Acrylonitrile
JAMES F. BRAZDIL, INEOS Technologies, Naperville Illinois, USA 60563
1. Introduction. . . . . . . . . . . . . . . . . . . . .
2. Physical and Chemical Properties . . . .
3. Production . . . . . . . . . . . . . . . . . . . . . .
4. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . .
5. Quality Specifications . . . . . . . . . . . . .
1. Introduction
Acrylonitrile [107-13-1] is a key intermediate
in the chemical industry for production of a
wide range of products. It is also referred to as
2-propenenitrile, propenenitrile, acrylic acid
nitrile, propylene nitrile, vinyl cyanide, and
propenoic acid nitrile. Its chemical formula is
C3H3N having a molecular mass of 53.064 and
the following chemical structure.
Acrylonitrile is produced commercially via
the propylene ammoxidation process (also
known as the SOHIO process), first commer-
cialized in 1960, by the reaction of propylene,
ammonia, and oxygen in presence of a hetero-
geneous catalyst.
C3 H6 NH3 1:5 O2 !C3 H3 N3 H2 O
Prior to the discovery of the propylene am-
moxidation process, acrylonitrile was largely
produced commercially via the ethylene cyano-
hydrin process [13].
C2 H4 OHCN! HOC2 H4 CN!C3 H3 NH2 O
This process was practiced by American
Cyanamid and Union Carbide in the United
States and by I. G. Farben in Germany. The
process involved the production of ethylene
cyanohydrin by the base-catalyzed addition of
HCN to ethylene oxide in the liquid phase at
about 60
C. A typical base catalyst used in this

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a01_177.pub3
1 6. Analysis . . . . . . . . . . . . . . . . . . . . . . . . 6
2 7. Storage and Transportation. . . . . . . . . 6
3 8. Economic Aspects . . . . . . . . . . . . . . . . 7
5 9. Environmental Protection . . . . . . . . . . 8
6 10. Toxicology and Occupational Health. . 8
step was diethylamine. This was followed by
liquid-phase or vapor-phase dehydration of the
cyanohydrin. The liquid-phase dehydration was
performed at about 200
C using alkali metal or
alkaline earth metal salts of organic acids,
primarily formates and magnesium carbonate.
Vapor-phase dehydration was accomplished
over alumina at about 250
C.
In addition, DuPont, American Cyanamid,
and Monsanto produced acrylonitrile on a com-
mercial scale by catalytic addition of HCN to
acetylene [4].
C2 H2 HCN!C3 H3 N
The process is catalyzed by cuprous chloride
in a dilute hydrochloric acid solution using a
stoichiometric excess of acetylene.
Commercial use of cyanohydrin- and acety-
lene-based processes ceased by 1970. They
were replaced by the lower-cost propylene
ammoxidation process.
Other chemical routes to acrylonitrile are:
. acetaldehyde and HCN [5]
CH3 CHOHCN!CH3 CHOHCN!C3 H3 NH2 O
. propionitrile dehydrogenation [6, 7]
CH3 CH2 CN!C3 H3 NH2
. propylene and nitric oxide [8, 9]
C3 H6 1:5 NO!C3 H3 N1:5 H2 O0:25 N2
2 Acrylonitrile

. and dehydration of acrylamide [10] resins, adiponitrile, and acrylamide. As a result,

CH2 CHCONH2 !C3 H3 NH2 O
None of these routes achieved large-scale
commercial application.
The growth in the demand for acrylonitrile
began in 1950 with the discovery and commer-
cial introduction of the acrylic fiber called Orlon
by DuPont. This spurred the discovery in the late
1950s of the propylene ammoxidation process
by SOHIO [11] and Distillers [12], indepen-
dently. The commercial introduction of this
revolutionary process by SOHIO resulted in the
dramatic reduction of the cost of acrylonitrile
production which in turn led to an exponential
increase in acrylonitrile demand [13] for a wide
range of chemical and polymer products. Acryl-
ic fiber remains the largest end use for acrylo-
nitrile along with the rapidly growing markets
for acrylonitrilebutadienestyrene (ABS)
the installed annual production capacity for
acrylonitrile has grown to more than 5 000 
103 t/a worldwide.
2. Physical and Chemical Properties
Acrylonitrile is a clear colorless liquid at room
temperature. It is a polar molecule due the
presence of the electronegative nitrile function-
al group that is conjugated with a carboncarbon
double bond.
Table 1 lists some physical and thermody-
namic properties of acrylonitrile [1419].
Acrylonitrile is miscible with a variety of
organic solvents including acetone, benzene,

Table 1. Physical properties of acrylonitrile [19]

Property Value Comments

Molar mass 53.06 g/mol

Density 0.806 g/mL at 20
C
Melting point 83.55
C
Boiling point 77.30
C at 101.3 kPa
Refractive index nD25 1.3888 589 nm, at 25
C
Miscibility in water 7.30 wt% at 20
C
Miscibility of water in acrylonitrile 3.08 wt% at 20
C
Viscosity 0.34 mm2/s at 25
C
Dielectric constant 38 at 33.4 MHz
Dipole moment 3.88 D neat, vapor
Vapor density 1.83 theoretical; air 1
Critical pressure 3.536  104 kPa
Critical temperature 245.8
C
Critical volume 3.790 mL/g
Surface tension 27.76 mN/m at 15.1
C
27.53 mN/m at 17.8
C
24.80 mN/m at 40.6
C
Ionization potential 10.75 eV by electron impact
Heat of combustion (liq.) 1761.8 kJ/mol
Flammability limits in air
Lower 3.0 vol% at 25
C
Upper 17.0 vol% at 25
C


Free energy of formation, DGf;g 195 kJ/mol at 25
C


Enthalpy of formation, DHf;g 185 kJ/mol at 25
C


Enthalpy of formation, DHf;l 150 kJ/mol at 25
C


Enthalpy of vaporization, DHf;vap 32.65 kJ/mol at 25
C
Heat of polymerization 72.4  0.2 kJ/mol
Molar heat capacity, liquid 111.1 kJ mol1  K1
Molar heat capacity, vapor 64.1 kJ mol1  K1 50
C, 101.3 kPa
Molar heat of fusion 66.15 kJ/mol
Entropy, gas 274 kJ mol1  K1 at 25
C, 101.3 kPa
Autoignition temperature 481
C in air
Flash point 0
C
Thermal conductivity 166 kW m1  K1 at 23
C
 Acrylonitrile 3

Table 2. Azeotropes of acrylonitrile [20] Table 4. Acrylonitrile vapor pressure over aqueous solutions at 25
C

Azeotrope Boiling Acrylonitrile Acrylonitrile, wt% Vapor pressure, kPa

point,
C concentration, wt %
1 1.3
Tetrachlorosilane 51.2 11 2 2.9
Water 71.0 88 3 5.3
Isopropyl alcohol 71.7 56 4 6.9
Benzene 73.3 47 5 8.4
Methanol 61.4 39 6 10.0
Carbon tetrachloride 66.2 21 7 10.9
Chlorotrimethylsilane 57.0 7

carbon tetrachloride, diethyl ether, ethyl ace- (C3H4O2 [79-10-7]). Acrylamide is also formed
tate, ethylene cyanohydrin, petroleum ether, directly from acrylonitrile by partial hydration
toluene, some kerosenes, and methanol. Com- using copper-based catalysts [2831]. This has
mon azeotropes of acrylonitrile are shown in become the preferred commercial route for
Table 2 [20]. The solubility of acrylonitrile in acrylamide production. Industrially important
water as a function of temperature is given in acrylic esters can be formed by reaction of
Table 3. The vapor pressure of acrylonitrile over acrylamide sulfate with organic alcohols.
aqueous solutions is shown in Table 4. Vapor- Methyl acrylate (C4H6O2 [96-33-3]) has been
liquid equilibria for other solutions have also produced commercially by the addition of
been published [2125]. methanol to acrylamide sulfate.
The chemical reactivity of acrylonitrile Other reactions of acrylonitrile include
stems from the presence of its two reactive sites DielsAlder addition to dienes, forming cyclic
at the carboncarbon double bond and the nitrile products; hydrogenation over metal catalysts to
functional group. The principal reactions are give propionitrile (C3H5N [107-12-0]) and pro-
polymerization and hydration [26, 27]. Acrylo- pylamine (C3H9N [107-10-8]), and the indus-
nitrile polymerizes readily and exothermically trially important hydrodimerization to produce
in the absence of a hydroquinone inhibitor, adiponitrile (C6H8N2 [111-69-3]) [3234].
especially when exposed to light. Polymeriza- Other reactions include addition of halogens
tion is initiated by free radicals, redox catalysts, across the double bond to produce dihalopro-
or bases and can be carried out in the liquid, pionitriles, and cyanoethylation of alcohols,
solid, or gas phase. Homopolymers and copo- aldehydes, esters, amides, nitriles, amines, sul-
lymers are most easily produced using liquid- fides, sulfones, and halides with acrylonitrile.
phase polymerization. Acrylonitrile undergoes
hydration with sulfuric acid to form acrylamide
sulfate (C3H5NO  H2SO4 [15497-99-1]), 3. Production
which can be converted to acrylamide (C3H5NO
[79-06-1]) by neutralization with a base, and Acrylonitrile is produced commercially by the
complete hydration to give acrylic acid catalytic vapor-phase propylene ammoxidation
process developed by SOHIO [35]. A schematic
Table 3. Miscibilities of acrylonitrile in water
diagram of the commercial process is shown in
Figure 1. The commercial process uses a fluid-
Temperature,
C Acrylonitrile Water in acrylonitrile, ized bed reactor in which propylene, ammonia,
in water, wt % wt % and air contact a solid catalyst at 400510
C and
0 7.1 2.1 50200 kPa gauge. The process uses a stoichio-
10 7.2 2.6 metric excess of ammonia and oxygen (as air). It
20 7.3 3.1 is a single-pass process with about 98% conver-
30 7.5 3.9
40 7.9 4.8
sion of propylene that typically consumes about
50 8.4 6.3 1.1 kg of propylene per kilogram of acryloni-
60 9.1 7.7 trile produced or less with the recent generations
70 9.9 9.2 of highly selective catalysts. A commercially
80 11.1 10.9
important coproduct from the acrylonitrile
4 Acrylonitrile
Figure 1. Simplified process flow diagram of the commercial propylene ammoxidation process
a) Fluidized bed reactor; b) Countercurrent absorber; c) Recovery column; d) Second recovery column; e) Fractionation
columns
process is HCN (about 0.1 kg per kg of acrylo-
nitrile), which is used primarily in the manufac-
ture of methyl methacrylate (CH2C(CH3)
COOCH3 [80-62-6]) and sodium cyanide
[143-33-9]. Another useful coproduct that can
be recovered from the process is acetonitrile
(CH3CN [75-05-8]) in typical yields of about
0.03 kg per kg of acrylonitrile produced. Ace-
tonitrile finds commercial use as an important
solvent in pharmaceutical manufacture and
other industrial solvent applications.
In the commercial practice of acrylonitrile
manufacture, the hot reactor effluent is
quenched with water in a countercurrent absorb-
er and unreacted ammonia is neutralized with
sulfuric acid. The resulting ammonium sulfate
can be recovered and used as a fertilizer. The
absorber off-gas containing primarily N2, CO,
CO2, and unreacted propylene is either vented
directly or first passed through an incinerator to
combust the hydrocarbons and CO. The acrylo-
nitrile-containing solution from the absorber is
passed to a recovery column that produces a
crude acrylonitrile stream overhead that also
contains HCN. The column bottoms are passed
to a second recovery column to remove water
and produce a crude acetonitrile mixture. The
crude acetonitrile is either incinerated or further
treated to produce solvent quality acetonitrile.
Acrylic fiber quality (99.2% minimum) acrylo-
nitrile is obtained by fractionation of the crude
acrylonitrile mixture to remove HCN, water,
light ends, and high boiling impurities. Disposal
of the process impurities has become an increas-
ingly important aspect of the overall process,
with significant attention being given to devel-
oping cost-effective and environmentally
acceptable methods for treatment of the process
waste streams. Current methods include deep-
well disposal, wet air oxidation, ammonium
sulfate separation, biological treatment, and
incineration.
Although acrylonitrile manufacture from
propylene and ammonia was first patented in
1949 [36], it was not until 1959, when SOHIO
developed a catalyst capable of producing
acrylonitrile with high selectivity, that commer-
cial manufacture from propylene became
economically viable [11]. Improvement in the
process since then has resulted primarily from
the development of new catalysts with increased
yields of acrylonitrile from propylene. These
catalysts are multi-component mixed metal oxi-
des mostly based on bismuthmolybdenum
oxide. The evolutionary development of the
multi-component molybdate-based ammoxida-
tion catalyst has been described [37]. The first
commercial production of acrylonitrile by SO-
HIO used the Bi9PMo12O52 bismuth-phospho-
molybdate propylene ammoxidation catalyst
supported on silica [35] with bismuth molyb-
date being the catalytically active phase. Higher
yields of acrylonitrile and nitrile products were
progressively achieved with the incorporation

of iron molybdates [38, 39]. Further improve-
ment was realized with the incorporation of
cobalt and nickel [40] molybdates along with
iron. Promotion with an alkali metal, e.g.,
potassium provides a further improvement in
selectivity to acrylonitrile [41].
Although the vast majority of acrylonitrile is
produced using molybdate-based catalysts,
antimonate catalysts are also used commercial-
ly. The iron-antimony-oxide based catalyst pro-
moted with tellurium, copper, molybdenum,
vanadium, and tungsten is used commercially
today [4245].
Because of the commercial importance of
propylene (amm)oxidation technology, a signif-
icant amount of research has been conducted to
elucidate the surface reaction chemistry and
solid state mechanisms of bismuth molybdate-
based catalysts [4651]. Kinetic studies with
deuterated propylene have shown the rate-de-
termining step to be abstraction of the a-hydro-
gen of propylene by an oxygen in the catalyst to
form a p-allyl complex on the surface. Acrolein
forms by further hydrogen abstraction and in-
sertion of lattice oxygen. Insertion of nitrogen to
form acrylonitrile occurs when isoelectronic
NH2 is present on the surface in the presence
of ammonia according to the following:
NH3 O2 surface lattice!NH2 surfaceH2 O
Further fundamental understanding of the
complex solid state and surface mechanisms of
propylene ammoxidation over bismuth molyb-
date-based catalysts has been obtained by
Raman-spectroscopic analysis [52, 53], X-ray,
and neutron diffraction [5459], X-ray absorp-
tion spectroscopy [60, 61], pulse-kinetic stud-
ies [51], and probe molecule investigations [62].
4. Uses
The major end use of acrylonitrile are acrylic
fiber, acrylonitrilebutadienestyrene (ABS)
resins, adiponitrile (NC(CH2)4CN [111-69-
3]), acrylamide (CH2CHC(O)NH2 [79-06-
1]), nitrile rubbers, and carbon fibers. Acrylic
fiber is the largest commercial use for acryloni-
trile as shown in Table 5. ABS and acrylamide
are expected to be the fastest growing uses for
acrylonitrile with carbon fiber also increasing
for high strength and low weight applications
Acrylonitrile 5
Table 5. End-uses of acrylonitrile
Product %
Acrylic fiber 42
ABS resins 34
Adiponitrile 8
Acrylamide 7
Nitrile rubber 5
Carbon fiber 2
Other 2
especially in the airline and automobile
industries.
Acrylic fiber is primarily used in the manu-
facture of apparel and home furnishings
(! Fibers, 8. Polyacrylonitrile Fibers,
! Fibers 5. Synthetic Inorganic, Chapter 5).
The growth in the acrylic fiber market has
declined compared to other uses of acrylonitrile.
Much of the acrylic fiber manufacturing capac-
ity has moved from the U.S. and Europe to Asia,
particularly to China.
ABS is a specialty high performance
polymer used mainly because of its high
strength, coloring characteristics, and proces-
sing ease. It is used in numerous automotive,
construction, appliance, and electronics appli-
cations (! Polystyrene and Styrene Copoly-
mers, Chapter 5, ! Polystyrene and Styrene
Copolymers, Chapter 2, and ! Polystyrene and
Styrene Copolymers, Section 4.1). SAN copo-
lymers are optically transparent and as such are
used in packaging, optical fibers, food contain-
ers among other applications.
Adiponitrile is used to manufacture hexam-
ethylenediamine (HMDA, C6H16N2 [124-09-
4]) by electrohydrodimerization, see ! Hex-
amethylenediamine, Chapter 4 and [32].
HMDA is the raw material for making
nylon-6,6.
Acrylamide is manufactured from acryloni-
trile by a copper-catalyzed process (! Acrylic
Acid and Derivatives, Chapter 3) [2831].
When polymerized, it finds large scale applica-
tion in wastewater treatment, oil production,
mineral processing, and paper manufacture.
Nitrile rubbers are butadieneacrylonitrile
copolymers that are used in the industry because
of their chemical, oil, and ozone resistance
along with high flexibility, stability, and heat
resistance (! Rubber, 4. Emulsion Rubbers,
Chapter 3). They are used mainly in the
6 Acrylonitrile

Table 6. Acrylonitrile product specifications [63] be stored in tightly sealed containers in a cool,
Properties Units Limit
well-ventilated area away from heat, sources of
ignition, and incompatible chemicals. Incom-
Acetone ppm 75 patible chemicals and materials to avoid are
Acetonitrile ppm 150
Acidity ppm 15
bromine, ammonia, amines, copper and copper
Acrolein ppm 10 alloys, strong acids, strong bases (e.g., potassi-
Aldehydes ppm 20 um hydroxide, sodium hydroxide), peroxides or
Appearance clear, free of suspended matter other free radical initiators, or strong oxidizers.
Color APHA 10
Copper ppm 0.1
Suitable storage materials are carbon steel and
Hydrogen cyanide ppm 5 stainless steel. Storage equipment must be elec-
Inhibitor (MEHQ) ppm 3545 trically grounded. Large storage tanks should be
Iron ppm 0.1 equipped with a vapor control system to prevent
Methacrylonitrile ppm 250
Methyl vinyl ketone ppm 10
release of vapor to the atmosphere. Available
Nonvolatile matter ppm 100 control systems include incineration, recovery
Oxazole ppm 80 through a condenser, absorption with a carbon
Peroxide ppm 0.2 filter and scrubbing. Nonsparking tools should
pH 6.07.5
Titration value (0.1 N H2SO4) mL 2
be used when opening or closing metal contain-
Water wt% 0.20.5 ers of acrylonitrile and containers must be
bonded and grounded during transfer of liquid
acrylonitrile. Nitrogen blanketing over liquid
manufacture of gaskets, seals, hoses, belts, and acrylonitrile can be used to reduce the potential
electrical cable jackets. for combustion of its vapors.
In addition to flammability, another primary
hazard of acrylonitrile storage and handling is
polymerization which is highly exothermic.
5. Quality Specifications Prevention of rapid polymerization is best
accomplished by ensuring that product specifi-
Typical commercial specifications for acryloni- cations are met and avoidance of incompatible
trile are given in Table 6. These acrylonitrile chemicals, materials, and conditions. The spe-
sales specifications are based on the require- cifications for acrylonitrile include the presence
ments of the acrylic fiber producers, the largest of a suitable inhibitor to prevent polymeriza-
end-use for acrylonitrile. tion. The most commonly used inhibitor system
is MEHQ (hydroquinone monomethyl ether
[150-76-5], 3545 ppm) and water (0.2 to 0.5
6. Analysis wt%). MEHQ inhibits free radical polymeriza-
tion. Water traps traces of acidic and basic
Standardized chemical analyses of acrylonitrile reactive intermediates. Complete absence of
have been developed and published for ensuring oxygen is to be avoided, because the MEHQ
product quality and meeting product specifica- inhibitor requires the presence of dissolved
tions [6469]. Among the most critical analyses oxygen to prevent polymerization. During com-
are color determination, HCN, inhibitor and mercial manufacture, handling, and storage of
water content. acrylonitrile, typically a sufficient quantity of
dissolved oxygen is present to activate the
MEHQ inhibitor. Additional incompatible con-
7. Storage and Transportation ditions are exposure to ultraviolet light, high
heat, and high pressure.
Acrylonitrile is stored for commercial purposes For any extended storage of acrylonitrile,
in steel drums and tanks. It is transported by monitoring should be used for any signs of
pipeline, by drums and by rail, ship, and barge in possible polymerization. Samples should be
tanks. Acrylonitrile is a toxic and flammable taken to look for haziness of the liquid which
liquid and its vapors can readily form explosive is an indication of polymerization, since poly-
mixtures in air at ambient conditions. It must acrylonitrile is insoluble in liquid acrylonitrile.
 Acrylonitrile 7

Also the pH of a 5 wt% aqueous solution of a
sample should be measured. If the pH is above
7.3, this is an indication of ionic polymerization
which is accompanied by the production of
ammonia. The temperature should be monitored
for an increase that would indicate reaction of
acrylonitrile. Also the level of MEHQ should be
checked to ensure that the inhibitor is not being
lost.
Storage, signage, and labeling of acryloni-
trile are regulated nationally and internationally
by the applicable governmental entities. In the
United States, the safe use, handling, and
storage of acrylonitrile and acrylonitrile-based
materials are regulated by the Occupational
Safety and Health Administration (29 CFR
1910.1045). Transportation of acrylonitrile in
the United States is regulated by the U.S. De-
partment of Transportation (DOT), in Canada
by the Canadian Regulations for the Transport
of Dangerous Goods (TDG), and internationally
by ADR/RID, ADN/ADNR, IATA, and the
International Maritime Organization (IMDG).
. Hazard Class: 3 (6.1)
. UN/NA Code: UN1093
. Packing Group: PG I
. Bill of Lading Description: UN1093, Acrylo-
nitrile, Stabilized, 3(6.1), PG I, FP 1
C,
Marine Pollutant
. Labels Required: Flammable Liquid and
Toxic, Marine Pollutant mark required
. Placards Required: Flammable Liquid and
Toxic
8. Economic Aspects
Beginning with the first commercial plant by
SOHIO in 1960, the propylene ammoxidation
process for manufacturing acrylonitrile has
Table 7. Major acrylonitrile producers 2010
Company Capacity, 106 t/a
INEOS 1.3
Asahi Kasei Chemicals 0.75
Ascend Performance Materials 0.51
PetroChina Jilin Petrochemical Co. 0.45
displaced all other commercial processes due
to its economic advantage with respect to pro-
duction and raw material costs. The continued
growth in demand for acrylonitrile worldwide
has spurred the development of several genera-
tions of new commercial catalysts with increas-
ing yields of acrylonitrile. The reported yields of
acrylonitrile from propylene have increased
from about 65% for the first commercial catalyst
to in excess of 80% with current complex
catalysts [11, 35, 7075].
The growth in the demand for acrylonitrile
has increased from about 3.5  106 t/a in 1986
to over 5  106 t/a. This represents a market
value of about $12  109. Acrylonitrile long-
term demand is expected to grow around 2% per
year. This requires addition one world-scale
production plant (typical capacity: 260 
103 t/a) every two to three years.
Installed worldwide production capacity for
acrylonitrile manufacture by propylene am-
moxidation is about 6  106 t/a. In addition,
catalytic ammoxidation process technology that
replaces propylene with propane feedstock has
been installed in a plant in Thailand having 200
 103 t/a acrylonitrile production capacity.
Table 7 lists the major producers of acrylonitrile
globally with associated production capacities.
Table 8 gives the regional distribution of
acrylonitrile production capacity. Acrylonitrile
produced in the USA has increasingly targeted
the export market, primarily to China. The
production capacity in Asia has grown

Table 8. Regional distribution of acrylonitrile production capacity, 106 t/a [76]

Region 2009 Actual 2010 Actual 2011 Estimate 2015 Forecast Distribution, %

North America 1.612 1.531 1.531 1.531 22.8

South America 0.088 0.088 0.088 0.088 1.3
Western Europe 0.881 0.840 0.840 0.840 12.5
Eastern Europe 0.262 0.262 0.262 0.262 3.9
Middle East 0.092 0.092 0.092 0.092 1.4
Asia Pacific 2.966 2.974 3.213 3.909 58.1
Total 5.901 5.787 6.026 6.722 100.0
8 Acrylonitrile
substantially in order to satisfy the growing
domestic demand for manufacture of acryloni-
trile-derived products, especially acrylic
fiber. In contrast, production capacity in the
USA and Europe has declined. It is expected
that this trend will continue accompanied by the
addition of production capacity in the Middle
East.
9. Environmental Protection
Effective safeguards, including emission con-
trols, pollution controls, and containment sys-
tems, are required to prevent or minimize the
release of acrylonitrile to the environment dur-
ing manufacture, handling, storage, and use.
Acrylonitrile is moderately toxic to aquatic life
with ecotoxicity of:
. LC50 Fathead Minnows 10.1 mg L1 96 h1
. IC50 Algae 10.95 mg L1 72 h1
It will degrade slowly in aquatic environ-
ments. In the atmosphere, acrylonitrile degrades
by photooxidation and will contribute to the
formation of smog by photochemical reaction
with volatile substances in air.
10. Toxicology and Occupational
Health
Acrylonitrile is toxic if ingested, inhaled, or
absorbed through the skin. It is corrosive as a
liquid or concentrated vapor causing skin burns
resembling second degree burns. Overexposure
to its vapors causes severe conjunctival and
respiratory irritation as well as headache, nau-
sea, vomiting, weakness, and dizziness. Extend-
ed exposure can lead to drowsiness, seizures,
hallucinations, loss of consciousness, and death.
These toxic effects may be delayed from any-
where between a few minutes to several hours
after exposure.
Acrylonitrile is a suspected cancer hazard
with the risk of cancer dependent on the level
and duration of exposure. It has been shown to
be weakly mutagenic in vitro but not in vivo
studies. Animal studies have shown harmful
effects on the developing fetus and on
reproduction when the mother is exposed to
toxic levels of acrylonitrile. Embryotoxic and
teratogenic effects have also been observed in
animals from exposure of the mother to toxic
doses. Studies conducted on acrylonitrile work-
ers in China have reported higher than expected
rates of reproductive effects and abnormal fetal
development. However, the reliability of these
studies has been questioned because of uncer-
tainties about data collection methodology,
chemical exposures, social and lifestyle influ-
ences, and inconsistencies with other informa-
tion [78].
It has also been reported that there is no clear
evidence that a relationship exists between in-
cidences of specific tumors and acrylonitrile
exposure based on epidemiological studies. The
data to date on occupational levels of human
exposure do not indicate a definitive correlation
between acrylonitrile and cancer. An analysis of
epidemiology studies concluded that the
results do not support a causal relationship
between acrylonitrile and all cancers or any
specific type of cancer [77]. Nevertheless,
acrylonitrile should be treated as a potential
carcinogen. Exposure levels should be kept as
low as possible. Any contact with liquid acry-
lonitrile is to be avoided.
The combustion products of acrylonitrile are
highly toxic including hydrogen cyanide, nitro-
gen dioxide, and carbon monoxide.
In the United States, the Occupational Safety
and Health Administration regulates acryloni-
trile as a cancer hazard (29 CFR 1910.1045).
The Permissible Exposure Limit (PEL) is 2 ppm
in air averaged over an 8 h period (Time
Weighted Average TWA). The Ceiling Limit
(CL) is 10 ppm averaged over a 15 min period.
Odor is a poor warning for acrylonitrile expo-
sure since the odor threshold is in the range of 13
to 20 ppm which is well above both the PEL and
CL. Toxicity levels for acrylonitrile have been
defined as follows [78]:
. Oral toxicity rat LD50 81 mg/kg
. Inhalation toxicity rat LC50 557 ppm/4 h,
946 ppm/4 h (by nose/sinuses); rat LCL0 >
1008 ppm/1 h
. Dermal toxicity rabbit LD50 226250 mg/kg
Table 9 lists occupational exposure limits for
various countries.

Table 9. Sample of acrylonitrile occupational exposure limits [19]
Country Time-weighted average(TWA) (usually 8 hours)
Australia 2 ppm; category 2 probable human carcinogen, skin
France 2 ppm (4.5 mg/m3)
Germany 3 ppm (TRK); A2 carcinogen, unmistakably carcinogenic
in animal experimentation only, skin
Hungary
Japan 2 ppm; skin
Russia 0.5 mg/m3
Sweden 2 ppm
United Kingdom 2 ppm; skin
United States OSHA-PEL 2 ppm; action level 1 ppm; skin
NIOSH-REL 1 ppm; occupational carcinogen, skin
ACGIH-TLV 2 ppm
A3 confirmed animal carcinogen with unknown
relevance to humans; skin
The National Institute for Occupational
Safety and Health (NIOSH) has designated
acrylonitrile as an occupational carcinogen. The
Recommended Exposure Limit (REL) for acry-
lonitrile set by NIOSH is ppm time-weighted
average over 8 h with a 10 ppm ceiling for 15
min. NIOSH has also established an Immedi-
ately Dangerous to Life and Health (IDLH)
value for acrylonitrile of 85 ppm. The Interna-
tional Agency for Research on Cancer (IARC)
downgraded acrylonitrile from a probable to a
possible human carcinogen, classification 2B.
Subsequently, the American Conference of
Governmental Industrial Hygienists (ACGIH)
revised their classification of acrylonitrile from
A2 suspected human carcinogen to A3
confirmed animal carcinogen with unknown
relevance to humans. The ACGIH Threshold
Limit Value (TLV) for acrylonitrile is 2 ppm
time-weighted average over eight hours [19].
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Acrylonitrile 9
Short term exposure limit (STEL) (usually 15 min)
15 ppm (32.5 mg/m3)
2 ppm, ceiling
1.5 mg/m3 ceiling
6 ppm; carcinogen; skin
10 ppm, ceiling
10 ppm, ceiling; IDLH85 ppm
(immediately dangerous to life or health)
not specified
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10 Acrylonitrile
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Seely, M.S. Friedrich, D.D. Suresh).
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Jevne, M.J. Seely).
74 INEOS USA LLC, US 7348291, 2008 (C. Paparizos, S.C. Jevne,
M.J. Seely).
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78 Material Safety Data Sheet Number 0000000892, INEOS USA
LLC, League City, Texas, 2009, www.ineosnitriles.com.