You are on page 1of 10


JAMES F. BRAZDIL, INEOS Technologies, Naperville Illinois, USA 60563

1. Introduction. . . . . . . . . . . . . . . . . . . . . 1 6. Analysis . . . . . . . . . . . . . . . . . . . . . . . . 6
2. Physical and Chemical Properties . . . . 2 7. Storage and Transportation. . . . . . . . . 6
3. Production . . . . . . . . . . . . . . . . . . . . . . 3 8. Economic Aspects . . . . . . . . . . . . . . . . 7
4. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 9. Environmental Protection . . . . . . . . . . 8
5. Quality Specifications . . . . . . . . . . . . . 6 10. Toxicology and Occupational Health. . 8

1. Introduction step was diethylamine. This was followed by

liquid-phase or vapor-phase dehydration of the
Acrylonitrile [107-13-1] is a key intermediate cyanohydrin. The liquid-phase dehydration was
in the chemical industry for production of a performed at about 200 C using alkali metal or
wide range of products. It is also referred to as alkaline earth metal salts of organic acids,
2-propenenitrile, propenenitrile, acrylic acid primarily formates and magnesium carbonate.
nitrile, propylene nitrile, vinyl cyanide, and Vapor-phase dehydration was accomplished
propenoic acid nitrile. Its chemical formula is over alumina at about 250 C.
C3H3N having a molecular mass of 53.064 and In addition, DuPont, American Cyanamid,
the following chemical structure. and Monsanto produced acrylonitrile on a com-
mercial scale by catalytic addition of HCN to
acetylene [4].
Acrylonitrile is produced commercially via C2 H2 HCN!C3 H3 N
the propylene ammoxidation process (also The process is catalyzed by cuprous chloride
known as the SOHIO process), first commer- in a dilute hydrochloric acid solution using a
cialized in 1960, by the reaction of propylene, stoichiometric excess of acetylene.
ammonia, and oxygen in presence of a hetero- Commercial use of cyanohydrin- and acety-
geneous catalyst. lene-based processes ceased by 1970. They
C3 H6 NH3 1:5 O2 !C3 H3 N3 H2 O were replaced by the lower-cost propylene
ammoxidation process.
Prior to the discovery of the propylene am-
Other chemical routes to acrylonitrile are:
moxidation process, acrylonitrile was largely
produced commercially via the ethylene cyano- . acetaldehyde and HCN [5]
hydrin process [13].
C2 H4 OHCN! HOC2 H4 CN!C3 H3 NH2 O

This process was practiced by American . propionitrile dehydrogenation [6, 7]

Cyanamid and Union Carbide in the United
CH3 CH2 CN!C3 H3 NH2
States and by I. G. Farben in Germany. The
process involved the production of ethylene . propylene and nitric oxide [8, 9]
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 C3 H6 1:5 NO!C3 H3 N1:5 H2 O0:25 N2

 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

2 Acrylonitrile

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

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

process is HCN (about 0.1 kg per kg of acrylo- light ends, and high boiling impurities. Disposal
nitrile), which is used primarily in the manufac- of the process impurities has become an increas-
ture of methyl methacrylate (CH2C(CH3) ingly important aspect of the overall process,
COOCH3 [80-62-6]) and sodium cyanide with significant attention being given to devel-
[143-33-9]. Another useful coproduct that can oping cost-effective and environmentally
be recovered from the process is acetonitrile acceptable methods for treatment of the process
(CH3CN [75-05-8]) in typical yields of about waste streams. Current methods include deep-
0.03 kg per kg of acrylonitrile produced. Ace- well disposal, wet air oxidation, ammonium
tonitrile finds commercial use as an important sulfate separation, biological treatment, and
solvent in pharmaceutical manufacture and incineration.
other industrial solvent applications. Although acrylonitrile manufacture from
In the commercial practice of acrylonitrile propylene and ammonia was first patented in
manufacture, the hot reactor effluent is 1949 [36], it was not until 1959, when SOHIO
quenched with water in a countercurrent absorb- developed a catalyst capable of producing
er and unreacted ammonia is neutralized with acrylonitrile with high selectivity, that commer-
sulfuric acid. The resulting ammonium sulfate cial manufacture from propylene became
can be recovered and used as a fertilizer. The economically viable [11]. Improvement in the
absorber off-gas containing primarily N2, CO, process since then has resulted primarily from
CO2, and unreacted propylene is either vented the development of new catalysts with increased
directly or first passed through an incinerator to yields of acrylonitrile from propylene. These
combust the hydrocarbons and CO. The acrylo- catalysts are multi-component mixed metal oxi-
nitrile-containing solution from the absorber is des mostly based on bismuthmolybdenum
passed to a recovery column that produces a oxide. The evolutionary development of the
crude acrylonitrile stream overhead that also multi-component molybdate-based ammoxida-
contains HCN. The column bottoms are passed tion catalyst has been described [37]. The first
to a second recovery column to remove water commercial production of acrylonitrile by SO-
and produce a crude acetonitrile mixture. The HIO used the Bi9PMo12O52 bismuth-phospho-
crude acetonitrile is either incinerated or further molybdate propylene ammoxidation catalyst
treated to produce solvent quality acetonitrile. supported on silica [35] with bismuth molyb-
Acrylic fiber quality (99.2% minimum) acrylo- date being the catalytically active phase. Higher
nitrile is obtained by fractionation of the crude yields of acrylonitrile and nitrile products were
acrylonitrile mixture to remove HCN, water, progressively achieved with the incorporation
Acrylonitrile 5

of iron molybdates [38, 39]. Further improve- Table 5. End-uses of acrylonitrile

ment was realized with the incorporation of Product %
cobalt and nickel [40] molybdates along with
iron. Promotion with an alkali metal, e.g., Acrylic fiber 42
ABS resins 34
potassium provides a further improvement in Adiponitrile 8
selectivity to acrylonitrile [41]. Acrylamide 7
Although the vast majority of acrylonitrile is Nitrile rubber 5
produced using molybdate-based catalysts, Carbon fiber 2
Other 2
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 especially in the airline and automobile
today [4245]. industries.
Because of the commercial importance of Acrylic fiber is primarily used in the manu-
propylene (amm)oxidation technology, a signif- facture of apparel and home furnishings
icant amount of research has been conducted to (! Fibers, 8. Polyacrylonitrile Fibers,
elucidate the surface reaction chemistry and ! Fibers 5. Synthetic Inorganic, Chapter 5).
solid state mechanisms of bismuth molybdate- The growth in the acrylic fiber market has
based catalysts [4651]. Kinetic studies with declined compared to other uses of acrylonitrile.
deuterated propylene have shown the rate-de- Much of the acrylic fiber manufacturing capac-
termining step to be abstraction of the a-hydro- ity has moved from the U.S. and Europe to Asia,
gen of propylene by an oxygen in the catalyst to particularly to China.
form a p-allyl complex on the surface. Acrolein ABS is a specialty high performance
forms by further hydrogen abstraction and in- polymer used mainly because of its high
sertion of lattice oxygen. Insertion of nitrogen to strength, coloring characteristics, and proces-
form acrylonitrile occurs when isoelectronic sing ease. It is used in numerous automotive,
NH2 is present on the surface in the presence construction, appliance, and electronics appli-
of ammonia according to the following: cations (! Polystyrene and Styrene Copoly-
mers, Chapter 5, ! Polystyrene and Styrene
NH3 O2 surface lattice!NH2 surfaceH2 O
Copolymers, Chapter 2, and ! Polystyrene and
Further fundamental understanding of the Styrene Copolymers, Section 4.1). SAN copo-
complex solid state and surface mechanisms of lymers are optically transparent and as such are
propylene ammoxidation over bismuth molyb- used in packaging, optical fibers, food contain-
date-based catalysts has been obtained by ers among other applications.
Raman-spectroscopic analysis [52, 53], X-ray, Adiponitrile is used to manufacture hexam-
and neutron diffraction [5459], X-ray absorp- ethylenediamine (HMDA, C6H16N2 [124-09-
tion spectroscopy [60, 61], pulse-kinetic stud- 4]) by electrohydrodimerization, see ! Hex-
ies [51], and probe molecule investigations [62]. amethylenediamine, Chapter 4 and [32].
HMDA is the raw material for making
4. Uses Acrylamide is manufactured from acryloni-
trile by a copper-catalyzed process (! Acrylic
The major end use of acrylonitrile are acrylic Acid and Derivatives, Chapter 3) [2831].
fiber, acrylonitrilebutadienestyrene (ABS) When polymerized, it finds large scale applica-
resins, adiponitrile (NC(CH2)4CN [111-69- tion in wastewater treatment, oil production,
3]), acrylamide (CH2CHC(O)NH2 [79-06- mineral processing, and paper manufacture.
1]), nitrile rubbers, and carbon fibers. Acrylic Nitrile rubbers are butadieneacrylonitrile
fiber is the largest commercial use for acryloni- copolymers that are used in the industry because
trile as shown in Table 5. ABS and acrylamide of their chemical, oil, and ozone resistance
are expected to be the fastest growing uses for along with high flexibility, stability, and heat
acrylonitrile with carbon fiber also increasing resistance (! Rubber, 4. Emulsion Rubbers,
for high strength and low weight applications 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 Table 7. Major acrylonitrile producers 2010
sample should be measured. If the pH is above Company Capacity, 106 t/a
7.3, this is an indication of ionic polymerization
which is accompanied by the production of INEOS 1.3
Asahi Kasei Chemicals 0.75
ammonia. The temperature should be monitored Ascend Performance Materials 0.51
for an increase that would indicate reaction of PetroChina Jilin Petrochemical Co. 0.45
acrylonitrile. Also the level of MEHQ should be
checked to ensure that the inhibitor is not being
lost. displaced all other commercial processes due
Storage, signage, and labeling of acryloni- to its economic advantage with respect to pro-
trile are regulated nationally and internationally duction and raw material costs. The continued
by the applicable governmental entities. In the growth in demand for acrylonitrile worldwide
United States, the safe use, handling, and has spurred the development of several genera-
storage of acrylonitrile and acrylonitrile-based tions of new commercial catalysts with increas-
materials are regulated by the Occupational ing yields of acrylonitrile. The reported yields of
Safety and Health Administration (29 CFR acrylonitrile from propylene have increased
1910.1045). Transportation of acrylonitrile in from about 65% for the first commercial catalyst
the United States is regulated by the U.S. De- to in excess of 80% with current complex
partment of Transportation (DOT), in Canada catalysts [11, 35, 7075].
by the Canadian Regulations for the Transport The growth in the demand for acrylonitrile
of Dangerous Goods (TDG), and internationally has increased from about 3.5  106 t/a in 1986
by ADR/RID, ADN/ADNR, IATA, and the to over 5  106 t/a. This represents a market
International Maritime Organization (IMDG). value of about $12  109. Acrylonitrile long-
term demand is expected to grow around 2% per
. Hazard Class: 3 (6.1) year. This requires addition one world-scale
. UN/NA Code: UN1093 production plant (typical capacity: 260 
. Packing Group: PG I 103 t/a) every two to three years.
. Bill of Lading Description: UN1093, Acrylo- Installed worldwide production capacity for
nitrile, Stabilized, 3(6.1), PG I, FP 1 C, acrylonitrile manufacture by propylene am-
Marine Pollutant moxidation is about 6  106 t/a. In addition,
. Labels Required: Flammable Liquid and catalytic ammoxidation process technology that
Toxic, Marine Pollutant mark required replaces propylene with propane feedstock has
. Placards Required: Flammable Liquid and been installed in a plant in Thailand having 200
Toxic  103 t/a acrylonitrile production capacity.
Table 7 lists the major producers of acrylonitrile
globally with associated production capacities.
8. Economic Aspects Table 8 gives the regional distribution of
acrylonitrile production capacity. Acrylonitrile
Beginning with the first commercial plant by produced in the USA has increasingly targeted
SOHIO in 1960, the propylene ammoxidation the export market, primarily to China. The
process for manufacturing acrylonitrile has 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 reproduction when the mother is exposed to
domestic demand for manufacture of acryloni- toxic levels of acrylonitrile. Embryotoxic and
trile-derived products, especially acrylic teratogenic effects have also been observed in
fiber. In contrast, production capacity in the animals from exposure of the mother to toxic
USA and Europe has declined. It is expected doses. Studies conducted on acrylonitrile work-
that this trend will continue accompanied by the ers in China have reported higher than expected
addition of production capacity in the Middle rates of reproductive effects and abnormal fetal
East. development. However, the reliability of these
studies has been questioned because of uncer-
tainties about data collection methodology,
chemical exposures, social and lifestyle influ-
9. Environmental Protection
ences, and inconsistencies with other informa-
tion [78].
Effective safeguards, including emission con-
It has also been reported that there is no clear
trols, pollution controls, and containment sys-
evidence that a relationship exists between in-
tems, are required to prevent or minimize the
cidences of specific tumors and acrylonitrile
release of acrylonitrile to the environment dur-
exposure based on epidemiological studies. The
ing manufacture, handling, storage, and use.
data to date on occupational levels of human
Acrylonitrile is moderately toxic to aquatic life
exposure do not indicate a definitive correlation
with ecotoxicity of:
between acrylonitrile and cancer. An analysis of
. LC50 Fathead Minnows 10.1 mg L1 96 h1 epidemiology studies concluded that the
. IC50 Algae 10.95 mg L1 72 h1 results do not support a causal relationship
between acrylonitrile and all cancers or any
It will degrade slowly in aquatic environ- specific type of cancer [77]. Nevertheless,
ments. In the atmosphere, acrylonitrile degrades acrylonitrile should be treated as a potential
by photooxidation and will contribute to the carcinogen. Exposure levels should be kept as
formation of smog by photochemical reaction low as possible. Any contact with liquid acry-
with volatile substances in air. lonitrile is to be avoided.
The combustion products of acrylonitrile are
highly toxic including hydrogen cyanide, nitro-
gen dioxide, and carbon monoxide.
10. Toxicology and Occupational In the United States, the Occupational Safety
Health and Health Administration regulates acryloni-
trile as a cancer hazard (29 CFR 1910.1045).
Acrylonitrile is toxic if ingested, inhaled, or The Permissible Exposure Limit (PEL) is 2 ppm
absorbed through the skin. It is corrosive as a in air averaged over an 8 h period (Time
liquid or concentrated vapor causing skin burns Weighted Average TWA). The Ceiling Limit
resembling second degree burns. Overexposure (CL) is 10 ppm averaged over a 15 min period.
to its vapors causes severe conjunctival and Odor is a poor warning for acrylonitrile expo-
respiratory irritation as well as headache, nau- sure since the odor threshold is in the range of 13
sea, vomiting, weakness, and dizziness. Extend- to 20 ppm which is well above both the PEL and
ed exposure can lead to drowsiness, seizures, CL. Toxicity levels for acrylonitrile have been
hallucinations, loss of consciousness, and death. defined as follows [78]:
These toxic effects may be delayed from any-
where between a few minutes to several hours . Oral toxicity rat LD50 81 mg/kg
after exposure. . Inhalation toxicity rat LC50 557 ppm/4 h,
Acrylonitrile is a suspected cancer hazard 946 ppm/4 h (by nose/sinuses); rat LCL0 >
with the risk of cancer dependent on the level 1008 ppm/1 h
and duration of exposure. It has been shown to . Dermal toxicity rabbit LD50 226250 mg/kg
be weakly mutagenic in vitro but not in vivo
studies. Animal studies have shown harmful Table 9 lists occupational exposure limits for
effects on the developing fetus and on various countries.
Acrylonitrile 9

Table 9. Sample of acrylonitrile occupational exposure limits [19]

Country Time-weighted average(TWA) (usually 8 hours) Short term exposure limit (STEL) (usually 15 min)

Australia 2 ppm; category 2 probable human carcinogen, skin

France 2 ppm (4.5 mg/m3) 15 ppm (32.5 mg/m3)
Germany 3 ppm (TRK); A2 carcinogen, unmistakably carcinogenic
in animal experimentation only, skin
Hungary 2 ppm, ceiling
Japan 2 ppm; skin
Russia 0.5 mg/m3 1.5 mg/m3 ceiling
Sweden 2 ppm 6 ppm; carcinogen; skin
United Kingdom 2 ppm; skin
United States OSHA-PEL 2 ppm; action level 1 ppm; skin 10 ppm, ceiling
NIOSH-REL 1 ppm; occupational carcinogen, skin 10 ppm, ceiling; IDLH85 ppm
(immediately dangerous to life or health)
ACGIH-TLV 2 ppm not specified
A3 confirmed animal carcinogen with unknown
relevance to humans; skin

The National Institute for Occupational 9 E. I. du Pont de Nemours, US 3184415, 1965 (E.B. Huntley, J.M.
Safety and Health (NIOSH) has designated Kruse, J.W. Way).
10 Ch. Moureau, Ann. Chim. Phys. 2 (1894) 187.
acrylonitrile as an occupational carcinogen. The 11 The Standard Oil Co., US 2904580, 1959 (J.D. Idol).
Recommended Exposure Limit (REL) for acry- 12 Distillers Company, GB 876446, 1959; US 3152170, 1964 (J.L.
lonitrile set by NIOSH is ppm time-weighted Barclay, J.B. Bream, D.J. Hadley, D.G. Stewart).
average over 8 h with a 10 ppm ceiling for 15 13 R.K. Grasselli, J.D. Burrington, J.F. Brazdil, Faraday Discus-
sions 72 (1982) 203.
min. NIOSH has also established an Immedi- 14 American Cyanamid, The Chemistry of Acrylonitrile, New York
ately Dangerous to Life and Health (IDLH) 1951, pp. 1119.
value for acrylonitrile of 85 ppm. The Interna- 15 Monsanto Chem., Acrylonitrile Handling and Storage, Pub. No.
tional Agency for Research on Cancer (IARC) 162, Jan. 1982.
16 J.F. Brazdil: Acrylonitrile, in Kirk-Othmer Encyclopedia of
downgraded acrylonitrile from a probable to a Chemical Technology, 4th ed., vol. 1, Wiley-Interscience, New
possible human carcinogen, classification 2B. York 1991, pp. 352369.
Subsequently, the American Conference of 17 M.A. Dalin, I.K. Kolchin, B.R. Serebryakov: Acrylonitrile,
Governmental Industrial Hygienists (ACGIH) Technomic, Westport, Conn., 1971, pp. 161162.
18 H.S. Davis, O.F. Wiedeman, Ind. Eng. Chem. 37 (1945) 482.
revised their classification of acrylonitrile from 19 INEOS Acrylonitrile Safe Storage and Handling Guide 2007 and
A2 suspected human carcinogen to A3 references therein;
confirmed animal carcinogen with unknown plugins/filemanager/files/2007_acrylonitrile_brochure.pdf (ac-
relevance to humans. The ACGIH Threshold cessed: March 2, 2012) .
20 L.H. Horsley, Anal. Chem. 19 (1947) 509.
Limit Value (TLV) for acrylonitrile is 2 ppm 21 M.A. Dalin, I.K. Kolchin, B.R. Serebryakov: Acrylonitrile,
time-weighted average over eight hours [19]. Technomic, Westport, Conn., 1971, p. 166.
22 N.M. Sokolov, Rev. Chim. 20 (1969) 169.
23 N.M. Sokolov, Proc. Int. Symp. Distill. 3 (1969) 110.
24 N.M. Sokolov, N.N. Sevryugova, N.M. Zhavoronkor, Theor.
References Osn. Khim. Tekhnol. 3 (1969) 449.
25 C.E. Funk, Jr., Ind. Eng. Chem. 43 (1951) 1153.
1 American Cyanamid Co., US 2690452, 1954 (E.L. Carpenter). 26 M.A. Dalin, I.K. Kolchin, B.R. Serebryakov: Acrylonitrile,
2 Stamicarbon N.V., US 2729670, 1956 (P.H. DeBruin). Technomic, Westport, Conn., 1971, pp. 120159.
3 Chem. Eng. News 23 no. 20, 1841 (Oct. 25, 1945). 27 American Cyanamid, The Chemistry of Acrylonitrile, New York
4 D.J. Hadley, E.G. Hancock (eds.): Propylene and Its Industrial 1951, pp. 2151.
Derivatives, Halsted Press, New York 1973, p. 418. 28 The Dow Chemical Company, US 3597481, 1971; US 3631104,
5 K. Sennewald: 5th World Petroleum Congress Proceedings, 1971; US Re 31430, 1983 (B.A. Tefertiller, C.E. Habermann).
Section IV, Paper 19, New York 1959, pp. 217227. 29 American Cyanamid, US 4048226, 1977 (W.A. Barber, J.A.
6 E. I. du Pont de Nemours, US 2554482, 1951 (N. Brown). Fetchin).
7 Rohm and Haas, US 2385552, 1945, (L.R.U. Spence, 30 American Cyanamid, US 4086275, 1978 (K. Matsuda, W.A.
F.O. Haas). Barber).
8 E. I. du Pont de Nemours, US 2736739, 1956 (D.C. England, 31 American Cyanamid, US 4178310, 1979 (J.A. Fetchin, K.H.
G.V. Mock). Tsu).
10 Acrylonitrile

32 Monsanto Chemical Co., US 3193480, 1965 (M.M. Baizer, C.R. 59 A.W. Sleight, in J.J. Burton, R.L. Garten (eds.): Advanced
Campbell, R.H. Fariss, R. Johnson). Materials in Catalysis, Academic Press, New York 1977, pp.
33 Imperial Chemical Industries Australia, US 3529011, 1970 (J. 181208.
W. Badham). 60 M.R. Antonio, R.G. Teller, D.R. Sandstrom, M. Mehicic, J.F.
34 Imperial Chemical Industries, EP 314383, 1989 (G. Shaw, J. Brazdil, J. Phys. Chem. 92 (1988) 2939.
Lopez-Merono). 61 M.R. Antonio, J.F. Brazdil, L.C. Glaeser, M. Mehicic, R.G.
35 J.L. Callahan, R.K. Grasselli, E.C. Milberger, H.A. Strecker, Ind. Teller, J. Phys. Chem. 92 (1988) 2338.
Eng. Chem. Prod. Res. Dev. 9 (1970) 134. 62 R.K. Grasselli, J.D. Burrington, Adv. Catal. 30 (1981) 133.
36 Allied Chemical & Dye Corp., US 2481826, 1949 (J.N. Cosby). 63 INEOS Acrylonitrile USA Product Specifications; www.ineos-
37 J.F. Brazdil, M.A. Toft: Ammoxidation in I.T. Horvath
(ed.): Encyclopedia of Catalysis, Wiley 2010, DOI: 10.1002/ tions.pdf (accessed March 2, 2012).
0471227167. 64 M.A. Dalin, I.K. Kolchin, B.R. Serebryakov: Acrylonitrile,
38 Knapsack-Griesheim, US 3226422, 1965 (K. Sennewald, W. Technomic, Westport, Conn., 1971, pp. 163165.
Vogt, J. Kandler, R. Sommerfeld, G. Sorbe). 65 Annual Book of ASTM Standards, E 1178-97, American Society
39 Knapsack-Griesheim, US Re 27718, 1973 (K. Sennewald, W. for Testing and Materials, Philadelphia, Pa., 1999.
Vogt, J. Kandler, R. Sommerfeld, G. Sorbe). 66 Annual Book of ASTM Standards, E 203-96, American Society
40 Nippon Kayaku Co., US 3454630, 1969 (G. Yamaguchi, S. for Testing and Materials, Philadelphia, Pa., 1999.
Takenaka). 67 Annual Book of ASTM Standards, E 299-97, American Society
41 The Standard Oil Co., GB 1319190, 1973 (R.K. Grasselli, A.F. for Testing and Materials, Philadelphia, Pa., 1999.
Miller, H.F. Hardman). 68 American Society for Testing and Materials: Standard Test
42 Nitto Chemical Industry Co., US 3716496, 1973 (T. Yoshino, S. Method for Water Using Karl Fischer Reagent, Annual Book
Saito, Y. Sasaki). of ASTM Standards, Philadelphia, Pa., 1982, Part 30, E-203,
43 Nitto Chemical Industry Co., US 3542843, 1970 (T. Yoshino, S. 815824.
Saito, Y. Sasaki, I. Nagase). 69 American Society for Testing and Materials: Standard Test
44 Nitto Chemical Industry Co., US 3591620, 1971 (T. Yoshino, S. Method for Trace Amounts of Peroxides in Organic Solvents,
Saito, Y. Sasaki, K. Moriya). Annual Book of ASTM Standards, Philadelphia, Pa., 1982, Part
45 Dia-Nitrix Co., US 8034736, 2011 (K. Miyaki, M. Yanagita, H. 30, E-299, 909912.
Watanabe, T. Karasuda). 70 The Standard Oil Co., US 4503001, 1985 (R.K. Grasselli, A.F.
46 J.D. Burrington, C.T. Kartisek, R.K. Grasselli, J. Catal. 87 Miller, H.F. Hardman).
(1984) 363. 71 The Standard Oil Co., US 6458742, 2002 (C. Paparizos, M.J.
47 C.R. Adams, T.J. Jennings, J. Catal. 2 (1963) 63. Seely, M.S. Friedrich, D.D. Suresh).
48 C.R. Adams, T.J. Jennings, J. Catal. 3 (1964) 549. 72 The Standard Oil Co., US 6965046, 2005 (C. Paparizos, M.J.
49 G.W. Keulks, J. Catal. 19 (1970) 232. Seely, M.S. Friedrich, D.D. Suresh).
50 G.W. Keulks, L.D. Krenzke, J. Catal. 61 (1980) 316. 73 The Standard Oil Co., US 7071140, 2006 (C. Paparizos, S.C.
51 J.F. Brazdil, D.D. Suresh, R.K. Grasselli, J. Catal. 66 (1980) Jevne, M.J. Seely).
347. 74 INEOS USA LLC, US 7348291, 2008 (C. Paparizos, S.C. Jevne,
52 J.F. Brazdil, L.C. Glaeser, R.K. Grasselli, J. Catal. 81 (1983) M.J. Seely).
142. 75 INEOS USA LLC, US 2011/0233460, 2011 (J.F. Brazdil, M.A.
53 L.C. Glaeser, J.F. Brazdil, M.A. Hazle, M. Mehicic, R.K. Grass- Toft, C.J. Besecker, M.J. Seely).
elli, J. Chem. Soc. Faraday Trans. 1 81 (1985) 2903. 76 Nexant, Inc.s ChemSystems PERP report Acrylonitrile, 09/10-
54 R.G. Teller, J.F. Brazdil, R.K. Grasselli, Acta Cryst. C 40 (1984) 2, Mew York November 2011.
2001. 77 P. Cole, J.S. Mandel, J.J. Collins, Regul. Toxicol. Pharmacol. 52
55 R.G. Teller, J.F. Brazdil, R.K. Grasselli, R.T.L. Corliss, J. (2008) 342.
Hastings, J. Solid State Chem. 52 (1984) 313. 78 Material Safety Data Sheet Number 0000000892, INEOS USA
56 R.G. Teller, J.F. Brazdil, R.K. Grasselli, W. Yelon, J. Chem. Soc. LLC, League City, Texas, 2009,
Faraday Trans. 1 81 (1985) 1693.
57 J.F. Brazdil, R.K. Grasselli, J. Catal. 79 (1983) 104.
58 J.F. Brazdil, L.C. Glaeser, R.K. Grasselli, J. Phys. Chem. 87
(1983) 5485.