TABLE OF CONTENTSGENERIC INFORMATION . . . . . . . . . . . . . . . . . . . .1PROPERTIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1

General Properties . . . . . . . . . . . . . . . . . . . . . . . . . . .1Stability and Reactivity . . . . . . . . . . . . . . . . . . . . . . .1

TRAINING AND JOB SAFETY . . . . . . . . . . . . . . . .2Employee Education and Training . . . . . . . . . . . . . .2Process Hazards Analysis . . . . . . . . . . . . . . . . . . . . .2

HEALTH INFORMATION . . . . . . . . . . . . . . . . . . . . .2Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2Industrial Hygiene . . . . . . . . . . . . . . . . . . . . . . . . . . .3First Aid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3Personal Protective Equipment . . . . . . . . . . . . . . . . .4

BULK STORAGE AND HANDLING . . . . . . . . . . . .5Building Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5Storage Equipment Guidelines . . . . . . . . . . . . . . . . .5Unloading into Storage Tanks . . . . . . . . . . . . . . . . . .7Tank and Equipment Cleaning and Repairs . . . . . .7

BULK TRANSPORT . . . . . . . . . . . . . . . . . . . . . . . . . .8Unloading Bulk Shipments from Tank Cars and Tank Trucks . . . . . . . . . . . . . . . . . . . .8Shipping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9

STORAGE AND HANDLING OF DRUMS . . . . . .9LABELING AND PLACARDING . . . . . . . . . . . . . . .9CONTROL OF VAPORS AND WASTE DISPOSAL . . . . . . . . . . . . . . . . . . . . . . . . . .12

General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12Air Pollution Control . . . . . . . . . . . . . . . . . . . . . . . .12Discharge to Navigable Waters . . . . . . . . . . . . . . . .13Discharge to Municipal Sewers . . . . . . . . . . . . . . . .13Disposal of Wastes . . . . . . . . . . . . . . . . . . . . . . . . . .13

EMERGENCIES . . . . . . . . . . . . . . . . . . . . . . . . . . . .13Fires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13Spill Hazards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .14Shipping Containers Damaged En Route . . . . . . . .15

ACKNOWLEDGMENTS . . . . . . . . . . . . . . . . . . . . .15APPENDIX:Partial List of Government Regulations and Agency Recommendations . . . . . . . . . . . . . . . . . .15

1. GENERIC INFORMATION

2. PROPERTIES2.1 General Properties

See Table IIAll referenced data (except for heat of combustion)

are the DIPPR (Design Institute for Physical PropertyData) values, when available, as of September 1993.The DIPPR Data Compilation File is developed underthe direction of the AIChE and is updated annually.This database is accessible for on-line computersearching. For more information contact:

American Institute of Chemical Engineers345 E. 47th StreetNew York, NY 10017Telephone (212) 705-7332

2.2 Stability and ReactivityVinyl acetate is always shipped containing a polymer-

ization inhibitor. Properly inhibited, vinyl acetate isstable under recommended storage conditions. Highertemperatures or contamination may cause rapid anduncontrolled polymerization. Pressure generation during such polymerization may rupture insufficientlyvented containers. Drums of vinyl acetate should bestored out of direct sunlight; the shelf life decreaseswith increasing temperature and decreasing inhibitorconcentration. For instance, drums inhibited with 3-5ppm hydroquinone may be stored at temperatures upto 30°C (86°F) for periods not exceeding 6 months.Drums of vinyl acetate inhibited with 14-17 ppmhydroquinone may be stored at temperatures up to30°C (86°F) for periods not exceeding 1 year. Bulk storage of vinyl acetate at ambient temperatures is anacceptable practice when there is turnover of the tankcontents every 60 days or less. Inhibitor levels should be monitored if a stability problem is suspected.

Although storage of vinyl acetate under either air orinert gas is acceptable, storage under air will result inthe head space’s having a flammable vapor compositionat normal temperatures. It is thus safer to blanket thevinyl acetate under an inert atmosphere. This is possiblebecause dissolved oxygen is not necessary for the

hydroquinone inhibitor to function effectively in vinylacetate storage and handling; the monomer is actuallymore stable the lower the oxygen concentration.Blanketing with a dry gas also eliminates contamina-

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Table I: Names

Chemical Name Vinyl AcetateCommon Name Vinyl AcetateSynonyms Acetic Acid, Vinyl Ester

Acetic Acid, Ethenyl EsterVinyl Acetate MonomerVAM™Ethenyl Acetate1-Acetoxyethylene

CAS Name Acetic Acid, Ethenyl EsterCA Registry Number 108-05-4Chemical Formula CH3COOCH=CH2

Table II :Properties and Characteristics of Vinyl Acetate

Formula Weight 86.09Physical State LiquidFlammable Limits (Vol. % LEL: 2.6in Air at 760 mm Hg) UEL: 13.4Flash Point

Tag Closed Cup (ASTM D 56) -8 °C (18 °F)Tag Open Cup (ASTM D 1310) -4 °C (25 °F)

Autoignition Temperature 426.9 °C (800 °F)Boiling Point at 760 mm Hg 72.7 °C (162.9 °F)Relative Evaporation Rate 8.9(n-Butyl Acetate = 1)Vapor Pressure

at 60 °C 487.4 mm Hgat 40 °C 222.1 mm Hgat 20 °C 89.1 mm Hg

Antoine Equation Coefficients Log P = A - (B/(T + C))Log = Base 10, T = °C, P = mm Hg Range = 10 to 83°C

A 7.51868B 1452.058C 240.588

Critical Temperature 246 °C Critical Pressure 574.0 psia (39.0 atm) Color Clear and colorlessSpecific Gravity (20/20 °C) 0.934Vapor Density (Air = 1.00) 2.97Viscosity at 20 °C 0.43 cpsFreezing Point -92.8 °C (-135 °F)Heat of Combustion (25 °C) -495.0 Kcal/mole Heat of Vaporization (1 atm) 87.6 cal/g Heat of Formation (liquid at 25 °C) -83.5 Kcal/moleHeat of Polymerization 21.3 Kcal/moleSpecific Heat at 20 °C (liquid) 0.46 cal/gram °COdor Not unpleasant,

sweetish smell in small quantities.

Reactivity Reactive with self and variety of other chem-icals. Stable when properly stored and inhibited. See Section2.2 for details.

Water SolubilityVinyl Acetate in Water at 20 °C 2.3 % by weight Water in Vinyl Acetate at 20 °C 1 % by weight

Light Sensitivity Light promotes polymerization

Electrical Conductivity at 23 °C 2.6 x 104 pS/m (1 S = 1 mho)

Refractive index, nD20 1.3953

Surface tension (20 °C) 23.6 dynes/cmCoefficient of cubical expansion .00137 per °C at 20 °C

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tion of the monomer with atmospheric moisture andthe attendant hydrolysis to acetic acid and acetaldehyde.

Because of vinyl acetate’s reactivity, it must be keptout of contact with peroxides, hydroperoxides, hydro-gen peroxide, azo compounds, and other polymerizationinitiators, as well as strong acids, alkalis or oxidizingagents. Exposure to sunlight, ultraviolet light, or X-rays may result in spontaneous polymerization.

Vinyl acetate should be stored and handled in rust-free carbon steel or mild steel equipment. Stainlesssteel, aluminum, and high baked phenolic-lined steelare also suitable. However, many other common liningmaterials are attacked by vinyl acetate. Copper, copperalloys (such as brass or admiralty metal), zinc and galvanized steel should not come into contact with vinylacetate because of possible adverse effects on end uses.

3. TRAINING AND JOB SAFETY3.1 Employee Education and Training

Because of the hazards associated with vinyl acetate,all personnel with responsibilities for handling itshould be made familiar with its properties and shouldbe thoroughly trained on the storage and handlingrequirements, including all applicable governmentoccupational safety, health and environmental regu-lations. Furthermore, the training should be conductedby persons with knowledge and experience in theseareas and must also, at a minimum, meet the require-ments of government regulations.

3.2 Process Hazard AnalysisEach step in the process of handling and using vinyl

acetate should be reviewed for hazards. The reviewshould cover the appropriateness of the equipment andthe procedures for using the equipment. The reviewteam should include personnel directly involved in theoperation, as well as technical and safety specialists.

The safety review must meet the requirements of government regulations (e.g., OSHA 29 CFR 1910.119)and should include evaluations of:■ process design and process controls■ personal protective equipment■ government regulations, including occupational

safety, health and environmental requirements ■ response to foreseeable emergency situations ■ safety equipment, such as shower and eyewash sta-

tions, fire extinguishers, alarms, ventilation, reliefdevices, grounding devices, etc.

Hazards identified by the review must be addressedin a timely manner. Process hazard analyses must alsobe repeated with a frequency defined by governmentregulations, or in the event of an incident.

Where engineering controls are used to control haz-ards, the purpose and importance of keeping them inservice and good repair must be part of the training ofthe personnel responsible for handling and using vinylacetate. Where extremely critical processing steps areidentified in advance, appropriate levels of supervisorycontrol should be established.

Where engineering controls cannot completely eliminatehazards, procedures must be in place to assure safetyand personnel must be supplied with and trained in theuse of personal protective equipment. Where appropri-ate, signs should be posted to emphasize the hazard,the use of protective equipment and limitation of accessto authorized personnel.

Standard operating procedures (SOPs) with safetyinformation and Material Safety Data Sheets (MSDSs)should be available to the workers at all times, andshould be the basis for training the workers. Audits ofwork practices should be conducted regularly to assurecompliance with all recommended safety and operatingguidelines.

4. HEALTH INFORMATION4.1 Toxicity

For current and more detailed information on chronicand acute toxicity of vinyl acetate, review your supplier’sMaterial Safety Data Sheet (MSDS) or contact yoursupplier.

As with all chemical substances, the health effectsassociated with vinyl acetate depend upon how much of the substance one is exposed to and the duration ofthat exposure. Exposure-related health effects usuallyincrease with increasing exposure levels (or concentra-tions) and exposure periods. It is also recognized thatfor most types of adverse health effects, there is a“threshold” level of exposure to the chemical belowwhich the effect will not occur.

Vinyl acetate’s odor may be pleasant at first, butquickly becomes more irritating. Its odor in air can bedetected at approximately 0.5 ppm. Vinyl acetate vaporis irritating to the eyes and respiratory tract; the liquidis irritating to the skin. Most people find concentrationsof 20 ppm to be irritating to the throat and experiencecoughing or hoarseness. Some people sense irritationat 4 ppm of vinyl acetate in air.

4.1.1 Acute Effects of Exposure

4.1.1.1 Ingestion (swallowing)Ingestion of vinyl acetate is not an anticipated route

of human exposure. Ingestion may cause severe irrita-tion or chemical burns of the mouth, throat, esophagusand stomach. Vinyl acetate is slightly toxic by ingestion.

4.1.1.2 Inhalation (breathing)Inhalation of vinyl acetate vapor may cause irritation

to the eyes, nose, throat and respiratory tract. Highlevels of exposure could result in pulmonary edema.Inhalation of mists or aerosols could result in irritationof the upper respiratory tract or nonspecific discomfortssuch as nausea, headache or weakness.

4.1.1.3 Dermal Contact (skin)Vinyl acetate has a defatting action and has resulted

in severe skin irritation with formation of blisters following industrial exposure. Vinyl acetate can beabsorbed through the skin.

4.1.1.4 Eye ContactVinyl acetate is a severe eye irritant and may cause

redness and swelling. Eye contact with the liquid canresult in severe corneal burns and may result in irre-versible injury.

4.1.2 Chronic Effects of ExposureThere are significant chronic effects from overexposure

to vinyl acetate. For current information on the chronictoxicity of vinyl acetate, review your supplier’s MaterialSafety Data Sheet (MSDS) or contact your supplier.

4.2 Industrial Hygiene

4.2.1 GeneralThe National Institute for Occupational Safety and

Health (NIOSH) and the American Conference ofGovernmental Industrial Hygienists (ACGIH) have bothrecommended exposure limits for vinyl acetate. NIOSHrecommends a 15 minute ceiling limit of 4 ppm, basedon sensory irritation. The ACGIH recommends an 8 hour Threshold Limit Value (TLV) Time-WeightedAverage (TWA) for vinyl acetate of 10 ppm and a 15minute short-term exposure limit (STEL) of 15 ppm.Verify these exposure limits with your supplier’s current MSDS.

The ACGIH has designated vinyl acetate as an “A3 Animal Carcinogen.” This designation refers to anagent which is carcinogenic in experimental animals ata relatively high dose, by route(s) of administration, atsite(s), of histological type(s), or by mechanism(s) thatare not considered relevant to worker exposure.

The International Agency for Research on Cancer(IARC) has evaluated vinyl acetate as a “Group 3” material, which indicates that it “is not classifiable as to its carcinogenicity to humans.”

Vinyl acetate should be handled in a well ventilatedarea or in completely closed systems. In the event of arelease of vinyl acetate, the area should be evacuatedimmediately. Only appropriately trained personnelequipped with appropriate safety equipment shouldenter the area. Full protective clothing (Section 4.4)should be worn when it is necessary to work in an environment contaminated with vinyl acetate.

4.2.2 Personal HygieneWorkers should be warned to avoid breathing vinyl

acetate vapors. Appropriate respiratory protectionshould be worn when exposure to vapors or mistsabove the established exposure limit may occur.Workers should be familiar with the location and oper-ation of respiratory protective equipment. They shouldbe instructed to immediately report any incident inwhich vinyl acetate has been inhaled. Safety showersand eyewash facilities should be provided in the areasin which vinyl acetate is being handled. Workersshould be trained to promptly wash any area of theskin exposed to vinyl acetate with large amounts ofwater. All contaminated footwear and clothing shouldbe removed immediately. Contaminated shoes andleather items should be appropriately disposed of.Contaminated clothing should be properly laundered.Home laundering of contaminated clothing is not recommended. Clothing must either be cleaned by anindustrial cleaning service familiar with vinyl acetateor properly disposed of.

4.3 First Aid

4.3.1 GeneralIn case of contact with vinyl acetate, first aid should

be started immediately. The patient should be referredto appropriate medical personnel, who should be pro-vided with the details of exposure and symptoms.

4.3.2 Ingestion (swallowing)The patient should be made to drink large quantities of

water or milk. Vomiting should not be induced, becausevinyl acetate may be aspirated into the respiratory tract.

4.3.3 Inhalation (breathing)The patient should be removed from the contami-

nated area to fresh air and should be monitored forsigns of respiratory distress. If breathing is difficult,supplemental oxygen may be needed. If breathing hasstopped, artificial respiration should be started.Respiratory tract irritation, bronchitis, pneumonitis orpulmonary edema may develop. Contact a physician.

4.3.4 Dermal Contact (skin)The exposed skin area should be thoroughly washed

with soap and water. If the exposed skin is not thoroughlywashed, blistering may develop 24 - 48 hours later.Contaminated shoes and other leather items should be

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properly disposed of. If irritation and pain persist afterwashing, contact a physician.

4.3.5 Eye ContactExposed eyes should be irrigated with large amounts

of water at room temperature for at least 15 minutes.The eyelids should be held open and away from theeyeball during the irrigation to insure contact of waterwith all tissue surfaces of the eyes and lids. Contact aphysician immediately.

4.4 Personal Protective Equipment

4.4.1 Availability and UsePersonal protective equipment is not an adequate

substitute for safe working conditions and compliancewith safety procedures on the part of employees. It is,however, in some instances, the only practical means ofprotecting the worker, particularly in emergency situa-tions. The proper use of personal protective equipmentrequires adequate training of workers. The personalprotective equipment described in the following para-graphs should be used when there is a potential foroverexposure to vinyl acetate.

4.4.2 Protective ClothingProtective clothing made of chemical- and fire-resistant

material must be worn in process areas. Whenever thesegarments become contaminated with vinyl acetate, theymust either be cleaned by an industrial cleaning servicefamiliar with these products or properly disposed of.

Full protective clothing should be considered as fol-lows: a chemical- and fire-resistant suit, gloves, bootsand eye and respiratory protection. See your supplier’sMaterial Safety Data Sheet or contact your supplier foradditional information.

For spills, emergencies and activities with the poten-tial for substantial or unknown exposure, use suppliedair respiratory equipment with full protective clothing.For routine operations with potential for minor liquidexposure and vapor exposure below established expo-sure limits, gloves, monogoggles and chemical apronsare satisfactory. For routine operations with potentialvapor exposure up to 10 times the established exposurelimits, NIOSH approved organic vapor respirators withfull face pieces should be added.

4.4.3 Foot ProtectionSafety footwear (OSHA 29 CFR 1910.136 / ANSI

Z41.1-1991) with built-in steel toe caps is recommendedfor most industrial operations. For added protectionagainst chemical contact, safety footwear of chemically-resistant material should be worn over leather safetyshoes.

Chemical-resistant safety footwear should be thoroughly cleaned before reuse. All footwear con-taminated with vinyl acetate on the inside should be properly disposed of.

4.4.4 Eye ProtectionSafety glasses must be worn as minimum eye pro-

tection (OSHA 29 CFR 1910.133 / ANSI Z87.1-1989).Side shields and/or chemical splash goggles are recom-mended for enhanced protection. Full eye protectionshould include face shields [full length, 20 cm (8 in.)minimum] with forehead protection in addition tochemical splash goggles when handling vinyl acetate.If vapor or mist exposure is sufficient to cause eye irritation or if an emergency situation exists, eye protection can be provided through the use of a fullface mask in conjunction with the appropriate respira-tory protection.

4.4.5 Respiratory ProtectionRespiratory protection equipment (OSHA 29 CFR

1910.134 / ANSI Z88.2-1992) must be a type approvedby NIOSH. This equipment must be carefully main-tained, inspected, cleaned and sanitized at regularintervals and should be cleaned and sanitized beforeuse by another person. Severe exposure to vinyl acetatemay occur during equipment cleaning and repairs,when decontaminating areas after a spill or in case ofthe failure of piping or equipment. Employees whomight be subject to such exposures must be providedwith approved respiratory protection, trained in its useand care and medically evaluated to ensure that theycan safely use the equipment. Available types of equip-ment are described as follows:■ Situations where potential exposure could be greater

than 1000 ppm: Use self-contained breathing appa-ratus (SCBA), positive pressure unit, which permitsthe wearer to carry a supply of breathing air in acylinder.

■ Situations where potential exposure could be 101 to1000 ppm: Use supplied air respirators, continuousflow, positive pressure.

■ Situations where potential exposure could be 11 to100 ppm: Use air purifying respirators (low levelconcentrations only). SCBAs allow considerable mobility. The length of

time this apparatus provides protection varies accord-ing to the amount of air carried and used. Wheremobility is required, only SCBA should be used.Supplied air respirators provide air from standard size breathing air cylinders or from other reliable respirable air sources. Conventional air compressors or plant air systems must never be used as a source ofrespirable air. Air purifying respirators provide conve-nient protection with considerable mobility. Theyshould be used only when exposure concentrations areknown to be at low levels. Follow the manufacturer’srecommendations for use.

4.4.6 Head ProtectionHard hats (OSHA 29 CFR 1910.135 / ANSI Z89.1-

1986) are recommended for protection from fallingobjects, overhead liquid leaks and chemical splashes.

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5. BULK STORAGE AND HANDLING

5.1 Building DesignEquipment and vessels containing vinyl acetate

should preferably be isolated from other facilities bywalls and floors of fire resistive construction. Standardfire walls are recommended for the isolation of largerequipment and storage tanks, while partitions of plaster on expanded metal lathe may be used to isolatesmaller equipment from other combustible materials.

At least two means of exit should be provided fromeach room or building in which vinyl acetate is storedor used. No portion of such a room or building should befurther than 75 feet from the nearest exit. Additionalexits should be provided depending upon the number of persons in the building. (See NFPA Standard #101,“Life Safety Code.”) All exit doors should open out inthe direction of travel and should be provided withpanic hardware. Fire doors should be of an approvedtype. A fire resistive stairwell with self-closing firedoors should be provided where hazardous operationsare carried out on upper floors.

Operations where large quantities of vinyl acetateare used should preferably be processed in outdoortype structures or housed in one-story buildings pro-tected by automatic sprinkler systems. Explosion ventsmay be used to reduce destructive damage to buildings,ducts, mixers, blenders, dryers and similar equipmentin which flammable vapors of vinyl acetate are liable toconcentrate. Explosion venting windows, roof and wallpanels, skylights, light windows, diaphragms, etc., maybe used to minimize building damage due to explosionpressures.

Since the required area of explosion vents dependsupon such factors as the intensity of an explosion,vapor temperature, type of structure, type of vent clo-sure, etc., the determination of vent ratios should bemade by experienced engineers. Consideration may begiven to explosion suppression systems. (Reference:NFPA Fire Codes, Vol. 9 – #68).

The need to segregate floor drains from sanitary orprocess sewer systems should be considered as well asthe question of adequate distances between chemicalstorage buildings and other buildings and processingequipment.

5.2 Storage Equipment Guidelines

5.2.1 Storage TankVinyl acetate should be stored in tanks made of rust-

free carbon or mild steel. Stainless steel, aluminum orhigh baked phenolic-lined steel are also suitable. How-ever, many other common lining materials are attackedby vinyl acetate. Copper, copper alloys (e.g., brass andadmiralty metal), zinc and galvanized steel should notcome into contact with vinyl acetate because this canresult in possible adverse effects on end uses. However,certain passivated zinc-based coatings may be accept-able. Consult your supplier for more information.

A newly constructed carbon steel tank should be prepared for service by sandblasting and vacuumcleaning. If the cleaned tank is not to be immediatelyfilled with monomer, it should be closed and blanketedwith dry air to retard rusting.

Type: Suitable for flammable liquidsMaterial: Rust free steel, high baked phenolic-lined

steel, stainless steel or aluminum.Design: American Petroleum Institute (API)Fittings: Nozzles for temperature sensors, manhole

cover, dip pipe, vent line, pressure and vacuum relief valve, emergency relief valve, manometer level gauge, high level alarm, overflow, fill and discharge.

The design for an above-ground tank should incorpo-rate a vertical shell, a flat bottom and a conical top.Some states may require that vinyl acetate be stored intanks with internal floating roofs. The design selectedshould allow uniform mixing of the contents with newdeliveries. The tank should be set on a concrete padwithin a concrete dike of sufficient capacity. A tankwell with a bottom drain line through the tank pad will provide complete tank drainage.

Bulk storage of vinyl acetate at ambient tempera-tures is an acceptable practice when there is turnoverof the tank contents every 60 days or less. Tanks nor-mally used for vinyl acetate monomer storage shouldbe painted white to minimize heat absorption duringthe summer months. Tanks should be well groundedelectrically. Refer to NFPA #77 “Static Electricity” forproper grounding procedures. The electrical resistancebetween the tank and ground must not exceed 5 ohms.Vinyl acetate storage tanks should have check valveson inlet lines and remote shutoff valves on outlet lines.

When filling, circulating or agitating vinyl acetate ina storage tank, care should be taken not to vigorouslydisrupt the liquid surface (causing a static charge)unless the tank vapor space is inerted.

Vinyl acetate storage tanks should not be locatednear heat or ignition sources or oxidizing agents suchas chlorine bleach and should be in well ventilatedareas. There should be secondary containment suffi-cient to handle spills. Emergency response equipmentshould be readily available.

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5.2.2 Temperature Measuring DeviceThe temperature sensing element should be placed

near the tank bottom to ensure that it is always in theliquid. In large bulk storage tanks, additional sensingelements should be installed. A high temperaturealarm should also be installed to warn of polymeriza-tion. It should activate at a temperature about 5°Cabove the normal temperature of the stored liquid.

5.2.3 Emergency Vent – Pressure Relief DeviceStorage tanks containing vinyl acetate must be

equipped with emergency vents sized according to therequirements stipulated in NFPA No. 30. Emergencyventing devices normally used for flammable liquidsare considered to give adequate fire protection. Thistype of device may not provide adequate relief in theevent of an uncontrolled or runaway polymerization.The vent and relief system should be checked fre-quently for plugging by polymer from condensedmonomer. Heat tracing can alleviate this problem.

5.2.4 Dip PipeType: Size of inlet pipe, full height of tankMaterial: Same as tank

The dip pipe must be electrically grounded to preventthe buildup of static electrical charges during tank filling.

5.2.5 Vent Line and AccessoriesA vent line and associated devices are required to

provide a dry blanket atmosphere over the monomer.This blanket allows for disposal of vapors, reducesemissions and prevents the hydrolysis of the vinylacetate. Although storage of vinyl acetate under eitherair or nitrogen is acceptable, nitrogen is the pad gas of preference, since the absence of oxygen preventsflammability in the tank’s vapor space and also mini-mizes polymerization of the vinyl acetate (see Section 2.2).

A conservation vent device may be used to minimizevapor emission and the amount of blanket gas required.If a positive pressure, dry atmosphere is provided, anauxiliary dryer is not required. If a dryer or overflow potis used, it should be checked frequently for plugging bypolymer from condensed monomer.

5.2.5.1 Dryer The drying agent should provide a dry vapor space

over the monomer to eliminate water contamination. It can be installed on the vent line, pad gas line or conservation valve inlet line. The drying agent is usually renewed every 3 to 6 months, depending onlocal climatic conditions. Care should be taken to prevent blocking due to polymer. Molecular sieves and calcium chloride are typical desiccants. Silica and alumina are not recommended.

5.2.5.2 Flame ArresterType: Approved by the Bureau of

Fire Underwriters

The installation of flame arresters on tanks holdingflammable liquids may be required by federal, state orlocal ordinances or by insurance companies. For propersafety, they must be installed correctly in any vapor(vent) line, with the exception of the emergency vent,which can be opened directly to the atmosphere. Flamearresters should be inspected at least once every 6months for blockage by polymer. When using closed circuit unloading, an additional flame arrester shouldbe installed in the vapor return line.

5.2.6 Overflow Seal PotIf the capacity of the tank is exceeded during trans-

fer of monomer from a delivery vehicle, the excessmonomer should flow through a properly designedoverflow seal pot or seal loop to a suitable receiver.

5.2.7 Pressure And Vacuum Relief ValveA pressure and vacuum relief valve is required to

prevent the collapse or rupture of the tank caused byplugging of the dryer, inadvertent closing of a valve inthe vapor line during closed circuit unloading or block-age in the vent line or flame arrester due to clogging by polymer. This device also allows inhalation/exhala-tion of the tank during extreme ambient temperaturechanges.

5.2.8 Liquid Level GaugeA differential pressure transmitter purged with dry

gas is preferred as the level measuring device. Thisgauge provides a continuous level readout with alarmcapabilities at any remote location. A high level alarmset at 85% of the tank capacity and a high level tankfeed line shutoff set at 90% are suggested. Manometer-type level gauges or equivalent are preferred overgauge glasses, should the differential pressure stylenot be used.

5.2.9 PumpsType: Centrifugal or self-priming centrifugalMaterial: Cast steel or stainless steel

Mechanical seals are typically used, but seal-less orcanned pumps are also acceptable. If tank cars or tanktrucks are to be unloaded from the top, a self-primingcentrifugal pump is recommended. CAUTION: If seal-less or canned pumps are used, heat generation can cause polymerization in thepump should flow be stopped.

Care should be taken to prevent dead-heading ofpumps in monomer service. The pumps can also beused to unload tank trucks not equipped with gearpumps and to transfer monomer from the storage areato reactors or other vessels. Pump motors should meet

6

the requirements outlined in Section 5.2.16 for electri-cal equipment and should be properly grounded.

5.2.10 PipeMaterial: Steel (schedule 40) or stainless steel

(schedule 10)

Steel piping should be cleaned of all grease and scaleadhering to the inner walls. All pipes should be paintedwhite or otherwise protected from the heat of directsunlight. All pipes should be pitched to drain and haveno deadheads. Pipelines and associated systems thatwill be dormant should be drained and cleared. Anymonomer remaining in the lines may polymerize.Nitrogen should be used to blow pipelines clean.CAUTION: Blowing lines with gases can generatestatic charges.

5.2.11 ValvesType: Polytetrafluoroethylene (PTFE)-sleeved

plug valves, globe valves, gate valves, ball valves

Material: Carbon steel, ductile iron or stainless steel

Ball valves with PTFE seals are suggested for on-offservice.

5.2.12 Gaskets Material: Compressed fiber, compressed graphite

or glass-filled PTFE.

5.2.13 FilterType: In-line cartridge filter Material: White cotton fiber or polypropylene

wound on a stainless core or stainless steel mesh

Rust particles or other particulate matter can be satisfactorily removed from vinyl acetate by means of a cartridge filter of the above type.

5.2.14 Fusible Link Check ValveSome localities in the United States stipulate the

installation of a fusible link check valve to stop the flowof monomer from storage tanks in case of a fire in thevicinity of the tank. When it is required, the checkvalve is placed in the line between the tank valve andthe pump.

5.2.15 High Level SwitchesAn ultrasonic type or differential pressure (dP) switch

is preferred for high level switches, which should be set at90% of tank level. A capacitance probe would be a sec-ondary choice for this application. Float switches tend tohave problems with plugging from condensed monomerthat has polymerized. Typically, the high level switch isdesigned to close an actuated valve in the tank feedline and can also be used to shut down the feed pump.

5.2.16 Electrical EquipmentElectrical devices and installations in areas where

vinyl acetate is handled should be suitable for Class I,Group D hazardous locations (as defined by Articles500 and 501 of the National Electrical Code.)

5.3 Unloading into Storage Tanks

5.3.1 Storage Tank Vent HandlingWhen bulk shipments are unloaded, the storage tank

vent gas may be returned to the shipping vessel througha vapor return line, or may be sent to a flare or inciner-ator. In each of these cases, the vent line must haveflame and/or detonation arresters properly installedand, in some cases, must have inert gas added to render the vent gas non-flammable, depending onapplicable regulations.

5.3.2 HosesTo help minimize static electric charge buildup, only

electrically continuous chemical transfer hoses shouldbe used for vinyl acetate.CAUTION: These hoses should not be relied on to be the primary electrical bond; bonding andgrounding cables must be used.

Dry disconnect hose connections that allow only afew drops of spillage when disconnected are available.They also prevent excessive spillage if the connection is accidentally broken during transfer. Contact yoursupplier for additional information.CAUTION: Hoses should be dedicated to single service.However, if they must be used for multiple service, theyshould be cleaned after use to avoid cross-contamination.

5.4 Tank and Equipment Cleaning and Repairs

This section provides general guidelines and sugges-tions for the preparation and cleaning of vinyl acetatetanks and equipment prior to entering for inspectionand repair. It is not intended to take the place of adetailed procedure written for the specific job and situation.

5.4.1 Preparation for the Job Tank and equipment cleaning should be under

the direction of thoroughly trained personnel who arefamiliar with all of the hazards and the safeguardsnecessary for the safe performance of the work. All precautions pertaining to education, protective equip-ment and health and fire hazards should be reviewedand understood. See appropriate sections of this manual.

A stepwise procedure for the entire job should bewritten and used to train all personnel involved with thework. The procedure should include specific instructionsregarding possible hazards with safe procedures fordealing with these hazards, and should designate suitable protective equipment necessary for the job.

7

5.4.2 Preparation of Tanks and Equipment The tank, equipment and associated lines to be

cleaned should first be electrically grounded and thenemptied of all liquid. In the case of large tanks, it isimperative that the tank vent and make-up system bein good working condition to keep from over-pressuringor collapsing the tank. The bulk of the liquid should betransferred to another vessel (for recovery or rework, ifnecessary) so that any heel of liquid is minimized. Theheel should then be drained into a suitable containerfor proper reuse or disposal. In the case of large storagetanks, it may be helpful to add about 6 inches of waterto the tank to “pick up” the material in the low spots ofthe tank. The liquids should be properly disposed of.CAUTION: The vapor space above even dilute aque-ous solutions of vinyl acetate may be flammable.

Then the vessel and piping to be cleaned should beisolated from all other systems by closing the propervalves. Wash and flush the equipment three or fourtimes with hot demineralized water, preferably 49 to66°C (120 to 150° F). The dirty wash water should becollected in a sump or other suitable vessel for properdisposal, taking into consideration all environmentaleffects. Steam may be used to remove final traces ofvinyl acetate. If polymer is present, a strong aqueousdetergent or caustic solution can be used to help loosenand remove it. CAUTION: Do not use caustic or alkali detergent solutions when liquid vinyl acetate is present orwith aluminum equipment. Finally, flush with cold demineralized water until theequipment temperature is below 38°C (100°F). Drain allthe water from the equipment.

Then the lines in and out of the tank or equipmentshould be disconnected and blinded for entry. Note:Even though the equipment has been flushed withwater, proper protective equipment should be wornwhen opening flanges. The equipment should then be purged with fresh air and the air should be testedfor vinyl acetate vapors and oxygen content by anapproved method before permitting personnel to enter.Tank entry is covered by OSHA standard for ConfinedSpace Entry, 29 CFR 1910.146 and the Lockout/TagoutRule for Control of Hazardous Energy, 29 CFR 1910.147.

6. BULK TRANSPORTVinyl acetate must be inhibited when stored or tran-

ported. Container cleanliness is essential. Tank carsand tank trucks used to transport other materials

should be cleaned and dried before reuse. Prior to load-ing, all containers should be inspected to assure theyare proper for vinyl acetate. Each container should beproperly secured and free of leaks before offering fortransportation. Empty containers containing a residueof vinyl acetate must be secured as if they were fullyloaded for the return trip to the supplier. All appropriatelabels must be on shipping containers. Containersmust never be totally filled; outage space must be leftto make room for thermal expansion.

6.1 Unloading Bulk Shipments from Tank Cars and Tank Trucks

The use of tank trucks and tank cars for the bulk transport of vinyl acetate is authorized by theDepartment of Transportation in regulations 49 CFR173.31 and 173.33, respectively. Section 173.242 liststhe type of bulk containers required for certainmedium hazard liquids. Rail transport is expanded in section 174 with the tank car specifications detailedin section 179. Section 177 expands the highway trans-portation requirements and Section 178 gives tanktruck specifications.

The use of tank cars with top unloading fittings ispreferred to minimize the chance of leakage or spillage.A dry nitrogen pad should be used on the car to makethe transfer or to provide suction to a pump. If the cardoes not have an eduction pipe for top unloading, onecan be inserted through the manway. Alternatively,bottom unloading tank cars may be used.

Upon arrival at the delivery site, the tank car or tanktruck must be inspected for leaks or damage. If thereare any problems, notify the supplier, the owner of thecar or truck and the railroad company even if the tankcan be unloaded safely. Always ensure that the dam-aged car or truck is in acceptably safe condition beforeit leaves your property.

When a tank car or tank truck arrives:■ Check the shipping papers against the placards

and labels and seals as appropriate to assure properidentification.

■ Check that the car or truck is parked within the designated containment area and that the connec-tions will reach the appropriate fittings.

■ Chock the wheels, set the brakes, shut down truckengines and set derails on tank car tracks.

■ Set up warning signs as appropriate.■ Use electrical bonding and grounding to minimize

static electricity buildup.■ Use grounded pumps or appropriately regulated dry

nitrogen pressure (never air) for transferring vinylacetate.

■ The tank truck driver must be out of the truck during unloading.

■ Always be sure the transfer equipment containsnothing to contaminate the vinyl acetate, especiallystrong oxidizers, acids or bases. Special care isrequired if dedicated equipment is not used.

8

■ Regulations may require the use of vapor control systems.

■ Emergency response equipment should be readilyavailable.

■ As long as the car or truck is connected to your sys-tem, it should be continuously attended by trainedpersonnel equipped with appropriate personal pro-tective gear.

■ If the car is open to the atmosphere during unload-ing, a flame arrester is recommended.

■ Prior to opening any covers, check the availability ofthe emergency shower and water for wash down.

■ Before a tank car manway cover, outlet valve cap orplug is opened, the car should be relieved of pressurethrough the vent valve.

■ Before removing caps on nozzles, be sure the valvesare closed. In some cases a valve may have leaked,building pressure between valve and cap. Always usecaution in removing caps even after having ventedthe tank car.

■ If hoses must be run across driveways, set up barri-cades to protect them.

■ Confirm that the tank to receive the material hassufficient room to hold the entire contents of thetruck or tank car.

■ If sample purging is done, a metal bucket (not plasticor other non-conducting container) electricallybonded to the sample line is required.

■ Before beginning transfer, check that any necessarysamples have been taken and check for proper align-ment from the car or truck to the tank.

■ Use low transfer rates (velocity of 3 ft/sec.) until thedip pipe in the tank being loaded is completely sub-merged in liquid, then complete transfer at amaximum of 15 ft/sec.

■ Do not make a transfer during an electrical storm.Your supplier may be consulted for advice on particular

situations. Also, the Association of American Railroadsprovides information on methods of loading andunloading non-pressure tank cars in its Pamphlet 34.

6.2 Shipping

6.2.1 Classification and RegulationsVinyl acetate is a hazardous material listed in the

DOT Hazardous Materials Table 49 CFR 172.101. It isalso a hazardous substance as defined by the EPA andlisted in Appendix A to the Hazardous Materials Table.49 CFR Sections 171 to 180 describe the DOT require-ments for shipping inhibited vinyl acetate by air,highway, rail and water.

6.2.2 DOT Shipping Information (as of May, 1994)Shipping name Vinyl acetate, inhibitedHazard Class 3 (Flammable liquid)UN/NA ID number UN 1301Packing group IIReportable quantity 5000 lb / 2270 KgPlacard FlammableLabel Flammable liquidEmergency response guide No. 26

7. STORAGE AND HANDLING OF DRUMS

Drums of vinyl acetate should be stored out of directsunlight; the shelf life decreases with increasing tem-perature and decreasing inhibitor concentration. Forinstance, drums inhibited with 3-5 ppm hydroquinonemay be stored at temperatures up to 30°C (86°F) forperiods not exceeding 6 months. Drums of vinyl acetateinhibited with 14-17 ppm hydroquinone may be storedat temperatures up to 30°C (86°F) for periods notexceeding 1 year. Storage areas should be well venti-lated and should be away from strong oxidizers, heatsources, ignition sources and combustible materials.

8. LABELING AND PLACARDINGContainers of vinyl acetate require proper labeling

before transporting storing, or handling. A MaterialSafety Data Sheet (MSDS) should be obtained, readand understood; it is available from your supplier.

A sample vinyl acetate label is shown on the nextpage. It includes the basic information on the MSDS,the flammable symbol, the CHEMTREC phone num-ber and the identity of the shipper.

Typically, a container of vinyl acetate will bear alabel similar to that shown on the following page. It willusually have a numbered seal to assure the materialhas not been tampered with. Trucks and tank carsshould carry the DOT placard with the flammablesymbol and the DOT ID number (see Section 6.2.2).

9

FLAMMABLE LIQUID

3

Vinyl acetate(Inhibited with hydroquinone)

DANGER!• Extremely flammable liquidand vapor

• Vapor may cause flash fire• May polymerize explosivelyif contaminated

• May cause skin and eye irritation• May cause allergic reaction• Possible cancer hazard:may cause cancer based onanimal data

Components, wt. % (CAS number): Vinyl acetate, 99.9% (108-05-4).

All components listed as required by federal, California, New Jersey andPennsylvania regulations.

Transportation informationShipping name: Vinyl Acetate, InhibitedHazard class: 3, Flammable Liquid United Nations no.: UN1301Packing group: IIEmergency Response Guide no.: 26DOT Reportable Quantity: 5000 lb/2270 kg

• Handling precautions:Keep away from heat, sparks and flame.Personal protective equipment may berequired for protection of eyes, skin and

respiratory system; see Material SafetyData Sheet for recommendations.Keepcontainers closed when not in use.Always open containers slowly to allowany excess pressure to vent. Do not get in eyes, or on skin or clothing. Do notbreathe vapor. Do not enter storage areaunless adequately ventilated. Use onlywith adequate ventilation. Do not load into compartments adjacent to heatedcargo. Use proper grounding procedureswhen transferring. Use spark-resistanttools. Wash thoroughly with soap andwater after handling.

• First aid:In case of eye contact, flush eyes with water at least 15 minutes. Call a physician.

• If inhaled, remove from contaminatedarea. If breathing has stopped, giveartificial respiration, then oxygen asneeded. Call a physician.

• In case of skin contact, removecontaminated clothing and wash affectedareas with large amounts of water. Call aphysician. Decontaminate soiled clothingthoroughly before re-use. Discardcontaminated leather clothing.

• If swallowed, the patient should bemade to drink large quantities of water ormilk. Vomiting should not be induced,because vinyl acetate may be aspiratedinto the respiratory tract.

• In case of fire:Use CO2 or dry chemical for small fires,alcohol-type aqueous film-forming foamor water spray for large fires. Water maybe ineffective but should be used to coolfire-exposed structures and vessels. Ifpotential for exposure to vapors orproducts of combustion exists, wearcomplete personal protective equipment,including self-contained breathingapparatus with full facepiece operated inpressure-demand or other positive-pressure mode.

• Unusual fire and explosion hazards:Rapid, uncontrolled polymerization cancause explosion. Vapor is heavier thanair and can travel considerable distanceto a source of ignition and flashback.Material creates a special hazardbecause it floats on water.

• In case of spill:Eliminate ignition sources. Contain spillto facilitate clean-up. If potential forexposure to vapors exists, wearcomplete personal protective equipment,including self-contained breathingapparatus with full facepiece operated inpressure-demand or other positive-pressure mode. Place leaking containersin well-ventilated area with spill contain-ment. If fire potential exists, blanket spillwith alcohol-type aqueous film-formingfoam or use water spray to

HMIS NFPA KeyHealth: 2 2 0 = Minimal Flammability: 3 3 1 = SlightReactivity: 2 2 2 = ModeratePersonal protective equipment:X - 3 = Serious

4 = Severe

For Chemical Emergency – spill, leak, fire, exposure or accident –

Prior tohandling this material,please refer to the current MaterialSafety Data Sheet forrecommended protective equipment and detailedhazard and precautionary information.

DANGER!After this container has been emptied, it may containresidual hazardous liquid or vapor.Avoid all contact.Keep away from heat, sparks and flame.Do not puncture, cut or weld on or near this container.

Vinyl Acetate, InhibitedUN1301

disperse vapors. Clean-up methods may include absorbent materials, vacuumtruck, etc. Avoid runoff into storm sewers and ditches which lead to naturalwaterways. Call the National ResponseCenter (800 424 8802) if the quantity spilled is equal to or greater than thereportable quantity (5000 lb/day) underCERCLA “Superfund”.

• Storage:To prevent hazardouspolymerization – Store in coolwell-ventilated area. Use only DOT-approved containers. Drums of VAinhibited with 3-5 ppm HQ should bestored at product temperatures notexceeding 30°C (86°F) and for periodsnot exceeding 6 months. Drums of VAinhibited with 14-17 ppm HQ should bestored at product temperatures notexceeding 30°C (86°F) and for periodsnot exceeding 1 year. Bulk storage of VAat ambient temperatures is an acceptablepractice when there is turnover of thetank contents every 60 days or less.Inhibitor levels should be monitored if a stability problem is suspected.

• Disposal of product and container:All notification, clean-up and disposalshould be carried out in accordance withfederal, state and local regulations.

94-D (12/31/93)

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9. CONTROL OF VAPORS AND WASTE DISPOSAL

9.1 GeneralThe proper personal protective equipment and safety

considerations have been discussed in other sections ofthis brochure. Emphasis should be placed on the pre-vention of leaks and spills through careful design andgood operating procedures.

Vinyl acetate is volatile and may give rise to vaporswith health effects as noted in your supplier’s MSDS.Careless handling, because of the low odor threshold(about 0.5 ppm), may elicit complaints from neighbors,particularly in urban areas.

Federal, state and local regulations require producersand users of chemical products to be fully aware of allapplicable laws and regulations. It is essential for pro-ducers and users to be aware of viable alternatives forsafe control of discharges and disposal of wastes andthat consideration be given to air, water (surface andground) and land pollution potential when handling,processing or disposing of vinyl acetate.

If a spill occurs, only trained and equipped personnelshould remain in the area for cleanup. The spilledmonomer must be collected and disposed of properly(see Section 10.2). Although small spills may be washeddown with water, their ultimate disposal must takeinto account local conditions, fire hazard and pollutionof the environment (see Section 10.2). Treatment of theaffected area with lime or other alkaline materials maybe desirable. Refer to Section 9.5 for information ondisposal of vinyl acetate waste.

A partial list of government regulations and agencyrecommendations for vinyl acetate can be found in theAppendix.

9.2 Air Pollution ControlAtmospheric emissions of vinyl acetate are subject to

federal, state and local regulations. Ozone in the atmo-sphere is a result of volatile organic compounds reactingwith nitrogen oxides in the presence of sunlight. Thevinyl acetate atmospheric half life has been calculatedto be 0.6 days.

Regulatory authorities may require stringent controlsfor vinyl acetate emissions because this monomer has alow odor threshold and may cause discomfort at lowambient air concentrations. Some regulations requirevapor recovery or other emission abatement systemsfor bulk storage, loading and unloading of volatileorganic compounds. Regulations may also require a

fugitive emission monitoring program which involvesinspection and maintenance of valves, pumps and com-pressors associated with the transfer of volatile organiccompounds.

All applicable governmental regulations for controllingair pollution should be reviewed to ensure compliance.The air pollution control division of most state environ-mental agencies is able to provide guidance on standardswhich must be met and any permits or other operatingauthority which may be needed.

Buildings used for processing or storage should bewell-ventilated to prevent local accumulation of vaporsand their effects upon personnel. Ventilation methodsinclude local exhaust and general dilution procedures.Local exhaust is most effective where vapors are emit-ted from local sources, such as liquid transfer points,pump houses and the reactor area. The method mayinvolve operation within an exhaust hood or removal ofvapors through ducts connected to an exhaust fan (seeSection 10.1.1 for specification of electrical equipment).General dilution ventilation may be used when vaporsare emitted from scattered points throughout a storageor processing area. In this method, vapors are dilutedand expelled by changing the air within the room orbuilding.

The ACGIH offers a publication entitled “IndustrialVentilation: A Manual of Recommended Practice.”This manual should be consulted for information on thedesign of exhaust hoods and ventilating equipment andrecommended dilution air change rates. Whicheverventilation procedure is adopted, the level of vaporscan be held to a minimum by keeping equipment ingood repair and by confining all volatile materials. Thisventilated air may require odor abatement.

Vinyl acetate emissions from point sources can bereduced by scrubbing with a caustic and/or an aminesolution, adsorption on activated carbon, venting to aflare, incineration or a combination of these methods.

9.2.1 Scrubbing with Caustic SolutionAir streams contaminated with vinyl acetate vapors

can be purified by absorbing the vapors in aqueoussodium hydroxide and/or amine solution. CAUTION: The system should be properly engi-neered to avoid direct contact of liquid vinylacetate with caustic or amine solutions.

Additional information and advice is available fromyour supplier. Note that discharge of the spent scrub-bing solution is regulated by federal, state and localauthorities.

9.2.2 Adsorption on Activated CarbonCanisters of activated carbon should only be used

after a scrubbing system as a finishing bed.CAUTION: During the adsorption process, oxidationand evolution of heat may occur, which can raise thetemperature of the adsorbent. At high vinyl acetate con-centrations, local overheating may ignite the system.

13

For this reason, a flame arrester should be installedbetween the vapor source and adsorption canisters.The activated carbon may be regenerated or disposedof after use. The disposal of the spent adsorbent is reg-ulated by federal, state, and local authorities.

9.3 Discharge to Navigable WatersFederal law prohibits discharge of pollutants to any

water without a permit. Some states have authority toissue permits under the National Pollutant DischargeElimination System (NPDES). For those which do not,an NPDES permit must be obtained from the Environ-mental Protection Agency (EPA). In some cases, a permitmay also be required from state or local authorities. Theterm “pollutant” is defined in such a way that traces ofvinyl acetate may be prohibited. Consult the “effluentguidelines” regulations promulgated for industriesspecified in the Clean Water Act. The water divisions ofmost state environmental agencies are able to provideguidance for the permits needed. In the permits, limitsare usually placed on a number of pollutant parame-ters. Those to which vinyl acetate contributes includeBOD5 (Biochemical Oxygen Demand – 5 day), COD(Chemical Oxygen Demand) and TOD (Total OxygenDemand), all of which measure the oxygen required todestroy the material under different conditions. Thefollowing table gives the available data on vinyl acetate,which is considered to be readily biodegradable (OECDtest, Guideline 301).

Table IIImg O2 Demand per mg Vinyl Acetate

Calc.COD TOD BOD5 BOD10 BOD20

1.43 1.67 0.63 1.03 1.36

Vinyl acetate is biodegradable in a biological treatmentsystem with properly acclimated bacteria. Vinyl acetateis hydrolyzed to acetic acid and acetaldehyde in freshwater with a disappearance rate of 8%/day at 20°C(68°F) and 5%/day at 4°C (39°F) at pH = 7.

9.4 Discharge to Municipal SewersDischarges which flow to a Publicly-Owned Treatment

Works (POTW) do not require an NPDES permit. ThePOTW may require a permit and there may be an ordi-nance specifying limits to specific parameters. In addition,there are Federal Pretreatment Regulations applicable todischarges to a POTW. There are some general and somespecific prohibitions. The POTW may be required to havea pretreatment program which may place certainrequirements on your discharge. The POTW should beable to provide all the information needed to meet allagency regulations. As long as the vinyl acetate is com-pletely dissolved in the discharge, (see solubility data intable II) it will be included in the measurement of BOD5.

9.5 Disposal of Wastes

Waste containing vinyl acetate must be treated ordisposed of at a federal, state or local authorized facility.As a liquid, this material cannot be disposed of directlyin a hazardous waste landfill. Preferred waste manage-ment is incineration or burning for heat recovery.Polymer may be disposed of in a permitted landfill orincinerated.

Aqueous waste streams containing dissolved vinylacetate can be treated in a biological digestion systemwhich is part of a plant wastewater treatment system.Trickle filters are not recommended for treatment ofvinyl acetate waste.

Though adequate dilution of concentrated wastes canreduce odor problems and fire hazard, direct dischargeof dilute wastes to municipal wastewater treatmentsystems may be inappropriate (see Section 9.4). Thetreatment method and its impact on sewage sludgemust be considered.

Vinyl acetate is toxic to fish and is a marine life hazard.Vinyl acetate is about twice as toxic to fish in soft wateras in hard water of pH=8.2. Waste containing vinylacetate could be hazardous under the ignitability criterion (Waste Code D-001 cited in 40 CFR 261) ofthe Resource Conservation and Recovery Act (RCRA).

10. EMERGENCIES10.1 Fires

10.1.1 Fire and Explosion HazardsVinyl acetate readily forms a flammable mixture with

air at ambient temperatures. Vinyl acetate has a flashpoint below 37°C (100°F) and is, therefore, classified as a “Flammable” liquid under Title 49 of the Code ofFederal Regulations (by the Department of Transpor-tation). Vapors are heavier than air and may travelconsiderable distances to an ignition source and flashback. Every precaution should be taken to preventexposure to flames, sparks or other ignition sources.

Static electricity is a particular problem when han-dling flammable materials; consequently, shipping andstorage containers, reaction vessels and transfer linesshould be electrically grounded and bonded. Electricaldevices and installations in areas where vinyl acetateis handled should be suitable for Class I, Group D haz-ardous locations (as defined by Articles 500 and 501 ofthe National Electrical Code). In setting up storage and handling facilities and procedures, care should betaken to conform with local ordinances and with the

14

regulations of underwriters and insurance companieswith respect to flammable liquids. Under fire conditions,rapid and uncontrolled polymerization can occur,resulting in an explosion.

10.1.2 Fire Fighting

10.1.2.1 ProceduresFire fighting individuals should be equipped with

self-contained breathing apparatus (SCBA) and com-plete personal protective equipment. Use water sprayto cool fire-exposed structures and containers and todisperse a vapor cloud if fire is not present. Drums ortanks containing vinyl acetate should be kept cool withwater (e.g. deluge system, fire monitor, etc.) to preventoverheating with resultant failure of the containerand/or polymerization of the monomer. Fire fightersmust also stay well away from involved vessels sinceplugging of relief valves and vent lines can occur whenthe uninhibited vapors polymerize, increasing the possibility of explosion. Do not presume that a vinylacetate vessel involved in a fire is safe just becauseventing has stopped. Unless the vent is obviously unobstructed, other indications such as pressure, temperature and noise must be considered.

10.1.2.2 Extinguishing Materials Use dry chemical, alcohol-type foam, universal type

foam or carbon dioxide for vinyl acetate fires. Vinylacetate and water are immiscible and therefore watermay be ineffective in extinguishing the fire but shouldbe used to keep fire-exposed containers cool. Use CO2 ordry chemical extinguishers for small fires and alcohol-type foam, universal-type foam or water fog for largefires. However, since vinyl acetate is lighter than waterand does not mix into water, care must be exercised notto spread burning monomer by a high velocity waterstream or through displacement by accumulated firefighting water. Vinyl acetate can float on water andspread fire. Water spray may be used to flush spills inorder to decrease exposures. Water spray can also beused to disperse vapors and protect personnel attempt-ing to stop a leak.

10.1.3 Fire Prevention Suggestions■ Locate vinyl acetate storage, handling and process-

ing equipment outside or in a non-combustible orfire-resistant building.

■ Do not allow combustible material, brush, weeds,etc., to accumulate around tanks.

■ Provide adequate venting for emergency conditionsin vessels used for storage, handling and processing.

■ Provide proper electrical equipment and adequategrounding for static electrical discharge.

■ When filling, circulating or agitating vinyl acetate in a storage tank, care should be taken not to vigor-ously disrupt the liquid surface (causing a staticcharge) unless the tank vapor space is inerted.

■ Regularly inspect equipment and storage facilities,especially vents and flame arresters.

■ Immediately correct any leaks in equipment.■ Provide adequate local exhaust and general ventila-

tion in the working area and carry out regular testswith a combustible gas indicator in any area wherevapors might accumulate.

■ Provide proper facilities to handle any accidentalspillage.

■ Provide adequate fire extinguishing equipmentincluding automatic sprinklers in storage and work areas.

10.2 Spill HazardsIn case of spills or leaks involving vinyl acetate

(a flammable liquid), all possible sources of ignitionshould be eliminated immediately. Only protected andtrained personnel should remain in the area. A recom-mended procedure for handling spills is:■ Try to locate and correct the source of the spill or leak.■ Assign trained personnel, with the proper personal

protective equipment, to the clean up operation.■ Cover the liquid vinyl acetate with sand and/or other

approved absorbent material.■ Allow the covering material to soak up the spilled

vinyl acetate.■ Remove the saturated absorbent to a safe area using

spark-proof tools and equipment.■ Dispose of the spilled material by biological oxidation

(usually <500 ppm) or by controlled incineration.Also properly dispose of any contaminated dirt orabsorbent materials.

■ Provide maximum ventilation obtainable until areais clean.

■ It is not advisable to wash spillage or leakage intothe sewer system; however, spills may be washed outof a building in an emergency.

■ Avoid run-off into storm sewers and ditches whichlead to natural waterways.

CAUTION: vinyl acetate and its aqueous solutions(containing greater than 0.5 wt %) can be fire hazards.

Call the National Response Center (1-800-424-8802),your Local Emergency Planning Committee (LEPC)and the State Emergency Response Committee (SERC)if the spill is a reportable quantity (see Section 6.2.2).Also, as required, state and other local authoritiesshould be notified even if the release amount is belowthe reportable quantity. All legally required reportsshould be made in a timely manner.

10.2.1 Small SpillsUse proper personal protection (see Section 4.4). If

the spill is in a laboratory, commercially available spillcleanup kits may be used and the appropriate instruc-tions should be followed. If an odor problem exists, addlime or other alkaline material.

15

10.2.2 Large SpillsUse proper personal protection (see Section 4.4). If

possible, contain the spill within a diked area, coverthe liquid with alcohol type foam to abate vaporizationand/or chance of ignition and proceed to recover thematerial in appropriate containers. Every effort mustbe made to keep the material out of sewers (danger ofexplosion) and surface waters.

In the event of accidental spillage of vinyl acetate to surface waters or to a municipal sewer system, theappropriate pollution control and water supply agen-cies must be notified. Floating booms are available forconfining floating liquids and should be kept on handwhere the possibility of spillage to waters exists. Withtheir use, the floating monomer can be pulled into asmaller area and skimmed off for recovery or disposal.Absorbing pads may also be used. These and otherabsorbents are useful on spills on the ground or surfacewaters and should also be kept on hand.

If contaminated dirt is classified as hazardous waste,under Federal Resource Conservation and RecoveryAct (RCRA) land ban rules, it must be incinerated in a rotatory kiln type incinerator.

10.3 Shipping Containers Damaged En Route

If a tank car or tank truck becomes damaged en routeso that it can not proceed safely to its destination, anevaluation should be performed to determine if it canbe moved to a location where the contents can be safelytransferred to another container. Police and firedepartments should be notified as well as CHEMTREC(toll free 1-800-424-9300). CHEMTREC will notify theproducer. The public should be restricted from the area.

11. ACKNOWLEDGMENTSGrateful appreciation is given to the respective

Technical, Safety, Health, Environmental, andManufacturing Departments of each Company for compiling the information presented in this publica-tion. Further appreciation is given to the Technical andEnvironmental, Health and Safety Affairs Departmentsof Celanese for coordinating the publication of this doc-ument.

References include:

Design Institute for Physical Property Data, AmericanInstitute of Chemical Engineers, 345 E. 47th St., NewYork, NY 10017.

Chemical Safety Data Sheet SD-75, Properties andEssential Information for Safe Handling and Use ofVinyl Acetate, Revised 1970, Manufacturing ChemistsAssociation, Inc., Washington, DC.

Vinyl Acetate Monomer Applications, Technical Data,Storage and Handling, 1989, Quantum ChemicalCompany, Cincinnati, OH.

Acrylate Esters: A Guide to Safety and Handling, 2ndEd., 1992; and Acrylic Acid: A Summary of Safety andHandling, 2nd Ed., 1991, published by the IntercompanyCommittee for the Safety and Handling of AcrylicMonomers (BASF Corporation, Celanese, Rohm andHaas Company and Union Carbide Corporation).

12. APPENDIXPARTIAL LIST OF GOVERNMENT REGULATIONSAND AGENCY/ASSOCIATION RECOMMENDATIONSFOR VINYL ACETATE

Compiled November 1, 1993

Legend: X–Applies; L – Listed; NL – Not Listed

American Industrial Hygiene Association Emergency Response Planning Guidelines . . . . . . . . . . . . . . . . . . . . . . . . . . . .L

NIOSH (National Institute for Occupational Safety and Health) Exposure Limits/IDLH Level . . . . . . . . . . . . . . . . . . .NL

American Conference of Governmental Industrial Hygienists (ACGIH) TLVs . . . . . . . . . . . . . . . . . . . . . .X

Canadian WHMIS (Workplace Hazardous Materials Information System) Ingredient Disclosure List (1% Rule) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .X

Chemical Inventories:United States – TSCA . . . . . . . . . . . . . . . . . . . . . . . .LOntario . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .L

Clean Air Act Section III Potential Human Health Hazards . . . . . . . . . . . . . . . . . . . . . . . .X

Clean Water Act Section 311 Hazardous Chemical . . . . . . . . . . . . . . . . . . . . . . . . . . .X

Department of Transportation (DOT) Hazardous Materials . . . . . . . . . . . . . . . . . . . . .X

International Agency for Research on Cancer (IARC) Unclassified and Probably Non-Carcinogenic Substances . . . . . . . . . . .X

Massachusetts Substance List . . . . . . . . . . . . . . . . . . .X

National Toxicology Program (NTP) Testing Program . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .X

New York State Bulk Storage . . . . . . . . . . . . . . . . . . . .X

Occupational Safety and Health Administration –

OSHA Air Contaminants . . . . . . . . . . . . . . . . . . . .NLOSHA PEL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .NLOSHA Process Safety Management Rule . . . . . . . . .X

16

APPENDIX – continuedPARTIAL LIST OF GOVERNMENT REGULATIONSAND AGENCY/ASSOCIATION RECOMMENDATIONSFOR VINYL ACETATE

Compiled November 1, 1993

Legend: X–Applies; L – Listed; NL – Not Listed

Pennsylvania Hazardous Substance List . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .X

Proposition 65 (Acetaldehyde Impurity) . . . . . . . . . . . . . . . . . . . . . . . .X

Resource Conservation and Recovery Act (RCRA), Land Disposal Restriction – Hazardous Constituents for Ground Water Monitoring . . . . . . . . . . . . . . . . . . . . . . .X

Superfund Amendments and Reauthorization Act (SARA) Title III, Section 313 Toxic Chemicals . . . . . . . . . . . . .X

Superfund Amendments and Reauthorization Act (SARA) Title III, Threshold Planning Quantities and Reportable Quantities (for 302, 304, 311, 312). . . . . . . . . . . . . . . . .X

Superfund Amendments and Reauthorization Act (SARA) Section 110 Priority Lists of CERCLA Hazardous Substances . . . . . . . . . . . . . . . . .X

Superfund Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) Hazardous Substances . . . . . . . . . . . . . . . .X

Toxic Substances Control Act (TSCA), Section 8(d) Health and Safety Data Rule . . . . . . . . . . . . . . . . . . . . . . . . . . .X

Clean Air Act 1990, Hazardous Air Pollutant . . . . . . . . . . . . . . . . . . . . . . . .X

SCAQMD Rule 443.1 VOC’s, VOC 932g/L: Vapor Pressure 92 mm Hg @ 20°C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .X