Vous êtes sur la page 1sur 22

CHAPTER - 1

Literature Survey

Literature Survey

1.0 INTRODUCTION
Acrylonitrile, vinyl cyanide, CH2=CHCN, is a colorless man-made liquid with a slightly
pungent odor. It was first prepared in 1893 by a French Chemist, Ch. Moreau, who
dehydrated ethylene cyanohydrin with phosphorus pentoxide. It is miscible with numerous
organic solvents including acetone, benzene, carbon tetra chloride, ethylene chlorohydrine
etc. Its prominent use came shortly before World War II in connection with the development
of copolymers for use in oil-resistant rubber. Since that time the demand for acrylonitrile has
dramatically increased due largely to acrylic fibers, first introduced commercially in 1950 by
DuPont under the trademark Orlon. Acrylonitrile has a boiling point of 77.3oC, a freezing
point of -83.55oC, and a vapor pressure of 100 mm Hg at 23.6 oC.In 1977, the U.S. Federal
Drug Administration declared acrylonitrile to be an indirect food additive and banned its use
in beverage containers and other food-packaging applications. The Environmental Protection
Agency (EPA) and the German MAK commission has classified acrylonitrile to be a human
carcinogen.
In 1947, Allied Chemical and Dye Corporation patented the manufacture of acrylonitrile via
an ammoxidation process of propylene but it was not until 1960 when Standard Oil of Ohio
(Sohio) developed the first commercially viable catalyst for this process. Today, over 90% of
acrylonitrile production in the world is based on the Sohio process. In this process,
propylene, oxygen, and ammonia are catalytically converted directly to acrylonitrile using a
fluidized-bed reactor operated at temperatures between 400oC and 500oC and gauge
pressures between 0.3 and 2 bar.
2 CH2=CHCH3 + 3 O2 + 2 NH3 2 CH2=CHCN + 6 H2O

Literature Survey

Acrylonitrile can be used to produce a wide variety of products. Such products are
adiponitrile (used in production of Nylon 66), ABS and SAN resins (automobile plastics),
acrylic fibers, acrylamide and nitrile-elastomers (oil-resistant rubber). Nearly 60% of the
acrylonitrile produced is used to make acrylic fibers. These acrylic fibers find use primarily
in wearing apparel and in home furnishings such as carpets and draperies.
1.1 ACRYLONITRILE
Table 1.1: Physical Properties of Acrylonitrile
Characteristic/Property
Common Synonyms

Data
AN; acrylon; carbacryl; cyanoethylene;
2 propenenitrile; vinyl cyanide

Molecular Formula

C3H3N

Chemical Structure

CH2 =CH-CN

Physical State

liquid

Molecular Weight

53.06

Melting Point

83.550C

Boiling Point

77.30C @ 760 mm Hg

Water Solubility

73 g/L (200C)

Density

0.8004

Vapor Density (air = 1)

0.25

Vapor Pressure

108.5 mm Hg @ 250C

Literature Survey

Reactivity

flammable and explosive,


(3.05 to 17.0% in air @ 250C)

Flash Point

00C (open cup)

Henry's Law Constant

8.8 x 10-5 atm m3/mole

Odor Threshold

40.4 mg/m3, average

Conversion Factors

1 ppm = 2.17 mg/m3, 1 mg/m3 = 0.4605 ppm delay

__________________________________________________________________________
Acetonitrile form azeotrope with some solvents. Compositions of some common
azeotropes are given in table 1.2
Table 1.2: Azeotropes of Acrylonitrile
Azeotropes

Boiling point, oC

Acrylonitrile concentration, % by weight

Water

71.0

88

Isopropyl alcohol

71.6

56

Benzene

73.3

47

Methanol

61.4

39

Carbon tetrachloride

66.2

21

Tetraachlorosilane

51.2

11

Chlorotrimethylsilane

57.0

Table 1.3: Solubility of Acrylonitrile at different temperature


Temperature, o C

Acrylonitrile in water, wt%

Water in acrylonitrile, wt%

-50

0.4

-30

1.0

Literature Survey

7.1

2.1

10

7.2

2.6

20

7.3

3.1

30

7.5

3.9

40

7.9

4.8

50

8.4

6.3

60

9.1

7.7

70

9.9

9.2

80

11.1

10.9

Table 1.4 Vapor pressure of acrylonitrile over aqueous solution


Acrylonitrile, wt%

Vapor pressure, kPa

Acrylonitrile, wt%

Vapor pressure, kPa

1.3

8.4

2.9

10.0

5.3

10.9

6.9

Acrylonitrile has been characterized using infrared, Raman and ultraviolet spectroscopies,
electron diffraction and mass spectroscopies.
Chemical properties
Acrylonitrile undergoes a wide range of reactions at its two chemically active sites, the
nitrile group and the carbon-carbon double bond. It polymerizes readily in the absence of a
hydroquinone inhibitor, especially when exposed to light. Polymerization is initiated by free
radicals, redox catalysts, or bases and can be carried out in the liquid, solid or gas phase.
1.1.1 Safety and Health Effect
The National Institute for Occupational Safety and Health (NIOSH) has recently been
informed that occupational exposure to acrylonitrile may be associated with an excess of
lung and colon cancer.

Literature Survey

In May 1977, E. I. du Pont de Nemours & Company, Inc., informed NIOSH of results of a
preliminary epidemiologic study demonstrating an excess of cancer among workers exposed
to acrylonitrile at a Du Pont textile fibers plant in Camden, South Carolina. Additionally, in
April, NIOSH received from the Manufacturing Chemists Association (MCA) a one-year
interim report of on-going ingestion and inhalation studies of acrylonitrile in laboratory rats;
the rats developed a variety of tumors, including carcinomas.
1.1.2 Background
Acrylonitrile is an explosive flammable liquid having a normal boiling point of 77C and a
vapor pressure of 80 mm (20C). The toxic effects of acrylonitrile are similar to cyanide
poisoning. The chemical structure of acrylonitrile, CH2=CHCN, resembles that of vinyl
chloride a material known to cause human cancer. Synonyms for acrylonitrile include
acrylon, carbacryl, cyanoethylene, fumigrain, 2-propenenitrile, VCN, ventox and vinyl
cyanide.
Approximately one and one-half billion pounds per year of acrylonitrile are manufactured in
the United States by the reaction of propylene with ammonia and oxygen in the presence of a
catalyst. A number of other processes have been used in the past. Current domestic producers
of acrylonitrile are American Cyanamid Company (New Orleans, Louisiana), E. I du Pont de
Nemours & Company, Inc. (Beaumont, Texas and Memphis, Tennessee), Monsanto
Company (Chocolate Bayou, Texas), and The Standard Oil Company (Ohio) (Lima, Ohio).
The major use of acrylonitrile is in the production of acrylic and modacrylic fibers by
copolymerization with methyl acrylate, methyl methacrylate, vinyl acetate, vinyl chloride, or
vinylidene chloride. Acrylic fibers, marketed under tradenames including Acrilan, Creslan,
Orlon, and Zefran, are used in the manufacture of apparel, carpeting, blankets, draperies, and
6

Literature Survey

upholstery. Some applications of modacrylic fibers are synthetic furs and hair wigs;
tradenames for modacrylic fibers include Acrylan, Elura, SEF, and Verel. Acrylic and/or
modacrylic fibers are manufactured from acrylonitrile by American Cyanamid Company
(Milton, Florida), Dow Badishe Company (Williamsburg, Virginia), E. I. du Pont de
Nemours & Company, Inc. (Camden, South Carolina and Waynesboro, Virginia), Eastman
Kodak Company (Kingsport, Tennessee), and Monsanto Company (Decatur, Alabama).
Other major uses of acrylonitrile include the manufacture of acrylonitrile-butadiene-styrene
(ABS) and styrene-acrylonitrile (SAN) resins (used to produce a variety of plastic products),
nitrile elastomers and latexes) and other chemicals (e.g., adiponitrile, acrylamide).
Acrylonitrile is also used as a fumigant. The U.S. Food and Drug Administration has
recently banned the use of an acrylonitrile resin for soft drink bottles.
NIOSH estimates that 125,000 persons are potentially exposed to acrylonitrile in the
workplace.
1.1.3 Catalyst of Am-Oxidation
The metal oxide catalyst used in the am-oxidation process for the production of acrylonitrile
is usually prepared by precipitation from solution. In this process, an aqueous metal salt
solution, consisting of bismuth nitrate and ammonium molybdate, is rapidly mixed to form
product precipitates. Depending on Bi/Mo ratio, pH, and the time of interaction, these
precipitates are filtered, washed, dried, and heated to temperatures of 500oC-800oC to form
the final catalyst. The catalyst is then sent to a grinder to obtain catalyst particles ranging
from 10-100 microns.
During the ammoxidation reaction process, small particles tend to fuse together to form
much larger ones. This process steadily deactivates the catalyst and reduces its activity.
7

Literature Survey

Catalyst activity can also be reduced during the reaction process by losses of oxygen
attached to the bismuth molecule. Re-oxidation of the catalyst occurs by adsorption and
dissociation of oxygen on anion vacancies associated with molybdenum. Anion vacancies on
the bismuth are re-oxidized by transfer of oxygen from the oxidized molybdenum
(Satterfield 276). Catalyst lifetime in the fluidized-bed reactor is approximately 1 year.
1.1.4 Production
Mannsville (2006) identified five producers of Acrylonitrile in the United States in 1992: BP
Chemicals; Cytec Industries; DuPont Company; Sterling Chemicals, Inc.; and Monsanto
Company. In 1994, the estimated total capacity of acrylonitrile production in the United
States is 3,080 million pounds (Mannsville 1994).
Major Investments and Exits
a) Sterling Chemicals Inc.

In February 2005, Sterling Chemicals Inc. (SCHI)

announced that it was exiting the acrylonitrile business and related derivative
operations. It shut down its 336,000 tonnes a year acrylonitrile plant. The exiting was
based on a history of operating losses incurred by its acrylonitrile and derivatives
business, and was made after a full review and analysis of the Company's strategic
alternatives.
b) Pemex. Pemex of Mexico closed both its 60,000 tonnes a year Tula acrylonitrile
(ACN) plant in mid-December 2005 and its 60,000 tonnes a year plant in Morelos,
Mexico in September 2005.
c) Capacities Commissioned Shanghai Secco Petrochemical commissioned its 260,000
tonnes a year acrylonitrile plant in China in spring 2005. The capacity of Daqing
Refining and Chemical Co Ltd is also increased by 30,000 tonnes a year.
8

Literature Survey

d) Indian Petrochemicals Limited (IPCL) IPCL is only one company ion India
who produce Acrylonitrile.
Acrylonitrile is a large-volume, commodity chemical. In 2005, the production capacity
worldwide had touched 6.47 million tonnes (14.5 billion pounds). Capacity compared with
consumption was in surplus. In 2000, the surplus capacity was around 250,000 tonnes. This
increased to over one million tonnes in 2005. This implies that capacity expanded at a much
faster rate than the expected consumption growth rate.
1.1.5 Uses
Acrylonitrile monomer is a chemical intermediate used in the production of acrylic fibers,
plastics, rubber elastomers, and other materials. It also undergoes reactions to form
compounds used as solvents, polymeric materials, plasticizers, and intermediates for dyes,
pharmaceuticals, and insecticides. AN is used to produce adiponitrile, a nylon intermediate,
and acrylamide. Styrene-acrylonitrile (SAN) and acrylonitrile-butadiene- styrene (ABS) are
high-impact resins derived from AN.

SAN resins are used in appliances, automotive,

houseware, and packaging applications. ABS resins are used in appliances, business
machines, telephones, transportation, recreation, luggage, and construction applications.
These resins have been losing market share to other plastics. However, there is potential for
growth in other acrylonitrile-based resins.
The major usages of ACN are in:
1. Acrylic textile fibers (accounting for over 52% of global ACN consumption) for use
in apparel, blankets, carpeting, upholstery, and industrial applications.
2. ABS/ SAN resins production (29%), where ACN is a co-monomer.

Literature Survey

3. Adiponitrile (9%), which is a nylon-66 intermediate.


4. Nitrile rubbers and acrylamide (7%).
Nitrile rubbers are used in automotive fuel lines, while nitrile elastomers are used as latex
coatings for oil resistant papers, leather, and textiles. Polyacrylonitrile (PAN), as a precursor
for carbon fiber, is used in high-strength applications including aircraft parts and golf club
shafts (Mannsville 1994). This market has been growing rapidly over the past few years, but
remains highly specialized and low volume.
1.1.6 Trends
Demand for acrylonitrile is growing at an average annual rate of 2 to 3 percent after the
1990/1991-market slowdown. It is estimated that production was roughly 2,926 million
pounds in 1994. U.S. capacity greatly exceeds domestic demand. About 40 percent of U.S.
production of acrylonitrile was exported in 1993. Increasing worldwide capacity for AN
production may limit U.S. exports in the future.
1.2 AMMONIA
Ammonia Molecular weight: 17.03 g/mol
Melting point: -78oC
Latent heat of fusion (1,013 bar, at triple point) : 331.37 kJ/kg
Liquid Density (1.013 bar at boiling point) : 682 kg/m 3 (250 K : 669 kg/m3) (300 K : 600
kg/m3) (400 K : 346 kg/m3)
Liquid Specific Heat Capacity (cp) (250 K : 4.52 kJ/kg.K) (300 K : 4.75 kJ/kg.K) (400 K :
6.91 kJ/kg.K)

10

Literature Survey

Liquid/gas equivalent (1.013 bar and 15oC (59oF)) : 947 vol/vol


Liquid Dynamic Viscosity (250K : 245 106 Ns/m2) (300K : 141 106 Ns/m2) (400K : 38 106
Ns/m2)
Boiling point (1.013 bar) : -33.5oC
Latent heat of vaporization (1.013 bar at boiling point) : 1371.2 kJ/kg
Vapor pressure (at 21oC or 70oF) : 8.88 bar
Critical point - Critical temperature: 132.4oC - Critical pressure: 112.8 bar
Gas Density (1.013 bar at boiling point) : 0.86 kg/m3
Gas Density (1.013 bar and 15oC (59oF)) : 0.73 kg/m3
Gas Compressibility Factor (Z) (the ratio of the actual volume of the gas to the volume
determined according to the perfect gas law) (1.013 bar and 15oC (59oF)) : 0.9929
Gas Specific Gravity (air = 1) (1.013 bar and 21oC (70oF)) : 0.597
Gas Specific volume (1.013 bar and 21oC (70oF)) : 1.411 m3/kg
Gas Specific Heat Capacity at constant pressure (cp) (1.013 bar and 15oC (59oF)) : 0.037
kJ/(mol.K)
Gas Specific Heat Capacity at constant volume (cv) (1.013 bar and 15oC (59oF)) : 0.028
kJ/(mol.K)
Gas Dynamic Viscosity (1.013 bar and 0oC (32oF)) : 0.000098 Poise
Gas Thermal conductivity (1.013 bar and 0oC (32oF)) : 22.19 mW/(m.K)
Gas Solubility in water (1.013 bar and 0oC (32oF)): 862 vol/ vol

11

Literature Survey

Gas Auto ignition temperature: 630oC


1.3 ACETONITRILE
1.3.1 Product Identification
Synonyms: Methyl Cyanide; Cyanomethane; Ethanenitrile; Ethyl nitrile
CAS No.: 75-05-8
Molecular Weight: 41.05
Chemical Formula: CH3 CH CN
Composition/Information on Ingredients
Ingredient

Acetonitrile
Acrylonitrile

CAS No

Percent

Hazardous

75-05-8

99.8 - 100%

Yes

107-13-1

< 0.001%

No

1.3.2 Hazards Identification


Emergency Overview
Danger! May be fatal if swallowed, inhaled or absorbed through skin. Affects
cardiovascular system, central nervous system, liver and kidneys. Flammable liquid
and vapor. May cause irritation to skin, eyes, and respiratory tract.
SAFETY DATA Ratings
-----------------------------------------------------------------------------------------------------Health Rating: 3 - Severe (Life)
12

Literature Survey

Flammability Rating: 3 - Severe (Flammable)


Reactivity Rating: 1 - Slight
Contact Rating: 3 - Severe (Life)
Storage Color Code: Red (Flammable)
1.4 ACROLEIN
Molecular formula: C3H4O
molecular weight: 56.06
density: 0.84
melting point: -87.7 C
boiling point: 52.5 C
flash point: -17.8 C
steamed pressure: 27,998 (20 C)
Index: 1.4017
toxicity LD50 (mg / kg): 46 rats by mouth.
Traits: colorless liquid with special spicy taste stimuli odor.
Solution: dissolve in water, ethanol and ether.
Purposes: for synthetic resin system and drugs.
Preparation or sources: the propylene oxidation or by the condensation of formaldehyde and
acetaldehyde in the system and more water loss.
1.5 ACRYLIC ACID
Acrylic acid or 2-propenoic acid is a chemical compound (formula C 3H4O2) and it is the
simplest unsaturated carboxylic acid with both a double bond and a carboxyl group linked to
its C3. In its pure form, acrylic acid is a clear, colorless liquid with a characteristic acrid
13

Literature Survey

odor. It is miscible with water, alcohols, ethers and chloroform. Acrylic acid is produced
from propylene, a gaseous product of oil refineries.
Acrylic acid undergoes the typical reactions of a carboxylic acid and, when reacted with an
alcohol, it will form the corresponding ester. The esters and salts of acrylic acid are
collectively known as acrylates (or propenoates). The most common alkyl esters of acrylic
acid are methyl-, butyl-, ethyl- and 2-ethylhexyl-acrylate.
Acrylic acid and its esters readily combine with themselves or other monomers (e.g amides,
acrylonitrile, vinyl, styrene and butadiene) by reacting at their double bond, forming
homopolymers or copolymers which are used in the manufacture of various plastics,
coatings, adhesives, elastomers as well as floor polishes and paints.
Chemical properties:
It is miscible with water, alcohol, ether, benzene, chloroform, and acetone. It polymerizes
readily in the presence of oxygen. Exothermic polymerization at room temperature may
cause acrylic acid to become explosive if confined. It is sensitive to heat and sunlight. It is
normally supplied as the inhibited monomer (inhibited with 200 ppm hydroquinone
monomethyl ether), but because of its relatively high freezing point it often partly solidifies
and the solid phase (and the vapour) will then be free of the inhibitor which remains in the
liquid phase. Even the un-inhibited form may be stored safely below the melting point, but
such material will polymerize exothermically at ambient temperature and may accelerate to a
violent or explosive state if confined. It is also a fire hazard when exposed to heat or flame.
Acrylic acid is incompatible with strong oxidizers, strong bases, strong alkalies and pure
nitrogen. It may polymerize (sometimes explosively) on contact with amines, ammonia,
oleum and chlorosulfonic acid, iron salts and peroxides. It may corrode iron and steel.
14

Literature Survey

1.6 HYDROGEN CYANIDE


Hydrogen cyanide is a chemical compound with chemical formula HCN. A solution of
hydrogen cyanide in water is called hydrocyanic acid. Hydrogen cyanide is a colorless, very
poisonous, and highly volatile liquid that boils slightly above room temperature at 26 C
(78.8 F). HCN has a faint, bitter, almond-like odor that some people are unable to detect
due to a genetic trait. Hydrogen cyanide is weakly acidic and partly ionizes in solution to
give the cyanide anion, CN. The salts of hydrogen cyanide are known as cyanides. HCN is a
highly valuable precursor to many chemical compounds ranging from polymers to
pharmaceuticals.
Stability
Stable. Incompatible with acids, strong oxidizing agents. Highly flammable.
Table 1.5: Property of Hydrogen Cyanide and Acrylic Acid

15

Literature Survey

Hydrogen cyanide
IUPAC name
Hydrogen cyanide
Other names
Hydrocyanic
acid
prussic
acid,
formonitrile
formic anammonide
carbon hydride nitride
Identifiers
CAS number
74-90-8
Properties
Molecular
HCN
formula
Molar mass
27.03 g/mol
Appearance
Colorless gas or pale
blue
highly volatile liquid
Density
0.687 g/cm, liquid.
Melting point -13.4C (259.75 K)
Boiling point
26C (299.15 K,
78.8F)
Solubility in Completely miscible.
water
Hazards
Main hazards Highly toxic, highly
flammable.
Flash point
17.78 C

Acrylic acid
IUPAC name
Other names

Identifiers
CAS number
Properties
Molecular
formula
Molar mass
Appearance
Density
Melting point
Boiling point
Solubility
water
Viscosity
Hazards
MSDS

Flash point

2-propenoic acid
Acroleic
acid
Ethylenecarboxylic
acid
Propene
acid
Propenoic
acid
Vinylformic acid
79-10-7
CH2=CHCOOH
72.06 g/mol
clear, colorless liquid
1.051 g/ml, liquid
12 C (285 K)
139 C (412 K)
in Unlimited
1.3 cP at 20 C
Corrosive
(C),
Dangerous for the
environment (N)
46 C

1.7 SUMMARY
1. Acrylonitrile (ACN) is a monomer, also known as propenitrile or vinyl cyanide is a
colorless liquid with a characteristic odor resembling peach seeds. Pure acrylonitrile is
very reactive and polymerises readily especially under the influence of light, whereby its
storage needs addition of polymerization inhibitors.

16

Literature Survey

2. ACN has varied application ranging from manufacture of acrylic fibers, styrene copolymers e.g. ABC and SAN, nitrile rubbers and as an intermediate for manufacture of
acrylates, acrylamide, drugs and Pharmaceuticals.
3. In India presently, there is only one unit manufacturing Acrylonitrile. The Company,
Indian Petrochemicals Corporation Limited (IPCL), Baroda, using Sohio technology
involving ammoxidation of propylene. Propylene, ammonia, and air are reacted over a
catalyst (Catalyst C-41 or C-49) in fluidised bed reactor to form some HCN and
acetonitrile, which is separated from ACN by distillation. The resulting acrylonitrile,
containing water and other impurities, is then further distilled to achieve a purity of 99%.
IPCL, Baroda had originally a Licensed/ Installed capacity to manufacture 24,000
tonne/annum of ACN, which has been increased to 30,000 tonne/annum after revamping.
The production of ACN has increased from 1ft,000 tonne in 1982-83 to 27,000 ton in
1991-92.
4. At IPCL, Baroda, the average capacity utilisation during the last decade has been around
84%. In some of the years low capacity utilisation has been due to shortage of basic raw
material propylene. IPCL gets process updates from SOHIO/BP chemicals in the form of
technical disclosures and licensee meetings for exchange of information.
5. There are two letters of intent issued for ACN manufacture in India, viz; Reliance
Industries Limited for 70,000 tonne/annum and Haldia Petrochemicals Ltd. for 50,000
tonne/annum. There is no progress on implementation by these two companies.
6. The demand of ACN in India based on end use pattern has increased from 27,500 tonne
in 1988-89 to 48,000 in 1990-91 and is expected to reach upto 62,000 tonne by end of

17

Literature Survey

1992-93. The gap in demand and supply which is approximately 34,000 tonne is
currently met through imports.
7. The only Indian manufacturer, IPCLhas increased the installed capacity from 24,000
tonne to 30,000 tonne per annum by modification in the plant design and operation
techniques with limited capital expenditure. The modifications include change of
Catalyst C-41 by C-49, modification in reactor cyclones, modification in air grid, feed
sparger, trickle valve and absorber to reduce reactor pressure at higher throughput. The
single stage quench system was modified by a two stage system and incinerator heat
input was reduced by introducing suitable additives.
8. IPCL has absorbed the technology as transferred by the process licensor adequately and
are able to operate the plant efficiently and effectively. The quality of ACN produced is
at par with International Standards. However, recovery of major by-product i.e. HCN
needs to be improved by IPCL and a more aggressive marketing of HCN may have to be
undertaken for additional operating benefits.
9. The world's proven technology licensor M/s. Sohio (now taken over by M/s.P.Chemicals)
are very conservative in their licensing policy. M/s. B.P. Chemicals themselves have a
ACN manufacturing facility of their own and their licensing policy will be restricted by
the responsibilities faced by licensor in India in terms of pollution control, safety
requirements, process yields, plant design etc. The consideration that in a slow growing
ACN international market, their own exports may be affected by additional plants, using
their technology will also be a restrictive factor in further licensing.
10. The salient features of major contemporary technologies have been discussed in this
report. The major process technologies available world wide are Sohio (Now B.P
18

Literature Survey

Chemicals), Montedision - UOP Nitto, PCUK/Distillers, OSW and SNAM process.


However, more than 90% of world wide ACN installed plants use Sohio technology.
11. The world wide production capacity of ACN in 1990 was 4216 thousand tonne per
annum. The actual production in the same year was about 3548 thousand tonne. The
world capacity of ACN is likely to touch 5313 thousand tonne by the end of year 1999
and world production is likely to touch 4537 thousand tonne by the end of the same year.
12. The major end use of ACN is Acrylic fiber industry which consumes more than 60% of
the total ACN produced, followed by ABC and SAN resins, adiponitrile and Nitrile
rubber industry.
13. World over currently ACN is manufactured using propylene ammoxidation technology.
More then 90% of the installed capacities for ACN are now based on this technology.
The ammoxidation technologies are based on either fluidised bed or fixed bed. The
reactor effluents in respect of each of these technology differ with the catalyst and
reactor configuration. A comparative analysis of different parameters of ammoxidation as
also technologies been carried out is described in Chapter 3 of this report.
14. There has been no research activity undertaken by IPCL in the area of ACN
manufacturing technology. Some efforts have been made in the pollution control and
waste treatment of various products coming out of the ACN plant of IPCL at Baroda and
the same have been beneficial.
15. The thrust areas identified for R&D activities in India related to ACN manufacturing
include, design of a heterogeneous catalysts for ammoxidation reaction and fluidised bed
reactor development.

19

Literature Survey

16. The R&D efforts being carried at International level have been studied and classified into
(a) Reactor modelling and apparatus design for reactions (b) Pollution controls and waste
treatment (c) ACN manufacturing technology (d) Purification of by-products and (e)
Catalyst structure, composition and their production. International Abstracts of patents
and other published references in each of the above areas have been presented in this
report. Indian patents taken by international process licensors have also been presented in
the report.
17. Due to certain recession in the Acrylic Fibre markets, there are some ACN plants which
have closed down in Europe because of slack market conditions. Some of these ACN
plants are available for sale.
18. In developing countries the developmental emphasis is on catalyst and process which
gives maximum yield of ACN from propane/propylene and minimum yield of byproducts i.e. Hydrocyanic Acid, it can only be incinerated being extremely poisonous.
The by-products value addition in such an eventuality becomes negative.
19. Propane ammoxidation is the thrust area of R&D for major process Licensor of ACN.
However, commercialization of the process technology is still awaited.

This

development is considered to be significant in view of large propane and restricted


propylene availability.
1.8 RECOMMENDATIONS
1. The setting up of new Acrylonitrile production facilities in India may ensure timely
setting up of downstream plants which can use all HCN produced, as byproduct. This
will avoid problem of pollution control and cost of incineration of HCN.

20

Literature Survey

2. There

has

been

no

development

in

the

areas

of

manufacturing

process

technology/process engineering etc. by either IPCL or NCL. Efforts must be made to


implement recommendations of high powered committee on thrust areas of research to
be undertaken at NCI. and IPCL.
3. In the context of recent liberalisation policy of Government, setting up of new ACN
capacity will be governed by following factors:
a) Adequate availability of basic raw materials namely propylene & ammonia
b) Opportuity cost of propylene when used for manufacturers of ACN & or other end
products like polypropylene
c) Possibility of setting up ACN capacity with Technology levels comparable to
international plants in other developed & developing countries. The acrylonitrile
from such a new plant should be available at prices & quality comparable to
international standards.
d) The proposed propane is oxidation technology is expected to be commercialized by
1995. M/s. BP/ Sohio will be the process licensor and the possibilities of licensing of
this new development are not very bright. The option before Indian (Present &
prospective) are:i) Wait for licensing of the new technology (May be after 5/6 years)
ii) Set up plant based on propylene and current Sohio technology of propylene am
oxidation
iii) Try to negotiate purchases of some ACN plant which have now ceased operation
& after refurbishing of worn out equipments and use it for additional demand

21

Literature Survey

satisfaction iv) Pursue BOC offers for P.S. absorption for propylene recovery and
using a plant combining dehydrogenation/absorption of unreached propylene and
ammoxidation of propylene.
Detailed discussions regarding actual states of BOC Technology reliability & efficiency
of the process and cost benefits can only be carried out by IPCL or prospective
entrepreneurs. They may also verify BOC claims by checking up experience of another
licensee. A decision can only be taken to accept this technology after such detailed
discussions, with process licensor and a user are carried out.
4. In view of restrictive licensing of process licensor of ACN, a possibility of setting up a
reconditioned plant, which may be available for sale in Europe, can be examined.
5. In view of the likely increase of consumption and lack of indigenous capacity for ACN
manufacture and reluctance of M/s. B.P. Chemicals for further licensing technologies,
IPCL's ability to set up new plant may perhaps be the only way to avoid large import and
foreign exchange outflow in the nineties for the country.
6. An organization having process and engineering expertise having close links with
research institutions, end users can be made responsible for new technology selection
and adoption.

22

Vous aimerez peut-être aussi