Acrylonitrile: Production, Properties, and Applications

Acrylonitrile ULLMANNS AWN iIn JAmEs F BrazpiL INEOS Technologies Naperville Illinois USA 60563 Z5 FER 249 a 1 Introduction 22 1 6 Analysis 0 c cece cece e cece 6 2 Physical and Chemical Properties 2 7 Storage and Transportation 6 3 Production0000085 3 8 Economic Aspects 7 4 1 OY a 9 Environmental Protection 8 5 Quality Specifications 6 10 Toxicology and Occupational Health 8 1 Introduction step was diethylamine This was followed by liquidphase or vaporphase dehydration of the Acrylonitrile 107131 is a key intermediate cyanohydrin The liquidphase dehydration was in the chemical industry for production of a performed at about 200C using alkali metal or wide range of products It is also referred to as alkaline earth metal salts of organic acids 2propenenitrile propenenitrile acrylic acid primarily formates and magnesium carbonate nitrile propylene nitrile vinyl cyanide and Vaporphase dehydration was accomplished propenoic acid nitrile Its chemical formula is over alumina at about 250C C3H3N having a molecular mass of 53064 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 HCCHCN acetylene 4 Acrylonitrile is produced commercially via CH HCNC3H3N 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 lenebased processes ceased by 1970 They C3HNH315 0CH3N3 HO were replaced by the lowercost propylene Prior to the discovery of the propylene am ammoxidation PTOCESS we er wpe Other chemical routes to acrylonitrile are moxidation process acrylonitrile was largely produced commercially via the ethylene cyano acetaldehyde and HCN 5 hydrin process 13 CyHyOLHCN HOCHCNC3HNH0 CHCHOHCNCH3CHOHCNC3H3NH3O This process was practiced by American propionitrile dehydrogenation 6 7 Cyanamid and Union Carbide in the United States and by I G Farben in Germany The CH3CH2CNC3H3NHz rocess involved the production of ethylene ae eyanohydrin by the basocatalyzed addition of propylene and nitric oxide 8 9 HCN to ethylene oxide in the liquid phase at about 60C A typical base catalyst used in this C3H615 NOC3H3N15 H20025 No 2012 WileyVCH Verlag GmbH Co KGaA Weinheim 10100214356007a01177pub3 2 Acrylonitrile e and dehydration of acrylamide 10 resins adiponitrile and acrylamide As a result CHCHCONEy CyENERO the installed annual production capacity for eee acrylonitrile has grown to more than 5000 x 3 None of these routes achieved largescale 10 ta 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 inthelate 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 conj ugated with acarboncarbon revolutionary process by SOHIO resulted in the double bond dramatic reduction of the cost of acrylonitrile production which in turn led to an exponential HCCHCN HCCHCN HC CHCN increase in acrylonitrile demand 13 for a wide range of chemical and polymer products Acryl Table 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 5306 gmol Density 0806 gmL at 20C Melting point 8355C Boiling point 7730C at 1013 kPa Refractive index np 13888 589 nm at 25C Miscibility in water 730 wt at 20C Miscibility of water in acrylonitrile 308 wt at 20C Viscosity 034 mms at 25C Dielectric constant 38 at 334 MHz Dipole moment 388 D neat vapor Vapor density 183 theoretical air 1 Critical pressure 3536 x 10 kPa Critical temperature 2458C Critical volume 3790 mLg Surface tension 2776 mNm at 151C 2753 mNm at 178C 2480 mNm at 406C Ionization potential 1075 eV by electron impact Heat of combustion liq 17618 kJmol Flammability limits in air Lower 30 vol at 25C Upper 170 vol at 25C Free energy of formation AG g 195 kJmol at 25C Enthalpy of formation AH 185 kJmol at 25C Enthalpy of formation AH 150 kJmol at 25C Enthalpy of vaporization AH evap 3265 kJmol at 25C Heat of polymerization 724 02 kJmol Molar heat capacity liquid 1111 kJ mol Ku Molar heat capacity vapor 641 kJ mol K7 50C 1013 kPa Molar heat of fusion 6615 kJmol Entropy gas 274 kJ mol K7 at 25C 1013 kPa Autoignition temperature 481C in air Flash point orc Thermal conductivity 166 kW m K7 at 23C Acrylonitrile 3 Table 2 Azeotropes of acrylonitrile 20 Table 4 Acrylonitrile vapor pressure over aqueous solutions at 25C Azeotrope Boiling Acrylonitrile Acrylonitrile wt Vapor pressure kPa point C concentration wt CSCS 1 13 Tetrachlorosilane 512 11 2 29 Water 710 88 3 53 Isopropyl alcohol 717 56 4 69 Benzene 733 47 5 84 Methanol 614 39 6 100 Carbon tetrachloride 662 21 7 109 Chlorotrimethylsilane 570 7 iii carbon tetrachloride diethyl ether ethyl ace C3H4O 79107 Acrylamide is also formed tate ethylene cyanohydrin petroleum ether directly from acrylonitrile by partial hydration toluene some kerosenes and methanol Com using copperbased 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 C4HO2 96333 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 107120 and pro polymerization and hydration 26 27 Acrylo pylamine C3HoN 107108 and the indus nitrile polymerizes readily and exothermically trially important hydrodimerization to produce in the absence of a hydroquinone inhibitor adiponitrile CsHgN 111693 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 C3HsNO H2SO 15497991 3 Production which can be converted to acrylamide C3HNO 79061 by neutralization with a base and Acrylonitrile is produced commercially by the complete hydration to give acrylic acid catalytic vaporphase 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 4005 10C and 0 71 21 50200 kPa gauge The process uses a stoichio 10 72 26 metric excess of ammonia and oxygen as air It 20 73 31 is a singlepass process with about 98 conver 30 75 39 40 79 43 sion of propylene that typically consumes about 50 84 63 11 kg of propylene per kilogram of acryloni 60 91 17 trile produced or less with the recent generations 70 99 92 of highly selective catalysts A commercially 80 11 109 vs a important coproduct from the acrylonitrile process is HCN about 01 kg per kg of acrylo nitrile which is used primarily in the manufac ture of methyl methacrylate CH2¼CCH3 COOCH3 80626 and sodium cyanide 143339 Another useful coproduct that can be recovered from the process is acetonitrile CH3CN 75058 in typical yields of about 003 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 offgas 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 nitrilecontaining 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 992 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 costeffective 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 multicomponent mixed metal oxi des mostly based on bismuthmolybdenum oxide The evolutionary development of the multicomponent molybdatebased ammoxida tion catalyst has been described 37 The first commercial production of acrylonitrile by SO HIO used the Bi9PMo12O52 bismuthphospho 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 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 4 Acrylonitrile Acrylonitrile 5 of iron molybdates 38 39 Further improve Table 5 Enduses of acrylonitrile ment was realized with the incorporation of Podt ge cobalt and nickel 40 molybdates along with iron Promotion with an alkali metal eg Acrylic fiber 42 ABS resins 34 potassium provides a further improvement in Adiponitile 8 selectivity to acrylonitrile 41 Acrylamide 7 Although the vast majority of acrylonitrile is Nitrile rubber 5 produced using molybdatebased catalysts Carbon fiber 2 Other 2 antimonate catalysts are also used commercial a ly The ironantimonyoxide 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 ammoxidation 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 ratede Much of the acrylic fiber manufacturing capac termining step to be abstraction of the ahydro ity has moved from the US and Europe to Asia gen of propylene by an oxygen in the catalyst to particularly to China form a 7rallyl 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 NH is present on the surface in the presence construction appliance and electronics appli of ammonia according to the following cations Polystyrene and Styrene Copoly 5 5 mers Chapter 5 Polystyrene and Styrene NH3O surface latticeNH surfaceH20 Copolymers Chapter 2 and Polystyrene and Further fundamental understanding of the Styrene Copolymers Section 41 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 datebased catalysts has been obtained by ers among other applications Ramanspectroscopic analysis 52 53 Xray Adiponitrile is used to manufacture hexam and neutron diffraction 5459 Xray absorp ethylenediamine HMDA CH6N2 12409 tion spectroscopy 60 61 pulsekinetic 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 nylon66 4 Uses Acrylamide is manufactured from acryloni trile by a coppercatalyzed 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 NCCH24CN 11169 tion in wastewater treatment oil production 3 acrylamide CHCHCONH 7906 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 manufacture of gaskets seals hoses belts and electrical cable jackets 5 Quality Specifications Typical commercial specifications for acryloni trile are given in Table 6 These acrylonitrile sales specifications are based on the require ments of the acrylic fiber producers the largest enduse for acrylonitrile 6 Analysis Standardized chemical analyses of acrylonitrile have been developed and published for ensuring product quality and meeting product specifica tions 6469 Among the most critical analyses are color determination HCN inhibitor and water content 7 Storage and Transportation Acrylonitrile is stored for commercial purposes in steel drums and tanks It is transported by pipeline by drums and by rail ship and barge in tanks Acrylonitrile is a toxic and flammable liquid and its vapors can readily form explosive mixtures in air at ambient conditions It must be stored in tightly sealed containers in a cool wellventilated area away from heat sources of ignition and incompatible chemicals Incom patible chemicals and materials to avoid are bromine ammonia amines copper and copper alloys strong acids strong bases eg potassi um hydroxide sodium hydroxide peroxides or other free radical initiators or strong oxidizers Suitable storage materials are carbon steel and stainless steel Storage equipment must be elec trically grounded Large storage tanks should be equipped with a vapor control system to prevent release of vapor to the atmosphere Available control systems include incineration recovery through a condenser absorption with a carbon filter and scrubbing Nonsparking tools should be used when opening or closing metal contain ers of acrylonitrile and containers must be bonded and grounded during transfer of liquid acrylonitrile Nitrogen blanketing over liquid acrylonitrile can be used to reduce the potential for combustion of its vapors In addition to flammability another primary hazard of acrylonitrile storage and handling is polymerization which is highly exothermic Prevention of rapid polymerization is best accomplished by ensuring that product specifi cations are met and avoidance of incompatible chemicals materials and conditions The spe cifications for acrylonitrile include the presence of a suitable inhibitor to prevent polymeriza tion The most commonly used inhibitor system is MEHQ hydroquinone monomethyl ether 150765 3545 ppm and water 02 to 05 wt MEHQ inhibits free radical polymeriza tion Water traps traces of acidic and basic reactive intermediates Complete absence of oxygen is to be avoided because the MEHQ inhibitor requires the presence of dissolved oxygen to prevent polymerization During com mercial manufacture handling and storage of acrylonitrile typically a sufficient quantity of dissolved oxygen is present to activate the MEHQ inhibitor Additional incompatible con ditions are exposure to ultraviolet light high heat and high pressure For any extended storage of acrylonitrile monitoring should be used for any signs of possible polymerization Samples should be taken to look for haziness of the liquid which is an indication of polymerization since poly acrylonitrile is insoluble in liquid acrylonitrile Table 6 Acrylonitrile product specifications 63 Properties Units Limit Acetone ppm 75 Acetonitrile ppm 150 Acidity ppm 15 Acrolein ppm 10 Aldehydes ppm 20 Appearance clear free of suspended matter Color APHA 10 Copper ppm 01 Hydrogen cyanide ppm 5 Inhibitor MEHQ ppm 3545 Iron ppm 01 Methacrylonitrile ppm 250 Methyl vinyl ketone ppm 10 Nonvolatile matter ppm 100 Oxazole ppm 80 Peroxide ppm 02 pH 6075 Titration value 01 N H2SO4 mL 2 Water wt 0205 6 Acrylonitrile Acrylonitrile 7 Also the pH of a5 wt aqueous solution of a Table 7 Major acrylonitrile producers 2010 sample should be measured If the pH is above Company SSstSsSapatity 10 73 this is an indication of ionic polymerization eo which is accompanied by the production of INEOS 13 Asahi Kasei Chemicals 075 ammonia The temperature should be monitored Ascend Performance Materials 051 for an increase that would indicate reaction of PetroChina Jilin Petrochemical Co 045 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 acrylonitrilebased 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 19101045 Transportation of acrylonitrile in from about 65 for the first commercial catalyst the United States is regulated by the US 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 35 x 10 ta in 1986 by ADRRID ADNADNR IATA and the to over 5 x 10 ta This represents a market International Maritime Organization IMDG value of about 12 x 10 Acrylonitrile long term demand is expected to grow around 2 per e Hazard Class 3 61 year This requires addition one worldscale e UNNA Code UN1093 production plant typical capacity 260 x e Packing Group PG I 10 ta every two to three years e Bill of Lading Description UN1093 Acrylo Installed worldwide production capacity for nitrile Stabilized 361 PG I FP 1C acrylonitrile manufacture by propylene am Marine Pollutant moxidation is about 6 x 10 ta In addition e Labels Required Flammable Liquid and catalytic ammoxidation process technology that Toxic Marine Pollutant mark required replaces propylene with propane feedstock has e Placards Required Flammable Liquid and been installed in a plant in Thailand having 200 Toxic x 10 ta 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 10 ta 76 Region 2009 Actual 2010 Actual 2011 Estimate 2015 Forecast Distribution North America 1612 1531 1531 1531 228 South America 0088 0088 0088 0088 13 Western Europe 0881 0840 0840 0840 125 Eastern Europe 0262 0262 0262 0262 39 Middle East 0092 0092 0092 0092 14 Asia Pacific 2966 2974 3213 3909 581 Total 5901 5787 6026 6722 1000 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 trilederived 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 9 Environmental Protection chemical exposures social and lifestyle influ ences and inconsistencies with other informa Effective safeguards including emission con tion 78 It has also been reported that there is no clear trols pollution controls and containment sys re evidence that a relationship exists between in tems are required to prevent or minimize the ws ws 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 ys a data to date on occupational levels of human Acrylonitrile is moderately toxic to aquatic life Lo ee with ecotoxicity of exposure do not indicate a definitive correlation between acrylonitrile and cancer An analysis of LCso Fathead Minnows 101 mg L 96 ho epidemiology studies concluded that the 1 1 results do not support a causal relationship e ICs Algae 1095 mg L 72h wees between acrylonitrile and all cancers or any It will degrade slowly in aquatic environ sp ecific type of cancer 77 Nevertheless sis acrylonitrile should be treated as a potential ments In the atmosphere acrylonitrile degrades ae carcinogen Exposure levels should be kept as by photooxidation and will contribute to the vp qs low as possible Any contact with liquid acry formation of smog by photochemical reaction wo lonitrile is to be avoided with volatile substances in air wo 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 19101045 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 8h 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 e Oral toxicity rat LDs9 81 mgkg after exposure e Inhalation toxicity rat LCsq 557 ppm4 h Acrylonitrile is a suspected cancer hazard 946 ppm4 h by nosesinuses rat LCLo with the risk of cancer dependent on the level 1008 ppm1 h and duration of exposure It has been shown to e Dermal toxicity rabbit LD5 226250 mgkg 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 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 timeweighted 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 timeweighted average over eight hours 19 References 1 American Cyanamid Co US 2690452 1954 EL Carpenter 2 Stamicarbon NV US 2729670 1956 PH DeBruin 3 Chem Eng News 23 no 20 1841 Oct 25 1945 4 DJ Hadley EG Hancock eds Propylene and Its Industrial Derivatives Halsted Press New York 1973 p 418 5 K Sennewald 5th World Petroleum Congress Proceedings Section IV Paper 19 New York 1959 pp 217227 6 E I du Pont de Nemours US 2554482 1951 N Brown 7 Rohm and Haas US 2385552 1945 LRU Spence FO Haas 8 E I du Pont de Nemours US 2736739 1956 DC England GV Mock 9 E I du Pont de Nemours US 3184415 1965 EB Huntley JM Kruse JW Way 10 Ch Moureau Ann Chim Phys 2 1894 187 11 The Standard Oil Co US 2904580 1959 JD Idol 12 Distillers Company GB 876446 1959 US 3152170 1964 JL Barclay JB Bream DJ Hadley DG Stewart 13 RK Grasselli JD Burrington JF Brazdil Faraday Discus sions 72 1982 203 14 American Cyanamid The Chemistry of Acrylonitrile New York 1951 pp 1119 15 Monsanto Chem Acrylonitrile Handling and Storage Pub No 162 Jan 1982 16 JF Brazdil Acrylonitrile in KirkOthmer Encyclopedia of Chemical Technology 4th ed vol 1 WileyInterscience New York 1991 pp 352369 17 MA Dalin IK Kolchin BR Serebryakov Acrylonitrile Technomic Westport Conn 1971 pp 161162 18 HS Davis OF Wiedeman Ind Eng Chem 37 1945 482 19 INEOS Acrylonitrile Safe Storage and Handling Guide 2007 and references therein wwwineosnitrilescomjscriptstinymce pluginsfilemanagerfiles2007acrylonitrilebrochurepdf ac cessed March 2 2012 20 LH Horsley Anal Chem 19 1947 509 21 MA Dalin IK Kolchin BR Serebryakov Acrylonitrile Technomic Westport Conn 1971 p 166 22 NM Sokolov Rev Chim 20 1969 169 23 NM Sokolov Proc Int Symp Distill 3 1969 110 24 NM Sokolov NN Sevryugova NM Zhavoronkor Theor Osn Khim Tekhnol 3 1969 449 25 CE Funk Jr Ind Eng Chem 43 1951 1153 26 MA Dalin IK Kolchin BR Serebryakov Acrylonitrile Technomic Westport Conn 1971 pp 120159 27 American Cyanamid The Chemistry of Acrylonitrile New York 1951 pp 2151 28 The Dow Chemical Company US 3597481 1971 US 3631104 1971 US Re 31430 1983 BA Tefertiller CE Habermann 29 American Cyanamid US 4048226 1977 WA Barber JA Fetchin 30 American Cyanamid US 4086275 1978 K Matsuda WA Barber 31 American Cyanamid US 4178310 1979 JA Fetchin KH Tsu Table 9 Sample of acrylonitrile occupational exposure limits 19 Country Timeweighted averageTWA usually 8 hours Short term exposure limit STEL usually 15 min Australia 2 ppm category 2 probable human carcinogen skin France 2 ppm 45 mgm3 15 ppm 325 mgm3 Germany 3 ppm TRK A2 carcinogen unmistakably carcinogenic in animal experimentation only skin Hungary 2 ppm ceiling Japan 2 ppm skin Russia 05 mgm3 15 mgm3 ceiling Sweden 2 ppm 6 ppm carcinogen skin United Kingdom 2 ppm skin United States OSHAPEL 2 ppm action level 1 ppm skin 10 ppm ceiling NIOSHREL 1 ppm occupational carcinogen skin 10 ppm ceiling IDLH85 ppm immediately dangerous to life or health ACGIHTLV 2 ppm not specified A3 confirmed animal carcinogen with unknown relevance to humans skin Acrylonitrile 9 32 Monsanto Chemical Co US 3193480 1965 MM Baizer CR Campbell RH Fariss R Johnson 33 Imperial Chemical Industries Australia US 3529011 1970 J W Badham 34 Imperial Chemical Industries EP 314383 1989 G Shaw J LopezMerono 35 JL Callahan RK Grasselli EC Milberger HA Strecker Ind Eng Chem Prod Res Dev 9 1970 134 36 Allied Chemical Dye Corp US 2481826 1949 JN Cosby 37 JF Brazdil MA Toft Ammoxidation in IT Horvath ed Encyclopedia of Catalysis Wiley 2010 DOI 101002 0471227167 38 KnapsackGriesheim US 3226422 1965 K Sennewald W Vogt J Kandler R Sommerfeld G Sorbe 39 KnapsackGriesheim US Re 27718 1973 K Sennewald W Vogt J Kandler R Sommerfeld G Sorbe 40 Nippon Kayaku Co US 3454630 1969 G Yamaguchi S Takenaka 41 The Standard Oil Co GB 1319190 1973 RK Grasselli AF Miller HF Hardman 42 Nitto Chemical Industry Co US 3716496 1973 T Yoshino S Saito Y Sasaki 43 Nitto Chemical Industry Co US 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Sleight in JJ Burton RL Garten eds Advanced Materials in Catalysis Academic Press New York 1977 pp 181208 60 MR Antonio RG Teller DR Sandstrom M Mehicic JF Brazdil J Phys Chem 92 1988 2939 61 MR Antonio JF Brazdil LC Glaeser M Mehicic RG Teller J Phys Chem 92 1988 2338 62 RK Grasselli JD Burrington Adv Catal 30 1981 133 63 INEOS Acrylonitrile USA Product Specifications wwwineos nitrilescommediafilesUS20Acrylonitrile20Specifica tionspdf accessed March 2 2012 64 MA Dalin IK Kolchin BR Serebryakov Acrylonitrile Technomic Westport Conn 1971 pp 163165 65 Annual Book of ASTM Standards E 117897 American Society for Testing and Materials Philadelphia Pa 1999 66 Annual Book of ASTM Standards E 20396 American Society for Testing and Materials Philadelphia Pa 1999 67 Annual Book of ASTM Standards E 29997 American Society for Testing and Materials Philadelphia Pa 1999 68 American Society for Testing and Materials Standard Test Method for Water Using Karl Fischer Reagent Annual Book of ASTM Standards Philadelphia Pa 1982 Part 30 E203 815824 69 American Society for Testing and Materials Standard Test Method for Trace Amounts of Peroxides in Organic Solvents Annual Book of ASTM Standards Philadelphia Pa 1982 Part 30 E299 909912 70 The Standard Oil Co US 4503001 1985 RK Grasselli AF Miller HF Hardman 71 The Standard Oil Co US 6458742 2002 C Paparizos MJ Seely MS Friedrich DD Suresh 72 The Standard Oil Co US 6965046 2005 C Paparizos MJ Seely MS Friedrich DD Suresh 73 The Standard Oil Co US 7071140 2006 C Paparizos SC Jevne MJ Seely 74 INEOS USA LLC US 7348291 2008 C Paparizos SC Jevne MJ Seely 75 INEOS USA LLC US 20110233460 2011 JF Brazdil MA Toft CJ Besecker MJ Seely 76 Nexant Incs ChemSystems PERP report Acrylonitrile 0910 2 Mew York November 2011 77 P Cole JS Mandel JJ Collins Regul Toxicol Pharmacol 52 2008 342 78 Material Safety Data Sheet Number 0000000892 INEOS USA LLC League City Texas 2009 wwwineosnitrilescom 10 Acrylonitrile