Special Report
Methyl isobutyl i sobutyl ketone ke tone (MIBK): A Techno-commercial Techno-commercial Profile
M
ethyl isobutyl ketone (MIBK) [CAS registry number: 108-10-1] is an organic compound with the formula (CH3)2CHCH2C(O)CH3. This colourless liquid, a ketone, is widely used as a solvent.
B.G. SAMPAT
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Physical and chemical properties MIBK is a clear liquid with a sweet odour; the odour threshold is 1.64-mg/m3 (0.4 ppm). It is moderately soluble in water.
MIBK can react violently with oxidizing and reducing agents. When heated, peroxides may form by autooxidation and may explode spontaneously. Table 1 Physical properties of MIBK Parameter
Value
Molar mass
100.16 g/mol
Appearance
Colourless liquid
Density
0.802 g/mL, liquid
Melting point
-84.7°C
Boiling point
117-118°C
Solubility in water
1.91 g/100 mL (20°C)
Refractive index (nD)
1.3958
Viscosity
0.58 cP at 20.0°C
Health and safety MIBK is a colourless liquid with a characteristic ketone odour. odour. It is highly ammable and vapours may travel to the source of ignition and ashback. It is soluble in water and miscible with most organic solvents and evaporates in air.
Chemical Weekly September 13, 2011 2011
It irritates the skin, eyes and respiratory tract and in high concentrations leads to nausea, headaches, dizziness and unconsciousness. It is on the hazardous air pollutants list. Analytical methods Gas chromatography combined with flame ionization or mass spectroscopy is a suitable technique for the determination of MIBK, which can be detected in air (by trapping with, e.g., charcoal), in water (e.g., headspace or extraction), and in biological tissues (e.g., headspace or extraction). Production process There are two main routes for MIBK production.
1.
MIBK is produced from isopropanol in a mixed ketones process. Di isobutyl ketone (DIBK) and acetone are co-products of this process. Aldol condensation
MIBK is produced from acetone with hydrogen by a three-step process of aldol condensation, dehydration and hydrogenation. Firstly, acetone undergoes an aldol condensation to give diacetone alcohol, which readily dehydrates to give mesityl oxide. Mesityl oxide can then be hydrogenated to give MIBK.
At present, the global production capacity for MIBK stands at 370,000tpa. Applications MIBK is used as a solvent for nitrocellulose, lacquers, and certain polymers and resins.
Precursor to 6-PPD Another major use is as a precursor to N-(1,3-dimethylbutyl)-N’-phenyl p-phenylenediamine p-phenylenediamine (6-PPD), an antiozonant used in tyres.
6-PPD is prepared by reductive coupling of MIBK with 4-aminodiphenylamine. Solvent and niche applications applications Unlike the other common ketone solvents, acetone and MEK, MIBK has quite low solubility in water, making it useful for liquid-liquid extraction.
HO
H2
Dehydration
Pd Acetone
Diacetone alcohol
Mesityl oxide
MIBK
201
Special Report Africa
Philippines
Indonesia
Other
Malaysia Thailand Western Europe
Mexico Central/Eastern Europe India
It has a similar polarity to ethyl acetate, but greater stability towards aqueous acid and base. It can be used to extract gold, silver and other precious metals from cyanide solutions, such as those found at gold mines, to determine the levels of those dissolved metals. Diisobutyl ketone (DIBK), a related lipophilic ketone, is also used for this purpose. MIBK is also used as a denaturing agent for denatured alcohol.
Central/South America
When mixed with water or isopro pyl alcohol, MIBK serves as a developer for PMMA electron beam lithography resist.
Rep. of Korea
China
MIBK is used as a solvent for CS in the preparation of the CS spray used currently by British police forces. MIBK, which occurs naturally in food, is a permitted avouring agent and is used in food-contact materials. It is a component of cellulose and polyurethane lacquers and paint solvents.
Japan
United States Fig. 1: World consumption of MIBK: 2007
Sasol 9% Shell 36%
It is also used in the manufacture of methyl amyl alcohol.
Rhodia 6%
Global outlook World MIBK statistics are difcult to estimate, but according to SRI Consulting, the world’s total capacity for making MIBK was 501,500tpa in 2009 and consumption was 402,200-tonnes. China accounted for 18.7% of the world total consumption, the United States for 17.9% and Western Europe 17.1%.
Reliance 2%
Mitsui 7%
Kyowa Hakko 4% Formosa 2% Arkema 4% Eastman 2% Showa Denko 5%
Dow 10% CNPC 2%
Celanese 8%
Others 1% Astra 2%
Fig. 2: Global MIBK market shares [2005]
202
Statistics show that the average annual growth of MIBK consumption in Asia has surpassed 10% in recent years. With the rapidly increasing demand for making rubber antioxidants with superior quality and high effect and for making coatings with high solid Chemical Weekly September 13, 2011
Special Report content, both the production and the consumption of MIBK already have shifted to Asia and especially mainland China. Globally, 64% of total MIBK out put is consumed as a solvent, 18% as an extraction solvent, 10% as rubber processing chemicals and 3% as surfactants. Consumption for solvent applications, which consume the majority of MIBK in most regions, is expected to stay relatively at in the developed regions. There may be some reformulation in certain MIBK applications as a
result of environmental regulations, but cost pressures may limit reformulation activity.
Table 2 Global MIBK capacity – 2008 [ktpa] Company
Location
Arkema
La Chambre, France
15
Carboclor
Campana, Argentina
8
Celanese
La Cangrejera, Mexico
50
Dow Chemical
Institute, West Virginia, US
35
Eastman Chemical
Kingsport, Tennessee, US
Jilin Chemical
Jilin, China
30
Kumho P&B
Yosu, South Korea
30
Kyowa Hakko
Yokkaichi, Japan
15
Lee Chang Yung Chemical
Lin Yuan, Taiwan
20
Mitsubishi Chemical
Mizushima, Japan
20
Mitsui Chemicals
Ichihara, Japan
30
Iwakuni, Japan
30
Ningbo, China
15
Reliance Industries [Formerly Nocil]
Thane, India
7
Rhodia Brasil
Paulinia, Brazil
25
Sasol Solvents
Sasolburg, South Africa
30
Shell Chemical
Berre, France
25
Pernis, the Netherlands
45
Showa Denka
Tokuyama, Japan
20
Taizhou Petrochemical
Taizhou, China
15
Zhenjiang LCY General Chemical
Zhenjiang, China
25
Ningbo Oceanking Chemical Developing
Source: ICIS plants & projects
Chemical Weekly September 13, 2011
Capacity
9
Some applications (especially anti-ozonants) are moving to Asia, particularly China where several ca pacity additions have come on-stream in the past three years. MIBK consumption for anti-ozonants is forecast to grow at an average annual rate of 4-5% in Asia and 0-1% in the United States and Western Europe. Overall, MIBK will experience positive growth in lube oil applications and as a froth otation agent (especially in actively mined regions). Global consumption will average growth of 2.5% per year. The strongest growth will be in Asia, and particularly China. China’s outlook China’s demand for MIBK has grown at a fast pace in the past decade. In the next ve years, both production and demand will continue to grow. China’s MIBK capacity was 84,000-tpa in 2009, made up of ve units in four companies. All these units use the acetone single-step process. PetroChina Jilin Petrochemical Co. Ltd. constructed two units in 2005 and 2007 respectively, mainly supplying the markets in northeastern and northern China. Other three factories are all located in eastern China, serving the consumers in eastern and southern regions.
Consumption of MIBK in China has been brisk, and both the capacity and the output have increased and the self-sufciency rate has kept going up in recent years. The average annual growth of MIBK consumption in China reached 15.5% between 2005 and 2009. The output and the consumption of MIBK were 47,600-tonnes and 75,200-tonnes respectively in 2009, an increase of 58.1% and 17.5% over the previous year. In China, MIBK is mainly used in the production of rub ber antioxidant 4020, or as a solvent for coatings. It is also used as extracting agent and diluting agent for various pesticides and medicines, extracting 203
Special Report Table 3 Imports of MIBK into India 2007-08 Country
2008-09
2009-10
Qty (Kgs)
Value (Rs)
Qty (Kgs)
Value (Rs)
Qty (Kgs)
Value (Rs)
0
0
0
0
375
34,579
62,199
11,370,044
141,885
33,133,818
174,076
26,935,109
0
0
18,100
1,456,150
0
0
1,231
60,767
2,554
77,829
3,643
110,894
93,000
6,008,111
307,000
15,486,733
1,265,200
72,792,512
Korea North
0
0
35,000
3,861,875
0
0
Korea South
283,257
19,971,828
3,898,677
245,758,953
1,750,539
117,133,062
Netherlands
575,000
36,416,076
498,400
40,951,093
1,549,000
81,264,418
0
0
0
0
3,000
263,582
633,200
35,826,165
117,990
8,771,169
369
242,165
4,289,769
248,302,790
2,605,080
180,091,463
3,002,070
170,397,634
60,000
3,629,848
62,239
4,506,927
69,760
4,561,799
1,014,270
67,971,406
4,704,560
347,438,788
4,878,262
329,344,594
0
0
0
0
28,852
1,795,200
UAE
52,200
3,556,611
21,070
1,697,905
0
0
USA
7,556,023
426,589,828
2,506,870
185,798,294
3,972,785
242,563,178
Total
14,620,149
859,703,474
14,919,425
1,069,030,997
16,697,931
1,047,438,726
Canada China France Germany Japan
Philippines Singapore South Africa Spain Taiwan Thailand
agent for rare metals, dewaxing agent for lube oils and also in the synthesis of surfactants. Rubber antioxidant 4020 is a leading variety of antioxidant for radial tyres. China is the second biggest tyre producer in the world. Owing to the explosive growth of radial tires, great quantities of antioxidants with high effect and low toxicity are needed. Because of its excellent properties, antioxidant 4020 has become the rubber antioxidant with the greatest consumption in tyre production worldwide. With the constant maturing of the production process of antioxidant 4020 and the further increase in the self-sufciency rate of raw material MIBK, the production of antioxidant 4020 in China has developed rapidly, making China the most important supplier and consumer 204
of antioxidant 4020 in the world. The consumption of MIBK in the production of antioxidant 4020 in China was 36,000-tonnes in 2009, accounting for 47.9% of the total. Shandong province is the biggest producer of antioxidant 4020 in China. New capacity Sasol Solvents new MIBK plant on
the Sasol One site in Sasolburg, South Africa was started up on 24th March 2010. The new plant doubles Sasol Solvents’ current MIBK production capacity to 60,000-tpa. No new capacity for MIBK is expected before 2015 in China. Indian scenario With the closure of Reliance Industries 7,000-tpa plant in Thane (earlier
Chemical Weekly September 13, 2011
Special Report Table 4 Exports of MIBK from India 2007-08
2008-09
2009-10
Country
Qty (Kgs)
Value (Rs)
Qty (Kgs)
Value (Rs)
Qty (Kgs)
Value (Rs)
Ethiopia
0
0
0
0
10
1,018
France
0
0
25
3,025
0
0
Iran
13,000
919,295
0
0
0
0
Israel
27,200
3,865,120
0
0
0
0
Malaysia
4
5,579
0
0
0
0
Mauritius
0
0
24
7,904
0
0
Nepal
0
0
330
39,600
14
3,370
Singapore
0
0
13,200
1,187,772
0
0
Sri Lanka
7,000
462,703
26,200
1,955,270
1
1,227
0
0
0
0
2,880
1,117,736
429,000
20,787,254
42,000
3,965,917
0
0
0
0
485
31,857
0
0
476,204
26,039,951
82,264
7,191,345
2,905
1,123,351
Switzerland UAE Unspecied Total
part of Nocil), there is currently no local production of MIBK in the country and the entire requirements are met through imports. Imports have increased from 14,620-tonnes in 2007-08 to around 17,000-tonnes in 2009-10. Imports during 2010-11 are estimated to be of the order of 21,530-tonnes valued at Rs. 1640 mn. Majority of the im ports are coming from Taiwan, South Africa, US, Netherlands, South Korea and Japan. The unit CIF value of imports has increased from Rs. 58.80 per kg Chemical Weekly September 13, 2011
in 2007-08 to Rs. 76.17 per kg in 2010-11. Exports on the other hand are negligible and have declined from 476-tonnes in 2007-08 to 3-tonnes in 2009-10. The MIBK market in India is estimated at around 22,000-tonnes. In India it is mainly used as an active solvent for many synthetic resins including cellulosics, vinyl copolymers, acrylics, alkyds, polyesters and epoxies. It is also used for developing highsolids coatings because of its combination of high solvent activity and low density, and also as an intermediate
in the production of synthetic rubber chemicals. In addition to its use as a solvent for inks, coatings, and adhesives, MIBK is used as an extraction agent in the dewaxing/deoiling of petroleum products and in pharmaceuticals. During the last four years, Indian demand for MIBK has increased at an annual compounded growth rate of 15%. Assuming that the demand for the next four years would continue to grow at the same rate, demand for the year 2014-15 can be projected to rise to 38,500-tonnes. 205
