Special Report

201 Chemical Weekly September 13, 2011

Methyl isobutyl ketone (MIBK): A Techno-commercial
Prole
2. 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 al-
cohol, 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 370,000-
tpa.
Applications
MIBK is used as a solvent for ni-
trocellulose, lacquers, and certain poly-
mers and resins.
Precursor to 6-PPD
Another major use is as a precursor
to N-(1,3-dimethylbutyl)-N-phenyl-
p-phenylenediamine (6-PPD), an anti-
ozonant used in tyres.
6-PPD is prepared by reductive
coupling of MIBK with 4-aminodiphe-
nylamine.
Solvent and niche applications
Unlike the other common ketone
solvents, acetone and MEK, MIBK
has quite low solubility in water,
making it useful for liquid-liquid ex-
traction.
M
ethyl isobutyl ketone
(MIBK) [CAS registry
number: 108-10-1] is an
organic compound with the formula
(CH
3
)
2
CHCH
2
C(O)CH
3
. This colour-
less liquid, a ketone, is widely used as
a solvent.
Physical and chemical properties
MIBK is a clear liquid with a
sweet odour; the odour threshold
is 1.64-mg/m
3
(0.4 ppm). It is moder-
ately soluble in water.
MIBK can react violently with
oxidizing and reducing agents. When
heated, peroxides may form by auto-
oxidation and may explode spontane-
ously.
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 -84.7C
Boiling point 117-118C
Solubility in
water
1.91 g/100 mL
(20C)
Refractive index
(n
D
)
1.3958
Viscosity 0.58 cP at 20.0C
Health and safety
MIBK is a colourless liquid with a
characteristic ketone odour. It is highly
fammable and vapours may travel to
the source of ignition and fashback. It
is soluble in water and miscible with
most organic solvents and evaporates
in air.
B.G. SAMPAT
Email: bgsampat@gmail.com
It irritates the skin, eyes and respi-
ratory tract and in high concentrations
leads to nausea, headaches, dizzi-
ness and unconsciousness. It is on the
hazardous air pollutants list.
Analytical methods
Gas chromatography combined
with flame ionization or mass spec-
troscopy 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 bio-
logical tissues (e.g., headspace or ex-
traction).
Production process
There are two main routes for
MIBK production.
1. MIBK is produced from isopropa-
nol in a mixed ketones process. Di
isobutyl ketone (DIBK) and ace-
tone are co-products of this pro-
cess.
Acetone
HO
H
2
Pd
MIBK
Dehydration
Mesityl oxide Diacetone alcohol
Aldol
condensation
Special Report
Chemical Weekly September 13, 2011 202
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.
When mixed with water or isopro-
pyl alcohol, MIBK serves as a deve-
loper for PMMA electron beam litho-
graphy resist.
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 favouring agent
and is used in food-contact materials.
It is a component of cellulose and
polyurethane lacquers and paint sol-
vents.
It is also used in the manufacture of
methyl amyl alcohol.
Global outlook
World MIBK statistics are diff-
cult to estimate, but according to SRI
Consulting, the worlds total capa-
city for making MIBK was 501,500-
tpa 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 West-
ern Europe 17.1%.
Statistics show that the average
annual growth of MIBK consumption
in Asia has surpassed 10% in recent
years. With the rapidly increasing de-
mand for making rubber antioxidants
with superior quality and high effect
and for making coatings with high solid
Fig. 1: World consumption of MIBK: 2007
Western Europe
China
United States
Japan
Rep. of Korea
Central/South
America
India
Central/Eastern Europe
Mexico
Other
Thailand
Malaysia
Indonesia
Africa
Philippines
Fig. 2: Global MIBK market shares [2005]
Sasol 9%
Rhodia 6%
Reliance 2%
Mitsui 7%
Kyowa Hakko 4%
Formosa 2%
Arkema 4%
Eastman 2%
Dow 10%
CNPC 2%
Celanese
8%
Astra 2%
Others 1%
Showa Denko 5%
Shell 36%
Special Report
203 Chemical Weekly September 13, 2011
content, both the production and the
consumption of MIBK already have
shifted to Asia and especially main-
land 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 surfac-
tants.
Consumption for solvent applica-
tions, which consume the majority of
MIBK in most regions, is expected to
stay relatively fat in the developed re-
gions. There may be some reformula-
tion in certain MIBK applications as a
result of environmental regulations, but
cost pressures may limit reformulation
activity.
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 con-
sumption for anti-ozonants is fore-
cast 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 posi-
tive growth in lube oil applications and
as a froth fotation agent (especially in
actively mined regions). Global con-
sumption will average growth of 2.5%
per year. The strongest growth will be
in Asia, and particularly China.
Chinas outlook
Chinas demand for MIBK has
grown at a fast pace in the past decade.
In the next fve years, both production
and demand will continue to grow.
Chinas MIBK capacity was 84,000-tpa
in 2009, made up of fve units in four
companies. All these units use the ac-
etone single-step process. PetroChina
Jilin Petrochemical Co. Ltd. construct-
ed two units in 2005 and 2007 respec-
tively, 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 capa-
city and the output have increased and
the self-suffciency rate has kept go-
ing up in recent years. The average an-
nual growth of MIBK consumption in
China reached 15.5% between 2005
and 2009. The output and the consump-
tion 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 extract-
ing agent and diluting agent for various
pesticides and medicines, extracting
Table 2
Global MIBK capacity 2008
[ktpa]
Company Location Capacity
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 9
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 Oceanking Chemical
Developing
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
Source: ICIS plants & projects
Special Report
Chemical Weekly September 13, 2011 204
Table 3
Imports of MIBK into India
2007-08 2008-09 2009-10
Country Qty (Kgs) Value (Rs) Qty (Kgs) Value (Rs) Qty (Kgs) Value (Rs)
Canada 0 0 0 0 375 34,579
China 62,199 11,370,044 141,885 33,133,818 174,076 26,935,109
France 0 0 18,100 1,456,150 0 0
Germany 1,231 60,767 2,554 77,829 3,643 110,894
Japan 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
Philippines 0 0 0 0 3,000 263,582
Singapore 633,200 35,826,165 117,990 8,771,169 369 242,165
South Africa 4,289,769 248,302,790 2,605,080 180,091,463 3,002,070 170,397,634
Spain 60,000 3,629,848 62,239 4,506,927 69,760 4,561,799
Taiwan 1,014,270 67,971,406 4,704,560 347,438,788 4,878,262 329,344,594
Thailand 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
the Sasol One site in Sasolburg, South
Africa was started up on 24th March
2010. The new plant doubles Sasol Sol-
vents current MIBK production capac-
ity to 60,000-tpa. No new capacity for
MIBK is expected before 2015 in China.
Indian scenario
With the closure of Reliance Indus-
tries 7,000-tpa plant in Thane (earlier
of antioxidant 4020 in the world. The
consumption of MIBK in the pro-
duction of antioxidant 4020 in China
was 36,000-tonnes in 2009, accounting
for 47.9% of the total. Shandong pro-
vince is the biggest producer of antioxi-
dant 4020 in China.
New capacity
Sasol Solvents new MIBK plant on
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 big-
gest 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, an-
tioxidant 4020 has become the rubber
antioxidant with the greatest consump-
tion in tyre production worldwide. With
the constant maturing of the production
process of antioxidant 4020 and the
further increase in the self-suffciency
rate of raw material MIBK, the produc-
tion of antioxidant 4020 in China has
developed rapidly, making China the
most important supplier and consumer
Special Report
205 Chemical Weekly September 13, 2011
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
Switzerland 0 0 0 0 2,880 1,117,736
UAE 429,000 20,787,254 42,000 3,965,917 0 0
Unspecifed 0 0 485 31,857 0 0
Total 476,204 26,039,951 82,264 7,191,345 2,905 1,123,351
part of Nocil), there is currently no lo-
cal 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
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 esti-
mated at around 22,000-tonnes. In In-
dia it is mainly used as an active solvent
for many synthetic resins including cel-
lulosics, vinyl copolymers, acrylics, al-
kyds, polyesters and epoxies.
It is also used for developing high-
solids coatings because of its combina-
tion 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 de-
waxing/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.