PLANT DESIGN PROJECT

DESIGN OF A PLANT TO PRODUCE 10 MILLION KG PER YEAR OF

METHYL ETHYL KETONE (MEK)
CHAPTER ONE
INTRODUCTION

BRIEF DESCRIPTION OF METHYL ETHYL KETONE (MEK)

Methyl Ethyl Ketone (MEK) also known as Butanone is a flammable liquid compound C4H8O
similar to acetone and it is used as a solvent. It is also an organic compound with the formula
CH3C(O)CH2CH3 and it is produced industrially on a large scale, but occurs in nature only in
trace amounts. Methyl Ethyl Ketone is a constituent of the smoke produced by tobacco during
the smoking of cigarettes causing an irritation to the nose or eyes of humans.

PHYSICAL AND CHEMICAL PROPERTIES OF METHYL ETHYL KETONE

Chemical Formula C4H8O

Molar Mass 72.107g.mol-1
Appearance Colourless Liquid
Odour Acetone-like
Density 0.805g/ml
Melting Point -86℃
Boiling Point 79.64℃
Solubility in water 27.5g/100ml
Vapor pressure 78mmHg(20℃)
Acidity(pH) 14.7
Viscosity 0.43Cp
APPLICATION OF BUTANONE (MEK)

 It is used as solvent for cellulose acetate, acrylic resin, paint, ink etc., as the binder for
dyes, as the dewaxing agent for lubricants, and as the vulcanization accelerator.

 Butanone dissolves polystyrene and many other plastics and it is sold as “model cement”
for connecting parts of scale model.

 It is used as reagent for the determination of cadmium, copper and mercury, as the
standard material for chromatographic analysis and as solvent for semiconductor
photolithography.

 Butanone is mainly used as a solvent in dewaxing lubricating oil, in the paint industry
and various resin solvents, in the vegetable oil extraction process and azeotrophic
distillation of refining processes.

 Butanone is also an intermediate for the preparation of medicines, dyes, detergents,

perfumes, antioxidants and certain catalyst.

 It is used in the manufacture of nail polish in cosmetics. As a solvent with a low boiling
point, it can reduce the viscosity of nail polish and has quick-drying properties.

ECONOMIC IMPORTANCE OF BUTANONE

Butanone contributes to the production of lubricants, plastics, textiles, nail polish, medicine,
detergents, perfumes, paints, vegetable oil, synthetic rubber and all of these contribute to the
growth and survival of the economy.

MEK CONSUMPTION IN NIGERIA

Over the past few years, the Nigerian Methyl Ethyl Ketone market and consumption rate has not
been on a steady upward nor downward trend as values continue to rise and fall year by year. A
study of the market and consumption from 2007 to 2015 shows that the Nigerien Methyl Ethyl
Ketone market soared up in 2015, up to 29 percent from the previous year. Generally,
consumption on the other hand slowed noticeably. The year with the highest rate of growth was
2010, when the market value climbed by 64 percent year over year. During the time period under
consideration, the market peaked at $1.8 million in 2007, but consumption did not recover from
2008 to 2015. In 2015, the amount of butanone (Methyl Ethyl Ketone) consumed in Nigeria
soared to 1.1K tonnes growing by 43% on 2014 figures. In 2015, the size of the butanone market
in Nigeria increased by 29 percent over the previous year, to $1.5 million. Consumption, on the
other hand, shrank over the time period under consideration. Butanone usage peaked in 2007 at
 $1.8 million; however, from 2008 through 2015, consumption was slightly lower. In 2015 the
market was predicted to begin an upward consumption trend during the next fifteen years, driven
by rising demand for butanone in Nigeria. However, contrary to the forecast in 2015, the
market's performance is predicted to deteriorate slightly over the next decade, since the butanone
market is expected to begin a declining consumption trend.(Butanone (Methyl Ethyl Ketone) -
Nigeria - Report, 2015)
ABOUT METHYL ETHYL KETONE MARKET:
The Methyl Ethyl Ketone market has witnessed growth from USD million to USD million from
2017 to 2022. The report focuses on the Methyl Ethyl Ketone market size, segment size (mainly
covering product type, application, and geography), competitor landscape, recent status, and
development trends. Furthermore, the report provides detailed cost analysis, supply chain.
Technological innovation and advancement will further optimize the performance of the product,
making it more widely used in downstream applications. Moreover, consumer behavior analysis
and market dynamics (drivers, restraints, opportunities) provides crucial information for knowing
the Methyl Ethyl Ketone market.

Corporate profiles include important information such as company reviews, products, and
services, financial data sources, as well as current programs and developments. Overall, the
report provides a comprehensive overview of the Methyl Ethyl Ketone global market, which will
help industry players, equipment manufacturers, and current players looking for expansion
opportunities, new players as they grow older. Finding opportunities with other partners to
support their strategy makes their business based on current data, and future prospects.

Target Audience of Methyl Ethyl Ketone Market

- Manufacturer / Potential Investors
- Traders, Distributors, Wholesalers, Retailers, Importers, and Exporters.
- Association and government bodies.

List of Top Key Players in Methyl Ethyl Ketone Market are

 Cetex Petrochemicals
 Maruzen Petrochemical
 Idemitsu Kosan Co Ltd
 Exxon Mobil Corporation
 Tasco Chemicals
 Shell Chemicals
 JXTG Nippon Oil and Energy Corporation
 Zibo Qixiang Petrochemical Industry Group Co.Ltd.
 Ineos Solvents
IMPORT AND EXPORT OF BUTANONE/METHYL ETHYL KETONE (MEK) IN
NIGERIA
Butanone Imports in Nigeria
From the period under review, between 2007 to 2020, the import volume and values have been
collated alongside Nigeria’s suppliers. Over the period under review, imports attained the peak
volume of 1.7 thousand tonnes in 2007 and since then import volume of butanone to Nigeria
recorded a significant decline in the volume imported. In 2015, the volume of butanone imported
into the country reached about 1.1 thousand tonnes, which is about 43% more than what was
imported the previous year.
In terms of value, the value of butanone imported into Nigeria attained its highest value ever
recorded in 2007 with an import value of $1.7M, the closest value to that was in 2015 with an
import value of $1.5M. As of 2020, the average butanone price amounted to $1,189 per tonne.

Butanone Suppliers to Nigeria

As of 2015, South Africa became the largest supplier of butanone to Nigeria with a supply
volume of 628 tonnes followed by the Taiwan with a volume of 125 tonnes and Belgium with a
volume of 82 tonnes. The average annual growth rate in terms of volume between 2007 to 2015
from South Africa totaled -2.7% and the remaining supplying countries recorded the following
average annual rate of import growth; Taiwan by +63% per year and Belgium -1.7% per year.
In terms of supply value, as of 2015, South Africa has the highest supply value to Nigeria with
about $861,000 which is roughly 59% of Nigeria’s butanone import value followed by Taiwan
with a value of $170,000 which is about 12% and then Belgium with a value of about 7.8%.
Other countries that supply butanone to Nigeria include; China, France, United Arab Emirates
and South Korea.

Butanone Exports in Nigeria

From the period under review, between 2007 to 2020, the export volume and values have been
collated alongside Nigeria’s buyers.In 2015, Nigeria recorded growth in export volume of
butanone by 68% (190 kg). Generally, Nigeria has experienced remarkable increase in butanone
exports over the years especially between 2013 to 2015 and is expected to retain steady increase
in years to come. In 2014, the growth rate of butanone export volume was at its peak with an
69% compared to the previous year.
In terms of value, 2013 showed the most prominent rate of growth with an increment of about
65% compared to the previous years. In 2015, the export price of butanone surged to $605 per
tonne and by 2020, the average butanone export price amounted to $703 per tonne.

Butanone Buyers from Nigeria

Nigeria is a net importer of butanone and as in terms of volume and value, imports still exceed
exports as it has only one major export destination which is Ghana. Till date Ghana still remains
the key foreign market for butanone exports from Nigeria (Butanone (Methyl Ethyl Ketone) -
Nigeria - Report, 2015).

THE CHALLENGES OF MEK INDUSTRIES OR COMPANIES IN NIGERIA AND

GLOBALLY
As with many rapidly developing markets, there are always challenges that have to be met and
overcome. Probably, the main challenge faced by Nigeria’s manufacturing sector is the
difficulties with intermittent power, while not a new challenge. It frustrates many manufacturers
that it remains a recurring theme. Along with that there are the issues with the currency and
freight movement but as the internal market builds and the ‘Made in Nigeria’ brand becomes
more reputable, hopefully these challenges can be worked through.

EXISTING PROCESS ROUTES

There are few processes listed below for the production of MEK:
1. Vapour phase dehydrogenation of 2-Butanol.

2. Liquid phase oxidation of n-Butane.

3. Direct oxidation of n-Butanes, Hoechst-Wacker process.

4. Direct oxidation of n-Butanes, Maruzen process

DESCRIPTION OF THE VARIOUS PROCESSES

VAPOR PHASE DEHYDROGENATION OF 2-BUTANOL
MEK is prepared by vapor phase dehydrogenation of 2-butanol. A 2-step process from butenes,
which are first hydrated to give 2-butanol is used. The dehydrogenation of 2-butanol is an
exothermic reaction (51 KJ/Kgmol). The reaction is as follows.

Dehydrogenation of 2-butanol.

The equilibrium constant for 2-butanol can be calculated as follows:

log Kp = -2790/T + 1.51*log T + 1.856

Where T = reaction temperature, K
Kp= equilibrium constant, bar.

The MEK concentration in the reaction mixture increases and reaches its maximum at
approximately 3500C. Copper, Zinc or Bronze are used as catalysts in gas phase
dehydrogenation. Commercially used catalysts are reactivated by oxidation, after 3 to 6 months
use.nThey have a life expectance of several years.

Sec-butyl alcohol is dehydrogenated in a multiple tube reactor, the reaction heat being supplied
by heat transfer oil. The reaction products leave the reactor as gas and are split into crude MEK
and hydrogen on cooling. The hydrogen is purified by further cooling. The crude MEK is
separated from uncreated reactants and by-products by distillation.

LIQUID PHASE OXIDATION OF n-BUTANE

MEK is produced as a by-product in the liquid phase oxidation of n-butane to acetic acid.
Autoxidation of n-butane takes place in the liquid phase according to the radical mechanism
yielding MEK as an intermediate and acetic acid as end-product with mass ratio 0.2:1.0 by non-
catalyzed liquid phase oxidation at 180C and 53 bars with remixing. Continuous oxidation under
plug flow conditions at 150C, 65 bars and a residence time of 2-7 minutes forms MEK and acetic
acid at a mass ratio of 3:1.

DIRECT OXIDATION OF n-BUTENES (HOECHST-WACKER PROCESS)

In direct oxidation of n-butanes by Hoechst-Wacker process, oxygen is transferred in a
homogenous phase on to n-butenes using redox salt pair, PdCl2 / CuCl2. 95 per cent conversion
of n-butanes can be obtained with MEK selectivity of about 86 percent.
Disadvantages of the process includes; Formation of chlorinated butanone and n-butryaldehyde
and causes corrosion due to free acids.

DIRECT OXIDATION OF n-BUTANES, MARUZEN PROCESS

The Maruzen process is similar to the Hoechst-Wacker process except that oxygen is transferred
by an aqueous solution of palladium sulphate and ferric sulphate. The process is commercially
good to get MEK via direct oxidation of n-butenes, but is generally not accepted due to
formation of undesirable by products. The process is patented and not much information is
available

PROCESS SELECTION
The vapour phase dehydrogenation process gives high conversion of 2-butanol and high
selectivity of MEK of about 95 moles%. Other advantages of this process include better yield,
longer catalyst life, simple production separation and lower energy consumption. In
dehydrogenation process, hydrogen as a by-product is obtained that can be used as a furnace
fuel. In dehydrogenation process, there is the feasibility of separating the MEK from the reaction
products. The dehydrogenation process can easily be carried out at moderate temperature and at
atmospheric pressure. In dehydrogenation process, 90-95% of MEK can easily be converted to
MEK.
Liquid phase oxidation of n-butanes produces MEK as a by-product in low quantity which is not
economical since MEK is the principal product needed. The Selective direct oxidation process
both produces undesired product such as formation of chlorinated butanone and n-butryaldehyde.
This process requires controlled conditions so it becomes uneconomical. Chromic acid and
sulphuric acid in aqueous acetone are required for selective oxidation of butanol and there causes
corrosion due to free acid from them while copper is mostly required for dehydrogenation of
butanol.
Of all the processes, comparing and contrasting their advantages and disadvantages, it has been
found that “dehydrogenation of secondary butyl alcohol” has more advantages and is more
economical compared to other processes. Other advantages of this process include better yield,
longer catalyst life, simple production separation and lower energy consumption. so this process
been selected for the process plant design.
SELECTED PROCESS DESCRIPTON(VAPOUR PHASE DEHYDROGENATION OF 2-
BUTANOL
There are two processes involved in the production of Butanone:

1. Hydration of crude butene to give butanol

2. Dehydrogenation of the sec-butanol to give Methyl Ethyl Ketone

HYDRATION OF CRUDE BUTENE TO GIVE BUTANOL

The production of the butanol (which is used as feed in the MEK production process) from the
hydration of crude butene involves the various sub-processes highlighted below;

1. Feed Preparation (feeds - Crude butene and Water)

2. Reaction
3. Separation
 Distillation
 Absorption
4. Recycle scheme

Feed Preparation (Crude butene and water)

A crude feedstock of n-butenes enters the process, Stream 1, at 23C and 101.33kPa and is
prepared for the reactor scheme through a series of alternating compressors and exchangers.
Stream 1 is compressed by Compressor 1 to 65.54C and 300kPa as Stream 2. It is then cooled to
55C and 299.85kPa, Stream 3, by cooler 1 with cooling water. Stream 3 is then compressed by
Compressor 2 to 76.21C and 502kPa as Stream 4, which is then cooled by cooler 2 to 43.50C
and 502kPa, in Stream 5. Stream 5 is pumped through Pump 1 as Stream 6 44.32C and 1002kPa.
Water enters the process, Stream 7, at 23C and 500kPa and is mixed with recycled water stream
at 70C and 995kPa. The resulting stream at 48.69C and 500kPa and is pumped by Pump 2 to
48.87C and 1002kPa, as Stream 8. Stream 6, the prepared butene feedstock, and Stream 8(water)
are mixed at 48.06C and 1002kPa as Stream 9. Stream 9 is heated with high pressure steam with
exchanger Heater 1 and becomes Stream at 79C and 1001kPa.

Reaction
Stream 10 enters the sec-butanol reactor and exits at 105C and 976kPa as Stream 11.

Separation (Distillation)
Stream 11 enters the separation tower in which separates the sec-butanol product
and excess water from the azeotropes, alcohols, and unreacted butenes. The azeotropes, alcohols,
and unreacted butenes exit the tower as Stream 12 at 126.09C and 960kPa and is purged from the
system. The sec-butanol product and excess water exit the tower as Stream 13 at 157.92C and
970kPa. Stream 13 is cooled with cooling water by cooler 3 to stream 14 at 40C and 199.98kPa.
Stream 14 is fed through pump 3 which becomes Stream 15, at 40.08C and 299.98kPa, and is
then heated with low pressure steam with Heater 2 to Stream 16, at 91.23C and 298.99kPa.

Separation (Absorption)
Stream 16 is fed to a reboiled absorber which separates pure sec butanol from a mixture of sec-
butanol and water. Stream 17 exits the reboiled absorber at 120.93C and 215kPa and is heated
with high pressure steam through Heater 3 to Stream 18 at 121.29C and 214kPa and exist as the
final product, the pure sec butanol with a mole fraction of 0.99 which is sent as a raw feed to the
process production of MEK. Stream 19 exist the reboiled absorber at 121.79C and 210kPa and is
recycled as water to the recycle scheme.

Recycle scheme
Stream 19 at 121.79C and 210kPa is fed through pump 4 to stream 20 at 112.1C and 995kPa.
Stream 20 is then cooled by cooling water by cooler 4 to stream 21 at 70C and 995kPa which is
then utilized as recycled water.

DEHYDROGENATION OF THE BUTANOL TO GIVE BUTANONE

The production of butanone from the dehydrogenation of butanol involves the various sub-
processes highlighted below;
 1. Feed Preparation (feed - Butanol)
2. Reaction
3. Absorption
4. Extraction
5. Solvent Recovery
6. Distillation

Feed Preparation(butanol)
In the dehydrogenation of 2-butanol, the feed of 2-Butanol from the previous process is mixed
with the recycle stream containing unreacted 2-butanol and is then pumped from the feed tank at
145kPa to a steam heater and heated up to 373K(100C) stream 24, the heating medium being
used is dry saturated steam at 140°C. This Stream 24 is further fed at 44kPa and 375K(100C) to
thermo-syphon vaporizer which is heated by the reactor vapor to 385K(112C). The heating
medium in vaporizer is heated reaction products discharged from the reactor at 673K(400C) i.e.
(Stream 25) and itself gets cooled down to 425K(152C).
Stream 25 is further fed to knockout drum to remove entrained liquid which is recycled
back(Stream 26 & 28) to the vaporizer. Knockout drum consists of a hollow vertical drum
having inclined sieve plates known as demister for the passage of clean gas. Separation in knock-
out drum is based on the principle of density difference of the liquid and the clean gas.
The dry alcohol vapours(Stream 27) from the knock-out drum at 133kPa and 385K(112C) are
fed to the super-heater 1 where they are heated to increase the temperature of the vapours to
573K(300C). The vapours are heated with the help of flue gases at high temperature of
813K(540C). The superheated vapours(Stream 30) are then compressed with the help of a
compressor to increase the pressure as well as increasing the temperature of the vapours to
355kPa and 583K(310C). The compressed (Stream 31) are then fed to the super-heater 2 to
increase the vapours temperature of 773K with the help of flue gases at 813K high temperature.

Reaction
The superheated vapours(Stream 32) are fed to the reactor in which the butanol is dehydrated to
produce MEK and hydrogen, according to the reaction:
CH3CH2CH3CHOH CH3CH2CH3CO + H2
The conversion of alcohol to MEK is 90 percent and the yield is taken as 100 percent. Initially,
preheated vapours of secondary-butyl alcohol are passed through a reactor containing a catalytic
bed of zinc oxide or brass (zinc-copper alloy) which is maintained between 400°C and 500°C. A
mean residence time of two to eight seconds at normal atmospheric pressures is required for
conversion from secondary-butyl alcohol to MEK.

The reaction product from the reactor at 160kPa and 673K(400C) are cooled to a suitable
temperature 425K(152C) in the vaporizer and the cooled products(Stream 34) are then fed to the
condenser where almost 80% of the MEK and unreacted 2-butanol are condensed and
sent(Stream 36) to the distillation column at 298K(25C) while the non-condensable hydrogen
with the un-condensed MEK and unreacted 2-butanol at 155kPa and 335K(59C) are sent to the
absorber as Stream 37.

Absorption
In the absorption column the uncondensed MEK and alcohol are absorbed in water. Around 98
percent of the MEK and alcohol can be considered to be absorbed in this unit, giving a 10
percent w/w solution of MEK. The water feed to the absorber is recycled(Stream 42) from the
next unit, the extractor. The vent stream from the absorber at 150kPA and 300K(27C) containing
mainly hydrogen, are dried and used as a furnace fuel.

Extraction
In the extraction column the MEK and alcohol in the solution sent from the absorber(Stream 40)
at 101kPa and 321K(48C) are extracted into tri-chloro-ethylene (TCE) which enters the
extraction column(Stream 45 recycle stream). The raffinate, water containing around 0.5 percent
w/w MEK, is recycled(Stream 42) to the absorption column. The extract, which contains around
20 percent w/w MEK, and a small amount of butanol and water, is fed(Stream 43) to the solvent
recovery. It is assumed that the extraction process is isothermal. All that streams come at
321K(48C) and leaves at 321K(48C).

Solvent Recovery
In the solvent recovery, the unit separates the MEK and alcohol from the solvent TCE. The
solvent containing a trace of MEK and water is recycled to the extraction column(Stream 45).
The bottom product is solvent, i.e., 1, 1, 2-trichloroethane and the distillate from this column is
MEK and alcohol. The recovery of solvent is 99.9%. The solvent is first cooled down to room
temperature and then fed to the extraction column(Stream 45) at 141kPa and 343K(70C)

Distillation
The distillate from the solvent recovery column(Stream 46) is fed to this distillation column
along with the condensate from partial condenser containing MEK and 2-Butanol, which is
mixed first and then fed into the column. The distillate is MEK at 101kPa, 303K(30C) and the
bottom product is 2-Butanol. The 2-Butanol discharged from the bottom of the column will be
sent back to the feed tank at 298K(25C).

ASSUMPTIONS MADE
1. Material loss between the steam heater and the second super-heater is negligible.

2. Only 98% of the MEK and 2-butanol entering the absorption column is absorbed.

3. MEK is 10% of the absorption product.

4. The raffinate from the extraction column contains 99.5% water, 0.5% MEK and no 2- butanol.
5. The extract contains 20% MEK.

6. No spillage across any unit operation.

7. Perfect separation in the absorption column

8. Perfect separation of TCE in the extraction column

Fig 1.0: Hydration of Crude Butene to 2-butanol

Fig 1.1: Dehydrogenation of 2-butanol to MEK

IMPROVED PROCESS FOR THE PREPARATION OF METHYL ETHYL KETONE
FROM SECONDARY BUTYLALCOHOL USNG AN IMPROVED COPPER SILCA
CATALYST
This invention relates to an improved process for the preparation of methyl ethyl ketone (MEK)
using a supported copper dehydrogenation catalyst. More specifically, the process developed in
the present invention relates to the production of methyl ethyl ketone by the dehydrogenation of
secondary butyl alcohol (SBA) using an improved copper catalyst supported on silica prepared
by a novel soligel method. Methyl ethyl ketone is an important industrial chemical and has been
widely used as a solvent in the vinyl resins and synthetic rubber industries. The dehydrogenation
of secondary butyl alcohol over various metal oxide catalysts at 250-400° C. results in the
formation of varying amount of unconverted alcohol, water and MEK. MEK is produced
commercially from SBA which undergoes catalytic dehydrogenation over a catalytic bed of zinc
oxide or brass (zinc-copper alloy). High activity, selectivity and stability make the system one of
the industrial catalysts available for alcohol dehydrogenation. The active copper catalysts are
known in the prior art for a long time for various dehydrogenation reactions, A recent Indian
Patent Application No 303/DEL/93 describes the conversion of secondary butyl alcohol to
methyl ethyl ketone using a copper catalyst supported on silica prepared by co-precipitation
technique. Although various methods are known in the prior art to prepare an active catalyst,
there is one or the other limitation with respect to either the activity or selectivity or the life time
of the catalyst. It is very important to control and optimize the preparation procedure so that
catalyst with high surface area, high metal area and good dispersion of the active metal on the
surface of the support can be obtained. All these criteria of the good dehydrogenation catalyst are
fulfilled when a novel method of preparation of the supported copper catalyst by sol gel method
is adopted. The preparation process comprises of reacting a alkoxide of silicon with an alkoxide
or any other convenient salt of copper in the presence of water or any other non-aqueous solvent
preferably aliphatic alcohols which dissolves the copper salt or copper alkoxide at a temperature
in the range of 20° to 90° C., drying the resultant gel at a temperature in the range of 100° to
150°C, and further calcining the dried powder at a temperature ranging from 250° to 500° C. The
alkoxide of silicon which may be advantageously used include ethoxide, isopropoxide or
butoxide. The salts of copper which may be used include chlorides, acetates, nitrates or any other
salt or complexes of copper. A significant feature in the preparation of the catalyst for the
process of the present invention is that precipitating agents such as ammonium hydroxide or any
other hydroxide is not used and thus there is no precipitation of any salt of the component used in
the present oxide. The catalyst thus prepared is amorphous in nature and has improved textural,
physical, chemical and mechanical properties with high surface area, low bulk density and high
dispersion of the copper. According to one embodiment of the present invention, the catalyst is
reduced under hydrogen flow insitu in the fixed bed reactor, the concentration of hydrogen being
varied from 10% to 100% and the rest is either nitrogen or argon. Generally, greater than 99%
selectivity to MEK is achieved while the conversion of secondary butyl alcohol was greater than
96% as compared to the hitherto known commercial catalyst with 90% activity and selectivity to
MEK equal to 95%. The present invention is further described with reference to the following
examples which are for illustrative purpose only and should not be construed to limit the scope
of the present invention.

EXAMPLE 1
Preparation of the Amorphous Copper Silica Catalyst
100 g of tetraethyl orthosilicate and 20 mole % of copper acetate dissolved in ethyl alcohol were
reacted together at 50° C. for 48 hours in presence of water as hydrolyzingagent. The blue
coloured gelthus obtained was dried at 100° C. for 24 hour and subsequently calcined at 300°C.
for 12 hour and treated under the flow of hydrogen (20%) for 8 hours at a temperature of 300°C.
The resultant catalyst was amorphous as evidenced by X-ray diffraction pattern and the
surface area of the sample was found to be 550 m/g.

EXAMPLE 2
1.5 g (-10 to 20 #) of the catalyst (surface area 575 m/g and the apparent bulk density 0.55 g/ml)
prepared by the process described in the example 1 is loaded in a 1 m long and 1.5 cm internal
diameter reactor provided with an axial thermocouple. The catalyst was reduced in 10% HN
mixture in a flow at 30 ml/min, raising the catalyst bed temperature slowly to 270° C. in 10hours
and holding at that temperature for about 5 hours. The concentration and the flow rate of
SBAwas adjusted to 10 ml per hour, i.e., LHSV of 5 h". The reactor was heated up to 240° C.
and the preheated feed of secondary butyl alcohol in its vapourized form was introduced over the
prereduced catalyst bed. The pressure at outlet was 1 bar. The products, both liquid and gaseous
were analysed by GC equipped with carbon wax column (2 m long) and kept at 110° C.
(isothermal) with FI detector using N as the carrier gas. In addition, the by-products such as
olefins along with the unconverted SBA were also quantitatively estimated. The SBA converted
was 97 mole % and the selectivity to MEK was 99.9%.

REVIEW OF PAST WORKS ON MEK PRODUCTION FROM DEHYDROGENATION

OF 2-BUTANOL.

1. Dehydrogenation of Sec-Butanol to Methyl Ethyl Ketone over Cu-ZnO Catalysts

Prepared by Different Methods: Co-precipitation and Physical Mixing
Cu-ZnO catalysts prepared by co-precipitation and physical mixing methods were characterized
to investigate the roles of ZnO by X-ray diffraction (XRD), N2O chemisorption decomposition
and evaluated for the vapour-phase dehydrogenation of sec-butanol (SBA) to methyl ethyl
ketone (MEK). ZnO not only could disperse Cu species, but also prevent Cu0 from sintering. Cu-
ZnO catalyst by co-precipitation method exhibited excellent reactivity. (Yun Feng Hu, 2013)

2. The Production of Methyl Ethyl Ketone from n-butene

In this preliminary design the production of methyl ethyl ketone (MEK) from normal butene,
with secondary butyl alcohol (SBA) as intermediate, is described. This design is split into two
parts. In the first part SBA is obtained from n-butene by absorption in sulphuric acid, followed
by hydrolysis with water. Sulphuric acid and SBA are separated in a stripper. The sulphuric acid
is reconcentrated and recycled to the absorber. The SBA is purified in an azeotropic distillation
unit, using di-isobutylene as entrained. In the second part of the design, SBA is vaporized and
fed to a multitubular, isothermal reactor, filled with a Cu/Ni on SiO2 catalyst. The SBA is
dehydrogenized; forming MEK and hydrogen. The hydrogen is purified and sold as a valuable
by-product. The MEK is purified in two fractionation columns and obtained with a purity of 99.1
wt."-%. The capacity of the plant is 33,731 tons of MEK per year. An economic evaluation
shows that this plant can pay itself back within approximately 1.5 to 2 years. (A.H. Amer, 1988),