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Special Report

Methyl ethyl ketone: A techno-commercial profile

Introduction
ethyl ethyl ketone [1] (MEK)
(CAS No.: 78-93-3), is a
flammable, colourless liquid
with a sharp, sweet butterscotch odour
reminiscent of acetone. It is soluble in
four parts water and miscible with alcohol, ether, acetone, and benzene. It is
lighter than water and may be expected
to float while rapidly dissolving .
It is unsymmetrical or mixed aliphatic ketone. Its IUPAC name is
2-Butanone. Other names are: Methylacetone and Meetco.
MEK is the second link in the homologous series of aliphatic ketones
and next to acetone, the most important
commercially produced ketone.

of MEK in the environment are exhaust


from jet and internal combustion engines, and industrial activities such as
gasification of coal. It is also found in
substantial amounts in tobacco smoke.
Properties
Physical properties[1]
MEK is a colourless liquid. Its odor
resembles that of acetone. It is only
partially miscible with water and it is
completely miscible with most organic
solvents. In fact, it forms binary and
ternary azeotropic mixtures in combination with water and several other
organic solvents (Table 1).
Chemical properties[1]
MEK is stable under normal conditions and in absence of air. It is unsaponifiable and does not form corrosive
products under hydrolysis. It is heat
and light stable. It only decomposes
after prolonged exposure of UV.

DIVYESH ARORA
&
MOHIT SHARMA
Jaypee Institute of Engineering &
Technology
E-mail: divyesh_134@yahoo.co.in
Self-condensation
Aldol condensation of 2 moles of
MEK yields a hydroxyketone, which
readily dehydrates to an unsaturated
ketone:
O
II
CH3CCH2CH3 + H2O2

OH
I
CH3CCH2CH3
I
OOH

Condensation with other compounds


Reaction with aldehydes gives
higher ketone, as well as ketals and cyclic compounds, depending on reaction
conditions. Ketones are produced by
the condensation of MEK with aliphatic esters. Sec-Butyl amine is formed by
reacting MEK with aqueous ammonia
and hydrogen:

It is produced in large quantities.


Nearly half of it is used in paints and
other coatings. It dissolves many substances and is used as a solvent in processes involving gums, resins, cellulose
It can be widely utilized in chemical
acetate, nitrocellulose coatings, in vinyl
films, in the synthetic rubber industry, synthesis. Its reactivity
O
NH2
plastics, textiles, in the production of centres on the carbonyl
II
I
Ni
paraffin wax, and in household pro- group and its adjacent
CH3CHCH2CH3 + H2O
CH3CCH2CH3 + NH3 +H2
ducts such as lacquer, varnishes, paint hydrogen atoms. Conremover, a denaturing agent for de- densation, ammonolysis, halogenations
An excess of MEK in this reaction
natured alcohol, glues and as a cleaning and oxidation can be carried out under will produce di-sec-butylamine. Reactagent. MEK is also used in dry erase the proper conditions. Some typical re- ing MEK with acetylene gives methyl
markers as the solvent of the erasable actions are described below.
pentynol, a hypnotic compound.
dye and in synthesis of
Table 1
MEK peroxide, a catalyst
Applications[1]
Physical properties of MEK
for some polymerization
MEK is consumed in large quantireactions.
ties
in
a variety of industries and appliValue
cations (Table 2).
Molecular weight
72.10
Natural occurrence[g]
o
79.6 C
MEK occurs naturally Boiling point
Environmental impact[g]
o
in volcanoes, forest fires, Melting point
When released into the soil, MEK
-86.35 C
and products of biologimay leach into groundwater & may
o
90.6 mm Hg at 25 C
cal degradation. It is made Vapour pressure
evaporate to a moderate extent. When
by some trees and found in Vapour density
released into water, it may biodegrade
2.41 (air = 1)
some fruits and vegetables
to a moderate extent, may evaporate to a
o
Density/specific gravity
0.805 at -20/4 C
in small amounts. Sources
moderate extent & is expected to have a
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Special Report
Table 2
How MEK is used in industries
Industry

Application

Adhesives manufacture

Carpet adhesive solvents

Electroplating

Cold-cleaning solvents

Electroplating

Vapour degreasing solvents

Laboratory chemicals

Solvents - extraction

Machinery manufacture and repair

Solvents

Metal degreasing

Solvents

Paint manufacture

Solvents

Paint stripping

Solvents

Paper coating

Solvents

Pesticide manufacturing (insecticides) Solvents


Printing

Solvents for flexography & gravure printing

half-life between 10 and 30 days. MEK is


not expected to significantly bio-accumulate. When released into the air, this material is expected to be readily degraded
by reaction with photochemically produced hydroxyl radicals & is expected to
have a half-life between 1 and 10 days.
Global scenario
In 2007, publicly available sources
reported global production for MEK
reached 1,141-kt (kilotons) (2.5 billion
pounds). Global demand for MEK was
1,100-kt (2.4 billion pounds).
Worldwide[h] MEK demand is
forecast to grow at 3.5% over next five
years, to 1.3-mt (million tons) by 2010,
according to SRI Consulting. Demand
growth will be driven by China, the
largest single consumer. Chinese demand is projected to grow at 8.5%/year,
Table 3
MEK growth prospects
Country
China
Rest of Asia (excluding China & Japan)
Western Europe
North America
190

while demand in the rest of Asia, excluding Japan, is expected to increase


at about 2.6%/year. Growth in Western
Europe will be almost flat over the next
four years (Table 3).
Application-wise consumption
pattern[h]
Coating solvents are the largest enduse for MEK, accounting for almost half
of worldwide demand. Adhesives are the
second-largest end use, accounting for
almost 20% of demand (Table 4,5).
Indian Scenario[j]
The current demand in India for MEK
is around 10,000-11,000 tons. India
is not self-sufficient to meet its demand,
so it imports MEK from various countries (Table 6). Cetex Petrochemicals
Ltd. is the only producer of MEK in the
country.
Processes available[2]
There are a few proGrowth cesses listed for the pro(%) duction of MEK.
8.5

Catalytic dehydro2.6 genation of secondary


0.0 butyl alcohol in gaseous
phase
1.0
MEK is prepared by

Table 4
Applications of MEK by end-use
Sector
Share of
demand [%]
Coatings/solvents
58
Adhesives
11
Printing inks
8
Chemicals &
7
pharmaceuticals
Magnetic tapes
4
Lube oil dewaxing
2
Others
10
Total
100
Table 5
Major companies producing MEK[i]
Country / Company
Capacity
(ktpa)
USA
Shell

136

Exxon Mobil

135

Idemitsu Petrochem

135

Japan
Toren Chemical

70

Maruzen Petrochem

40

Brazil
Oxiteno

90

Germany
Sasol Solvents

65

Taiwan
Tasco Chemical

60

Taiwan Synthetic

15

France
Atofina

50

Romania
Petro Brazi

40

Thailand
Bangkok Synt.

20

South Korea
SK Corp.

15

vapor phase dehydrogenation of 2-butanol. The dehydrogenation of 2-butanol is an exothermic reaction (51 KJ/
Kg mol).
Chemical Weekly April 27, 2010

Special Report
Table 6
Imports of MEK into India [2007-08]
[Tons]

Less economic advantage than


liquid phase oxidation of n-Butane.
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 oxidao
tion at 180 C and 53 bars with remixing. Continuous oxidation under plug
Chemical Weekly April 27, 2010

234 234

200

170 170

150

62

62

39

50

39

Other Asian
Countries

Japan

0
Middle East

Eastern Europe
& Africa

North America

Western Europe

Central & South


America

100

Global consumption of MEK


600

2002
2007

490

500
400
400
300
213 220
200

180 193
129 133

flow conditions at 150 C, 65 bars and


a residence time of 2-7 minutes forms
MEK and acetic acid at a mass ratio of
3:1.
This process has slight economic advantage over the dehydrogenation of 2-butanol. But the key factor
is availability and price of butane.
Direct oxidation of n-Butenes
(Hoechst-Wacker process)
In direct oxidation of n-butanes

36

47

25

28

Central & South


America

17

Other Asian
Countries

14

Japan

100

Middle East

The disadvantages are:

245 254

250

Eastern Europe
& Africa

High conversion of 2-butanol;


High selectivity of MEK of about
95 mole %;
Better yield;
Longer catalyst life;
Simple production separation; and
Lower energy consumption.

2007

Western Europe

Advantages of the process are:

2002

296 296

North America

This is a primary process. The


MEK concentration in the reaction
mixture increases and reaches its
o
maximum at approximately 350 C.
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. They have a life expectance of several years.

300

Thousands of Metric Tons

Import
672
2,036
1,467
3,286
39
1,087
45

Thousands of Metric Tons

Country
Taiwan
Japan
China
South Africa
Singapore
UK
Netherlands

Global production of MEK


350

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 per
cent.
Disadvantages of the process are:
Formation of chlorinated butanone
and n-butryaldehyde; and
Causes corrosion due to free acids.
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Special Report
Table 7
Comparative study of all the processes
Catalytic dehydro- Liquid phase
genation
oxidation

Direct oxidation Direct oxidation

Sec-Butyl
benzene hydro
peroxide

Raw material/(s)

Sec-Butyl alcohol

Butane

Butenes

Butenes

Sec-Butyl
benzene

Main products

MEK

Acetic acid

MEK

MEK

Phenol & MEK

MEK

Chlorinated
butanone and nbutryaldehyde

Chlorinated butanone and n-butryaldehyde

By-products

Current status

88-90%

10-12%

Not accepted.

Not accepted

Uneconomical.

Catalysts

Copper, zinc or
bronze

Non-catalysed

PdCl2 / CuCl2

Palladium sulphate
& ferric sulphate

Zeolite beta

Conversion

Higher conversion
rate; 80-95%

Low conversion

95%

95%

Catalyst life

Several years

Small

Small

Selectivity

95%

86%

90%

Yield

Very high

Very low

High

High

Equivalent to
phenol

Energy consumption

Very low

Very low

High

Economical feasibility

Less than liquid


phase oxidation

Very high

Not known

Uneconomical

Process separation

Very simple

Not known as
process is
patented

Not known as process is patented.

Phenol & MEK


are both
produced

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 nbutenes, but is generally not accepted
due to formation of undesirable by
products. The process is patented and
not much information is available.
192

Sec-Butylbenzene hydroperoxide
process
This process comprises the steps
of oxidizing sec-butylbenzene to obtain a reaction liquid containing secbutylbenzene hydroperoxide as the
main product, concentrating the reaction liquid by means of a distillation
column to obtain a bottom liquid containing sec-butylbenzene hydroperoxide as the main component from
the column bottom and decomposing
the bottom liquid to obtain phenol and
MEK.

This process is good in that it


manufactures both phenol and MEK,
which are important products in
chemical industry. However, the disadvantage is that the process is uneconomical.
Detailed process description catalytic dehydrogenation of SBA
in gaseous phase
Preheater (Steam Heater)
In the dehydrogenation of 2-butanol, the cold feed of SBA is mixed with
Chemical Weekly April 27, 2010

Special Report

Figure 1: Flow sheet of preparation of MEK from SBA

recycle stream and then pumped from


the feed tank to a steam heater and heated up to 374K (Stream 1), the heating
medium being used is dry saturated
steam at 160C.
Vaporizer
This Stream 1 is further fed to thermosyphon vaporizer which is heated by
the reactor vapor. The heating medium
in vaporizer is heated reaction products
discharged from the reactor at 673K
i.e. (Stream 5) and itself gets cooled
down to 425K.
Knockout drum
Stream 2 is further fed to knockout drum to remove entrained liquid.
Knockout drum consists of a hollow
vertical drum having inclined sieve
plates known as demister for the passage of clean gas. Separation in knockChemical Weekly April 27, 2010

out drum is based on the principle of


density difference of the liquid and the
clean gas.

we need to supply heat from outside


and that is being supplied by the flue
gas, which is produced in the furnace.

Super heaters
The liquid separated will be recycled and the dry alcohol (Stream 3)
will be fed to super heaters steam and
stream attains a temperature of 673K
(Stream 4). The combustion reaction of
hydrogen takes place in a furnace and
the hydrogen is taken from the absorption column. The heat of combustion of
hydrogen is very high so its heat is being utilized here.

The MEK concentration in the reaction mixture increases and reaches


o
its maximum at approximately 500 C.
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. They have a life expectance of several years.

Reactor (Multi-Tubed Reactor)


Stream 4 is fed to the multi-tubed
reactor where dehydrogenation reaction takes place. The reaction is endothermic and the reactor is isothermal, so
in order to maintain 400C temperature

Condenser
In the condenser about 80% MEK
and SBA are condensed (Stream 7),
which is sent for storage while the other
stream (Stream 8), which contains saturated non-condensable hydrogen along
with MEK and SBA at the temperature
of 358K.
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Special Report
Absorption column
The vapour is passed on to the
bottom of the packed bed absorption
column where MEK and SBA are absorbed in water. Absorption of MEK
is 98% and SBA is 96% in water. The
water (Stream 9) is recycled from the
extraction column and its rate is controlled to provide an aqueous effluent
containing 10% MEK.
Extraction column
The aqueous effluent (Stream 10)
from the absorber is pumped into an
extraction column where it is contacted with solvent 1,1,2-trichlorethane
(Stream 11) to extract MEK and SBA.
This solvent is selected because it has
the maximum partition coefficient
(3.44), in comparison to other solvents.
The raffinate comprises of mainly water, which is fed back to the absorption
column.
Solvent recovery column
The trichloroethane extract phase
(Stream 14) is pumped to a distillation
column for the separation of solvent.
Initially it is preheated to 371K. The
bottom product is solvent, i.e. 1,1,2-trichloroethane and the distillate from
this column (Stream 15) is MEK and

194

alcohol. The recovery of solvent is


99.5%. The solvent is first cooled down
to room temperature and then fed to the
extraction column.
MEK product still
The distillate from the Solvent Recovery Column is fed to this distillation
column along with the liquid from the
condenser (Stream 7), which is mixed
first and then preheated to 354K and
then fed into the column (Stream 16).
The distillate is MEK and the bottom
product is SBA. The SBA discharged
from the bottom of this column (Stream
19) will be sent back to alcohol feed
tank; therefore it is cooled and then
stored (Stream 20). The MEK product
will be cooled and stored in a storage
tank (Stream 18). The MEK produced
is 99% pure.
References
1. Ullmanns Encyclopaedia Industrial Organic Chemicals, Volume
2, (pp. 971- 981).
2. John J McKetta, William A. Cunningham, Encyclopaedia Chemical
Processes, (pp. 32-49).
3. Distillation, in Robert E. Treybal,
Mass Transfer Operations, pp.
435-441.

4. Liquid Liquid Extraction, in


Robert E. Treybal, Mass Transfer
Operations, pp. 505.
Websites
a. MEK sales specifications, www.
exxonmek.com/publicfiles/fluids/
aliphatic/northAmerica/sales_specifications_pdf, as on 2nd July
2009.
b. Chemical Profile, MEK; www.
scorecard.org; as on 4th July 2009.
c. PERP Program, www.nexant.com,
as on 5th July 2009.
d. MEK, www.weblakes.com, as on
7th July 2009.
e. Production sec-Butyl alcohol via nbutane hydration, www.fripps.com,
as on 8th July 2009.
f. Unit operations, www.chemistryreact.org, as on 10th July.
g. Dr. R.B. Williams, International
programs of chemical safety, www.
inchem.org , as on 12th July.
h. Eluira Greiner, MEK, Chemical
Weekly, January 17th, 2007.
i. ICB, Global MEK capacity, www.
ICIS.com, as on 13th July.
j. Subhadip Sarkar, Cetex Petrochemicals, www.expressindia.com; as on
15 July.

Chemical Weekly April 27, 2010