EXECUTIVE SUMMARY

1.0 RELEVANCE OF DMF TO INDUSTRY

1.1 Dimethyl formamide (DMF) is an excellent solvent and finds major
applications in acrylic fibre, PU processing, drugs and pharmaceu-
ticals, dyes industries and other applications such as paints and
pigment manufacture. DMF is a colourless, transparent, odourless,
mobile and neutral liquid at room temperature, having a high boiling
point. It is miscible with a wide range of organic as well as inorganic
substances including water to be an excellent solvent of dipolar and
aprotic nature.
DMF is stable even at its boiling point (153°C) under atmospheric
pressure unless alkali, acid or a certain type of halogenated hydrocation
coexists. Therefore, it can be distilled without causing any effect to
its quality.
However, DMF will show thermal degradation at 350°C or higher
temperature and form carbon monoxide and dimethylamine.
DMF may also show a photo chemical degradation by application of
ultraviolet rays. When boiled in an aqueous solution, DMF will be
hydrolyzed gradually to form formic acid and dimethylamine which
are weakly acidic and basic respectively. Therefore, partial ionization
will occur to show an increase in the electrical conductivity of the
solution.
DMF forms stable complex compounds with HC1, SO3, POC13, BF3,
heavy metal salts etc., under suitable conditions and they are used
as catalysts. Caution should be exercised on DMF reactions with
halogenated compounds, nitrates and chromic acids.
1.3 MANUFACTURING PROCESSES
Two processes dominate present-day commercial preparation of
DMF:
1) Direct synthesis
2) Two step process
1.3.1 Direct Synthesis
The direct or one-step synthesis of DMF begins with either pure
carbon monoxide or a gas stream containing carbon monoxide. This
is reacted in a continuous process with N.N-dimethylamine (DMA),
by using a solution of alkali alkoxide (usually sodium methoxide) in
methanol as catalyst. Methyl formate is presumably formed as an
intermediate. The reaction mixture passes over an external heat
exchanger to remove the excess heat generated and to ensure
thorough mixing of the components.
The reaction is conducted between 0.5 and 11 MPa at 50~200°C. The
reaction mixture exits the reactor through a decompression cham-
ber. In addition to N,N-dimethylformamide, the crude product
contains methanol. Acertain amount of acid or water deactivates any
catalyst present resulting in the formation of sodium formate.
Dissolved carbon monoxide, together with inert gases, escapes from
the mixture during decompression and the off-gases are removed by
combustion. Preliminary distillation is followed by second distilla-
tion in a separate column, here, dimethyl formamide is separated
from methanol which contains traces of N, N-dimethylamine. Further
distillation results in a product of 99.9% purity.
1.3.2 Two-Step Process
The two step process for the synthesis of N,N-dimethylformamide
differs from direct synthesis because methyl formate is prepared
separately and introduced in the form of 96% pure (commercial -
grade) material. Equimolar amounts of methyl formate and N,N-
dimethylamine are subjected to a continuous reaction at 60-100°C
and 0.1 - 0.3 MPa. The resulting product is a mixture of N,N-
dimethylformamide and methanol. The purification process involves
distillation and is analogous to that described for direct synthesis.
However, no separation of salts is required because no catalysts are
involved in the process. Due to the corrosive properties of both
starting materials and products, stainless steel has to be used as
material of construction for production facilities.
2.0 INDIAN INDUSTRY STATUS
2.1 DMF Supply Scenario
Till late 1991, the country's entire DMF requirement was met through
imports.
Presently, only RCF Ltd., has the capacity to produce DMF in India.
 Their 2,500 TPA plant at Thai, based on technology from Acid Amine
Technologies Inc., USA is likely to go into commercial production
shortly. They are likely to double their capacity to 5,000 TPA by 1996.
The decision to expand will be taken after the 2,500 TPA DMF plant
is fully operational through the CO route.
Vam Organic Chemicals initiated work on a 3,000 TPA DMF project
at Gajraula with technology from UCB, Belgium. They are planning
only one step in this process. They will procure methyl formate from
outside and react it with DMA to obtain DMF. The plant engineering
is complete and is likely to go on stream shortly.
Alkyl Amines Chemicals Limited is also setting up a plant to
manufacture 3,000 MT of DMAC/DMF.
There is no scope for additional capacity (in case RCF doubles their
capacity to 5,000TPA) till 1999-2000, considering a demand projec-
tion of around 7,400 tonne by 1999-2000.
2.2 DMF Demand Scenario
DMF finds its domestic end use in the following applications :
i) as a solvent in acrylic fibre production;
ii) in the manufacture of drugs and Pharmaceuticals;
iii) in polyurethane (PU) processing and
iv) other miscellaneous application such as dyes tuffs, paints,
pigments etc.
Estimated percentage consumption by each end-use sector is given
below.
Acrylic Fibre • 44%
Drugs and Pharmaceuticals 38%
Polyurethane Processing 8%
Miscellaneous 10%
TOTAL... 100%
DMF demand in India is expected to nearly double from the level of
2150 tonne in 1991-92 to 4100 tonne by 1995-96. The increase in
demand is mainly due to upward trend in acrylic fibre production
capacity.
3.0 INTERNATIONAL SCENARIO
3.1 Globally, DMF technology is licensed by only two companies one is
Acid-AmineTechnologies Inc. USA and the other is UCB. SABelguim.
Other global manufacturers - ICI.U.K., BASF, Germany, Air Prod-
ucts, U.S.A., and Dupont, U.S.A., are not interested in supplying or
licensing technology or know-how for producing DMF.
The technology licensors are :
1) Acid - Amine Technologies Inc.
P.O. Box - 8733, Woodcliff Lake
New Jersey - NJ 07675
U.S.A.
They are involved in the business of technology transfer, complete
process simulation and conceptual design, licensing of chemical
production know-how, design of chemical plants, risk analysis,
preparation of market, technical and feasibility studies and research
studies in catalysts, membrane separations and distillation.
Plants available world wide are mainly based on the technology
supplied by AAT, USA.
2) U.C.B. S.A.
Rue D Anderlecht 33
B 1620 Drogenbos
Belgium
They are involved in the manufacture of DMF with a total installed
capacity of 15,000 TPA. Their process of manufacture involves the
reaction of Dimethylamine and Methylformate. UCB S.A. has sup-
plied technology to VAM Organics (India) Ltd.
3.2 Total installed capacity is estimated around 3 lakh tonne world wide
compared to a total demand of about 1.8 lakh tonne (including
captive use). There are 16 existing plants world wide. USA, Brazil and
Canada share 24% of the total capacity, Europe (Germany, Spain,
U.K., Belgium) share 38% of the total installed capacity, where as
balance is shared by other countries.
Globally, demand is shrinking or atleast stagnant especially in
Europe and America due to environmental reasons.
3.3 SALIENT FEATURES OF CONTEMPORARY TECHNOLOGIES
i) Acid-Amine Technologies Inc, USA
This technology involves the direct reaction of carbon monoxide (CO)
and dimethyl amine (DMA) in the presence of sodium methylate in
methanolic solution as a catalyst at an elevated temperature of 120°C
and a pressure of 20 Kg/cm2 inagasloop reactor to produce dimethyl
formamide (DMF), which is further purified to high quality solvent
and fibre grade product. Solvent and excess dimethyl amine are fed
back to the reactor and catalyst is removed continuously from the
system. The process reaction is as follows :
120°C, 20 Kg/cm 2
(CH3)2 HN + CO (CH3)2 NCOH
Na methylate in methanolic
solution
Yield of DMF varies from 95% to 98%. Energy is required in the form
of electricity as well as steam for heating. Requirement per tonne of
DMF are as follows :
Steam - 0.85T/T of DMF
Electricity - 44 KWH/T of DMF
Environmental and Safety Aspects
The gaseous effluents in the form of inert gases and CO are flared
through a flare stack system and get burnt when it comes in contact
with the oxygen in the atmosphere. Thus pollution is kept under
control.
ii) U.C.B. S.A., Belgium
In this process, methyl formate is first produced from carbon
monoxide and methanol under high pressure and at 60-100°C
temperature in the presence of sodium methylate. The methyl
formate is distilled and then reacted with dimethylamine at 80-100°C
and at a low pressure. The DMF is then purified and distilled.
The process reaction is as follows :
60-100°C
CO + CH3OH HCOOCH3 (methylformate)
Na methylate
(80-100°C)
HCOOCH3+(CHJ2NH HCON (CH3)2+CH3OH
(DMF)
 Requirement per tonne* of pure DMF are as follows :
Steam - 1.2 T/T of DMF
Electricity - 52 KWH/T of DMF
3.4 Technology Selection by Indian Companies
A. RCFLtd.
1) There was no domestic manufacture of DMF till late 1991. Its
entire requirements were met through imprts, presently around
2,500 TPA. Thus as an import substitution project, it was
expected to save the country substantial foreign exchange of
around 2.5 million dollars per year.
2) The company already had production of both di-methyl amine
and carbon monoxide at its fertilizer plant. Given the fact that
DMF uses these products as basic raw materials, the project was
a good forward integration strategy.
The project was also in keeping with RCF's corporate image as
a leading public sector unit which is incidentally, the largest
fertilizer and chemical company in Asia.
RCF opted for AAT technology on the following counts :
1) World-wide, AAT technology has greater acceptance than
UCB, with the former accounting for more than60% of the
global DMF installed capacity.
2) RCF had earlier obtai ned AAT Technology for their existing
methyl amines plant and were satisfied with AAT's technol-
ogy and back-up services.
3) AATprocess used raw materials already available with RCF.
B) VAM Organic Chemicals Ltd.
They have opted for the technology from UCB, Belgium. Process
uses dimethylamine and methyl formate instead of dimethyl
amine and CO.
3.5 Comparative Evaluation of the Two Technologies
The project economics of UCB technology is less favourable to AAT
technology even if DMAis produced at site as methanol is a byproduct
in the case of the UCB technology which contains excess DMA or
excess methylformate depending on the reaction conditions. This
methanol has to be recycled either to methylamine plant or methyl

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 formate plant. This leads to an increase in the number of process-
steps and therefore increase in the cost of production. It also leads
to a setting up of a methylamftie or methyl formate plant to improve
the economics. Despite these investments, the overall economics
cannot still be better than the AAT technology.
3.6 DEVELOPMENTS AT THE INTERNATIONAL LEVEL
Globally, Acid Amine Technologies Inc., USA is the only significant
DMF technology licensor. Discussions held with Dr. Ian Williams,
President AAT reveal that most R & D efforts at AAT concentrate on
two aspects :
a) Catalyst improvement aimed a t :
1) Maximizing DMF yield
2) Optimizing process parameters to control cost i.e. lower
energy requirement per tonne of DMF.
b) Improving quality of input DMA to improve yield and purity of
DMF.
UCB SA, Belgium had originally obtained Leonard/AAT process
technology. Their plant has been operational for more than 20 years.
They have reportedly modified/optimised the process to a level where
by they are competent enough to license their technology.
Varioias patents have been registered by different firms to manufac-
ture DMF, claiming better yields involving different raw materials.
The following patents have been registered :
Preparation of DMFfrom formamide & methanol with quartemary
ammonium compound as a catalyst.
DMF production by catalytic reaction of formamide and ethanol
involving quarternary ammonium compound as a catalyst.
DMF preparation from synthesis gas and ammonia or formamide
in presence of platinum metal catalyst.
Recovery of DMF by successive condensation of side fractions of
the solvent vapour in the production of acrylonitrile and polyure-
thane filaments.
3.7 INTERNATIONAL COMPETITIVENESS OF THE INDIAN DMF
INDUSTRY
With over capacities and shrinking/stagnant demand world wide, it
 is expected that fierce global competition will continue and this puts
smaller DMF plants (like RCF and VAM Organics) into disadvantage.
Higher prices of raw material inputs (dimethylamine, carbon monox-
id£^methyl formate) and rjoor economies of scale may result in higher
cos\ ol p r o b u ^ i T ^ f i f c S R S ^ ^ (
T (CIF Bombay). RCF's ex-works price is around Rs. 55,000/- per
tonne. At this price it may not be able to compete with any global
manufacturer. On the contrary, free imports may affect RCF and VAM
Organics.
4.0 R&D EFFORTS, TECHNOLOGY ABSORPTION AND GAPS
4.1 R&D activities are carried out at AAT. Mainly research and develop-
ment pertains to :
1) Catalyst improvement;
2) DMA Purity enhancement;
3} Overall reduction ofproduction cost [mainly through (1) and (2)].
Some patents have been registered by various firms to manufacture
DMF in order to reduce overall project cost and increase yields,
involving different catalyst and cheaper raw materials than the
present commercial process. Commercial economics of these pro-
cesses however are yet to be evaluated.
4.2 Technology Absorption Efforts
RCF's DMF plant with CO as a raw material has still not been
commissioned due to some problems in. the CO separation plant for
which know-how was obtained from M/s. KTI. This problem has now
been largely overcome and the plant is expected to be commissioned
through the CO route in the near future. Efforts for absorbing
technology and making further improvements are only possible when
the plant has been properly commissioned under the designed
conditions.
RCF has a good track record in absorbing and updating imported
technology. For example, improvements made in the methylamine
plant at Trombay, which is based on the old Leonard Technology,
was licensed to M/s. AAT for implementation in the plant supplied
by them to their Turkish clients at fees US $ 30,000. Similarly, it
is expected that absorption and updation of DMF technology is
very much within the capabilities of RCF after the plant is
commissioned.

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4.3 TECHNOLOGY GAPS/THRUST AREAS
a) Product
As mentioned earlier RCF has collaborated with AAT. The product
obtained on trial runs is meeting the international specifications/
standards and the grades available are either as 99.9% solution or
100% anhydrous. In order to utilize the above solvent, one should
keep abreast of developments of AAT in order to maintain interna-
tional standards and develop it accordingly for the specific end-use
grade in the Indian context.
b) Raw Materials
Basic raw material required to manufacture DMF by AAT technology
are Dimethylamine and Carbon monoxide. DMA plant facilities at
RCF have been setup in collaboration with AAT, USA, hence the DMA
specifications/standards meet international standards. CO is recov-
ered with Cosorb solvent imported from M/s. KTI, USA. However,
requirement of this solvent is only about 10 m 3 every four years
depending on the proper operation of the plant and degradation of the
solvent.
c) Utilities
Utilities are mainly in terms of electricity, steam and water. RCF's
plant is yet not on full stream, hence rated requirement of power,
steam and water has to be verified once the plant is at the peak level
of production.
d) Capital Equipments
Instruments like DDCS were obtained from Instrumentation Ltd,
where as instruments like CO meters were imported, which need to
be developed indigenously.
e) Safety
Enough care has been taken to control pollution by employing flare
stack system and various other measures are taken to control
adverse environmental effects by adhering to good manufacturing
practices.
J) Training
Under the collaboration agreement signed between RCF and AAT,
four RCF personnel were trained at AAT, USA. RCF may be developed
to the status where its DMF plant can be a training center for South

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 Asian nations adopting AAT technology, hence earning foreign
exchange.
g) Application
DMF is mainly used as a solvent in/the acrylic fibre manufacture and
PU processing. RCF should initiate more interaction with end-users
in India and try to tap export potential as our product is expected to
meet international standards.
5.0 RECOMMENDATIONS
5.1 Technology Acquisition
Foreign collaboration for technology acquisition may be allowed for
time being. Once the requisite technologies have been absorbed, the
need for technology collaboration may cease except in certain areas
where specific equipment imports will have to be made.
5.2 Technology Development
An alternative route can be explored to obtain DMF. For example the
patented process of DuPont involves the reaction of formamide and
methanol to produce DMF. This process is claimed to give better yield
and lower cost of production per unit production of DMF. Research
work in this direction can be initiated in a joint collaborative effort by
NCL, Pune and RCF, Bombay.
5.3 Applications
New application development projects may be taken up by RCF. One
of the areas could be more usage in the drugs and pharmaceutical
industry as an extracting solvent. Existing end-users can also help
in developing the product in the Indian context to meet new applica-
tions.
5.4 Capital Equipment Indigenisation
While sufficient expertise is available for fabrication of equipments
like vessels and heat exchangers, capabilities of vendors for proper
design of package units like gas dryers and low temperature chilling
plants are limited. Detailed engineering contractors may properly
evaluate such designs and advise the vendors in the overall interest
of indigenisation.
5.5 Product Cost
Efforts may be made to improve the process in order to bring down the
cost of production to make it competetive with the imported product.
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