इंटरनेट मानक Disclosure to Promote the Right To Information Whereas the Parliament of India has set out to provide a practical regime of right to information for citizens to secure access to information under the control of public authorities, in order to promote transparency and accountability in the working of every public authority, and whereas the attached publication of the Bureau of Indian Standards is of particular interest to the public, particularly disadvantaged communities and those engaged in the pursuit of education and knowledge, the attached public safety standard is made available to promote the timely dissemination of this information in an accurate manner to the public. “जान1 का अ+धकार, जी1 का अ+धकार” “प0रा1 को छोड न’ 5 तरफ” Mazdoor Kisan Shakti Sangathan Jawaharlal Nehru “The Right to Information, The Right to Live” “Step Out From the Old to the New” IS 14984 (2001): 1,3-Butadiene - Code of Safety [CHD 8: Occupational Safety, Health and Chemical Hazards] “!ान $ एक न’ भारत का +नम-ण” Satyanarayan Gangaram Pitroda ““IInnvveenntt aa NNeeww IInnddiiaa UUssiinngg KKnnoowwlleeddggee”” “!ान एक ऐसा खजाना > जो कभी च0राया नहB जा सकता हहहहै””ै” Bhartṛhari—Nītiśatakam “Knowledge is such a treasure which cannot be stolen” _fJ IS 14984:2001 i mm 1,3-$yl< H–q?al * Indian Standard 1,3-BUTADIENE — CODE OF SAFETY ICS 13.300; 71.080.10 0 BIS 2001 BUREAU OF INDIAN STANDARDS MANAK BHAVAN, 9 BAHADUR SHAH ZAFAR MARG NEW DELHI 110002 October 2001 Price Group 4 Chemical Hazards Sectional Committee, CHD 7 FOREWORD This Indian Standard was adopted by the Bureau of Indian Standards, after the draft finalized by the Chemical Hazards Sectional Committee had been approved by the Chemical Division Council. 1,3-Butadiene is commercially produced by cracking of naphtha and subsequent fractionation or extractive distillation. It can also be produced by dehydrogenation of butanes orbutenes. 1,3-Butadiene ischiefly used astheprincipal monomer forthemanufacture ofvarious grades ofrubber, namely, Styrene butadiene rubber (SBR), Acrylonitrile butadiene styrene rubber (ABS) or Polybutadiene rubber (PBR). It also finds its use inrocket fuels, inplastics and resins. There is no 1S0 standard on this subject. In preparation of this code assistance has been derived from the following publications: a) Butadiene safety manual, Polymer Corporation Limited, Sarni& Ontario. b) Safe storage and handling of butadiene, Shri. A. H. Mazumdar, Synthetics and Chemicals L“imited, Mumbai. c) Dangerous properties of industrial materials, N. Irving Sax. 6th Edition. d) Handbook of reactive chemical hazards, L. Bretherick, Sunbery Research Center, British Petroleum Company Limited. e) Encyclopedia ofpolymer sciences andtechnology. f) Occupational diseases, U.S. Department of Health, Education and Welfare, National Institute for Occupational Health. g) MSDS Canadian center for occupational health and safety. h) Chemical safety data sheet (Royal Society of Chemistry; Vol. 3). ---- The composition of the Committee responsible for formulation of this standard is given in Annex A. — / — IS 14984:2001 Indian Standard 1,3-BUTADIENE — CODE OF SAFETY 1 SCOPE 4.1.7 UN NO.— 1010 1.1 This standard prescribes physical and chemical 4.1.8 UN Hazard Class — 2.1 properties of 1,3-Butadiene, the nature of hazards 4.1.9 Hazchem Code — 2WE associated with it,preventive measures forcontrolling the hazards, and essential information on storage, 4.2 Physical Properties handling, Iabelling, transportation, waste disposal, 4.2.1 Description training of personnel, personal protective equipment, first aid and fire fighting. 1,3-Butadiene is a colorless stable liquid at temperature below its boiling point but at room 1.2 This standard does not, however, deal with any specifications for design of buildings, chemical temperature itisacolorless gas. Ithas characteristic engineering plants, method and ingredients used in odour. Odour threshold value is 1.8. It is a highly the manufacture, equipment for waste disposal and flammable andpotentially explosive when mixed with operation control. air. 4.2.2 SoIubility 2 REFERENCES The gas is slightly soluble in water, more soluble in The Indian Standards listed below contain provisions methanol and ethanol, but readily soluble in other which through reference in this text, constitute provisions ofthis standard. Atthetime ofpublication, organic solvents. the editions indicated were valid. All standards are 4.2.3 Boiling Point, “C— (–) 4.4 subject to revision, and parties to agreements based on this standard are encouraged to investigate the 4.2.4 Freezing Point, “C— (–)108.9 possibility of applying the most recent editions ofthe 4.2.5 Specljic Gravity (Liquid), with respect to water standards indicated below: at IS No. Title 30“c :0.6023 2148:1981 Flameproof enclosures forelectrical 50Oc apparatus (second revision) :0.5818 4155: 966 Glossary of terms relating to 4.2.6 Specijic Gravity (Gas), with respect to air at chemical and rad iation hazards and 15°C— 1.877 hazardous chemicals 4.2.7 Refractive Index at (–) 25 “C— 1.4292 4167: 980 Glossary of terms relating to air pollution (first revision) - 4.2.8 Viscosity (–1OO”Cto+140”C),Liquid— 0.07 cp 3 TERMINOLOGY 4.2.9 Viscosi&, Vapour (–50”C to +300”C) — 30 to 146Pp For the purpose of this standard, definitions given in IS 4155 and 1S4167 shall apply. 4.2.10 Critical Properties 4GENERAL INFORMATION AND PROPERTIES a) Critical Pressure, MPa :4.32 b) Critical Temperature, “C :152 4.1 General Information 4.2.11 Spectflc Heat (Cp) in kcalikg-°C, at 4.1.1 Common Name — Butadiene; Bivinyl; Divinyl; Erythrene; Pyrolylene; Vinylethylene; Biethylene Gas Liquid 4.1.2 Chemical Name — 1,3-Butadiene (-) 45 “c 0.308 0.518 15°C 0.332 0.551 4.1.3 Chemical Formula — CIHG 38°C 0.356 0.558 4.1.4 Molecular Structure — HZC=CH-CH=CH2 4.2.12 Heat of Vaporization in kJ/mole at 4.1.5 Molecular Mass — 54.09 (-) 4.441°C :21.98 4.1,6 CAS Registry No. — 106-99-0 25°C :20.88 1 IS 14984:2001 4.2.13 Vapour Pressure, MPaat 4.4.2 Auto Ignition Temperature, “C— 420 (-)4.41 “c :0.1013 4.4.3 Explosive Limits in Air, Percent (v/v) 0“c :0.1173 Lower Explosive Limit (LEL) :2 20‘c :0.2351 Upper Explosive Limit (UEL) :11,5 40“c :0.4288 4.4.4 Butadiene vapours being heavier than air, tend 60“C :0.7247 tospread andflashback from ignition source. Storage 80“C :1.1505 ofuninhibited butadiene maypresent aspecial hazard, 100‘c :1.7342 ifitissubjected toelevated temperature onaccount of which it would rapidly polymerize, generating heat, 4.2.14 Miscibility of Water, at –40 to +60°C pressure and rupture of the vessel and explosion. (liquid), 0.2 to 0.02 percent (w/w) Further, oxidizing agents, phenols, aldehydes, rust 4.2.15 Miscibility in Water, at 760 mm of Hg, (gas) (iron oxides), oxides of nitrogen, nitrates carbonyls, — 0.02 percent (w/w) oxygen, air would cause serious fire and explosion hazard when come into contact with butadiene with a 4.3 Chemical Properties little friction orheat. Butadiene derived fi-omnaphtha contains trace of acetylenes therefore, should not be 4.3.1 Peroxide Formation and Polymerization allowed to come in contact with acetylide forming Uninhibited butadiene combines with oxygen or air metals, such as, copper, silver, magnesium, mercury, to form explosive peroxides and popcorn polymers. alkali metals and alloys thereof. Acetylides of these Being a diene aliphatic hydrocarbon, it is highly metals areunstable and could be ignited by friction of reactive to form polymers/rubbers like PBR, SBR, heat to explode. In view of above the recommended ABS. 1,3-butadiene forms 3types of polymers: maximum allowable concentration in refined butadiene are following: a) Dimer — Dimer formation takes place atall temperature and rate of dimer formation in- Acetylene : 65 ppm creases with increasing temperature and has Carbonyls : 100ppm atendency to depositon the walls ofthe con- VinylAcetylene: 150ppm tainer. To agreat extent itissoluble inliquid butadiene. Inhibitor minimizes theformation The vapours of butadiene, if not inhibited can form of the dimer. Storage at 100Cor below can polymers invents or flame arrestors of storage tanks, minimize dimer formation. causing their blockage. b) Heavy polymer — This is dark rubber like In butadiene refining columns, the presence of vinyl material, forms inliquid phase andcancause acetylene in butadiene vapour phase should not be plugging of lines and equ ipment. Presence allowed to gobeyond 40 moles percent because vinyl of peroxides tends to produce this polymer. acetylene may initiate explosion above this limit. The solid polymer may ignite spontaneously when exposed to the air and must be kept Polymerization of butadiene is accelerated by rusty wet until removed from the hazardous area, iron. In order to minimize this, iron surface should be and if possible, destroyed under supervision treated with 2-3 percent NaN02 which subsequently (see 4.4.4). should be washed ftee from nitrates before being put to butadiene service. c) Popcorn polymers — This is formed under normal processing conditions in the vapour Peroxides and polyperoxides in butadiene are also phase. Itistough andresinous. Trace ofoxy- hazardous andthese canbedestroyed from thesurface gen,oxidizing agentsandthepresenceofseed of equipment by treating with 20 percent NaOH at of popcorn polymer will initiate the format- about 50°C. In butadiene recommended maximum ion. allowableconcentration ofdimer,oxygen andperoxide are following: 4.3.2 Reaction with Oxides of Nitrogen Dimer : 0.2 percent Butadiene reacts with oxides of nitrogen to form unstable compounds which when heated can cause Oxygen : 0.3 percent explosion even in inert atmosphere. Peroxides : 10ppm 4.4 Fire and Explosion Hazard Properties 4.5 Corrosion Properties 4.4.1 Flash Point, “C— (–)18 Butadiene isnon-corrosive. 2 — IS 14984:2001 5 TOXICITY INFORMATION AND HEALTH This material has also shown, in several independent EFFECTS studies, to cause mutations of bacteria. 5.1 Toxicity Information 6 PERSONAL PROTECTIVE EQUIPMENT 5.1.1 TLV— 2 ppm (4.4 g/m3) Wheneverthere isdangerofliquidorvapour butadiene coming incontact with eyes, safety goggles should be 5.1.2 STEL — 20 ppm (40 g/m3) worn. Faceshieldswithcuptypevapour safetygoggles 5.1.3 IDLH — 20000 ppm (40 g/m3) will give the best protection. Hard helmets should be used in plant areas to guard against accidental leaks 5.1.4 LCJO(Inhalation, Rat)—20000 ppm(250g/m3) and also from falling tools, etc. For further protection 5.1.5 LD50 (Oral, Rat)—5480 mglkg rubber, PVC aprons and safety shoes should be worn. Self contained breathing apparatus (SCBA), positive 5.1.6 LDj(, (Oral Mouse) — 3210 mg/kg pressure hose mask, air line masks are recommended. 5.2 Routes of Entry IndustrialCanistertypegasmaskswillaffordprotection against concentration not exceeding 2 percent. Butadiene can make an entry through inhalation (respiration) or through contact with liquid (skin). NOTE—Respirato~ protective equipment mustbecarefully maintained,inspected,cleanedandsterilizedatregular’intervals andalwaysbeforeusebyanotherperson. 5.3 Health Effects 5.3.1 Odour Threshold Concentration 7 STORAGE, HANDLING, LABELLING AND TRANSPORT Death can occur if inhaled for 23 minutes air containing 25 percent butadiene. 7.1 Storage 5.3.2 Irritation Effect 7.1.1 Mode Eye and respiratory irritation at 2 percent Beingextremely flammable andpotentially explosive concentration. Contact may cause irritation with on contact with air, oxygen and oxidizing agents, redness and excess tearing. Skin contact may cause butadiene should be stored in liquid form under irritation with redness and possible swelling. pressure at ambient temperature away from potential Inhalation may cause irritation to the respiratory tract source of ignition or sparks and oxidizing agents. It with nausea, headache, fatigue can cause death. should be inhibited with 0.01 to 0.02 percent of para tertiary butyl catechol (PTBC). For pressure storage a -- 5.3.3 At concentration below the LEL (2 percent) it vessel in the form of sphere is most favoured. can cause mild narcotic effect, irritation to the eyes, Refrigeration storage isalso done. Usually itisstored mucous membrane, drowsiness, lethargy, etc. at 10°Ctominimize dimer formation. Threaded piping 5.3.4 Effect qf Repeated (Chronic) E xposure shouldbeavoided. Castironpartsorequipment should not be used. Drainage should be provided. The Repeated skin exposure may cause dermatitis. inhibitor content must be checked periodically. The Repeated exposure of butadiene vapours may cause storage should be free from air or oxygen. Storage kidney and lever injury. vesselshouldnotbemadeofcopper,magnesium, silver 5.3.5 Liquid butadiene on contact with skin causes or alkaline earth alloys. frost bite due to rapid evaporation. Before filling the storage vessels with butadiene the 5.3.6 Inhalation may cause irritation totherespiratory tank andalllinesshould bemade free from air,oxides tract, withnausea, vomitting, blurred vision,headache, of nitrogen, phenols and oxidizing agents. fatigueandunconsciousness. Lackofoxygencancause During unloading operation, the container, the tank death. from which it is being unloaded and truck chassis 5.3.7 Skin contact may cause irritations, with redness should be electrically connected and grounded to and possible swelling. Exposure to liquid may cause prevent spark. frost bite. Cylinders of butadiene should be stored upright in a Eye contact may cause irritation, with redness and cool, dry, wellventilated location, away from sources excess tearing. Exposure toliquidmaycausefreezing. of heat, open flames and sparks. The storage area shouldbesegregatedfromsuppliesofoxygen,chlorine Effects ofrepeated (chronic) overexposure: Repeated and other oxidizing chemicals and gases and skin exposure may cause dermatitis. Repeated combustible materials. A cylinder should not be exposure of butadiene vapours may cause kidney and subjected totemperature above 55°C. lever injury. 3 - ‘,. —. IS 14984:2001 7.1.2 Ventilation not be used for any other product. The tanker should , also follow UN Code 1010 for transportation of =1 Good ventilation isrequired inrooms orstoragewhere dangerous goods. butadiene is stored. Storage in pits, depressions and “~ basements should be avoided. 7.4.2 Proper warning, a label and signs should be ,, marked onthetanker. The tanker must have aplacard .4 7.1.3 Flooring L class label of “Flammable”. A slight pressure above y Fire resistant flooring should be laid in storage areas. atmosphere should be maintained inside the filled Adequate drainage should be provided to drain away tanker out of contact with air or oxygen. Two fire the liquid from the storage tank and minimize fire extinguishers should be fixed on each tank lorry. exposure of the tanks. A suitably designed Dike is 7.4.3 Only trained drivers should be employed for desirable transporting butadiene. 7.1.4 Electrical Fittings 7.4.4 The storage, transportation and handling of Explosion proof electrical fittings conforming to butadiene should conform to the Gas Cylinder Rules, group IIBofIS2148 should beused instorage areas. 1981 and its storage, transportation and handling in All metal surfaces with which butadiene come in vessel should conform to the Static and Mobile contact must be grounded or bonded so that the Pressure Vessels (Unjired) Rules, 1981 administered resistance to ground does not exceed 7 ohms. This bythe chief controller of explosives. will prevent static charges. Lighting protection device should be installed to prevent fire from lighting. 8 SPILLAGE/LEAKAGE AND WASTE DISPOSAL 7.2 Handling 8.1 Spillage/Leakage Butadiene should beunloaded through aclosedsystem 8.1.1 Regular inspection of equipment and vessels using vapour return line and compressor or inert gas containing butadiene should be made to detect or pressure. All precautions must be taken to guard prevent leaks. Soap solution may be used but no against health and fire hazard whenever butadiene is matches or open flames should be used to check the handled. Suppliers instructions should always be leaks.Ifspillage orleakage develops, ignition sources followed and all caution markings be strictly adhered should beeliminated andpeople should be kept away to. Leaks should not be present. If transfer is done because butadiene in contact with air will form into a tanker, the tankers’ design and construction flammable/explosive mixtures. ., should be asper BIS forbutadiene. The lagging ofthe pipelines should be checked well. 8.1.2Tomuchexposure maycausedizziness, lethargy, eye irritation and if liquid, frost bite. 7.3 Labelling 8.1.3 The area around the spillage should be wetted The following label,inadditiontoorcombination with down with large quantities of water and allow the any label, warning required by statutes regulations, liquid to dissipate. The spillage can be absorbed on ordinance isrecommended for butadiene. sandandshoveledcarefully tosafeareasanddestroyed by burning. Spillage can be diluted with PTBC Nameofmaterial : 1,3-BUTADIENE(INHIBITED) dissolved in toluene before mixing with sand. Good Danger : Extremely flammable liquid and ventilation should be there so that gas should be gasunderpressure. Liquidcauses dissipated below itslowerexplosively limit. Sand and frost bums, may form explosive shovel should be readily available. peroxides on exposure to air. Do not breathe vapour. 8.2 Waste Disposal Do not get in eyes, or skin, or clothing, 8.2.1 Solid waste will be usually polymeric materials Use with adequate ventilation. (Popcorn polymer) with gaseous or liquid butadiene Keep away from heat and open flame. absorbed sometimes. Do not drop acylinder. 8.2.2Beforecollectingthewastefromlinesandservice tanks, all equipment should be depressurized and the 7.4Transport gases are vented out safely below the explosive limit 7.4.1 Butadiene is usually transported through or to a burning flare. After the removal of the gases pipelines and tankers. Since butadiene istransported the polymeric wastes can be treated with 20 percent at a low temperature to prevent polymerization, the NaOH solution at 48-50”C to decompose/destroy the tank should be insulated. Butadiene tankers should peroxide and polyperoxides, if any, are formed. 4 I 1s 14954: ZUul Otherwise, the waste could be removed under wet 10.1.4 Each employee should be periodically given condition andburnt intoapit/incinerator, adding small refresher training on safety measures associated with quantities at intervals. Popcorn polymers are butadiene. unsaturated innature andtend to ignite when exposed toair.Hence itshould beremoved under wetcondition 10.2 HEALTH MONITORING with water. Pre-employment examination arerequired forpersons who would be exposed to butadiene. In general, 9 FIRE PREVENTION AND FIRE FIGHTING asthmatic persons and those suffering from acute or 9.1 Fire Prevention chronic diseases of the respiratory system should not be exposed to butadiene vapours. A periodic health 9.1.1 Explosion/tlame proof electrical equipment examination including chest x-ray should be per- should be used in place where butadiene is handled. formed on all employees exposed to butadiene. A Static charge, flames, ignition sources, lights, thorough investigation should bemade ofanychanges oxidizing agents, copper, magnesium, silver, alkali referable to the respiratory system revealed by the earth metal alloys should not be present where examination. Periodical examination should be done butadiene is handled. Sampling should not be done annually. Proper records should bemaintained sothat during lightning and hail storm. variation if any, could be studied and remedies be 9.1.2 All metal surfaces with which butadiene comes suggested by the physician. into contact must be grounded so that resistance to ground does not exceed 7ohms. 11 FIRST AID 9.2 Fire Fighting 11.1 Affected persons showing signs of excessive butadiene inhalation should be removed atonce from Cool the butadiene container which is on fire with the contaminated area. If breathing has stopped, fine spray of water without putting out the flame till artificial respiration should be started immediately. the valve supplying the gas is isolated. Cut off All contaminated clothing and shoes should be butadiene supply to the fire before attempting to removed. extinguished using COZ,dry chemical powder (DCP), foam and water fog. Attempt to cool the nearby 11.1.1 Eyes equipment and tanks which are handling and storing Immediately flusheyeswithplenty ofwaterforatleast flammable liquids and gases. Donot use waterjet. 15minutes. hold eyelids apart while flushing to rinse entire surface ofeye and lidswith water. Get medical 9.3 Air Monitoring of the Work Place attention. Periodical air monitoring should be carried out to 11.1.2 Skin assess the exposure risk, and necessary control measures should be implemented to maintain the Incase of cold burn, immediately place affected area ambient concentration ofbutadiene below TLV. in warm water (41‘C) and keep at this temperature until circulation returns. Get medical attention. 10 TRAINING AND HEALTH MONITORING 11.1.3 Ingestion 10.1 Training No emergency care anticipated. This material isagas 10.1.1 Thetrainer should befamiliar withthecontents at standard temperature and pressure. ofthesafety datasheet. Persons whohandle butadiene should be instructed carefully inthe accepted method 11.1.4 Inhalation of handling and be appraised of the use of protective Remove to fresh air. If not breathing, give artificial equipment for safe handling. respiration. Ifbreathing isdifficult, qualified personnel 10.1.2 During training stress should be laid on may administer oxygen, get immediate medical hazardous properties of butadiene due to fire and attention. explosions, soasto impart an indelible impression on 11.1.5 Other Instructions the persons who handle butadiene. Remove and dry-clean or launder clothing soaked or 10.1.3Allworkers should befamiliarwiththelocation soiledwiththismaterial before reuse. Dry cleaning of of safety showers, alarm boxes, emergency ventilation contaminated clothing may be more effective than system,firstaidboxes,fireextinguishersandhoselines, normal laundering. Inform individuals responsible for protective equipment, gas masks and artificial cleaning ofpotential hazards associated with handling respiration methods. They should be given training in contaminated clothing. the methods of operation ofthe equipment mentioned. 5