Special Report
PRODUCT PROFILE
Monochloroacetic acid: A techno-commercial profile
M
Introduction
O onochloro-
Cl acetic acid
OH
(ClCH2COOH),
commonly abbreviated as MCA or
MCAA, is one of the most important
halogenated derivatives of acetic acid.
It is a colourless solid and exists in
three crystal modifications — alpha
(mp 63°C), beta (mp 56.2°C), and
gamma (mp 52.5°C). Commercial
MCA consists of the alpha form. It is
also available commercially in a water
solution.
MCA is a reactive compound that
can undergo various reactions to form
a number of intermediates. Markets for
MCA and derivatives include drilling
fluids, plastic stabilizers, herbicides, sur-
factants and pharmaceuticals. Increasing
use of MCA in oilfield applications, in
tin stabilizers for processing PVC res-
ins and in surfactants has offset stalled
consumption in phenoxy herbicides.
The most important industrial uses
of MCA are in the production of cel-
lulose ethers (predominantly CMC),
thioglycolic acid and herbicides. MCA
is also used in the manufacture of am-
photeric surfactants, glycine, cyanoace-
tic acid, phenoxyacetic acid and chloro-
acetic acid esters.
Production
There are four main ways to synthe-
size MCAA:
Reaction of vinylidene chloride
(VDC) with oxygen to chloroacetyl
chloride (CAC) and hydrolysis. This
is the least used of the methods.
Hydrolysis of trichloroethylene
(TCE) using sulphuric acid as a
catalyst. This method produces a
highly pure product, which can be
important since mono-, di- and tri-
Chemical Weekly May 10, 2011
chloroacetic acids are difficult to
separate by distillation.
CCl2CHCl + 2H2O ClCH2CO2H + 2HCl
Chlorination of acetic acid and sub-
sequent purification by crystalliza-
tion; and
Chlorination of acetic acid and subse-
quent purification by hydrogenation.
CH3COOH + Cl2 lCH2CO2H + HCl
The last one is the prevalent manu-
facturing method that enables produc-
tion at significantly lower cost than
alternatives and results in the highest
available level of purity. The two major
producers worldwide have such capa-
bilities.
MCAA is offered commercially
mainly as 100% flakes or 80% water
solution.
Direct chlorination route
On an industrial scale, MCA is
usually manufactured by direct chlori-
nation of acetic acid, but the reaction
results unavoidably in a rather crude
product, comprising, in addition to
the desired MCA, major amounts of
dichloroacetic acid (DCA) and some-
times trichloroacetic acid (TCA), as
well as residual acetic acid.
PANKAJ DUTIA
pankaj@chemicalweekly.com
It has particularly been found to be
practically impossible to eliminate the
formation of the troublesome by-pro-
duct DCA. The amount of DCA acid
appearing in the ultimate product varies
in general from about 1% to 6%, de-
pending upon the specific technique of
chlorination applied. In many industrial
applications, however, such amounts of
impurities are not acceptable for MCA,
and it is therefore specified for many
applications that the DCA content of
the product must not exceed values of
0.5% by weight and frequently even a
lower percentage.
The undesirable by-products, in parti-
cular the DCA, must therefore normally
be removed from the MCA raw product
before further use. Whereas acetic acid
could be easily removed, e.g. by distilla-
tion, it is practically impossible, because
of the proximity of the boiling points of
MCA (189°C) and of DCA (194°C), to
separate these species by distillation in a
reasonably economic way.
It has therefore been tried to remove
the higher chlorinated acetic acids
from the main product by recrystalliza-
tion techniques or by selective catalytic
hydrogenation of the crude product.
Recrystallization can decrease the
concentration of DCA in the crude
product mixture by a factor of about
four in one single recrystallisation
stage; for instance from about 3% to
about 0.75%. Normally more than one
stage is required to meet the usual in-
dustry demands. In addition to the re-
quirement of passing a two-stage puri-
fication, the recrystallization produces
197
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Table 1
Applications of MCA
Agrochemicals Bulk drugs Chemical intermediates Toxicology
2,4-D acids & salts Ibuprofen EDTA Glycolic acid
Dimethoate Diclofenac sodium Cyanoacetic acid Thioglycolic acid
Chloroacetyl chloride Caffeine Carboxy methyl cellulose Carboxylic acid
(CAC) (CMC)
Trichloroacetyl chloride Vitamins Sodium CMC Chloro acetamides
(TCAC)
2,4,5- T Glycine Carboxy methyl starch Mercapto acetic acid
N-(p-Hydroxy phenyl) Methyl monochloro acetate Sarcosines
glycine
Adrenaline Sodium monochloro acetate Coumarin
(SMCA)
Barbiturates Acetyl chloride Betaines
Phenyl acetic acid

large amounts of mother liquor contain- Uses gives thioglycolic acid, which is used
ing major quantities of MCA and about Industrially, MCA is used in the as a stabilizer in PVC and a component
18-40% by weight of DCA, which has production of a wide variety of use- in some cosmetics. In its largest scale
generally been discarded as waste. ful compounds, e.g. drugs, dyes, pes- application, MCA is used to prepare the
ticides. Most reactions take advan- thickening agent carboxymethyl cellu-
In the conventional process for the tage of the high reactivity of the C-Cl lose and carboxymethyl starch.
hydrogenation (or dechlorination) of a bond.
crude mixture of MCA, DCA and TCA, Production
the crude mixture is fed to a reactor and MCA is the precursor to the herbi- In India four units in the organized
a catalyst is suspended therein. Excess cide glyphosate. The herbicides MCPA sector and a dozen units in the small
hydrogen gas is introduced to the reactor (2-methyl-4-chlorophenoxyacetic acid) scale sector are engaged in making
from below. The outgoing gas comprising and dimethoate are prepared by alkyla- MCA. The total capacity for MCA is
hydrogen chloride (HCl) and excess hy- tion with chloroacetic acid. MCA is estimated at 100,000-tpa. Since most of
drogen is scrubbed with water removing converted to chloroacetyl chloride, a the capacity is in the small-scale sector,
the HCl; so that the purified residual hy- precursor to adrenaline (epinephrine). the unit-wise production details are not
drogen gas can be returned to the reactor. Displacement of chloride by sulphide available.

Off-gas Trichloroethylene H2SO4

absorption To the atmosphere
Acetic acid Gas Off-gas
absorption Vapour
32% HCl Hydration of trichloroethylene
HCI ~ 80%
CHCl=CCI2 ~ 15%
Reaction mixture
Acetic anhydride recycling

Acetic anhydride Vacuum distillation

Spent sulphuric
Hydrogenation

Distillation
Chlorination

MCAA crystallisation acid H2SO4 CICH2COOH melt

Dissolution

Gaseous chlorine MCAA

recrystallisation

Marketable
Hydrogen MCAA

Fig. 1: Schematic of MCA production from acetic acid/anhydride Fig. 2: Schematic of MCA production from trichloroethylene

198 Chemical Weekly May 10, 2011

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Table 2 of total production is in the western in Sulzbach/Taunus, Germany, is one of

Physical properties of MCA region. Production of MCA has been the world’s largest producers of MCA
Parameter Value growing at around 6 to 8 % per annum. and a leading manufacturer of sulphur-
and chlorine-based specialty interme-
Boiling point 188°C CABB Karnavati Chemicals, IOCL diates with a strong presence in Europe,
Melting point 57°C Chemicals & Pharmaceuticals Ltd., North America and South America. Due
Flash point 126°C Rayalseema Hi-Strength and Megh- to the alliance with Karnavati, CABB
mani Finechem are the four major pro- is establishing a presence in Asia and
Relative vapour density 1.4
ducers in the organised sector. a platform for further growth into the
Molecular mass 94.5 Asian market with MCA, SMCA and
Exclusive limits >8 CABB Karnavati the company’s specialty intermediates
(volume % in air) Karnavati Chemicals was started by portfolio. CABB will invest in safety,
five enterprising industrialists in 1993 quality and in doubling MCA capacity
Table 3 to manufacture MCA for the agro- up to 35,000-tpa.
Standard specifications of MCA chemical and API industry in India. It
Characteristic Standard started with a production capacity of In March 2011, CABB was ac-
specification 300-tpa, but currently has two plants in quired by an investment firm, Bridge-
Ahmedabad with a combined capacity point from AXA Private Equity.
MCA purity 99.0% min. to produce up to 22,000-tpa of MCA.
DCA contents 0.4% max. Meghmani Finechem
Acetic acid 0.3-0.4% The company is presently the lar- The Ahmedabad-based Megh-
gest manufacturer of MCA and sodium mani Organics Ltd. (MOL), promoted
Moisture 0.3- 0.4% monochloroacetate (SMCA) in India. the chlor-alkali project of Meghmani
Set point 60-64OC Finechem Ltd. (MFL), at the cost of
CABB GmbH, Sulzbach, Germany Rs. 550-crore. The fully-integrated
Total MCA production is estimated acquired the majority stake of Karnava- plant, with a manufacturing capacity of
at 60,000-tons in 2009-10. Around 80% ti Rasayan Ltd. CABB, headquartered 142,000-tpa of caustic soda, is located
at Dahej in Bharuch district of Gujarat.
Table 4
MCA capacity in India In order to leverage the inherent
Companies Location Capacity [tpa] strengths along with the availability of
CABB Karnavati Gujarat 22,000 basic raw materials like caustic soda
and chlorine from in-house source,
Meridian Chem-bond Gujarat 7,250 MOL has invested in projects for manu-
Rayalseema Hi-Strength Hypo Andhra Pradesh 6,000 facture of 2,4-D – a widely used herbi-
cide – as well as MCA (the intermediate
IOCL Punjab 7,200 for 2,4-D).
Meghmani Finechem Gujarat 12,000
Mutual Chemical Gujarat 2,400 Manufacture of MCA and TCAC
commenced in Q3, 2010 and in the
Siddharth Chlorochem Gujarat 1,200 Second phase, 2,4-D production com-
ACI Industrial Gujarat 2,400 menced in Q4, 2010. The company
has an installed capacity of 9,600-
Anugrah Inorganics Gujarat 6,000
tpa for 2,4-D acid and 12,000-tpa for
Shree Chlorochem Gujarat 5,500 MCA, which will generate 2,400-tpa of
Swati Chemicals Gujarat 4,200 TCAC.
S.R. Drugs Andhra Pradesh 5,000
IOCL Chemicals & Pharmaceuticals
Others 18,850 Ltd.
Total 100,000 IOL Chemicals & Pharmaceuticals
(IOLCP) was established in 1986. It is

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one of the largest manufacturers of APIs
and specialty chemicals with presence in
over 52 countries across the world.
Its product portfolio includes APIs
like ibuprofen, specialty chemicals
such as ethyl acetate, acetic anhydride,
isobutyl benzene, MCA and acetyl
chloride and bulk chemicals such as
glacial acetic acid.
The company has capacity of 7,200-
tpa for MCA, which it has plans to ex-
pand it further to 10,000-tpa by 2012.
International trade
MCA is being exported as well as
imported into the country. While im-
ports are in small quantities – ranging
between 1,500 to 2,000 tons – exports
are in the range of 15,000 to 25,000-
tons.
Exports are mainly to the regions
such as Turkey, Russia, Poland, Argenti-
na, Brazil, Italy, Indonesia and Mexico.
Imports are mainly from US, Japan and
Germany. The unit fob value earned
Table 5
Exports of MCA – its salts and esters from India
Years Quantity
[Tons]
2005-06 9,028
2006-07 23,350
2007-08 18,264
2008-09 15,436
2009-10 19,408
from exports has ranged between Rs.
40 to Rs. 45 per kg., while unit CIF
value paid on imports has been around
Rs. 39 to Rs. 48 per kg.
Consumption and demand
The domestic consumption of MCA
is estimated to be around 35,000 to
40,000-tons and exports around 20,000
to 25,000-tons. Agrochemical interme-
diates, pharmaceuticals and CMC are
the major end-use segments.
The domestic demand has been
growing at around 8% per annum. As-
suming the same growth going forward,
the domestic demand by the year 2014-15
is expected to reach at 56,000-tons. Add-
ing an export demand of around 30,000-
tons, a total demand of around 86,000-
tons can be projected by 2014-15.
The current total capacity in the in-
dustry is estimated at 100,000-tons and
capacity utilisation is only around 60%.
By 2014-15, the capacity seems to be
sufficient to meet the projected demand
by increasing capacity utilisation. How-
Value Unit FOB value
(Rs. Mn) [Rs/kg]
402.62 44.59
997.14 42.70
760.57 41.64
770.46 49.91
786.58 40.52
ever, if export demand increases, there
might be scope for expansion of capaci-
ties.
Global trends
In 2004, global demand for CMC
was estimated at 455,000-tonnes,
with capacity at 560,000-tpa. Capa-
city in Europe amounted to 250,000-
tpa, with demand at 225,000-tonnes.
Some 50% of the net exports from
Europe, totalling 50,000-tonnes was
to the US. A lot of imports to the US
were in the form of highly purified
sodium monochloroacetate (SMCA),
which is used in production of betaines.
Global MCA capacity in 2008 is
estimated at 1.1-mtpa; while output
was at 760,000-tonnes.
The leading manufacturers are
Akzo Nobel Industrial Chemicals
BV (Amersfoort, the Neth­erland) and
CABB GmbH (Sulzbach, Germany),
with a combined capacity of about
350,000-tpa. More than 100 producers
in China account for a capacity of about
550,000-tpa, while output in 2008 was
about 330,000 tonnes.
Over the last few years, much of the
capacity increase has been observed in
China and India, while output has de-
clined in Japan and Western Europe.
Presently there is only one manufacturer
of MCA in the CIS, and majority of
the demand is met by imports. In 2008,
the Russian market consumed about
5,000-tonnes of MCA.

Table 6 Worldwide demand for MCA is ex-

Imports of MCA – its salts and esters into India pected to grow at the rate of 2% annu-
ally, but demand for the highest purity
Years Quantity Value Unit CIF value
is expected to grow at the rate of 6-8%.
[Tons] (Rs. Mn) [Rs/kg]
The majority of the growth will be in
2005-06 2,141 84.14 39.29 Asia, with that in China possibly being
2006-07 1,604 66.38 41.38 over 8%/year.
2007-08 1,754 56.73 32.34
About 32% of global demand for
2008-09 1,559 66.87 42.89
MCA is for production of CMC with
2009-10 1,511 71.86 47.55 30% used for production of herbicides,

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Table 7
Top-10 export destinations for MCA, salts & esters from India
2007-08 2008-09 2009-10
Quantity Value Quantity Value Quantity Value
[Tons] [Rs Mn] [Tons] [Rs Mn] [Tons] [Rs Mn]
Italy 4,510 183 4,065 206 3,991 164
Argentina 1,146 51 311 17 1,888 80
Mexico 735 26 231 11 1,806 59
Indonesia 605 26 468 21 1,778 72
Turkey 4,095 168 3,248 154 1,610 57
Poland 699 29 444 21 1,382 55
Brazil 1,854 80 758 38 1,358 59
Russia 1,830 74 1,946 103 1,264 41
Iran 107 5 505 27 717 32
UK 213 9 161 8 440 21
Sum of above 15,794 651 12,136 606 16,234 640
Others 2,471 109 3,300 164 3,174 147
Total 18,265 761 15,436 770 19,408 787

Japan 6% Surfactants Table 8

Agrochemi-
China 11% cals 30% Demand for MCA in China by
India 8% 43%
application
Americas Segment Demand Annual
6%
(Tons) growth %
Pesticides 109,000 4
CMC 83,000 7
Pharma- 22,000 6
ceuticals
Cellulosics TGA
Europe
37% 32% 10% Others 80,000 5
Others 17% Exports 10,500
Fig. 3: Capacity for MCA by country Fig. 4: MCA end-use pattern
Total 304,500 5

2,4-D and dimethoate. In India and
China, it is an ingredient in glypho-
sate. 10% is used for production of
thioglycolic acid, 11% for mild am-
photeric surfactants and 11% for esters,
cyanoesters and malonates. CMC ac-
counts for more than 40% of consump-
tion in Europe and in the US, 20% of
consumption is for surfactants.
Demand for betaine stabilisers is ex-
pected to grow and demand for tin alkyl
thioglycolates is expected to increase
as they are used as substitutes for PVC
stabilisers based on lead. With the intro-
duction of glyphosate and other more
benign products, demand for 2,4-D
is expected to decline.
China
By the end of 2008 there were more
than 100 MCA producers in China.
Major producers include Hebei Don-
ghua Chemical Group, Akzo Nobel
Chloroacetic Acid Chemical (Taixing)
Co., Ltd., Wuxi Greenapple Chemical
Industry Co., Ltd., Hebei Shijiazhuang
Synthesis Chemical Plant, Shijia-
zhuang Hengyi Chemical Co., Ltd. and
Shandong Huayang Science and Tech-
nology Co., Ltd.
Akzo Nobel’s Taixing site, which
now boasts production capacity of
60,000-tpa, is the largest of its kind
in China. The total capacity in China
is 550,000-tpa. The output and con-
sumption was around 330,000-tons in
2008.

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