INTRODUCTION

Prior to 1960, acrylonitrile 107-13-1 (also called acrylic acid nitrile, propylene nitrile, vinyl
cyanide, propenoic acid nitrile) was produced commercially by processes based on either
ethylene oxide and hydrogen cyanide or acetylene and hydrogen cyanide. The growth in
demand for acrylic fibers, starting with the introduction of Odon by Du Pont atound 1950,
spurred efforts to develop improved process technology for acrylonitrile manufacture to
meet the growing market (see FIERS ACRYLIC). This resulted in the discovery in the late
1950s by Sohio (1) and also by Distillers (2 of a heterogeneous vapor-phase catalytic process
for acrylonitrile by selective oxidation of propylene and ammonia, commonly referred to as
the propylene ammoxidation process Commercial introduction of this lower cost process by
Sohio in 1960 resulted in the eventual displacement of all other acrylonitrile manufacturing
processes . Todav over 90 % ofthe approximately 4,000,000 metac tons produced worldwide
each year use the Sob o developed aninoxidation process . Acrylonitrile is among the top 50
chemicals produced in the United States as a result of the tremendous growth in its use as a
starting material for a wide range of chemical and polymer products. Acrylic fibers remain
the largest use of acrylonitrile; other significant uses are in resins and nitrile elastomers and
as an intemediate in the production of adiponitrile and acrylamide

Physical Properties

Acrylonitrile (C3H3N, mol wt 53.064) is an unsaturated molecule having a carbon-carbon

double bond conjugated with a nitrile group. It is a polar molecule because of the presence
of the nitrogen heteroatom. There is a partial shift in the bonding electrons toward the more
electronegative nitrogen atom, as represented by the following heterovalent resonance
stnuctures
 INTRODUCTION

Chemical Properties

Acrylonitrile undergoes a wide range of reactions at its two chemically active sites, the
nitrile group and the carbon-carbon double bond. Detailed descriptions of specific reactions
have been given (19,20). Acrylonitrile 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. Homo polymers
and copolymers are most easily produced using liquid-phase polymerization (see
ACRYLONTRILE POLSTMERs). Acrylonitrile undergoes the reactions typical of nitriles
,including hydration with sulfuric acid to fon acrylamide sulfate (CH, NO H SO, 15497.99-1),
which can be converted to acrylamide (C H NO 79-061 by neutralization with a base; and
complete hydrolysis to give acrylic acid (C,HO2 79-10-7) Acrylamide (qv) is also

formed directly from acrylonitrile by partial hydrolysis using copper-based catalysts (21-24),
this has become the preferred commercial route for acrylamide production. Industrially
important acrylic esters can be formed by reaction of acrylamide sulfate with organic
alcohols. Methyl acrylate (C4H6O2, 96-33-37) has been produced commercially by the
alcoholysis of acrylamide sulfate with methanol Reactions at the activated double bond of
acrylonitrile include Diels-Alder addition to dienes, forming cyclic products; hydrogenation
over metal catalysts to give propionitrile (C3 H5 N,[ 107-12-0]) and propyl amine (C3H9N,[
07-10-8]; and the industrially important hydro dimerization to produce adiponitrile (C6
H8N2,[111-69-3])(25-27). Other reactions include addition of halogens across the double
bond to produce dihalopropionitriles, and cyanoethylation by acrylonitrile of alcohols,
.aldehydes, esters, amides

MANUFACTURE
 INTRODUCTION

Methods of Production

Today nearly all acrylonitrile is produced by ammoxidation of propene. Although the

first report of the preparation of acrylonitrile from propene occurred in a patent by

the Allied

Chemical and Dye Corporation in 1947, it was a decade later when Standard Oil of
Ohio

Sohio) developed the first commercially viable catalyst for this process. Today, all of (
the

United States capacity and approximately 90 % of the world capacity for acrylonitrile
is

based on the Sohio process

1- Sohio Process

In the Sohio process propene, oxygen (as air), and ammonia are catalytically

converted directly to acrylonitrile using a fluidized-bed reactor operated at

temperatures of

:)C and gauge pressures of 30 – 200 kPa (0.3 – 2 bar° 500 – 400

CH2=CH-CH3 + 2NH3 + 3O2 ⎯→ 2CH2=CH-C≡N + 6H2O2

2-Production from Ethylene Cyanohydrin 2.1.2

Germany (I.G. Farben, Leverkusen) and the United States (American Cyanamid) first

produced acrylonitrile on an industrial scale in the early 1940s. These processes

were based

on the catalytic dehydration of ethylene cyanohydrin. Ethylene cyanohydrin was

produced

from ethylene oxide and aqueous hydrocyanic acid at 60 °C in the presence of a

basic

catalyst. The intermediate was then dehydrated in the liquid phase at 200 °C in the
presence

.of magnesium carbonate and alkaline or alkaline earth salts of formic acid

HO-CH2-CH2-C≡N ⎯→ CH2=CH-C≡N + H2O

 INTRODUCTION

An advantage of this process was that it generated few impurities; however, it was
not

economically competitive. American Cyanamid and Union Carbide closed plants

based on

this technology in the mid-1960s

3- Production from Acetylene and Hydrocyanic Acid 2.1.3

Before the development of the propene ammoxidation process, a major industrial

.route to acrylonitrile involved the catalytic addition of hydrocyanic acid to acetylene

H-C≡C-H + HCN ⎯→ CH2=CH-CN

Although a vapour-phase reaction has been reported, the commercial reaction usually was

carried out at 80 °C in dilute hydrochloric acid containing cuprous chloride. Unreacted

acetylene was recycled. The yield from this reaction was good; however, the raw materials

were relatively expensive, some undesirable impurities, divinylacetylene and methyl vinyl

,ketone, were difficult to remove, and the catalyst required frequent regeneration. Du Pont

American Cyan-amid, and Monsanto employed this process until about 1970

Uses of Acrylonitrile

:Acrylonitrile is used as

.A raw material for the production of synthetic fibres, plastics and synthetic rubber •

One of the reasons for the versatility of Acrylonitrile is that it can form copolymers

.with other unsaturated compounds, such as styrene and butadiene, for example

.A raw material for acrylic acid, acrylic esters, acrylic amide, carbon fibre •

,In the synthesis of compounds used for the production of adhesives, anti-oxidants •

binders for dyestuffs and emulsifiers

PRODUCTION CAPACITY

Today over 90% of the approximately 4,000,000 metric tons produced worldwide each year
.use the sohio-developed ammoxidation process.