Guidelines for the distribution of Acrylonitrile

Acrylonitrile
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Notice
The information, specifications, procedures, methods and recommendations herein are presented in good faith, are believed to be accurate and reliable, but may well be incomplete and/or not applicable to all conditions or situations that may exist or occur. No representation, guarantee or warranty is made as to the accuracy, reliability or completeness of said information, specifications, procedures, methods and recommendations or that the application or use of any of the same will avoid hazards, accidents, losses, damages or injury of any kind to persons or property or that the same will not infringe patents of others or give desired results. Readers are cautioned to satisfy themselves as to the suitability of said information, specifications, procedures, methods and recommendations for the purposes intended prior to use.
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2 Product Classification and properties 8
2.1 General description 8 2.2 Physical properties 8 2.3 Chemical properties 9 2.4 Uses 9 2.5 Classification and Labelling 11 2.6 Transport classifications 12
3 Specific chemical hazards 13 3.1 Polymerization hazards 13 3.2 Inhibition 13
4 Health concerns 14 4.1 Ingestion 16 4.2 Inhalation 16 4.3 Effects on skin & eyes 16 4.4 Long term effects 16 4.5 Medical treatment 16
5 Personal protective equipment 18 5.1 First Aid Box 18 5.2 Breathing protection 18 5.3 Eye protection 18 5.4 Hand protection 18 5.5 Foot protection 18 5.6 Body protection 18 5.7 Safety showers 19 5.8 Walkie-talkie 19 5.9 Materials required for first aid and medical treatment 19
6 Environmental considerations 20 6.1 Environmental hazards 20 6.2 Fire and explosion hazards 20 6.3 Destruction of Acrylonitrile 20 6.3.1 Larger quantities 20 6.3.2. Smaller quantities (in the kilograms range) 20
6.4 Breakdown of Acrylonitrile in the soil 21
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7 Transport 22 7.1 Design and construction of Rail Tank Cars (RTC’s) 22 7.2 Design and construction of road tankers 22 7.3 Design and construction of tank containers 22 7.4 Design and construction of tank ships and barges 22 7.5 Loading operations 23 7.6 Unloading operations 24 7.7 Acrylonitrile transport by road 25 7.8 Acrylonitrile transport by rail 26 7.9 Acrylonitrile transport by water 27 7.10 Personal safety equipment 28 7.11 Product training for road tanker and tank containers drivers 28 7.12 Safety auditing of road hauliers 29
8 Storage 30 8.1 Safety auditing of bulk storage terminals 30 8.2 General considerations 30 8.3 Storage and Handling of Acrylonitrile 31 8.4 Preparation of Tanks and Equipment for Cleaning and Repairs 32 8.5 Sampling and Analytical Techniques 33
9 Emergency response 34 9.1 Alarm system and emergency plan 34 9.2 Assistance scheme in respect of transport incidents 34 9.3 Measures in the event of release of Acrylonitrile 34 9.4 Fire-fighting 35
10 List of acronyms / abbreviations 36
Table of contents
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Appendix 1 38 Design and construction of Rail Tank Cars (RTC’s)
Appendix 2 42 Design and construction of road tankers and tank containers
Appendix 3 46 Design and construction of tank ships and barges
Appendix 4 49 Design and construction of storage tanks
Appendix 5 59 Inspection loading list of transport equipment
Appendix 6 62 Inspection unloading list of transport equipment
Appendix 7 63 Safety visit scheme for reception and storage facilities at Acrylonitrile customer premises
Appendix 8 64 Acrylonitrile unloading/storage checklist
Appendix 9 67 Guidance notes for Acrylonitrile unloading/storage checklist
Appendix 10 69 General instructions for Acrylonitrile road tanker drivers
Appendix 11 72 Instructions in writing for road transport
Appendix 12 73 Member Companies of the Cefic Acrylonitrile Sector Group
Table of contents
1.1
Although Acrylonitrile is a hazardous material in terms of flammability, polymerization activity and toxicity, it can be distributed and handled safely provided that appropriate precautions are observed.
1.2
The transport of Acrylonitrile in bulk is subject to National regulations within Europe. In addition, the international movement of Acrylonitrile by road, rail, sea or inland waterways is subject to agreements which lay down specific and mandatory requirements.
1.3
These Guidelines have been prepared by Cefic (European Chemical Industry Council) Acrylonitrile Sector Group to establish appropriately high standards of safety for the transport of Acrylonitrile.
1.4
These Guidelines take into account the transport of Acrylonitrile in bulk in road tankers, Rail Tank Cars, sea-going tankers, river barges and tank containers. They cover all aspects of the transport. Reference to existing regulatory controls is only made where this is considered necessary for the purpose of clarification.
1.5
The Cefic Acrylonitrile Sector Group recommends that these Guidelines are adopted by all parties who are involved in the distribution of Acrylonitrile.
1.6
In order to facilitate effective supervision in storage and transport, all involved parties had to make sure that transport equipment meets the design and construction requirements of national and international regulations. In addition it is recommended that transport equipment is designed and constructed in accordance to the guidelines in this document.
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1.7
These guidelines will be periodically reviewed by the Sector Group members.
1.8
The transport companies must be assessed in accordance to Cefic SQAS (Safety Quality Assessment System) with good result.
A review meeting of producer and Transport Company is recommended after every new assessment.
1.9
The weight to be attached to particular guidelines is indicated by the following usages: a) “Should” implies a recommendation based upon the judgement of experienced people but recognises that
some discretion is appropriate. b) “Must” is a definite requirement, but is normally limited to procedures essential to adequate design or sound
operation.
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2.1 General Description Acrylonitrile (acrylic acid nitrile, 2-propenenitrile, cyanoethylene, vinylcyanide, AN, ACN, CH2 = CH - CN) is commercially produced by ammoxidation of propylene in the presence of ammonia. The commercial product is liquid, colourless, clear, flammable and poisonous and has an irritant effect on the skin.
CAS Number: 107-13-1. Index Number: 608-003-00-4. EEC Number: 203-466-5 (EINECS Number).
2.2 Physical Properties
Boiling point 77.3 °C (171.1°F)
Burning velocity (in air) 0.47 m/s
Critical temperature 246 °C (474.8°F)
Density (at 20°C) 806 kg/m3
Melting point - 83.5 °C (-118.3°F)
Molecular weight 53.1
Refractive index n25 D = 1.3888
Solubility (20°C) 7.35 wt % ACN in water 3.1 wt % water in ACN
METRIC UNITS SI UNITS
Heat of vaporization 147 kcal/kg 615 kJ/kg
Specific heat 0.5 kcal /kg, °C 2.09 kJ/kg, °C
Surface tension (at 24 °C) 0.0065 kcal/m2 0.0273 J/m2
Vapour pressure (20 °C) 0.12 bar 12 kPa
Viscosity (20 °C) 0.4 cP 0.4 mPa.s
Reference: Handbook of Chemistry and Physics, volume 88 (2007-2008)
2 Product classification and properties
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Acrylonitrile is miscible with many organic solvents such as alcohols, ethers, acetone, benzene, carbon tetrachloride, ethylacetate, ethylene cyanhydrin, toluene, petroleumether and kerosenes. Azeotropes are formed between Acrylonitrile and many of these solvents.
2.3 Chemical Properties
lower limit: 3 upper limit: 17
Flash point • Tag open cup • Tag closed up
-5 °C (23 °F) -1 °C (30.2 °F)
Ignition group G 1
METRIC UNITS SI UNITS
Heat of polymerization - 337 kcal/kg - 1412 kJ/kg
Reference: Handbook of Chemistry and Physics, volume 88 (2007-2008)
Acrylonitrile is a versatile chemical intermediate. The presence of both olefinic and nitrile groups permits a large variety of reactions. The nitrile group can undergo hydrolysis, hydrogenation, esterification and reduction. Reactions of the double bond include polymerisation, copolymerisation, cyanoethylation, cyclisation and halogenation. Mixtures of Acrylonitrile with air are flammable. In its liquid state, Acrylonitrile has a tendency to polymerise, which can however be prevented by the addition of phenolic (e.g. methyl ether of hydroquinone or amine-based stabilizers and small quantities of water. By adding concentrated caustic alkali or concentrated sulphuric acid, polymerisation can be accelerated to such an extent that it may assume an explosive nature. Acrylonitrile has no corrosive effect on metals. So stainless steel, carbon steel and aluminium/magnesium are used as materials for storage tanks. (For product quality reasons, avoid contact with copper or copper alloys).
2.4 Uses Acrylonitrile is used as: • A raw material for the production of synthetic fibres, plastics and synthetic rubber. One of the reasons for the
versatility of Acrylonitrile is that it can form copolymers with other unsaturated compounds, such as styrene and butadiene, for example.
• A raw material for acrylic acid, acrylic esters, acrylic amide, carbon fibre. • In the synthesis of compounds used for the production of adhesives, anti-oxidants, binders for dyestuffs and
emulsifiers.
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Exposure Scenarios
There are five exposure scenarios for uses of Acrylonitrile plus one for manufacture. These cover production of acrylic and mod-acrylic textile fibres; Production of ABS and SAN plastics; Monomer for production of nitrile rubbers; other intermediate uses; laboratory reagent. Full details can be obtained from the Acrylonitrile suppliers. The following use codes are covered;
SECTORS OF USE DESCRIPTION
SU 8 Manufacture of bulk
SU 9 Manufacture of fine chemicals
SU 10 Repackaging
SU 12 Manufacture of plastic products; including compounding and conversion
SU 22: Professional uses
PROCESS CODES
PROC 1 Used in closed process, no likelihood of exposure
PROC 2 Used in closed continuous process with occasional controlled exposure
PROC 3 Use in closed batch process (synthesis or formulation)
PROC 4 Use in batch and other process (synthesis) where opportunity for exposure arises
PROC 8b Transfer of substance or preparation/charging/discharging from/to vessel/large containers at dedicated facilities
PROC 9 Transfer of substances or preparation into small containers (dedicated filling line, including weighing)
PROC 15 Laboratory uses
ENVIRONMENTAL RELEASE CODES
ERC 6a Industrial use resulting in the manufacture of another substance (intermediates)
ERC 6c Industrial use of monomers for manufacture of thermoplastics
ERC 6d Industrial use of process regulators for polymerisation processes in production of resins, rubbers, polymers.
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2.5 Classification and Labelling 2.5.1 Classification according to EU Dangerous Substances Directive (DSD)
Highly Flammable (F) R11 Toxic (T) R23/24/25 Carc. Cat. 2 R45 Irritant (Xi) R37/38, R41, R43 Dangerous for the Environment (N) R51/53
2.5.2 Labelling according to EU directive 67/548/EEC F, T, Xi, N R 45- 11-23/24/25-37/38-41-43-51/53 S 9-16-53-45-61 + S 27 (*)
(*) S 27* is not an EU requirement but is recommended.
2.5.3 Classification and Labelling according to Regulation (EC)1272/2008 (CLP)
CLASSIFICATION
Flammable Liquid Category 2 Carcinogenicity Category 1B Reproductive Toxicity Category 2 Acute Toxicity (Oral) Category 3 Acute Toxicity (Dermal) Category 3 Acute Toxicity (Inhalation) Category 3 Eye Corrosion/Irritation Category 1 Skin Corrosion/Irritation Category 2 Specific Target Organ Toxicity Single Exposure Category 3 (H335) Skin Sensitization Category 1 Aquatic Toxicity Chronic Category 2
H225 Highly flammable liquid and vapour. H301 Toxic if swallowed. H311 Toxic in contact with skin H315 Causes skin irritation. H317 May cause allergic skin reaction. H318 Causes serious eye damage H331 Toxic if inhaled. H335 May cause respiratory irritation. H350 May cause cancer. H361d Suspected of damaging the unborn child. H411 Toxic to aquatic life with long lasting effects.
Labelling Signal word: Danger
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RID - ADR - ADN
UN NUMBER 1093
PACKING GROUP I
UK HAZCHEM CODE: 3WE Hazard Diamonds – Flammable + toxic + environmental hazard
THE CLASSIFICATIONS FOR HEALTH PROTECTION ARE
EmS 3-02
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3 Specific chemical hazards
3.1 Polymerisation hazards Under some conditions, Acrylonitrile may undergo polymerisation. The polymerisation reaction is highly exothermic; the heat released can lead to additional polymerisation accelerating to the point where it becomes out of control. Monomer can vaporise at elevated temperatures and can cause sufficient pressure to rupture storage vessels.
Hazardous conditions can result from any of the following, even when the Acrylonitrile is properly inhibited: • Contact with free radical catalysts such as peroxides and hydroperoxides. • Mixing with basic/alkaline material such as sodium hydroxide, potassium hydroxide and ammonia. • Mixing with Lewis acid catalysts such as boron trifluoride, titanium tetrachloride and sodium borohydride. • Contact with strong mineral or organic acids. • Exposure to high energy radiation such as UV light, X-rays and gamma rays.
The storage of inhibited Acrylonitrile does not normally give a polymerisation hazard.
3.2 Inhibition The material is stabilised/inhibited against spontaneous polymerisation prior to dispatch with: • Water: 0.25 – 0.5% by weight. • MEHQ: 30-50ppm (Monomethylether of Hydroquinone). • Oxygen: trace amount.
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4 Health concerns
Acrylonitrile is toxic if inhaled or swallowed or in contact with the skin. Skin contact causes blistering; the eyes and mucous membranes are particularly at risk. Symptoms of acute exposure are headache, nausea, dizziness and vomiting. After substantial exposure, the symptoms are unconsciousness, spasms and cessation of breathing. These symptoms can be delayed several hours after exposure. Acrylonitrile must be regarded as if it is potentially carcinogenic to man. If any contact with Acrylonitrile has taken place or is suspected, immediate consultation of medical service is strongly recommended.
The effects of Acrylonitrile on humans, animals and environment have been extensively studied and documented:
Toxicity by inhalation (LC50)
DURATION VALUE
1578 ppm 557 ppm
1810 ppm 473 ppm
DURATION VALUE
2005 SNF (RTI unpublished, 2005) Rat 4-hours 200 mg/kg (LD10)
1995 BUA Rabbit Various 148-693 mg/kg
1969 Vernon et al Rabbit 24-hours < 200 mg/kg
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1995 GDCh/BUA Various 25 to 186 mg/kg
1969 (1990) Vernon et al Rat 81 mg/kg
1983 WHO Mouse 25-48 mg/kg
General assessments on effects of Acrylonitrile on humans, animals and environment:
• European Union Risk Assessment Report. (2004) Acrylonitrile, CAS No. 107-13-1. Vol 32. European Chemicals Bureau, European Commission Joint Research Centre.
• IARC Monographs 19 (1979) and 71 (1999) Class 2B. • Environmental Health Criteria 28: Acrylonitrile, WHO (1983). • Environmental Hazard Assessment: Acrylonitrile, Nielsen et al. (1993). • BUA-Stoffbericht 142; Acrylonitrile, GdCh (1994). • The Sapphire Group, Inc. (unpublished, 2004) Toxicological Review of Acrylonitrile (CAS No. 107-13-1).
Prepared for The Acrylonitrile Group, Inc. • REACH Generic Chemical Safety Report for Acrylonitrile, AN REACH Consortium (2010).
REACH DNELs for Industrial exposure scenarios
SYSTEM DERMAL INHALATION
Acute Dermal Irritant/ sensitizer
10 mg/m3 (4.5 ppm) Local Inhalation exposure regarded as protective
Long-term Dermal Irritant/ sensitizer
1.4 mg/kg bwd/d* 1.8 mg/m3 (0.8 ppm) 2.7 mg/m3 (1.0 ppm)
(*) Dermal irritant/sensitizer; value provided only for assessment of PPE
NOTE: Acrylonitrile is classified as an IARC 2b Carcinogen (possible human carcinogen/ EU GHS 1B, May Cause Cancer. At the time of publication the 8 h TWA OEL for Acrylonitrile in most Member States and Switzerland was 2 ppm, but 1 ppm in the Czech Republic and 3 ppm in Slovakia and Slovenia, based on potential cancer risk.
The systemic long-term REACH DNEL is based on potential irritation risk and is regarded as protective of any potential cancer risk.
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4.1 Ingestion Ingesting Acrylonitrile is potentially fatal and will cause severe irritation of the mouth, throat and digestive tract. Gastro-intestinal burns are also likely. This may have the effects of causing respiratory complications, nausea or vomiting. Onset of typical signs of intoxication may be rapid and fatal.
4.2 Inhalation Breathing Acrylonitrile at a concentration of 22 mg/m3 and higher for 20 to 45 minutes causes headaches, nausea and disorientation. Specific levels of Acrylonitrile causing death are not reported, but animal experiments suggest that, as far as inhlalation is concerned, exposure to Acrylonitrile at 500 to 2000 mg/m3 for to 3 hours could be fatal. Simultaneous exposure to some organic solvents may enhance the toxicity of Acrylonitrile.
4.3 Effects on skin and eyes Liquid Acrylonitrile is absorbed into the body via the skin, and the same non-specific symptoms of systemic poisoning occur as with inhalation of Acrylonitrile vapour. Moreover, exposure of the skin to liquid Acrylonitrile can cause skin irritation, redness and blistering. Local injury can occur a few hours after contact with the liquid. Liquid Acrylonitrile has a burning effect on the eyes. Development of allergic dermatitis is possible after skin contact.
4.4 Long term effects In the course of several long-term tests in which Acrylonitrile was administrated to rats both orally and via inhalation, a carcinogenic effect was detected. There is a significant epidemiological database on humans exposed to Acrylonitrile at work. These data do not suggest a consistent correlation between Acrylonitrile and cancer in humans at occupationally relevant exposures. Presently, however, Acrylonitrile should be regarded as potentially carcinogenic to man.
No clear evidence for a relationship of Acrylonitrile exposure and the incidence or the mortality of specific tumours can be derived from these epidemiological studies. On the basis of the available results of experimental and epidemiological studies, it cannot be evaluated whether or not the carcinogenic effects in the rat are relevant for man because the mechanism of carcinogenesis is unknown. It is therefore recommended to keep exposure to Acrylonitrile as low as possible both at the workplace and in the environment, and that skin contact with the liquid has to be avoided.
Reference: Cole, P. Mandel JS and JJ Collins 2008, Acrylonitrile and cancer: A review of the epidemiology, Regul. Toxicol. Pharmacol. (2008), doi:10.1016/j.yrtph.2008.09.004
4.5 Medical Treatment The first priorities are decontamination and obtaining rapid medical attention. On site Emergency medical attention will require subsequent assessment by a doctor or in a hospital Emergency Unit. Those treating victims of Acrylonitrile poisoning should make sure that they are equipped with the necessary personal protective equipment and that those exposed are properly decontaminated. Where Acrylonitrile poisoning is evident, pay attention to the vital functions (breathing and blood circulation) and the effects on the skin, eyes, liver and central nervous system. Acrylonitrile can be absorbed via inhalation or contamination of the skin.
Health concerns Chap 4
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All exposed patients should be evaluated by a medical doctor before being released. Where symptoms progress or the person is unconscious, establishment of intra venous access as soon as possible for IV Antidote treatments is essential. Current antidote regimes should be checked with National Poison Centres:
Typically the following are proposed: • Germany / Austria: 4-DMAP and sodium thiosulphate. • France: Hydroxycobalamine plus sodium thiosulphate. • Italy: Hydroxycobalamine and sodium thiosulphate. • Spain: Hydroxycobalamine plus sodium thiosulphate. • NL: Hydroxycobalimine and sodium thiosulphate. • U.K.: Sodium nitrite followed by sodium thiosulphate/dicobalt edetate (severe confirmed cases). • U.S.A.: Amylnitrite plus sodium nitrite and sodium thiosulphate.
Please refer to your national poison centres for the most up-to-date information. Hydroxycobalimine and sodium thiosulphate are recommended, but please contact national poison centre for the latest treatment.
(*) Please note that the recommended antidotes differ from country to country, and are under constant review. Cyanide antidotes are theoretically useful but clinically unproven in Acrylonitrile poisoning. Please refer to your national authorities for current recommendations.
Health Concerns Chap 4
5 Personal protective equipment
5.1 First Aid Box Locations where Acrylonitrile is handled should be equipped with suitable first-aid units, containing, in addition to the normal first aid requisites, a written procedure on how to handle exposures to Acrylonitrile. Detailed information could also be find in the Safety Data Sheet.
5.2 Breathing protection For work purposes, air masks must be equipped with clear view face piece, speaking diaphragm and air demand regulator. The air will be supplied from a portable air cylinder, or air supply hose from air tanks or long duration cylinders. The use of a positive pressure mask gives greater protection and is preferred.
Escape masks must only be used for emergency purposes due to potential saturation of the filter and should only be used once.
5.3 Eye Protection Eye protection must be worn at any time.
5.4 Hand protection Preventive: disposable gloves made of high quality butyl rubber or neoprene. Repressive: (Pressurised) see Body protection section (5.6).
5.5 Foot protection Butyl rubber knee-length boots (Wellingtons). Leather footwear are not recommended in cases of operations with increased risk such as loading and unloading in case of skin contact with heavier-than air Acrylonitrile vapours.
5.6 Body protection Preventive: PVC or neoprene (for usage one time only) overall with a close-fitting hood and an elastic fitting around wrists and ankles.
Repressive: Pressurised butyl rubber gas-tight suit with an independent air supply.
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Personal protective equipment Chap 5
5.7 Safety showers Quick-opening safety showers conveniently located in exposure area. Consideration must be given to providing an activation…