps to
reboiler piping having insufficient 6000 b/d of each component, 1100
Initial calculations and test run head. The results of these tests were b/d of isobutane must leave with
With this information in hand, we used to develop the final scope of the bottom product unless the distil-
proceeded to evaluate all aspects of modifications recommended to late rate set point is changed by the
the system. Tower operation was improve tower performance, max- panel operator. Similar results occur
simulated and rigorously verified imise isobutane recovery, and max- if the feed composition changes
against the operating data. Tray imise refinery profit. instead of the feed rate.
Q2 Ascent.indd 2 15/03/2021 11:52

This mode of operation can be
seen in Figure 3, which shows con- 25%
siderable variation in bottom prod-
uct isobutane concentration at any Current operation trends
20%
given tower charge rate. The con- to be here - low pressure
At
sole operator had to make manual
mol% 1C4 in Btms

adjustments to the reboiler duty and 15%
distillate flow rate in response to
At
changes in feed rate and composi- 10%
tion resulting from changes in crude Current operation could be here -
higher reboiler duty and higher jet flood
slate or SGP operation. 5%
It should be noted that this type of If additional condenser
capacity is added, operation
scheme can work with continuous 0%
operator intervention. However, 90 100 110 120 130 140 150
this column was only one part of Condenser pressure, psig
a larger operating unit, and so the
butane splitter received reduced Figure 2 iC4 in Btms vs pressure and jet flood at constant charge
attention. As would be expected,
this resulted in frequent operation cal operation. Thus the column was sure variations expected from day
at less than optimum conditions shown to be ultimately limited by to night and summer to winter. The
since the ‘non-material balance’ its hardware rather than by its con- existing on-line distillate analyser
type of control scheme required fre- trol scheme. was deemed accurate and reliable
quent operator intervention. Looking for a permanent solu- enough to cascade to the distillate
Maximum separation occurs tion, it was desired to convert the flow controller, and this was rec-
when the reboiler and condenser control system into a ‘material bal- ommended to provide the desired
duties are maximised bringing the ance’ type scheme which would material balance and composition
vapour and liquid flows up to the allow the control system to auto- control.
limits of the column diameter, no matically maintain product puri- An advanced process control
matter what the tower charge rate ties by adjusting the tower material (APC) system for the butane splitter
is. This duty-maximising mode of balance in response to feed rate or existed, but its use had been discon-
operation is illustrated in Figure 2 composition changes. The chosen tinued. Ascent recommended the
which shows how separation could control scheme2 is very close to the APC system be put back into service.
be improved by increasing reboiler existing control scheme, only need- The APC could be used to imple-
duty and column traffic at a higher ing a new control variable to use as ment the strategy of maximising the
pressure. the basis for adjusting the distillate reboiler duty up to a tray flooding
This concept was applied during flow. A typical overhead tempera- limit at all times and minimising
the test run, and the results showed ture control system was reviewed tower pressure only after the reboiler
that current operation could be and rejected, with the tower over- and tray limits had been reached.
markedly improved. During the head temperature too insensitive a
test run, the reboiler steam flow was variable for good control, particu- Trays
set near the observed limit and was larly in light of the operating pres- The tower was simulated to match
not adjusted for changes in tower
charge rate. The tower pressure
was allowed to increase as required 30
to maintain total condensation of
the overhead vapour. The distillate
25
composition was continually moni-
tored and the distillate rate adjusted
iC4 in BTMS (mol%)
as needed. As Figure 3 shows, the 20

isobutane recovery was improved,
particularly at lower charge rates. 15
Whereas previous operation at a
low charge rate might have seen 10
12-17% isobutane in the tower bot-
toms, the changes in operating strat- 5 Test Run
egy resulted in 5-10% isobutane in Historical
the tower bottoms. With no capi- 0
tal investment, isobutane recovery 6 7 8 9 10 11 12
was markedly improved. At higher Charge rate
charge rates, the data shows that the
test run results were similar to typi- Figure 3 Charge rate vs iC4 in bottom nC4 product
Q2 Ascent.indd 3 15/03/2021 11:52

column limit. Several aspects of the
reboiler system needed verification
to ensure the performance required.
As previously mentioned, the
maximum reboiler steam rate was
17’-11” limited. Beyond this limit, the con-
18”
16’-8½” densate flow became erratic and
13’-8”
the steam control valve would
13’-6” swing. During the test run, the
12’-0” steam let-down valve was swing-
C/L 10’-7” ing between 55% and 65% open,
9’-2” with the reboiler supply pressure
10”
7’-8” then varying from 52 psig to 60
5’-9”
NLL psig. The condensate valve var-
5’-1”
6” ied from 32% to 38% open during
this time. It appeared the reboiler
could not condense any more steam
past the observed maximum rate,
at which point steam would blow
through and the condensate flow
became two-phase. Trying to meas-
Figure 4 Kettle reboiler piping and elevations ure two-phase flow with an orifice
plate resulted in erratic condensate
the observed flows, temperatures, ciency from 73% to 85% would flow meter output and unstable
and purities. The number of theoret- reduce the isobutane in the bottom operation. Also, with steam blow-
ical stages in the tower was adjusted product at design conditions from ing through the exchanger and
to match the observed product puri- 24.5% to 22.6%. This would result the condensate level control valve
ties and reflux rate. The existing in an estimated $1 million annual no longer maintaining back pres-
high capacity trays were rated using benefit to the refinery, which justi- sure, the steam chest pressure in
the simulation results and found to fied a complete retray. A different the reboiler dropped, reducing the
be lightly loaded at approximately type of high capacity tray, expected LMTD available and therefore limit-
57% of flood. This result was con- to have a higher efficiency, was rec- ing heat transfer.
firmed by several gamma scans ommended even though the capac- Initial thoughts were that the
made while the tower was at lower ity increase over the existing high reboiler was under-surfaced. Lack
feed rates, which showed no signs capacity trays was marginal. of surface area could have been the
of flooding. cause for the inability to condense
Despite the lack of flooding, the It was determined via more steam and provide more
efficiency of the existing trays was reboiling duty to the tower. From
a concern. The efficiency was esti- simulation that new, the symptoms observed, concluding
mated to be approximately 73%. the reboiler was fouled instead of
This was roughly in agreement with higher efficiency trays under-surfaced (or under-surfaced
a previous 2001 estimate of 68% because of excessive fouling) is also
efficiency, and a vendor estimate would increase the perfectly reasonable. However,
of 70-75% efficiency for this type of other possibilities needed evalu-
tray. The observed tray efficiency is
isobutane recovery ation as well. A poorly designed
lower than typically expected for a with no other changes condensate system, improper con-
iC4/nC4 system, which could reach densate flow meter installation, and
100% or more with conventional to the tower reboiler hydraulics were all possi-
trays. Tray efficiency is crucial in bilities to be considered.
this system and similar systems Reboiler review The reboiler was thermally rated
with relatively close boiling points The butane splitter utilises a ket- and was found to be approximately
and low relative volatility differ- tle type reboiler that is intended to 67% over-surfaced at project design
ence. This is particularly true for take the total liquid coming from conditions, even with a conservative
this tower, since the number of the chimney tray as its feed. Steam fouling factor. The over-surface was
trays is on the low side for a typical that is let down from 175 psig to much higher at the observed oper-
butane splitter. approximately 55 psig is used on ating conditions, which had a lower
It was determined via simula- the tube side to heat the process charge rate and lower reboiler duty.
tion that new, higher efficiency liquid. Concerns about the reboiler The conclusion drawn from this
trays would increase the isobutane were expressed at the project kick- review was that the reboiler size
recovery with no other changes to off meeting, and it was noted that was adequate, fouling was unlikely
the tower. An increase in tray effi- the reboiler was considered to be a to be limiting the reboiler, and the
Q2 Ascent.indd 4 15/03/2021 11:52

cause of the reboiler issues lay else- was not being effectively used to maintaining the liquid level on the
where. A recommendation was separate iso- and normal butane. chimney tray at approximately 50%
made to pull the bundle for clean- • Liquid from the bottom tray, of the chimney height, the following
ing during the turnaround, in case it which is richer in isobutane, modifications were required:
was severely fouled. bypassed the reboiler completely, • The existing 10” reboiler feed line
A hydraulic review of the process further increasing the isobutane was replaced with new 16” piping,
side of the reboiler system was per- lost to the bottom product. Once including new 16” nozzles on the
formed. The existing reboiler had a the reboiler reached 100% vaporisa- butane splitter and on the reboiler
10” liquid feed line, an 18” vapour tion all of the tower bottom product shell. The tower’s internal reboiler
return line, and a 6” liquid product came from liquid that spilled over draw piping was also replaced with
line. As Figure 4 shows, a chimney the chimneys and bypassed the 16”.
tray collects the bottom tray liq- reboiler. • The standpipe on the chimney
uid and feeds it to the reboiler via Including a reboiler bypass in the tray was removed. This eliminated
a standpipe. The relative elevations simulation, such that the 175 g/m the stagnant volume present below
of the tower and reboiler provided tower bottom product was com- the top of the standpipe and helped
only 4’-8½” of liquid static head to posed entirely of bypassed bottom reduce the pressure drop. The new
drive the liquid flow to the reboiler tray liquid while the reboiler vapor- 16” reboiler draw was installed
and the vapour return flow back ised 100% of the 950 g/m fed to it, flush with the tray deck and a vor-
into the tower. The bottom tray liq- improved the simulation match to tex breaker was placed over the new
uid, primarily normal butane, is plant data. opening.
very light, and the static head avail- Ascent recommended the tower • The existing 18” vapour return
able equated to approximately 1 psi be gamma scanned to verify that line, reboiler and tower nozzles, and
of driving force. The low driving insufficient hydraulic head existed Schoepentoeter were replaced with
force immediately made this circuit to force flow through the reboiler 24”.
suspect; a hydraulic limitation had rather than overflowing the chim- • An impingement plate mounted
a high probability of being a major neys. A liquid level at the top of the inside the reboiler shell at the exist-
cause for the reboiler limitation. chimneys would prove the reboiler ing feed nozzle was removed as
Detailed hydraulic calculations of hydraulic limitation hypothesis that part of the nozzle replacement.
the reboiler feed and return piping bottom tray liquid was spilling over A new impingement plate was
indicated that the liquid head avail- the chimneys and bypassing the attached to the tube bundle instead.
able on the chimney tray to over- reboiler. A gamma scan would also This increased the open area at the
come the piping frictional losses check for unexpected tray flooding, reboiler feed nozzle, resulting in a
was marginal for the observed oper- help determine if there was equip- lower pressure drop through the
ation, and definitely insufficient for ment damage, and look for any nozzle.
design conditions. The reboiler cir- unexpected issues inside the tower. • Two non-condensable vents were
cuit capacity was estimated to be As expected, the gamma scans added to the reboiler channel, one
950-1100 g/m. showed the chimney tray to be liq- at the top of the channel and one
Based on detailed hydraulic cal- uid full up to the level of the chim- underneath the partition plate. The
culations, it was hypothesised that neys at nearly all charge rates. It lower vent is typically left cracked
a significant amount of liquid was was confirmed that this was the open during operation. Venting
overflowing the chimneys and biggest bottleneck in the tower – non-condensable gases such as air
bypassing the reboiler. A restricted bottom tray liquid was bypassing and CO2 reduces the risk of corro-
reboiler feed rate would explain the the reboiler because of insufficient sion and also improves heat trans-
following observed issues around hydraulic head, limiting the reboiler fer efficiency. The vents also help
the reboiler: duty and allowing excess isobutane purge air from the reboiler during
• As steam to the reboiler was to escape into the bottom normal start-up.
increased, liquid vaporisation in butane product. • In order to improve reboiler con-
the reboiler reached 100%. Past The detailed plant match data, trol stability, the steam flow con-
that point, more steam was being simulation, and calculations were trol point was moved from the flow
brought in than could be con- thus validated with gamma scans, meter on the condensate to a flow
densed. This excess steam left with resulting in complete confidence meter on the steam supply line.
the condensate, and the two-phase that a cause had been found and Measuring marginally sub-cooled
condensate flow gave an unstable could be fixed with appropriate condensate with a flow meter
flow measurement which resulted modifications. invites flashing and inaccurate
in both the condensate flow con- To achieve the required reboiler measurements as compared to more
trol valve and 175# steam let-down duty at the new design conditions, accurately measuring the single
valve opening and closing rapidly. which would increase the vapour/ phase steam flow.
• The reboiler duty could not be liquid traffic in the tower up to the Fixing the reboiler feed limita-
increased enough to get the tower flood point, a reboiler feed rate of tion, with no other changes, was
vapour load up to the tray flooding 1600 g/m was needed. To achieve expected to reduce isobutane in the
limit. The available tower diameter the desired 1600 g/m of flow while bottom product from 24.5% to 17%
Q2 Ascent.indd 5 15/03/2021 11:52

convincing the site to execute the
30 project on such a compressed sched-
Pre-Revamp
Post-Revamp ule. A partnership with Ascent and
25 the tray technologists was another
key enabler, as the tray rating and
data sheets could be developed in
iC4 in BTMS (mol%)
20
parallel to the overhead condens-
ing and reboiler development work.
15
The tower revamp work was to be
performed in a running unit, which
10
added safety and constructibility
concerns.
5 Once project execution was initi-
ated, installation of the new trays
0
6 7 8 9 10 11 12
proved to be difficult and time
Charge rate
consuming. Upon entry, the col-
umn was found to be out-of-round
Figure 5 Charge rate vs iC4 in bottom nC4 product, post-revamp and the new trays were found to
have some fabrication deficien-
at design conditions. When combin- capacity for operation during warm cies. The tray fabrication issues
ing the reboiler modifications with weather. were addressed in a temporary
new, higher efficiency trays, isobu- The following modifications were construction shelter at the site, and
tane in the bottom product was recommended to increase the con- installation required constant fit-up
expected to be reduced even further densing capacity during the sum- corrections with the tray panels
to 13.2%. mer months. themselves.
The tubes of all the condenser bays Fitting up the tray panels and
Condenser review were scheduled to be replaced in getting buy-off from process engi-
Eight parallel air cooler bays are kind during the turnaround due to neering inspection initially seemed
used to condense overhead vapour their poor condition. Four of the tube as though it would bust the sched-
from the butane splitter. As dis- bundles had fin counts of six fins per ule. However, process engineering
cussed previously, isobutane recov- inch, while the other four bundles ensured quick responses and the
ery is maximised when the tower is used tubes with 10 fins per inch. To tray installers improved fit-up tim-
operated at its tray flooding limit at maximise heat transfer area within ing efficiency. As new trays were
the lowest pressure the condensers the existing bundle design, Ascent being flown up the tower by crane,
can achieve as limited by rundown recommended that all replacement the next trays were being modified
hydraulics. tubes be 10 fins per inch. using a new weld plan and cor-
The existing air coolers were rigor- Rigorous analysis of the exchang- rected drawings within the tempo-
ously rated. Due to improved isobu- ers showed that increased air rary construction shelter. This effort
tane recovery, there is an incentive flow was a relatively inexpensive allowed the project to meet the orig-
to maintain the tower pressure close method to increase the condensing inal schedule.
to 100 psig during hot weather. duty. Ascent recommended new Installation of the new, larger
This incentive is shown in Figure fans and higher powered motors. reboiler supply and return nozzles
2. The rigorous condenser rating Five of the motors included varia- in the 50-year-old tower shell also
showed that an inlet air temperature ble frequency drives with automatic proved to be a challenge. In the end,
of approximately 80°F (27°C) was controls to improve controllability. the reboiler related work required
required for the existing condens- Increasing the condenser capacity, 57% of the total project investment,
ers to maintain a tower pressure of when combined with the other rec- 25% went to the trays, and 18%
100-105 psig when the tower is oper- ommended changes, was expected went to the condensers.
ating at or near the flood point. At to reduce isobutane in the bottom
the design air inlet temperature of product from 13.2% to 10.1% at Revised operation
95°F (35°C), the existing condensers design conditions. Most of Ascent’s recommendations
would maintain the column pres- were implemented during the shut-
sure at approximately 125 psig when Project execution down. The reboiler and condenser
operating the tower close to its flood The design portion of the project modifications described previously
point. was fast-tracked, taking just seven were all completed. New high
At project kick-off, the condens- months from kick-off meeting to capacity trays of the same type but
ers were believed to have excess column shutdown. Fast-tracking a with efficiency enhancements were
capacity, but current operation was capital project within a large organ- installed.
deceiving because of the reboiler isation can be a project of its own. Performance of the tower, as
limitations. An incentive actually Clear justification for each piece of measured by isobutane in the bot-
existed to increase the condensing the scope to be executed was key in tom product, improved markedly
Q2 Ascent.indd 6 15/03/2021 11:52

upon start-up. One set of data taken shortly after
start-up showed 14.5% isobutane in the column bot-
tom product at 113% of the design charge rate. This
was a considerable improvement on previous tower
performance, particularly considering a temporary
limitation on reboiler steam supply in place at the
time. A review of the refinery isobutane purchases a
month after start-up showed annualised savings of
$2.6 million. This isobutane recovery benefit did not
include the economic impact of being able to blend
more butane into gasoline. Longer term post-revamp
operation is plotted against pre-revamp operation in
Figure 5.
There is still room for additional improvements. The
APC was configured and placed into service well after
the modified tower had been returned to operation.
Some enhancements were made as operating expe-
rience was gained, such as increasing the maximum
allowable tower pressure drop. When in service, the
APC can minimise the isobutane losses, although at
times the isobutane losses are not minimised in favour
of meeting other objectives. Operations does not con-
sistently use the APC, however, and the reasons for
this should be explored.
Conclusion
These results demonstrate the success that can be
achieved when all aspects of the system are carefully
examined. A detailed plant match simulation and
detailed equipment calculations are crucial to identi-
fying the opportunities and solutions. Studies such as
this isobutane recovery effort often reveal opportuni- Vacuum Systems
ties for higher throughput, improved operation, and
increased profits that were not previously known or Process-integrated solutions
considered. In many cases, relatively minor changes for ejector vacuum systems
often lead to large increases in unit performance and
profitability.
References GEA supplies steam jet vacuum

1 Kister H Z, Distillation Operation, McGraw Hill Inc, p492. systems and hybrid vacuum pumps,
2 Kister H Z, Distillation Operation, McGraw Hill Inc, p498. optimizing production processes
to reduce costs and environmental
Joseph (Joe) Musumeci is the founder of Ascent Engineering,
Inc., Houston, Texas, a process engineering and development firm pollution. You can rely on 90 years
serving the refining industry. Since 1997, he has been responsible for of experience and thousands of
managing Ascent’s consulting and process design projects, from unit references in numerous industrial
operations support and technical management to troubleshooting,
debottlenecking, and grassroots process designs encompassing all sectors all over the world. And
refining process units. He holds a BS in chemical engineering from thousands of satisfied customers
Texas A&M University and is a registered professional engineer in the can‘t be wrong.
state of Texas. Email: Joe.Musumeci@AscentEngineering.com
For contact details:
John Estill is a Senior Lead Process Engineer with Ascent Engineering,
Inc. He has worked on refinery and chemical plant engineering gea.com/contact
projects since 1991, from conceptual studies to detailed engineering
design to troubleshooting. He holds a BS in chemical engineering
from Texas A&M University.
Email: John.Estill@AscentEngineering.com
Greg Mitchell is Production Technical Supervisor with Shell Norco
and was the client process engineer for this work. He has worked
in design roles for a variety of projects and has worked in refining
production since 2010. He holds a BS in chemical engineering from
the University of Arkansas.
Email: Gregory.Mitchell@Shell.com
Q2 Ascent.indd 7 15/03/2021 11:52

sinopec.indd 1 12/03/2021 13:06
Selecting catalysts for marine fuels production
Accelerated activity and stability testing of hydrotreating catalysts
ABRAR HAKEEM Q8 Research

ED OUWERKERK Catalyst Intelligence
C
atalyst activity and stability
are important factors in boost- BLOCK 1 BLOCK 2 BLOCK 3 BLOCK 4
ing the refining margin of
units like reformers, hydrocrackers,
and hydrotreating units. A refinery Feed
has little influence on feedstock and

product prices, but can increase its
margin by selecting the best catalyst
for the unit configuration and by
wisely planning its activity over the
cycle.
A western European refiner
wanted to select a catalyst best
suited to its 100 m3 single bed Figure 1 Layout of reactors in different heating blocks (1-4) in the catalyst testing unit
hydrodesulphurisation (HDS) reac-
tor operating at medium pressure and process conditions (pressure, be within the operating window of
with the aim of producing marine hydrogen/oil ratio, temperature, the actual process conditions used in
fuels. The aim is to produce fuels LHSV, hydrogen purity) used in the the refinery.
in three separate modes using three reactor. Deactivation of hydrotreat- The term accelerated deactiva-
different Urals feed cuts. The main ing catalysts occurs typically due to tion has no strict definition for a
product components using three coke formation, metals deposition, catalyst and can apply to different
different feed cuts are: 50 ppm sul- and sintering of active sites.1 In the sets of process conditions used in a
phur industrial gasoil (IGO), 800 case of processing middle distillates pilot unit, depending on the type of
ppm sulphur marine gasoil (MGO), (kerosene or gasoil), the metal con- test. Many times, accelerated tests
and 4500 ppm sulphur low sulphur tent of the feed is low and catalyst are designed with process variables
fuel oil (LSFO). In view of the size deactivation occurs most likely due which are never experienced in a
and duration of the catalyst sup- to coke deposition over its lifetime.2,3 real process and can result in differ-
ply contract, the refinery decided In the case of heavier feedstocks ent deactivation mechanisms that
to perform catalyst testing and not (atmospheric residue, vacuum may not be relevant for actual sta-
base its catalyst selection on vendor resid), catalyst deactivation occurs bility comparison between the cat-
claims alone. Q8 Research together most likely by both metal deposi- alysts.4 The term completely loses
with Catalyst Intelligence designed tion on catalysts and coke formation. its purpose when it is referred to
an experimental protocol for catalyst Moreover, hydroprocessing catalyst without indicating the actual pro-
testing which guided the selection deactivation is possible for all feeds cess conditions (pressure, tempera-
of the best performing catalyst. The due to the sintering of active sites ture, hydrogen/oil, LHSV) at which
catalyst testing was performed at Q8 over its lifetime. Sintering of active the respective catalysts were oper-
Research under actual process con- sites is directly related to tempera- ated.1,5 The experimental set-up in
ditions with actual feedstock used in ture and can be enhanced when the our case is designed in such a way
the refinery. reactors are operated at higher tem- that performance feedback at start
A maximum cycle length for peratures near to the end of life of of run (SOR) conditions is obtained
the catalyst is highly desirable. the catalyst, or at high temperatures from separate parallel reactors,
Moreover, it is beneficial for the during operations, caused by upsets and accelerated deactivation feed-
refinery to have lower hydrogen in the commercial reactor. back is obtained from another set
consumption and at the same time To evaluate hydroprocessing cat- of parallel reactors. The conditions
meet all product specifications. The alysts’ stability, it is essential to per- selected for accelerated deactiva-
catalysts used for hydrotreating form an accelerated aging test, as it tion are within the operating range
have a lifetime ranging from one to is not practically feasible to run a of a commercial hydrotreatment
six years, depending on the compo- test for the exact lifetime of the cat- reactor. Moreover, the design of the
sition of the feed (gasoil, vacuum alyst. However, the parameters used experiment allows a comparison of
gasoil, atmospheric resid, and so on) to design the accelerated test must differently operated reactors under
cat Q8.indd 1 15/03/2021 11:59

Refinery feed streams used to perform catalyst testing
Design of experiment
The experiment was designed in
Analysis Straight run gasoil Light vacuum gasoil Heavy vacuum gasoil such a way that the activity as well
(SRGO) (LVGO) (HVGO) as the stability of the catalysts could
Density 15°C, kg/l 0.8445 0.8902 0.9242 be compared within a relatively
Sulphur, wt% 0.83 1.42 1.88
Total aromatics, wt% 30.2 34.9 51.8 short period (30 days). For compar-
Simulated distillation ison of activity, heating blocks 1 and
IBP, wt% 134 174 324 2 were run close to the SOR temper-
10, wt% 216 286 392 ature for different feeds. For insight
20, wt% 239 318 415
40, wt% 273 358 445 into catalyst deactivation, conditions
60, wt% 306 387 472 were repeated using LVGO feed (see
80, wt% 345 415 503 Table 2). During commercial oper-
95, wt% 388 444 541 ation, catalyst deactivation is meas-
FBP, wt% 422 478 594
Contaminants ured by an increase in the required
Ni/V, wtppm <1 <1 <2 weighted average bed temperature
As, wtppm <0.05 <0.05 <0.1 (WABT) to meet the required sul-
phur specification. Typical deac-
Table 1 tivation rates in middle distillate
hydrotreatment is around a 0.5-2°C
uniform hydrotreatment conditions small scale reactors (<20 ml) for test- increase in WABT per month. To
at the end of the test. ing commercial catalysts from dif- measure this deactivation with some
ferent vendors. Higher amounts of accuracy, a normal test programme
Experimental poisons (metals) and other foulants would typically require three
A 16-flow parallel reactor unit was were absent from the feedstocks (see months or longer. In parallel, heat-
used to perform catalyst testing. It Table 1), so no hydrodemetallisation ing blocks 3 and 4 were run close
has four different heating blocks catalyst beds were loaded into the to EOR temperatures (395-405°C) to
(see Figure 1). Each heating block reactors. accelerate deactivation. The hydro-
contains four reactors which can Hydrotreatment catalysts from gen to oil ratio, hydrogen purity and
be set at different temperature to two different vendors (CatY and total operating pressure remained
allow testing of multiple process CatZ) were compared to evaluate the same for all test conditions. In
conditions simultaneously. All of their performance. The catalysts addition, as was the case with heat-
the experiments were performed at were loaded in 8 mm ID reactors ing blocks 1 and 2, catalysts were
the same pressure, hydrogen purity, and packed with inert silicon car- finally tested by a repeat condition
liquid hourly space velocity (LHSV), bide to ensure that plug flow cri- using LVGO feed to evaluate deac-
and hydrogen/oil ratio as is used in teria are maintained (no bypassing tivation (see Table 2). In this repeat
an actual reactor in the refinery. and limited axial dispersion). Three condition, the catalyst from each
In order to have equal internal different feeds (see Table 1) were vendor can now be assessed at both
mass transfer influence on catalyst used to compare the performance normal as well as accelerated deacti-
performance from different vendors, of the catalysts under typical refin- vation conditions.
the catalyst extrudates as received ery process conditions. A common
were sorted in a length range of 2-4 wetting and activation/sulphiding Results and discussion
mm. A customised robot is used at procedure was implemented and Catalyst testing (blocks 1 and 2) was
Q8 Research to perform catalyst sort- agreed with all the catalyst ven- carried out around the target efflu-
ing and size distribution analysis. dors. Dimethyl disulphide (DMDS) ent sulphur concentration for dif-
This is an important step, as smaller was added (3 wt%) to straight run ferent types of feed (see Table 2) by
catalyst particles allow more sur- gasoil for catalyst sulphidation/ adjusting the temperature. A pseudo
face area and hence higher activity. activation. Catalyst activation was first order kinetic plug flow reac-
Uniform size distribution is critical followed by a SOR temperature tor model was used to model the
to provide precise comparison of cat- of 360°C using straight run gasoil hydrodesulphurisation reaction rate
alyst activity, especially when using (SRGO) feed. obtained at different temperatures
Experimental design using four different heating blocks for simultaneous comparison of catalyst activity
and stability at different conditions
Heating blocks 1 & 2 Heating block 3 Heating block 4

Duration (LSHV = 2 h-1) (LSHV = 2 h-1) (LSHV = 4 h-1)
(days) Feed Sulphur (ppmw) Purpose / T (°C) Purpose / T (°C) Purpose / T (°C)
5 Straight run gasoil (SRGO) 50 SOR activity (360-364) SOR activity (360-364) SOR activity (360-364)
9 Light vacuum gasoil (LVGO) 800 SOR activity (360-364-368) EOR deactivation (395) EOR deactivation (395)
12 Heavy vacuum gasoil (HVGO) 4500 SOR activity (352-360-364) EOR deactivation (405) EOR deactivation (405)
3 Light vacuum gasoil (LVGO) 800 SOR deactivation (360-368) EOR deactivation (360-368) EOR deactivation (360-368)
Table 2
cat Q8.indd 2 15/03/2021 11:59

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becht.indd 1 12/03/2021 12:49

TOS Sulphur Purpose / T
FEED Purpose / T (°C) Purpose / T (°C)
(days) (ppmw) (°C)
Straight run SOR activity SOR activity SOR activity
5 50
gas oil (SRGO) (360) (360) (360)
Light vacuum EOR
SOR activity EOR deactivation
9 gas oil 800 deactivation
Normalised rate constant (h-1) (360-364-368) (395)
Normalised rate constant (h-1)
Normalised rate constant (h-1)

(LVGO)
CatY SRGO feed CatY (395)feed
LVGO CatY HVGO feed
Heavy vacuum
CatZ CatZ
EOR CatZ
12 gas oil 4500 deactivation
(352-360-364) (405)
(HVGO) (405)
Light vacuum SOR EOR
EOR deactivation
3 gas oil 800 deactivation deactivation
(360-368)
(LVGO) (360-368) (360-368)
Table 2 360 362 364 358 360 362 364 366 368 370 350 352 354 356 358 360 362 364
T, ˚C T, ˚C T, ˚C
Results and Discussion
Figure 2 Start of run activity comparison at different temperatures for two commercial hydrotreating catalysts
Catalyst testing (blocks 1 and 2) was carried out around the target effluent sulphur
concentration for different types of feed (see Table 2) by adjusting the temperature. A
and using different feeds. The appar- functionality towards removal of the 2), CatY and CatZ experienced dif-
ent first first
pseudo orderorder
ratekinetic
constantplugfor
flow
thereactor model types
refractory was used to modelspecies
of sulphur the ferent feeds and temperature in the
hydrodesulfurisation reaction rate obtained at different
catalysts at different temperatures present in heavier hydrocarbons, temperatures andorusing different
range 352-368°C (see Table 2). The
feeds. The apparent first order rate constant for the catalysts at different temperatures
was calculated as follows and com- other properties related to catalyst sulphur concentration was in the effluent
calculated
pared as follows
for each feed (seeand compared
Figure 2): fordesign,
each feed
both of Figure
(see which2):
were outside at the end of catalyst testing (TOS =
the scope of this study. 30 days) compared to the sulphur
/0112
k (T) = LHSV +ln . (7) 89 It is interesting to see how perfor- concentration at the start (TOS = 4
/10034156
mance evaluation can change based days) for each catalyst were at sim-
where k(T) is the apparent first on the type of feedstock with the ilar levels (see Figure 3a). This indi-
order reaction rate constant, Cfeed same catalysts. This underlines the cates that, after 30 days of operation
iswhere
werek(T) finally
the sulphur is the tested by
apparent
concentration
ainorder
first repeat condition
the reaction
value of rate using testing
LVGO
constant,
catalyst Cfeedfeed tosulphur
is theusing
and
evaluate deactivation (see
at SOR temperatures, it is difficult
Table
concentration 2). In
in this
the repeat
feed, LHSV condition,
is the liquid
feed, LHSV is the liquid hourly actual feed and process conditions the catalyst
hourly space from each
velocity and vendor
C A
could
is the be compared
;<<=>;?@ to measure to SOR
catalyst deactivation for
space and
concentrationEOR of
velocity, deactivation
and sulphur
C effluentinisthe
T
rates.
the effluent
con- for at Tantemperature.
accurate comparison of cat- diesel hydrodesulphurisation cata-
centration of sulphur in the effluent alysts. By analysis of concentration lyst. This was expected with typical
For
at T LVGO and HVGO feeds, CatZ showed
temperature. ofbetter
aromaticsactivity
in compared
the liquidtoeffluent, Figure 2). rates of around 0.5-2°C
CatY (see deactivation
However, in the case of SRGO feed CatY showed
For LVGO and HVGO feeds, CatZ no significant difference in hydro- of WABT higher activity compared to CatZ at similar
per month.
Experimental
process conditions design
(see Figure using
2). It four
seems different
that CatY heating
is better blocks
designed for
for simultaneous
middle comparison of
showed better activity compared to gen consumption was observed Indistillates
parallel reactors containing
withcatalyst
CatY lower
(see Figure activity
density 2). feed and
However, stability
but lower in the at different
functionality
between theconditions
towards removal
two of the(CatY
catalysts refractory
CatY types
andofCatZ catalysts (blocks 3
sulphur
case of species
SRGO feed, present CatYin heavier
showed hydrocarbons,
and CatZ).or other properties related toand catalyst
4), catalysts were tested at a
Time-on HEATING 1&2 3 4
higher activity
design which compared
it was not possible to CatZ To evaluate
to investigate catalyst-1 deactivation, higher
in this study. temperature (EOR). With
-Stream
at similar process BLOCKS
conditions (see LVGO feed (LSHV was= 2used
h ) during (LSHVthe = 2 h ) feeds
-1
different (LSHV and= actual
4 h-1) EOR con-
FigureTOS 2). It seems that CatY is bet- Sulphur first and the last stage of catalyst Purpose ditions
/T (395-405°C), both catalysts
ter designed
FEED Purpose / T (°C) Purpose / T (°C)
(days) for middle distillates (ppmw) testing under the same conditions. (°C) deactivated significantly during the
with lower density feed but lower At SOR conditions (blocks 1 and test period. Sulphur concentration
Straight run SOR activity SOR activity SOR activity
in the effluents of CatY and CatZ
5 50
gas oil (SRGO) (360) (360) at the start(360) (time on stream [TOS]
a SOR conditions EOR conditions = 4 days) was significantly lower
Light vacuum b EOR than during the last stage (TOS = 30
1400 1400
9 gas oilTOS = 4 days 800 TOS = 4 daysdeactivation days). CatZ is better in terms of sta-
(360-364-368) (395)
1200 (LVGO) TOS = 30 days 1200 (395) bility compared to CatY, as effluent
TOS = 30 days
sulphur in the case of CatZ is much
Heavy vacuum EOR lower thanEOR for deactivation
CatY at TOS = 30
SOR activity
Effluent sulphur, ppm
Effluent sulphur, ppm
1000 1000
12 gas oil 4500 deactivation days (see Figure 3b).
(352-360-364) (405)
800 (HVGO) 800 (405) Testing at EOR temperatures,
Light vacuum SOR EOR which are within the actual tem-
perature range EOR of deactivation
commercial oper-
3 600
gas oil 800 600
deactivation deactivation
ation, is a (360-368)
good choice to evaluate
400 (LVGO) 400 (360-368) (360-368)deactivation rates in a short period
Table 2 of time. As the commercial reac-
200 200 tor operates in an adiabatic mode,
Results and Discussion the temperature increases along the
0
Catalyst CatY testing (blocks 0 length of the bed. This means that,
CatZ 1 and 2) was carried CatYout around CatZ the target effluent sulphur
even at the SOR conditions of a com-
concentration for different types of feed (see Table 2) by adjusting the temperature.
mercial A
reactor, the lower catalyst
pseudo first order kinetic plug flow reactor
Figure 3 Catalyst deactivation by comparing sulphur concentration during repeat model was used to model the
bed in the reactor will also experi-
hydrodesulfurisation
conditions at start and end of run reaction
using LVGOrate obtained
feed: (a) start of runatconditions
different temperatures and using
ence higher different(depend-
temperatures
feeds. The apparent first order rate constant for the catalysts at different temperatures rise
experienced by the catalysts; (b) End of run conditions experienced by the catalysts ing on the temperature was in the
calculated as follows and compared for each feed (see Figure 2):
66 PTQ Q2 2021 /0112 www.digitalrefining.com
k (T) = LHSV +ln . (7) 89
/10034156
cat Q8.indd 3 15/03/2021 11:59

where k(T) is the apparent first order reaction rate constant, Cfeed is the sulphur
of
5. AMeasure
and
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transformation
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ments
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and
feedstocks
indicate metal
in the
References
oils yield
With
and
byproducts
Such
content streams
heavy
is ofthis
coke only
well-controlled
of which
crudes the
formation. 5.6%.
approach, can
cracking
often Thus, the
build
optimised
Over have the
focusup
reactions
its a heterogeneous
on isthree-day
blending
high
lifetime, the analysing
that catalyst
viscosity,
a operations
occur
catalyst catalyst
in issues
and
high
maythe in the previou
commercial
immediately
1 upcoming unit after using start-up, Z-HD20.
requirements for cleaning. Predictive ana- whereas
Christensen P, Hearn A, Yeung T, The future for hydrocracking, part I, PTQ, a break-in
exhibits
known result tosome both
cause higher
aconcentrations
problem yield Inand
such ofselectivity
as vibration for
ain amono-
pump nisms were in
which
upstream
salt
experience
For
period
lytics
Q4 2017. amaximise
content,
turns isEuropeanainlagging
reactor,
typicallyhigh deactivation.
the while
sintering use
refiner
required
indicator ofactive
all
of low
the
operating
for inthe
into cost
chlorides
sites.
situ aFCCsolids
aThis unit
refineryin or
300
sulphiding.
leading the
is one
t/h typical
streams
feed
unstable
indicator A oftwo- are
the
typ-
and or borylated
compressor.
catalyst
ensure
converted
asphaltenes, methane
poison
meeting
to Sonic
hydrochloric
high is
the
sulphur than
monitors
organic
required
acid. the
levels, canThe homogeneous
vanadium be added
specifications
high reactions found
naphthenic to the
are: catalyst.
in device
closest the
acid process safety
2 reasons
stage
ical time
and Importantly, why
with
allows actionthe
American the
recycle
savings
Petroleum activity
comparison
to be
Institute, of
hydrocracker
taken a regenerated
between
before
Recommended having
losses in catalyst
Practice situ a is
three-year
sulphiding
areUiO-67-Mix
incurred.
932-B, signif-
Design,
to
or and
the
high when
feedlimits
metals vibration
stream.(tocontent. reduce team
Catalyst exceedsthe
This found a certain
fouling
quality
causes 6that in MOF
level,
aFigure
giveaway)
significant FCC alerts
has are
problems can
beenthe be The system
icantly
cycle,
and
The
Materials, restored
estimates
UltraCAT
final step
Fabrication, afterindicate
preactivation
is coke
adding
Operation, removal.
that
AI
and is MACH
orshown
Inspection Around
knowledge intechnology
Guidelines 80-90%
based 1.
for of
could
ana-
Corrosion the
main
such without
sent to
caused advise
instruments iridium
by operators
organic
to +had
increase no that
iron effectremedial
which
refinery on methane
can action
block
profitability. borylation.
is theneeded.pores and, because
improve
lytics
NH3 (g)+
Control inas
hydrodesulphurisation
that low
the
HCl can
(g)
Hydroprocessing desalting
bottom
→ generate
NH4 Reactorline
Cl -
efficiency
and byEffluent
(s)correct $10–20 because
hydrodenitrification
advice
Air million
Cooler takingofper
(REAC) uncontrolla-
in activity
all ele-is
cycle.
Systems, Third
bleIn-line
A The
Prescriptive
of
emulsions, theteam
blending catalyst
water also
analytics
(to carried
and when
a adds
product
salt out
the a new
carry-over detailed
level
tank, layer
becomes
ship,
or oiloptimisation
of or sophisti-
carry-un- very
pipe- oil supply and
typically
ments
Edition, Jun 2019.of
Francis restored
thecatalytic with
situationreaction
Humblot, a simple
and thenconditions
New coke
provide clear
Business burn-off,
Developer, depending
actions Arkema, to
line),
der
3 on NHhow
of
cation
into high
whenthe to
the – thethis
all
desalter methodology,
often
blending
NH4 effluent depends
components moving
water. on the it
are using
from
specific
continuously a UiO-67-
product
catalyst in different m
Conclusion
Thiochemicals, the S (g)commercial +
HSmay -
(s)middle
Lin H, Lagad V, Evaluating ammonium chloride corrosion potential with
resolve (g) +it. H2This →action
francis.humblot@arkema.com; require distillate
human (without
intervention
Vijay Srinivas, Ni/V
sourced Mix-Ir
based
3
design from as
to a and the
broader catalyst
production process by screening
based
process. approach. several different
In deliver- • High tempe
in Drawbacks
feed) the the
hydrotreating are &processing
reduced reactor units
throughput,
was and/or
operated storage
increased
during tanks
its foul-
life-
water partial pressure, NACE International Conference and Expo, Paper No.
Shell
or, where
Principal
C-H Catalysts
Scientist,
inert process
solvents. Technologies,
Arkema, isUsing
trusted,
Thiochemicals
C6D thenin ascollaboration
automated,
R&D,
thebesolvent vijay.srinivas@ auto-with
led to
and
ing ing
These
8960, 2017.
time. and prescriptive
HighSintering
simultaneously reactions
corrosion, temperature analytics,
ofpassed
are
wastewater zeolites there
through
exothermic
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used
treatment a and to
staticin a
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Zeolyst,
matic
2
arkema.com has
maintenance
bis(pinacolborane) developed requests. a new
conversion nano-engineered
12
of 19% and a zeolite
much
4 most thatadvancedprocesses,
lyst isare prevented activities
approach and
through
that J, systems ofregenerator used in the
design isplant ble of supplyi
(reactants gaseous aoffers distinct advantages
higher
Toba K, energy
Suzuki T, costs.
Kawano The K, and function
Sakai productsEffect of are
aMACH, solids).
demulsifier
relative humidity When to
on
favour
hydrocracking
The
This formation
catalyst
work of
catalyst
manufacturer
process polyaromatic
adds technology,
has species
amonoborylated
prescribed
large amountand less
procedureof adsorp-
featuring data to
arelower yield
interconnected. of 3.3% Prescriptive
ammonium chloride corrosion in refineries, Corrosion, 2001, 67 (5). for analytics looks methane.
at data system could
over
tionthe
break
mesopores of
sulphide which
other
temperature
the
hydrogenthe controls
blending
oil/water
that catalyst. on
enable defined
the the
options
emulsion,
Any heat
catalyst
VGO for
as
deviation transfer
that blending
salt
surface,
molecules the
frompointoiland
which
andcan
this the
components
is be leads
those
procedure aver-
reached,
sepa- to
of
6 processing
Conversely,
streams
and when
across
calculations,
these, the
and
Shargay C, Marciniec S, Analyzing water washing requirements for low common and solvent
pinpoints
generates
sophisticated
a large
tetrahydrofu- signa- ing three bitu
and
cokepushed
rated
heavier
should
amount age
finished
easily
formationfeeds
be
of temperatures
especiallyproduct,
from
toon
reviewed
additional enterthe bywith
the the
it the
water. in NH
catalyst.
more the
ability
the
information.During regenerate
to adapt
partial
In
efficiently.
3catalyst aoil 30-day to unit
pressure,
production
manufacturer
However, fluctuations
period itto does
salts pro-
often can
with
and
ran
tures was
and employed,
patterns of 98%
data
severity hydroprocessing units, NACE International, Paper No. 04646, 2004. conversion
that are happening of the borylation
in advance duction lines,
in
EOR
6 not the
form
higher
Refiners
approved. tect
blending
and
amounts
temperature
increase the
deposit
can catalyst
streams
leverageof
the achieved; in
such
conditions,
number from
quality,
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MACH of excessive
quick
locations
significant
technology
KPIs breakers
for switch
in temperatures.
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to
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(12-15°C) to
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Cl. to
staff.
reagent
Shargay
ofof an event. was
C, Literature survey on REAC however, corrosion, theNH major
HS vs, NH product In
heater in wint
ingtionator,
into
tivation (Uniformity
different
heavy was typically
crude product
observed of in
oils. the
in grades,
theThey coke
both overhead,
areand burn
catalysts so
surface without
on.
in the
(CatY active top
and creating
pump-
agents
CatZ).
4 4
today’s
Thiswas
NACE Spiked
process strategic
Corrosion feed
borylated is
Technology objectives
sulphiding
entirelytetrahydrofuran, because,
of
automated,
Week, TEG a metal
205X compared
and
with oxide the
only
(STG-34) data with
hydrotreat-
3.8% and
Information the
yield
Critically, too, the approach also • Normal tem
The
around,
and
However,
previous
ing
model hot
have successful
ofcatalyst
spots
hence
a tendency
CatZ
generation
performance
monoborylated
Exchange Minutes, St. Louis, MO, 2019. is
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References structure
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flow
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and
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rate particle
validation
phase.
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models – is
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the hydrogenation for catalyst
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Below
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molecular
issues.
Today temperatures
beyondcrude
240°C,
154,
is operating
2010, oil
weight,
Windows, First Edition, May 2014.the diet
256-263. and
abilityand/or
soluble
reduction
correctly. damage
of in usetoluene or
conventional
reaction or destroy
‘import’
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Ben We
ment, also and expect to
pharmaceutical see 2019
Leviton is a process engineer with Fluor Canada Ltd. With eight years’ witness
industries. the continuing
Nitro-aromatic roll- Previously, at
In-line
The rate
have
Elsevier
difficult
flow and
ISBN conversion
blending
asphaltenes-resins
noor impact
978-0-444-53556-6.
higher
in the trend on margin,
temperature will
ofdownstream
gasoline drop.
complex
lower into
range is
units.
quality product
soluble feeds
of 220-240°C, intanks the while and/
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experience
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compounds in a new
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on
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Applied co-opetition’.
simulation
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Catalysis an and
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aromatic
General The
analysis.
548, ring.opportunity
2017, He 114-121.
holds a BSc
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Accelerated chemicals
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Ha is a Technical Fellow, Process Technology with Fluor Canada
platinum, plant, recognise palladium,
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take
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University of Science and Technology and a PhD in chemical engineering
autonomous and
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from the University of Alberta.
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ried
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Catalysis, out on
2012, in are
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Rodwell is Senior Director, Process Technology with Fluor Canada
conversion
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outlook .indd 7 q2 tupras.indd 2 17/12/2018 13:12

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14/09/2020 14:03
FCC SOx additives and security of supply
Rare earth prices could accelerate again as a result of trade tensions
TOM VENTHAM, CJ FARLEY and NATALIE HERRING

UNICAT B.V. and G. W. Aru, LLC
A
lthough it happened nearly thus only impacting importers of can only absorb SO3, the efficiency
a decade ago, refiners and rare earth components and raw of SOx removal would be severely
suppliers still bear scars from materials, not those exporting final limited if SO2:SO3 equilibrium was
the last spike in rare earth prices catalysts or additives. not quickly restored local to the SOx
that occurred in 2010-2012 and the Here, our focus is on cerium oxide additive absorption site.6 Cerium
severe impact this had on refinery as a component of FCC SOx reduc- oxide is included in the additive for-
bottom lines. Export restrictions on tion additives, and how alterna- mulation to assist oxidation of SO2
rare earth raw materials imposed by tive additive supply options offer to SO3 and improve effectiveness.
China, which accounts for 94% of a solution to manage risk. Utilising It has been found that SOx addi-
global production, caused a 30-fold a broad approach to sourcing SOx tives lacking cerium oxide result in
increase in market price of some reduction additives, Unicat and G. low overall SOx absorption, meas-
of these commodities.1 This hurt W. Aru, LLC offer security of sup- ured commercially as low pick-up
the refining industry in two areas ply and high performance. efficiency.7 The final step is SOx
due to a reliance on particular rare additive regeneration in the FCC
earths: lanthanum oxide, which is SOx reduction chemistry riser/reactor. Here, a non-mobile
a key component of FCC fresh cat- SOx reduction additives typically vanadium component is used to
alyst,2 and cerium oxide, which is comprise of three key components, promote reduction of absorbed sul-
a crucial component of FCC SOx each having a different function phate to hydrogen sulphide. H2S
reduction additives.3 is removed from the process in the
The use of a catalyst additive is a The most effective FCC dry gas stream. Once the H2S
known straightforward and flexi- is released, magnesium sulphate
ble way to meet FCC SOx emission way to determine returns to magnesium oxide and is
limits and has become accepted available for further SOx pick-up in
technology for many refiners. which SOx additive the regenerator.6 This circular pro-
Alternatives for rare earth com- cess continues until activity is lost
ponents in FCC catalyst and SOx is best for your through sintering of cerium oxide
additive formulations were studied, and densification of the magne-
and although thrifting and opti-
FCC operation is by sia-alumina phase.
misation helped minimise short- performing a series Although use of rare earths has
term pain, effective alternatives been a sensitive issue for refiners
were not successfully implemented of industrial trials due to past experiences of price
before the rare earth bubble burst spikes, high performance SOx addi-
in 2012.9 Therefore the refining tives need to correctly balance each
industry remains in a precarious within the FCC operation. The larg- component of the tri-functional
position and at the mercy of future est proportion of a SOx additive by system to function efficiently. FCC
price spikes, with China remaining mass is magnesia-alumina mixed unit configuration and operation
the major producer of rare earths.4 metal oxide sorbent, which is effec- will dictate the relative importance
Reports suggest a likelihood that, in tive for absorbing sulphur trioxide of each component where formu-
the case of faltering trade talks with (SO3) in the regenerator as mag- lations may be optimised for full
the US, China could implement nesium sulphate. The magnesia to burn, partial burn, or low reactor
new trade sanctions on rare earth alumina ratio determines whether temperature operation. For exam-
minerals.4 A harbinger of this pos- the additive is referred to as a spi- ple, in typical full burn units the
sibility was seen in May 2019 when nel or hydrotalcite-type with low limiting factor for SOx pick-up is
prices of rare earth materials spiked or high magnesia content respec- believed to be absorption site avail-
almost 50% merely on rumours of tively. SOx is a combination of SO3 ability. Conversely, in partial burn
another embargo.5 It is expected and SO2 where these species exist in operations oxidation of reduced sul-
that future sanctions would apply equilibrium, which favours SO2 in phur species to SO3 is critical. For
to raw materials rather than fin- the approximate proportions 95% low riser temperature operation,
ished goods containing rare earth, SO2 to 5% SO3.6 Since the sorbent otherwise called diesel or distillate
cat unicat.indd 1 15/03/2021 12:06

design enhancements were intro-
80 duced during the turnaround. This
70
USB starts is also true for emergent operational
issues following unit shutdown or
60 start-up compared to stable oper-
50 ation. In all cases, it is appropriate
to re-evaluate SOx additive perfor-
ppm
40
mance to ensure the best perform-
30
ing additive is selected for the
20 operation.
10
Ultra SOxBuster additives
0
Date Ultra SOxBuster (USB) additives are
offered by G. W. Aru, LLC to refin-
SOx addns. SOx add. wt% ers in North America, and under
the Unicat brand in Europe and
1.0 20 around the world. These additives
Scaled addition rate compared to MAX
USB starts
0.9 18 are produced by manufacturing
0.8 16 partners in China and other loca-
0.7 14 tions worldwide. Chinese man-
% of additions
0.6 12 ufacturers have been producing
0.5 10 high quality additives for domestic
0.4 8 markets for many years. SOx addi-
0.3 6 tives conforming to standards of
0.2 4 western catalyst and additive man-
0.1 2 ufacturers, for example in the US
0.0 0 and Europe, have been developed
Date in China for use in Chinese refiner-
ies. The quality of these additives
Figure 1 (a) Time plot of Refinery A flue gas SOx emissions (b) Time plot of Refinery is consistent with those produced
A SOx additive additions. Vertical lines indicate shutdowns and the start of USB-M60 trial in western markets but cost struc-
ture differs significantly. Access to
mode, good SOx additive regen- pick-up factor (PUF), as defined in these FCC additives is now made
eration is essential for release of the following equation, is a calcula- available to refiners outside of
sulphate, which is less favourable tion typically used to quantify SOx China with local technical support
at lower temperatures. Many refin- additive effectiveness: close to the end user. Moreover, the
ers find that they switch between sourcing approach taken by G. W.
such modes frequently. In these Daily PUF = (mass of SOx removed per day) / Aru, LLC and Unicat means refin-
cases, it is best practice to select (mass of SOx additive added per day) ers are offered a wide selection of
the optimum SOx additive for the SOx additive types to ensure the
current operational strategy as it is Daily PUF may initially be esti- best SOx additive is selected for
also found that some SOx additive mated through simulation models the operation. Included in the Ultra
types are incompatible with certain or from experience of similar FCC SOxBuster range are USB-M30 and
modes of operation. In all cases, a unit responses. However, an accu- USB-M60, which contain approx-
SOx additive with the appropri- rate daily PUF should be validated imately 35 wt% and 60 wt% MgO
ate magnesium to aluminium ratio by industrial test as local fluctu- respectively. These additives have
and with good dispersion within ations in the regenerator (such as similar physical properties and
the particle should be selected. In spent catalyst mixing or maldis- ceria and vanadium content as SOx
summary, a superior SOx reduc- tribution) or riser (regeneration additives currently used by refiners
tion additive should excel in all efficiency) operation can greatly today.
three of these areas, and refiners affect true SOx additive response
should work with a competent in any FCC unit. Daily PUF from Trial at a US refinery (Refinery A)
additive supplier to ensure the cor- an industrial test for one FCC unit Ultra SOxBuster-M60 was evalu-
rect SOx additive is chosen for their cannot be assumed to be a direct ated at Refinery A, which is a site
operation. facsimile of daily PUF expected for in the US belonging to a major
another FCC unit, no matter how international oil refining company.
SOx reduction additive trial similar the operation. The same Results were compared against a
The most effective way to determine can be said regarding SOx additive top selling competitive SOx additive
which SOx additive is best for your performance straddling a major that had been in use at this site for
FCC operation is by performing turnaround, particularly if known many years on a continuous basis.
a series of industrial trials. Daily mechanical issues were repaired or As both additives are hydrotalcite
cat unicat.indd 2 15/03/2021 12:06

based with similar physical prop-
erties, performance on a per mass
45
basis was expected to be similar. Mean USB = 97.2
Like-for-like performance would 40
give the refiner access to an alter- 35
native, lower cost SOx reduction 30
Frequency, %
Mean Base = 95.3
additive to achieve their compliance 25
requirements. Proving the perfor- 20
mance of USB-M60 also gives this
15
refiner confidence that SOx control
costs would be manageable should 10
cerium oxide prices again escalate 5
following trade disputes. Unicat 0
92 93 94 95 96 97 98 99 100
and G. W. Aru, LLC uses their
SOx reduction, %
knowledge of FCC operations and
experience of SOx additive perfor- Base USB-M60
mance to analyse the trial results
35
and determined that USB-M60’s
performance exceeded that of the 30
Mean Base = 29.8
competitive SOx additive.

25
Upon commencing the trial,
Frequency, %
the first indication of a positive 20

response with USB-M60 was that
15
flue gas SOx emissions were main- Mean USB = 33.5
tained at the required low level (see 10
Figure 1a). Additive consumption
5
is also maintained within normal
range to achieve this low SOx emis- 0
20 25 30 35 40 45 50 55 60
sions level (see Figure 1b). Although
Daily pick-up factor, lb/lb
these first views are positive, deeper
analysis is required. This starts with
comprehensive unit monitoring Figure 2 (a) Histogram of Refinery A SOx reduction (b) Histogram of Refinery A daily
analysis using time plots to ensure pick-up factor
An industry certain target results (such as fre- However, viewing bulk aver-
quency and reliability of exceeding age data does not account for unit
recognised technique 95% SOx reduction or number of shifts and fluctuations which are
days under 20 ppm SOx emissions, unavoidable in the majority of FCC
to differentiate for example). Histograms are used operations. Also not accounted
to further contextualise the results for are certain dynamic variations
performance in observed (see Figure 2). Using and sensitivities that are impor-
FCC operations is these methods of analysis con- tant in SOx additive trials, such
firms that the performance of USB- as changes in SOx additive addi-
cross-plotting M60 exceeded that of the previous tion rate or addition strategy. An
additive. industry recognised technique to
absence of, or to account for, funda- Refinery A mean average FCC data during SOx additive trials
mental changes in FCC feed proper-
ties, operation, or catalyst properties Period Baseline USB trial
throughout the trial period that Feed S, wt% 0.21 0.22
may corrupt test data or challenge Feed CCR, wt% 0.94 1.14
trial validity. Once representative Rgn. dense T, °F 1324 1320
Cat. circ., tpm Base Base x 0.98
test periods are identified, average Air:coke, wt/wt = =
results are compared to determine Excess O2, vol% 2.0 2.3
superficial quantitative differences Slurry S: Feed S, wt/wt 2.9 3.0
between test periods (see Table 1). Slurry S, wt% 0.6 0.7
SOx additive addns., lb/day Base Base x 1.09
Although average data offers a SOx reduction, % 95 97
convenient overview of trial results, Daily pick-up factor, lb/lb 30 34
it gives little information on repeat- SOx emissions, ppm 24 19
ability, consistency, presence of
outliers, or the ability to achieve Table 1
cat unicat.indd 3 15/03/2021 12:06

fits and gives refiners access to new
technology.
40
35 References
Flue gas SOx, ppm
30 1 Bradsher K, Prices of Rare Earth Metals

25 Declining Sharply, 2011; Available from:
https://www.nytimes.com/2011/11/17/
20
business/global/prices-of-rare-earth-metals-
15 declining-sharply.html.
10 2 Vogt E T C, Weckhuysen B M, Fluid catalytic
cracking: recent developments on the grand
5
old lady of zeolite catalysis, Chemical Society
0 Reviews, 2015(20).
0 1
SOx additive additions, scaled in comparison to MAX = 1 3 Magnabosco L M, Fluid Catalytic Cracking
VII: Materials, Methods and Process
Base USB-M60 Innovations, Studies in Surface Science and
Catalysis, ed. Occelli M L, 2007, Elsevier B. V.,
40 340.
35 4 Rogers J, Stringer D, Ritchie M, China Gears
30 Up to Weaponize Rare Earths Dominance in
Daily PUF, lb/lb
Trade War, 2019, available from: https://www.

25
bloomberg.com/news/articles/2019-05-29/
20 china-gears-up-to-weaponize-rare-earths-
15 dominance-in-trade-war.
5 Castellano R, China Trade - Invest Based On
10
Rare Earth Price Hikes, 2019, available from:
5 https://seekingalpha.com/article/4267839-
0 china-trade-invest-based-on-rare-earth-
0 1
price-hikes.
SOx additive additions, scaled in comparison to MAX = 1
6 Sadeghbeigi R, Fluid Catalytic Cracking
Handbook, Third ed., 2012, Elsevier.
7 Fletcher R, Catalyst additives reduce rare
Figure 3 (a) Refinery A SOx emissions plotted as a function of SOx additive additions, and
earth costs, PTQ, Q1 2012.
(b) Refinery A daily PUF plotted as a function of SOx additive additions
8 Answers to the 2010 NPRA Q&A FCC
Questions, 2010.
differentiate performance in FCC Conclusion 9 Fletcher R, High Rare Earths Prices! Options
operations is cross-plotting. This Introduction of Ultra SOxBuster for Reducing FCC Catalyst Costs, CatCracking.
method is used to observe changes additives offers refiners the oppor- com, Dusseldorf, October 17-21 2011.
in key dependent variables at a tunity to increase cost savings and
fixed single independent variable. future-proof themselves against
Cross-plots show that at constant potential rare earth price spikes.
SOx additive addition, SOx emis- Industrial trials have been con- Tom Ventham holds a Sales and Technical
position with Unicat. With an intimate
sions are 25% lower with USB-M60 ducted that prove superior per-
knowledge of FCC additives, hydrogen plant
than with the previous additive (see formance versus incumbent SOx
catalysts and purification applications,
Figure 3a). As expected, daily PUF reduction additives. Results from he holds a master’s degree in chemical
for USB-M60 is higher compared to one such trial have been discussed engineering from Imperial College, London
the competitive additive (see Figure here. and is a Chartered Member of the Institute of
3b). This is taken as the clearest con- UNICAT and G. W. Aru, LLC Chemical Engineers (IChemE).
clusion of relative additive perfor- help refiners to reduce environ-
mance: USB-M60 is 20-25% more mental control costs through use of CJ Farley is an independent consultant
efficient than the previously used FCC additives and support from an working with G.W. Aru, LLC. His 30-year
additive. experienced team. G. W. Aru LLC, background with FCC includes operations,
Following complete, multi-fac- Unicat Catalyst Technologies, Inc. optimisation, debottlenecking, hardware
design and reliability, and catalyst and
eted, and precise analysis by FCC and Magma Catalysts are partners
additives innovation and commercial
technical service engineers, conclu- to bring cost-effective and innova-
performance. He graduated from Purdue
sions can be drawn that USB-M60 tive catalyst solutions including University with a chemical engineering degree
outperformed the previous SOx the Magma steam methane reform-
reduction additive at Refinery A ing catalyst to refiners worldwide.
Natalie Herring is Director of Technology with
(see Table 1). This increased perfor- This alliance utilises Unicat’s G. W. Aru, LLC. Her experience in FCC additives
mance directly translates into cost existing support infrastructure includes R&D, scale-up, commercialisation
savings for the refiner as well as an and management of regulatory and technical sales. In her current role, she
ability to improve FCC SOx control requirements such as REACH in focuses on bringing innovative technologies
through use of a more active and the European Union. This collabo- to refiners. She holds a PhD in chemistry from
therefore more responsive additive. ration has brought multiple bene- Virginia Commonwealth University.
cat unicat.indd 4 15/03/2021 12:06

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j screens.indd 1 12/03/2021 13:01

Designing steam heat exchangers and Designing steam heat exchangers and tracing systems
Fundamentals must be considered when designing an industrial steam system to avoid p
failure or under-performance
tracing systems ALEX CHU Swagelok
Fundamentals must be considered when designing an industrial steam system to avoid
When designing a steam heat exchanger or steam heat tracing system, a full understand
premature failure or under-performance
overall process and how the system will operate is essential. Inadequate performance c
ALEX CHU attributed to a design engineer’s failure to consider all characteristics of a steam system
Swagelok engaging in the design process, a thorough review of the steam system’s operating para
documentation must be conducted to understand the context of the application (see Fig
Failure to do so will result in inappropriate control or selection of system components.
W
hen designing a steam Figure 1 A thorough
heat exchanger or steam review of a steam
heat tracing system, a heat exchanger
full understanding of the overall system’s operating
parameters and
process and how the system will
documentation is
operate is essential. Inadequate required to design a
performance can often be attrib- proper system
uted to a design engineer’s fail-
ure to consider all characteristics
of a steam system. Before engag-
ing in the design process, a thor-
ough review of the steam system’s
operating parameters and doc-
umentation must be conducted
to understand the context of the some simple guidelines and proven or a combination of different meth-
Figure 1 A thorough review of a steam heat exchanger system’s operating parameters a
application (see Figure 1). Failure field techniques. The following rec- ods, will prevent condensation
to do so will result in inappropri- documentation is required
ommendations should to design from
be reviewed a proper system
forming or ensure that if it
ate control or selection of system and implemented into your facili- does form it is diverted away from
components. Engineers
ty’s steammust understand
system the basicthe
design, mainte- fundamentals
control valveof industrial
to a steamsteam
trap systems to preve
Engineers must understand the nance, andfailure
premature specification program whereAfter
or under-performance. it cana be evacuated from
comprehensive the of industrial he
review
basic fundamentals of industrial before determining the equipment system.
applications across different locations and industries, the most common issues can be ca
steam systems to prevent prema- for your next steam heat exchanger
into incorrect component selection orFollow
poor turndown
installationratio
practices. The most common issu
ture failure or under-performance. and tracing system. guidelines
After a comprehensive review of observed include: for control valves
industrial heat transfer applica- Eliminate steam supply condensate To control process temperatures
tions across different locations and • Unacceptable
build-up effectively, correctly sized control
end-product quality
and carry-over
industries, the most common issues Control valves are required
• Premature failure oftocomponents
con- valves must be specified. The most
can be categorised into incorrect trol process steam flow between important consideration when
component selection or poor instal-
• Poor temperature control
0% and 100%. When there is either choosing a control valve is the
lation practices. The most common •
low or no Inadequate
steam flowheat transfer
in the system, turndown capability, rangeability,
issues that are observed include: • Water
condensate canhammer
build up before the or working range of the valve.
• Unacceptable quality of end inlet• of Fouling
the control valve
of the and
heat cause equipment
transfer Due to physical valve design con-
products water hammer. In addition, if constraints, all valves will exhibit some
• Code and standard violations
• Premature failure of components densate flows through a steam con- uncontrollable flow because of
• Poor temperature control trol valve at high velocities, it can sealing tolerances and the linearity
• Inadequate heat transfer Best
causepractices
premature forwear
steam to system
the valvedesign
of flow, especially at the extreme
• Water hammer Designing
internals anda proper industrial
subsequent steam
failure to system does
ranges of the not have
valve to be complicated if engineer
stroke.
• Fouling of the heat transfer control
some or seal.
simple guidelines and proven field Here are some The
techniques. guidelines for recommendations
following the sh
equipment There are several methods to turndown ratios of control valves:
• Code and standard violations keep condensate from accumu- • Cage control: 40:1 turndown
lating. For example, installing a ratio provides the highest degree of
Best practices for steam system drip leg prior to the valve, adding controllability
design insulation improvements, correctly • Globe control valve: 30:1 turn-
Designing a proper industrial grading the steam line, or installing down ratio
steam system does not have to be a steam separator prior to the con- • Regulating valve: 20:1 turndown
complicated if engineers adhere to trol valve. Each method on its own, ratio
q2 swagelok.indd 1 15/03/2021 12:17

Figure 2 Installing Avoid back pressure within heat
a pressure gauge transfer equipment
before and after a Condensate drainage is a criti-
control valve and on cal consideration when design
a condensate return
engineers create heat transfer
leg after the steam
trap helps to provide
equipment for steam systems.
accurate data for Condensate drainage is accom-
monitoring a steam plished by either gravity or a
system pressure differential. If possible,
heat transfer equipment should be
installed to promote gravitational
drainage with no vertical lift before
or after steam traps. This is crucial
Figure 2 Installing a pressure gauge before and after aincontrol valve andthat
any application on ahas
condensate
a modu- return leg
For steam applications, in addi- that when steam cools down inside lating steam control valve.
after the steam trap helps to provide accurate data for monitoring
tion to the turndown ratio, it is a closed volume, it will condense.
a steam system
Certain applications do not
recommended to avoid using the Since condensate can occupy only allow for gravitational drainage,
lower and upper 20% of the valve up to 1/1700th of the total volume and when that happens it is crit-
stroke – the lower 20% to avoid of its mass compared to when it ical that condensate devices, like
excessive velocitiesInstall vacuum
across the breakers
is in gas phase, a vacuum will be steam traps or control valves, are
Vacuum breakers
valve seat and the upper 20% for formed. are essential equipment when steam notsystems
subjectedare isolated
to backfrom the steam supply
pressure.
controllability. and are not open toWhen atmosphere. Equipment
steam systems that requires
are isolated, vacuum breakers
Unanticipated back includes
pressure,steam lines,
If control valves kettles,
are notplatesized vacuum
or shell breakers
and tube heat prevent
exchangers, systemand anywhich results
other in condensation
equipment not ratedcol- for vacuum
properly, the results can be poor collapse from external pressures. lecting in the equipment, leads
use.
process temperature control, pre- As a result, most steam equipment to premature failures and perfor-
The reason they are necessary is that when steam cools down inside a closed volume, it will
mature wear of the valve seats, and requiring air vents and vacuum mance problems and can create
excessive noise. condense. Since condensate
breakers will can occupy
have only up to 1/1700th
designated of the total
water hammer, volumetemper-
inadequate of its mass
compared to when it is in gas phase, a vacuum will be formed.
installation points specified by the ature control, reduced efficiency,
When
Install pressure gauges steam
before andsystems are isolated,
equipment vacuum breakers
manufacturer. These prevent systemissues.
and corrosion collapse from external
after the control valve should
pressures. As a result, not be
most ignored.
steam equipment requiring air vents and vacuum breakers will have
Pressure gauges (see Figure 2) will
designated installation points specified by the equipment Prevent superheatedThese
manufacturer. steamshould not be
provide the basic information nec- Install automatic air vents In most cases, steam heating appli-
ignored.
essary to understand the condi- When a steam system is shut down cations demand 100% quality sat-
tions at each part of the system. or being maintained, air will leak urated steam supply; this level of
Install automatic
This will aid performance verifica- intoair vents
the system. This air must be quality refers to steam containing
WhenItaissteam
tion and troubleshooting. good system
purged is shut
beforedown
the or being can
system maintained, air will leakdroplets
be no entrained into theofsystem.
conden-This air must
practice to install a be
pressure
purged beforereturned
gauge the system back
cantobeservice.
returned If air
backis to sate or vapour.
service. If air isSuperheated steam, from the
not purged properly
before and after asystem,
control itvalve not in
will result purged properly and
slow start-ups fromcould
the sys- or steam
form thin boundaryat a layers
higher on temperature
heat transfer surfaces,
and on the condensate return leg tem, it will result in slow start-ups than its saturation point, should
creating an insulating effect that will inhibit efficient
after the steam trap. This provides and could form thin boundary be prevented from entering the
heat transfer. A boundary layer of air only one
thousandth
accurate data to assist in under- of an layers
inch thickon have
heat the same surfaces,
transfer efficiency of heat
heat transfer
transfer as 13 inches
process. of copper or
Superheated
three inches of cast iron.
standing the pressure characteris- creating an insulating effect that steam will degrade performance
Steam traps
tics of the steam passing throughshouldwillnotinhibit
be relied on toheat
efficient venttransfer.
air as theybecause
are usually located
it has lessatenergy
the lowestper part of the
the steam heat exchanger. In addi- A boundary layer of air only one unit volume than saturated
system and therefore cannot be relied on to do it properly since hot air tends to rise and be trapped steam
tion, all pressure gauges
at theshould
highest thousandth
bepoint. An air ventof an inch on
fitted thick
thehas
endtheof aunless
steam it is accounted
main, for within
or at the highest point on a piece
installed with a coil siphon (pig- same efficiency of heat transfer as the original design. Superheated
of equipment in conjunction with a
tail) to prevent high temperature 13in of copper or 3in of cast iron.
vacuum breaker, will open when air is present.
steam supply can be conditioned
This occurs due
damage and doubleto the differential
block isolation temperature between
Steam traps should notthe
be air and the
relied by steam.
installing a desuperheater.
valves to allow maintenance. on to vent air as they are usually
Avoid back-pressure located
withinat the
heatlowest
transfer part of the Lockout ball valves
equipment
system and therefore
Condensate drainage is a critical consideration when
Install vacuum breakers cannot Ball valves
be design are acreate
engineers common, safe,
heat transfer
Vacuum breakers equipment
are essential relied on to do it properly since hot reliable, and cost-effective
for steam systems. Condensate drainage is accomplished by either gravity or a pressure option
equipment when steam systems air tends to rise and be trapped at that allows for leak-tight isolation
differential. If possible, heat transfer equipment should be installed to promote gravitational
are isolated from the steam supply the highest point. An air vent fit- and quick identification of isolation
and are not open to atmosphere. ted on the end of a steam main, or states in a steam system because of
Equipment that requires vacuum at the highest point on a piece of the handle orientation. Ball valves
breakers includes steam lines, ket- equipment in conjunction with a 2in or smaller can be purchased 3
tles, plate or shell and tube heat vacuum breaker, will open when with locking handles, which is a
exchangers, and any other equip- air is present. This occurs due safety best practice for a lockout or
ment not rated for vacuum use. to the differential temperature tagout. Before installation, contact
The reason they are necessary is between the air and the steam. safety and inspection departments
q2 swagelok.indd 2 15/03/2021 12:17

to be sure the installations comply Ensure that when blowing down
with any site or local regulations the strainer, the discharge is vented
dealing with lockout or tagout pro- to a safe location. Strainers should
cedures for steam systems. be installed in the horizontal posi-
tion, so that condensate does not
Correct steam trap sizing collect in the strainer body.
There are many designs of steam
traps. Different designs cater to Education is key
different applications and some Figure
Figure 43 A Y-strainer serves
A Y-strainer servesasasaafilter
filterto
to removeTraining courses
contaminants are lines
from steam available
to prevent
designs are more reliable than oth- premature failure or fouling of
remove contaminants from steam linesdownstream components and the steam system
to teach engineers about how to itself
ers in certain cases. In a steam heat to prevent premature failure or fouling of enhance your facility’s steam sys-
exchanger application, for example, When installing
downstream a strainer,and
components always install a blowdown
the steam valveare
tems and withdesigned
a lockout facility. This will improve
to educate
strainer maintenance. Ensure that when blowing down the strainer, the discharge is vented to a
system itself
mechanical-type steam traps will you about specific industries and
safe location. Strainers should be installed in the horizontal position, so that condensate does not
be best suited to a modulating flow needs. Inquire with your manufac-
collect in the strainer body.
and pressure environment. Steam turer’s representatives about train-
heat tracing applications, on the Install a strainer
Education is key to prevent ing at your facility.
other hand, allow for a much wider foreign contamination
Training courses are available to teach engineers about how to enhance your facility’s steam
variety of steam trap designs, but Steam and
systems linesarecan contain
designed corrosion
to educate you about specific industries and needs. Inquire with your
are still application specific. and maintenance
manufacturer’s debris, about
representatives putting
training at your facility.
The sizing of the steam trap control valve trims, isolation valve
depends on maximum and min- seats, and steam trap seats at risk
imum flows through the system. of failure or fouling. Installing a Alex Chu is Engineering Manager with
Designers must also think about strainer, which will act like a filter, Swagelok Bristol and an Industrial Steam
System SME for the Swagelok Company
the requirements for priming, air will keep foreign objects out of the
Field Engineering Group, providing training
venting, functional testing, and critical parts of the steam system
and engineering evaluation services. He is
mounting options. Generally, uni- (see Figure 3). experienced in analytical Instrumentation,
versal mounts are best for smaller When installing a strainer, furnace combustion, and steam systems
steam traps because they are eas- always install a blowdown valve to solve fluid system challenges. He
ier to maintain and replace if with a lockout facility. This will holds a degree in electrical and electronic
necessary. improve strainer maintenance. engineering.
q2 swagelok.indd 3 15/03/2021 12:17

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Neutralising amine selection for crude units
Making a proper selection of neutralising amine chemistry is a challenging task
ERIC VETTERS
ProCorr Consulting Services
E
ven though crude units have
been around for a long time,
maintaining long term reliable Feedstock
operation continues to be a chal-
lenge. The unit design, operating
conditions, feedstocks, and corrosion
Operating Reliable
control programme must all work Unit Design
Conditions Operation
together to achieve reliable oper-
ation (see Figure 1). If any part of
the system is out of sync, the whole Corrosion control
unit will suffer. With constantly programme
changing feedstocks and operating
conditions, as well as some unique
challenges posed by many opportu-
nity crudes, it can be a challenge to Figure 1 Factors influencing crude unit overhead corrosion and their interaction
keep everything running properly.
The neutraliser system is a critical steam in the overhead system will Neutraliser selection primer
part of the corrosion control pro- produce a highly corrosive, very Neutralising amine selection is typ-
gramme on crude tower overhead low pH steam condensate stream. ically based on a few key param-
systems. This article will focus on To control pH and reduce corrosion, eters. Basically, the neutralising
understanding and applying some bases such as ammonia or amines amine must be a strong enough base
basic concepts to the design of neu- (referred to commonly as neu- to raise the pH at the water dew
traliser systems and on some more traliser or neutralising amine) are point enough to control corrosion
subtle aspects of neutraliser selec- injected into the overhead system. at acceptable levels. It also must not
tion that are often overlooked. If these neutralising compounds are form salts ahead of the initial point
improperly employed, they can also where free water is present, either
Corrosion control basics lead to fouling and/or corrosion from condensation or injection
Some of the residual salts remain- through the formation of ammo- of water wash. It should be read-
ing in desalted crude hydrolyse to nium chloride or amine hydrochlo- ily available at a reasonable price.
form HCl in the crude furnace. The ride salts. Petersen, Lordo, and McAteer1 go
HCl then ends up in the overhead To prevent formation of salts and into more depth on this subject.
system of the atmospheric tower. to quickly dilute any acids pres- The nature of any neutraliser salts
There can also be light organic ent, a water wash stream is often that might form is an important
acids in the crude oil as well as injected into the overhead system. consideration in neutraliser selec-
light organic acids formed from The water wash, which is typically tion. Some amines, such as ethylene
the thermal degradation of naph- water recycled from the overhead diamine (EDA), will form a solid
thenic acids in high TAN crudes, accumulator, can be injected into salt which is a fouling and under
which also put additional acids into the overhead line or into the inlets deposit corrosion concern. Other
the overhead system. Neutraliser of heat exchangers. The net water amines, such as monoethanol amine
demand can easily increase by from the overhead accumulator con- (MEA), form liquid salts at typical
50-100% when switching to a high tains a mixture of organic and inor- process conditions. The liquid salts
TAN crude slate. Opportunity ganic acids and bases. This water tend to corrode more aggressively
crudes often are difficult to desalt, is commonly used as wash water than solid salts. Liquid salts tend to
which increases the amount of HCl in the desalter, which provides a be more of a corrosion concern with
formed. They may also contain potential route for these acids and some fouling potential from the cor-
tramp amine byproducts of H2S bases to get back to the crude tower. rosion products that form, whereas
scavengers. This recycling of amines will be dis- solid salts tend to be more of a foul-
If nothing is done to neutralise cussed in more detail in the desalter ing concern with some level of under
these acids, the condensation of section. deposit corrosion also occurring.
q2 procorr.indd 1 15/03/2021 12:13

The salt point, that is the temper- • Tramp amines The distribution coefficient is
ature where the chloride salt of the • Overhead temperature sometimes also called the partition-
amine begins to form as a free phase, • Desalting ing coefficient, although strictly
is another important consideration speaking the two are not the same.
in neutraliser selection. The goal is Water wash vs no water wash The partitioning coefficient calcula-
to select an amine neutraliser that The use of an overhead water wash tion is the same as the distribution
does not begin to form a salt ahead typically increases the flexibility coefficient except that it does not
of the water dew point. After the the refinery has when it comes to include ionised forms of the solute
bulk water dew point is reached, selecting a neutraliser. The water in the calculation.
the water solubility of the salts pre- wash forces an immediate water If enough amine partitions to the
cludes formation of a separate salt dew point, which greatly reduces desalted crude, then it is possible to
phase. This approach to neutraliser the risk of salt formation that could form an amine chloride salt in the
selection provides the pH control otherwise occur during the more atmospheric tower. Amines which
desired without the formation of cor- gradual cooling that happens in have a high partitioning coefficient,
rosion and fouling inducing salts. In overhead condensers. With no per- and/or those with higher natural
the absence of a water wash it can ceived risk of salt formation, refin- salt points, increase the probabil-
be challenging to find an amine that ers and chemical suppliers are ity of having salt formation via this
will actually accomplish its mission typically happy to use a stronger recycle route. The effect of desalter
without forming salts. base with higher salt forming ten- operation on amine distribution is
Because the amines tend to dencies because these neutralisers discussed later.
behave independently of each other are cheap and effective for the The different risk related to water
in forming salts, amine blends intended purpose of neutralising wash is the effect of water carry-
are sometimes used to reduce the HCl. Water wash also reduces the over from the overhead accumula-
salt formation temperature. For risks associated with changing pro- tor back to the atmospheric tower
instance, a 50/50 molar• blend Overhead cess conditions such as tempera- via the reflux. This risk is espe-
oftemperature
two different amines would cut the ture and chloride concentrations, cially a concern when water wash
• Desalting
amine• partial
Overheadpressure
temperaturein half com- assuming that the water wash rate is started for the first time or the
pared• toDesalting
the use of 100% of either
Water wash vs is no
adjusted
water wash to account for upward rate is substantially increased in an
amine. Some suppliers may use five shifts in overhead temperature. existing unit. A trend in recent years
The use of an overhead water wash typically increases the flexibility the refinery has
or more Wateramines washblended into awash
vs no water neu- When water wash is injected close at many US refineries has been to
when it comes to selecting a neutraliser. The water wash forces an immediate water
traliser product. to the neutraliser injection point, process increasing volumes of very
The use of an overhead water wash typically increases the flexibility the refinery has
For any given amine, dew the point,
salt whichthere is reduces
greatly practically the riskspeaking no that
of salt formation light
couldshale
otherwise crudes
occur and conden-
when it comes to selecting a neutraliser. The water wash forces an immediate water
point or sublimation point during the is moreamount
gradualof neutraliser
cooling that happensthat in could
overheadbe condensers.
sates. IncreasedWith nooverhead and wash
which greatly reduces theadded which would lead directly water rates that
defined by happyresult from these
dewthis equation:
point, risk of salt formation that could otherwise occur
perceived risk of salt formation, refiners and chemical suppliers are typically to
during the more gradual cooling thatto salt
happens formation in
in overhead condensers. the overhead
With no feedstock changes will increase the
use a stronger base with higher salt forming tendencies because these neutralisers are
Kp = Pamine *perceived
PHCl risk of salt formation, system.
[1] refiners and chemical suppliers are typically happyload to on the overhead accumulator,
cheap and effective for the intended purpose of neutralising HCl. Water wash also
There is a risk, however,
use a stronger base with higher salt forming tendencies because these neutralisers are
that is which can lead to increased water
Kp is the dissociation constant reducesfor the risks
oftenassociated
overlooked. with changing
This is process
the riskconditions such as temperature and
of carry-over.
cheap and effective for the intended purpose of neutralising HCl. Water wash also
the salt, which is a strong chloride function salt formation
concentrations, assuming inthat thetheatmospheric Entrained
water wash rate is adjusted water from
to account for the accumu-
reduces the
of temperature. risks and
Pamine associated
PHCl with
are changing process conditions such asistemperature and carries dissolved salts with it.
upward shifts tower when
in overhead overhead
temperature. water
When water recy-
wash islator
injected close to the
the partial pressures
chloride of the
concentrations, amine injection
assuming
neutraliser cled
that the back
water washto the
point, there
ratedesalter.
is adjustedAmines
is practically
to account for
speaking no amount Whenof the salts are
neutraliser that carried back to
and HClupward respectively. The value
shifts in overhead of are When
temperature. organic water bases,
wash and as such
is injected closethey
to the the tower with wet reflux, they tend
could be added which would lead directly to salt formation in the overhead system.
Kp defines the maximum
neutraliser amount
injection point, thereofis practically
have atspeaking
least some no amount affinity for the thatto deposit on the trays as the water
of neutraliser
amine and HCl that can exist There
in is
the a risk, however, that is
hydrocarbon often overlooked.
phase. How much Thisof is theboils
risk ofoffsalt formation in theselection can
. Neutraliser
could be added which would lead directly to salt formation in the overhead system.
vapour phase at that temperature. atmosphericIf tower
the amine partitions
when overhead water into the crude
is recycled back toimpact howAmines
the desalter. the resulting
are problems
the product Thereofis the
a risk, however,
partial that is often overlooked.
pressures Thisthe is the risk ofissalt formation in the
organic bases,oil andrather
as such than
they havewater primar-
at least some manifest
affinity for themselves
the hydrocarbon phase.(corrosion or
of the amine and tower
atmospheric chloride
whenpresent
How much of ily
overhead water ais recycled
the amine function
partitionsof
back tothe distribution
the desalter.
into the crude
Amines are
oil rather than fouling).
the waterChanging
is primarily neutraliser
a will
is greaterorganic
than bases,
the dissociation
and as such con-
they have coeffi cient
at least some andaffinity
the for relative rates of phase.
the hydrocarbon not typically undo any fouling that
function of the distribution coefficient and the relative rates of crude oil and wash water.
stant Kp How thenmuch
saltsofwill form.partitions
the amine If the into crude oil oil
the crude and wash
rather water.
than the waterWater
is primarily hasa occurred prior to the change,
temperature where the saltsWater formentrainment
is entrainmentfrom the desalter also increases the effective amount of partitioning
from the desalter also although it can stop it from getting
function of the distribution coefficient and the relative rates of crude oil and wash water.
ahead of the bulk water dew to thepoint
desalted increases
crude. the effective amount of worse.
Water entrainment
then a corrosive salt phase will from the desalter also increases the effective amount of partitioning
The form.
distributionpartitioning
coefficient, D, toisthe
thedesalted
ratio of thecrude.
solute concentrationFor units withtono
in octanol thewater wash the
Ironically, thedesalted
to the productcrude.usedsolute
to con- The distribution
concentration in water: 1 coeffi cient, D, is risks are a bit diff erent. The primary
trol corrosion can helpcoefficient,
The distribution cause corro-D, is the the
ratioratio
of the of the concentration
solute solute concentrationin octanol to the risk of salt formation is in the over-
sion if misapplied.
solute concentration in water:1 in octanol to the solute concentra- head system itself. Without a water
The following discussion covers tion in water:1 wash to force the dew point, the salt
a number of different crude tower forming characteristics in the over-
design and operating parameters head system are closely linked to
[2]
that can impact neutraliser selection: [2] the type and amount of neutraliser
• Overhead water wash vs no water used as well as the amount of chlo-
[2]
wash rides present. As these values go up
q2 procorr.indd 2 15/03/2021 12:13

and down, the corrosion risk is con- where neutraliser demand is being MEA is the primary amine that
stantly changing as well. estimated based on the amount of is common as both a tramp amine
From a practical standpoint, there acids present, such as in a chemical and a neutralising amine. Refineries
should never be more neutraliser bid process, the amine recycle usu- that use MEA in their amine treat-
recycling back to the crude tower ally does not need to be accounted ing system or which have prob-
than is present in the overhead sys- for except to the extent that hydro- lems with H2S scavengers in their
tem, so the highest risk for salt for- carbon solubility renders the amine crude supply, should avoid the use
mation is in the overhead system unavailable to neutralise acids in of a neutraliser product containing
and not the tower when no water the water phase. MEA. In addition to the salt forma-
wash is employed. When trying to tion risks mentioned previously,
use an ionic model to estimate the Tramp amines having multiple sources of MEA
salt point, great care must be taken Tramp amines can make it into can make the challenge of trouble-
to use the correct quantity of amine. the crude unit from four primary shooting MEA related contamina-
One approach is to measure the sources – slop, make-up water to tion problems difficult.
actual amine concentration in the the desalter, neutralisers in the
overhead accumulator boot water, steam supply, and H2S scavenger Overhead temperature
but most refineries do not have treated crude. Slop systems are Overhead temperature plays a dual
the capability of doing that analy- most likely to pick up the amines role in impacting amine behav-
sis. If significant salt is forming in used in the refinery treating systems iour in a crude column. Firstly, the
the overhead system, the overhead – typically MEA, DEA or MDEA. amount of amine that can be present
water, however, will not reflect the Similar to slop, treating amines in the overhead system before salts
total amine present because some can end up in the sour water sys- form is a strong function of temper-
of it is depositing as salts in the tem and make it to the crude unit ature. Secondly, the temperature
condensers. A second approach when stripped sour water is used can have a significant impact on the
is to use the measured chlorides as desalter wash water. Neutralisers amount of hydrocarbon leaving the
and the actual neutraliser injection are amines added to steam to pre- top of the column.
rate. This approach, however, does vent acidic condensate formation. Kp is a function of temperature for
not take into account the recycle of For best control and troubleshoot- ammonia.2 Over the temperature
neutraliser back to the crude tower ing, different amines should be used range from 200 to 300°F where most
via the desalter or reflux (either via in the steam and crude overhead crude tower overheads typically
entrained water or neutraliser sol- neutralisers. operate, the value for Kp increases
ubility in hydrocarbon). For units Crude oil that has been treated by roughly an order of magnitude
that use an alkanol amine (such as with triazine will contain either for every 30°F increase in tem-
MEA) and have desalters that oper- MEA or methyl amine depending perature. For constant pressure,
ate with an acidic pH, this second on which amine was used to man- vapour rate, and chloride content,
approach may be reasonable. For ufacture the product. MEA is by this change in Kp with temperature
units that have desalters operating far the most common amine found means that every 30°F increase in
at high pH and/or that use alkyl in H2S scavenger treated crude oil overhead temperature would allow
amines in their neutraliser, this today. Triazine is also sometimes a 10x increase in ammonia before
approach can lead to under-predic- used to reduce the H2S load to solid ammonium chloride would
tion of the salt point and the result- the flare stack. Great care should start to form. While the absolute
ing overhead corrosion risk. In this be taken to ensure that the MEA values of Kp will be different for
case, a third approach is to use the byproduct of flare system scaveng- amines, Kp would still be expected
actual neutraliser injection rate plus ing cannot end up back in the crude to undergo similar relative changes
an estimate for the amount of amine unit. with increasing temperature. Ionic
recycle based on desalter operating Amines mostly behave inde- modelling can be used to quantify
conditions and/or estimated recy- pendently of each other when cal- this effect.
cle via reflux. The best (most con- culating salt points, so with regards As the crude tower overhead tem-
servative) overall approach is to to neutraliser selection the primary perature increases, the total volume
use the larger overhead amine rate concern is when the tramp amine of hydrocarbon going overhead
as estimated from both the actual is the same as one of the amines in would be expected to increase at
injection plus estimated recycle and the neutraliser. In that situation, the a constant crude charge rate and
amine rate estimated from the boot amine sources can become addi- composition. The increase in over-
water concentration plus estimated tive in nature, thus increasing the head hydrocarbon decreases the
recycle. salt formation risk. For instance, in partial pressure of any amines and
This latter approach should pro- a crude unit that uses a neutraliser HCl present, which has the effect
vide the most realistic estimate of containing MEA, the MEA partial of decreasing the potential for salt
the real salt formation potential of a pressure is calculated based on the formation. The effect on salt forma-
given neutraliser. Any neutralising MEA in the neutraliser plus the tion potential of increased hydro-
amine recycle reduces the amount MEA entering the crude tower via carbon decreasing contaminant
of neutraliser needed, so in the case tramp sources. partial pressures is normally much
q2 procorr.indd 3 15/03/2021 12:13

cally significantly more expensive
100% than single amine products, but
Ammonia the costs are normally easy to jus-
90% Ethylenediamine (EDA) tify based on the improved oper-
Monoethanolamine (MEA)
80% Dimethylethanolamine (DMEA) ating flexibility. Blended amine
Percent of amine in oil phase
Diethanolamine (DEA) neutralisers are especially valuable

70% Methylethanolamine (MDEA)
Methoxpropylamine (MOPA) to the refiner trying to maximise
60% Morpholine diesel production, which normally
Ethylmorpholine
involves operating the crude tower
50%
overhead temperature as low as
40% possible to minimise naphtha yield.
Some refineries will use a lower
30%
cost neutralising amine when the
20% refinery is operating in a maximum
gasoline mode and an amine blend
10%
when in a maximum diesel mode to
0
0 1 2 3 4 5 6 7 8 9 10 11 12
lower neutraliser cost without sub-
pH
stantially increasing corrosion risk.
Desalting
Figure 2 Desalter partitioning characteristics of some common amines As mentioned previously, when
Taken from An In-Depth Look at Amine Behavior in Crude Units Using Electrolyte-Based Simulation, atmospheric tower overhead water
NACE Paper No. 05570.3 is used as desalter wash water,
some of the amine will partition to
smaller than the impact of increas- choosing a neutralising amine. For the crude oil phase in the desalter
ing temperature on Kp. The inverse, a low crude tower overhead tem- and end up in the atmospheric
however, is also true. Decreasing perature, a neutraliser with a strong tower. Routing the overhead water
the overhead temperature decreases affinity for the aqueous phase in to the sour water stripper (SWS) can
the hydrocarbon partial pressure the desalter and a low salt forma- greatly reduce the risk through dilu-
(increases PHCl and Pamine) and at the tion potential (high value of Kp) is tion, but it will also consume addi-
same time decreases the value of Kp required. Often times in such sys- tional energy and SWS capacity. If
(decreases the amount of allowable tems these dual objectives cannot stripped sour water (SSW) is then
HCl and amine before salts start to be met with a single amine so the used as desalter wash water there
form). chemical supplier is forced to use will still be neutralising amines in
In terms of neutraliser selection, a blend of amines to minimise salt the SSW, but at a lower concentra-
the lower the overhead tempera- formation risk in the crude column. tion than if the overhead water were
ture is, the less flexibility there is in Blended amine products are typi- routed directly to the desalter. The
neutralising amines will have been
diluted by other water sources feed-
100% ing the SWS.
Methylamine
Figures 2 and 3 show the typical
90% Diethylamine partitioning behaviour of a variety
of amines in a desalter.3 The actual
Ethylamine
80% Isopropylamine
percentage of a given amine that
Percent of amine in oil phase
n-Propylamine
70% Trimethylamine
Diethylamine
goes out with the desalted crude
60% Isobutylamine will depend on the amine, the per-
n-Butylamine
sec-Butylamine
centage of wash water used, the
50% n-Pentylamine temperature in the desalter, and the
40% pH of the desalter water. The crude
oil used may potentially have a
30%
small impact as well. These figures
20% are indicative only because they
were generated for a system with
10%
a specific hydrocarbon composi-
0 tion, percentage of wash water, and
0 1 2 3 4 5 6 7 8 9 10 11 12
temperature.
pH
These figures clearly show that
both the pH and nature of the
Figure 3 Desalter partitioning characteristics of common alkyl amines amine compound play critical roles
Taken from An In-Depth Look at Amine Behavior in Crude Units Using Electrolyte-Based Simulation, in determining how the amine will
NACE Paper No. 05570.3
behave in a desalter. Alkyl amines
q2 procorr.indd 4 15/03/2021 12:13

tend to have a much stronger affin-
ity for hydrocarbon than do the
alkanol amines. The oxygen func- Original neutraliser injection point
tionality in alkanol amines greatly X1
enhances their affinity for the
aqueous phase in a desalter. When
X2
selecting the neutralising amine, it Crude for preheat
is important to understand where Crude Water wash and revised
the crude tower overhead water Tower neutraliser injection point
is going to be routed and the over- X3
all quality of the wash water (pH) Ovhd
used in the desalter. Routing over- X4
Accum
head water directly to the desalter Cooling water
and running the desalter with

high pH wash water both tend to
reduce the flexibility in neutralising
amine selection. Routing overhead
water to the SWS and maintaining Figure 4 Overhead system for Case 1
low desalter wash water pH allow
greater flexibility in neutraliser ing objectives can sometimes be in • If the second criteria cannot be
selection at the cost of creating addi- conflict with each other, thus requir- met a water wash is needed to pre-
tional SWS feed, and potentially the ing costs and benefits to be weighed vent corrosion and fouling.
need to acidify the desalter wash very carefully. To minimise the There are also a number of addi-
water. amount of neutraliser that goes to tional design considerations that
Some refineries will inject an acid the desalter, it would be desirable to are beyond the scope of this article,
into the desalter to lower the wash route the overhead water to the sour such as filmer injection and water
water pH and reduce the partition- water stripper first instead of going wash system design.
ing of amines into crude oil. Acids directly to the desalter. Sour water Other factors such as shock con-
commonly used for this purpose strippers, however, often inject caus- densation, neutraliser injection
are citric, acetic, and hydroxy acids tic into the feed to enhance ammonia location, and variable operating
such as glycolic acid. Besides add- stripping, resulting in relatively high conditions can also impact neutral-
ing substantially to the refinery pH stripped sour water. The bene- iser selection. Failure to properly
chemical costs, the acids can each fit of reduced amine to the desalter consider the actual conditions that
create their own set of negative must be weighed against any nega- can exist either in normal operation
side effects.4 Desalter acidification tive impacts on partitioning behav- or during abnormal operational
can lead to overhead corrosion, iour due to higher pH of stripped periods can result in corrosion from
increased neutraliser consumption, sour water feed to the desalter improper neutraliser selection or
fouling, and increased BOD/COD instead of tower overhead water. through injecting the neutraliser at
loading on the wastewater system. Also, the impact on sour water strip- the wrong location.
While use of acids to lower desalter per capacity utilisation and operat- These issues can best be illus-
wash water pH can be beneficial, it ing cost need to be factored into the trated through the use of some real
is critical that the refiner makes sure analysis. life case studies.
that the cure is not worse than the With these key considerations in
problem being addressed. neutraliser selection in mind, let us Case 1
More recently, Dorf Ketal has look at some basic principles in the The refinery in Case 1 has a crude
introduced an aldehyde based design of overhead systems and tower overhead system (see Figure
reactive adjunct chemistry into the some examples of how to apply this 4). The unit processes a high salt
market. The chemistry converts the information. content crude in a single stage
amine to a non-salt forming, water desalter, and overhead chlorides
soluble imine. The amine conver- Design principles for overhead average 150 ppm. The overhead
sion has the beneficial side effect corrosion control temperature at the time when the
of lowering the pH of the water Some basic principles in the design problems occurred ranged between
in the desalter without the need of the corrosion control system for 280°F and 300°F (138-149°C). The
for acid injection and its negative crude tower overheads are: first two exchangers in the over-
side effects. Initial trials of the new • Inject the neutralising amine head system, X1 and X2, are raw
chemistry have been promising, but ahead of the first point where it is crude vs overhead exchangers with
more time is required to fully evalu- possible to form liquid water in the titanium bundles and carbon steel
ate the impact of this new chemistry system. shells.
on refinery operation. • Select a neutralising amine that To maximise crude preheat and to
When deciding how to design and does not form a separate salt phase reduce the quantity of wash water
operate the crude unit, the operat- ahead of the water dew point required, the wash water is injected
q2 procorr.indd 5 15/03/2021 12:13

point of 204⁰F (96°C, from which the
250–279 (Avg = 265) conclusion was that shock conden-
sation of water was not a concern.
X2 In reality, though, the lowest
202–279 (Avg = 244)
Channel tube wall temperature had to be
much lower than predicted as evi-
denced by the temperature survey
156–218 (Avg = 180) Coldest temperatures
results shown in Figure 5. During
near tube inlet a time period when the insulation
was off X-2 for an automated ultra-
Figure 5 Skin temperature profile on X-2 sonic thickness (AUT) inspection, an
infrared temperature survey of the
between the crude vs overhead shell. During that downtime, cor- shell was also performed. The most
exchangers and the water coolers. rosion was discovered on the X-2 interesting thing to note was that
Historically, the neutralising shell and corroded areas were built the temperature along the bottom of
amine had been injected ahead of up with weld overlay to full shell the shell averaged only 180°F (82°C)
the first exchanger. Because of the thickness of 0.28 in. Six weeks after compared to a measured outlet
high chlorides, amine chloride salts the exchangers were put back in ser- temperature of over 260°F (127°C).
formed in the first two exchangers, vice, the X-2 shell holed through. This temperature data indicates
and they suffered high, chronic cor- During the root cause analysis that the liquid which condensed
rosion rates of 0.75-2 mm/y on the that followed the event, several on the upper tubes in the bundle
shells and outlet piping. The tita- interesting contributing factors continued to subcool as it flowed
nium bundles did not corrode, but came into play. Firstly, the chemi- down the bundle and that it did not
the neutraliser formed liquid amine cal supplier based water dew point mix uniformly with the rest of the
chloride salts which flowed off of calculations on normal operation of vapour in the exchanger.
the bundles and onto the CS shells the tower overhead system. With This temperature along the bot-
and outlet piping where aggres- more detailed analysis of the oper- tom of the exchanger is representa-
sive corrosion occurred. The chem- ating data, it was determined that tive of the liquid film that forms on
ical supplier modelled the system about 2% of the time the water dew the tube surface, which is signifi-
and determined that the water dew point would actually be expected to cantly different from the bulk tem-
point would not occur in the first occur in X-2 based on the vendor’s perature that a process simulator
two exchangers so that, if no neu- predicted minimum tube wall tem- would calculate or the temperature
traliser were present, the corrosion perature in X-2. indicator in the outlet line would
should go away. The second finding was that tem- measure.
Two months after the neutral- peratures in the exchangers were One approach to estimating the
iser injection was moved to the significantly cooler than the chem- coldest tube wall temperature is
water wash downstream of the ical supplier had predicted. Their to take the average of the cold
first two exchangers, X-1 and X-2 calculations had predicted a min- stream inlet temperature and the
were taken out of service during a imum tube wall temperature of hot stream outlet temperature. In
planned shutdown to replace X-1’s 214°F (101°C) and a water dew this example, if the outlet tempera-
ture is 260°F (127°C) and the crude
inlet temperature is 80°F (27°C), this
is first exchanger coming in from
Filmer
Neutraliser
the tank farm, the coldest tube wall
temperature would be estimated at
X-1-1 X-1-2 170°F (77°C), which is reasonably
To frac To frac close to the temperature measured
Water wash Water wash along the bottom of the shell in this
Crude X-2-1 X-2-2 case.
Tower In this case, when the neutraliser
C-1
Frac feed injection was relocated, the neutral-
X-3-1 X-3-2 iser was no longer being injected
ahead of the water dew point, and
extremely aggressive corrosion
X-4-1 X-4-2 occurred. In many systems without
Cooling water Cooling water
a water wash, the second objective
cannot be met and corrosion will
occur due to salt formation, which
To accumulator
was the case in this system before
the neutraliser relocation was done.
Figure 6 Overhead system for Case 2 In some systems, there is a lot of
q2 procorr.indd 6 15/03/2021 12:13

naturally occurring ammonia or
there are tramp amines present, and
a salt point is reached ahead of the 270
neutraliser salt point. In such sys-
tems, a water wash is the only prac- 250
tical approach to preventing salt
formation. 230
Corrosion risk Supplier 2
Case 2 210
This crude unit had two banks of Supplier 1
exchangers that used crude tower 190

overhead to preheat feed to another
column (see Figure 6). Water wash Est. Tube wall temperature
170
was injected between the first and Turnaround
OH temperature
second exchanger in each bank. The

150
exchangers had titanium bundles
and carbon steel shells, and the top
exchangers in each bank (X-1-1 and Figure 7 This graph indicates that after the neutraliser change there was an extended
X-1-2) had long term corrosion rates period of time when the estimated salt point was significantly higher than the tube
of approximately 0.38 mm/y. wall temperature
A routine inspection a year after
a turnaround revealed that the was estimated that the lower con- range of process conditions and
average corrosion rate since the centration of amine A in supplier 1’s actual local conditions in the piping
previous turnaround had acceler- product reduced the salt point of A and exchangers. Simply relying on
ated to over 3.8 mm/y in the area by about 15°F. a bulk temperature predicted from
highlighted in red in Figure 6. This Those approximate salt points are a simulation or temperature indica-
change in corrosion triggered much plotted along with the estimated tor output may not accurately rep-
more frequent inspection, which minimum tube wall temperature in resent the actual conditions when
soon determined that the real corro- Figure 7. In the time before the turn- corrosion may occur. Additionally,
sion rate was more like 12.5 mm/y. around, the minimum wall temper- the presence of tramp amines in
A number of possible causes were ature and the salt point were very the unit and the potential to recycle
explored, but the final conclusion close to each other. When supplier 2 amines to the crude tower via the
was that a neutraliser change that took over and switched neutraliser desalter can further complicate the
had occurred when the refinery products, the salt point became sig- neutraliser selection process. If the
changed chemical suppliers caused nificantly higher than the minimum refiner and chemical supplier make
the corrosion in these exchangers. tube wall temperature, which signif- the effort to consider all of these fac-
Neither supplier had been rou- icantly increased the amount of salt tors when selecting their neutralis-
tinely tracking salt points in the that would have formed and thus ing amine, a lot of future problems
overhead system, which made the the amount of corrosion. can be avoided.
analysis more difficult. During As an interim measure, the chem-
the time frame in question, there ical supplier switched to a multiple References
did not appear to be any change amine blended neutraliser prod- 1 Peterson P R, et al, Choosing a neutralizing
in overhead chlorides or other key uct to at least get back to historic amine corrosion inhibitor, PTQ, Summer 2004.
variables that could be linked to corrosion rates. Ultimately, the 2 Stephenson C C, The dissociation of
ammonium chloride, The Journal of Chemical
corrosion in these exchangers. refinery decided to upgrade the
Physics, Vol. 12, No. 7, Jul 1944.
After the turnaround, the over- metallurgy on the shells to eliminate
3 Lack J, An in-depth look at amine behavior in
head temperature averaged 8°F the chronic corrosion problems and crude units using electrolyte-based simulation,
hotter than it had before the turn- to increase operating flexibility. NACE Paper No. 05570, 2005.
around, which normally would 4 Lordo S, et al, Desalter acidification
reduce corrosion risk, although the Conclusions additives and their potential impacts on crude
change in estimated tube wall tem- Making the proper selection of units,NACE Paper No. 08556, 2008.
perature was small (see Figure 7). neutralising amine chemistry is a
Supplier 1 had been using a three- challenging task at many refiner-
Eric Vetters is the President of ProCorr
amine blend (amines A, B and C). ies, especially with the wide range
Consulting Services LLC in Owasso, Oklahoma.
Supplier 2 elected to use a single of opportunity crudes available in
He spent 33 years working for a major oil
amine product that used only amine the marketplace. Besides traditional company in a variety of refinery process
A. As part of supplier 2’s trouble- considerations like cost and base engineering and corrosion positions. Since
shooting effort, they did several strength, a number of other factors 2014 he has run his own consulting business
salt point calculations that showed need also to be considered. Making providing process and corrosion services for
a typical salt point of about 215°F good decisions also requires a refineries.
(102°C) for neutralising amine A. It detailed understanding of the full Email: ewvetters@yahoo.com
q2 procorr.indd 7 15/03/2021 12:13

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ohl.indd 1 10/03/2017 16:12

Energy network monitoring and optimisation
A software program for optimisation of an energy network supports decisions on
equipment use in refineries that produce and import power
ELIF GÜL GÖÇER, ELIF MELEK ÖZTÜRK, GÜLŞEN ŞAHIN ANDAŞ, YAHYA AKTAŞ and ELIF METE
Tüpraş
O
ptimisation of energy costs ware. However, the software did nc = (T2s-T1)/(T2-T1)
and use is among the most not exactly match refinery configu-
important factors affecting rations, and software updates could where T2s is the isentropic outlet
operating expenditure and compet- not be adapted by the end user. temperature of the compressor, and
itiveness in the refining sector. In Eventually, the expected results T1 and T2 are the inlet and outlet
order to reduce energy costs, there could not be achieved by the soft- temperature of the compressor.
are many options to consider such ware. The most important objective The work done by the compressor
as benchmarking internal and exter- of the program developed here is to is calculated using:
nal best practices and optimising provide a decision support system (
+, -
the use of existing capacity. that reflects the refinery in a realis- 𝑊𝑊" = 𝐶𝐶%& 𝑇𝑇( (𝑟𝑟%
+,
− 1)/𝑛𝑛3 𝑛𝑛4
We think we can do this through tic way, and determines the load at
a new conceptual framework, which equipment should operate where Cpa is the specific heat of air,
energy optimisation, which means with which type of fuel. In addi- γa is a constant(1.4), nm and nc are the
using – and not using – energy in tion, the program is able to produce, mechanical and isentropic efficiency
the refinery to maximise the reliabil- buy, or sell output for electricity of the compressor. Energy balance
ity of processes for both safety and trade on an hourly basis by taking around the combustion chamber is
economic performance. For this rea- into account the electricity/steam expressed using:1
son, Tüpraş refineries operate their balance in the refinery and current
own power plants to meet energy electricity purchase/sell unit prices. 𝑚𝑚" 𝐶𝐶$" 𝑇𝑇& + 𝑚𝑚( 𝐻𝐻𝐻𝐻( + 𝑚𝑚( 𝐶𝐶$( + 𝑇𝑇( = ,𝑚𝑚" + 𝑚𝑚( -𝑇𝑇𝑇𝑇𝑇𝑇
demand.
In these power plants, energy Methodology where ma is the mass flow of air,
is produced by conventional and Within the scope of the Energy mf is the mass flow of fuel, Cpf is
waste heat boilers, and gas and Network Monitoring and Optimi- the specific heat of the fuel, HVf is
steam turbines with different capac- zation Program, an interface has the heating value of the fuel, Tf is
ities and efficiencies which have been developed wherein 25 different the fuel temperature, and TIT is the
been commissioned at different items of equipment can be selected inlet temperature of the turbine. The
times. The refineries are also con- from the palette by means of drag shaft work produced in the turbine
nected to the local grid. Thus, elec- and drop. Power plant and process is calculated by:1
tricity traded between the refineries units are defined. 1
𝑊𝑊" = 𝐶𝐶%& 𝑇𝑇𝑇𝑇𝑇𝑇𝑛𝑛" (1 − 1 )/𝑛𝑛5
and the electricity grid is an option. When modelling process units, ./ 0
.2
In refineries, there is energy con- energy conservation, mass conser- 𝑟𝑟%
suming equipment including fur- vation, and data collected from the where nt is the efficiency of the tur-
naces, boilers, exchangers, pumps, field are used. Gas turbine model- bine and γg is a constant value of
and compressors. Different types ling is described in this section. A 1.33. The network can be calculated
of fuel can be fired in the furnaces gas turbine compresses air for the from the difference between Wt and
and boilers. The energy demand of combustion process. High pres- Wc.
pumps and compressors is supplied sure and high velocity gas expand
by turbines or electrically driven through the turbine to produce Steps in optimisation
motors. When electricity and steam work. During the compression of The optimisation program consists
demand and production costs are air, the ratio of compression is cal- of three main components:
considered, the need for a decision culated by:1 • The database
support tool which ensures effective • Modelling and optimisation
management of the utility system rp = Pr2/Pr1 • Interface and reporting
arises. Hence the Energy Network
Monitoring and Optimization where, rp is the compression ratio, The database
Program has been developed. and Pr1 and Pr2 are the inlet and outlet At this stage of the project, adapters
Previously, energy optimisation pressure of the compressor. The isen- that are independent of each other
was performed via commercial soft- tropic efficiency is calculated by: 1 and which collect data from differ-
Q2 tupras.indd 1 15/03/2021 12:37

ent data sources were developed. analyses were performed for the • The optimisation results were
The process data measurements are equipment in the system, and inde- compared with past production
impaired due to errors in measure- pendent variables that could affect plans, and software deficiencies
ment, processing, and transmission. their performance were deter- were eliminated.
These errors can be classified as gross mined. Through the process data In the program, general algebraic
errors and random errors. Gross source, historical data of determined modelling system (GAMS) software
errors include major errors caused by dependent and independent var- is used as the platform for an optimi-
sensor calibration shifts, sensor sur- iables was collected. By means of sation solver. The objective function,
face contamination, and sensor fail- regression analysis based on the his- parameters, and linear equipment
ure. Random errors are minor errors torical data, dependent variables that models were transferred to the plat-
caused by noise and external condi- affect equipment performance and form. The objective function, the
tions. These errors lead to inconsist- their strength of impact were deter- models of equipment, and other con-
ency in measurement and refinery mined. As a result of this study constraints consist of linear equations
applications, such as simulation and ducted on a SPSS statistics program, and inequalities. Since the decision
optimisation, and decision support the sensitivity of models was com- variables are continuous and consist
systems that use these measurements pared with the field data. of integer variables, a mixed integer
produce false results. In order to create equipment mod- linear programming (MILP) method
The detection of gross errors is els, an infrastructure was developed was preferred and the CPLEX 12
performed using various filters in which the thermodynamic prop- solver was used. The GAMS based
for these data. The data is filtered erties of water, steam, and fuel rings CPLEX solver uses branch-bound
according to upper and lower lim- can be defined. Thus composition, and branch-cut algorithms.
its and measurement quality. The density, enthalpy, entropy, and heat
effect of an error is reduced by capacity are calculated instantly. The User interface and reporting
using the last good value or a safe efficiencies of equipment and model The interface and reporting were
value instead of the detected error. parameters may vary according to developed as user friendly models.
In addition, data received in differ- the characteristics of the utility ring. Some 25 different items of equip-
ent units is adapted to the SI system Thanks to this infrastructure, models ment could be chosen from the pal-
to ensure integrity between data. of equipment compatible with the ette by a drag and drop method,
The equipment in the energy field have been created. flow diagrams could be created, and
network is defined in the diagram After a detailed regression anal- there is access to online field data.
developed within the program. The ysis for each item of equipment, an Optimisation results could be com-
identified equipment, rings, and optimisation model covering the pared by reports.
parameters are stored in the SQL whole utility system was devel- Equipment on the palette could
database. Refinery, process, and oped. The objective of optimisation be easily identified visually to add it
equipment ontologies are designed is to assemble a production plan in to flow diagrams. Simple flow dia-
in order to make collected data order to produce steam and electric- grams are created by adding equip-
meaningful. In this way, how much ity which are required by the refin- ment to the diagram. Each time a
utility each equipment produces ery at the lowest cost. The methods new item of equipment is added,
or consumes and the total energy and practices in this context are: the system requests and records its
demand of a refinery for a given • The constraints of equipment and name, unit, and equipment specific
time are determined. The data process units have been identified. data. The names and connection
warehouse had been designed for At this stage, the operating ranges points of equipment can be easily
the storage of collected and seman- of equipment, emission limits, and revised or deleted.
tically related data. The average risks that could endanger refinery There are equipment pages
hourly data from process is stored operations were studied. including design and technical
in the data warehouse. This archive • Independent variables to be used parameters. Detailed data required
provides the opportunity to conduct in optimisation were decided. These for modelling and optimisation can
studies related to past data. variables include whether an item be entered, controlled, and revised
of equipment is operated, its operat- through these equipment pages.
Modelling and optimisation ing load, and its mode of operation. Using the interface, a user can list
Equipment that produces and con- • Algorithms that perform sensi- all online field data and optimisa-
sumes energy, such as boilers, gas tivity analyses for the optimisation tion reports including a required
and steam turbines, waste heat boil- algorithm and achieve global min- optimisation action list. In addition,
ers, turbines, and electrically driven ima instead of local minima have since the previous data is stored,
motors, are defined within the scope been tested in complex equation the user can obtain the field data of
of the program. In order to build an systems. any defined time period using the
optimisation model, firstly the inde- • The objective function of an opti- interface. Besides optimisation of
pendent and dependent variables misation model is to minimise the online field data, the user can study
of equipment and the relationship sum of fuel costs, costs occurring the optimisation of offline case stud-
between them must be determined. during equipment switch, and risk ies, what-if scenarios, and feasibility
Therefore detailed thermodynamic costs. analysis for future investments:
Q2 tupras.indd 2 15/03/2021 12:37

REFINING
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TECHNOLOGY CONFERENCE
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ref india ad new v5.indd 1 24/02/2021 10:36

1. Reporting stack gas emissions: various filters within the error detec- gas emissions arising from planned
emissions from the stack gases of tion mechanism. Measurement error, actions. This information can be
furnaces and boilers can be fol- communication error, and other user used in the carbon market, in which
lowed by the program. Also, any types are informed. Turkey may be included.
limits of emissions can be defined.
8. Offline scenario analysis: for 14. Multi-period optimisation: the
2. Diagram application: using the a feasibility study for a planned program has a sub-structure of
diagram, equipment can be added investment in the field or to study hourly period optimisation instead
by a drag and drop method, defin- different scenarios, the user can of instant optimisation.
ing any connections between equip- change the diagram, run the optimi-
ment. Models of the equipment sation, and observe the effects of the 15. Closed circle application: optimi-
can be entered or recalled from the changes on refinery balances and sation results can be applied in the
database, and their parameters can energy costs. field by control tools without an
be defined to equipment models. operator. Tüpraş’ process security
Setting up flow diagrams using the 9. Energy performance indicators: as procedures do not allow this kind of
equipment’s optimisation studies in the other applications, it is pos- application.
can be applied. sible to calculate and report key
performance indicators such as Output and results
3. Sensitivity and cost analysis: elec- equipment efficiencies and energy The Energy Network Monitoring
tricity is produced from gas tur- consumption. and Optimization Program is a
bines and steam turbine generators, decision support system to enable
and steam is produced from con- 10. Live access to field data: unlike the supply of refinery steam and
ventional boilers and waste heat other software, it is able to commu- electricity at minimum cost and
boilers of gas turbines. Since each nicate with different refinery data- least environmental effect by live
item of equipment has a different bases without requiring manual monitoring of energy producer and
efficiency, it is difficult to separate access to other historian databases consumer equipment in the energy
the fuel costs for steam and electric- and applying adapter software at network. In the scope of the devel-
ity. Using this software, marginal the stage of accessing field data. oped user interface:
costs and average costs of steam • Equipment relationships are
and electricity can be easily calcu- 11. Data filtering: as in other applica- established from the flow diagram
lated and reported. tions, the minimum and maximum created by drag and drop.
limits for field data are defined and • Equipment models and model
4. Equipment library: there is an the data is filtered. The major advan- parameters are determined.
equipment library containing data tage of the program developed for • Different sources of field data are
for 25 different types of equipment. Tüpraş is that it eliminates depend- accessed.
When new equipment is added to ency on outside and is open for new • Optimisation study reports are
the diagram, default parameters development. If needed, below prop- obtained for required time intervals.
and formulations can be taken from erties can be added to the program The aim of the optimisation stud-
the library and any revisions can be and usage range can be expanded. ies is that the refinery’s energy
applied. needs are met by using fuel
12. Electricity cost management: the resources more efficiently. Increased
5. Integrated historical database: the software can be run iteratively by energy efficiency by optimisation
application automatically obtains the user to create different scenar- also decreases flue gas emissions.
the hourly average only field data ios for different electricity prices With the help of a SOx limit
and keeps it in the database. This and quantities. However, the user defined in the system, the use of
provides the opportunity to make has to create the proposals based on fuels with high sulphur content is
calculations using any previous the program’s results, submit them restricted. Therefore environmental
hourly field data. All historical to the market financial reconcilia- damage is avoided and penalties are
data is kept in storage, available for tion centre (PMUM), and enter the limited.
future possible project evaluations. accepted proposal as input to the Efficient management of the
software. It is useful to automate this energy network enables the use of
6. Functional reporting: in order to process given that it will be repeated water resources more efficiently and
meet the different needs of users, every day routinely and every time so decreases water consumption. The
it is possible to generate different the production plan is changed. In amount of water lost in the system or
reports using calculation results future, a tool can be developed that becoming dirty is monitored live.
made using field data as well as will communicate with the PMUM’s Tüpraş is both producer and con-
optimisation results. web server to run the process and sumer of electrical energy. Therefore
require only user approval. it is imperative to minimise costs
7. Detection and filtering of incorrect by using the electricity market effi-
field data: this is the process of pass- 13. Integration of carbon market: the ciently. Because prices agreed in
ing data taken from the field through developed software can foresee flue the market change periodically and
Q2 tupras.indd 3 16/03/2021 13:42

Base case and optimisation results of case study lectual property rights of the project,
a patent application has been made.
Base case Optimisation result
Steam Turbine Generator-1, MW 5.0 0.0 1 Mete E, M Turkay, Energy Network
Steam Turbine Generator-2, MW 6.5 0.0 Optimization in an Oil Refinery, Proc. PSE 2018,
Steam Turbine Generator-3, MW 0.0 6,0 and Mete E, Energy Network Optimization in
Steam Turbine Generator-4, MW 2.4 4.7 an Oil Refinery, Master Thesis, Koç University,
Gas Turbine-1, MW 19.9 19.9
Istanbul.
Gas Turbine-2, MW 21.3 21.3
Import power from grid, MW 4.8 8.0 Elif Gül Göçer is an Energy Management
Refinery electricity demand, MW 59.9 59.9 Engineer at Tüpraş Izmir refinery and is a junior
Steam turbine generators total, t/h 201 177.5 chemical engineer gaining orientation with
different process units.
Steam consumption Elif Melek Öztürk is Energy Management
Boiler-1 steam production, t/h 0.0 0.0
Supervisor at Tüpraş Izmir refinery. She has
Boiler-2 steam production, t/h 41.0 62.0
Boiler-3 steam production, t/h 0.0 0.0 experience in energy efficiency improvement,
Boiler-4 steam production, t/h 0.0 0.0 energy production and consumption
Boiler-5 steam production, t/h 0.0 0.0 optimisation, energy efficiency performance
Boiler-7 steam production, t/h 0.0 0,0 monitoring for different process units, and ISO
Boiler-8 steam production, t/h 78.0 63.9 50001 energy management systems. She holds
Boiler-9 steam production, t/h 80.7 50.0 a BSc in chemical engineering.
Total steam production from boilers, t/h 199.7 175.9 Gülşen Şahin Andaş is an Energy Management
Total utility operating cost, $/hr 8522.6 8114.0
Superintendent with nine years’ experience
in energy efficiency benchmarking and
Table 1 improvement studies for different units,
developing short/long term energy roadmaps,
hourly, the optimisation program four steam turbine generators are online/offline energy optimisation, and ISO
creates an output by taking into opened to optimisation for elec- 50001 energy management systems. She holds
account the refinery’s capacity for tricity production. Three of the a BSc in chemical engineering and a MSc in
engineering management.
electricity production and network steam turbine generators have both
Yahya Aktaş is Production Sustainability
electricity purchase and sale price. medium pressure steam extraction Manager at Tüpraş Izmir refinery in Turkey. He
As a result, the profitability ratio and condensate stages while the has 20 years of refinery experience, mainly in
obtained from trade with the electric- fourth has only medium pressure process improvements, furnace, and boiler
ity market has increased. steam extraction. The boilers’ load combustion control and safety systems,
and on/off status is opened to opti- burners, waste heat boilers and HC lost control
Case study misation for steam production. subjects. He holds a BSc in chemical engineering
In this scenario, the effect of an and a master of business administration (MBA).
increase in the import limit for elec- Conclusion Elif Mete is Energy Management Supervisor
at Tüpraş Head Office. She has experience
tricity from the grid is studied to The developed program has a mod-
in energy efficiency improvements, energy
establish optimum working condi- ular structure that can be applied to production and consumption optimisation,
tions (see Table 1). different sectors. It has potential for and energy efficiency performance monitoring
The refinery’s electricity import use in refining, petrochemicals, steel, for different process units, and holds a BSc in
limit is increased from 5 MW to paper, chemicals, and electricity pro- chemical engineering and MSc in industrial
8 MW, and two gas turbines and duction. In order to protect the intel- engineering.
Petrogenium.
Independent Technical and Business Consultancy for Asset Owners
Getting the most out of your assets - now and in the future
• Safety & Reliability
• Margin Maximisation & Cost Improvement
• Digital Transformation & Decarbonisation

• Training & Knowledge Transfer
With thousands of combined years experience we know what it takes to succeed
because experience matters www.petrogenium.com
Q2 tupras.indd 4 15/03/2021 12:37

WWW.ZWICK-ARMATUREN.DE
H2-Re
ady!
TRI-CON
SERIES FOR H2
APPLICATIONS
zwick.indd 1 12/03/2021 12:51

Delayed coking as a sustainable
refinery solution
Fuel grade coke is a serious environmental pollutant but the producer, the delayed
coking process, can be a contributor to future sustainable development in refineries
MARCIO WAGNER DA SILVA Petrobras

JOHN CLARK Coke Consulting Company
T
he challenge facing the refin-
ing industry in the medium Air cooler Compressor
term will be to remain eco- Fuel gas

nomically relevant in the face of & LPG
increasing process costs (heavier, Coke Coke Quench
higher sulphur crudes and environ- Drum Drum
mental emission restrictions of its Light coker

final products). Refinery production Distillation
naphtha
of automotive fuels produces heavy column

Steam
petroleum residuals, for example Feed
vacuum residue (VR). The viability Switch
valve
of refineries has historically been
primarily based on revenues gen- Pump Heat exchanger
erated by lighter fuels (LPG, petrol, Fired heater
diesel, and jet fuel). However, as
heavier crude oils are increasingly Figure 1 Typical arrangement of a delayed coking unit
processed, the volumes of straight
run VR are expected to increase. As profitability and competitiveness gasoils) from residual streams which
a consequence, refineries will have for refiners through higher refining would normally be used as diluents
to rely on hydrocracking and car- margin. in fuel oils production.
bon rejection technologies to aug- Delayed coking is a carbon rejec- The typical feed stream for
ment lighter hydrocarbon distillates, tion technology using heavy petro- delayed coking units is the residue
with associated costs. Nowadays, leum residues to produce lighter from the vacuum distillation process
the capacity to add value to the hydrocarbon distillates (inclusive that contains the heavier fractions
bottom barrel streams represents of naphtha and coker gasoil) and of processed crude oil. However,
great competitive advantage among green coke as a solid by-product. streams like decanted oil from the
refiners, especially considering such While production philosophy over FCC unit and asphaltic residue pro-
stricter regulations as IMO 2020. the delayed coking process has his- duced in solvent deasphalting can
This imposes a significant reduction torically maximised lighter distil- be in the feed stream to the delayed
in the sulphur content of marine fuel late production, its potential role as coking unit, depending upon the
oils, requiring even more capacity both a business and environmental refining scheme adopted by the
to treat bottom barrel streams, espe- enabler has to date not fully been refiner. Another possibility is to
cially for refiners processing heavier exploited. This article examines the send the residue from atmospheric
crude oils. role of delayed coking in the con- distillation directly to the delayed
In this scenario, process units text of generating environmentally coking unit; in this case, the unit
called bottom barrel processing, sustainable refinery solutions for design is modified, demanding
which are able to improve the qual- heavy petroleum residues to address greater robustness in the fractionat-
ity of crude oil residue streams (VR, future market reforms, specifically ing and gas compression section.
gas oils, and so on) or convert them in the case of fuel grade coke. Due to their thermal cracking
to higher added value products, characteristics (low availability of
gain strategic importance, mainly Delayed coking technologies – a hydrogen during the reactions), the
in countries that have large heavy general overview streams produced by a delayed cok-
crude oil reserves. These process Delayed coking employs the thermal ing unit have a high concentration
units are fundamental to comply cracking concept under controlled of olefinic compounds which are
with environmental and quality conditions to produce light and chemically unstable. Furthermore,
regulations, as well as to ensure middle streams (LPG, naphtha, and due to the processing of residual
Q2 Petrobas.indd 1 15/03/2021 12:33

streams that have high contaminants The recycle ratio varies normally
content like nitrogen, sulphur, and between 5% and 10% (in units ded-
metals, refiners that apply delayed icated to producing fuels) and the
coking units need high hydrotreat- refiner seeks to operate the unit with
ing capacity to convert these streams as low a recycle ratio as possible
into added value products which in order to maximise the capacity
meet contaminants levels accord- of the plant in processing residual
ing to the environmental regula- streams. The reactor tempera-
tion. Figure 1 shows the process flow ture is close to 430°C and is linked
scheme for a typical delayed coking to the fired heater temperature.
unit. Throughout the thermal cracking
The feed stream is fed into the reactions, the temperature falls due
bottom of the main fractionat- to the endothermic characteristics of
ing tower. Here it is mixed with the reactions.
the heavier fraction of the thermal The pressure in the reactor can
cracking products and then sent vary from 1 bar to 3.5 bar. In units
to the fired heater, where thermal optimised for producing fuels, the
cracking reactions are initiated. The variable is maintained at lower lev-
conditions are controlled so that the els. When the unit is dedicated to
reactions are completed in the coke producing high quality coke, the
drums. The residence time in the unit is operated at higher pressures.
fired heater must be the lowest pos- Reactor cycle time is linked to the
sible to minimise coke precipitation function performed by delayed cok-
in the fired heater tubes. A way of ing in the refining scheme. Units
minimising coke formation in the dedicated to producing fuels oper-
walls of tubes is steam injection to ate in shorter cycles, and units opti-
raise the velocity and consequently mised to produce high quality coke
reduce the residence time. operate in longer cycles.
After the fired heater, the feed The coke produced normally is
stream is sent to the coke drum or seen as a by-product of the delayed
reactor, where the thermal reactions coking unit; however, in some cases,
are completed and coke is depos- the delayed coking process is opti-
PROCESS AND ited. The thermal cracking products mised to produce high quality coke,
are removed from the top of the and coke becomes the principal
MEMBRANE reactor and receive an injection of product of the process.
quench with a cold process stream Depending on the feedstock qual-
TECHNOLOGY (normally heavy or middle gasoil) ity to be processed, three types of
and directed to the main fractiona- coke can be produced:
tors, where the products are sepa- • Shot coke/fuel grade coke is poor
↘ EMISSION CONTROL rated. Coke deposited in the reactor quality coke produced from feed-
is removed through a cut with water stock with a high asphaltenes and
↘ PRODUCT under high pressure (about 250 bar). contaminants (sulphur, nitrogen,
RECOVERY Delayed coking is a process that and metals) content; normally, this
occurs in batch. In order to make type of coke is commercialised as
↘ GAS SEPARATION a semi-continuous process, it is fuel.
always employed as pairs of reac- • Sponge coke: in this case, the feed-
↘ LIQUID SEPARATION tors, wherein one reactor is under stock has a lower asphaltenes and
reaction, the other is in the decoking contaminants content, and the coke
step, and so on. The delayed cok- can be directed as raw material for
ing process occurs in cycles that can anodes production in the aluminium
vary from 14 to 24 hours. industry.
www.borsig.de
The main operational variables of • Needle coke production requires
BORSIG GmbH
the delayed coking unit are: recycle the processing of feedstock with a
Phone: + 49 (0)30 4301-01 ratio, which is the quantity of the high aromatics content (decanted
Fax: + 49 (0)30 4301-2236 total feed stream that corresponds oil from the FCC, for example), and
E-mail: info@borsig.de
Egellsstrasse 21
to the heavier fraction of the reaction these products are sent as raw mate-
13507 Berlin products mixed with the fresh feed; rial for producing anodes in the steel
Germany reactor temperature, normally con- industry.
sidered in the top of the coke drum; Production of high quality coke
pressure in the top of the reactor; requires quality control of the
and the time of the reactor cycle. feed stream. In most cases, refin-
Q2 Petrobas.indd 2 15/03/2021 12:33

ers choose to install delayed coking
units focusing on the production Naphtha from delayed coking Hydrotreated naphtha
of middle and light distillates.

Therefore unit optimisation to pro- Naphtha Naphtha
hydrotreating
Catalytic
reforming
Reformate Gasoline
pool
duce needle coke occurs only in spe-
cific cases. Atmospheric
FCC naphtha
While lighter distillates generated

distillation Kerosene
column Hydrotreating
by delayed coking are further pro- Propylene Jet fuel
cessed within the refinery (to meet
Propylene
stringent petrol and diesel speci- Crude splitter
Propane to LPG pool
fications), green coke may be sold oil Light gasoil Diesel

to market as-is (fuel grade or shot
Hydrotreating
pool
coke), or calcined (needle or sponge LPG LCO Heavy
coke) prior to sale. The chemistry of gasoil
Heavy gasoil
the delayed coking process involves FCC
thermal cracking of heavy refinery Fuel oil

pool
residuals at 450-510°C in the heater Vacuum gasoil
Deasphalted oil
tubes, producing lighter distillates
Delayed coking
(naphtha, coker gasoil, and resid- Vacuum
distillation
Atmospheric
ual oil). The process also produces residue Solvent Asphaltic residue
higher molecular weight radicals Vacuum residue deasphalting
which rapidly polycondense in the

reactor at 430-490°C, forming solid Figure 2 Refining configuration relying on solvent deasphalting and delayed coking units
green coke.
For the most part, process con- ally excludes it from higher value phur based emissions, fuel grade
ditions are tailored to maximise non-fuel markets (sponge or needle coke combustion contributes in
distillate over fuel grade coke pro- coke). excess of 11 million tonnes of SOx
duction (‘white product’ mode). Approximately 91 million tonnes on an annual basis.
This involves higher temperatures, of fuel grade coke are produced • Although the calorific value of
lower pressures, and lower recycle annually. While this represents over fuel grade coke is substantially
ratios, and is enhanced by lighter 70% of global coke production, it higher than that of coal, it com-
feeds. The green coke produced is commands the lowest market value mands only 60-70% of its market
largely sold as fuel grade coke in the while generating the highest SOx value.
energy market, which is the subject emissions. Fuel grade coke is uti- • In future, if coal is replaced by
of this discussion. Alternatively, lised as a solid fuel (in cement kilns cleaner/renewable energy tech-
process conditions may be altered and power stations), releasing par- nologies, it is simply not mined.
to favour coke laydown (‘carbon’ ticulate matter, metals, SOX, NOx, However, fuel grade coke is pro-
mode) in the case of sponge or nee- and CO2 into the atmosphere. duced as a by-product of the refin-
dle coke production. The value of fuel grade coke com- ery value chain. Thus, even if it is
pared to coal (based on substantial removed from the solid fuel mar-
Fuel grade coke variation in coal qualities, averaged ket, it will still be produced. Thus to
Although considered a low value data reported in literature has been reduce its environmental footprint
by-product, fuel grade coke has spe- used) for incineration in power sta- a non-fuel application would be
cific potential to enhance the role of tions may be compared: beneficial.
delayed coking as an environmental • Fuel grade coke has a substan-
enabler. Fuel grade coke (typically tially higher calorific value than Synergies between delayed coking
18-25% of delayed coker production) coal given its lower ash content, and other residue upgrading
acts as a contaminant ‘sink’, concen- although it has a higher greenhouse technologies
trating sulphur, nitrogen, metals, gas component (emitting 10% more In some refining schemes, deas-
and asphaltenes within the solid CO2 per unit of energy produced). phalting and delayed coking units
carbon matrix. As its name implies, • Fuel grade coke has a higher sul- can be complementary technologies
it is sold into the solid energy mar- phur content (up to 7%) compared (see Figure 2).
ket based on its comparatively high to coal (typically 1-4%). In the refining scheme shown
calorific value and low ash content. • Globally, annual use of coal in in Figure 2, deasphalted oil is fed
It is sold as green (raw) coke and power stations is in the region of 8 to the FCC unit to produce LPG,
not calcined, to maximise the cal- billion tonnes. Annual production of naphtha, LCO, and so on, while the
orific value aided by hydrocarbon fuel grade coke is orders of magni- asphaltic residue is applied to pro-
volatiles (8-18%). A combination of tude lower at approximately 91 mil- duce fuel oil and asphalt. It is fun-
high contaminant (especially sul- lion tonnes. damental to understand that, in the
phur, vanadium, and nickel) levels • Although coal (by sheer volume) current scenario, the combination
and isotropic microstructure usu- is the largest source of global sul- of solvent deasphalting and FCC
Q2 Petrobas.indd 3 15/03/2021 12:33

The influence of sulphur
Hydrotreated naphtha
compounds on refinery products
Isomerisation
Sulphur may be present in
many natural forms in crude oil.
Naphtha Naphtha Catalytic Reformate Gasoline Understanding its nuances contrib-
utes to understanding its distribu-
hydrotreating reforming pool
Atmospheric HCC naphtha

tion throughout refinery processes
distillation and products. Sulphur is present
column
Hydrotreating
Jet fuel in three main forms: thiols, organic
Kerosene sulphides, and thiophenes.
Sulphur may be present as ther-
mally unstable thiols (R-SH or
Crude
oil Light gasoil Diesel
Hydrotreating
pool Ar-SH). These may be associated
with aliphatics or aromatics (as
Kerosene
side chains such as thiophenols).
Heavy gasoil
HCC Given their thermal instability, they
are typically destroyed by thermal
Diesel
Fuel oil
Coker Light pool
naphtha gasoil Heavy hydrocracking or FCC reactions to
gasoil
form H2S. Higher molecular weight
Vacuum Delayed coking thiols may form reactive radicals
(during delayed coking), crosslink-
Atmospheric distillation
residue Coke
Vacuum residue
ing with adjacent heavy aromat-
ics to form stable high molecular
weight sulphides (Ar-S-Ar). Because
Figure 3 Process arrangement with a coking/hydrocracking configuration sulphur has the same valency as
oxygen, the cross-linking reactions
is possible only for refiners with cracking refining scheme, fuel oil of phenols and thiophenols are
access to low sulphur crude oils. production is reduced to the mini- remarkably similar. These organic
Both processes are unable to reduce mum necessary. Delayed coking and sulphides typically report to the
drastically the sulphur content in hydrocracking units raise the pro- coke fraction.
the final derivatives, hence in the duction of higher value products, Thermally stable sulphur spe-
refining scheme shown in Figure 3 like naphtha, diesel, and jet fuel. cies may even survive severe FCC
significant hydrotreating capacity is The role of a delayed coking unit reaction conditions. They include
needed to produce marketable crude to process vacuum residue and pro- organic sulphides (dibenzosulphide
oil derivatives. Despite this restric- duce streams capable of conversion and dibenzodisulphide deriva-
tion, the synergy between FCC and to high quality transportation fuels tives) and orthiophene derivatives
solvent deasphalting units offers a after adequate hydrotreating reveals (a five-membered condensed ring
relatively low capital and operat- another interesting possible synergy structure, C4H4S technically clas-
ing cost alternative by comparison between residue upgrading technol- sified as aromatic heterocycles).
with hydrogen addition alternatives ogies. While in some cases delayed Processing heavier crude oils
for bottom barrel upgrading such coking and solvent deasphalting increases the concentration of stable
as deep hydrotreating or hydroc- technologies can be regarded as sulphur species (sulphide or thio-
racking units. Refiners operating competitors since both units pro- phene derivatives) both in straight
in markets with high demand for cess vacuum residue, they can also run vacuum residues and conse-
transportation fuels can achieve be complementary (see Figure 2). In quently in green coke.
high yields of middle distillates some cases, the asphaltic residue
(higher than 40%), a good result con- produced by a solvent deasphalting Delayed coking as an environmental
sidering the relatively low capital unit can be fed to a delayed coking solution and market enabler
investment when compared to the unit to maximise yields of higher The coke fraction acts as a sulphur
hydrocracking alternative. added value streams and minimise ‘sink’ (within the stable carbon
Despite the high capital cost, the the production of fuel oils. matrix) by virtue of the delayed
synergy between delayed coking The choice of residue upgrading coking process. While the environ-
and hydrocracking can significantly technology by refiners normally mental potential of concentrating
raise capacity to add value to bot- involves an economic analysis and stabilising sulphur in the coke
tom barrel streams, especially for which takes into account the refin- fraction (to reduce SOx emissions)
refiners processing heavier and ery production focus (middle distil- is evident, incinerating it as a solid
sourer crude oils. Figure 3 shows lates, light products, or lubricants), fuel essentially reverses this bene-
a coking/hydrocracking configu- the market that will be served, and fit. However, in contrast, refineries
ration to reach high bottom barrel the synergy between processes that go to great lengths (with associated
conversion. will be applied in the chosen refin- costs) to remove sulphur (as H2S)
In the case of the coking/hydro- ing scheme. from petrol and diesel derivatives to
Q2 Petrobas.indd 4 15/03/2021 12:33

digitalrefining.com is the most extensive It provides a constantly growing
source of freely available information on database of technical articles,
all aspects of the refining, gas and company literature, videos, industry
petrochemical processing industries. news and events.
dr copy 20.indd 1 15/03/2021 15:10

comply with stringent environmen- based on eco-toxicology reports is tially ‘distressed’ heavy petroleum
tal legislation. Thus, the efficacy of considered extremely low residue volumes to augment the
the aforementioned regulations on Finding a non-fuel application for production of lighter hydrocarbons.
absolute SOx atmospheric emission fuel grade coke permanently elim- Apart from hydrogenation pro-
reductions is largely diminished by inates it as a potential SOx emis- cesses, delayed coking is the only
incinerating fuel grade coke. sion source. This ‘cradle to grave’ other process with the potential to
Given the ability of delayed cok- elimination approach reinforces the stabilise sulphur. A non-fuel coke
ing to concentrate and stabilise potential for oil companies to adopt application would substantially
sulphur within the carbon matrix, a philosophy of sulphur steward- reduce SOx emissions.
the value of fuel grade coke may in ship over refinery processes. In While other carbon rejection pro-
future be interpreted less by virtue a highly competitive market, oil cesses such as FCC produce liquid
of its low market value but rather companies may benefit by diver- volumes of by-product heavier res-
as a stable environmental vehicle to sifying their product offering and idues, delayed coking is able to sta-
reduce absolute SOx emissions by marketing this sustainable initiative. bilise these high molecular weight
finding a non-fuel application. However, holding oil companies molecules within an inert solid car-
To reduce its environmental accountable for the costs of currently bon matrix.
footprint, the volatiles content of unlegislated emission initiatives Removing heavy petroleum resi-
fuel grade coke (8-18%) would would not be reasonable or econom- dues from the energy market further
require low temperature calcina- ically viable. enables fast-track implementation
tion (approximately 900°C). While Over the past two decades, the of cleaner medium term technolo-
carbon is a naturally inert mate- environmental drive to reduce SOx gies such as natural gas, with spe-
rial, calcination would densify the emissions from petrol and diesel has cific emphasis on energy efficiency
microstructure while stabilising the largely exhausted the probability and SOx emissions. Whilst there
sulphur, nitrogen, and metal con- that these products could be further is a market demand for petrol and
taminants within the carbon matrix. regulated. However, national gov- diesel, heavy petroleum residues
Low temperature calcination (espe- ernments rely on environmental sus- will be produced irrespective of
cially in a reducing atmosphere) tainability mandates to cement their current or future market disposal
would not release volatile sulphur service offering to an increasingly requirements.
compounds as the kinetics of their climate conscious electorate, while Apart from delayed coking,
dissociation from the carbon matrix at the same time guaranteeing a sus- another sustainable option may be
are associated with higher tem- tainable petrol and diesel market to convert vacuum residuals to bitu-
peratures (1500°C-1800°C). From (at least over the medium term) to men for the production of asphalt
an environmental viewpoint, this their electorate. Thus it is reasonable roads. As a non-fuel application, it
would reduce the potential for vol- that future SOx regulation will be stabilises sulphur in a thermoelas-
atile leaching into ground water enforced over high impact markets tic polymer matrix, eliminating SOx
and substantially increase the flash- (including fuel grade coke, shipping emissions. There is a global drive to
point. The coke could be used as a bunker fuels, low efficiency heavy build reliable roads, thereby enhanc-
filler in asphalt roads, construction residue fuels, and coal). Partnerships ing national transport networks.
material, resin encapsulation, or between oil companies and govern- Additionally, there is a direct cor-
landfill. ments (in the form of performance relation between the development
Finding a non-fuel based sus- based incentives) to reduce absolute of road networks and national eco-
tainable application for fuel grade SOx emissions may prove beneficial nomic prosperity. Both a bitumen
coke will require an examina- with regard to sustainability targets application and delayed coking will
tion of its environmental stability. while protecting economic refinery provide sustainable solutions to
The US Environmental Protection viability. accommodate potentially distressed
Agency (EPA) has classified the As an enabling process, delayed heavy residue volumes as they are
environmental stability of coke (as coking offers several economic and removed from energy markets.
a calcined variant) in the following sustainable benefits. As heavy petro-
manner: leum residues are slowly removed Conclusion
• Does not vaporise in ambient from energy markets (burner fuels The production of heavy petro-
atmospheric conditions or bunker fuels) due to energy effi- leum residues is an inevitable con-
• Does not react with or dissolve in ciency and emissions concerns, sequence of demand for gasoline
water delayed coking offers a sustainable and diesel. In future, energy market
• Is chemically inert processing option, thus negating the outlets for heavy petroleum resi-
• Sulphur bound within the carbon immense costs incurred by disposal dues may be curtailed due to emis-
matrix is chemically and physically in an environmentally appropriate sion concerns and competition from
stable at ambient temperatures manner. cleaner technologies. The potential
• Does not degrade when exposed When processing heavier crudes financial and environmental ben-
to light (on a straight run distillation basis), efits of delayed coking to process
• Is not biodegradable delayed coking is able to accommo- these heavy residues are immense,
• The potential environmental harm date increased volumes of poten- although they have as yet not been
Q2 Petrobas.indd 5 15/03/2021 12:33

fully exploited. In as much as green waxy oil, University of Pretoria Press, Pretoria, Marcio Wagner da Silva is a Process Engineer
coke enables delayed coking to pro- 2011. and Project Manager with Petrobras in São José
vide a stable ‘sink’ for sulphur, its 3 Clark J, MSc (Eng) dissertation: Delayed dos Campos, Brazil. He has extensive experience
incineration effectively reverses this coking of South African petroleum heavy in research, design, and construction in the oil
benefit, contributing to substantial residues for the production of anode grade and gas industry, developing and coordinating
coke and automotive fuels, University of the
SOx emissions, negating initiatives projects for operational improvement and
Witwatersrand Press, Johannesburg, 2008. debottlenecking bottom of the barrel units.
to restrict sulphur levels in automo-
4 Congressional Research Service, Petroleum He holds a bachelor’s degree in chemical
tive fuels. As cleaner, more efficient coke: Industry and environmental issues, engineering from the University of Maringa
energy technologies replace heavy 2013, CRS, www.everycrsreport.com/reports/ (UEM), Brazil, a PhD in chemical engineering
petroleum residues in fuel mar- R43263.html from the University of Campinas (UNICAMP),
kets, they will need to be processed 5 EPA, Types of economic incentive and Brazil, MBA in project management from
in an environmentally sustainable hybrid-based approaches, 2017, EPA, www. Federal University of Rio de Janeiro (UFRJ) and
manner to affect an absolute reduc- epa.gov/environmental-economics/economic- is certified in business from Getulio Vargas
tion of SOx emissions. Delayed incentives Foundation (FGV).
coking offers a realistic enabling 6 Etter R, Production and use of a premium John Clark is a fossil fuel scientist and industrial
option in terms of refinery integra- fuel grade petroleum coke, Patent publication development specialist. He has substantial
number WO2000010914A1, World Intellectual experience in fossil fuels research and
tion, distressed heavy residues, SOx
Property Organization, 1999, www.patents. sustainable product and business development.
emission targets, and lighter hydro-
google.com/patent/WO2000010914A1/en He specialises in delayed coking chemistry
carbon production to drive busi- 7 Liu G, Peng Z, Yang P, Wang G, Sulphur in coal and coke markets, and has made considerable
ness initiatives in an increasingly and its environmental impact from Yanzhou contributions in aluminium, steel, bunker fuel,
environmentally restricted market. mining district, China, Chinese Journal of heavy petroleum residues, coal to oil, bitumen,
By removing fuel grade coke from Geochemistry, 2001, vol. 20, no. 273. and energy value chains. He has lectured as an
energy markets, significant contri- 8 Petro Industry News, 2020, What is Petcoke? honorary professor on a pro bono basis at the
butions are made to reduce absolute And What is it Used For?, International Labmate University of the Witwatersrand (South Africa)
SOx emissions. Limited, www.petro-online.com/news/fuel-for- and held a seat on the executive council of
thought/13/breaking-news/what-is-petcoke- an international coal industry consortium in
Further reading and-what-is-it-used-for/33235 the USA. A seasoned international lecturer
1 Calkins W H, The chemical forms of sulphur 9 Speight J G, Heavy and Extra-Heavy Oil and industrial adviser to academic, industry,
in coal: a review, Fuel, vol. 73, no. 4, 1994, 475- Upgrading Technologies, 1st ed., Elsevier Press, and government audiences, he holds a BSc
484. 2013. in chemistry, MSc (Eng) in heavy petroleum
2 Clark J, PhD Thesis: The production of highly 10 Robinson P R, HSU C S, Handbook of shipping fuels and a PhD (Applied Materials
anisotropic needle-like coke from aliphatic Petroleum Technology, 1st ed., Springer, 2017. Engineering) in sustainable needle coke.
Q2 Petrobas.indd 6 15/03/2021 12:33

Boosting tube-side heat transfer
Tube insert technologies can improve heat exchanger performance by enhancing
tube-side heat transfer coefficients in two-phase applications
NATHAN HILL
CALGAVIN
F
or single-phase applications, flow conditions typically yield
it is generally understood that poor tube-side heat transfer coef-
tube inserts will yield the great- ficients, which subsequently limit
est benefits in viscous or otherwise the overall performance of the heat
slow-moving fluids, due to the low exchanger. In these conditions,
heat transfer coefficients arising in tube inserts can often provide sig-
laminar and transitional flow. In nificant increases in the heat trans-
such cases, it can be possible to sig- fer coefficient. Calgavin provides
nificantly optimise the design or Figure 1 hiTRAN wire matrix element a freely downloadable
being inserted in a tube software
performance of the heat exchanger. Figure
Figure 11hiTRAN
hiTRAN wire matrix
wire matrix element element tool,
being hiTRAN.SP,
inserted whichin a tube can assist
The criteria which determine being inserted into a tube with the specification of hiTRAN
whether tube inserts could be effec- elements in single-phase
tive in two-phase flow conditions applications.
are more complex than for single While multi-phase streams
phase. The presence of a second are preferentially allocated
phase necessarily introduces con- to the shell-side of a heat
cerns about phase change equi- exchanger – owing to the
libria, flow separation, and mass greater volume and design
transport. The design engineer first Figure 2 Dye injection test showing (A) laminar
Figure 2 Dye injection test showing adjustability – thereand are (B)
nevertheless
pseudo-turbulent flow
needs to consider how these factors (A) laminar and (B) pseudo-turbulent many
Figure 2 Dye injection test showing (A) laminar and (B) exceptions where allocation to
pseudo-turbulent flow
contribute to the overall thermal the tube-side is necessary. For exam-
performance, to determine whether processes. Using tube-side enhance- ple, in air-cooled heat exchangers,
For applications with single-phase fluids, the criteria to decide the suitability of tube in
the enhancement mechanism of ment can be an attractive proposi- operating with a high pressure fluid,
For applications with single-phase fluids, the criteria to decide the suitability of tube ins
a particular tube insert will use- tion if the tube-side
straightforward. heat transfer
Laminar is when using
and transitional flow expensive
conditions corrosion-re-
typically yield poor tube-s
fully improve or change the flow a limiting factor,Laminar
straightforward. and provides an sistant flow
and transitional materials, or where
conditions such allo-
typically yield poor tube-si
conditions. transfer
additionalcoefficients, which subsequently
degree of freedom in the cation would limit the overall
yield performance
a more optimal of the heat ex
This article will identify some transfer
design. coefficients, which subsequently thermal limit the overall performance of the heat exc
In these conditions, tube inserts can oftendesign.
provide significant increases in the hea
general examples of two-phase hiTRAN
In these is one example
conditions, tubeofinserts
a tube-can In oftentwo-phase
provide applications, there
significant increases in the heat
applications where tube-side coefficient.
side enhancement Calgavin provides aIt freely
technology. downloadable
are additional factorssoftware
to consider tool, hiTRAN.SP, w
coefficient.
is a type Calgavin provides a freely
due downloadable software tool, of hiTRAN.SP, wh
enhancement with Calgavin’s assist withoftheremovable tube insert
specification of hiTRAN to the added
elements complexities
in single phase applications.
hiTRAN Thermal Systems can be whichwith
assist consists of a matrix ofofwire
the specification hiTRAN mass transport,
elements phase phase
in single separation,
applications.
particularly effective. We will dis- While multi-phase
loops supported withstreams
a centralarecorepreferentially
and vapour-liquidallocatedequilibrium.
to the shell-sideA of a heat exc
cuss the underlying flow regimes While multi-phase
wire (see Figure 1). streams
The wire are preferentially
matrix tube insert allocated
will nottoonly the shell-side
generate of a heat exch
in these cases and how they are
owing to the greater volume and design adjustability – there are nevertheless many ex
generates turbulence by interrupt- turbulence but will also disrupt the
augmented. This will allow us to
owing to the
ing theallocation
greater volume
normal fluid flow,
and design adjustability
which isinterface between
– there are nevertheless many exc
the two phases,
where to the tube-side necessary. For example, in air-cooled heat exc
define some basic criteria to help the increases
where the rate
allocation to theof tube-side
convective is provide
necessary. additional
For example,contact surface
in air-cooled heat exch
design engineer decide if it would operating
heat transfer withanda high-pressure
virtually elimi-fluid, forwhen usingphase,
the liquid expensiveand altercorrosion-resistant
the mat
operating
nates the with a high-pressure
transition between fluid, when using expensive corrosion-resistant mate
be worthwhile to consider using where such allocation wouldlami-
yield aphase
morechangeoptimalbehaviour
thermal due design.to the
tube-side enhancement. nar and turbulent flow (see Figure increased
where such allocation would yield a more optimal thermal design. pressure drop. Therefore,
Various forms of tube-side heat In two-phase
2). The applications,
packing density there itare
of the wire additionaltofactors
is important considertowhich consider due to th
transfer enhancement technologies Inmatrix
two-phase applications,
can be finely adjusted totheresuit are additionalcontrols
phenomenon factorstheto perfor-
consider due to the
complexities of mass transport, phase separation and vapour-liquid equilibrium. A tu
have been used widely in industry a prescribed pressure drop, and the mance of a given heat exchanger,
complexities of mass transport, phase separation and vapour-liquid equilibrium. A tub
to help improve the performance geometry
will not onlyof the loops isturbulence
generate varied to but andwillhow thisdisrupt
also may be the affected by thebetween the two
interface
of tubular heat exchangers. The achieve
will optimum
not only performance.
generate turbulence butenhancement
will also disrupt mechanism of a tube
the interface between the two
adoption of these technologies is provide additionalwith
For applications contact surface for
single-phase the liquid phase, and alter the phase change b
insert.
provide
fluids, additionaltocontact surface for the liquid studying
phase, and alterwhere
the phase change be
driven by the need to reduce the due tothe
thecriteria
increased decide the
pressure suit- Through
drop. Therefore, cases
it is important to consider which phen
overall cost of new equipment and ability
due of tube
to the insertspressure
increased are straight-
drop. hiTRAN
Therefore, hasit is
been used in
important two-
to consider which pheno
to increase the efficiency of existing controls
forward. the performance
Laminar of a given
and transitional heatfluids,
phase exchanger,
it has been andpossible
how this to may be affecte
controls the performance of a given heat exchanger, and how this may be affected
enhancement mechanism of a tube insert.
enhancement mechanism of a tube insert.
100 PTQ Q2 2021 Through studying cases where hiTRAN has been used in two-phase fluids, it h
Through studying cases where hiTRAN has been used in two-phase fluids, it ha
possible to determine some criteria for cases where it is likely to provide measur
possible to determine some criteria for cases where it is likely to provide measura
significant improvements in performance.
significant improvements in performance.
Q2 calgavin.indd 1 15/03/2021 14:25
determine some criteria for cases Revamp of an ethylene vaporiser with hiTRAN
where it is likely to provide measur-
able and significant improvements Before retrofit hiTRAN (after retrofit)
in performance. Ethylene flow rate, kg/s 14.5 21.1
Temperature in/out, °C -100/-1 (sat.) -100/30 (superheated)
Vaporisers Pressure in/out, bar 40/39.9 40/39.7
Heat transfer coefficient, W/m²K 613 2390
Although there is no rigorous defi- Duty, kW 261 618
nition of a vaporiser, the term is
typically applied to heat exchang- Table 1
ers where a liquid stream is con-
verted completely into a vapour. the droplets and breaking them up the process fluid is assigned to the
Some vaporisers also require sensi- through collisions with the wire tube-side and partially boils along
ble heating of the sub-cooled liquid, matrix. the tube length.
and super-heating of the vapour. In lower pressure applications, a
In many cases, the process fluid Case study disadvantage of the vertical thermo-
will arrive at sub-zero temperatures, A tube-side ethylene vaporiser, syphon is the high static pressure
with the heating medium signifi- designed as a BEU-type shell-and- head which effectively sub-cools
cantly hotter. The local temperature tube heat exchanger (702 tubes, 4m the liquid at the inlet. Therefore, a
differences can exceed 100°K, which straight length), was found to per- certain portion of the tube length is
often leads to the occurrence of form below the required duty when needed to first heat the liquid to its
film boiling – a condition where in service. Analysis of the process boiling point. This reduces the total
the liquid at the heat transfer sur- conditions and thermal design indi- amount of surface area available for
face rapidly vaporises and forms an cated significant areas of film boiling carrying out the intended process of
insulating vapour layer. In regions were present. The exchanger was boiling the liquid.
of film boiling, the heat transfer retrofitted with hiTRAN, and the The performance of a thermo-
coefficient is very low and can sig- subsequent increase in heat transfer syphon can be optimised by mini-
nificantly limit the performance of performance indicated the suppres- mising the tube length filled with
the heat exchanger. sion of film boiling. After the retro- sub-cooled liquid. However, this
Additionally, at near-complete fit, the vaporiser was able to meet its may be difficult to achieve if the
levels of vaporisation, high veloc- required duty (see Table 1). liquid is viscous or if the recircu-
ities can cause liquid droplets to lation rate is low, as laminar flow
become suspended within the Vertical thermosyphon reboilers can occur and limit the local heat
vapour and form a mist. The liquid A thermosyphon reboiler (caland- transfer coefficient. This can be
droplets do not easily evaporate, ria) is a common case of a distilla- compounded during periods of
because the rate of heat transfer tion column reboiler, whereby the low duty operation, where there
through the vapour phase and force driving the circulation is due can be a significant decrease in
into the droplets is relatively poor. to the density change of the boiling performance relative to the design
Consequently, the presence of mist fluid. In a vertical thermosyphon, condition.
flow can lead to liquid carry-over Installation of a hiTRAN matrix
in the outlet of the heat exchanger. only into the sub-cooled liquid zone
In applications where liquid cannot can improve the rate of heat transfer
be tolerated in subsequent parts into the liquid (see Figure 3). This
of the process, mist flow must be allows the liquid to reach boiling
avoided. point earlier, extending the sur-
Film boiling and mist flow can face area available for boiling and
not only reduce the effectiveness of improving the achievable duty for a
a vaporiser, but also create signifi- given size heat exchanger. The boil-
cant uncertainties in the prediction ing zone is kept free of the matrix to
of the performance. hiTRAN offers ensure minimal impact on the total
a potential solution for an affected pressure drop, which could oth-
vaporiser. The increased convec- erwise affect the recirculation rate
tive heat transfer cools the internal through the reboiler.
surface of the tubes, and the wire
matrix introduces a physical dis- Forced flow reboilers
ruption within the vapour film. The A forced flow reboiler is similar
combination of these effects sup- in operation to a thermosyphon,
presses the onset of film boiling, except in this case a pump is used
increasing the local heat flux. The to deliver a controlled flow rate
technology can also disperse mist FigureFigure
3 hiTRAN3element
hiTRAN element
used to reduce usedthrough
to reduce the exchanger
the heat sub-cooled length in a thermosyph
tubes.
flow by increasing the rate of heat the sub-cooled length in a thermosyphon The considerations for applying
transfer through the vapour into tube hiTRAN in a forced flow reboiler
Installation of a hiTRAN matrix only into the sub-cooled liquid zone can improv
www.digitalrefining.com heat transfer into the liquid (see Figure 3). This allows the liquid
PTQ Q2 2021 to
101 reach boiling
extending the surface area available for boiling and improving the achievable du
size heat exchanger. The boiling zone is kept free of the matrix to ensure minim
Q2 calgavin.indd 2 the total pressure drop, which could otherwise affect the recirculation
15/03/2021rate
14:25 through
change in flow behaviour (see Figure 5). The wire matrix breaks up the liquid-vapour interfa
and increases the formation of liquid slugs. This continuously refreshes vapour onto the he
transfer surface, aiding further condensation. There is also enhancement of the convect
heat transfer coefficients due to increased turbulence.
In such cases, there is a lower pres-
sure drop penalty and a more sig-
nificant increase in the heat transfer
coefficient due to the induced tur-
bulence in the liquid film.
The condensation of multiple-
component mixtures introduces a
simultaneous requirement for sen-
sible cooling of the vapour, as well
as removal of the latent heat. The
sensible cooling requirement can
Figure 5 Comparison of phase stratification be substantial for mixtures with a
Figure
between 5 Comparison
plain tubes and hiTRAN of phase stratification wide boiling plain
between range.tubes Furthermore,
and hiTRAN
accumulation of the more volatile or
Figure
Figure 4 4hiTRAN
hiTRAN inducesinduces turbulence through the fifilm
in a liquid lm which, combined non-condensable components near
turbulence in a liquid film with the low temperature differ- the vapour-liquid interface creates a
The flowence,regime
significantlywithin a condenser
limits the overall will mass vary continuously
transfer resistance as along the tube length. T
the con-
are generally similar to the vertical effectiveness
conditions may beofshear-controlled
the heat exchanger. near thedensation
inlet but process
become proceeds. The heat
gravity-controlled as the vapo
The condensation of multiple-component
thermosyphon. The most significant
mixtures introduces a simultaneous
Falling film evaporators can be transfer through the liquid film may
requirement for
improvements
sensible cooling areofmade
the vapour, fraction
by reduc- andas
as improved
well velocity decrease.
by ensuring
removal of thegoodThe
latent hiTRAN
con- matrix
alsoThe
heat. mayparticularly
be sensible
poor, becooling
partiallyininstalled
cases only in the are
ing the tube length filled with sub- vective heat transfer in the liquid where the condensate is viscous.
requirement where maximum enhancement is possible, to minimise the penalty in pressure drop.
cooled liquid. can be substantial
However, as the flow for film, mixtures with a wide
and fully distributing the boiling
liq- Inrange.
addition Furthermore,
to enhancement of
rate is controlled by the pumping uid around the tube wall. hiTRAN the convective heat transfer coeffi-
accumulation of the more volatile or non-condensable components near the vapour-liquid
force, the pressure drop becomes can help to introduce turbulence in cients in the bulk vapour and liquid
less of a creates
interface controlling factor.
a mass If Case
transfer study
suf- resistance
the liquid as film, theimproving
condensation the rate film, proceeds.
process the turbulence Thegenerated
heat by a
ficient capability is available from of heatBXM-type
A horizontal transfer. Additionally,
shell-and-tube whenheat hiTRAN
exchanger matrix(490 more
tubes, thoroughly
5m long), condensing a
transfer
the pump, through the liquid
additional film may fialso
enhancement tted be poor,
in the particularly
opposite directionin cases
to mixeswherethe the condensate
various components
along more of the tube length mixture
may theof flaromatic
uid fl ow, hydrocarbons
the wire matrix and
pro- inert
in components
the vapour. using cooling water,
This prevents the suffered from
is viscous.
be possible. videsvapour
excessive a solid carry-over.
route for entrainedA region liq-of gravity-controlled
build-up of volatileflow andwas non-con-
suspected near the
In addition
Furthermore, to enhancement
the enhancedofheat the convective
uid to travelheat towards transfer
the tubecoefficients in the bulk
walls, densing vapour and
components at the heat
transfer coefficient varies more outlet of the helps
which condenser,
maintain with
the poor
film. heat transfer.transferhiTRAN
surface. matrix was partially installed in the
liquid film, the turbulence generated by a hiTRAN matrix more thoroughly mixes the various
evenly with the flow rate, and fluc-
final 2m of the tube length. The heat transfer performance was improved, resulting in a 45%
tuations will cause
components in thea morevapour. signifi - Vertical
This prevents the build-up of volatileHorizontal
condensers and non-condensing
condensers
cant change in pressure drop. reduction This When in athe
condensing
outlet vapour fluid ismass
required Horizontal
fraction. This allowed tube-side condensa-
for increased economy of the
components
can improve atthe thestability
heat transfer
of bothsurface.
on the tube-side, a vertical orientation may be necessary where the
forced flow and thermosyphon process tionduemay to be
improved
preferredproduct to allowrecovery.
nat- geometry of the heat exchanger is
reboilers at varying loads. ural drainage of the liquid under constrained in this orientation, for
Horizontal condensers gravity. Here, a film of condensate example air-cooled heat exchangers
Falling film evaporators Conclusion
forms on the tube surface and falls and U-type shell-and-tube units. The
Horizontal
In a tube-side tube-side
falling film condensation
evapora- down may betube necessary Thewhere the general
geometry of the heat
Tube insertsthecan bewalls. condens-
an attractive and beneficial considerations
solution when for vertical
designing a tubular he
tor, a thin fi lm of liquid descends ing process is usually very
exchanger is constrained in this orientation, for example air-cooled heat exchangers and U- eff ective, condensation also apply to horizon-
the inside surface of the tubes exchanger and however withthere
poorare heatcertain situations
transfer propertiestal condensation.
on the tube-side. However, in hori- streams introdu
Two-phase
type shell-and-tube
gradually evaporates.units. Thefilm
Falling general
whenconsiderations
the heat transfer forcan
vertical
be lim- condensation
zontal tubes,also apply
the force to
of gravity acts
evaporation is usually employed additional
itingcomplications
and where hiTRAN and limitations
may be due to phase to
tangentially separation
the direction andofvapour-liquid
flow equilibriu
horizontal condensation.
when the process fluid is tempera-
However, in horizontal
benefihiTRAN
cial.
tubes, the force of gravity
and can
acts tangentially to
Calgavin’s Thermal Systems may be therefore
able to signifi
provide cantly affect by improving t
benefits
ture-sensitive,
the direction ofnecessitating
flow and can thetherefore
use For the condensation
significantly affectofthepure sub-
fluid the fluid distribution
distribution within the within
tube. the tube.
of a heating medium which isconvective not stances, heatthetransfer,
heat transfer achieving
is domi- a moreIf homogeneous
the fluid velocity fluidormixture,
vapour and disrupting t
Ifsignifi
the fluid velocity or vapour
cantly hotter than the prod- fraction
natedis high enough,
by the removal the flow regime
of latentInheat is regarded as shear-
interface between the phases. eachfraction
case itis is high importantenough, the
to identify the controll
uct. However, this low mean tem- and resistance through
controlled. The effect of gravity is negligible compared to the momentum of the fluid, and the liquid fl ow regime is regarded as
perature difference can be a limiting phenomena,
film. The in order to define
application of the
hiTRANpotential scope for enhancement.
shear-controlled. The effect of grav-
turbulent flow
factor for the results
thermal in high heatmust
design. transferbe coefficients.
carefully considered Application ity of is hiTRAN
negligible incompared
these to the
A consequence of using only con- against the sensitivity of the fluid’s momentum of the fluid, and tur-
conditions is not
vective boiling advisable due
(evaporation) to the
is that highpoint
boiling pressure to thedrop penalty.
operating pres- bulent flow results in high heat
the heat transfer coeffi cient of this sure. The
On the other hand, gravity-controlled flow tends to occur in regions increased pressure drop of transfer
low fluidcoeffivelocity
cients. Application
and of
process can be low, in comparison may lower the boiling point, which hiTRAN in these conditions is not
low
withvapour
nucleate fraction.
boiling.Stratification
When pro- ofwill the off twosetphases creates a pool
any improvements in ofadvisable
liquid atdue thetobottom
the high of pressure
cessing fluids with high viscosities heat transfer. hiTRAN is applied drop penalty.
the tube, which effectively reduces the surface area available for condensing the remaining
or low mass flow rates, the flow effectively in conditions where On the other hand, gravity-con-
regime Furthermore,
vapour. within the liquid a lowfilmvelocity
can vapour
results in velocities
poor heat aretransfer
low, and through trolled flow tends
the vapour phase. to occur in
be laminar. The heat transfer is then where the condensate film is found regions of low fluid velocity and
controlled by thermal conduction to be in laminar flow (see Figure 4). low vapour fraction. Stratification
Q2 calgavin.indd 3 15/03/2021 14:25

of the two phases creates a pool Case study benefits by improving the convec-
of liquid at the bottom of the tube, A horizontal BXM-type shell-and- tive heat transfer, achieving a more
which effectively reduces the sur- tube heat exchanger (490 tubes, homogeneous fluid mixture, and
face area available for condensing 5m long), condensing a mixture of disrupting the interface between the
the remaining vapour. Furthermore, aromatic hydrocarbons and inert phases. In each case, it is important
a low velocity results in poor heat components using cooling water, to identify the controlling phenom-
transfer through the vapour phase. suffered from excessive vapour car- ena, in order to define the potential
In gravity-controlled conditions, ry-over. A region of gravity-con- scope for enhancement.
hiTRAN proves to be effective as trolled flow was suspected near the A selection of general examples is
it induces a significant change in outlet of the condenser, with poor presented where hiTRAN has been
flow behaviour (see Figure 5). The heat transfer. hiTRAN matrix was found to be successful in achieving
wire matrix breaks up the liquid-va- partially installed in the final 2m of increased overall heat transfer. This
pour interface and increases the the tube length. The heat transfer may serve as a guide to the design
formation of liquid slugs. This con- performance was improved, result- engineer to consider some of the
tinuously refreshes vapour onto ing in a 45% reduction in the outlet common limitations of two-phase
the heat transfer surface, aiding vapour mass fraction. This allowed flow, and the opportunities for
further condensation. There is also for increased economy of the pro- using the technology to optimise or
enhancement of the convective heat cess due to improved product improve heat exchanger designs.
transfer coefficients due to increased recovery.
hiTRAN and hiTRAN.SP are trademarks of
turbulence. CALGAVIN.
The flow regime within a con- Conclusion
denser will vary continuously along Tube inserts can be an attractive and Nathan Hill is a Thermal Process Engineer
the tube length. The conditions may beneficial solution when design- with CALGAVIN’s engineering team. He is
primarily responsible for evaluating customers’
be shear-controlled near the inlet ing a tubular heat exchanger with
exchangers for use with hiTRAN Thermal
but become gravity-controlled as poor heat transfer properties on
Systems and Twisted Tape inserts. He also
the vapour fraction and velocity the tube-side. Two-phase streams provides technical advice relating to the
decrease. The hiTRAN matrix may introduce additional complications design of heat exchangers with tube-side
be partially installed only in the and limitations due to phase sep- enhancement, and the use of hiTRAN.SP
areas where maximum enhance- aration and vapour-liquid equilib- software. He graduated from the University of
ment is possible, to minimise the rium. Calgavin’s hiTRAN Thermal Manchester with a master’s degree in chemical
penalty in pressure drop. Systems may be able to provide engineering.
ERTC 2018
managing
LIVE WEBINAR
Presenter: Mark Dyson, MBA
VP Mobile Water Services,
Veolia Water Technologies
metals assets
PTQ / DIGITALREFINING
n
Ensuring business
continuity with
usiness, we
er of petro-
reliable and secure
One metric ton of catalyst (2205 lb) is
about US$80 000 at current prices, so the
anies, ship- treated
Short Cut Corporation iswater
losing $32 000-
g precious $40 000 on every metric ton it sells.
s, of course. To illustrate an additional risk of selling to a
em manage broker, in many countries the pre-existing lia-
TUESDAY 11 MAY 2021

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clean-up, the lawsuits, and more.
www.digitalrefining.com/news/1006371
Disappearing Assets Incorporated
Unfortunately, another thing that must be
w addressed is ethical compliance. Disappearing

Assets fell victim to one of the bad guys: a pre-
WATER TECHNOLOGIES
ciouswww.digitalrefining.com
metals refinery that cheated. PTQ Q2 2021 103
in
Mobile Water
In this example, the trick was essentially
‘legalised theft’: the precious metals refiner
tion used something other than a verified weight

and an accurate assay as the basis for its
Q2 calgavin.indd 4 16/03/2021 13:34
payment to Disappearing Assets. To be clear;
Crude logistics scheduling
Upgraded crude scheduling enabled a refiner to increase its use of opportunity
crudes for higher margin
AURELIO FERRUCCI Prometheus SRL

MANOJ KUMAR HPCL - Mittal Energy Limited
G
eneration of a refinery’s ing the user’s intervention only to Concurrently with cargo recep-
operations plan requires the manage significant issues requiring tion, some tanks are unloaded
capability to monitor and appropriate action. and fed in parallel (three to five
determine the quality and the com- Furthermore, integration of eco- pumping channels) to a pipeline.
position of crude oil to be processed nomically driven optimisation meth- The blend resulting from parallel
in the crude unit as well as its avail- ods generates operational plans to pumping must respect the quality
ability date. Batches fed to the CDU maximise the processing of opportu- constraints required for CDU pro-
must fit both quality constraints set nity crudes while meeting the CDU‘s cessing at the other end of the pipe-
by the operations department and feedstock quality requirements. line. Batches exiting the pipeline can
simultaneously maximise the con- Significant time saving enables either be fed directly to the crude
tent of opportunity crude oils for schedulers to explore a greater unit or go to refinery storage.
the best processing margin. number of options, resulting in a
Poor scheduling can erode up to more effective and optimised sched- DSS modules
5% of the theoretical monthly result uling plan. It is a tool that supports, Prometheus has developed a set of
predicted by linear programming in the same environment and with technologies for crude oil character-
planning models and can result in the same model, development of isation, plant simulation, and blend-
higher ship demurrage costs. Thus, both long and short term scheduling calculations and has integrated
optimisation of crude oil logistics is ing tasks: them into five modules, designed to
fundamental, especially when the • Long term scheduling models can support the most relevant planning
available crude inventories are lim- calculate and update in a few min- and scheduling tasks.
ited and it is difficult to segregate utes the evolution of the status of all These modules can work stan-
crude quality. tanks and pipelines in the logistic dalone to perform a specific set
Prometheus has developed a tool, network. It is able to define cargo of scheduling tasks, or share data
Proraf, which offers an innovative arrival dates and to identify solu- and processes in case of extended
algorithm to concurrently manage tions in case of unforeseen opera- solutions:
crude oil logistic events (reception, tional changes. • CUTS is a crude assay data elab-
transfer, and processing) and pre- • Short term scheduling models oration for database building and
dict the hourly evolution of the sta- enable detailed instruction reports recutting. This module provides
tus of all tanks. to be issued and store validated crude oil data for all the other
Crude data, simulation, and opti- operational results (that is, actually modules.
misation techniques are integrated executed operations) into a central- • Simraf refinery LP optimisation is
by an algorithm which is also able ised historical database which can integrated with process plant simu-
to work high-level transfer instruc- provide the information to repro- lation models for yield and quality
tions where the sequences of tank duce details of past activity. calculations. This module supports
loading/unloading operations are This article describes the technol- ordinary and strategic planning
not detailed. ogy and reports a case study illus- tasks.
The calculation engine man- trating its implementation for the • Proraf provides modelling and
ages the service requests associated scheduling of crude supply oper- optimisation of logistics.
with material transfers according ations for an Indian petrochemical • Prolav provides modelling
to specified priorities and selection refining complex. and optimisation of processing
criteria, to bring each event to com- The operator’s maritime depot operations.
pletion as fast as possible. This sim- receives a variety of crude oils of • Ottmix provides LP optimisation
ulation highlights real bottlenecks variable quality (in terms of sul- of blending operations.
to manage to prevent operational phur content, acidity, and API). The These modules support short term
problems. number of available tanks does not scheduling tasks.
The software can solve autono- enable proper quality segregation, The crude scheduling model
mously the major components of therefore each tank’s evolving com- described in this article applies the
the scheduling problem, requir- position must be tracked. CUTS and Proraf modules. Further
q2 prometheus.indd 1 25/03/2021 15:52

integration with other DSS modules
to model crude oil processing and 100
finished product blending opera-
Business plan result (% Max value)

95 4.5 4.5
tions is in the design phase.
17.9
90
7.5
Crude scheduling 10.6
Figure 1 summarises the findings of 85

100.0 5.4
a study carried out to identify the 80
97.2
refining operations which mostly 5.4

impact the difference between the 75
theoretical result expected from the
70
business plan and the actual result. 74.5
According to these results and for 65

various reasons, the actual refin-
pl e
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ay
it y
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aw
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pared to the planning figure, by
ta
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ud
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st
Ca
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Qu
he P
ed
cr
vi
Fe
up to 25%. One of these reasons is
or
En
Po
sc
improper crude logistics manage-
Un
ment (reception facilities, deposits,
and pipelines) which can represent, Figure 1 Actual refinery result versus original business plan
for a mid-sized refinery, an annual
$15-20 million loss: this is particu- for the best processing margin. of both activities requires the capa-
larly true when variability of feed- Typically in this framework, bility to simulate the evolution over
stocks forces operators to monitor crude quality and cargo size is input time of the status of crude logistic
the quality of their crude refinery from planning while scheduling assets (tanks, tank farms, pipelines),
tanks or to store different crude can define the arrival dates of car- depending on supply programme,
types separately to prevent quality goes as well as handling operations transfer operations and processing
contamination. throughout the logistics network up runs.
Typically, the average residence to the crude unit.
time of crude oil in refinery inven- In the case of definition of cargo Long term scheduling
tories is too low to enable proper arrival dates, the impact of this Long term scheduling assesses the
quality segregation, and it is funda- material intake on crude logistics feasibility of crude reception and
mental to improve the intelligence must be foreseen. transfer operations, in terms of
of tools dedicated to the sched- Given the supply programme, it is blend quality and reliability, within
uling of logistic assets, to man- crucial to plan handling operations a time horizon of a few months for a
age the quality of the stocks finally to avoid undesirable contamination, given schedule of crude cargo arriv-
fed to refinery crude units. In such especially in the case of different als. The goal is to assure an ordered
cases, the crude scheduling process operating modes based on differ- cargo arrival plan, timely unload-
becomes critical, and great effort ent crude qualities, and to optimise ing of cargoes at the maritime ter-
and investment is made to improve batches by maximising the use of minal with no demurrage costs, and
performance in this area. opportunity crudes. blending to maximise consumption
Figure 2 lists the leading causes The two main classes of sched- of heavy/opportunity crudes. A
of economic losses arising from uling activities differ by specific typical time horizon is 90-120 days.
poor scheduling of crude oil logis- objective and time horizon; they For example:
tics. In practice, LP models assume are long term scheduling and short • M: current month, day 0-30 (Short
the capability to process optimal term scheduling. Proper execution term horizon).
crude mixes in refinery crude units
for the whole period, while in fact
feedstock availability depends on
the supply schedule and the logistic MONTHLY PLAN ACTUAL CASE
constraints involve unforeseen qual-
ity contamination. Any crude is available at the Crude availability depends
beginning of the period. on supply programme.
In this case, the refiner must
exploit all degrees of freedom avail- Perfect quality segregation Crude quality contamination
(no crude contamination). happens.
able during the operational plan-
ning and scheduling process to Intermediates yields and Different mixes with different
quality calculated assuming yield and quality of
maximise the final result. Crude the optimal crude state. intermediates.
batches fed to the CDU must fit the
quality constraints set by the opera-
tions department and maximise the
content of opportunity crude oils Figure 2 Monthly plan vs actual case

■ Crude arrivals gates and deviations from the original sched- tive scenarios, a lot of it is wasted
dates are fixed (with three days ule that occurred in the period. inputting and updating data.
variability) Actual operations are set in the The Prometheus algorithm
■ Once an actual cargo reception model and recalculated to align to applies a paradigm change. In fact,
date and time is available, the simu- reality the status of the tanks and it autonomously proposes a solu-
lation must be re-run to check the feasibility of the sched- tion (that is, the origin and desti-
• M+1: next month, day 31-60 (nom- uled blends. Short term scheduling nation tank of a given service) after
ination horizon). supports the publication of daily processing ‘high level’ instructions
■ Known: quality, size, and num- operative instructions as well as the from the user. Setting the criteria for
ber of cargoes (nominated cargoes) historicisation of actual movements. tank selection in different situations
■ Unknown: arrival gates The typical time horizon for short is much faster than preparing the
■ Task: to define the contractual term scheduling is one month (30 detail of every transfer; this poten-
arrival dates days). tially reduces the time for modelling
• M+2/M+3: following month(s), In this case, the scheduler uses a tremendously. On the other hand,
day 61 to 90-120 (buy horizon). model to: the tool must provide the user with
■ No information available • Re-schedule short term operations the flexibility to orientate the solu-
■ Task: suggest the quality to handle unexpected events (minor tion to account also for constraints
and the size of the cargoes to be changes, delays, or unforeseen shut- which are not explicit in the model
purchased downs) and to update the simula- but which are taken into account
With this activity, the sched- tion baseline accordingly. while generating the schedule.
uler defines the arrival dates of the • Calculate the status of the tanks To enable the software to pro-
crude cargoes to be nominated (typ- based on actual operation account- pose reliable and feasible solutions,
ically at M+1) and finalises cargo ing for schedule deviations: the Prometheus has made available in
grades, quantity, and arrival dates logistic model can be used to keep the same environment crude char-
for the months M+2 and M+3. track of the crude composition of acterisation data and MIP opti-
For these purposes, the scheduler the tanks. misation, and has developed a
sets up a model of the logistic net- • Reconcile operations: for each simulation algorithm which is able
work and uses it to: planned transfer, the scheduler to exploit these tools to generate the
• Simulate the evolution in time of adjusts the planned quantity to the schedule automatically.
tank content considering arrivals, actual one. Following research based on user
pipeline dispatches, and process- • Store the results of the past feedback, Prometheus was able to
ing. The simulation aims to check operation (after reconciliation) to develop a fast and effective algo-
the feasibility of cargoes’ reception data historian so that they can be rithm based on deep integration
schedule considering the status of retrieved to support future schedul- of crude assay data (bulk and frac-
the tanks at reception dates (vol- ing activities. tion properties, economics), and
ume and quality) and contemporary • Publish operating instructions for a sophisticated simulation engine
transfer and processing activities. a horizon of about 10 days. enabling, at the same time, high
• Plan the composition of the crude Even though the horizon is level set-up of transfer events, the
batches. The scheduler must track shorter than in the case of long term flexibility to change and orientate
the composition of the batches fed scheduling, this activity is also time the solution, and economics-driven
to pipelines and crude units to pre- consuming (the input required is MIP optimisation models to run
vent issues during processing steps. much more detailed). Thus, using automatically to optimise batches.
• Define contractual arrival dates a tool supporting the reconciliation This simulation engine takes into
for ‘nominated’ cargoes for the four activities is particularly useful. account operational and quality
months covered by the simulation. constraints, suggests the sequence
• Estimate arrival dates for ‘to buy’ Logistic simulation of handling operations, and requires
cargoes, providing feedback to the Requirements only a few minutes for a long term
planning department and trading Both long and short term sched- scheduling solution.
departments charged with the pur- uling require the availability of a
chase of new cargoes. model able to calculate the evo- Crude assay data
The long term simulation of lution of the status of the logis- CUTS is the Prometheus module for
a crude logistics operation is a tics assets depending on the events the construction and management
time-consuming activity and the occurring in the simulation period. of the crude oil characterisation
availability of a fast simulation tool Tools used to develop and run database. This application features
is fundamental to enable the evalua- such models usually feature a time a proprietary technology (multidi-
tion of alternative scenarios. consuming modelling phase (all mensional regression) specifically
transfer data must be manually developed to elaborate crude assay
Short term scheduling entered), and need to update such information to produce a consistent
Short term scheduling aims to data when any deviation from the library which can provide the data
update the status of tanks dur- plan occurs. Basically, instead of for all the properties of any fraction
ing the current month, considering spending time evaluating alterna- of any crude blend, irrespective of

the source, form, and consistency of CUTS fundamental properties
the input assay.
CUTS characterises every crude Property unit Blending rule Boiling range
oil as a mixture of pure components Weight TBP Yield, wt% Linear weight Whole crude
Volume TBP Yield, vol% Linear volume Whole crude
(C5-) and ‘pseudo-components’ Density@15°C, kg/dm3 Linear volume Whole crude
(C6+), which cover the entire crude Sulphur content, wt% Linear weight Whole crude
boiling range. Each pseudo-com- Mercaptan sulphur content, wt% Linear weight Whole crude
ponent includes pure components Kinematic viscosity @50°C, CST Index weight Whole crude
Kinematic viscosity @100°C, CST Index weight Whole crude
boiling in a narrow range of 10°C. Acidity, mg KOH/gr Linear weight Whole crude
For each property, CUTS uses mul- Aromatics content (FIA), vol% Linear volume Gasoline
tidimensional regression to cre- Naphthenic content (FIA), vol% Linear volume Gasoline
ate distribution curves and allows Paraffin content (FIA), vol% Linear volume Gasoline
Aromatics content (gas chromatography), wt% Linear weight Gasoline
harmonisation of the shape of the Naphthenic content (gas chromatography), wt% Linear weight Gasoline
resulting curves. Paraffin content (gas chromatography), wt% Linear weight Gasoline
Table 1 lists the fundamen- Octane Number Motor Method (MON) Linear volume Gasoline
tal properties managed, the Octane Number Research Method (RON) Index volume Gasoline
RON+ Tetra Ethyl Lead 0.5 Index volume Gasoline
relative blending rule, and a mean- RON+ Tetra Methyl Lead 0.5 Index volume Gasoline
ingful boiling range (with prop- Reid Vapour pressure, psia Index volume Gasoline
erty values estimated for each Cyclopentane content, wt% Linear weight Gasoline
pseudo-component). Cyclohexane content, wt% Linear weight Gasoline
i-Hexanes content, wt% Linear weight Gasoline
Proraf enables the user to define n-Hexane content, wt% Linear weight Gasoline
the list of quality specifications to Benzene content, wt% Linear weight Gasoline
be considered to track the quality Methylcyclopentane content, wt% Linear weight Gasoline
of tank contents or to set up qual- Naphthalenes, vol% Linear volume Mid Distillates
Freezing Point, °C Index volume Mid Distillates
ity constraints for tanks or crude Cloud Point, °C Index volume Mid Distillates
blends (in case of quality-controlled CFPP, °C Index volume Mid Distillates
parallel sequences). Pour Point, °C Index volume Mid Distillates
It is possible to consider almost Refraction Index @20°C Index volume Mid Distillates
Refraction Index @70°C Index volume Mid Distillates
any characterisation property but, Aniline Point, °C Linear weight Mid Distillates
since a high number of quality spec- Total nitrogen content, ppm wt Linear weight Mid Distillates and residua
ifications involves longer comput- Basic nitrogen content, ppm wt Linear weight Mid Distillates and residua
ing time, it is recommended to find Ash content, ppm wt Linear weight Mid Distillates and residua
Asphaltenes C5 content, wt% Linear weight Mid Distillates and residua
a good trade-off between the con- Asphaltenes C7 content, wt% Linear weight Mid Distillates and residua
straints needed to characterise the Conradson Carbon residue, wt% Linear weight Mid Distillates and residua
tanks and the calculation resources. Nickel content, ppm wt Linear weight Mid Distillates and residua
Proraf foresees four types of qual- Vanadium content, ppm wt Linear weight Mid Distillates and residua
Wax content, wt% Linear weight Mid Distillates and residua
ity specifications. For each type, it is
necessary to define a specific set of Table 1
parameters to enable their retrieval
from the CUTS library:
• Bulk: a whole crude referring PRORAF OTHER TOOLS
property. It can be either a generic
property (density, sulphur, viscos- INPUT INPUT
PERIOD PERIOD
ity) or the yield of a fraction. Simulation period start and end dates Simulation period start and end dates
• Cut: a crude oil’s fraction refer-
BASELINE BASELINE
ring property (for example, the Tanks and pipelines status at start date Tanks and pipelines status at start date
acidity of the 150-250°C fraction).
EVENTS DATA EVENTS DETAILS
• Crude: the amount of a given Generalities List of operations
crude oil in the mix. Origin tank selection criteria
Destination tank selection criteria
• Crude type: the amount of a given
crude type in the mix.
SIMULATION UPDATE
The simulation algorithm
Proraf differs from other sched- OUTPUT OUTPUT
uling tools because the detailed EVENTS DETAILS TANKS STATUS
list of operations associated with List of operations Tank and pipeline status at EVERY
date of the simulation period
each transfer event is an output of TANKS STATUS
the simulation instead of an input. Tanks and pipeline status at EVERY
date of the simulation period
While other systems simulate the
impact of the set of transfer opera-
tions input by the user on the status Figure 3 Proraf approach compared to other scheduling tools

• Pipeline: connecting tanks can
be one way, two-way or a simple
EVENTS connection
Crudes • Tank operations: to model oper-
Supply carriers
LINKING PIPES
ations triggered by loading or
ORIGIN DESTINATION
Supply continuous
SEQUENCE SEQUENCE unloading
Transfers • Docks: cargo mooring points
Processings • Ships’ templates: different types
of available crude carriers
Figure 4 Event structure • Crude types: crude oil associations
• Quality specifications: modelling
of the tanks, Proraf can generate the • Volume and pumping (load/ the quality of crude oil batches
set of transfer operations based on unload) constraints • Calendars: defining timetables for
the high level instructions provided • Status (volume and content) and tank operations or events
(see Figure 3). availability The logistic network groups
This difference reduces tremen- • Handling operations (drainage, tanks in tank farms which can be
dously the time needed to produce/ measurements) actual or logical, depending on
update the scheduling plan, both for • Quality specifications (quality con- the simulation. It is easy to mod-
long and short term scheduling. straints set for the receiving tank) ify and update: Proraf’s graphi-
The simulation algorithm of • Batch quality targets (in case of cal user interface enables the user
Proraf can handle ‘high level’ parallel pumping) to customise the behaviour of each
instructions and propose a solution • Pipeline quality tracking object to reproduce actual operating
without needing to specify in detail • Tank selection logics and procedures.
the sequences of origin and destina- exceptions Once the logistics are defined, it
tion for tanks involved in a transfer. The calculation run generates the is necessary to define the transfer
The user can specify in detail ori- details of the operations associated events occurring during the simu-
gin, destination quantity, and flow with each transfer event as well as lation period. Proraf features four
rate (as in the case of other sched- the time evolution of the status of types of events that model all types
uling tools) but can also delegate to any asset in the logistic network. of operation; each event is defined
the algorithm the selection from a by general information (start date,
set of tanks of which tank to use at Batch optimisation engine flow rate, quantity, calendars), ori-
a given moment (‘Sequence’). In this Proraf uses an optimised blending gin sequence (set of origin tanks
case, Proraf suggests the best tank function, enabling it to determine and selection criteria), destination
for the requested service, based on origin tanks and blending ratios in sequence (set of destination tanks
user criteria. the case of automatic parallel ori- and selection criteria), and linking
The algorithm splits the simula- gin sequences. When required, the pipes (see Figure 4).
tion period into time slots and elab- algorithm automatically formalises The algorithm uses this informa-
orates them in series from first to a mixed integer programming opti- tion to select, for each time slot,
last. For each transfer event, the misation problem applying the con- the origin and destination tanks
engine generates a list of service straints set, and solves it to find the as well as transfer flow rate. The
requests to the connected objects origin tank of each pumping chan- events editor enables the defini-
(tanks, tank farms, pipelines) repre- nel and the related pumping flow tion of each transfer as well as the
sented in the logistic structure and rate. related parameters (type, calcu-
manages these requests according The simulation algorithm then lation mode, origin, destination,
to specified priorities and selection uses this result to elaborate on the volume, flow rate, and quality con-
criteria, to bring each event to com- transfer event until the solution is straints). In this environment, it is
pletion as fast as possible. applicable. When for some reason also possible to set high level trans-
The system manages various types the solution becomes unfeasible (for fer instructions.
of transfer events such as carrier and example, one of the origin tanks
pipeline crude reception, transfers, empties) a new problem is formal- Results
and processing. The following infor- ised based on the updated scenario. The simulation calculates, with
mation defines each event: hourly resolution, the evolution of
• General data (start date, flow rate, Model set-up the status of all the tanks as well as
quantity, calendars) The simulation model foresees the the detail of material transfers. An
• Origin and destination sequences preliminary set-up of a logistic net- exhaustive report section is also
(set of tanks and selection criteria) work; Proraf features the following featured.
• Linking pipes modelling objects: Examples of the different types of
The algorithm selects origin and • Tank: modelled with their actual reports generated by the simulation
destination tanks from the specified geometrical properties, pump- – all exportable in Excel – include:
sequences and defines the transfer ing constraints, and quality • Gantt chart reporting the events
flow rate based on: specifications with transfer origin and destination

63000
60000
BLT1 BHU1 MYA1 KU21 ARM1
57000
54000
51000
48000
45000
42000
39000
Volume (m3)
36000
33000
30000
27000
24000
21000
18000
15000
12000
9000
6000
3000
0
18
18
18
18
18
18
18
18
18
18
18
18
18
18
18
0
0
/2
/2
/2
/2
/2
/2
/2
/2
/2
/2
/2
/2
/2
/2
/2
4
5
/0
/0
/0
/0
/0
/0
/0
/0
/0
/0
/0
/0
/0
/0
/0
06
08
10
12
14
16
18
20
22
24
26
28
30
02
04
Time
Figure 5 HMEL overview – tank status with graphical evolution of composition
details and highlighting transfer GGSR receives its crude oil sup- margins than with lighter crude
issues of any kind. ply from a crude oil terminal sit- oils.
• Quality, composition, and ori- uated at Mundra via a pipeline. Blending is realised by paral-
gin tanks of all the crude oil batches The oil is imported from abroad lel feeding of more tanks – typi-
fed to the pipelines and CDUs dur- and serves the domestic market, cally four or five channels – to the
ing the simulated period, both on a providing motor fuels to Euro-VI pipeline. For every crude batch
daily average and a batch base. specifications and petrochemical fed to the pipeline, the sched-
• Status (volume, composition, products. uler must decide the best pumping
and quality) of all inventories at The refinery has a complex multi- composition.
a selected date/time with hourly unit configuration, plus utilities The scheduling tool must track
resolution. and offsites, cross country pipeline, the quality of the tanks as well as
• Graphical representation of ship crude oil terminal, and marine facil- their availability at the moment in
discharge events with detail of the ities. Its crude supply logistics ena- which it is necessary to generate a
activity of the receiving tanks (load- ble the reception of crude feedstocks new crude blend and identify the
ing, unloading, locked, on hold). from the world market. Cargoes are most economical recipe.
• Tank status table with graphical unloaded into the tanks of the mar- HMEL was already using a crude
and tabular evolution of the status itime terminal, then pumped to the scheduling tool but in 2017 the
of all tanks. refinery’s crude oil tank farm via a company began cooperating with
• Tank graph with overall evolution 1000 km pipeline. The volume of the Prometheus to develop a new tool
of the composition of the selected tank farm is 240 000 m3 (see Figure better fitted to its requirements and
tank. 5). aiming to:
• Pipeline line fill at any selected The refinery receives crude oils • Accelerate development of the
time during the simulation period. which are highly variable in qual- scheduling plan, especially for long
ity in terms of sulphur, API value, term scheduling.
Case study acidity, and asphaltenes and which • Support the scheduler for bet-
Guru Gobind Singh refinery (GGSR) must be blended appropriately to ter control of the quality of blended
is owned by HPCL-Mittal Energy meet the quality constraints set by crude-mix batches entering the
Limited (HMEL), a joint venture the operations department. pipeline as feedstock for the CDU.
between HPCL and Mittal Energy The blending operation is carried • Provide quick analysis of alter-
Investment Pte Ltd, and is located out in the maritime terminal. The nate scenarios for an early response
at Phulokhari, Bathinda, Punjab, goal of the scheduling process is to plan to manage an unexpected
India. The current annual crude oil meet the quality requirements set event such as delayed arrival of a
processing capacity is 11.3 million by operations and planning, and to cargo (see Figure 6).
tonnes (225 000 b/d) and the refin- maximise the use of heavy/oppor- The implementation project
ery became operational in 2012. tunity crude oils to provide higher started in November 2018, and

INDIA 2021
REFINING
TECHNOLOGY CONFERENCE
1 Single point mooring
Corporate office
2 Crude oil terminal at Noida
at Mundra Punjab 4
Haryana
3 1017 Km Crude oil
Rajasthan 3
pipeline (28”/30” dia)
from Mundra to
Bathinda
2 Gujarat
4 11.3 MMTPA refinery 1
complex at Bathinda
Figure 6 HMEL refinery crude reception scheme
the last module was delivered in with minimum user intervention.

20-21 SEPTEMBER August 2019. It assesses optimal crude blends for
2021 the pipeline or CDU, maximising
Benefits the use of heavy/opportunity crude
THE SHANGRI-LA, The economic objective function oils in compliance with feed quality
applied by the automatic optimisa- constraints.
NEW DELHI tion engine available in Proraf tends The system enables:
to maximise the use of low value • CDU/pipeline feed quality
opportunity crude oils, correspond- tracking.
SPONSORSHIP ing to an increase in refinery margin • Automatic calculation of a sched-
by 1-2 cents/bbl. uling solution and CDU product
The automatic calculation algo- yields and qualities.
rithm enabled updating the sched- • Obtaining a solution to crude
Refining India 2021 uling plan in a few minutes scheduling problems in less time.
has a limited number enabling: a precise cargo arrival • Analysis of alternative scenarios.
sequencing plan for uninterrupted • Better economics compared to
of sponsorships crude availability in optimum other scheduling tools.
available, which are cargo parcels; and a quick analysis • Using the same tool and model
designed to help of different scenarios for an effec- can be used for long and short term
tive response to unexpected events scheduling.
companies raise their such as a cargo’s arrival delay, or HMEL - Guru Gobind Singh
profile at the event, as a supplier confirms for a loading refinery successfully implemented
date different to the nominated this tool in 2019 and now uses it to
well as showcase their one. This helps to minimise demur- support its crude oil scheduling
products and services rage costs by 1-2 days every quar- activities.
to the 225+ attendees ter. The algorithm enables a quick
blend feasibility check for timely
decisions on opportunity cargo PRORAF and CUTS are a mark of Prometheus.
purchases.
Conclusion Aurelio Ferrucci is Executive Vice President of

Integrating crude characterisa- Prometheus SRL.
tion, simulation, and optimisation Email: aurelio.ferrucci@prometh.it
technologies, Proraf is a decision
support system to optimise man- Manoj Kumar is an Assistant General Manager
agement of ship discharge and with HPCL – Mittal Energy Ltd.
https://refiningindia.com
coastal storage tanks automatically Email: Manoj.Kumar2@hmel.in

ptq&a extra
Q What are the likely causes and solutions for severe fouling in But after this first step, despite good desalting efficiency, a
a vacuum unit’s preheat section? further improvement can be achieved by injecting a caustic
replacer in the desalted crude.
A Celso Pajaro, Head Engineered Solutions Refinery AME, Caustic injection downstream of the desalter is recognised
Sulzer Chemtech, celso.pajaro@sulzer.com as a cheap and effective method to reduce overhead corro-
The question is not so clear about the nature of the atmo- sion, but unfortunately at the same time NaOH can be det-
spheric residue and/or the streams that exchange heat with rimental because it can contaminate the bottom streams
it. These are some potential causes: affecting the downstream units.
• Low velocity of the atmospheric residue in the tubes (it Caustic is itself a foulant agent; moreover, sodium is a
should be above 6 ft/s) well-known dehydrogenation catalyst, hence it is a coke pro-
• Leakage in the heat exchanger that allows the hot stream moter – it increases the coking rate in the downstream unit
into the residue creating compatibility problems (for instance VDU) HEX train and furnaces.
• Mixing different types of atmospheric residues (paraffinic Together with this, it is worth mentioning that caustic is
and non-paraffinic sources) that have compatibility problems also responsible for catalyst poisoning in downstream cat-
leading to asphaltene precipitation. alytic plants (FCC unit, hydrocracking unit, residue desul-
• Paraffinic residues stored at low temperatures which allow phurisation and, so on) and for the production of low-quality
the precipitation of solid wax. fuel oil (fouling problems in the burners, for instance in the
power station or in the fuel oil furnaces).
A Marco Roncato, Senior Product Manager Process In order to manage all issues, Chimec has developed a
Development & Marketing, CHIMEC SpA, mroncato@chimec.it caustic replacer, Chimec 3034, to substitute completely or
The fouling affecting a vacuum distillation unit (VDU) HEX partially the injection of NaOH downstream of the desalter;
train depends a lot on the VDU’s position in the process it is completely organic and metal free which means it has no
stream: impact on coke promotion and catalyst deactivation.
1) Downstream of a crude unit The overall effect is the reduction of caustic and sodium
2) Downstream of a cracking unit (for instance a content in the atmospheric residue.
visbreaking) This implies no risk of NaOH induced fouling in the pre-
heat trains.
Case 1 (downstream a crude unit)
In this case, the fouling content of the VDU feed can be both: Managing fouling precursors
• Inorganic (everything not removed at desalter stage will After ‘cleaning’ the VDU feed (by maximising the desalt-
end up – concentrated – in the atmospheric residue, that is er’s efficiency and reducing NaOH injection), the following
VDU feed) action is to inject a suitable dispersant chemical in the VDU
■ sediment deposits feed able to provide protection from both organic fouling
■ sand (mainly due to asphaltenes deposition) and the inorganic
■ corrosion products variety.
■ salts
■ caustic injected in the crude oil after the desalter Case 2 (downstream a cracking unit)
• Organic In this case, together with inorganic and organic fouling,
■ slops there is also the strong presence of a further fouling portion,
■ sludges which usually becomes predominant – coke deriving from
■ destabilised asphaltenes cracking processes and heavy gums due to olefinic polymer-
■ heavy paraffins isation reactions.
Which of the two will be predominant depends on the For such units, usually the situation is more severe,
intrinsic nature of the crude diet (more or less clean, more or because of the presence of coke and the higher amount of
less stable) and on desalter performance. asphaltenes in the feed and generally lower stability.
Therefore, the dispersant must be more specific and stron-
Cleaning of VDU feed ger compared to the one injected into the feed of VDUs pro-
For the inorganic part, the first measure is to maximise cessing atmospheric residue.
desalting efficiency: with lower basic sediment and water, Moreover, it is necessary to tackle the polymerisation reac-
and lower caustic injection in the desalted crude, their con- tions through the injection of a stabiliser, so the olefins can-
centration in the VDU feed will be lower as will their role in not form heavy gums.
reducing the heat exchangers’ performance. In such a situation, if possible the chemicals have to be
For more than four decades, Chimec has developed a pro- injected directly into the cracking unit’s MF bottom so
gramme – based on demulsifiers together with analytical that they can act from the very beginning, before coke and
and software tools – aimed at helping refineries in improving asphaltenes can settle and polymers are formed, fouling
the desalter’s performance. downstream equipment.

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PTQ Q2 2021 Digital Edition

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PETROLEUM TECHNOLOGY QUARTERLY

SOx REDUCTION NEUTRALISING

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21 A smart approach to tank dewatering

27 Delivering drop-in renewable fuels

39 Amine anomaly in a mild hydrocracker

47 Dividing wall revamp boosts octane and throughput

55 Taking a holistic approach to a revamp

63 Selecting catalysts for marine fuels production

69 FCC SOx additives and security of supply

75 Designing steam heat exchangers and tracing systems

79 Neutralising amine selection for crude units

87 Energy network monitoring and optimisation

93 Delayed coking as a sustainable refinery solution

100 Boosting tube-side heat transfer

104 Crude logistics scheduling

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And, our catalyst experts can offer insight,

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H2 recycle O2 in the inlet gas No -traces Few %

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Raw material & process Chemical building blocks Present Future

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The challenges of today’s refining industry—from rising environmental standards to getting

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FAWAZ AL SAHAN, OMAR AL ZAYED and FAWAZ AL HADLAQ

carbon losses, and crude quality. The sound velocity dewatering

Sound velocity dewatering system Figure

hydrocarbon at operating temperature. This can be found in the literature or c