Chapter 1 INTRODUCTION

INTRODUCTION

History:-

Acrylonitrile (ACN), Propenenitrile, Vinyl cyanide, CH 2=CH—C=N,

was first prepared in 1893 by the French chemist Charles, Moreu by
dehydration of acryl amide or ethylene cyanohydrin using phosphorus pent
oxide.

Acrylonitrile remained a laboratory curiosity until the end of the First

World War. Its industrial importance emerged around 1930, when it was
used in Germany and the United States to manufacture nitrile rubber, Buna
N, a copolymer of butadiene and Acrylonitrile, displaying high resistance to
hydrocarbons. Acrylonitrile gained in importance shortly before World War
II, when it was discovered that it could (as a copolymer) greatly increase the
resistance of synthetic rubbers to oil and solvents. During World War II,
nitrile rubbers were produced on a modest commercial scale in both
Germany and the United States.. Since then, its applications have expanded
considerably, including textile fibers, synthetic resins, elastomers, and
intermediates of organic syntheses.

At present, world production is about 2.700,000 metric tons/yr, and

Acrylonitrile is one of the building blocks of the chemical industry

Nearly all the Acrylonitrile produced worldwide is obtained by the

ammoxidation of propylene. Furthermore, nearly 90 per cent of installed
production capacities employ the Sohio process. This company has
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Chapter 1 INTRODUCTION
developed a whole series of increasingly better-performing catalysts, with
the first commercial achievement dating from 1960. The other technologies
of this type offering an industrial character are those of Chemie Linz, OSW
(Osterreichische Stickstoff Werke), Montedison/UOP (Universal Oil
Products), SNAM (Societa Nazionale Metanodotti), and Ugine/Distillers
(PCUK/Distillers).

The earlier methods were the following:

(a) Addition of hydrogen cyanide to ethylene oxide to form cyanohydrin,

which is then dehydrated to Acrylonitrile. Developed by IG Farben. This
process was adopted by American Cyanamid and Union Carbide, and then
abandoned in 1965.

(b) Reaction of hydrogen cyanide with acetylene, developed by Bayer,

used by American Cyanamid, Du Pont, Monsanto until 1970.

(c) Production of lactonitrile from acetaldehyde and hydrogen cyanide,

and its dehydration to Acrylonitrile. Developed and industrialized by
Hoechst in Greisheim (Knapsack-Greisheim) until 1959, it is still partly
used by the Japanese company Nusashino to manufacture lactic acid by
lactonitrile hydrolysis.

(d) Ammoxidation of propylene by nitrogen oxides, commercialized by

Du Pont in Beaumont, Texas, until 1966.

Many developments are currently under way to employ ethylene. Propane

and butane directly.

PHYSICAL PROPERTIES
► Acrylonitrile is a colorless liquid at normal temperatures and pressure and
has a faint characteristic odor. The chemical formula for Acrylonitrile is
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Chapter 1 INTRODUCTION
CH2=CH-C=N. Acrylonitrile has several synonyms and trade names
including:
► Propenenitrile.
► Vinyl Cyanide.
► Cyanoethylene
► Acrylon®
► Carbacryl ®
► Fumigrain ®
► Ventox ®

Selected physical and chemical properties of Acrylonitrile are presented in Table

Acrylonitrile is relatively volatile with a vapor pressure of 13.3 kPa (1.9 psi) at
25°C (77°F) and a boiling point of 77.3°C (171.1°F). It readily ignites and can
form explosive mixtures with air. In addition, Acrylonitrile polymerizes
explosively in the presence of strong alkalinity. Acrylonitrile is photo chemically
reactive and has an estimated atmospheric residence time 5.6 days. Atmospheric
residence time represents the time required for a quantity of an individual
chemical to be reduced to 1/e.

Property Value

Molecular weight 53.06

Boiling point, 0C
At 103.3 kPa* 77.3
At 66.65 kPa 64.7
At 33-33 kPa 45.5
At 13.33 kPa 23.6
At 6.665 kPa 8.7

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Chapter 1 INTRODUCTION
Critical pressure, kPa 3.535 x 103

Critical temperature, 0C 246.0

Cryoscopic constant, mol% / 0C 2.7

Density, g/L
At 20"C 806.0
At 25 C 800.4
At41cC 783.9

Dielectric constant at 33.5 MHz 38

Dipole moment, C.mc

Liquid 1.171 x Ifl-29
Vapor 1.294 x 10 -2B

Entropy, vapor at 250C, 101.3 kPa, 273.9

J/(mol.K)d

Entropy of polymerization, liquid, 25°C, -109

J/(mol-K)

Explosive mixture with air at 250C, vol%

Lower limit 3.05
Upper limit 17.0 ± 0.5

Flash point (tag open cup), 0C -5

Freezing point, 0C -83.55 ± O.O5

Gibbs energy of formation, vapor at 195.4

25°C, kJ/mol

Heat capacity, specific, liquid, kJ/(kg-K) 2.094

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Chapter 1 INTRODUCTION
Heat capacity, specific, vapor, kJ/(kg-K)
At 50°C, 101.3 kPa 1.204
T (K) from 77-1000°C, at 101.3 kPa 0.53 +26.23 x 10-4T-
86.03×10-8T2

Heat of combustion, liquid at 25°C, -1.7615 x 103

kJ/mol

Heat of formation at 250C, kJ/mol

Vapor 189.83
Liquid 151.46

Heat of fusion, kJ/mol 6.635 x 103

Heat of polymerization, kJ/mol -72.4 ± 2.1

Heat of polymerization at 74.50C, kJ/mol -76.5

Heat of vaporization at 101.3 kPa, 32.65

kJ/mol
Ignition temperature, °C 481.0

Molar refraction, D line 15.67

Parachor at 40.6=0 151.1

Polarizability at 250C 266

Refractive index 1.3911-1.39142

n20D

n25D 1.3888
t
t from 10-35 0C n D = 1.4022-0.000539t
n20C 1.38836
n20F 1.39890
n20G 1.4078
Solubility Parameter, (J/mL)1/2 21.48
Surface tension at 24°C, mN/m (=dyn/cm) 27.3

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Chapter 1 INTRODUCTION

Surface tension of aqueous solution c = 0.223d-0.0018d2 +

0.00013d3
c from 0—6 wt%, d, mN/m (=dyn/cm)
1.83 (air = 1.0)
Vapor density, relative Log p = 6.6428 - 1.6447 x
103/T (K)

Viscosity at 25°C, mPa-s (=cP) 0.34

CHEMICAL PROPERTIES:-
Acrylonitrile is very reactive, due to the presence of both an electron-
accepting nitrile group and a double bond. Pure acrylonitrile polymerizes
readily, especially under the influence of light. Storage of acrylonitrile
requires the addition of polymerization inhibitors. The chemical reactions of
acrylonitrile have been discussed in great length and detail. A brief
summary follows.

Reactions of the Nitrile Group:-

Hydration and Hydrolysis:- . In concentrated 85% sulfuric acid, partial hy-
drolysis of the nitrile group produces acrylamide sulfate, which upon
neutralization yields acrylamide; this is the basis for acrylamide's commercial
production. In dilute acid or alkali, complete hydrolysis occurs to yield acrylic
acid.
Partial hydrolysis to acrylamide or complete hydrolysis to acrylic acid can
be achieved depending on the concentration of the acid used. The partial

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Chapter 1 INTRODUCTION
hydrolysis with sulfuric acid to acrylamide sulfate as intermediate product is
the basis for commercial production of acrylamide. Hydration and hydrolysis
reactions catalyzed by hydrochloric acid give good yields of 3-
chloropropionamide or 3-chloropropionic acid
Alcoholysis:- Acrylonitrile is converted to acrylic esters with primary
alcohols in the presence of sulfuric acid. Imido ethers are formed by reaction of
acrylonitrile with alcohols in the presence of anhydrous halides.
NH-HX

CH2=CHCN + ROH + HX XCH2CH2—C—OR

Reactions with Olefins and Alcohols: - The Hitter reaction occurs with
compounds such as olefins and secondary and tertiary alcohols which form
carbonium ions in acid, and N-substituted acrylamides are formed.
Reactions with Aldehydes and Methylol Compounds. Catalyzed by sul-
furic acid, formaldehyde and acrylonitrile react to form either 1,3,5-
triacrylylhexahydro-s-triazine or N,N'-methylenebisacrylamide, depending on
the conditions. Similarly, in the presence of sulfuric acid, N-methylolbenzamide
reacts to yield mixed bisamides. N-Methylolphthalimide reacts to give N-
phthalimidomethylacrylamide.
Reactions of the Double Bond:-
Diels-Alder Reactions. Acrylonitrile acts as a dienophile with conjugated
carbon-carbon double bonds to form cyclic compounds. On the other hand,
acrylonitrile can act as a diene. For example, with tetrafluoroethylene 2,2,3,3-
tetrafluorocyclobutanecarbonitrile forms; and with itself, dimers of cis- and
trans-cyclobutanedicarbonitriles form at high temperatures and pressure. The
activation energy for acrylonitrile cyclodimerization has been reported to be 90.4
kJ/mol
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Chapter 1 INTRODUCTION
Hydrogenation. With metal catalysts, an excellent yield of propionitrile is
attained, which can be further hydrogenated to propylamine.
Halogenation. At low temperatures, halogenation proceeds slowly to pro-
duce 2, 3-dihalopropionitriles. In the presence of pyridine, addition of
chlorine forms 2,3-dichloropropionitrile quantitatively. At elevated
temperatures, without UV light, 2,2,3-trihalopropionitrile is obtained; with UV
light, both 2,2,3- and 2,3,3-isomers are formed. Simultaneous chlorination and
alcoholysis occur to give 2,3-dichloropropionic acid esters.
Hydroformylation.:-In a process also known as the oxo-synthesis,
acrylonitrile reacts with a mixture of hydrogen and carbon monoxide, catalyzed
by cobalt octacarbonyl, to give β-cyanopropionaldehyde. This reacts with
hydrogen cyanide and ammonia, and then hydrolysis produces glutamic acid on
a large commercial scale.
Hydrodimerization.:- The reductive dimerization of acrylonitrile can be
done either chemically or electrochemically to form adiponitrile.
Hydrodimerization with its derivatives also takes place.
Reactions with Azo Compounds:-. Meerwein reactions of diazonium
halides with acrylonitrile take place at low temperatures, catalyzed by cupric
chloride, to yield 2-halo-3-arylpropionitriles. Reactions with diazomethane
compounds lead to pyrazolines and finally cyclopropanes. Reactions with 9-
diazofluorene produce a cyanocyclopropane derivative, with the generation of
nitrogen. Phenyl azide reacts with acrylonitrile to yield a heterocyclie nitrile at
room temperature or an open-chain nitrile at elevated temperatures.
Reactions of Both Functional Groups . Hydrolysis of
acrylonitrile catl- yzed by hydrochloric acid yields 3-chloropropionic acid.
Alcoholysis and chlorination occur simultaneously in the presence of sulfuric
acid. Similarly, alcoholysis and hydro chlorination also occur. Addition of both
ammonia and hydrogen produces both trimethylenediamine and propylamine.
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Chapter 1 INTRODUCTION
Treatment of acrylonitrile with hydrogen peroxide at neutral to slightly alkaline
pH, yields glycidamide. Similarly, treatment with water, containing
ammonium sulfide or a weak base, forms bis(2-carboxamidoethyl)sulfide or
poly(β-alanine).
Cyanoethylation Reactions (Michael-Type Additions). Most
compounds with a labile hydrogen atom can add on the double bond of acrylonitrile
to form cyanoethyl groups; that is, the primary products are 3-substituted
propionitrile.

CH2=CHCN + RH RCH2CH2CN

A large number of useful reactions fall into this category. Examples of

these reactions are carbon Cyanoethylation in which aldehydes, ketones, esters,
nitriles, nitro compounds, sulfones, aliphatic and aromatic hydrocarbons, or
haloforms add to acrylonitrile; nitrogen Cyanoethylation where amines,
ammonia, anilines, or amides add; oxygen Cyanoethylation where alcohols,
phenols, water, hydroperox-ides, oximes, or hydrogen peroxide react; sulfur
Cyanoethylation in which sulfides, bisulfides, or sulfhydryl compounds add;
hydrogen halide cyanoethylaphonates, boranes, silanes, or tin hydrides. In
addition, many natural and synthetic polymers possessing labile hydrogen
atoms, such as cotton, jute, gums, lignin, proteins, modified cellulose,
poly(vinyl alcohol) (PVC), and acetone-formaldehyde and methyl ethyl
ketone-formaldehyde condensates, react with acrylonitrile to yield cyanoethyl
derivatives.

USES:-

Total acrylonitrile demand in 1974 was 2 megatons per year. This demand
was comprised of 613 kt/yr in the United States, 830 kt/yr in Western Europe,
9
Chapter 1 INTRODUCTION
and 600 kt/yr in Japan. The bulk of acrylonitrile production today goes into
three major use areas:

 Acrylic fibers,

 Copolymer resins ("plastics"),

 Nitrile rubbers.

Acrylic Fibers.
The spectacular increase in acrylonitrile monomer output that began in the
late 1960s can be attributed to a drastic fall in the price of the monomer—
brought about by improved manufacturing methods using propylene as raw
material—and to consumer acceptance of acrylic fibers for clothing and textiles.
More than half of the present acrylonitrile monomer production goes into
fibers. Acrylic fibers, due to their excellent properties, have succeeded in
penetrating the traditional markets for wool (see Acrylic and modacrylic
fibers).
Copolymer Resin ("Plastics'').
Acrylonitrile-containing plastics, particularly the resins acrylonitrile-
butadiene-styrene (ABS), constitute the second largest application of
acrylonitrile monomer. These resins contain approximately 25-30%
acrylonitrile. There is a rapid increase in the demand for ABS in engineering-
related markets, such as pipe and fittings, automotive parts, appliances,
furniture, building components, packaging, and other applications where its
mechanical strength, resistance to chemicals and hydrocarbons, and ease of
manufacture make it a suitable replacement for many traditional materials.

Nitrile Rubbers and Resins.

Nitrile rubber is used extensively in the engineering and process industries.

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Chapter 1 INTRODUCTION
It is resistant to chemicals, oils, solvents, heat ageing and abrasion; it has good
dielectric properties and good flexibility at low temperature. High-nitrile barrier
resins are beginning to penetrate the food packaging industry, where a great
potential for growth exists, particularly in the carbonated beverage container
market

Growth Potential.
Growth rates of at least 10% are foreseen through 1985. It is predicted that
the United States demand for acrylonitrile will be one megaton per year in
1980. The main areas of new growth are nylon-6, 6, and thermoplastic barrier
resins (high acrylonitrile content) such as Vistron's Barex 210 resin, Monsanto's
Cycle-Safe and Lopac, Borg-Warner's Cyclopac, or Du Font's NR 16. The
nitrile harrier resins have become established in the food, cosmetic, and
chemical packaging industry and their breakthrough into the soft-drink
container field has been forecast.
It is predicted that barrier resins could replace ABS as the second largest
consumer of acrylonitrile by the early 1980s. The potential demand for
acrylonitrile for barrier resins alone is larger than the present world
acrylonitrile capacity.

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Chapter 1 INTRODUCTION

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 Chapter 1 INTRODUCTION

Estimated Consumption of Acrylonitrile by Product type in 1984

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 Chapter 1 INTRODUCTION

Market %Total ACN Consumption

Acrylic Fibers 37.7
Exports 21.3
ABS / SAN 17.1
Resins
Adiponitrile 9.5
Acryl amide 3.1
Nitrite 2.9
Elastomers
Barrier Resins 1.2
Miscellaneous 4.0
Miscellaneous includes fumigants for tobacco, fatty amine
production, cyanoethylation of Alcohols and Amines.

Worldwide ACN Production, 103 ton:-

Region 1997 1998

Western Europe 1073 1112

Eastern Europe 189 182

United States 1483 1324

Japan 729 730

Far East / Asia 779 841

Africa / Middle East 147 152

Latin America/Mexico 232 246

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Chapter 1 INTRODUCTION

Total Production 4642 4587

ECONOMIC ASPECTS-

Although known to chemists for eighty years, acrylonitrile was not

an important product until World War II, when it was used as a feed
stock in the production of oil-resistant rubbers. Because of its high
price, dictated by the older manufacturing methods, acrylonitrile
production lagged until the late 1960s.
The introduction of the Sohio process in 1960 revolutionized the
economics of making ACN. The low cost of propylene and ammonia as
raw materials substantially reduced the cost of the monomer, thereby
stimulating research into new applications for acrylonitrile. The resulting
market development has, in turn, stimulated the spectacular growth in
production capacity, e.g., United States production rose from less than
100 kilotons in 1960 to 640 kt in 1974, and then slipped somewhat in 1975
due to the effects of a recession on market demand. The main production
areas are the United States, Europe, and Japan.
Since 1960, the cost of producing acrylonitrile has been coming down, at
first due to the introduction of ammoxidation processes, and subsequently
due to the use of improved catalysts and the increasing size of the
producing units. This trend was reversed in 1974, when the increase in
crude oil prices resulted in increased costs for propylene and ammonia
and consequently the production cost of acrylonitrile. It is expected that the
enforcement of ever increasing environmental standards will have an
adverse effect on the production cost of acrylonitrile.

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Chapter 1 INTRODUCTION

As with other bulk chemicals, raw materials are the major cost factor in
producing acrylonitrile. Using 1976 prices, raw materials account for 70%
of the cost of making acrylonitrile via the ammoxidation process. However,
improved yields of acrylonitrile are expected to result from the current
emphasis on catalyst research. In 1965, Catalyst 21 replaced Catalyst A in
the Sohio process; in 1970, Catalyst 21 was in turn replaced by Catalyst 41,
the current catalyst. Nitto Industries and Sohio recently made a joint
announcement of Catalyst NS733A, which is said to further reduce
production costs of acrylonitrile.
Production and Price History of Acrylonitrile
Year U.S.A. selling
price, Production, 1000 metric tons
$/metric ton
U.S.A. Western Europe Japan

1960 450 102

--- ---
1961 410 111 42 30

1962 360 161 45 40

1963 340 203 46 90

1964 350 265 53 160

1965 300 345 71 170

1966 280 320 124 200

1967 270 299 165 223

1968 187 456 231 315

1969 NAa 516 328 420

1970 NA 472 438 ---

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Chapter 1 INTRODUCTION

1971 198 441 620 ---

1972 NA 506 740 595

1973 NA 568 890

----
1974 396 640 940 650

1975 528 554 1030 ----

1976 583 --- ----

----
NA = Not available.

ANALYTICAL AND TEST METHODS:-

Numerous instrumental and chemical techniques are available for the
determination of acrylonitrile. The method of choice is directed by the
concentration and the medium involved. For direct assay of acrylonitrile,
titrimetric procedures are frequently used. Dodecyl mercaptan reacts with
acrylonitrile under base catalysis; excess mercaptan is then back-titrated
with an acid bromate-iodide solution, or alternatively, for colored
solutions, with silver nitrate. Hydrolysis of the nitrile with strong base gen-
erates ammonia, which can then be determined by Nessler's reagent.
For dilute solutions, both gas chromatography and polarography are
rapid, sensitive, and precise. Small amounts of acrylonitrile can be
separated from other components by azeotropic distillation with alcohols,
followed by polaro-graphic or chromatographic analysis.
For monitoring of acrylonitrile in ambient air, a measured quantity of
an air sample is drawn through a charcoal tube, followed by quantitative
extraction with a carbon disulfide-acetone (98:2) mixture for gas
chromatographic analysis. Reliable results can be attained even when <l-
ppm acrylonitrile is present. A comprehensive review and a description of

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Chapter 1 INTRODUCTION

the development of environmental test methods for air, water, soil, and
sediment samples have been done.

Storage and Transport:-

. Acrylonitrile must be stored in tightly closed containers in cool, dry, well-

ventilated areas away from heat, sources of ignition, and incompatible
chemicals. Storage vessels, such as steel drums, must be protected against
physical damage, with outside detached storage preferred. Storage tanks
and equipment used for transferring acrylonitrile should be electrically
grounded to reduce the possibility of static spark-initiated fire or explosion.
Acrylonitrile is regulated in the workplace by OSHA

Acrylonitrile is transported by rail car, barge, and pipeline. Department of

Transportation (DOT) regulations require labeling acrylonitrile as a
flammable liquid and poison.

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