PCE 464 TECHNOLOGY OF PETROLEUM REFINING

COURSE CONTENT
Introduction (General Processing Scheme, Primary Treatment)
Refinery Operation
Crude Distillation
Conversion Processes
➢ Coking Processes
➢ Fluid Catalytic Cracking
➢ Hydrocracking
➢ Alkylation
➢ Polymerization
Quality Improvement Processes
➢ Hydrotreating
➢ Catalytic Reforming
➢ Isomerization
➢ Visbreaking
➢ Desulphurization
Others

WHAT THE COURSE IS ABOUT

The course generally focusses on:

1. The processing of Petroleum Crude Oil to more usable products such as petrol, diesel,
lubricating oils and petroleum waxes as well as bitumen.
2. The optimizing of the refining operations to obtain high quality products, to reduce cost of
operation and also reduce the effect of operations on refinery workers, refinery equipment
as well as the environment.

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MOTIVATION
The refinery process is a capital intensive unit operation with a very competitive product range
and for that matter, refiners wish to undertake their operations in a very cost effective manner
without compromising on the quality of products as well as the health and safety of the workers
and the environment. This course seeks to highlight the various steps needed to be taken in order
to achieve the bigger objective of the refinery operation. The various refinery unit operations
would be looked at in order to appreciate the entire refining process.

WHY THE COURSE IS IMPORTANT

This course is significant because it seeks to introduce students to the petroleum refining process,
the various product upgrading processes etc. The petroleum refinery adds value to the well sought
after crude oil in order to produce the various fuels needed to drive various industry most especially
the transportation of people and goods.

COURSE OBJECTIVES
The main objectives of this course is to discuss the fundamental concepts of petroleum
refining operations and the operating principles and apply those concepts to real
engineering problems encountered at the refineries. This course will provide an overview
of what one needs to know to appreciate the operations in any standard petroleum refinery.
The goal is to provide students with the theoretical or analytical background to understand
petroleum refining operations and tackle sort of complex problems encountered at the
refinery.

COURSE EXPECTED LEARNING OUTCOMES

By the end of this course, students are expected to be able to:

Understand what the petroleum refinery is about

Appreciate the distillation of crude oil to finished fuel products for use.
Understand the various products that can be obtained from the refining operation and know
their uses.
Appreciate the various conversion processes employed in the refineries.
Understand the various upgrading processes used in refineries to improve on product
qualities.

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 Know the various catalysts that are used in refinery operations.

COURSE READING LIST

Robert Meyers (2003) Handbook of Petroleum Processes 3rd Edition, McGraw-Hill
Professional
James G. Speight (2017) Handbook of Petroleum Refining, Taylor & Francis; CRC Press
James H. Gary, Glenn E. Handwerk (2001) Petroleum Refining-Technology and
Economics 4th Edition; CRC Press
Mohamed A. Fahim, Taher A. Al-Sahhaf and Amal Elkilani (2009), Fundamentals of
Petroleum Refining; Elsevier Science
Kayode Coker (2018) Petroleum Refining Designs and Applications 1st Edition Scrivener
Publishing, Wiley
James G. Speight (1997) Petroleum Chemistry and Refinery, CRC Press
James G. Speight (2010) The Refinery of the Future, William Andrew
Robert E. Maples (2000) Petroleum Refinery Process Economics, 2nd Edition, PennWell

COURSE ORGANIZATION
A quick quiz would be taken either before, during or after a lecture
Three (3) Assignments would be given
Mid-semester examination at the university-specified time (A quiz could be taken in place
of it)
Final Examination (70%)
Contact time: Students can contact me on my personal line between 9 am and 5 pm

PRE-REQUISITE COURSE KNOWLEDGE

The needed basic knowledge includes:
Separation Processes/Mass Transfer
Material and Energy Balances
Heat Transfer
Thermodynamics

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TABLE OF CONTENTS
COURSE CONTENT.......................................................................................................................................... i
WHAT THE COURSE IS ABOUT ....................................................................................................................... i
MOTIVATION ................................................................................................................................................. ii
WHY THE COURSE IS IMPORTANT ................................................................................................................ ii
COURSE OBJECTIVES ..................................................................................................................................... ii
COURSE EXPECTED LEARNING OUTCOMES .................................................................................................. ii
COURSE READING LIST ................................................................................................................................. iii
COURSE ORGANIZATION .............................................................................................................................. iii
PRE-REQUISITE COURSE KNOWLEDGE......................................................................................................... iii
CHAPTER ONE ............................................................................................................................................... 1
INTRODUCTION ............................................................................................................................................. 1
PETROLEUM CRUDE OIL ................................................................................................................................ 1
HISTORY OF PETROLEUM CRUDE OIL ........................................................................................................... 2
COMPOSITION OF CRUDE OIL ....................................................................................................................... 3
CRUDE OIL SOURCES ..................................................................................................................................... 3
CLASSIFICATION OF CRUDE OIL HYDROCARBONS ........................................................................................ 4
CLASSIFICATION OF CRUDE OIL .................................................................................................................... 7
CHAPTER TWO .............................................................................................................................................. 9
REFINERY OPERATION................................................................................................................................... 9
CRUDE OIL PRETREATMENT PROCESSES ...................................................................................................... 9
Desalting ....................................................................................................................................................... 9
Desalter ......................................................................................................................................................... 9
Types of Desalters ....................................................................................................................................... 10
Types of Desalting chemicals ...................................................................................................................... 10
Desalting Efficiency ..................................................................................................................................... 10
Types of dehydrators .................................................................................................................................. 12
Desalting/Dehydration ................................................................................................................................ 13
CHAPTER THREE .......................................................................................................................................... 14
CRUDE DISTILLATION .................................................................................................................................. 14
CHAPTER FOUR ........................................................................................................................................... 16
CONVERSION PROCESSES ........................................................................................................................... 16
COKING........................................................................................................................................................ 16

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FLUID CATALYTIC CRACKING ....................................................................................................................... 21
HYDROCRACKING ........................................................................................................................................ 29
ALKYLATION ................................................................................................................................................ 30
POLYMERIZATION ....................................................................................................................................... 33
OTHER REFINERY SUPPORTING PROCESSES ............................................................................................... 34
CHAPTER FIVE ............................................................................................................................................. 38
QUALITY IMPROVEMENT PROCESSES ......................................................................................................... 38
HYDROTREATMENT..................................................................................................................................... 38
VISBREAKING............................................................................................................................................... 42
CATALYTIC REFORMING .............................................................................................................................. 44
ISOMERIZATION .......................................................................................................................................... 47
PRODUCT BLENDING ................................................................................................................................... 49

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TABLE OF FIGURES
Figure 1: The famous Lucas Gusher oilwell in Spindletop, Texas ................................................. 2
Figure 2: Crude oil sources ............................................................................................................. 4
Figure 3: Examples of naphthenes commonly present in crude ..................................................... 6
Figure 4: Crude desalter unit......................................................................................................... 11
Figure 5: Crude distillation ........................................................................................................... 15
Figure 6: Sponge coke derived from a petroleum feedstock that shows abundant pore structure.
....................................................................................................................................................... 16
Figure 7: Typical needle coke derived from a petroleum feedstock ............................................. 17
Figure 8: Delayed coking .............................................................................................................. 18
Figure 9: Fluid coking process ...................................................................................................... 19
Figure 10: Flexicoking process ..................................................................................................... 20
Figure 11: Y- zeolite Figure 12: ZSM-5 ................................................................................ 23
Figure 13: FCC configuration ....................................................................................................... 24
Figure 14: The heart of FCC ......................................................................................................... 24
Figure 15: Flowsheet of an FCC process ...................................................................................... 25
Figure 16: Hydrotreating: flow scheme ........................................................................................ 41
Figure 17: Visbreaking Flowsheet ................................................................................................ 42
Figure 18: Alternative Visbreaking flowsheet .............................................................................. 43
Figure 19: Catalytic reforming scheme......................................................................................... 46

LIST OF TABLES

Table 1: Compositions of crude oil ................................................................................................. 3

Table 2: Optimum operating condition for an FCC unit to produce maximum Petrol (Gasoline) 26
Table 3: Typical Catalytic Reforming Feedstock and Product Analysis (vol%) .......................... 44
Table 4: Operation conditions and yield ....................................................................................... 48

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 CHAPTER ONE
INTRODUCTION
What is oil refining?
It is an industry which processes crude oil into more useful petroleum products such as petrol,
diesel fuel, asphalt base, heating oil, kerosene and liquefied petroleum gas by fractional distillation.

It is a weight gaining industry.

Petroleum refining results in output greater than the input because of changes in the overall density
of the refined products relative to that of the input oils.
The major raw materials required in petroleum refinery are crude oil and water (for
cooling).
The study of petroleum refining begins with describing the major feedstock which is the
crude oil and the range of products that are produced by the various processes.
Crude oil comes from different parts of the world and has different physical and chemical
characteristics. On the other hand, the products that are produced have to meet market
requirements and hence certain specifications need to be complied with.
Oil refining is a key activity in the CPI.
As of January 2020, there are 697 refineries worldwide. In 2019, the world’s refinery
capacity reached over 101 million barrels per day
Goal of oil refining is in two folds:
➢ Production of fuels for transportation, power generation and heating; and
➢ Production of raw materials for the CPI.
Oil refineries are complex plants but are relatively mature and highly integrated

PETROLEUM CRUDE OIL

Petroleum crude oil, or simply crude oil, is a naturally occurring, flammable and usually
dark brown or greenish colored liquid found primarily in underground geological
formations.
Crude oil consists of a complex mixture of hydrocarbons of various molecular weights plus
other chemical compounds.

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HISTORY OF PETROLEUM CRUDE OIL
Petroleum, in one form or another, has been used since ancient times. About 2400 years
ago (450 BC), oil and asphalt pitch pits existed near Babylon. In those ancient times, it was
used occasionally as medicine to treat various diseases. It was also used as fuel,
construction mortar, road paving, and for waterproofing ships.
The Latin word petroleum was first used to describe petroleum crude oil by the German
mineralogist Georg Bauer (also known as Georgius Agricola) in 1546. The Greek word for
petroleum is ''πετρέλαιον'', meaning "rock oil".
The first oil well drilled at Spindletop in southeast Texas, known as the "Lucas Gusher",
was completed when petroleum crude oil gushed forth on January 10, 1901. The oil
reservoir underneath Spindletop was formed by a salt dome.
The Lucas Gusher become known as the oil well that started the birth of the oil industry in
Texas. It initially produced about 100,000 barrels per day (16,000 cubic metres per day),
more than the combined production from all of the oil wells then existing in the United
States.

Figure 1: The famous Lucas Gusher oilwell in Spindletop, Texas

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COMPOSITION OF CRUDE OIL
On average, crude oils are made of the following elements or compounds:

Carbon – 83-87%
Hydrogen – 10-14%
Sulphur – 0.5 to 6% (hydrogen sulphide, sulphides, disulphides, elemental sulphur)
Nitrogen - less than 1% or higher (basic compounds with amine groups)
Oxygen - less than 1% or higher (found in organic compounds such as carbon dioxide,
phenols, ketones, carboxylic acids)
Metals - less than 1% (nickel, iron, vanadium, copper, arsenic)
Salts- less than 1%(sodium chloride, magnesium chloride, calcium chloride)

Table 1: Compositions of crude oil

Element Average Hydrocarbon Weight Percent
Weight percent
Carbon 83-87 Paraffins 30
Hydrogen 10-14 Naphthenes 49
Nitrogen 0.1-2 Aromatics 15
Oxygen 0.1-1.5 Asphaltics 6
Sulphur 0.5-6
Metals ˂ 0.1

CRUDE OIL SOURCES

Both crude oil and natural gas are predominantly mixtures of hydrocarbons. At typical ambient
conditions of pressure and temperature, the lower molecular weight hydrocarbons methane,
ethane, propane and butane occur as gases, while the higher molecular weight hydrocarbons
(pentane and higher) are in the form of liquids or solids. However, in the underground oil
reservoirs, the proportion which is gas or liquid varies depending on the subsurface pressure and
temperature conditions and on the phase diagram of the petroleum mixture.

Crude oil consists mostly of hydrocarbons with small amounts of other chemical compounds that
may contain nitrogen, oxygen or sulphur. It may also contain trace amounts of metals such as iron,
nickel, copper and vanadium. The average elemental composition of petroleum crude oil and the
average distribution of the different hydrocarbons in the various crude oils are shown in the

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adjacent tables. The exact elemental composition varies widely from formation to formation but
the proportion of chemical elements vary over fairly narrow limits.

The distribution of the different types of hydrocarbons in petroleum also varies considerably from
one crude oil reservoir to another which means that the properties of the various crude oils are
quite different.

Figure 2: Crude oil sources

CLASSIFICATION OF CRUDE OIL HYDROCARBONS

The hydrocarbons in crude oil can generally be divided into four categories:

Paraffins
Napthenes
Aromatics
Asphaltics
Classification of hydrocarbons (Paraffin)
These can make up 15 to 60% of crude and have a carbon to hydrogen ratio of 1:2.
These are generally straight or branched chains.
Paraffins are the desired content in crude and what are used to make fuels. The shorter the
paraffins are, the lighter the crude is.

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 They have the general formula CnH2n+2, where n is the
Number of carbon atoms. The simplest alkane is methane (CH4), which is also represented
as C1.
They generally have from 4 to 40 carbon atoms per molecule, although some molecules
may be present that have less than 5 or more than 40 carbon atoms.
Normal paraffins (n-paraffins or n-alkanes) are unbranched straight chain molecules.
Each member of these paraffins differs from the next higher and the next lower member
by a –CH2– group.
They have similar chemical and physical properties, which gradually changes with
increasing carbon atoms in the chain.
Isoparaffins (isoalkanes) are branched-type hydrocarbons that exhibit structural
isomerization. Structural isomerization occurs when two molecules have the same atoms
but different bonds.
Butane and all succeeding alkanes can exist as straight-chain molecules (n-paraffins) or
with a branched-chain structure (isoparaffins).
Classification of hydrocarbons (Napthenes)

These can make up 30 to 60% of crude and have a carbon to hydrogen ratio of 1:2.
These are cyclic compounds and can be thought of as cycloparaffins (have at least one ring
of carbon atoms).
They are higher in density than equivalent paraffins and are more viscous.
They have the general formula CnH2n.
The common naphthenes present in crude oil have rings with five or six carbon atoms.
These rings usually have alkyl substituents attached to them. Multi-ring naphthenes are
present in the heavier parts of the crude oil.

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Figure 3: Examples of naphthenes commonly present in crude

Classification of hydrocarbons (Aromatics)

These can constitute anywhere from 3 to 30% of crude.
They are undesirable because burning those results in soot.
They have a much less hydrogen in comparison to carbon than is found in paraffins.
They are also more viscous.
They are often solid or semi-solid when an equivalent paraffin would be a viscous liquid
under the same conditions.
Examples of these compounds are toluene and xylene.
Their presence in crude is undesirable as they facilitate catalyst deactivation and coke
deposition during processing.

Classification of hydrocarbons (Asphaltics)

These average about 6% in most crude.
They have a carbon to hydrogen ratio of approximately 1:1, making them very dense.
They may have a molecular weight of 800 to 2500.
They are generally undesirable in crude, but their 'stickiness' makes them excellent for use
in road construction.

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CLASSIFICATION OF CRUDE OIL
The petroleum industry generally classifies crude oil by the geographic location of the reservoir
from which it is produced (e.g., West Texas Intermediate, Brent, or Oman), its API gravity (an oil
industry measure of density), and by various non-hydrocarbon components (especially sulphur
content)

Crude oil may be considered "light" if it has a low density or "heavy" if it has a high density and
it may be referred to as "sweet" if it contains relatively little sulphur or "sour" if it contains
substantial amounts of sulphur.

The end result of all the classification helps determine the price of a specific barrel of crude as
well as how much demand there is for that particular oil.

Light crude oil is more desirable than heavy oil since it provides a higher yield of gasoline and
sweet oil is more desirable than sour oil because it has fewer environmental problems and requires
less refining to meet sulphur content standards of refined fuels. Each crude oil has a unique
composition and set of physical properties which are delineated by crude oil assays performed in
petroleum laboratories.

Classification of Crude Oil based on Location

Some of the common petroleum crude oils (many of which are known as "benchmark crude oils")
are:
West Texas Intermediate is a very high-quality, sweet, light oil. It is a North American oil.
Brent Blend is a blend of 15 oils from the Brent and Ninian oil fields in the East Shetland
Basin of the North Sea.
Dubai Crude is a Middle Eastern sour oil from Dubai.
Arabian Crude is a Middle Eastern oil from Saudi Arabia.
Tapis Crude is a Far Eastern oil from Malaysia.
Minas Crude is a Far Eastern oil from Indonesia.
Pembina encompasses crude oils from Western Canada.
Russian Export Blend is a mixture of several crude oils exported by Russia.

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Classification of Crude Oil based on Sulphur Content
Two major classes of crude based on the presence of sulphur are known. These are:

Sweet crude: Crude oil with less than 0.5 wt % sulphur is referred to as low sulphur or
sweet and
Sour crude: Crude oil with more than 0.5 wt% sulphur is referred to as high sulphur or
sour.
Crude oils contain sulphur hetero-atoms in the form of elemental sulphur (S), dissolved
hydrogen sulphide (H2S), carbonyl sulphide (COS), mercaptans (Thiols) and thiophenes.
Mercaptans are made of an alkyl chain with –SH group at the end (R–SH). Examples of
mercaptans are methyl mercaptan (CH3SH), n-butyl mercaptan (CH3CH2CH2CH2SH) etc.
In sulphides and disulphides, the sulphur atom replaces one or two carbon atoms in the
chain (R–S–R` or R–S–S–R`). These compounds are often present in light fractions.
Thiophenes are polynuclear aromatic compounds in which the sulphur atom replaces one
or more carbon atoms in the aromatic ring. They are normally present in heavier fractions.

Classification of Crude Oil based on API gravity

The API gravity is the standard specific gravity used by the oil industry, which compares the
density of oil to that of water through a calculation designed to ensure consistency in measurement.
API stands for the American Petroleum Institute, which is the industry organization that created
this measure.

API gravity = (141.5/Specific Gravity) – 131.5

The API gravity is used to classify oils as light, intermediate or heavy. As the “weight” of
an oil is the largest determinant of its market value, API gravity is exceptionally important.
The API values for each “weight” are as follows:
➢ 20 degrees or less, it is graded as 'heavy', (API gravity ≤ 20o = heavy)
➢ those with an API gravity of 40.1 degrees or greater than that is known as 'light'(API
Gravity ≥ 40.1o) and
➢ if the oil ranges between 20 and 40.1 degrees, it is graded as 'intermediate' (40.1o˂API
>20o

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 CHAPTER TWO
REFINERY OPERATION
CRUDE OIL PRETREATMENT PROCESSES
Desalting
Removal of salts from crude is called Desalting

Desalter
The equipment used for the removal of salts, suspended solids and water soluble trace metals/slits,
iron oxides, sand etc.
Purpose of Desalting
To reduce fouling and plugging of crude oil fractionators and exchangers due to salt
deposition.
To reduce rate of corrosion of crude oil fractionators.
To avoid lengthy and expensive plant shut downs.
To reduce consumption of Neutralizers.
To remove Metals which may poison Reformer Catalyst.
To achieve more than average Plant Life.
Crude Oil Salt Chemistry
These salts are mainly chlorides and sulphates of Calcium and Magnesium like NaCl,
MgCl2, CaCl2 and MgCl2.
Chlorides hydrolyzed to hydrochloric acid cause severe corrosion.
CaCl2 + H2O → Ca(OH)2 +HCl
Salts act as catalyst to Plugging of Exchangers and formation of coke (hot spots) in heater
tubes.
Salts in residue contain high ash content causing degradation of product.
Salts are generally measured in PTB (parts per thousand barrels).
Salts concentration in crude depends upon the Source of Crude.

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Types of Desalters
Natural Desalter

Chemical Desalter

Electro Chemical Desalter

Natural Desalter
Desalter in which Settling time is given to salts, sediments, water and sludge which under gravity
settled down in the bottom of Vessel and then drained.

Chemical Desalter
Desalter in which chemical is added to the crude in order to remove salts, sediments, water
and sludge.

Chemicals reduce the surface tension for making removal of salts and water easy.

NOTE: Both Natural and Chemical Desalter are useful for crude having low salts or for Batch
Process.

Electrochemical Desalter
Desalting process by use of chemical along with electric field.
Demulsifier used as chemical while electrodes connected to step up transformer used for
electric field generation.

Types of Desalting chemicals

Soap: migrates to interface and weakens interfacial films.
Polar: Migrates to interface and alters polarity, so particles will coalesce.
H2O Soluble : Acts as Soap or Polar but remain in water phase
Ionic: Increase Electric conductivity, which increase tendency to demulsify.

Desalting Efficiency
Desalter efficiency can be calculated as:

SE = (Si – So ) * 100 / Si

10
where:
SE is salt removal efficiency (%)
Si is salt content of raw crude oil (ptb)
So is salt content of desalted oil (ptb).
Ptb stands for Pounds per Thousand Barrels
Desalter efficiency should be 90-95 %

Figure 4: Crude desalter unit

The salt content should be lowered to between 5.7 and 14.3 kg/1000 m3 (2 and 5 PTB)
Poor desalting has the following effects:

Salts deposit inside the tubes of furnaces and on the tube bundles of heat exchangers
creating fouling, thus reducing the heat transfer efficiency
Corrosion of overhead equipment
The salts carried with the products act as catalyst poisons in catalytic cracking units

Crude desalter unit operation variable

Desalting temperature – affect settling rate, typical desalting temperature can vary between
50 and150 oC (122 and 302 oF)

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 Washing water ratio – affect in salt removal, Kuwait crude (31.2 API) requires 7–8 vol%
water addition relative to the crude rate
Water level - Raising the water level reduces the settling time for the water droplets in the
crude oil, thus improving the desalting efficiency
Washing water injection point
Demulsifier injection rate
Type of washing water - relatively soft to prevent scaling, slightly acidic with a pH in the
range of 6, free from hydrogen sulphide and ammonia
Pressure drop in the mixing valve - A pressure drop between 0.5 and 1.5 bar (7.4 and 22
psi) is used

Types of dehydrators
Dehydrator types used in industry are basically classified according to their construction. They
are:
Vertical
Spherical
Horizontal
Vertical Dehydrator
It is composed of a cylindrical vessel having a diameter of 3m, a height of 5m and a total
volume of about 30 m3.
Electrodes are found inside and electric energy given by two transformers each with a
capacity of 5kW. The hydrated crude moves up while the water is drawn from the base.
Disadvantage is the ineffective removal of water.
Spherical Dehydrator
The first construction of this type was made in 1955-1970.
Volume of vessel: 600m3
Diameter of 10.5m
Treatment capacity of about 300-500m3/h
Similar principles employed as the vertical
The disadvantages are :
➢ Less efficiency
➢ High material of metal used
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Horizontal Dehydrator
Widely used in industry
Operating pressure of 1.8MPa and temperature up to 160 degrees Celsius
Volume: 160-200m3
Diameter of 3.4m and length of up to 23m.
Desalting/Dehydration
An important process in the refining process is to remove these contaminants so as to
reduce corrosion, plugging, and fouling of equipment and to prevent poisoning catalysts in
processing units.
The two most typical methods of crude-oil desalting are chemical (thermo-chemical) and
electrostatic separation and both use hot water as the extraction agent.
In chemical desalting, water and chemical surfactant (demulsifiers) are added to the crude,
which is heated so that salts and other impurities dissolve or attach to the water, then held
in a tank to settle out.
Electrical desalting is the application of high-voltage electrostatic charges to concentrate
suspended water globules in the bottom of the settling tank. Surfactants are added only
when the crude has a large amount of suspended solids.
Through the dehydration of petroleum crude in industry using the thermo-chemical , water
is significantly reduced to about 0.5-1.0% simultaneously, significant quantities of salt are
also removed in that process.
The dilution factor for desalting is 4-7% (vol.) of the petroleum crude being processed.
The most significant equipment used in the desalting/dehydration process is the electric
dehydrator.

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 CHAPTER THREE
CRUDE DISTILLATION
The first and the most fundamental step in the refining process (after the crude oil has been cleaned
and any remnants of brine removed) is distillation, which is often referred to as the primary refining
process. Distillation involves the separation of the different hydrocarbon compounds that occur
naturally in a crude oil into a number of different fractions (a fraction is often referred to as a cut).

In the atmospheric distillation process (Fig.), heated crude oil is separated in a distillation column
(distillation tower, fractionating tower, atmospheric pipe still) into streams that are then purified,
transformed, adapted, and treated in a number of subsequent refining processes, into products for
the refinery's market.

The lighter, more volatile, products separate out higher up the column, whereas the heavier, less
volatile, products settle out toward the bottom of the distillation column. The fractions produced
in this manner are known as straight run fractions ranging from (atmospheric tower) gas, gasoline,
and naphtha, to kerosene, gas oils, and light diesel, and to (vacuum tower) lubricating oil and
residuum.

The feed to a distillation tower is heated by flow through pipes arranged within a large furnace.
The heating unit is known as a pipe still heater or pipe still furnace, and the heating unit and the
fractional distillation tower make up the essential parts of a distillation unit or pipe still.

The pipe still furnace heats the feed to a predetermined temperature— usually a temperature at
which a predetermined portion of the feed will change into vapor. The vapour is held under
pressure in the pipe in the furnace until it discharges as a foaming stream into the fractional
distillation tower. Here the unvaporized or liquid portion of the feed descends to the bottom of the
tower to be pumped away as a bottom nonvolatile product, whereas the vapours pass up the tower
to be fractionated into gas oils, kerosene, and naphtha.

14
Figure 5: Crude distillation

15
 CHAPTER FOUR
CONVERSION PROCESSES
COKING
Coking is a severe method of thermal cracking used to upgrade heavy residuals into lighter
products or distillates. Coking produces straight-run gasoline (Coker naphtha) and various middle-
distillate fractions used as catalytic cracking feedstock. The process completely reduces hydrogen
so that the residue is a form of carbon called "coke."

Three typical types of coke are obtained (sponge coke, honeycomb coke, and needle coke)
depending upon the reaction mechanism, time, temperature, and the crude feedstock.

In delayed coking the heated charge (typically residuum from atmospheric distillation towers) is
transferred to large coke drums which provide the long residence time needed to allow the cracking
reactions to proceed to completion.

Figure 6: Sponge coke derived from a petroleum feedstock that shows abundant pore structure.
[Link]

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Figure 7: Typical needle coke derived from a petroleum feedstock.
[Link]

Delayed Coking
Heavy feedstock is fed to a fractionator. The bottoms of the fractionator are fed to coker drums via
a furnace where the hot material (440°-500°C) is held approximately 24 hours (delayed) at
pressures of 2-5 bar, until it cracks into lighter products. Vapors from the drums are returned to a
fractionator where gas, naphtha, and gas oils are separated out. The heavier hydrocarbons produced
in the fractionator are recycled through the furnace.

After the coke reaches a predetermined level in one drum, the flow is diverted to another drum to
maintain continuous operation. The full drum is steamed to strip out uncracked hydrocarbons,
cooled by water injection, and de-coked by mechanical or hydraulic methods.

The coke is mechanically removed by an auger rising from the bottom of the drum. Hydraulic
decoking consists of fracturing the coke bed with high-pressure water ejected from a rotating
cutter.

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Figure 8: Delayed coking

Fluid Coking and Flexicoking

Both FLUID COKINGTM and FLEXICOKINGTM use fluid bed technology to thermally convert
heavy oils such as vacuum residue, atmospheric residue, tar sands bitumen, heavy whole crudes,
deasphalter bottoms or cat plant bottoms.

FLEXICOKING goes one step further than FLUID COKING: in addition to generating clean
liquids, FLEXICOKING also produces a low-BTU gas in one integrated processing step that can
virtually eliminate petroleum coke production.

The advantages are: flexibility to handle a variety of feed types; high reliability with the average
service factor between 90 -95%; large single train capacity provides an economy of scale that
lowers investment cost; able to process 65 kB/SD of 20 wt% Conradson Carbon resid in a single
reactor; time between turnarounds routinely approaches two years; able to process very heavy feed
stocks such as deasphalter bottoms at high feed rates.

Additional FLEXICOKING benefit: Integrated gasification of up to 97% of gross coke production.

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The Fluid Coking Process
The fluid coking residuum conversion process uses non-catalytic, thermal chemistry to achieve
high conversion levels with even the heaviest refinery feedstocks.

Since most of the sulphur, nitrogen, metals, and Conradson Carbon Residue feed contaminants are
rejected with the coke, the full-range of lighter products can be feed for an FCC unit.

Use as a single train reduces manpower requirements and avoids process load swings and frequent
thermal cycles that are typical of batch processes such as delayed coking.

The configurations available with fluid coking are: extinction recycle, once-through, and once-
through with hydroclones.

Figure 9: Fluid coking process

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The Flexicoking Process
 Flexicoking is a thermal technology for converting heavy feedstocks to higher margin
liquids and producing, a low BTU (i.e. a low energy content) gas, instead of coke.
 The conversion of coke to clean fuel gas maximizes refinery yield of hydrocarbons.
 The carbon rejection process results in lower hydrogen consumption than alternative
hydrogen-addition systems.
 The low BTU gas is typically fed to a CO boiler for heat recovery but can also be used in
modified furnaces/boilers; atmospheric or vacuum pipestill furnaces; reboilers; waste heat
boilers; power plants and steel mills; or as hydrogen plant fuel, which can significantly
reduce or eliminate purchases of expensive natural gas.
 The small residual coke produced can be sold as boiler fuel for generating electricity and
steam or as burner fuel for cement plants.

Figure 10: Flexicoking process

20
FLUID CATALYTIC CRACKING
Catalytic cracking was developed in 1920 by Eugene Houdry for residue upgrading and
was later commercialized in 1930.
The Houdry process was based on cyclic fixed bed configuration. Later upgrading of the
catalytic cracking process resulted in the use of the fluidized bed hence its current name
Fluid (Fluidized) Catalytic Cracking (FCC).
Fluid catalytic cracking (FCC) is a process by which heavy (high molecular weight) low-
value petroleum fractions are upgraded into higher value products having low molecular
weight.

The feedstock
The main feedstock used in an FCC unit is the gas oil with average boiling point between 316oC
and 566oC.
Other possible feedstocks to the FCC unit include:
Atmospheric distillate,
Coking distillates,
Visbreaking distillates,
Vacuum gas oil (VGO),
Desulphurised atmospheric residue and
Desulphurised and deasphalted vacuum residue.
The main limitation on feedstocks to the FCC unit is its Carbon Residue (CR) and its metal content
(The presence of nitrogen in the feedsock beyond 0.2% is undesirable).
Products
The following are the possible products from the FCC unit
Gasoline- heavy gasoline (which is the main product),
LPG
light gases-H2, C1 , C2
light cycle gas oil (LCO)- blend component for diesel
heavy cycle gas oil (HCO)- optional for fuel oil
Diesel along with very important petrochemical feedstock such as:
➢ Propylene

21
 ➢ C4 gases such as isobutylene, isobutane, and butane.
The FCC process provides around 50% of all transportation fuels and about 35% of total gasoline
pull.
FCC Reaction
The main reactions involved in catalytic cracking are:
Cracking
Isomerization
Hydrogenation
Dehydrogenation
Cyclization
Condensation
Alkylation and dealkylation
The major primary reactions taking place are:

Long chain paraffin converted to smaller paraffin and olefins

Alkyl naphthene converted to naphthene and olefins
Alkyl aromatic converted to aromatic and olefins
Multi-ring naphthene converted to alkylated naphthene with fewer rings
Olefins go through cracking to form LPG and other olefins and they go through cyclization
to form naphthene.
Thermodynamics of FCC Reactions
Cracking reaction consists of both endothermic and exothermic reaction.
However, overall, cracking may be thought of as being endothermic and hence heat has to
be supplied to facilitate the reaction.
The heat for the FCC process is supplied by the combustion of the deposited coke on the
catalyst during its regeneration.
The high volume of products caused by the cracking requires the operating pressures to be
low (1 – 5 bar) whiles the highly endothermic nature requires the use of high temperatures
of between 480 – 550oC.

22
FCC Catalyst
The catalyst used in a FCC reactor is basically a mixture of zeolite Y and a co-gelled
mixture of silica and alumina, known simply as silica – alumina.
The proportion of the zeolite is a minimum of 3% and a maximum of 25%.
The FCC catalyst is in a powdered form with average particle size of 75 µm and a surface
area of about 800 m2/g.
In cracking of long chain paraffins ZSM-5 zeolite is added to improve the octane rating of
the cracked product.

Figure 11: Y- zeolite Figure 12: ZSM-5

FCC Configuration
The basic configuration of the FCC unit is a reactor (riser) and a regenerator.
The catalyst is circulated between them where is it deactivated in the riser and regenerated
in the regenerator.
There are two basic types of FCC unit in use today. These are the ‘Side-by-Side’ and
Stacked or Orthoflow types.

23
Figure 13: FCC configuration

F = Feed, P = Products, S = Steam, FG = Flue gas, A = Air

The Heart of FCC

Figure 14: The heart of FCC

24
FCC Process Description
The three main functions in the FCC process are:
Reaction- feedstock reacts with catalysts and cracks into different hydrocarbons
Regeneration- catalyst is regenerated by burning off coke; and re-circulated to reactor.
Fractionation- cracked hydrocarbon stream is separated into various products like LPG,
gasoline, light cycle oil and heavy cycle oil.
Steam and the feedstock heated up to 316 – 427oC enters the riser where it comes into contact with
the regenerated catalyst at a temperature of 649 – 760oC. Due to the high velocity of the steam and
the vaporized feedstock the regenerated catalyst is aerated or fluidized as it rises through the riser:
this result is an intimate contact between the catalyst and the vapourized feedstock which
subsequently lead to the cracking of it after about 2 – 10s. The cracked products together with the
fluidized catalyst pass through a cyclone inside the riser which separates the products from the
catalyst. The separated product is sent to a fractionation column where it is separated into the
required products whiles the settled catalyst is systematically siphoned into the regenerator to be
regenerated.

Figure 15: Flowsheet of an FCC process

25
Table 2: Optimum operating condition for an FCC unit to produce maximum Petrol (Gasoline)
Variable Value

Reactor Feed Rate, MBPSD 40

o
230
Feed Temperature, C
Catalyst/Oil Ratio 5.4
Catalyst Circulation Rate, tons/min 21.7
Catalyst Makeup Rate, tons/day 2.5
o
533
Riser Outlet Temperature, C
Dispersion Steam, wt% feed 0.9
Stripping Steam, tons/ton catalyst 0.0213
Reactor Pressure, psig 30
Regenerator Pressure, psig 33
o
727
Regenerator Temperature, C
o
735
Flue Gas Temperature, C

FCC Yield Correlation

For these correlations conversion (CONV%) is defined as:

The cycle stock is the portion of the feedstock which is not cracked to fractions lighter than
gasoline.
CONV% + Cycle Stock% = 100
Thus if conversion is 75% then the percentage cycle stock would be 25%.

26
Modified Catalytic Cracking Processes
Resid FCC (RFCC) Process: The RFCC process uses similar reactor technology as the
FCC process and is targeted for residual feeds greater than 4 wt-% Conradson carbon. A
two stage regenerator with catalyst cooling is typically used to control the higher coke
production and resulting heat.

Deep Catalytic Cracking (DCC)

➢ Milli Second Catalytic cracking (MSCC) Process: Improvements in riser termination

devices have led to significant decreases in post-riser residence time and post-riser
cracking. The benefits of shorter catalyst-and oil contact time have been lower dry gas
yields, lower delta coke on catalyst and more selective cracking to gasoline and light
olefins.
Due to improvement in reactor design there is lower regenerator temperature and higher
catalyst recovery
➢ Petro FCC Process
The Petro FCC process targets the production of petrochemical feedstock rather than fuel products.
This new process, which utilizes a uniquely designed FCC unit, can produce very high yields of
light olefins and aromatics when coupled with aromatics complex. The catalyst section of the Petro
FCC process uses a high-conversion, short-contact time reaction zone that operates at elevated
reactor riser outlet temperatures.
➢ Indmax Technology- Residue to Olefin
Some of the special features of the technology are:
1. Operational features of Indmax technology
• Very high cat/oil ratio (15-25)
• Higher riser temperature (>5500 C)
• Higher riser steam rate
• Relatively lower regeneration temperature.
2. Benefits
• LPG 35-65 wt%
• Propylene 17-25 wt% feed
• High octane petrol (gasoline) (95+)
3. Multifunctional proprietary catalyst
27
 • Higher propylene selectivity
• Superior metal tolerance
• Lower coke mate
Maximizing Propylene Output in FCC

New FCC processes are being operated to maximize the yield of propylene due to growing demand
of propylene.

28
HYDROCRACKING
Cycle oils and coker distillates are the typical feedstocks
High quality jet fuel and diesel production is targeted
Overall reaction is exothermic

Cracking is promoted on silica-alumina sites of the catalyst. Hydrogenation promoted by

palladium, molybdenum sulphide or tungsten sulphide compounds. Since catalyst gets poisoned
with organic nitrogen compounds, hydrotreater catalytic reactors are used before hydrocracking
reactors to safeguard the hydrocracking catalysts

Excess hydrogen also aids in preventing catalyst coking. Operating conditions of the
hydrocracking reactor: 340 –425 oC and 70 –200 bar. Reactors use fixed or moving bed reactors
in which fixed beds are more common. Packed beds: Cold shot reactors are used in which cold H2
is used to cool the hot streams. Guard reactors are used before hydrocracking catalyst within the
reactor column itself.

Moving beds: Feed allows movement of the catalyst for good mixing. After reaction, the product
gets mixed with water and enters a three phase separator.

The three phase separator generates three streams namely sour water stream, organic stream and a
gas stream.

The gas stream again enters a phase separator to remove entrained organic stream after cooling.

The gas stream is subjected to H2S removal using amine scrubber. The organic stream eventually
enters a steam stripper further stabilize the organic stream. In this fractionator, a gas stream
and a sour water stream are generated.

Eventually, the stabilized organic stream is sent to a multi-product fractionators to

generate light naphtha, heavy naphtha, kerosene, diesel and residue. Steam is used to enhance
the product quality.

29
ALKYLATION
In an alkylation process, olefins are reacted with isoparaffins to yield alkylate product. The basic
purpose of alkylation is to enhance the octane number of the feed stock. For instance, octane
number of butane alkylate is about 92 –97. This is due to the formation of a hydrocarbon with
side chain arrangement of carbon and hydrogen atoms.

Reaction mechanism
There are three basic reaction steps to achieve alkylation:
Step 1 involving Carbonium ion formation: In this reaction, alkene reacts with a proton
(acid catalyst) to produce a proton substituted olefin. The proton substituted olefin
reacts with isoparaffin to generate a reactive carbonium ion and alkane.
Step 2 involving carbonium ion intermediate formation: In this reaction, the
carbonium ion formed in step 1 reacts with the olefin to produce an
intermediate carbonium ion.
Step 3 involving regeneration of carbonium ion: In this reaction, the intermediate
carbonium ion reacts with the isoparaffin to produce alkylate product and carbonium
ion. Thus carbonium ion is again regenerated to take part in step 2 reactions along with
other additional unreacted olefin molecules.
Reaction conditions
To avoid olefin polymerization, high isobutane to olefin ratios are used.

Typical isobutene to olefin ratios are 5:1 to 15:1

Acid catalysts are used. Primarily sulphuric acid (H2SO4) or HF are used.

Depending on the acid catalysts choosen, the process complexity varies. We present both process
technologies to indicate the pertinent process complexity.

Reaction operating temperature: 10 -20 oC using H2SO4 and 25 –40 oC using HF

Reaction temperature: 4.4 bar for H2SO4 and 7.8 bar for HF

When H2SO4 is used refrigeration is used.

When HF is used, refrigeration is not used.

30
Sulphuric Acid Based Alkylation Process Technology
Caustic wash: The feed mixture (olefin + C4 compounds) are first subjected to caustic wash.
During caustic wash, sulphur compounds are removed and spent caustic is recycled back
to the caustic wash. Fresh caustic solution is added to take care of the loss

Refrigeration: The olefin feed enters a refrigeration unit to reduce the feedstock temperature.

Alkylation reactor: The reactor is arranged as a series of CSTRs with acid fed in the first
CSTR and feed supplied to different CSTRs. This arrangement is for maximizing the conversion.

In the alkylation reactor it is important to note that the olefin is the limiting reactant and
isoparaffin is the excess reactant.

The alkylator unit therefore will have two phases in due course of reaction namely the
olefin + isoparaffin mixture which will be lighter and the alkylate stream which will be heavier
and will be appearing as a bottom fraction if allowed to settle.

Since excess isoparaffin is used, the isoparaffin can be easily allowed as a bypass stream.

Eventually, the alkylate product from the last reactor will be taken out as a heavy stream.-
Thus, the alkylation reactor produces two streams. These are (a) isoparaffin rich organic
phase and (b) alkylate rich phase along with acid and isobutane phases.-These streams should
be subjected to further purification.

Phase separator: It so happens that the acid enters the organic rich stream and will be subjected
to phase separation by settling. Similarly, the olefin/isoparaffin mixture will be also separated
by gravity settling. Thus the phase separator produces three streams namely (a) olefin +
isoparaffin rich phase (b) acid rich stream (c) alkylate rich stream.

Olefin + Paraffin processing: The olefin + paraffin stream is first subjected to compression
followed by cooling. When this stream is subjected to throttling and phase separation, then the
olefin + paraffin rich stream will be generated. The propane rich stream from this stream is
generated as another stream in the phase separator.

Propane defractionator: The propane rich stream after cooling is fed to a fractionator where
propane is separated from the olefin+isoparaffin mixture. The olefin+isoparaffin mixture is
sent back to mix with the olefin feed.

31
Caustic wash for alkylate rich stream: The caustic wash operation ensures to completely
eliminate acid concentration from the alkylate.

Alkylate fractionation: The alkylate is fed to a distillation column that is supplied with
isobutane feed and alkylate feeds to produce isobutane as a top product and alkylate + butane
mixture as a bottom product.

Debutanizer: The debutanizer separates butane and alkylate using the concept of distillation

HF Process Technology
The process is similar to the sulphuric acid plant. However, additional safety issues make the
process complex.

The feed is first subjected to drying followed by pre-cooling. After pre-cooling the reaction
mixture, the reaction mixture is fed to a reactor.

Unlike CSTRs in series here impeller reactors are used. The reactor consists of cooling tubes to
absorb the heat generated. The reaction products enters a settler where oil and the HF are separated.
Since there can be traces of HF in the oil rich phase and vice-versa additional processing is
followed.

The HF rerun column removes traces of oils from the bulk of the HF. Thus HF purified
will be recycled back to the reactor. The bottom product thus generated in this unit is acid oils.

A HF stripper is used to remove the HF in lower quantities from the alkylate product. Eventually,
the HF stripper produces HF that is sent back to the reactor and the alkylate product.

The alkylate product is sent to a deisobutanizer and depropanizer units. The final alkylate
product is produced by using a deflourinator which is basically a caustic wash or adsorption unit.
Finally, n-butane + alkylate is produced as the bottom product.

32
POLYMERIZATION
Olefin polymerization to yield polymer gasoline is primarily carried out to obtain polymers with
good octane numbers. The octane number of the polymer gasoline product is not greater
than the octane number of the products produced from reforming and alkylation. Instead,
comparatively poor quality product is obtained. But for the sake of enhancing octane number
polymerization is carried out.

On the other hand, polymer gasoline has more vapour pressure than the corresponding
alkylation products. Therefore, in both ways, polymer gasoline product quality is lower than
that obtained from the alkylation unit.

Typical feedstock for polymerization process are C3and C4 olefins that are obtained from
catalytic cracking

The end product from polymerization reactor is a dimer or a trimer of the olefins.

Reaction mechanism and operating conditions

Reaction mechanism comprises of four basic steps

Carbonium ion formation (Step 1): Here, olefin reacts with acid catalyst to yield carbonium ion.

Additon reaction (Step 2): Carbonium ion reacts with olefin to generate intermediate carbonium
ion

Regeneration (Step 3): The intermediate carbonium ion converts to the dimer and generates back
the proton on the catalyst surface

Isomerization (Step 4): Straight chain proton substituted olefins convert to isomeric carbonium
ions. -Catalysts used: Acid catalysts (H2SO4) are used.

Temperature: 150 –220 oC are used. Too high temperatures give tar deposits.

Pressure: 25 –100 atms.

Caustic wash: C3-C4 olefin feed subjected to caustic wash to remove H2S and other sulphur
compounds (such as mercaptans). These tend to poison the catalyst.

33
Water scrubbing: Eventually water scrubbing is carried out to remove dissolved impurities and
generate waste water.

Polymerization reactor: The reaction mixture is heated, compressed and fed to a polymerization
reactor. The reactor design is a shell and tube type design where catalyst is placed in the tube for
the reaction to take place and cooling water is circulated in the shell side to control the temperature
increase due to the exothermic reaction.

Fractionation: Subsequently, the reactor product is fed to a depropanizer and debutanizer to

produce propanes, butanes and polymer gasoline. The polymeric product is further stabilization
using hydrogenation stabilizer which converts any freely available double bonds to single bonds.
The end product is polymer gasoline.

The propane produced is partially recycled to the reactor and the other part taken out as a product.

OTHER REFINERY SUPPORTING PROCESSES

Introduction:
If we analyze the petroleum refinery, other than hydrocarbon balances, two other components
balances need to be considered.

These are sulphur and hydrogen.

It is a fact that the refinery has good number of hydrotreaters which needs to be fed with hydrogen
to generate the H2S. This hydrogen is primarily generated from the catalytic reforming unit.

Now the question that are posed in the refinery are:

➢ How to handle H2S for following environmental legislations

➢ How to purify the reformer H2gas stream to meet the required inlet specifications in
various hydrotreaters, hydrocracking and isomerisation units.
➢ How to produce H2 additionally, as the reformer off gas may not be able to meet the
H2demands in various hydrotreaters.

When the above question is answered, in due course, we get the two major supporting processes

➢ Hydrogen production and purification process

34
 ➢ Sulphur recovery process.-We first discuss hydrogen production and purification
process followed with the sulphur recovery process.

HYDROGEN PRODUCTION
Hydrogen can be produced in many ways namely:

➢ Partial oxidation of heavy ends

➢ Steam reforming of various product stocks
➢ Methane steam reforming.

Amongst these, methane steam reforming is more famous for hydrogen production

Depending upon the process, the hydrogen production consists of four basic reactions:

➢ Reforming: Here, methane reacts with water molecules to form CO and H2 at about 20
bar and 800 oC. The reacton is endothermic.
➢ CO shift reaction: In this reaction, CO is converted to CO2and H2 by reacting with
water. The reaction is usually carried out on a catalyst. There are two types of shift
reactions namely high temperature shift or low temperature shift. In the high
temperature shift, the reaction is carried out on iron oxide or chromia catalyst at
about 350 –550 oC. In the low temperature shift, the reaction is carried out at 200
–250 oC using copper or zinc oxide on alumina.
➢ Gas purification: The CO2 is separated by passing the product gases through
amine scrubber
➢ Methanation: The remaining CO2 and CO are converted back to methane using
nickel-alumina catalyst in a reversible reaction scheme at 400 oC.

Feed purification: Feed pretreated to remove sulphur and halogens traces. H2S is removed using
zinc oxide catalysts. Organic sulphur removed by hydrotreating and H2S removal from the feed.
Halogens are removed using adsorption technique.

Furnace reactor: The methane steam reforming reaction occurs in a furnace which is fed with the
hydrocarbons mixed with steam. The steam to carbon ratio varies and is about 2.5 –3.5. The
furnace reactor consists of reactor tubes packed in the furnace chamber. The reactor tubes consist
of the nickel oxide catalyst for carrying out the reaction.

35
Shift reactors: The furnace reactor product is sent to both high temperature and low temperature
shift reactors. It is interesting to note that these reactors operate at low temperatures. Therefore,
cooling is carried out for the furnace reactor product and steam is generated. Similarly, steam is
generated after the high temperature shift reactor also.

Absorber stripper: The absorber stripper is used for CO2 removal of the product emanating from
the low temperature shift reactor.

Methanation reactor: Here, traces of the CO2 and CO are converted to CH4 and H2O using nickel
catalyst and reversible reaction scheme. The product from methanation reaction consists of 97 %
H2

Alternatively, in some modern refineries, the low temperature shift reactor product is fed to
a pressure swing adsorption (PSA) unit which produces 99.9 % hydrogen as a main product.

The PSA also produces a tail gas which is used as a fuel in the furnace used in the reformer process.

PSA technology also is incapable for CO and CO2 removal as the adsorbents are not competent
enough to separate these components to a large extent. But they can effectively do separation
when hydrocarbons are present but not oxides in the hydrogen rich stream. Therefore, from
PSA perspective as well it is important to remove CO2 bulk with amine scrubbing followed with
methanation reaction for both CO and CO2 conversion.

CLAUS SULPHUR RECOVERY

In a furnace reactor, H2S is partially oxidized with air to produce water and SO2. The reaction is
highly exothermic. Therefore, steam is generated using the products from the furnace reactor.

The remaining H2S is then sent to a converter at about 250 oC to allow the reaction between H2S
and SO2 and produce Sulphur and water. The emanating product is at 290 oC

The second reactor (H2S to SO2) is having severe equilibrium limitations. Therefore, it is sent to
two to three reactors for maximizing conversion.

After each converter, the product stream is cooled and sent to another reactor. Subsequently,
Sulphur is removed as a product from the coolers. Finally tail gas is obtained from the last
converter which consists of unreacted H2S, N2 and O2.

36
The tail gas requires treatment as well. This is because the gas consists of components such as
H2S, CS2 etc. The tail gas is fed with air to another burner and converter that converts sulphur
compounds to H2S. The H2S thus generated is separated using amine scrubbers. The H2S thus
recovered is sent as a recycle stream to the partial oxidation reactor.

37
 CHAPTER FIVE
QUALITY IMPROVEMENT PROCESSES
HYDROTREATMENT
Catalytic hydrotreating is a hydrogenation process used to remove about 90% of
contaminants such as nitrogen, sulphur, oxygen, and metals from liquid petroleum
fractions.
If these contaminants are not removed from the petroleum fractions they can have
detrimental effects on equipment, catalysts, and the quality of the finished product.
Typically, hydrotreating is done prior to processes such as catalytic reforming so that the
catalyst is not contaminated by untreated feedstock.
Hydrotreating is also used prior to catalytic cracking to reduce sulfur and improve product
yields, and to upgrade middle-distillate petroleum fractions into finished kerosene, diesel
fuel, and heating fuel oils.
In addition, hydrotreating converts olefins and aromatics to saturated compounds.
Hydrotreating for sulphur removal is called hydrodesulphurization.
In a typical catalytic hydrodesulphurization unit, the feedstock is dea. The clean gas is then
suitable as fuel for the refinery furnaces. The liquid stream is the product from
hydrotreating and is normally sent to a stripping column for removal of H2S and other
undesirable components.
In cases where steam is used for stripping, the product is sent to a vacuum drier for removal
of water.
Hydrodesulphurized products are blended or used as catalytic reforming feedstock.
The hydrotreating catalyst is a porous alumina matrix impregnated with combinations of
cobalt (Co), nickel (Ni), molybdenum (Mo) and tungsten (W).

Chemistry of Hydrotreating
Desulphurization
➢ Mercaptans:

➢ Disulphides:

38
 ➢ Thiophenes

Denitrogenation
➢ Pyrrole:

➢ Pyridine:

Deoxygenation
➢ Phenol

Hydrogenation of chlorides

Hydrogenation of organo-metallic compounds and deposition of metals

39
40
Figure 16: Hydrotreating: flow scheme

41
VISBREAKING
Visbreaking is a mild form of thermal cracking that lowers the viscosity of heavy crude-oil residues
without affecting the boiling point range.

Residuum from the atmospheric distillation tower is heated (425-510ºC) at atmospheric pressure
and mildly cracked in a heater.

It is then quenched with cool gas oil to control over-cracking, and flashed in a distillation tower.

Visbreaking is used to reduce the pour point of waxy residues and reduce the viscosity of residues
used for blending with lighter fuel oils. Middle distillates may also be produced, depending on
product demand.

The thermally cracked residue tar, which accumulates in the bottom of the fractionation tower, is
vacuum-flashed in a stripper and the distillate recycled.

Figure 17: Visbreaking Flowsheet

 Alternatively, vacuum residue can be cracked. The severity of the visbreaking depends
upon temperature and reaction time (1-8 min).
 Usually < 10 wt% of gasoline and lighter products are produced.

42
Figure 18: Alternative Visbreaking flowsheet

43
CATALYTIC REFORMING
Catalytic reforming is an important process used to convert low-octane naphthas into high-octane
gasoline blending components called reformates. Reforming represents the total effect of
numerous reactions such as cracking, polymerization, dehydrogenation, and isomerization taking
place simultaneously.

Depending on the properties of the naphtha feedstock (as measured by the paraffin, olefin,
naphthene, and aromatic content) and catalysts used, reformates can be produced with very high
concentrations of benzene, toluene, xylene, (BTX) and other aromatics useful in gasoline blending
and petrochemical processing.

Hydrogen, a significant by-product, is separated from the reformate for recycling and use in other
processes.

Table 3: Typical Catalytic Reforming Feedstock and Product Analysis (vol%)

Component Feed Product

Alkanes 45-55 30-50
Alkenes 0-2 0
Naphthenes 30-40 5-10
Aromatics 5-10 45-60

44
A catalytic reformer comprises a reactor and product-recovery section.
There is a feed preparation section comprising a combination of hydrotreatment and distillation.
Most processes use Pt as the active catalyst. Sometimes Pt is combined with a second catalyst
(bimetallic catalyst) such as rhenium or another noble metal.
There are many different commercial processes including platforming, powerforming,
ultraforming, and Thermofor catalytic reforming.

Some reformers operate at low pressure (3-13 bar), others at high pressures (up to 70 bar). Some
systems continuously regenerate the catalyst in other systems. One reactor at a time is taken off-
stream for catalyst regeneration, and some facilities regenerate all of the reactors during
turnarounds.

In the platforming process, the first step is preparation of the naphtha feed to remove impurities
from the naphtha and reduce catalyst degradation. The naphtha feedstock is then mixed with
hydrogen, vaporized, and passed through a series of alternating furnace and fixed-bed reactors
containing a platinum catalyst.

The effluent from the last reactor is cooled and sent to a separator to permit removal of the
hydrogen-rich gas stream from the top of the separator for recycling.

The liquid product from the bottom of the separator is sent to a fractionator called a stabilizer
(butanizer). It makes a bottom product called reformate; butanes and lighter go overhead and are
sent to the saturated gas plant.

45
Figure 19: Catalytic reforming scheme

46
ISOMERIZATION
Isomerization of Light Naphtha
Isomerization is the process in which light straight chain paraffins of low RON (C6, C5 and C4)
are transformed with proper catalyst into branched chains with the same carbon number and high
octane numbers.
The hydrotreated naphtha (HTN) is fractionated into heavy naphtha between 90–190 oC (190–380-
degree F) which is used as a feed to the reforming unit.
Light naphtha C5 – 80 degrees C (C 5-- 180 F) is used as a feed to the isomerization unit. There
are two reasons for this fractionation:
The first is that light hydrocarbons tend to hydrocrack in the reformer.
The second is that C6 hydrocarbons tend to form benzene in the reformer. Gasoline
specifications require a very low value of benzene due to its carcinogenic effect.
Isomerization is a reversible and slightly exothermic reaction:
n-paraffin converted to i-paraffin
The conversion to iso-paraffin is not complete since the reaction is equilibrium conversion limited.
It does not depend on pressure, but it can be increased by lowering the temperature. However
operating at low temperatures will decrease the reaction rate.
For this reason, a very active catalyst must be used.
Isomerization Catalysts
There are two types of isomerization catalysts:
the standard Pt/chlorinated alumina with high chlorine content, which is considered quite
active, and
Pt/zeolite catalyst
The standard Pt/chlorinated alumina
This bi-functional nature catalyst consists of highly chlorinated alumina (8–15 w% Cl2)
responsible for the acidic function of the catalyst.
Platinum is deposited (0.3–0.5 wt%) on the alumina matrix. Platinum in the presence of hydrogen
will prevent coke deposition, thus ensuring high catalyst activity.
The reaction is performed at low temperature at about 130 degrees C (266 degree F) to improve
the equilibrium yield and to lower chlorine elution.

47
The standard isomerization catalyst is sensitive to impurities such as water and sulphur traces
which will poison the catalyst and lower its activity.
Pt/zeolite catalyst
Zeolites are crystallized silico-aluminates that are used to give an acidic function to the catalyst.
Metallic particles of platinum are impregnated on the surface of zeolites and act as hydrogen
transfer centres.
The zeolite catalyst can resist impurities and does not require feed pretreatment, but it does have
lower activity and thus the reaction must be performed at a higher temperature of 250 degrees C
(482 F).

Table 4: Operation conditions and yield

Operating condition Pt/Chlorine Alumina Pt/Zeolite catalyst

catalyst

Temperature (oC ) 120–180 250–270

Pressure (bar) 20–30 15–30

Space velocity (h-1) 1–2 1–2

H2/HC (mol/mol) 0.1–2 2–4

Product RON 83–84 78–80

48
PRODUCT BLENDING
Why blend?
Refining processes do not generally produce commercially usable products directly but
semi-finished products which must be modified by blending to meet product specifications.
Product qualities on the other hand are modified in some cases to improve on their
properties for specific market demands.
Product qualities are predicted through correlations that depend on the quantities and the
properties of the blended components.
Blending
One of the most critical economic issues for a petroleum refiner is selecting the optimal
combination of components to produce the final products.
Gasoline blending, for instance, may have as many as 8-15 different hydrocarbon streams
to consider as a blend stock. This may be as a result of the different gasoline and naphthas
that are obtained from different processes.
Modern gasoline may be blended to meet simultaneously 10-15 different quality
specifications such as:
➢ Vapour pressure
➢ Boiling points
➢ Sulphur content
➢ Stability
➢ Aromatic content
➢ Olefin content as well as other local governmental or market restrictions
➢ Linear programming employing a mathematical technique is used in recent years to
arrive at the most optimal and economical composition and blends in order to achieve
the quality as well as the maximum operating profit.

Blending with additives

Additives are added to petroleum products eg. Gasoline to improve on the properties such as:
Antiknock
Stability (antioxidants and metal deactivators), etc.

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Antiknock additives

➢ Almost all countries in the world have phased out automotive leaded fuel.

➢ Different additives have replaced the lead compounds. The most popular additives
include aromatic hydrocarbons, ethers and alcohol (usually ethanol or methanol).

✓ MMT
➢ Methylcyclopentadienyl manganese tricarbonyl (MMT) is used in Canada and in Australia
to boost octane.
➢ It also helps old cars designed for leaded fuel run on unleaded fuel without need for
additives to prevent valve problems.

✓ Oxygenate blending

✓ Oxygenate blending adds oxygen-bearing compounds such as MTBE, ETBE and ethanol.
The presence of these oxygenates reduces the amount of carbon monoxide and unburned
fuel in the exhaust gas. In many areas throughout the US, oxygenate blending is mandated
by EPA regulations to reduce smog and other airborne pollutants.

Fuel stabilizers (antioxidants and metal deactivators)

Gummy, sticky resin deposits result from oxidative degradation of gasoline upon long
term storage. These harmful deposits arise from the oxidation of alkenes and other
minor components in gasoline
Previously, catalytically or thermally cracked gasolines are most susceptible to
oxidation. The formation of these gums is accelerated by copper salts, which can be
neutralized by additives called metal deactivators.
This can be prevented through the addition of 5–100 ppm of antioxidants, such
as phenylenediamines and other amines.

Estimation of properties of the blend

Product qualities are predicted through correlations that depend on the quantities and the
properties of the blended components.

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 The desired property Pblend product may be determined using the mixing blend rule as
follows:

Where Pi is the value of the property of component i and qi is the mass, volume or molar
flow rate of component or fraction of the component i contributing to the total amount of
the finished product.
The equation applies to properties that are additive (linear) like specific gravity, boiling
points and sulphur content.

In cases where the property is not linear specific correlations are used. The non-linear
properties include viscosity, flash point, pour point, aniline point, RVP and cloud point.

Reid Vapour Pressure (RVP) Blending

RVP is the vapour pressure at 100 oF of a product determined in a volume of air 4 times
the liquid volume. Since RVP is not a linear property an RVP blending index is used. This
index may be determined as follows:

Where

is the RVP Blending index for component i and is the RVP of component I in psi.
Thus the RVP of the blended product can then be estimated by:
Where:

is the volume fraction of component i

Flash Point Blending

The flash point is the lowest temperature at which vapours arising from a petroleum
fraction (or crude oil) ignites.
The flash point index ( ) of a component i can be determined using any of the following
correlations:

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 Where : is the flash point of component i in K.
The flash point of the blend is then determined using the following equation:

Where: is the flash point index of component i and is the volume fraction or
mass fraction of component i.

Pour Point Blending

The pour point is the lowest temperature at which oil can be stored and still capable of
flowing or pouring. Pour point blending indices are used when blending. These indices
blend linearly on a volume basis as follows:

Where xvi is the volume fraction of component i, and BIPPi is the pour point index of
component i that can be determined using the following correlations:

Where PPi is the pour point of component i, in oR.

Cloud Point Blending

Cloud point is the lowest temperature at which oil becomes cloudy and the first particles
of wax crystals are observed as the oil is cooled gradually under standard conditions.

Where xvi is the volume fraction of component i, and BICPi is the cloud point blending index
of component i that can be determined from the following correlation:

Where CPi is the cloud point temperature of component i, in K.

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Aniline Point Blending
The aniline point is the minimum temperature at which equal volumes of aniline and the
oil become completely miscible.
The aniline point indicates the degree of aromaticity of a petroleum fraction.
The aniline point of a blend is determined using the following formula:

Where xvi is the volume fraction of component i, and BIAPi is the aniline point index of
component i which is given by the following correlation:

Where APi is the aniline point of component i in oC.

Smoke Point Blending

The smoke point is the maximum flame height in millimeters at which the oil burns without
smoking when tested under standard specified conditions.
The smoke point of a blend is determined using the following correlation:

Where SPBlend is the blend smoke point in mm, APBlend and SGBlend are the aniline point and
specific gravity of the blend respectively. The specific gravity of the blend is estimated
using the following mixing rule.

Where xvi is the volume fraction of component i, and SGi is the specific gravity of
component i.

Viscosity Blending

Viscosity is not an additive property. As a result, viscosity blending indices are used to
determine the viscosity of the blend. The viscosity index of the blended product is
determined as follows:

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 Where xvi is the volume fraction of component i, and BI vis i is the viscosity index of
component i which can be determined as follows:

Where vi is the viscosity of component i in cSt (centi – Stokes).

Gasoline Octane Number Blending

The octane number is a characteristic of spark engine fuels such as gasoline.

Octane number is a measure of a fuel’s tendency to knock in a test engine compared to
other fuels.
The Posted Octane Number (PON), used commercially for gasoline is the average of the
Research Octane Number (RON) and Motor Octane Number (MON). PON is also known
as road octane number.
The difference between RON and MON is called the fuel sensitivity (S).
The octane number of a blended product can be obtained using the following relation:

Where is the volume fraction of component i and is the octane number of component
i. The octane number index is as follows:

Where is the octane number of the blended product and is the blending
index of component i .

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