IS 14984: 1,3-Butadiene - Code of Safety

14 Pages·2001·1.4 MB·English

by  Bureau of Indian Standards

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IS 14984 (2001): 1,3-Butadiene - Code of Safety [CHD 8:
Occupational Safety, Health and Chemical Hazards]
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“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).

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The composition of the Committee responsible for formulation of this standard is given in Annex A.

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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

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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.

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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.

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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.

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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.

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