Methyl Ethyl Ketone Sampat

Special Report

Methyl ethyl ketone – A techno-commercial profile

M

ethyl ethyl ketone (MEK or
2-butanone) is an organic compound with the formula
CH3C(O)CH2CH3. Its CAS number is
78-93-3.
The colorless liquid ketone has a sharp, sweet odour of butterscotch and acetone. It is produced industrially on a large scale, and also occurs in trace amounts in nature. It is soluble in water and is commonly used as an industrial solvent. With natural and synthetic resins, MEK produces solutions with low viscosity and high solids content.

Properties
The physical and chemical properties of MEK are determined largely by its carbonyl group. MEK engages in reactions typical of saturated aliphatic ketones. These include condensations with amines, aldehydes and many other organic compounds, hydrolysis (catalysed with acid or base), oxidation via concentrated oxidizing acids or acidic peroxides, and reduction with hydrogen and metal catalysts.
None of these reactions is likely to be important in nature.
On the other hand, MEK and other methyl ketones will react with halogens and hypo halides in aqueous solution to
Table 1
Physical properties of MEK
Appearance
Molar mass
Density
Melting point
Boiling point
Solubility in water
Refractive index (nD)
Viscosity
198

Colorless liquid
72.11 g mol-1
0.8050 g/cm3
-86oC
79.64oC
27.5 g/100 ml
1.37880
0.43 cP

B.G. SAMPAT
E-mail: [e-mail]
MEK is an irritant, causing irritation to the eyes and nose of humans, but serious health effects in animals have been seen only at very high levels.
When inhaled, these effects included birth defects.

form a carboxylic acid and a haloform.
The reaction provides a specific test for methyl ketones, and may produce chloroform in chlorinated water supplies contaminated with methyl ketones.
MEK and other ketones are photochemically reactive when excited by wavelengths occurring in the atmosphere and produce free radicals, which lead to the formation of photochemical smog. MEK is stable under ordinary conditions but can form peroxides on prolonged storage; these may be explosive.
MEK can also form explosive mixtures with air. It is very soluble in water, miscible with many organic solvents, and forms azeotropes with water and many organic liquids.
Health effects
MEK can react with most oxidizing materials, and can produce fires.
It is moderately explosive; it requires only a small flame or spark to cause a vigorous reaction. MEK fires should be extinguished with carbon dioxide, dry chemicals or alcohol foam. Concentrations in the air high enough to be flammable are also intolerable to humans, due to the irritating nature of the vapour.

Emissions of MEK will continue to be regulated as a volatile organic compound because of its contribution to the formation of tropospheric (groundlevel) ozone.
Analytical methods
Several analytical methods exist for the measurement of MEK at environmental levels in air, water, biological samples, waste and other materials.
In the more sensitive methods, MEK is trapped and concentrated either on a solid sorbant or as a derivative of
2,4-dinitrophenylhydrazine (DNPH).
Absorbed MEK and other volatile organic compounds are desorbed, separated by gas chromatography and measured with a mass spectrometer or flame ionization detector. Derivatized
MEK is separated from related compounds by high performance liquid chromatography and measured by ultraviolet absorption.
In media such as solid waste and biological materials, MEK must first be separated from the substrate by methods such as solvent extraction or steam distillation. High concentrations of MEK in air can be monitored continuously by infrared absorption.
Detection limits are 3-µg/m3 in air,
0.05-µg/litre in drinking water, 1.0-µg/ litre in other types of water, 20-µg/litre in whole blood and 100-µg/litre in urine. Chemical Weekly July 5, 2011

Special Report
PRODUCTION PROCESS
Dehydrogenation of sec-butyl alcohol
MEK is produced mainly by dehydrogenation of sec-butyl alcohol. In the
USA, one process uses sec-butyl alcohol vapour at 400-550°C oxidized with a zinc oxide catalyst. Reaction gases are condensed and the condensate fractionated in a distillation column. The yield of MEK is
85-90%. Any uncondensed reaction gases are scrubbed with water or a non-aqueous solvent and the waste stream from the scrubber, which contains MEK and reaction by-products, is either recycled or discarded. In Europe, sec-butyl alcohol is dehydrogenated over Rainey nickel or copper chromite catalyst at 150°C.
Oxidation of n-butane
MEK is also produced by the oxi-

dation of n-butane, either as the main product or as a by-product in the manufacture of acetic acid. Liquid butane reacts with compressed air in the presence of a transition metal acetate catalyst, normally cobalt acetate, and the reaction product phase is separated. The hydrocarbon-rich phase is recycled to the reactor and the aqueous phase with
MEK is withdrawn and purified. MEK and other organic compounds with low boiling points are separated from acetic acid by distillation. Reaction conditions determine whether MEK or acetic acid is the principal product.
Other methods
Other methods exist for the commercial manufacture of MEK, but there is no evidence that any of these alternatives are of current importance.
Mexico

Central/Eastern Europe
Middle East

Oceania
Other

India
Central/South America
China

Other Asia

Rep. of Korea

Taiwan

United States

Japan
Western Europe
Fig. 1: World consumption of MEK – 2009
[Ref: SRI Consultants]
Chemical Weekly July 5, 2011

In addition to manufacture by the chemical industry, MEK and other carbonyls are incidentally produced as components of exhaust from jet and internal combustion engines and from industrial activities such as retort distillation of oil shale and gasification of coal.
Applications
As a solvent
MEK is an effective and common solvent and is used in processes involving gums, resins, cellulose acetate and nitrocellulose coatings and in vinyl films. For this reason, it finds use in the manufacture of plastics, textiles, in the production of paraffin wax, and in household products such as lacquer, varnishes, paint remover, a denaturing agent for denatured alcohol, glues, and as a cleaning agent. It has similar solvent properties to acetone, but has a significantly slower evaporation rate.
MEK is also used in dry erase markers as the solvent of the erasable dye.
As a welding agent
As MEK dissolves polystyrene, it is sold as “polystyrene cement” for use in connecting together parts of scale model kits. Though often considered an adhesive, it is actually functioning as a welding agent in this context.
Miscellaneous uses
MEK is the precursor to methyl ethyl ketone peroxide, a catalyst for some poly merization reactions. In addition to industrial uses, MEK is an ingredient in a variety of consumer products such as lacquers, varnishes, spray paints, paint removers, sealers and glues. In both consumer products and industrial applications, MEK is frequently only one of several components in a mixture of organic solvents. MEK is also used as an extraction solvent in the processing of foodstuffs and food ingredients, e.g., in fractionation of fats and oils, decaffeination of tea and coffee, and extraction of flavorings.
199

Special Report
Table 2
Global capacity for MEK [2009]

[ktpa]
Capacity
55
20
10
40
5
30

Company
Arkema
Bangkok Synthetics
Carboclor
Celanese
Cetex Petrochemicals
China Bluestar Harbin Petrochemical

Location
La Chambre, France
Mab Ta Phut, Thailand
Campana, Argentina
Pampa, Texas, US
Chennai, India
Harbin, China

ExxonMobil Chemical
Exxon Chemical
Fushun Petrochemical
Hebei Zhongjie Petrochemical
Heilongjiang Petrochemical
Idemitsu Kosan
Jiangsu Taizhou Petrochemical
Jinan Co.
Lanzhou Petroleum Processing &
Chemical Complex
Lee Chang Yung Chemical Industry
Maruzen Petrochemical
Oxiteno Industria & Comercio
Petrobrazi
Sasol Solvents

Baton Rouge, Louisiana, US
Fawley, UK
Fushun, China
Cangzhou, China
Daqing, China
Tokuyama, Japan
Taizhou, China
Jinan, China
Lanzhou, China

135
135
40
30
12
40
30
10
30

Lin Yuan, Taiwan
Ichihara, Japan
Triunfo, Brazil
Brazi, Romania
Moers, Germany
Secunda, South Africa
Pernis, Netherlands
Ulsan, South Korea
Lin Yuan, Taiwan
Kawasaki, Japan
Dushanzi, China

30
170
40
30
70
55
90
50
120
90
30

Shell Chemical
SK Corp
Tasco Chemical
Tonen Chemical
Xinjiang Dushanzi Tianli High &
New Tech Co.
Zibo Wixiang Tengda Chemical

Zibo, China

20

Source: ICIS

Years
2005-06
2006-07
2007-08
2008-09
2009-10
2010-11 (Apr-Sep)
2010-11(Est.)
200

Table 3
Imports of MEK into India
Quantity
Value
(Tons)
(Rs.Mn)
13,544
592
17,758
758
22,091
1,033
20,668
1,312
24,556
1,135
11,126
643
31,500
-

UV
(Rs/kg)
43.71
42.68
46.76
63.48
41.19
57.79
-

Global outlook
MEK is a mature product with most of its applications growing slowly. Regionally, the European and US markets are flat. Growth is concentrated in Asia with the Chinese market being the main driver. MEK consumption is expected to grow at an average annual rate of 1.9% during 2011-2014, according to a 2010 MEK market outlook report. Most of this growth will come from Asia-Pacific, as the global recession shrunk consumption significantly in developed market regions, particularly in 2009. MEK consumption may increase modestly during 2011-2014 in developed regions as the market tries to regain some lost volume. Coating solvents remains the major consumer of MEK, with around 50% of MEK consumed worldwide by this application in 2009. There will be little change in the world MEK market breakdown by 2014. Printing ink, which makes up around 10% of the MEK market, is projected to experience the highest growth rate during 2010-2014, particularly in China. In Asia, the supplies of
MEK have tightened significantly due to closure of the largest MEK facility in
Japan due to devastating earthquake of
11th March, 2011.
There were three big MEK producing factories in Japan:

Maruzen
Petrochemical
with
170,000-tpa capacity in Chiba;

Tonen Chemical in Kawasaki with
90,000-tpa capacity; and

Idemitsu Kosan with 40,000-tpa capacity in Tokuyama.
But Maruzen Petrochemical has been closed due to damage incurred during the earthquake.
As per the market reports, Japanese producers have started reducing their exports in order to meet their domestic shortages. Due to this, prices are likely to increase in Asian market in future.
Chemical Weekly July 5, 2011

Special Report

Country
Belgium
Canada
China
France
Germany
Israel
Italy
Japan
Korea South
Nepal
Netherlands
Saudi Arabia
Singapore
South Africa
Taiwan
Thailand
UAE
UK
USA
Total

Table 4
Countrywise imports of MEK during last three years
2007-08
2008-09
Qty(Kgs)
Value(Rs.)
Qty(Kgs)
Value(Rs.)
0
0
0
0
180
9,514
0
0
1,190,500
57,227,872
1,123,000
57,003,086
0
0
0
0
309
6,345
1,073
235,050
1,494
149,909
0
0
567
135,432
0
0
2,525,000
119,840,202
999,000
39,924,272
1,512,557
67,959,925
24,850
1,301,265
0
0
0
0
2,443,683
120,286,825
2,222,959
137,728,476
150,000
6,819,091
0
0
318,200
16,177,916
866,440
57,746,318
10,709,187
498,923,563
9,021,613
614,640,809
784,730
39,930,375
3,609,484
234,423,672
60
15,266
0
0
1,200
90,895
0
0
2,453,540
105,581,634
2,759,732
161,909,371
15
3,399
39,981
7,179,993
22,091,222
1,033,158,163
20,668,132 1,312,092,312

Indian market outlook
Cetex Petrochemicals Ltd. (CPL) is the only producer of MEK in India.
As compared to global market, CPL is a small player with production capacity of 5000-tpa.
The annual total demand in
India for MEK is estimated at about
30,000-tonnes. CPL’s production alone cannot meet the Indian demand. Thus the requirement is met through imports. The major uses for MEK in India are for printing / printing inks, followed by adhesives industry and paints.
Table 3 provides data on imports of MEK into India during last six years. As can be noted imports have increased from 13,544 tons in
Chemical Weekly July 5, 2011

2005-06 to around 31,500 tons in the year 2010-11. The unit cif value paid on imports has increased from Rs. 41 per kg to Rs. 58 per kg during the same period.

2009-10
Qty(Kgs)
Value(Rs.)
2,880
756,916
42
1,204
553,050
25,677,318
15,000
2,761,200
4,260
531,296
0
0
0
0
4,308,080
196,972,505
0
0
16,000
172,627
550,640
23,207,733
0
0
0
0
9,317,000
419,633,530
6,045,946
296,158,545
0
0
0
0
3,740,761
168,977,242
2,323
394,575
24,555,982 1,135,244,691

Imports have registered annual compounded growth rate of 17.3 per cent during the period 2005-06 to 2010-11.
Table 4 provides data on imports of MEK country-wise. The
UK, South Africa, Taiwan and Japan are the major suppliers of MEK to India. Imports from UK, South
Africa and Taiwan constituted 80% of the total imports during the year
2009-10.
Demand projection
The demand for MEK has been growing at over 15 per cent per annum during last 5 to 6 years. However, assuming a conservative rate of 12 per cent per annum, a demand of around 52,000-tons can be projected for the year 2015-16.
201