PRODUCT SAFETY

BULLETIN

Propylene Oxide
CT U D

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PRODUCT SAFETY

BULLETIN

Propylene Oxide

DEVELOPED BY THE ENVIRONMENTAL, HEALTH AND SAFETY DEPARTMENT LYONDELL CHEMICAL COMPANY
MARCH 1996 REVISION 1

FOREWORD
Lyondell Chemical Company is dedicated to continuous improvement in product health, safety and environmental performance. Included in this effort is a commitment to support our customers by providing guidance and information on the safe use of our products. For Lyondell Chemical, environmentally sound operations, like environmentally sound products, make good business sense. Lyondell Chemical Company Product Safety Bulletins are prepared by our Environmental, Health and Safety Department with the help of experts from our manufacturing and research facilities. The data reflect the best information available from public and industry sources. This document is provided to support the safe handling, use, storage, transportation and ultimate disposal of our chemical products. This Product Safety Bulletin should be evaluated to determine applicability to your specific requirements. Please make sure you review the government regulations, industry standards and guidelines cited in this bulletin that might have an impact on your operations. Lyondell Chemical Company is ready to support our customers safe use of our products. For additional information and assistance, please contact your Lyondell Chemical Company customer representative.

iii

IN CASE OF A TRANSPORTATION EMERGENCY, CALL: CHEMTREC 1-800-424-9300 International (call collect) 703-527-3887 FOR MORE INFORMATION ABOUT OUR PRODUCT, CALL: Lyondell Chemical Company Customer Service 1-888-777-0232
We are pleased to provide you with the most recently revised PO Product Safety Bulletin, please discard any previous versions of this document. The changes made are summarized below. Summary of changes made in Revision 1: - New rail car hook-up - Upper and Lower Flammable limits - Recommended Gasket material - Electrical Conductivity - OEL reduced to 5 ppm - Reporting of transportation in incidents changed from ACERS to CHEMTREC - Propylene oxide is no longer packaged in drums - Label information has been updated - ACC funded Passive Dosimeter method has been added (Appendix V) - Sections of the Regulatory Summary (Appendix VII) have been updated: Clean Air Act Resource Conservation and Recovery Act Safe Drinking Water Act Department of Transportation Occupational Safety and Health Administration Toxic Substances Control Act Connecticut Manufacturing Employer Hazardous Materials Notification Act Florida Employee Right-to-Know Law Illinois Toxic Substances Disclosure to Employees Act Illinois Chemical Safety Act Louisiana Hazardous Materials Information, Development, Preparedness and Response Act Massachusetts Spill Reporting Michigan Critical Materials New Jersey Spill Tax New York Bulk Storage Registration/Release Reporting Rhode Island Hazardous Substance Right-to-Know Act Canadian National Pollutant Release Preventory Japanese List of Existing and New Chemical Substances Korean List of Existing Chemicals Philippines List of Existing Chemicals - Glossary of Terms updated
iv

This bulletin is provided as a service without charge to our customers and contractors and should be utilized at their own discretion and risk. It is intended for persons with specialized knowledge and technical skills, which are required for proper understanding and interpretation of the information contained herein. The information was obtained from sources believed to be reliable and is based on industry practices prevailing at the time of compilation, which are subject to change and may be subject to variance. The information in this bulletin is provided without any warranty, expressed or implied, regarding its accuracy and completeness. Recipients are expected and advised to undertake their own inquiry and study, and be trained in the environmental, health an safety requirements of the product. Customers and contractors should also be familiar with applicable federal, state, and local laws and regulations. References to a specific product line or any list of suppliers is provided as a matter of convenience, and is not an endorsement or recommendation of a particular brand or company. In addition, the information was prepared and is to be used only for this product. If the product is used as a component in, or in combination with, another product, the information may not be accurate or applicable. For the above reasons, and because the conditions and methods of handling, storage, use and disposal of the product are beyond our control and may be beyond our knowledge, we do not assume any responsibility and expressly disclaim any liability for loss, damage or expense arising out of or in connection with the use of the information set forth herein, and the handling, storage, use or disposal of the product. This document contains dated material. Recipients are advised to evaluate the timeliness of information cited. The latest revision of this Product Safety Bulletin can be obtained by contacting Lyondell Chemical Company Customer Service.

TABLE OF CONTENTS
1.
1.1 1.2 1.3 1.4 1.5

GENERAL INFORMATION
PRODUCT IDENTIFICATION PHYSICAL PROPERTIES TYPICAL VALUES INSTABILITY HAZARDS REACTIVITY HAZARDS

7.
7.1 7.2 7.3

ENVIRONMENTAL
SPILLS AND LEAKS WASTE DISPOSAL CONTAINER DISPOSAL

8.
8.1 8.2 8.3

PRODUCT STORAGE
STORAGE TANKS OFF-LOADING STATION WORKPLACE LOCATION

2.
2.1 2.2 2.3 2.4

OCCUPATIONAL HEALTH
HAZARD ASSESSMENT OCCUPATIONAL EXPOSURE LIMITS FIRST AID MEDICAL MANAGEMENT

9.
9.1 9.2 9.3

TRANSFER OPERATIONS
TANK CARS TANK TRUCKS ISO TANKS

3.
3.1 3.2 3.3 3.4 3.5 3.6

PERSONAL SAFETY AND HEALTH

SITE FACILITIES HYGIENE PRACTICES RESPIRATORY PROTECTION CHEMICAL PROTECTIVE CLOTHING DIRECT READING INSTRUMENTS AIR SAMPLING AND ANALYSIS

10.
10.1 10.2 10.3 10.4 10.5

TANK CLEANING AND EQUIPMENT REPAIR

WORK PREPARATION CONTROL OF HAZARDOUS ENERGY CONFINED SPACE ENTRY EQUIPMENT CLEANOUT MAINTENANCE AND INSPECTION

4.
4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10

ENGINEERING
BULK STORAGE PIPING ELECTRICAL AREA CLASSIFICATION PUMP SPECIFICATIONS INSTRUMENTATION RELIEF REQUIREMENTS LEAK DETECTION DEVICES MATERIAL REQUIREMENTS VAPOR CONTAINMENT SYSTEM CHEMICAL COMPATIBILITY

11.
11.1 11.2

TRANSPORTATION REGULATORY REQUIREMENTS

CLASSIFICATION MARKING, LABELING AND PLACARDING PACKAGING TRANSPORTATION EMERGENCIES

11.3 11.4

12.
I II III IV V VI VII VIII

APPENDICES
CONVERSION FACTORS WORLDWIDE OCCUPATIONAL EXPOSURE LIMITS NAMES AND ADDRESSES OF MANUFACTURERS NIOSH METHOD 1612 ACC FUNDED METHOD PASSIVE DOSIMETER REFERENCES REGULATORY SUMMARY GLOSSARY OF TERMS

5.
5.1 5.2 5.3 5.4

FIRE SAFETY
FIRE AND EXPLOSION HAZARD FIRE PREVENTION FIRE SUPPRESSION FIRE FIGHTING

6.
6.1 6.2 6.3

HAZARD COMMUNICATION
OSHA HAZARD COMMUNICATION SARA TITLE III STATE REGULATIONS

PRODUCT SAFETY BULLETIN

1. GENERAL INFORMATION
1.1 Product Identification
2Methyloxirane Alkyl Epoxide Propylene oxide 1,2Propylene oxide 1,2Epoxypropane Propene epoxide Propene oxide 75569 C3H6O sucrose, sorbitol, trialkanol amines, and trimethylolpropane. Polyether polyols are reacted with various diisocyanates to form polyurethane foams and resins. The second largest use of propylene oxide is the production of propylene glycol and lesser amounts of coproduced dipropylene glycol and higher propylene glycols. These glycols are used in the manufacture of unsaturated polyester resins, solvents, antifreeze, humectants and plasticizers. Propylene oxide is also used to manufacture functional fluids by reaction of propylene oxide or mixtures of propylene oxide and ethylene oxide with glycols, glycerine, alcohols and phenols. The types of functional fluids produced include heat transfer fluids, hydraulic fluids and lubricants. Other propylene oxide derivatives include block copolymers of propylene oxide and ethylene oxide which have been found to be efficient and versatile surfactants. Propylene oxide-based surfactants can also be produced by the propoxylation of various alcohols. The water solubility of propylene glycols below a molecular weight of 800 makes propylene oxide especially useful in these applications. Propylene oxide is also used as a reactant to produce alkanol amines from ammonia or amines and as an intermediate in the production of allyl alcohol. It can also be homopolymerized to produce polypropylene oxide. Applications for propylene oxide are shown in Figures 13 and 1-4.

Chemical Name Chemical Family Common Names

CAS# Formula

1.1.1

Chemistry

Lyondell Chemical Company uses proprietary technology to manufacture propylene oxide. In one process, ethylbenzene is reacted with oxygen to form ethylbenzene hydroperoxide. The ethylbenzene hydroperoxide is subsequently used to epoxidize propylene to yield propylene oxide and methyl benzyl alcohol. In an alternative process, isobutane is substituted for ethylbenzene and, through analogous chemistry, tertiary butyl alcohol is the co-product. Methyl benzyl alcohol and tertiary butyl alcohol can then be dehydrated to styrene monomer and isobutylene, respectively (see Figures 1-1 and 1-2).

1.1.2

Applications

The polyurethane industry is the largest consumer of propylene oxide. It utilizes polyether polyols made by reacting propylene oxide alone or in combination with other alkylene oxides. The most common initiators are polyols or polyamines such as glycerine, glycols, pentaerythritol, ethylenediamine, toluenediamine,

G E N E R A L I N F O R M AT I O N

Lyondell Chemical Technology - Ethylbenzene Route

O OH CH2 CH3
PEROXIDATION
Ethylbenzene

CH CH3 + O2
Ethylbenzene Hydroperoxide

O OH CH CH3
EPOXIDATION

OH CH CH3 CH2 CH CH3 + O

Propylene Oxide Methyl Benzyl Alcohol

+ CH3 CH = CH2
Ethylbenzene Hydroperoxide Propylene

OH CH CH3
DEHYDRATION
Methyl Benzyl Alcohol Styrene

CH = CH2 + H2O

Figure 1-1

Lyondell Chemical Technology - Isobutane Route

CH3 CH3 C CH3 + O2
PEROXIDATION

CH3 CH3 C CH3 O OH

Tertiary Butyl Hydroperoxide

H
Isobutane

CH3 CH3 C CH3 + CH3 CH = CH2

EPOXIDATION

CH3 CH2 CH CH3 + CH3 C CH3 O

Propylene Propylene Oxide

O OH
Tertiary Butyl Hydroperoxide

OH
Tertiary Butyl Alcohol

CH3 CH3 C CH3

DEHYDRATION

CH3 CH3 C = CH2 + H20

Isobutylene

OH
Tertiary Butyl Alcohol

Figure 1-2

MAJOR USES FOR PROPYLENE OXIDE

PROPYLENE OXIDE

POLYETHER POLYOLS
Lubricants Polish Formulations Solvents Surfactants

PROPYLENE GLYCOLS Antifreeze Cosmetics Coupling Aids De-icing fluids Emulsifiers Functional Fluids Heat Transfer Solutions Humectant (food & tobacco) Low Toxicity Coolants Lubricants Pet Food Softeners Solvents Surfactants

Cosmetics Defoamers Emulsifiers Functional Fluids Greases

URETHANES

Rigid Foam Automotive Seating Bedding Carpet Underlay Cushioning Packaging Adhesives Auto Body Components CASE Caulks Elastomers Fibers RIM, Misc. Sealants Sports Equipment Surface Coatings

Flexible Foam

Non-Foam

UNSATURATED POLYESTER RESINS Adhesives Laminates

Flotation Furniture Insulation Construction Refrigeration Luggage Machine Housings Packaging

G E N E R A L I N F O R M AT I O N

Figure 1-3

Printed on Recycled paper

OTHER PROPYLENE OXIDE DERIVATIVES

PROPYLENE OXIDE

G E N E R A L I N F O R M AT I O N

GLYCOL ETHERS

PROPOXYLATED NATURAL PRODUCTS

PROPOXYLATED AMINES

Cleaning Compounds Coatings Cosmetics Functional Fluids Solvents Binders - Board and Pigments Coatings Thickeners

Chemical Intermediates Cosmetics Polish Formulations Reactive Solvents/Gas Sweetening Surfactants

MISCELLANEOUS

Propylene Carbonate Chemical Intermediate Natural Gas Purification Aid Plasitcizers Solvent

Allyl Alcohol Chemical Intermediate

Propylene Oxide Elastomers

Figure 1-4

G E N E R A L I N F O R M AT I O N

1.2

Physical Properties Table 1-1 Propylene Oxide Physical Properties

Property

Value

Property

Value

Physical State Color Boiling Pt. Molecular Wt. Freezing Pt. Density @25C(77F) Density of Satd Liquid Vapor Density Vapor Pressure Viscosity of Satd Liquid Visc. of Vapor Index/Refraction @25C @20C Coeff. of Cubical Expansion @20C Crit. Temperature Crit. Pressure Crit. Volume Crit. Compress. Acentric Factor Heat/Combustion, Liquid @25C Heat/Formation, Vapor @25C

Liquid Colorless 34.2C (93.6F) 58.08 112C (169.6F) 0.823 g/cc (6.87 lb/gal) See Figure 1-5 and Table 1-2 See Figure 1-6 Table 1-3 See Figure 1-7 See Figure 1-8 1.3632 1.3670 0.00151C 1 209.1C 4.92 MPa 3.2025 cc/g 0.0513 ft 3/lb 0.228 0.2683 458.28 Kcal/mol 22.17 Kcal/mol

Heat of Formation, Liquid @25C Heat/Fusion @ 112C Heat/Vaporization Heat Capacity of Satd Liquid Enthalpy of Satd Liquid Heat Capacity of Vapor Enthalpy of Satd Vapor Surface Tension Thermal Conduct. of Satd Liquid Thermal Conduct. of Vapor Flash Point (TCC) Auto Ignition Upper Explo. Limit Lower Explo. Limit Solubility @20C

28.84 Kcal/mol 1560.9 cal/mol 2809.7 BTU/lbmol See Figure 1-9 See Figure 1-10 See Figure 1-11 See Figure 1-12 See Figure 1-13 See Figure 1-14 See Figure 1-15 See Figure 1-16 37C (35F) 464C (867F) 37 vol% 1.7 vol% 39.5% in Water 12.5% Water in Alcohol: Ether: 82.6 wt% 70.32 mol% 6.70 x 10 30 x m 2.4 x 108mhos/cm

Sat. Conc. in Air @ 25C Dipole Moment Electrical Conductivity

G E N E R A L I N F O R M AT I O N

Density of Saturated Liquid as a Function of Temperature

1.00

Density of Saturated Liquid (g/cc)

PROPYLENE OXIDE

0.95

0.90

0.85

0.80

0.75

0.70

0.65

0.60

0.55

0.50 -100

-80

-60

-40

-20

20

40

60

80

100

120

140

160

180

Temperature (C)

Figure 1-5

Density of Vapor @ 1 Atmosphere as a Function of Temperature

2.6

PROPYLENE OXIDE

2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 0 20 40 60 80 100 120 140 160 180 200 220 240 260 280

Density of V apor x 10

(g/cc)

Temperature (C)

Figure 1-6 6
Printed on Recycled paper

G E N E R A L I N F O R M AT I O N

Table 1-2 Propylene Oxide Density as a Function of Temperature

Temperature C F Lbs. Per Sp. Gr. U.S. Gallon to 60C Temperature C F Lbs. Per Sp. Gr. U.S. Gallon to 60C

4.4 5.0 5.6 6.1 6.7 7.2 7.8 8.3 8.9 9.4 10.0 10.6 11.1 11.7 12.2 12.8 13.3 13.9 14.4 15.0 15.6 16.1 16.7 17.2 17.8 18.3 18.9 19.4 20.0 20.6 21.1

40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70

7.083 7.077 7.072 7.066 7.060 7.055 7.049 7.043 7.038 7.032 7.026 7.021 7.015 7.009 7.003 6.998 6.992 6.986 6.980 6.975 6.969 6.963 6.957 6.951 6.946 6.940 6.934 6.928 6.922 6.917 6.911

1.0164 1.0156 1.0148 1.0140 1.0131 1.0123 1.0115 1.0107 1.0099 1.0091 1.0082 1.0074 1.0066 1.0058 1.0050 1.0041 1.0033 1.0025 1.0017 1.0008 1.0000 0.9992 0.9983 0.9975 0.9967 0.9958 0.9950 0.9942 0.9933 0.9925 0.9917

21.7 22.2 22.8 23.3 23.9 24.4 25.0 25.6 26.1 26.7 27.2 27.8 28.3 28.9 29.4 30.0 30.6 31.1 31.7 32.2 32.8 33.3 33.9 34.4 35.0 35.5 36.1 36.7 37.2 37.8

71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100

6.905 6.899 6.893 6.887 6.881 6.875 6.870 6.864 6.858 6.852 6.846 6.840 6.834 6.828 6.822 6.816 6.810 6.804 6.798 6.792 6.786 6.780 6.774 6.768 6.762 6.756 6.750 6.744 6.738 6.732

0.9908 0.9900 0.9891 0.9883 0.9875 0.9866 0.9858 0.9849 0.9841 0.9832 0.9824 0.9815 0.9807 0.9798 0.9790 0.9781 0.9772 0.9764 0.9755 0.9747 0.9738 0.9729 0.9721 0.9712 0.9703 0.9695 0.9686 0.9677 0.9669 0.9660

G E N E R A L I N F O R M AT I O N

Table1-3 Propylene Oxide Vapor Pressure as a Function of Temperature

Temperature C F

Vapor Pressure mm Hg psia psig

Temperature C F

Vapor Pressure mm Hg psia psig

-28.00 -26.00 -24.00 -22.00 -20.00 -18.00 -16.00 -14.00 -12.00 -10.00 -8.00 -6.00 -4.00 -2.00 0.00 2.00 4.00 6.00 8.00 10.00 12.00

-18.40 -14.80 -11.20 -7.60 -4.00 -0.40 3.20 6.80 10.40 14.00 17.60 21.20 24.80 28.40 32.00 35.60 39.20 42.80 46.40 50.00 53.60

40.20 45.43 51.21 57.60 64.65 72.39 80.89 90.20 100.38 111.50 123.60 136.76 151.06 166.55 183.31 201.42 220.97 242.02 264.66 288.99 315.08

0.78 0.88 0.99 1.11 1.25 1.40 1.56 1.74 1.94 2.16 2.39 2.64 2.92 3.22 3.54 3.89 4.27 4.68 5.12 5.59 6.09

14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00 32.00 34.00 34.48 35.00 40.00 45.00 50.00 55.00 60.00 65.00 70.00 75.00

57.20 60.80 64.40 68.00 71.60 75.20 78.80 82.40 86.00 89.60 93.20 94.06 95.00 104.00 113.00 122.00 131.00 140.00 149.00 158.00 167.00

343.04 372.96 404.93 439.05 475.42 514.16 555.35 599.13 645.59 694.85 747.02 760.00 774.24 922.24 1091.51 1284.06 1502.00 1747.51 2022.85 2330.38 2672.54

6.63 7.21 7.83 8.49 9.19 9.94 10.74 11.59 12.48 13.44 14.45 14.70 14.97 17.83 21.11 24.83 29.04 33.79 39.12 45.06 51.68 0.00 0.28 3.14 6.41 10.13 14.35 19.10 24.42 30.37 36.98

G E N E R A L I N F O R M AT I O N

Viscosity of Saturated Liquid as a Function of Temperature

PROPYLENE OXIDE
0.90

Viscosity of Saturated Liquid (cps)

0.85 0.80 0.75 0.70 0.65 0.60 0.55 0.50 0.45 0.40 0.35 0.30 0.25 0.20 -40

-35

-30

-25

-20

-15

-10

-5

10

15

20

25

30

35

40

Temperature (C)

Figure 1-7

Viscosity of Vapor @ 1 Atmosphere as a Function of Temperature

1.75

PROPYLENE OXIDE

1.70 1.65

(cps) Viscosity of V apor x 10

3

1.60 1.55 1.50 1.45 1.40 1.35 1.30 1.25 1.20 1.15 1.10 1.05 1.00 0.95 0.90 0.85 0.80 40 60 80 100 120 140 160 180 200 220 240 260 280 300

Temperature (C)

Figure 1-8 9

G E N E R A L I N F O R M AT I O N

Heat of Vaporization as a Function of Temperature

115

PROPYLENE OXIDE

Heat of V aporization (cal/g)

110

105

100

95

90

85

80

75

70 40 50 60 70 80 90 100 110 120 130 140 150

Temperature (C)

Figure 1-9

Heat Capacity of Saturated Liquid (cal/g C)

H eat Capacity of Saturated Liquid as a Function of Temperature

0.510

PROPYLENE OXIDE

0.505

0.500

0.495

0.490

0.485

0.480

0.475

0.470

0.465

0.460

-30

-25

-20

-15

-10

-5

10

15

20

25

30

35

Temperature (C)

Figure 1-10 10
Printed on Recycled paper

G E N E R A L I N F O R M AT I O N

E n t h a l p y of Saturated Liquid as a Function of Temperature

120

PROPYLENE OXIDE

Enthalpy of Saturated Liquid (cal/g)

110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30 -40 -100

-80

-60

-40

-20

20

40

60

80

100

120

140

160

180

Temperature (C) Reference: Saturated Liquid PO at 0C

Figure 1-11

H e a t Capacity of Vapor (Ideal Gas) as a Function of Temperature

0.50

PROPYLENE OXIDE

0.48

Heat Capacity of V apor (cal/g C)

0.46

0.44

0.42

0.40

0.38

0.36

0.34

0.32

0.30

0.28 0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300

Temperature (C)

Figure 1-12 11

G E N E R A L I N F O R M AT I O N

E nthalpy of Saturated Vapor as a Function of Temperature

185

PROPYLENE OXIDE

Enthalpy of Saturated V apor (cal/g)

180 175 170 165 160 155 150 145 140 135 130 125 120 115 110 105 100 95 -100 -80 -60 -40 -20 0 20 40 60 80 100 120 140 160 180

Temperature (C) Reference: Saturated Liquid PO at C

Figure 1-13

S urface Tension as a Function of Temperature

26 24

PROPYLENE OXIDE

22

Surface T ension (dynes/cm)

20

18

16

14

12

10

0 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200

Temperature (C)

Figure 1-14 12
Printed on Recycled paper

G E N E R A L I N F O R M AT I O N

Thermal Conductivity of Saturated Liquid as a Function of Temperature

1.80

Thermal Conductivity of Saturated Liquid 2 (cal/hr cm C/cm)

1.78 1.76 1.74 1.72 1.70 1.68 1.66 1.64 1.62 1.60 1.58 1.56 1.54 1.52 1.50 1.48 1.46 1.44 1.42 1.40 -60 -55 -50 -45 -40 -35 -30 -25 -20 -15 -10 -5 0 5 10 15 20 25 30 35

P ROPYLENE OXIDE

Temperature (C)

Figure 1-15

C/cm)

Thermal Conductivity of V apor @1 Atmosphere as a Function of Temperature

0.105 0.100 0.095 0.090 0.085 0.080 0.075 0.070 0.065 0.060 0.055 0.050 0.045 0.040 0.035 40 60 80 100 120 140 160 180 200 220 240 260 280

PROPYLENE OXIDE

Thermal Conductivity of V apor (cal/hr cm

Temperature( C)

Figure 1-16 13

G E N E R A L I N F O R M AT I O N

1.3

Instability Hazards

1.4

Reactivity Hazards

Propylene oxide is a stable material that will not decompose under normal conditions of temperature and pressure.

Propylene oxide may react vigorously with oxidizing materials, anhydrous metal chlorides, acids, bases, claybased adsorbent materials, and peroxides. Propylene oxide mixed with ammonium hydroxide, chlorosulfonic acid, hydrochloric acid, hydrofluoric acid, nitric acid, oleum (fuming sulfuric acid), or sulfuric acid causes violent reactions. Propylene oxide reacts slowly in neutral water. However, the presence of acids or bases in water will catalyze the hydrolysis of propylene oxide, and a vigorous reaction may occur.

14

PRODUCT SAFETY BULLETIN

2. OCCUPATIONAL HEALTH
2.1 Hazard Assessment
2.1.2 Repeated Exposures
In short-term, repeated animal exposure studies, concentration of propylene oxide above 1000 mg/m3 (420 ppm) were irritating to the eyes and respiratory tract, causing lung edema (fluid in the lungs) and central nervous system depression. After repeated oral doses of propylene oxide, slight depression of body weight and slight liver damage were reported at 300 mg/kg but not at 100 or 200 mg/kg.

The primary route of exposure to propylene oxide is through inhalation of fugitive emissions in the workplace. Propylene oxide is likely to be readily absorbed through the respiratory tract and, although no firm data is available, rapidly metabolized by conjugation with glutathione or hydrolyzed to 1,2propane diol (propylene glycol). Acutely, propylene oxide is a severe skin, eye and respiratory irritant. Long-term studies in animals have clearly shown that high exposure levels of propylene oxide can induce malignant tumors and should be considered a possible human carcinogen (see Section 2.1.6).

2.1.3

Reproductive and Developmental Toxicity

2.1.1

Acute Effects of Over Exposure

Single exposures to liquid propylene oxide can cause severe skin and eye irritation, which may lead to necrosis (cell death) if not treated promptly. There are reports in the literature which indicate that propylene oxide may induce dermal sensitization in workers. Exposure to high vapor concentrations can cause irritation of the eyes and respiratory tract as well as central nervous system effects such as incoordination and general depression. Propylene oxide generally does not cause adverse effects to the skin if it can freely evaporate. However, confinement under clothing or in shoes prevents evaporation resulting in irritation, blistering and possible burns. Contact with even dilute solutions of propylene oxide (10%) can cause irritation, blistering and burns with a single short term exposure. In animal studies single oral doses of propylene oxide ranging from 520 mg/kg to 1140 mg/kg have been reported to be lethal to various animal species. Inhalation exposure to 9500 mg/m3 (approximately 4000 ppm) for four hours has been reported to be the median lethal concentration in rats. The data indicates that propylene oxide is slightly toxic in single exposures.

Propylene oxide has been reported to have only minimal reproductive effects in male and female rats at exposure levels up to 300 ppm. There were no significant variations from control animals in any of the reproductive indices measured. Propylene oxide (500 ppm) induced only minimal body weight changes in pregnant rats and a slight skeletal variation in the offspring. Propylene oxide is not considered to be a reproductive hazard in animals.

2.1.4

Genetic Toxicology

Propylene oxide is a direct alkylating agent and has induced genetic mutation in several in vitro test systems, with and without metabolic activation. However, in whole animal studies propylene oxide did not appear to be active as a mutagen.

2.1.5

Chronic Effects of Over Exposure

Although there are no epidemiologic data available concerning the effects of long-term, repeated exposures of humans to propylene oxide, there is sufficient evidence from animal studies that this reactive chemical can cause cancer and should be considered a possible human carcinogen.

2.1.6

Carcinogenicity

In two separate inhalation studies in rats, propylene oxide induced adenomas in the nasal passages at approximately 700 mg/m3 (300 ppm). In a third inhalation study, hyperplasia of the nasal epithelium of the rats was

15

O C C U P AT I O N A L H E A LT H

reported in addition to an increase in the number of tumors in the tumor-bearing animals. The National Institute for Occupational Safety and Health (NIOSH), the International Agency on Research for Cancer (IARC), and the National Toxicity Program (NTP) consider propylene oxide to be a possible human carcinogen.

victims clothing unless wearing appropriate protective apparel. The removal of clothing from the victim is important to minimize continued skin contact, and to prevent continued off gassing of propylene oxide during transport to an emergency care facility. Emergency transport services should be equipped to provide continual flushing of the skin and eyes, especially when the victim is complaining of burning or irritation.

2.2

Occupational Exposure Limits

2.3.1

Eye Contact

The U.S. Department of Labor, Occupational Safety and Health Administration (OSHA) under 29 Code of Federal Regulations (CFR) 1910.1000 (see Appendix V for citations) has established a permissible exposure limit (PEL) for propylene oxide of 100 ppm as an 8-hour timeweighted average (TWA). The PEL was derived from the threshold limit value (TLV) set by the American Conference of Governmental Industrial Hygienists (ACGIH) in 1968. ACGIH recommends that exposures be maintained below 20 ppm, as an 8-hour time-weighted average. Appendix II presents occupational exposure limits established by agencies around the world. The National Institute for Occupational Safety and Health (NIOSH) has classified 400 ppm of propylene oxide as immediately dangerous to life and health (IDLH). This limit represents a condition that poses a threat of exposure to airborne contaminants when that exposure is likely to cause death or immediate or delayed permanent adverse health effects or prevent escape from such an environment. Lyondell Chemical Company recommends to maintain exposures, where reasonable and achievable, below 5 ppm as either an 8-hour or 12-hour time weighted average.

Flush eyes immediately with copious amounts of cool water for at least 15 minutes, periodically lifting the lower and upper lids to enhance flushing. Individuals splashed with propylene oxide may require assistance in locating emergency eyewash stations and flushing the eyes. Medical attention should be provided as soon as possible, and an ophthalmologist should be available for consultation.

2.3.2

Skin Contact

If propylene oxide contacts the skin, immediately flush the contaminated skin with water. If the propylene oxide contacts clothing, remove clothing and flush affected area with water for at least 15 minutes. While under deluge shower, continue to remove clothing, watches, rings, or anything that might prevent complete flushing of propylene oxide. If skin irritation or reddening is noted, seek medical attention.

2.3.3

Inhalation

2.2.1

Warning Properties

Propylene oxide has a sweet, ether-like odor that is readily perceived at elevated concentrations. It is not certain if olfactory fatigue occurs promptly as with other similar compounds.

If overcome from inhalation of propylene oxide, victim should be moved from contaminated atmosphere into fresh air at once by persons properly equipped with appropriate personal protective equipment (PPE). Treat for shock if necessary. If victim has stopped breathing, administer cardiopulmonary resuscitation (CPR) immediately. Red Cross first aid trained individuals, or equivalent, should administer CPR. Caution should be used to prevent responder exposure to propylene oxide from the victim. Once revived, keep the victim warm and calm. Seek prompt medical attention.

2.3.4

Ingestion

2.3

First Aid

Personnel providing assistance to a victim should be cautious not to contaminate themselves by touching the

In the unlikely event of propylene oxide ingestion, give the patient, if conscious, a pint of lukewarm water. Do not induce vomiting. Seek prompt medical attention.

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O C C U P AT I O N A L H E A LT H

2.4

Medical Management

determine pre-existing conditions that may be aggravated by exposure to propylene oxide. Because propylene oxide may cause dermatitis, persons with pre-existing skin disorders may be more susceptible to the effects of this chemical. For individuals with impaired pulmonary function, especially those with obstructive airway diseases, breathing propylene oxide may exacerbate symptoms. While propylene oxide is not known as a liver toxin in humans, the importance of this organ in the biotransformation and detoxification of foreign substances should be considered before exposing persons with impaired liver function. Similarly, propylene oxide is not known as a kidney toxin. However, due to the importance of this organ in the elimination of toxic substances, special consideration should be given to those with impaired renal function. A specific protocol for initial medical examination should be developed by an occupational health physician before hiring individuals who may be exposed to propylene oxide.

Victims who have been acutely exposed to propylene oxide and treated utilizing the initial emergency first aid treatment procedures outlined in Section 2.3 may require further emergency medical treatment. This may include assessment of the extent and severity of tissue injury by appropriate diagnostic studies and procedures. Advanced life support should be provided to all victims with evidence of respiratory injury or extensive skin burns. Employers are required by OSHAs Medical Services and First Aid Standard, 29 CFR 1910.151, to provide for medical personnel in cases of medical emergency and/or employee illness. In the absence of a clinic or hospital facility in close proximity, the employer may have on site persons who are adequately trained in appropriate first aid techniques to handle medical emergencies. If no medical personnel are located at the facility, contact should be made with an occupational health physician or hospital emergency room to plan for medical emergencies. During the planning stages, hospital selection should be based on whether the hospital is equipped to handle chemical emergencies and, if necessary, perform chemical decontamination. Copies of the propylene oxide material safety data sheet (MSDS) or this Product Safety Bulletin should be provided and reviewed with medical personnel.

2.4.2

Periodic Screening

2.4.1

Initial Medical Screening

Prospective employees who will work with or around propylene oxide should be medically evaluated to

Employees potentially exposed to propylene oxide should receive routine medical evaluations. Periodic medical screening is an effective tool for the identification and prevention of occupational disease. Employers should consult with their occupational health physicians to determine the specific protocol to be followed. Considerations include several factors, such as type of work performed and the employees age.

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3. PERSONAL SAFETY AND HEALTH

3.1 Site Facilities
Protective clothing used during the handling of propylene oxide, including gloves, aprons, protective suits and respirators, should be properly decontaminated using mild soap/detergent and water. Nonimpervious clothing should be sealed in containers to prevent vapors from escaping into the air until laundered or disposed. Clothing may be laundered, provided that personnel handling these materials are aware of the hazards of propylene oxide. Articles such as wallets, belts and shoes constructed of leather, and other items that cannot be effectively decontaminated should be disposed of properly as contaminated waste (see Section 7.3).

If a potential for contact with propylene oxide liquid exists in work areas where it is handled or stored, quick drenching facilities and equipment should be provided. This should include deluge showers and eyewash stations. These items should be installed, tested and maintained in accordance with the American National Standards Institute, Inc. (ANSI) Z358.1 (see Appendix V for citations). Employees should be familiar with the location and operation of this safety equipment. If contaminated clothing is laundered, appropriate facilities should be provided. Propylene oxide will evaporate from clothing potentially increasing the risk of fire, explosion and employee exposure. Site facilities should include closed containers for clothing storage and engineering controls to limit employee exposure. Personnel who will be handling contaminated clothing should be trained and fully aware of the methods available to protect themselves, including the use of personal protective equipment and methods to determine vapor concentrations. While showering is not required for persons working with propylene oxide, a shower facility may be useful in first aid procedures for dermal exposure.

3.3

Respiratory Protection

3.2

Hygiene Practices

Proper personal hygiene practices should be used when working with and around propylene oxide. Employees should be familiar with good work practices to avoid direct contact with propylene oxide. They should also be familiar with decontamination procedures for equipment. Propylene oxide should not be handled or stored in areas where personnel take breaks (such as lunch rooms) or in areas that are not designed for propylene oxide storage. Hygiene practices that should be enforced for employees working with propylene oxide include prohibiting the consumption and storage of food, use and storage of tobacco products, and application and storage of cosmetics. After handling and prior to eating, smoking, drinking, applying cosmetics or using toilet facilities, personnel should thoroughly wash their hands and faces with lukewarm water and mild soap or detergent.

The Occupational Safety and Health Administration (OSHA) requires that exposures to propylene oxide be maintained to levels below 100 ppm, as an 8-hour timeweighted average. The American Conference of Governmental Industrial Hygienists (ACGIH) recommends that such exposures be maintained below 20 ppm, as an 8-hour time-weighted average. Lyondell Chemical Company recommends, where reasonable and achievable, to maintain exposures below 5 ppm as either an 8-hour or 12-hour time-weighted average. To accomplish this, good industrial hygiene practice suggests the use of engineering controls, such as local exhaust ventilation at all significant points of emission. However, if engineering controls are not technically feasible, are being installed, or fail to control exposure and need to be supplemented, respiratory protection may be provided for employee protection. Respirators may also be needed for nonroutine operations such as confined space entry into tanks and in emergency situations arising from spills/leaks and fire/explosions involving propylene oxide. Respirators should be used when employee exposure exceeds established limits. Due to the poor warning properties of propylene oxide (high odor and eye irritation thresholds), air-purifying respirators should not be used. National Institute for Occupational Safety and Health and Mine Safety and Health Administration (NIOSH/MSHA)-approved airline respirator or self contained breathing apparatus (SCBA) with a full

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facemask operated in a positive pressure mode may be used during routine and nonroutine work activities. Where the exposure can exceed 400 ppm (IDLH level) or when an oxygen deficient atmosphere exists, air line respirators must be equipped with an auxiliary SCBA escape pack operated in the positive pressure mode. Work locations where the potential for spills and leaks of propylene oxide exists should have escape respirators conspicuously displayed. For emergency escape purposes only, a full facemask air-purifying respirator (gas mask) may be used. Respirators designed for escape purposes are never to be used for entry into an environment contaminated with propylene oxide above the established exposure limits. Table 3-1 provides for the selection of respiratory protection. Respirators contaminated with propylene oxide can be decontaminated using lukewarm water with mild soap or detergent. Propylene oxide may permeate through and degrade the elastomeric materials of the respirators. Therefore, precautions must be taken to prevent direct contact with the liquid propylene oxide. Degraded respirators should be discarded.

3.4

Chemical Protective Clothing

Personal protective equipment (PPE) should be provided to personnel during routine and nonroutine handling, spill cleanup, and fire fighting involving propylene oxide. Personal protective clothing is necessary to prevent exposure to vapor or liquid during both routine and nonroutine work activities. Select chemical protective clothing according to the working conditions and the potential for contact with liquid or vapor. Chemical protective ensembles range from safety glasses, hard hats and safety shoes to chemical protective suits with an air supply. Materials must be selected giving consideration to the chemical properties of propylene oxide. Factors that should be considered include the chemical resistance, durability, flexibility, thermal limits, cleanability and lifetime of the material.

3.4.1

Eye Protection

Chemical safety goggles, cup-type plastic of gas-tight design, equipped with impact-resistant lenses, should be worn whenever the potential for exposure to vapor or

Table 3-1 Propylene Oxide Respiratory Protection Selection Guide

Condition Minimum Respiratory Protection*

400 ppm OR LESS

Any airline respirator with a full facemask, helmet, or hood. Any Self Contained Breathing apparatus (SCBA) with a full facemask. SCBA with a full facemask operated in pressuredemand or other positive pressure mode. A combination respirator which includes a supplied-air respirator with a full facemask operated in pressuredemand or other positive pressure or continuous-flow mode and an auxiliary SCBA operated in pressure-demand or other positive pressure mode. SCBA with a full facemask operated in pressure-demand or other positive pressure mode. Any gas mask providing protection against organic vapors. Any escape SCBA.

GREATER THAN 400 ppm OR ENTRY INTO UNKNOWN CONCENTRATIONS

FIRE FIGHTING ESCAggPggE

* Only NIOSH approved and MSHA certified equipment should be used. 20

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Table 3-2 Propylene Oxide Permeation Test Data*

CONCENTRATION: 100% Breakthrough Thickness Time (cm) (hours)

Resistant Material

Permeation Rate (g/cm2 min)

BUTYL RUBBER NATURAL RUBBER POLYETHYLENE/TYVEK POLYVINYL ALCOHOL TEFLON /NOMEX/TEFLON

0.06 0.02 NA NA 0.05 3.03

2.20 <0.01 0.05 0.60 2.55 0.02

42.08 1973.4 90.0 90.0 0.02 99999.99

VITON

* Only NIOSH approved and MSHA certified equipment should be used. liquid is present. A face shield (8-inch minimum) may be worn to provide added splash protection. These eye protective measures should meet ANSI Z87.1 specifications. Individuals wearing contact lenses while working with or around propylene oxide should wear chemical safety goggles at all times. The potential for increase in eye injury of contact lens wearers exposed to chemicals has not been determined. A conservative approach in PPE selection is warranted.

3.4.4

Skin Protection

Impervious protective clothing suitable for a particular work activity should be worn. Clothing can range from gloves and an apron to a full-containment suit. Propylene oxide was tested against a variety of chemical protective clothing (CPC) materials. Protective clothing and gloves made of butyl rubber or Teflon should provide protection from contact with liquid for at least 2 hours (see Table 3-2). However the quality and thickness of the CPC may vary between manufacturers. Therefore, manufacturer specific propylene oxide permeation data should be obtained and evaluated before selection. Where the potential for exposure to propylene oxide liquid exists, workers should wear a liquid-tight containment suit or slicker suit. These suits are designed to protect employees from skin contact with propylene oxide. All suits should be routinely inspected to identify any damage or wear. If tears are observed, exit the contaminated area and replace the clothing. Protective clothing used in a contaminated environment should be properly decontaminated prior to handling by unprotected individuals and reuse. To decontaminate the protective clothing wash with a mild soap/detergent and water.

3.4.2

Head Protection

Hard hats should be worn where there is danger from falling objects or overhead leaks and spills. Hard hats should meet the requirements of ANSI Z89.1 specifications for protection. Manufacturers have adapted hard hats so that ear protection and faceshields may be easily attached. If, due to the specific circumstances, a hard hat is not required, a hood made of chemically impervious material may be worn.

3.4.3

Foot Protection

Heavy rubber overboots should be provided and worn over leather shoes or boots to protect the leather from contamination. Leather items absorb propylene oxide, thereby increasing the risk of dermal (skin) exposure, and cannot be effectively decontaminated. Rubber boots should be worn under pant legs to prevent propylene oxide from entering the boot.

3.5

Direct Reading Instruments

Propylene oxide is readily analyzed by a variety of direct reading instruments. The advantage of using direct

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reading instruments is that real-time analysis and instantaneous air concentrations can be determined by trained personnel. The value of a real-time analysis, in terms of prevention of injury and illness, is considerable. Direct reading instruments that have been successfully used to measure propylene oxide are combustible gas indicators, infrared spectrophotometers, flame ionization detectors, photoionization detectors and colorometric detector tubes. Appendix III contains a partial list of product vendors. Limits of detection vary between these instruments and should be evaluated to ensure proper use. The proper selection, calibration, use and interpretation of direct reading instruments requires the services of a professional industrial hygienist or other knowledgeable person. The output from these instruments may require interpretation depending on the presence of other chemicals.

tube. This can be substituted with the use of passive samplers, which use the diffusion characteristics of the material instead of an active sampling pump. These methods have been extensively developed and evaluated for use with propylene oxide. The National Institute for Occupational Safety and Health (NIOSH) has developed Method Number 1612 for sampling and analysis of propylene oxide (see Appendix IV). The method recommends sampling with standard sized coconut charcoal tubes and analysis by gas chromatography. In addition, Lyondell Chemical Company has funded the development and validation of a passive diffusion badge method (See Appendix V) This method recommends sampling with the 3M 3520 passive sampler and analysis by gas chromatography. These methods for air sampling and analysis are the primary means to determine worker exposures over extended periods. When considering the use of these methods for determination of employee exposure, it is important that a monitoring program is developed by professional industrial hygienists. This program should include the sampling strategy, quality assurance and statistical analysis of results.

3.6

Air Sampling and Analysis

When assessing worker exposure to propylene oxide, an extended sampling period is desirable. The most common method of air sampling is collection on a sorbent media over an extended period of time. Air is drawn at a predetermined rate by a sampling pump into a charcoal

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PRODUCT SAFETY BULLETIN

4. ENGINEERING
This section is included for use as a guideline. It is not intended to be a design handbook and does not relieve the user from exercising competent engineering judgment or using qualified professional personnel to meet the specific requirements. The information contained is only applicable to the specific chemical compound identified in Section 1 General Information, 1.1 Product Identification. Mixtures or compounds using propylene oxide will require additional engineering studies to determine the applicability of the enclosed information.

4.5

Instrumentation

Independent high level alarms and/or shutdowns should be provided to avoid overflow of propylene oxide storage vessels. Storage tanks should be equipped with temperature sensors.

4.6

Relief Requirements

4.1

Bulk Storage

The construction of low pressure propylene oxide storage tanks should be in accordance with American Petroleum Institute (API) 620 (see Appendix VI for citations), 650 and National Fire Protection Association (NFPA) 30. Higher pressure storage vessels should comply with American Society of Mechanical Engineers (ASME) Code, Section VIII, Division 1. Carbon steel is acceptable but should be clean and rust free. Liquid propylene oxide should enter through the bottom of the tank. Incoming liquid should be prevented from free falling through the tank vapor space (see Section 8).

The requirements of API RP2000 should be followed for low pressure vertical storage tanks. Pressure relieving systems for pressure vessels are defined in API RP520 parts 1 and 2. Flame arresters, when required, should follow the requirements of API RP028 and 2210, Underwriters Laboratory (UL) 525 and NFPA 30.

4.7

Leak Detection Devices

Secondary containment areas in confined spaces should be monitored with instrumentation able to detect the lower flammability limit of propylene oxide in air. Instruments that have been successfully used to measure propylene oxide are combustible gas indicators, infrared spectrophotometers, flame ionization detectors and photoionization detectors (see Section 3.5).

4.2

Piping

Piping and piping components should comply with the latest edition of American Society of Mechanical Engineers/American National Standards Institute (ASME/ANSI) B31.3.

4.8
4.8.1

Material Requirements
Gaskets

4.3

Electrical Area Classification

Flat Ring (sheet): Grafoil GHE, dimensions per ANSI B16.21. Spiral Wound: Flexitallic CG, 100 percent graphite-filled, dimensions per ASME B 16.20.

All electrical equipment should be Class 1, Group B*.

4.4

Pump Specifications

4.8.2

O Rings

Kalrez 2035, Teflon, Chemraz 505 or equivalent. Centrifugal: Any carbon steel API 610 type, designed with mechanical seals and either Kalrez 2035, Teflon or Chemraz 505 secondary seals. Rotary: Any type made for hydrocarbon service with mechanical seals. This type of pump should be checked regularly for gear wear.

4.8.3

Pipe Thread Dope

Teflon paste or tape; check continuity across connection to ensure grounding.

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ENGINEERING

4.8.4

Pump Seals

4.9

Vapor Containment System

Component materials for mechanical seals should include: Stationary Faces: tungsten carbide or silicon carbide. Rotation Faces: carbon. Elastomers: Kalrez 2035, Chemraz 505 or Teflon.

The requirements of API RP2000 should be followed for low pressure vertical storage tanks. Vapor containment systems for pressure vessels are defined in API RP520 parts 1 and 2. Flame arresters, when required, should follow the requirements of API RP2028 and 2210, UL 525 and NFPA 30.

4.8.5

Valve Packing

Die-formed Rings: graphite-based. Bonnet Gaskets: metal reinforced flexible graphite.

4.10

Chemical Compatibility

4.8.6

Hoses

Stainless steel double-braided corrugated type with suitable pressure/temperature rating.

Propylene oxide is incompatible with oxidizing materials, anhydrous metal chlorides, acids, bases, clay-based adsorbent materials, peroxides, inorganic chlorides and any acetylide-forming metals, such as aluminum, copper and copper alloys, including brass and bronze.

24

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PRODUCT SAFETY BULLETIN

5. FIRE SAFETY
5.1 Fire and Explosion Hazard 5.2 Fire Prevention

Propylene oxide is an extremely flammable liquid that is classified by Occupational Safety and Health Administration (OSHA) 29 Code of Federal Regulations (CFR) 1910.106 (see Appendix V for citations) as a Class 1A flammable liquid. The National Fire Protection Association (NFPA) Code 30 defines propylene oxide as a Class 1A flammable liquid. For application of the National Electric Code (NEC-NFPA 70), propylene oxide is a Class 1, Group B* flammable liquid. Vapors of propylene oxide at concentrations between 1.7% and 37% in air can explode if an ignition source is present. Propylene oxide vapor is heavier than air and may travel a considerable distance to a source of ignition and flash back. All precaution necessary for the safe handling and storage of a volatile flammable liquid or vapor should be strictly observed with propylene oxide. Aqueous mixtures as low as 0.75% propylene oxide may be flammable. Storage areas should be designed to prevent exposure of propylene oxide containers to fire (see Section 8.1). Section 9 provides recommendations for the safe unloading and transfer of propylene oxide which are necessary to minimize the fire and explosion hazard while performing these operations. If this material is involved in a fire, prevent unauthorized individuals from entering the area, and evacuate the area downwind from the fire. Fires should be fought from a safe distance upwind. Thermal decomposition products, such as carbon dioxide, carbon monoxide and perhaps other toxic gases and vapors, may be generated. Propylene oxide, when involved in a fire, burns rapidly with tremendous heat. Figure 5-1 on the following page provides propylene oxide flammability limits in air. Heat may build pressure and cause rupture of closed containers. A water fog may be used to cool the containers. Water may be ineffective as an extinguishing agent. Prevent liquid from entering water sources and sewers by building dikes as necessary to contain flow.

Propylene oxide, when ignited, burns rapidly with high heat. Due to the high vapor pressure of propylene oxide, it is capable of readily forming explosive mixtures. Sources of ignition, including heat, sparks, flames and static electricity, must be avoided. Compliance with this basic rule requires continual oversight and management. Meeting this rule should typically include the following combination of work practices and mechanical controls: a strong no smoking policy in areas where propylene oxide is used the use of non-sparking tools while working with or near propylene oxide-containing equipment grounding of metallic containers/vessels in which the material is stored bonding and grounding of metallic receiving containers stringent welding, cutting and burning permit systems implementation of inside and outside storage methods that comply with legal requirements and good industry practice.

5.2.1

Static Electricity

As with other flammable liquids, the transfer of propylene oxide can create static electricity charges, which can act as an ignition source of the flammable vapors. The charge can develop when the liquid flows or is poured through air. To reduce or eliminate this, bonding and grounding is required by federal regulations, OSHA 29 CFR 1910.107, building and fire codes and industry practice (NFPA 70, NFPA 77, NFPA 30). Bonding provides a low resistance path to current flow between two surfaces which are physically separated or become separated. Per NFPA 77, a maximum of 1 megaohm is acceptable, but generally much lower values are possible. Grounding connects the containment vessels, pipes, etc. to a grounding electrode (ground) in the earth by means of conductors welded/attached to both the equipment and the ground. A 10 ohm maximum is the recommended value for the resistance of the cable and ground.

25

FIRE SAFETY

Flammability in Air

100

90

10

80

20

PROPYLENE OXIDE

70

30

(% )

de

60

40

xi

ne

50

50

ir (%

le

ro

py

5
20 10 100 90

40

60

NOT FLAMMABLE
30 70

80

FLAMMABLE

90

100 80 70 60 50 40 30 20 10

Nitrogen (%)

To determine if a mixture of propylene oxide is flammable, find the concentration of propylene oxide and the air or nitrogen concentration. Follow both lines until they intersect. If they intersect within the shaded area, the mixture is flammable.

Figure 5-1

5.3

Fire Suppression

Lyondell Chemical Company has determined that propylene oxide fires are extremely difficult to extinguish. Alcoseal, a film forming fluoroprotein foam [FFFP] manufactured by Angus Fire, Ltd, has superior extinguishing properties under test conditions. Other foams may be effective. However, the manufacturer should be contacted to check their foams effectiveness in fighting propylene oxide fires. A 6% solution of Alcoseal applied at a rate of 0.25 gallons per minute per square foot of fire surface through an NFPAII type 2 foam applicator is appropriate. Foam applied directly to open surface fires will require a higher concentration 26

and/or a higher application rate. Due to propylene oxides low flash point and high vapor pressure, propylene oxide may reignite from hot surfaces. To determine the amount and locations of extinguishing equipment necessary to extinguish a propylene oxide fire, an evaluation of a worst case fire scenario is necessary. Calculations to determine the quantities of Alcoseal that should be available should use 0.25 gallons of Alcoseal per minute per square foot of the storage area. Propylene oxide is soluble in water and the resulting solution requires substantial dilution to control the PO vapor above the mixture. In confined spaces, such as
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FIRE SAFETY

sumps or sewers, a dilution greater than 150 to 1, or less than 0.75% propylene oxide, maybe necessary to prevent PO vapor concentrations above 20% LEL. Portable fire extinguishers should be placed in the vicinity where propylene oxide is handled or stored and in areas where the potential for spills or leaks exists. Class B dry chemical or foam extinguishers should be used when fighting small propylene oxide fires. NFPA 10 contains guidelines for the correct selection, use, distribution, inspection, maintenance, and recharging of portable fire extinguishers and should be referred to when designing a work area.

Fire fighters should use full protective clothing and equipment, including National Institute for Occupational Safety and Health/Mine Safety and Health Administration (NIOSH/MSHA)-approved self-contained breathing apparatus (SCBA) with full facemask operated in the pressure demand mode (see Sections 3.3 and 3.4). Water spray can be used to disperse vapors to protect the fire fighters who may be attempting to stop a leak. If a fire is controllable or propylene oxide containers are not exposed to direct flame, an evacuation zone with a minimum radius of 1,500 feet may be needed. If the fire becomes uncontrollable or propylene oxide containers are exposed to direct flame, a evacuation zone with a minimum radius of 5,000 feet may be required. In some instances, depending on specific facility hazards, it may be prudent to allow a propylene oxide fire to burn itself out. A qualified fire fighting expert should make this decision. After a fire has been extinguished, residual propylene oxide contamination may occur. This may require a cleanup of the liquid. Individuals who engage in such a cleanup should be thoroughly trained in proper techniques and have received training in accordance with the OSHA Hazardous Waste Operations and Emergency Response (HazWOpER) standard, 29 CFR 1910.120 (see Section 7).

5.4

Fire Fighting

If a facility relies on community fire companies for fire response, information regarding propylene oxide operations and storage should be provided. Information should include facility layouts indicating the storage locations and quantities of propylene oxide. Drills should be conducted periodically with the fire company and facility information updated on a regular basis. If a facility chooses the option of an internal fire brigade for structural firefighting, then compliance with the OSHA Fire Brigade Standard is required. These requirements as defined in 29 CFR 1910.156 include the organization of a fire brigade, the personal firefighting equipment and training requirements.

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6. HAZARD COMMUNICATION
6.1 OSHA Hazard Communication
The International Agency for Research on Cancer (IARC), the National Institute for Occupational Safety and Health (NIOSH), the National Toxicology Program (NTP) and the Environmental Protection Agency (EPA) consider propylene oxide a possible human carcinogen based on animal studies. For a complete discussion of the health effects of propylene oxide see Section 2.

Under Hazard Communication and Worker Right to Know laws, employees should be informed of the potential hazards of chemicals in the workplace. At the federal level, the Occupational Safety and Health Administration (OSHA) Hazard Communication Standard 29 Code of Federal Regulations (CFR) 1910.1200 (see Appendix V for citations) requires that employers who use hazardous chemicals in their workplace, including propylene oxide, develop written programs and train employees on the potential hazards and protective measures.

6.1.1.2 Methods of Detection

Propylene oxide cannot be detected by odor or irritation response at concentrations below 200 ppm and is, therefore, considered to have poor warning properties. Above 200 ppm propylene oxide has a sweet ether-like odor. In the event of sensory detection of propylene oxide, recommended exposure guidelines may have been exceeded. To determine propylene oxide concentrations in air, measurements can be made using air sampling equipment. A variety of instruments are available to provide instantaneous or continuous monitoring of propylene oxide concentrations in air. Direct reading instruments including combustible gas indicators, infrared spectrophotometer, flame and photoionization detectors, and colorometric detector tubes (see Section 3.5) can be used to monitor for propylene oxide. When assessing worker exposure to propylene oxide, personal breathing zone samples should be collected to determine compliance with the established exposure limits (see Section 3.6).

6.1.1

Worker Training

As a user of propylene oxide, an employer should provide information and training to employees on its hazards, the methods for detecting releases and methods of protection from exposure. This information should be included in your Hazard Communication Training Program. To assist you in this effort, the following summary information is provided.

6.1.1.1 Hazards
Propylene oxide is a flammable liquid with a low boiling point and a high vapor pressure. Propylene oxide vapors are heavier than air and may travel long distances along the ground. These vapors are flammable and will burn or explode. Exposure to propylene oxide can occur through any route of exposure but most commonly occurs through inhalation, skin or eye contact. If inhaled, short-term exposure to propylene oxide in high concentrations will cause pulmonary edema (fluid in the lungs and may cause narcotic effects. Skin contact with propylene oxide can result in irritation or chemical burns, depending on the concentration of the liquid and the duration of skin contact. Eye contact with liquid propylene oxide may result in chemical burns. High vapor concentrations may cause eye irritation.

6.1.1.3 Methods of Protection

Hazard Communication Training should include information on methods of protection that can be used by employees handling propylene oxide. This should include the engineering and administrative controls employed, as well as the personal protective clothing and equipment (PPE) to be worn (see Sections 3.3 and 3.4).

6.1.2

Labeling

All incoming containers of this product are accompanied by a product label providing health and safety information. The product label is a primary source of

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information for safe handling of this material. Lyondell Chemical Company product labels contain the material identification, principal hazards, and Lyondell Chemical Companys name, address and telephone number (see Figure 6-1). Containers of propylene oxide or mixtures containing propylene oxide in concentrations greater than or equal to 0.1% must be labeled in accordance with the OSHA Hazard Communication Standard. Department of Transportation (DOT) labeling requirements for propylene oxide are presented in Section 11.2. Each vessel into which propylene oxide is transferred should be clearly identified as to its contents and the hazards of the materials it contains. Many firms elect to employ the National Fire Protection Association (NFPA) 704, Standard System for the Identification of the Fire Hazards of Materials (Hazard Diamond) as a means of inplant communication to workers, contractors and firefighters. The appropriate numerical hazard classifications for propylene oxide are as follows:

6.2

SARA Title III

The Emergency Planning and Community Right to Know Act of 1986 , also referred to as the Superfund Amendment and Reauthorization Act or SARA Title III, requires facilities which use or store propylene oxide to notify their state emergency response commissions and work with local authorities to develop emergency response plans. Users of propylene oxide should read the SARA Title III regulations and familiarize themselves with its requirements. Since propylene oxide is a potentially hazardous chemical, facilities should submit to their local emergency planning committee (LEPC) a copy of their MSDS or their chemical inventory list. If a facility uses or stores more than the threshold planning quantity (TPQ) of 10,000 pounds of propylene oxide in a year, the facility should submit an annual Tier I or Tier II Report to state and local agencies. This inventory listing should include all mixtures of propylene oxide in excess of 0.1% concentration.

Health (Blue): 2 Fire (Red): 4 Reactivity (Yellow): 2

6.3

State Regulations

6.1.3

Material Safety Data Sheets

An Lyondell Chemical Company material safety data sheet (MSDS) is provided to customers with the first order of the new year and with the first order after any change or revision to the MSDS. Material Safety Data Sheets are the primary means of providing information regarding the safe storage, handling, use and ultimate disposal of Lyondell Chemical Company products. While the product MSDS is an invaluable source of health and safety information, it may not supply information specific to the actual uses of the product. When the information provided does not adequately fulfill your needs, contact Lyondell Chemical Company through customer service at 1-888-777-0232. Lyondell Chemical Company material safety data sheets are available in several languages and formats. While the additional downstream sales of this product, or materials containing this product, are the responsibility of the distributor, Lyondell Chemical Company will support your hazard communication efforts.

State or local regulations, while patterned after the federal legislation, may have different or contain more stringent requirements. Specific state regulations should be reviewed in order to assess the applicability of these regulations to the use of propylene oxide.

6.3.1

New Jersey Right To Know

New Jersey has adopted the SARA regulations as an amendment to the New Jersey Worker and Community Right To Know Act (NJSA34:5A1). With these regulations New Jersey has established a zero threshold for reporting of propylene oxide to state and local agencies. This law also requires that the Chemical Abstract Services (CAS) numbers appear on all containers which contain propylene oxide in concentrations of 0.1% or greater in the workplace.

6.3.2

Pennsylvania Right To Know

The Pennsylvania Worker and Community Right to Know Act classifies propylene oxide as an environmental hazard and as a special hazard. The Pennsylvania regulations are similar to the federal regulations. However, these regulations require additional

30

H A Z A R D C O M M U N I C AT I O N

MSDS No. P000012-1-OSHA-AE

PROPYLENE OXIDE LABEL INFORMATION

Manufacturer: Lyondell CHEMICAL COMPANY 1221 McKinney Street Houston, TX 77010 Telephone Numbers EMERGENCY 800/424-9300 CHEMTREC 800/245-4532 LYONDELL CHEM CUSTOMER SERVICE 888/777-0232 INFO ONLY

Other Company Names: Use Statement: Physical Hazards: Health Hazards:

Precautionary Measures:

DOT Information: DOT Hazard Class: DOT RQ (based on Material): DOT Hazardous Material Proper Shipping Name:

PO For industrial use only Keep out of reach of children Extremely flammable Signal Word: DANGER Highly reactive Severe eye irritant Severe skin irritant Inhalation hazard Ingestion hazard Skin contact hazard Causes cancer in lab animals Do not handle near heat, sparks, or open flame Do not store near combustible materials Keep container tightly closed when not in use Avoid contact with eyes, skin and clothing Avoid prolonged or repeated breathing of gases, vapors or mists Use only with adequate ventilation/personal protection Prevent contact with food, chewing, or smoking materials Wash thoroughly with soap and water Do not take internally UN/NA ID No.: UN 1280 DOT Packing Group: 1 3 (flammable liquid) 100 lbs. Propylene Oxide Component Name Propylene Oxide

CAS no. 75.56-9

Composition Amount (Wt.) AP 100 %

RQ 100 lbs.

If overcome by exposure, remove victim to fresh air immediately. Give oxygen or artificial respiration as needed. Obtain emergency medical attention. Prompt action is essential. Eye Contact: In case of eye contact, immediately rinse with clean water for 20-30 minutes. Retract eyelids often. Obtain emergency medical attention. Skin Contact: Immediately remove contaminated clothing. Wash skin thoroughly with mild soap and water. Flush with lukewarm water for 15 minutes. If sticky, use waterless cleaner first. Obtain emergency medical attention. Ingestion: If swallowed, give lukewarm water (pint/ 1/2 liter) if victim completely conscious/alert. DO NOT INDUCE VOMITING. Risk of damage to lungs exceeds poisoning risk. Obtain emergency medical attention. In case of spill: Extremely flammable liquid. Release causes immediate fire/explosion hazard. Extinguish all ignition sources. Impound/recover large land spill; soak up small spill with inert solids. On water, may biodegrade. Contain/collect rapidly to minimize dispersion. Report per regulatory requirements. Protective Equipment: Respiratory: Use only U.S. National Institute for Occupational Safety and Health (NIOSH)/U.S. Mine Safety and Health Administration (MSHA) approved supplied air or self-contained breathing apparatus operated in a positive pressure mode. Eye: Both chemical splash goggles and face shield must be worn. Skin: Impervious protective suit with integral or tight-fitting gloves, boots, and full head and face protection must be worn. Label No.: LP000012 Version No.: 1 Date: 1 September 1993 Figure 6-1

Instructions: First Aid: Inhalation:

In case of fire, use: Alcohol type foam; Dry chemical; Polydol foam

31

H A Z A R D C O M M U N I C AT I O N

information through use of labels, MSDSs, and workplace inventories.

6.3.3

California Proposition 65

Californias Safe Drinking Water and Toxic Enforcement Act of 1986 (Proposition 65) requires that warnings must be provided to individuals if there is a potential for exposure to propylene oxide.

32

PRODUCT SAFETY BULLETIN

7. ENVIRONMENTAL
Aqueous solutions of propylene oxide degrade and convert to propylene glycol with an average half-life of 13 days, through hydrolysis in fresh water, and to chloropropanol in sea water in only 2 days. The length of time for propylene oxide degradation will vary based on the conditions of the aquatic medium. Aquatic organisms metabolize propylene glycol. Both propylene glycol and chloropropanol are readily biodegraded. Propylene oxide may contaminate the soil from accidental spills and uncontrolled rainwater runoff from contaminated areas. Degradation in wet soil occurs through hydrolysis, as discussed previously. In dry soil propylene oxide will evaporate into the air. Propylene oxide tends to be very mobile in the soil. Studies indicate that propylene oxide, based on its water solubility and conversion to propylene glycol and chloropropanol, will not accumulate in aquatic or terrestrial life forms. If possible, all pumps and ancillary equipment should be located outside the primary containment area and should be provided with curbing to collect drips, leaks and minor spills. Drain valves may be installed at the low point of the containment area or sump. During normal operations all drain valves should be in a closed position. To minimize soil and ground water contamination in the event of a propylene oxide spill, the containment areas should be designed and constructed of impermeable materials such as concrete, synthetic liners or compacted clay. Since concrete is not totally impervious, other measures should be taken to prevent soil and groundwater contamination. Use only compatible sealants on cracks and concrete joints because propylene oxide may degrade certain epoxy resins. In the event of a propylene oxide release to the environment equal to or greater than 100 pounds, the National Response Center must be notified. The telephone number of the National Response Center is 1800-424-8802. This reporting requirement is a provision of Sections 103(a) and (b) of the Comprehensive Emergency Response Compensation and Liability Act of 1980 (CERCLA), as amended. The reportable quantity (RQ) for propylene oxide is 100 pounds. Reportable quantities are listed in 40 Code of Federal Regulations (CFR) Part 302, Table 302.4 (see Appendix VI for citations). In addition to the above reporting requirement, Section 304 of the Superfund Amendments and Reauthorization Act of 1986 (SARA) requires that a release to the environment of hazardous substances in quantities equal to or greater than their RQs be reported to state and local authorities. These agencies are location specific and should be included in the facilitys emergency response plan. Any accidental discharge of propylene oxide or waste containing propylene oxide into the municipal sewer system should be reported immediately to local authorities. The discharge should be diluted with copious quantities of water to reduce the fire and explosion hazard. National Pretreatment Standards, 40 CFR 403.5, prohibit the discharge of pollutants that may create a fire or explosion hazard in the sewer system or publicly owned treatment works (POTW). 33

7.1

Spills and Leaks

Facilities involved in the storage and/or handling of propylene oxide should be designed to contain and/or control spills from process areas and loading and unloading operations. Soil and groundwater contamination from an accidental spill of propylene oxide can be minimized by installation of curbs, sumps and impervious containment areas. Concrete curbing with a minimum one percent slope or earth diking with a minimum two percent slope from the point of the potential spill to a collection basin or sump should be used to retain propylene oxide within the containment area, thus minimizing worker exposure and overall environmental impact. The total volume of the containment area should be adequate to handle a worst case release of propylene oxide. For storage tanks the capacity of the containment area is generally the volume of the largest storage tank in the diked area. Design of the diking or curbing should also provide an allowance for accumulated rainfall. Pumps, piping and equipment, designed to operate within potential spill areas, should be compatible with propylene oxide (see Section 4) and free of potential ignition sources.

E N V I R O N M E N TA L

In the event of a spill of propylene oxide, all nonessential personnel should be evacuated. All ignition sources must be extinguished immediately. After donning the appropriate personal protective equipment (see Section 3), the spill should be covered with Alcoseal FFFP foam or equivalent (see Section 5.3) to minimize potential fire hazard from vaporization of the propylene oxide. Depending on the volume and location of the spill, it can be recovered by vacuum truck or absorbed with solid sorbent (see Section 4.10) and placed in drums for disposal. Residual propylene oxide in the containment area should be flushed with water into a sump or collection area for subsequent treatment or disposal.

If propylene oxide process waste is treated biologically at a POTW, the local authority should be consulted to determine appropriate requirements. If propylene oxide is biologically treated onsite and then discharged to surface waters, the treatment plan effluent should comply with federal and state discharge permit provisions. Propylene oxide and solutions of propylene oxide and water may exhibit a closed cup flash point less than 140 F. As a result, these materials are considered ignitable hazardous wastes. The RCRA, as amended, provides criteria that define a hazardous waste (40 CFR 261) and lists of chemicals specifically covered by regulation. Testing of process waste streams and spilled material is recommended to determine the applicability of these regulations. Acceptable methods for disposal of RCRA hazardous wastes containing propylene oxide are combustion in a RCRA permitted incinerator or a boiler that is in compliance with the RCRA burner and industrial furnace (BIF) regulations found in 40 CFR 266. In addition, the treatment of all hazardous wastes, including wastewaters, contaminated soils, and sludges may be subject to the RCRA Land Disposal Restrictions (LDR) found in 40 CFR 268. Hazardous waste may be held onsite for up to 90 days without a RCRA permit, provided that the waste is placed in approved containers (40 CFR 262). State regulations may specify design requirements for temporary hazardous and non-hazardous waste accumulation areas.

7.2

Waste Disposal

Propylene oxide is an extremely flammable liquid and is hazardous when discharged to the environment. In areas where propylene oxide may be released or handled, access should be limited to required personnel only. Occupational Safety and Health Administration (OSHA) regulation 29 CFR 1910.120 applies to the handling of spills of propylene oxide waste. This regulation applies to personnel engaged in the following: hazardous waste response under CERCLA, cleanup operations under the Resource Conservation and Recovery Act (RCRA), operations involving hazardous waste storage, hazardous waste sites and emergency response. Aqueous solutions, containing low concentrations of propylene oxide, can be treated biologically in a waste treatment plant. Biological treatment can also be considered for disposal of minor spills provided that the system is acclimated to propylene oxide and propylene glycol, and the treatment system has obtained any required permit approvals. Discharge of aqueous solutions of propylene oxide from minor spills into a municipal treatment system must be approved by the regulating authority prior to discharge. Incineration of contaminated soil and liquid propylene oxide is also an acceptable disposal alternative.

7.3

Container Disposal

Empty propylene oxide containers are considered nonhazardous waste. Lyondell Chemical Company recommends that empty propylene oxide containers be rinsed with water to remove residual product prior to disposal. Container disposal should be in accordance with applicable federal and state regulations. Empty containers which have not been water washed should be considered a potential fire/explosion risk due to residual propylene oxide vapor. These containers should not be cut, burned, soldered, or welded.

34

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PRODUCT SAFETY BULLETIN

8. PRODUCT STORAGE
Considerations in the design and construction of propylene oxide storage and handling facilities are flammability, environmental contamination and worker exposure. The specific requirements for receiving and storage facilities and for handling of propylene oxide will depend on several factors, including volumes stored or handled, container type, mode of transportation, processes utilized at the facility and proximity to other hazardous materials. The proper design and construction of storage and handling facilities requires the consultation with competent professional engineers. nearby sources of ignition, accessibility for fire fighting, and impact of a vapor cloud explosion on nearby areas. Installations should comply with NFPA 30 and NFPA 70 regarding these issues. Note that according to NFPA and OSHA, propylene oxide is a Class 1A flammable liquid. Propylene oxide tanks should be designed and constructed at twice the absolute vapor pressure of propylene oxide at the planned operating temperature. Atmospheric propylene oxide storage tanks (see Figure 81) should be designed and constructed in accordance with NFPA 30 as it applies to Class 1A liquids. This standard is intended to ensure that tanks possess sufficient structural strength and pressure relief systems to prevent catastrophic loss of contents in either normal service or under fire conditions (see Section 4). American Petroleum Institute (API) Standard 620, Recommended Rules for Design and Construction of Large, Low-Pressure Storage Tanks should be applied to the design and construction of propylene oxide storage tanks at low pressures. A typical pressure storage tank (ASME Pressure Vessel) for propylene oxide can be seen in Figure 8-2.

8.1

Storage Tanks

Requirements for atmospheric tank storage, including secondary containment, are presented in NFPA 30. This code requires that storage of propylene oxide in an unprotected facility should be situated at least 3 times the distances from a property line presented in Table 8-1 below. A protected storage facility, should be at least 112 times the distances presented in the table. Considerations in site selection and tank spacing include proximity to other flammable material storage facilities,

Table 8-1
Capacity Tank Gallons Minimum Distance in Feet from Property Line Which is or Can be Built Upon, Including the Opposite Side of a Public Way Minimum Distance in Feet from Nearest Side of Any public Way or from Nearest Important Building on the Same Property

275 or less 276 to 750 751 to 12,000 12,001 to 30,000 30,001 to 50,000 50,001 to 100,000 100,001 to 500,000 500,001 to 1,000,000 1,000,001 to 2,000,000 2,000,001 to 3,000,000 3,000,001 or more

5 10 15 20 30 50 80 100 135 165 175

5 5 5 5 10 15 25 35 45 55 60 35

36
TO CONTAINMENT DEVICE 4 18 12 8 13 5 13 REFRIGERATION SYSTEM 3 NITROGEN SUPPLY 19

P RO D U C T S TO R AG E

MAXIMUM FLOW CAPACITY OF PRESSURE CONTROL VALVE (8) SHALL NOT EXCEED RELIEF CAPACITY OF CONSERVATION VENT (4)

13 PROPYLENE OXIDE LT 7 13 LI 6 13 17 13 13 14 16 14 9. FILTER 10. PUMP 11. PRESSURE GAUGE W/DIAPHRAGM SEAL 12. CHECK VALVE 13. BLOCK VALVE 7. LEVEL TRANSMITTER 8. PRESSURE CONTROL VALVE 1 M 9 13 10 M

12

15 2 TI 3

11 13 TO PROCESS 12 13 14

Typical Atmospheric Storage Tank Configuration

FROM TANK CAR (Figure 9-1) OR TRUCK 13 (Figure 9-4) 12 13

1. CONTAINMENT DIKE

14. APPROVED GROUND 15. N.F.P.A. IDENTIFICATION CODE 16. APPROVED LEAK DETECTION (IF REQUIRED) 17. MIXING EDUCTOR 18. PRESSURE GAUGE 19. PRESSURE SAFETY VALVE

2. TEMPERATURE INDICATION

3. MANWAY

4. CONSERVATION VENT

5. EMERGENCY RELIEF DEVICE

6. LEVEL INDICATION

Figure 8-1

Printed on Recycled paper

This figure illustrates a typical configuration, and is not intended to be used as a design specification. Qualified professionals must exercise engineering judgment to establish site specifications that meet applicable requirements

TO CONTAINMENT DEVICE NITROGEN SUPPLY

TO CONTAINMENT DEVICE

MAXIMUM FLOW CAPACITY OF PRESSURE CONTROL VALVE (13) SHALL NOT EXCEED RELIEF CAPACITY OF PRESSURE SAFETY VALVE (1)

TO SHUTDOWN INTERLOCKS AND ALARMS (H & L) 13 13

FROM TANK CAR (see Figure 9-1) OR TRUCK (see Figure 9-4)

4 15 12 1 19 5 15 15 15 LT PROPYLENE OXIDE PC REFRIGERATION SYSTEM

DIP TUBE

LT LI

TI

18
2 15 2 15 3 9 7 8 17 15

10 M 11 15 TO PROCESS 16 8 15

RECYCLE

Typical Pressure Storage Tank Configuration

14

17 8

1. PRESSURE SAFETY VALVE 8. APPROVED GROUND 9. FILTER 10. PUMP

7. OUTLET LINE

13. PRESSURE CONTROL VALVE 14. N.F.P.A. IDENTIFICATION CODE 15. BLOCK VALVE 16. CHECK VALVE 17. CONTAINMENT DIKE 18. TEMPERATURE INDICATION 19. LEVEL TRANSMITTER

2. TANK SUPPORT

3. TANK DRAIN

4. SAFETY RAILING

5. MANWAY

11. PRESSURE GAUGE W/DIAPHRAGM SEAL 12. PRESSURE CONTROLLER (SPLIT RANGE)

6. LEVEL TRANSMITTER W/OUTPUT GAUGE

P RO D U C T S TO R AG E

Figure 8-2

This figure illustrates a typical configuration, and is not intended to be used as a design specification. Qualified professionals must exercise engineering judgment to establish site specifications that meet applicable requirements

37

P RO D U C T S TO R AG E

Storage tanks should be situated within containment systems which are capable of providing detection and control of an accidental release of propylene oxide. Containment system design and operation should conform with NFPA 30. Tank venting systems should comply with API RP2000, Venting Atmospheric and Low-Pressure Storage Tanks. These standards require, at a minimum, that instrumentation at the loading station warns the operator of the potential for overfilling and that a totally independent device shuts off flow whenever overfill is imminent. Neither device is to be used as a regular operating tool for determining tank level. Bulk storage tanks should be vented to a containment device which eliminates discharges of propylene oxide vapors to the atmosphere. The containment device should be designed to prevent the passage of a flame from one container to another. Refrigeration units may be used to keep storage temp below 70F to minimize polypropylene oxide formation. The National Electric Code (NFPA 70) outlines electrical requirements for the handling, transport, and storage of propylene oxide and other Class 1, Group B* flammable liquids. It also requires that whenever flammable liquids are stored or transferred, their containers should be effectively bonded and grounded to prevent static electricity.

surrounding areas. Adjacent unloading areas should be segregated by curbing. At a minimum, the surface of the unloading area under and around the bulk transport vessel should be constructed of concrete or ballast installed over a synthetic impermeable barrier suitable for the retention of propylene oxide. The drainage surfaces should be pitched with a grade of at least 1% towards the collection basin or sump. The sump or catchbasin should have fire seals and be equipped with instruments that will detect liquid levels and the presence of propylene oxide vapor. Rain water and spilled liquids trapped inside the containment area are to be disposed of through the sump or catchbasin. Discharge valves from the collection area should be closed under normal conditions. Accumulated liquids should be disposed of by a trained operator, after determining the liquids composition. Lighting adequate for nighttime unloading operations should be provided, unless it is certain that only daytime unloading is to be performed. A suitable method of discharging container contents should be provided. Acceptable methods include gravity flow, pumping from top via a dip pipe or pressurization with nitrogen. If nitrogen is used, the facility shall be designed to avoid overpressurization of the vessel. Furthermore, a means of collection and environmentally acceptable treatment of the vapor (for example, flaring or scrubbing) should be provided. Vapor containment systems should be designed to remove or recover vapor (see Section 4).

8.2

Off-Loading Station

The installation for off-loading tank cars and tank trucks of propylene oxide should be designed, maintained and operated to meet current standards for fire protection, worker safety and environmental protection. Loading racks should be located at least 150 feet from all equipment and tanks. Electrical wiring and devices should comply with the requirements of NFPA 70. Piping throughout the installation should comply with NFPA 30 or with American Society of Mechanical Engineers/American National Standards Institute (ASME/ANSI) B31.3. Collection systems should be large enough to contain the worst credible accidental release of propylene oxide, plus an additional volume for flush water and rain water. The unloading area should be curbed to divert spillage into the drainage system and prevent run-off into the

8.3

Workplace Location

Processing operations utilizing propylene oxide should be located and operated to minimize the potential risk of fire and explosion. The minimum distance of a processing vessel to any adjoining property or building is based on the stability of the chemical (NFPA 30). Where a vessel is located in a building and the exterior wall facing the vessel is more than 25 feet away and has a 2-hour fire rating, these distance requirements may not apply. When a 4-hour or greater fire resistant wall is provided, there are no distance requirements. In the case of propylene oxide, the wall must also be explosion resistant.

38

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P RO D U C T S TO R AG E

Processing equipment, such as pumps, heaters and filters, should be kept at least 25 feet from the property line or should be separated by a wall which has a 2-hour fire rating and is explosion resistant. The operating facility should be accessible from at least one side for fire fighting. Facilities storing or using propylene oxide should be provided with either a gravity or continuous mechanical exhaust ventilation system. If propylene oxide is

dispensed within the room, mechanical ventilation is required. If air is mechanically exhausted, the system should be designed to provide a minimum of 1 cubic foot per minute (CFM) of exhaust per square foot of floor area, but not less than 150 CFM. The ventilation system in any dispensing area should be equipped with an audible alarm to warn of equipment failure. The ventilation system should be designed to maintain the area below 25% of the lower explosive limit for propylene oxide or 6,000 ppm.

39

PRODUCT SAFETY BULLETIN

9. TRANSFER OPERATIONS
Propylene oxide should be transferred and handled following written operating procedures developed for the specific facility. This section provides guidelines used by Lyondell Chemical Company in our handling of propylene oxide. Operating procedures should include the hazards associated with this product (see Section 6) and the selection of personal protective clothing and equipment (see Section 3). Only workers properly trained in these operating procedures should handle propylene oxide.

9.1.1

Work Preparation

The following procedures have been developed to assist in the safe offloading of propylene oxide. A suggested unloading checklist is also provided (see Figure 9-2). 1. Center the tank car with the unloading station. 2. 3. 4. 5. Set brakes and chock wheels on tank car. Connect ground cable to car and check for continuity of connections. Be sure blue flag and derailer are in place. Locate metal caution signs in front of and/or behind the tank car. An additional sign should be located at the rail siding switch. These signs (minimum 12 x 15 inches) should read STOPTANK CAR CONNECTED. Remove the housing cover pin and lift pressure dome cover. This will expose all valves and fittings which are required for unloading and sampling (see Figure 9-3). Inspect for leakage around valves and fittings in the pressure dome area by pouring soapy water on the connections only and checking for bubbles. If leaks are detected, stop work and make repairs. Sample tank car to confirm contents. The procedure is as follows: Sample the tank car through the sample line, which is located in the pressure dome area (see Figure 9-3). Fill the sample bottle leaving approximately 20% vapor space to allow for expansion. If closed sampling system is not employed, proper personal protective equipment should be used. 9. Determine the available storage tank capacity and the liquid level in the tank car before transfer.

9.1

Tank Cars

During unloading, the tank car should be connected to a vapor balance or equalizing system or blanketed with an inert gas, such as nitrogen gas, depending on the unloading system design (see Figure 9-1). 6. Piping systems and track rails should be connected to a common earth ground. The tank car should be bonded to the discharge system. Continuity of ground should be checked prior to off loading. All fixed components of the unloading system must be outside an area of 22.5 feet above the rails and 8.75 feet on each side of the track center line. Electrical equipment, telephone and intercom systems in the area should comply with Class 1, Group B*. An automatic deluge sprinkler system should protect the loading facility and dome area of the tank car. It should provide for both cooling and dilution in a ratio of 150 parts water to one part propylene oxide. A fire- water monitor should be located near the tank car dome and should have an unobstructed path to the target. A 3050 pound dry-powder fire extinguisher should be present. Eyewash and safety shower stations should be located on both ground and platform levels at the tank car rack. There should be emergency block valves or shut-off switches in the liquid and vapor line permanent piping that can be operated locally and remotely. If a pump is used, there should be a switch at a remote location to shut the pump down. Workers should identify all pipelines so that proper alignment can be made. Tank cars will be unloaded in accordance with 49 CFR 174 Subpart C.

7.

8.

9.1.2

Unloading Procedures

The unloading sequence is as follows: 1. Attach nitrogen line to the vapor valve. 2. Attach flexible hoses to the liquid unloading valves. Stainless steel double-braided accordion-type hoses with two-way shutoff quick-disconnect couplings are recommended. If dry disconnect couplings are not used, purge all lines and connections with nitrogen before transferring propylene oxide. Pressure tank car to 60 psig and hold for one minute. If pressure cannot be maintained, use a soap and 41

3.

T R A N S F E R O P E R AT I O N S

water solution to identify leak. After the leak has been corrected, proceed to Step 4. 4. Open vapor valve and use a regulator to adjust the nitrogen pressure to equalize that of the tank car. This will force liquid propylene oxide into the pump and keep the vapor phase of the tank car out of the flammable limits.

tank trucks are pressurized with nitrogen before shipment. The unloading valve is located at the rear of the truck (see Figure 9-4). The tank truck unloading facility should be in a relatively remote, level location distant from general activity and ignition sources. Use of road barriers and warning lights is recommended to restrict traffic or other operations from the unloading area. Workers who are properly trained should use only nonsparking tools during unloading of the tank truck. The tank truck should be grounded. All electrical equipment, including telephone and intercom systems, should be Class 1, Group B*. Workers should use either steel pipe and swing joints for truck liquid and vent connections or flexible stainless steel hoses to connect the units fixed piping to the truck connections. Since these hoses are probably the most vulnerable part of the unloading process, workers should inspect and pressure test them frequently and store them in a protected location. There should be emergency block valves in the liquid and vapor line permanent piping that can be operated locally and remotely. If a pump is used, there should be a switch at a remote location to shut the pump down. Workers should identify all pipelines so that proper alignment can be made.

CAUTION: Do not let nitrogen pressure exceed 90% of the rated relief valve pressure. 5. Open the liquid unloading valve and allow propylene oxide to fill the pump. This valve must be opened slowly to avoid activating the excess flow valve. Start pump and begin pumping propylene oxide to the storage tank.

CAUTION: A positive pressure should be maintained on the tank car to keep the pump from pulling a vacuum on the car; monitor this closely. 6. Monitor liquid level on storage tank to identify when the transfer is complete. A density gauge or a bulls eye in the transfer line can also be used. When the tank car is empty, shut down the pump. Clear transfer line using nitrogen. Close the unloading line valve to the storage tank and the storage tank vent. Close the tank car vapor valve and the tank car liquid unloading valve. Vent transfer line of pressure. Pressurize tank car to 15 psig with nitrogen for return trip. Disconnect transfer, nitrogen and storage tank vent lines. Test for leakage by pouring soapy water over the valves. If no bubbles are detected, close and secure dome cover. If bubbles are detected, retighten all valves and retest. If leaks are still detected, stop work make repairs. Disconnect the ground cable. Remove the wheel chocks, derailer, blue flag and caution signs.

7.

8.

9.2.1

Work Preparation

9.

10. Reverse tank car placards to Residue for return trip. 11. Leave the car brakes engaged for the railroad crews to release. 12. If there were any mechanical problems with the tank car, advise Lyondell Chemical Company Customer Service (1-888-777-0232).

The following procedures have been developed to assist in the safe offloading of propylene oxide. Also, provided in Figure 9-5 is a suggested unloading checklist. 1. Chock both sides of one tank truck wheel; set brakes. 2. 3. 4. 5. Connect ground cable and check for continuity. Check bill of lading and verify sample to confirm contents. To prevent truck movement during unloading, the driver is not to remain in the cab. Inspect hoses, pump and valves for cleanliness, leaks and other defects.

9.2

Tank Trucks
9.2.2
1.

Propylene oxide is shipped in Department of Transportation (DOT) MC331 steel tank trucks, 20 to 25 psig, with a capacity of up to 7,000 gallons. After filling, 42

Unloading Procedures

Connect storage tank vapor recovery line to tank truck.

ATM
22 9 11 NITROGEN SUPPLY 11 11 11 15 17 17 12 13 11 7 11 10 11 TO STORAGE See Figure 8-1 and 8-2 10 14 8 M 16

FROM SHUTDOWN INTERLOCKS

2 1 DOT 105J 23 3

Typical Tank Car Configuration

PROPYLENE OXIDE

19 4 18 CHEMTREC 800/424-9300

20 19 4 21

1. VAPOR VALVE 10. CHECK VALVE 11. BLOCK VALVE 12. FLEX. HOSE ASSEMBLY W/2" NPT CONN.

9. PRESSURE SAFETY VALVE (N2)

17. APPROVED GROUND 18. CHEMTREC EMERGENCY NUMBER 800/424-9300 19. HANDRAIL 20. HAND BRAKE WHEEL 21. DERAILER 22. PRESSURE GAUGE 23. DOT CLASSIFICATION NO.

2. MANWAY (see Figure 9-3)

3. LIQUID VALVE

4. PLACARD (Figure 11-2 & 11-3) (ALL 4 SIDES) W/2" NPT CONNECTIONS

13. DRY DISCONNECT & FLEX. HOSE ASSEMBLY 14. NITROGEN HIGH POINT PURGE W/BLOCK VALVE 15. PUMP 16. PRESSURE GAUGE W/DIAPHRAGM SEAL

5. WHEEL CHOCKS

6. APPROVED GROUND CLAMP

7. FILTER

8. PRESSURE CONTROL VALVE

T R A N S F E R O P E R AT I O N S

Figure 9-1

This figure illustrates a typical configuration, and is not intended to be used as a design specification. Qualified professionals must exercise engineering judgment to establish site specifications that meet applicable requirements

43

T R A N S F E R O P E R AT I O N S

PROPYLENE OXIDE UNLOADING CHECKLIST

Tank Car Number: Operator:
Prior to Unloading Tank Car

Date: Time:
AM/PM
Yes No

Wheels chocked and hand brakes engaged .................................................................s Blue flag and derailer in place ........................................................................................s Metal caution signs located in front of and behind tank car...........................................s Eyebath and safety shower flushed and ready...............................................................s Ground cable connected to car and checked for continuity ..........................................s Pressure dome inspected for leakage around valves and fittings..................................s Bill of lading checked and sample verified.....................................................................s Storage tank capacity and tank car liquid level determined before filling......................s Load and vent-back lines connected, purged and tested for leaks...............................s Proper piping alignment made and checked .................................................................s Open transfer lines and monitor liquid level ...................................................................s Qualified operator in attendance during transfer............................................................s After Unloading Tank Car

s s s s s s s s s s s s

Yes No s s s s s s s s s s s s Figure 9-2

When tank car is empty, shut down the pump................................................................s Transfer line blown clear of Propylene Oxide..................................................................s Unloading line valve closed to the storage tank and the storage vent...........................s

Tank car vapor valve and liquid unloading valve closed ................................................s Transfer line vented of pressure......................................................................................s Tank car pressured to 15 psig with N2 for return trip.......................................................s Transfer, nitrogen and storage tank vent lines disconnected .........................................s Test for leakage and secure dome cover........................................................................s Ground cable disconnected ...........................................................................................s Tank car placards reversed to Residue .......................................................................s Blue flag, metal caution signs and derailer device removed..........................................s Wheel chocks removed...................................................................................................s

44

T R A N S F E R O P E R AT I O N S

Typical Tank Car Dome Configuration

NITROGEN

LIQUID

LIQUID

LIQUID 1 2

LIQUID 1

B C C

NITROGEN

6 A C 1
LIQUID

7 C 1
LIQUID

2 C C 4

6 SECTION "C-C" NITROGEN OR VAPOR BALANCE LINE 1 2 B 3 MANWAY BONNET SIDE COVER (ACCESS TO VALVES) 7

SECTION "B-B"

1. 2. 3. 4.

STRAIGHT BALL VALVE GAUGING DEVICE SAFETY VALVE 225# EDUCTION PIPE

5. SUPPORT 6. THERMOWELL 7. SAMPLE LINE

SECTION "A-A"

9
Figure 9-3

This figure illustrates a typical configuration, and is not intended to be used as a design specification. Qualified professionals must exercise engineering judgment to establish site specifications that meet applicable requirements

45

46
ATM 1 1 11 17 13 13 3 18 5 19 15 20 21 6 8 7 9 9 7 7 12 13 M 4 MC-331 2 NITROGEN SUPPLY OR VAPOR BALANCE LINE FROM SHUTDOWN INTERLOCKS ATM

ATM

T R A N S F E R O P E R AT I O N S

16

10

TO STORAGE: See Figures 8-1 & 8-2 13 15 14 13

22

Typical Tank Truck Configuration

CHEMTREC 800/424-9300

1. PRESSURE RELIEF VALVE 7. GROUND WIRE 8. REAR END PROTECTION 9. WHEEL CHOCKS 10. CERTIFICATION DATE 11. PRESSURE GAUGE

6. APPROVED GROUND CLAMP

12. FILTER 13. BLOCK VALVE 14. PUMP 15. CHECK VALVE 16. PRESSURE GAUGE W/DIAPHRAGM SEAL

17. PRESSURE CONTROL VALVE 18. FLEX. HOSE ASSEMBLY 19. GLOBE VALVE 20. GLOBE VALVE 21. FLEX. HOSE ASSEMBLY 22. CHEMTREC EMERGENCY NUMBER 800/424-9300

2. DOT CLASSIFICATION NO.

3. ROTARY GAUGE (LIQUID LEVEL)

4. THERMOMETER AND PRESSURE GAUGE

5. PLACARD (Figure 11-4, 11-5, 11-6)

(ALL 4 SIDES)

This figure illustrates a typical configuration, and is not intended to be used as a design specification. Qualified professionals must exercise engineering judgment to establish site specifications that meet applicable requirements

Figure 9-4

T R A N S F E R O P E R AT I O N S

2.

Connect transfer line to liquid unloading valve and nitrogen line to vapor valve. Stainless steel doublebraided accordion-type hoses with two-way shutoff quick-disconnect couplings are recommended. If dry disconnect couplings are not used, purge all lines and connections with nitrogen before transferring propylene oxide. Pressure tank truck to 60 psig and hold for one minute. If pressure cannot be maintained, use a soap and water solution to identify leak. After the leak has been corrected, proceed to Step 4. Confirm that the vent-back and liquid inlet valves at the storage tank are open. Slowly equalize the pressure on the truck and the storage tank. Maintain nitrogen pressure below 20 psig on tank truck. Nitrogen pressure and/or a pump may be used to unload tank truck. The unloading valve must be opened slowly to avoid activating the excess flow valve. CAUTION: A positive pressure of at least 10 psig should be maintained on the tank truck to keep from pulling a vacuum on the truck; monitor this closely.

7.

Open the valves in the liquid line on the tank truck at the emergency block valve and at the pump suction and discharge. Start the unloading pump. Check for leaks and for proper operation. Shut down the pump when the tank truck is empty. Blow transfer lines clear of propylene oxide by using an inert gas. Close all valves and vents. Vent transfer lines of pressure by blowing back into truck with nitrogen. Disconnect transfer, nitrogen and storage tank vent lines. Check to ensure placards meet DOT requirements.

8.

3.

9.

4.

10. Disconnect ground cable and remove wheel chocks.

9.3

Iso Tanks

5. 6.

Propylene oxide is shipped in DOT 51 and intermodal tank type IM 101. These tanks contain approximately 6,000 gallons of propylene oxide under a nitrogen blanket of between 15 to 25 psig. The unloading valve is located at the rear of the tank (see Figure 9-6). The iso tank work preparation and unloading procedures are the same as the tank truck procedures located in Section 9.2.

47

T R A N S F E R O P E R AT I O N S

PROPYLENE OXIDE UNLOADING CHECKLIST

Tank Truck Number: Operator:
Prior to Unloading Tank Truck

Date: Time:
AM/PM
Yes No s s s s s s s s s s s

Wheels chocked and parking brakes engaged..............................................................s Ground cable to trailer connected and checked for continuity ......................................s Check billing of lading ....................................................................................................s Eyebath and safety shower flushed and ready...............................................................s Placard placed on windshield.........................................................................................s Inspected for leakage around valves and fittings...........................................................s Verify sample to confirm contents...................................................................................s Storage tank capacity and tank truck liquid level determined before filling...................s Load and vent-back lines connected, purged and tested for leaks...............................s Proper piping alignment made and checked .................................................................s Qualified operator in attendance during transfer............................................................s After Unloading Tank Truck

Yes No s s s s s s s s s s s s Figure 9-5

When tank truck is empty, shut down the pump .............................................................s Transfer line blown clear of Propylene Oxide..................................................................s Unloading line valve closed to the storage tank and the storage vent...........................s

Tank truck vapor valve and liquid unloading valve closed .............................................s Transfer line vented of pressure......................................................................................s Tank truck pressured to 15 psig with N2 for return trip....................................................s Transfer, nitrogen and Storage Tank Vent lines disconnected ........................................s Inspected for leakage around valves and fittings...........................................................s Ground cable disconnected ...........................................................................................s Placards proper for shipment .........................................................................................s Placard removed from windshield...................................................................................s Wheel chocks removed...................................................................................................s

48

ATM 17 25 15 15 14 16 13 6 10 12 5 9 (2) 11 IM-101 24 1 18 NITROGEN SUPPLY OR VAPOR BALANCE LINE

PROPYLENE OXIDE 2 FROM SHUTDOWN INTERLOCKS 26 21 28 8 27 CHEMTREC 3 4 21 22 22 800/424-9300 7 23 19 15 20 M TO STORAGE 15 See Figure 8-1 and 8-2 16 16

Typical IMO Tank Configuration

1. TANK FRAME 2. TANK SHELL IN STAINLESS STEEL WITH INSULATION AND ALUMINUM CLADDING PROTECTION 3. MALE BOTTOM DISCHARGE 4. DATA PLATE 5. LADDER 6. WALKWAY 7. STEAM HEATING (NOT USED FOR P.O. SERVICE) 8. THERMOMETER

9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19.

SAFETY RELIEF VALVES (2) W/TANK MANHOLE NITROGEN INLET PROVISION FOR FILLING/DRAIN SYSTEM BALL VALVE FLEX HOSE ASSEMBLY BLOCK VALVE CHECK VALVE PRESSURE RELIEF VALVE PRESSURE CONTROL VALVE FILTER

20. 21. 22. 23. 24. 25. 26.

PUMP PRESSURE GAUGE W/DIAPHRAGM SEAL GROUND WIRE FLEXIBLE HOSE ASSEMBLY DOT CLASSIFICATION NO. PRESSURE GAUGE DOT PLACARD (Figure 11-2) ALL 4 SIDES 27. CHEMTREC EMERGENCY NUMBER 800/424-9300 28. CARRIERS NAME CONTAINER OWNER/LESSORS NAME CERTIFICATION DECALS

T R A N S F E R O P E R AT I O N S

Figure 9-6

This figure illustrates a typical configuration, and is not intended to be used as a design specification. Qualified professionals must exercise engineering judgment to establish site specifications that meet applicable requirements

49

PRODUCT SAFETY BULLETIN

10. TANK CLEANING AND EQUIPMENT REPAIR

10.1 Work Preparation
The proper preparation for tank cleaning and equipment repair is necessary to prevent exposure to hazardous chemicals. Preparation should include a clear definition of the tasks to be performed, an identification of hazardous materials and related hazardous conditions. A hazardous work permit system should be used to identify the job related hazards and plan for the safe completion of this work. Employee protection should include the use of engineering controls and the selection of personal protective equipment (PPE) (see Section 3). Tanks and equipment that contained propylene oxide vapor or liquid should be cleared of residual material before starting cleaning and/or repair. Liquids should be removed from a low point. Residual liquid and vapor should be either flushed with water or another suitable material, and vapor should be purged with nitrogen. Only workers properly trained should be involved in the cleaning and repair of tanks and equipment that have previously held propylene oxide (see Section 3). Eyewash and safety showers should be located near the work operation. Appropriate fire extinguishing equipment should be present (see Section 5.3). Appropriate respiratory protection for propylene oxide vapor exposures (see section 3.3) may also be required.

10.4

Equipment Cleanout

If a new tank is to be put into service, it is critical that it be clean of all rust, dirt, grease and water. Soap or detergents and water should be used to remove grease and oils. The cleaned surface should be rinsed with water until a neutral pH is obtained. No solvents containing organic or inorganic chlorides should be used. If a grease must be used in a tank, a totally fluorinated lubricant must be used. Iron oxide is a catalyst for propylene oxide polymerization. To eliminate loose rust (iron oxide) and scale from inside a tank, a high pressure fresh water blast is effective. Acidic or basic cleaning or pickling systems should be avoided because their residues can cause vigorous reaction of propylene oxide. After this step, the tank walls should be dried and the bottom cleaned of all solids and water. The tank should then be purged with nitrogen gas down to a 3% concentration of residual oxygen (see Figure 5-1). This will provide a safety factor greater than 3 in case any air pockets remain during purging. After out of service equipment has been padded with nitrogen gas, the manways should be marked as follows: DANGER DO NOT ENTER PADDED WITH N2.

10.2

Control of Hazardous Energy

A facility must have procedures for controlling hazardous energy sources that comply with the requirements of 29 CFR1910.147. The procedures protect workers in areas where propylene oxide vessels or equipment are cleaned, maintained, or entered. After system is purged, ensure that all potential sources of propylene oxide or hazardous energy are physically tagged and/or locked out, and affected persons notified.

10.5

Maintenance and Inspection

Preventive maintenance and inspection of containers, hoses, pumps, fittings, fire protection equipment and refrigeration units used for propylene oxide should be conducted. An adequate supply of spare parts for refrigeration units should be maintained. Overpressure and overfill detectors and combustible gas detectors should be maintained and calibrated regularly. Some insulating materials reduce the auto ignition temperature of propylene oxide. New insulating materials should be tested prior to use. The inspection program should also include daily inspection of equipment, storage areas, and monitoring of ventilation systems.

10.3

Confined Space Entry

10
51

OSHA (29 CFR 1910.146) establishes requirements for entry into confined spaces. For confined spaces that typically contain propylene oxide, a lower flammability limit of 1.7 volume percent should be used to determine permit requirements.

TA N K C L E A N I N G

AND

E Q U I P M E N T R E PA I R

Preventive maintenance schedules should be developed for critical equipment such as fire fighting equipment, combustible gas detectors, pumps, safety relief valves, gaskets and emission control equipment.

10
52

PRODUCT SAFETY BULLETIN

11. TRANSPORTATION REGULATORY REQUIREMENTS

The Distribution Safety Program of Lyondell Chemical Company has been implemented in accordance with the Chemical Manufacturers Associations Responsible Care Distribution Code of Management Practices. Not every authorized U.S. Department of Transportation (DOT), International Maritime Organization (IMO), International Civil Aviation Organization (ICAO) or International Air Transport Association (IATA) packaging is addressed in this chapter. Lyondell Chemical Company has selected transport routes and modes in concert with packaging configurations to develop and implement risk reduction alternatives. The U.S. DOT Hazardous Materials Regulations (HMR) codified in Title 49 Code of Federal Regulations (CFR) were reauthorized by The Hazardous Materials Transportation and Uniform Safety Act (see Appendix VI for citations) in November, 1990. A simplified summary of the effective dates for provisions of various promulgating HMR Final Rules can be found in 49 CFR 171.14. The Department of Transportation recognizes that the implementing systems will be unavoidably mixed during the transition period. Shippers are encouraged to use either Implementing Final Rules or the current DOT system as consistently as possible. Federal regulations describe authorized procedures to properly package, mark, label, placard and manifest shipments. These procedures depend upon the quantity and type of hazardous material and the method of transport of the substance. If one plans to transport hazardous material internationally by air, then the requirements of the IATA and ICAO must be met. Shipment by water requires compliance with the IMO regulations. Special training in Classification, Marking, Labeling, Placarding and Packaging is required to offer PO for transport. The required training is defined in 49 CFR 172.700. A Canadian shipment or package of propylene oxide may be transported by tank car or tank truck within the United States if it is in compliance with the requirements of DOT 49 CFR 171 or the regulations of Transport Canada and the Transportation of Dangerous Goods Act, Part IV. A transborder consignment of propylene oxide from the U.S. to Canada may also be made under the same provisions. Per the Transport Dangerous Goods Regulations, a Canadian approved emergency response plan for PO will be assigned a registration number which must appear on the shipping papers before a shipment in Canada can take place.

11.1

Classification

Propylene oxide is listed in the Hazardous Materials Table (49 CFR 172 Subpart B); therefore, it is designated as a hazardous material for transportation purposes. Propylene oxide is assigned a hazard classification of 3 with a packaging group (PG) designation of I. The designation PG I implies that the degree of danger present is great. The identification number is UN1280. The DOT shipping requirement is Propylene oxide, 3, UN1280, PG I, RQ (49 CFR 172 Subpart C).

11.2

Marking, Labeling and Placarding

General and specific requirements concerning marking, labeling, placarding and the preparation of shipping papers are found in 49 CFR 172 and depend on the transport mode, packaging configuration and quantity of hazardous material being transported. Markings are placed on opposing sides of bulk packagings (less than 1,000 gallons capacity) and on each side and each end for a greater capacity (bulk) packaging. Marking, labeling and placarding requirements are detailed in 49 CFR 172 Subparts D, E and F respectively. Subparts E and F have pictorials of labels and placards. A flammable liquid label and flammable placard are required (see Figures 11-1 and 11-2). Each bulk packaging, other than a tank car, that is required to be placarded when it contains a hazardous material must remain placarded when it is emptied, unless it meets the special requirements of Subpart F. Special placarding provisions for rail apply for residues (see Figure 11-3).

11
53

11.3

Packaging

Packaging exemptions are not permitted. Special provisions are included in the Hazardous Materials Table

T R A N S P O R TAT I O N R E G U L AT O R Y R E Q U I R E M E N T S

49 CFR 172.101. For combination packagings in limited quantities, if glass inner packagings (including ampoules) are used, they must be packed with absorbent material in tightly closed metal receptacles before packing in outer packagings. Aluminum construction materials are not authorized for any part of a packaging which is normally in contact with the propylene oxide. If Intermodal (IM) 101 portable tanks are used, the minimum test pressure is 6 bars (1 bar=14.5 psig). Bottom outlets and pressure relief devices of IM 101 portable tanks will conform to 49 CFR 173 Subpart B and 49 CFR 178 Subpart H, respectively. Propylene oxide transported in IM portable tank must be completely covered with an inert gas. Lyondell Chemical Company uses nitrogen. Non-bulk packaging is specified in Part 173, Subpart E, while bulk packaging is addressed in 49 CFR 173, Subpart F.

BL AC

ED

FLAMMABLE LIQUID

BL

AC

Figure 11-1

11.3.1 Tank Trucks

Lyondell Chemical Company ships propylene oxide in DOT Specification MC 331 cargo tank trucks. These tanks have a capacity of up to 7,000 gallons. Once filled with propylene oxide, the cargo tank truck is pressurized to 2025 pounds per square inch gauge (psig) with a nitrogen pad. The pressure relief system will meet the requirements in 49 CFR 178 Subpart J. Bottom outlets of the cargo tank are equipped with internal self-closing stop-valves meeting the requirements of Subpart J. See 49 CFR 173 Subpart B for limitations on the use of pressure unloading. Requirements for the test and inspection of cargo tanks, minimum qualifications for inspectors and testers, test and inspection markings, and reporting and record retention requirements can be found in 49 CFR 180 Subpart E. These regulations should be reviewed in detail to establish inspection protocols for tank trucks used in the transport of propylene oxide. For your convenience sample tank truck unloading procedures can be found in Section 9.2.
W H IT E

ED

1280
3
W H IT E

BLACK

WHITE WHITE
BL AC

ED

11.3.2 Tank Cars

11
54

IT

Tank cars used to transport propylene oxide are cylindrical and constructed of steel. While there are various types of cars authorized, with its increased safety features Lyondell Chemical Company uses a Specification DOT 105 insulated and pressurized tank car with a thermal protection system and full head shields.

1280
RESIDUE

BLACK

Figure 11-3

Figure 11-2

ED W H IT E R ED

T R A N S P O R TAT I O N R E G U L AT O R Y R E Q U I R E M E N T S

Propylene oxide may be transported by rail if it is originally consigned or subsequently reconsigned to a party having a private track (49 CFR 171.8) or to a party using railroad siding facilities which are equipped for piping the propylene oxide from the tank car to permanent storage. When unloading at a railroad siding facility, the delivery and complete unloading of the tank car must be made to permanent storage tanks of sufficient capacity to receive the entire contents of the car (see 49 CFR 174 Subpart G). Tank cars will be unloaded in accordance with 49 CFR 174 Subpart C (see Section 9.1). While other tank cars are authorized in 49 CFR 173 Subpart F, Lyondell Chemical Company uses DOT Specification 105J tank cars. Per the same Subpart, riveted tank cars are not authorized. Placarding will be in accordance with 49 CFR 172 Subpart F. The red Flammable placard (see Figure 11-2) will be used. When a tank car is emptied to the maximum extent practicable, the FLAMMABLE placard is replaced with a RESIDUE placard (see Figure 11-3).

11.3.4 Marine Transportation

The transport of propylene oxide on passenger vessels is forbidden. For cargo vessels the U.S. DOT specification and UN Standard packaging is constructed of materials that will not react dangerously with or be decomposed by the propylene oxide (see Section 1.5). 49 CFR 176 defines the requirements for shipment of flammable liquids such as propylene oxide over water. Lyondell Chemical Company transports propylene oxide in packagings such as ISO tanks on container ships or barges. Vessel/barge owners must comply with 46 CFR 153, Code for the Construction and Equipment of Ships Carrying Dangerous Chemicals in Bulk (the BCH Code), and Regulations for the Control of Pollution by Noxious Liquid Substances in Bulk. There are Coast Guard and IMO regulations governing vessel/barge operation and construction. The application and maintenance of a nitrogen blanket for propylene oxide in an ISO tank is detailed in 46 CFR 153.500. An independent inspector is employed for quality and quantity measurements to insure that the propylene oxide is loaded in uncontaminated tanks.

11.3.3 ISO Tanks

International Organization for Standardization (ISO) tanks are a specific class of Intermodal (IM) tanks designed and constructed to permit their use interchangeably in two or more modes of transport. Lyondell Chemical Company uses DOT Intermodal 101 or IMO Type I portable tanks. These tanks contain approximately 6,000 gallons of propylene oxide under a nitrogen blanket of 1525 psig. Another steel portable tank is Specification DOT 51. However, it is for domestic use only. Specification requirements for IM 101 steel portable tanks which are authorized to carry propylene oxide are delineated in 49 CFR 178 Subpart H. The IM 101 tank is transported only on a drop-chassis trailer with a resulting lower center of gravity. Periodic inspections of the chassis should be made. Intermodal portable tanks with a capacity of at least 5,000 liters (1,900 gallons) may not be loaded to a filling density of less than 80 percent by volume (see 49 CFR 173 Subpart B).

11.3.5 Air Transportation

Propylene oxide may be transported domestically and internationally by air in specific packagings and quantities. These specific requirements should be reviewed thoroughly prior to offering propylene oxide for international air transport. The IATA and ICAO requirements must be met for international shipment. However, they have generally been incorporated in 49 CFR. Propylene oxide is authorized to be prepared for air transport and to be transported by motor vehicle prior to international air shipment (49 CFR 171).

11.4

Transportation Emergencies

Lyondell Chemical Company markets its products in a manner which is considerate of the health and safety of customers, transporters and the general public. However, even with the best of preparations, emergencies can occur.

11
55

T R A N S P O R TAT I O N R E G U L AT O R Y R E Q U I R E M E N T S

All Lyondell Chemical Company Material Safety Data Sheets (MSDS) contain a 24 hour telephone number for the CHEMical TRansportation Emergency Center (CHEMTREC). The CHEMTREC numbers are (800) 424-9300 or call collect (202) 483-7616. These numbers are staffed 24 hours a day.

the filing of a detailed hazardous materials incident report by the carrier.

11.4.2 Transport of Propylene Oxide Residue

If a discharge of propylene oxide occurs during transport, an official of the federal, state or local government may require immediate removal to prevent further consequences, according to 49 CFR. This may be accomplished without preparation of a manifest, and the Environmental Protection Agency (EPA) does not require the freight carrier to have an EPA identification number. If a hazardous waste transporter is used, they must have an EPA identification number (40 CFR).

11.4.1 Reporting Requirements

The response and reporting requirements which may be necessary in the event of a transportation incident involving propylene oxide are detailed in 49 CFR 171. These requirements, which vary with the severity of the incident, require immediate notification to the DOT and

11
56

PRODUCT SAFETY BULLETIN

APPENDIX I CONVERSION FACTORS

Symbols for Abbreviations of Units
R in ft yd mi gal bbl h Rankine temperature (R = 9/5Kelvin) inch foot yard mile U.S. gallon barrel hour lb oz lb-mol Btu hp m g Pa pound (av) ounce (av) pound mole British thermal unit horsepower meter gram Pascal

To convert the numerical value of a property expressed in one of the units in the left-hand column of the following tables to the numerical value of the same property expressed in one of the units in the top row of the same table, multiply the original value by the factor in the block common to both units. The SI unit is listed first in each table. Factors with less than seven significant digits are exact as written.

Units of Mass
kg g metric ton ton (US) lb oz

1 kg 1 1g 1x10 3 1 metric ton 1000. 1 ton (US) 907.1847 1 lb 0.45359237 1 oz 0.02834952

1000. 1 1x10 6 9.071847x10 5 453.59237 28.34952

1x10 3 1x10 6 1 0.9071847 4.5359237.10 4 2.834952x10 5

1.102311x10 3 1.102311x10 6 1.102311 1 0.0005 3.200x10 5

2.204623 2.204623x10 3 2204.623 2000. 1 0.0625

35.27396 0.03527396 35273.96 32000. 16. 1 (1 Liter = 1 dm 3)

Units of Volume
m
3

dm

cm

yd

ft

1m3 1 dm 3 1 cm 3 1 yd 3 1 ft 3 1 in 3 1 gal 1 bbl 1m 1 dm 3 1 cm 3 1 yd 3 1 ft 3 1 in 3 1 gal 1 bbl

3

1 1x10 3 1x10 6 0.7645549 0.02831685 1.638706x10 5 3.785412x10 3 0.1589873

in
3

1000. 1 1x10 3 764.5549 28.31685 0.01638706 3.785412 158.9873

gal

1x10 6 1000. 1 7.645549x10 5 28.31685x10 3 16.38706 3785.412 1.589873x10 5

bbl

1.307950 1.307950x10 3 1.307950x10 6 1 0.03703704 2.143347x10 5 4.951132x10 3 0.2079475

35.31467 0.03531467 3.531467x10 5 27. 1 5.787037x10 4 0.1336806 5.614558

6.102374x10 61.02374 0.06102374 46656. 1728 1 231. 9702.

264.1721 0.2641721 2.641721x10 4 201.9740 7.480519 4.329004x10 3 1 42.

6.289812 6.289812x10 3 6.289812x10 6 4.808905 0.1781076 1.030715x10 4 0.02380952 1

(1 Liter = 1 dm 3)

I
57

C O N V E R S I O N FA C T O R S

Units of Density
kg m
3

g cm

lb ft

lb in

lb gal

1 kg m 3 1 g cm 3 1 lb ft 3 1 lb in 3 1 lb gal 1

1 1000. 16.01847 27679.91 119.8264

0.001 1 0.01601847 27.67991 0.1198264

0.06242795 62.42795 1 1728. 7.480519

3.612728x10 5 8.345403x10 3 0.03612728 8.345403 5.7870370x10 4 0.1336806 1 231. 4.3290043x10 3 1 (1 g dm 3 = 1 kg m 3)

Units of Pressure
Pa bar dyne cm
2

kg(wt) cm

atm

1 Pa 1 bar 1 dyne cm 2 1 kg(wt) cm 2 1 atm 1 torr 1 lb in 2 1 in Hg(60F) 1 in H2O(60F) 1 Pa 1 bar 1 dyne cm 2 1 kg(wt) cm 2 1 atm 1 torr 1 lb in 2 1 in Hg(60F) 1 in H2O(60F)

1 1x10 5 0.1 98066.5 101325.0 133.3224 6894.757 3376.85 248.835

torr

1x10 1 1x10 6 0.980665 1.013250 1.333224x10 3 0.06894757 0.0337685 2.48835x10 3

5

10. 1x10 6 1 980665. 1013250. 1333.224 68947.57 33768.5 2488.35

in Hg(60F)

1.019716x10 1.019716 1.019716x10 6 1 1.033227 1.359510x10 3 0.07030696 0.0344343 2.53741x10 3

5

9.869233x10 6 0.9869233 0.9869233x10 8 0.9678411 1 1.315789x10 3 0.06804596 0.0333269 2.45581x10 3

lb in
3

in H2O(60F)

7.500617x10 750.0617 7.500617x10 4 735.5592 760. 1 51.71493 25.3285 1.86642

1.450377x10 14.50377 1.450377x10 5 14.22334 14.69595 0.01933678 1 0.489757 0.0360895

4

2.961340x10 29.61340 2.961340x10 5 29.0408 30.0058 0.0394812 2.04183 1 0.0736885

4

4.01872x10 3 401.872 4.01872x10 4 394.103 407.197 0.535786 27.7089 13.5706 1

Units of Dynamic Viscosity

Pa s kgf s m
2

poise

cP

lbf s in

lbf s ft

1 Pa s 1 kgf s m 2 1 poise 1 cP 1 lbf s in 2 1 lbf s ft 2

1 9.80665 0.1 0.001 6894.758 47.88026

0.1019716 1 0.01019716 1.019716x10 4 703.0697 4.882428

10 98.0665 1 0.01 68947.58 478.8026

1000. 9806.65 100. 1 6894758. 47880.26

1.450377x10 4 1.422334x10 3 1.450377x10 5 1.450377x10 7 1 6.944444x10 3

0.02088543 0.2048161 2.085543x10 3 2.088543x10 5 144. 1

Units of Thermal Conductivity

Wm K
1 1

cal s 1 cm 1 K 1

cal/hr cm 1 K 1

Btu s 1 ft 1 R 1

Btu hr 1 ft 1 R 1

I
58

1 W m 1 K 1 1 1 cal s 1 cm 1 K 1 418.4 1 cal/hr cm 1 K 1 0.1162222 1 Btu s 1 ft 1 R 1 6230.646 1 Btu hr 1 ft 1 R 1 1.730735

2.390057x10 3 1 2.777778x10 4 14.89160 4.136555x10 3

8.604205 3600. 1 53609.77 14.89160

1.604970x10 4 0.06715194 1.865332x10 5 1 2.777778x10 4

0.5777892 241.7471 0.06715197 3600. 1

PRODUCT SAFETY BULLETIN

APPENDIX II WORLDWIDE OCCUPATIONAL EXPOSURE LIMITS PROPYLENE OXIDE

TWA 8* Country (mg/m3) (ppm) STEL* (mg/m3) (ppm)

Austria Belgium Denmark Finland France Germany Indonesia Italy Japan Korea Mexico Netherlands Norway Romania Sweden Switzerland Taiwan United Kingdom United States/America CIS (Formerly USSR)

120 240 12 12 50 6 240 240 50 50 240 240 2 100 200 5 6 50 240

50 100 5 5 20 2.5 100 100 20 20 100 100 1 42 85 Maximum ceiling concentration 2 2.5 20 100 360 1 Skin Irritant 360 150 150 240 100 25 10

Venezuela Yugoslavia

240 240

100 100

* Note: Refer to documents of the appropriate country for up-do-date information.

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PRODUCT SAFETY BULLETIN

APPENDIX III NAMES AND ADDRESSES OF MANUFACTURERS

Fire Fighting Foam FFFP Armour Ltd. 7235 Standard Drive Dorsey, Maryland 21076 (301) 796-8836 Bacharach 625 Alpha Drive Pittsburgh, Pennsylvania 15238 (412) 963-2000 MSA P.O. Box 426 Pittsburgh, Pennsylvania 15230 1-800-MSA-2222 The Foxboro Company Foxboro, Massachusetts 02035 (203) 853-1616

Combustible Gas Detectors TLV Sniffer

Explosimeter

Infrared Spectrophotometer MIRAN 1B2 MIRAN 1BX MIRAN 101 MIRAN 103 MIRAN 1B MIRAN 1A Flame Ionization Detectors Century OVA 128 Century OVA 108 Photoionization Detectors Photovacs TIP

The Foxboro Company Foxboro, Massachusetts 02035 (203) 853-1616 Photovac International Corp. 739B Park Avenue Huntington, New York 11743 1-800-387-5700 Hnu Systems Inc. 160 Charlemont Street Newtown Highland, Michigan 02161 (617) 964-6690

HNU Model P101

II
61

NAMES

AND

ADDRESSES

OF

M A N U FA C T U R E R S

Colorometric Detector Tubes Propylene Oxide (use Ethylene Oxide Nos. 163 or 163L)

Sensidyne 16333 Bay Vista Drive Clearwater, Florida 34620 1-800-451-9444 Drager Vendor: Protech Safety Equipment Inc. P.O. Box 4280 37 East 21st Street Linden, New Jersey 07036 1-800-526-4121

Propylene Oxide (use Ethylene Oxide No. 67 28241

III
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APPENDIX IV NIOSH METHOD 1612 PROPYLENE OXIDE

C3H60 METHOD: 1612, Issue 2 MW: 58.08 CAS: 75-56-9 EVALUATION: Partial RTECS: TZ2975000 Issue 1: 15 May 1985 Issue 2: 15 August 1994 liquid: d 0.8287 g/mL @ 20C BP 34C: MP - 104C; VP 59 kPa (442 mm Hg; 58% v/v) @ 20C: explosive range 1.7 to 37% (v/v) in air

OSHA: 100 ppm NIOSH: lowest feasible (carcinogen); Group 1 Pesticide ACGIH: 20 ppm (1 ppm = 2.37 mg/m3 @ NTP) SYNONYMS:
SAMPLING

PROPERTIES:

1,2-epoxypropane: methyloxirane
MEASUREMENT

SAMPLER: solid sorbent tube (coconut shell charcoal, 100 mg/50 mg) FLOW RATE: 0.01 to 0.2 L/min VOL - MIN: 0.5 L @ 100 ppm - MAX: 5 L SHIPMENT: refrigerated SAMPLE STABILITY: not determined FIELD BLANKS: 2 to 10 field blanks per set
ACCURACY

TECHNIQUE: GAS CHROMATOGRAPHY, FID ANALYTE: propylene oxide DESORPTION: 1 mL CS2; stand 30 min INJECTION VOLUME: 5 L TEMPERATURE -INJECTION: 190C -DETECTOR: 255C -COLUMN: 40C, 6 min; 50C/min to 250C

CARRIER GAS: N2, 1 mL/min; makeup 29 mL/min COLUMN: 30 m x 0.32-mm fused silica capillary column, 1.0 m DB-5 [2] CALIBRATION: propylene oxide in CS2 RANGE: 0.03 to 3 mg per sample [2] ESTIMATED LOD: 0.01 mg per sample PRECISION (Sr): 0.029 @ 0.6 to 2.4 mg per sample [1]

RANGE STUDIED: 121 to 482 mg/m# [1] (5-L samples) BIAS: - 1.8% ^rT): 0.085 [1] OVERALL PRECISION (S ACCURACY: 11.9%

APPLICABILITY: INTERFERENCES:

The working range is 8 to 295 ppm (20 to 700 mg/m3) for 5-L air sample [1]. None found

OTHER METHODS: This revises method S75 [3]. REAGENTS: 1. Propylene oxide (PrO), reagent grade.* 2. Carbon disulfide (CS2), chromatographic quality.* 3. Hexane, reagent grade.* 4. Calibration stock solution, 10 mg/ml in carbon disulfide. 63

NIOSH METHOD 1612

5. 6. 7. 8.

Desorption efficiency (DE) stock solution, 150 mg/mL, in hexane. Nitrogen, purified. Hydrogen, purified. Air, compressed, filtered.

* See Special Precautions EQUIPMENT: 1. Sampler: glass tube, 7 cm long, 6-mm OD, 4 mm ID, flame-sealed ends with plastic caps, containing two sections activated (600C) coconut shell charcoal (front + 100 mg; back = 50 mg) separated by a 2-mm urethane foam plug. A silylated glass wool plug precedes front section and a 3-mm urethane plug follows the back section. Pressure drop across the tube at 1L/min airflow must be less than 3.4 kPa. Tubes commercially available. 2. Personal sampling pump, 0.01 to 0.2 L/min, with flexible connecting tubing. 3. Shipping container, with bagged refrigerant. 4. Gas chromatograph, FID, integrator, and column (page 1612-1). 5. Vials, 2-mL PTFE-lined caps. 6. Syringes, 10 L readable to 0.1 L and other convenient sizes for preparing standards. 7. Volumetric flasks, 10-mL. 8. Pipet, 1-mL. SPECIAL PRECAUTIONS: Carbon disulfide is toxic and a dangerous fire and explosion hazard (flash point = -30C). Propylene oxide is a suspect carcinogen and is extremely flammable (flash point = -37C) [4]. Hexane is extremely flammable. Work with these only in a hood. SAMPLING: 1. Calibrate each personal sampling pump with a representative sampler in line. 2. Break the ends of the sampler immediately before sampling. Attach sampler to personal sampling pump with flexible tubing. 3. Sample at an accurately known flow rate between 0.01 and 0.2 L/min for a total sample size of 0.5 to 5 L. 4. Cap the samplers and pack securely for shipment in an insulated container with bagged refrigerant. Refrigerate upon receipt. SAMPLE PREPARATION: 5. Place the front and back sorbent sections of the sampler tube in separate vials. Discard the glass wool and foam plugs. 6. Add 1.0 mL CS2 in each vial. Attach cap to each vial. 7. Allow to stand 30 min with occasional agitation. CALIBRATION AND QUALITY CONTROL: 8. Calibrate daily with at least six working standards over the range 0.01 to 3 mg propylene oxide (PrO) per sample. a. Add known amounts of PrO or calibration stock solution to CS2 in 10-mL volumetric flasks and dilute to the mark. b. Analyze together with samples and blanks (steps 11 and 12). c. Prepare calibration graph (peak area vs. mg PrO). 9. Determine desorption efficiency (DE) at least once for each lot of charcoal used for sampling in the calibration range (step 8). Prepare three tubes at each of five levels plus three media blanks. a. Remove and discard back sorbent section of a media blank sampler. b. Inject a known amount (1 to 20 L) of DE stock solution directly onto front sorbent section with a microliter syringe. c. Cap the tube. Allow to stand overnight. d. Desorb (steps 5 through 7) and analyze together with working standards (steps 11 and 12).

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NIOSH METHOD 1612

e. Prepare a graph of DE vs. mg PrO recovered. 10. Analyze three quality control blind spikes and three analyst spikes to ensure that the calibration graph and DE graph are in control. MEASUREMENT: 11. Set gas chromatograph according to manufacturers recommendations and to conditions given on page 63. Inject sample aliquot manually using solvent flush technique or with autosampler. NOTE: If peak area is above the linear range of the working standards, dilute with CS2, reanalyze, and apply the appropriate dilution factor in calculations. 12. Measure peak areas. CALCULATIONS: 13. Determine the mass, mg (corrected for DE) of PrO found in the sample front (Wf) and back (Wb) sorbent sections, and in the average media blank front (Bf) and back (Bb) sorbent sections. NOTE: If @Wb > Wf /10, report breakthrough and possible sample loss. 14. Calculate concentration, C, of PrO in the air volume sampled, V (L): (Wf + Wb - Wf - Wb) 103 C = ____________________, mg /m3 V EVALUATION OF METHOD: Method S75 was issued on February 14, 1975 [3], and validated over the range 121 to 482 mg/m3 at 24C and 766 mm Hg ^rT, was 0.085, with an average recovery of 94.4% at the OSHA standard level. using a 5-L sample [1]. Overall precision, S Desorption efficiencies averaged 0.88, 0.95, and 0.96 at 0.6, 1.2, and 2.4 mg propylene oxide per sample, respectively. Breakthrough (5% on back section) occurred at 45 min when sampling an atmosphere of propylene oxide containing 484 mg/m3 in dry air at 0.185 L/min. At this time, the front section contained 4 mg propylene oxide. Breakthrough in humid air and storage stability were not determined. REFERENCES: [1] Documentation of the NIOSH Validation Tests, S75, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-185 (1977), available as GPO Stock #017-033-00231-2 from Superintendent of Documents, Washington, DC 20402. [2] DataChem. Inc., NIOSH Sequences #65 99, 6722, 6723 (unpublished, 1989). [3] NIOSH Manual of Analytical Methods, 2nd Ed., Vol. 2 S75 U.S. Department of Health Education and Welfare, Publ. (NIOSH) 77-157-B (1977). [4] NIOSH/OSHA Occupational Health Guidelines for Chemical Hazards, U.S. Department of Health Human Services, Publ. (NIOSH) 81-123 (1931), available as GPO Stock #017-033-00337-8 from Superintendent of Documents, Washington, DC 20402 METHOD REVISED BY: George Williamson, NIOSH/DPSE.

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APPENDIX V ACC-FUNDED METHOD PASSIVE DOSIMETER

ISSUED: FORMULA: M.W.: OSHA: ACGIH: December 28, 1994 C3H60 58.08 100 ppm 20 ppm PROPERTIES: Liquid, d 0.8287 g/mL; BP 34C; MP -112C

SYNONYMS: 1,2-epoxypropane; methyloxirane; CAS #75-56-9

SAMPLING MEASUREMENT

SAMPLER: Charcoal badge, (3M 3520 passive sampler) FLOW RATE: NA TIME -MIN: 15 min at 0.2 ppm -MAX: 8 hours SHIPMENT: routine SAMPLE STABILITY: >7 days at 20C FIELD BLANKS: 10% of samples, minimum of 2

TECHNIQUE: Gas Chromatography, FID ANALYTE: propylene oxide DESORPTION: 1.5 mL carbon disulfide INJECTION VOLUME: 1 L TEMPERATURE -INJECTION: 150C -DETECTOR: 300C -OVEN: 60C for 8 min, 10/min to 120C, 30/min to 180C for 1.5 min

ACCURACY

RANGE STUDIED: 0.4 to 37 ppm (8 hour samples) BIAS: not significant; average recovery = 107.3% (n = 20) OVERALL PRECISION: (Sr) 0.056

CARRIER GAS: He2, 4 psi COLUMN: Restek Rtx-5, 30 m x 0.53, 5.0 m film CALIBRATION: propylene oxide in carbon disulfide, n-heptane internal standard RANGE: 0.5 to 2000 g per sample ESTIMATED LOD: 0.3 g PRECISION: (Sr) 0.056 at 10 to 2000 g per sample

APPLICABILITY: The working range is 0.04 to 37 ppm for an 8 hour sample. INTERFERENCES: OTHER METHODS: REAGENTS: 1. Solvent: carbon disulfide, chromatographic quality. n-Heptane is used as an internal standard. The solution is made about 50 g/mL in n-heptane by adding about 5 mg per 100 mL. The same batch of solvent should be used to prepare standards and extract samples for the entire sample set. Propylene oxide, high purity for standard preparation. Calibration standards: accurately weigh about 20 mg propylene oxide into a 10 mL volumetric flask containing the solvent. Dissolve in the solvent prepared as described above and dilute to the mark. Make serial dilutions down to a concentration of about 1 g/mL. Helium, high purity. Hydrogen, high purity. Compressed air, high purity. 67 None known NIOSH 1612

2. 3.

4. 5. 6.

AC C - F U N D E D M E T H O D P A S S I V E D O S I M E T E R

EQUIPMENT 1. Sampler: 3M Passive Charcoal Badge #3520, containing two sections of a charcoal strip collector. 2. Gas chromatograph with flame ionization detector 3. Capillary gas chromatographic column, 95% dimethylpolysiloxane, 5% phenyl, 30 m x 0.53 mm, 5.0 m film thickness. (Restek Corp. No. rety10154) 4. Vials, 2 mL GC vials. 5. Pipets and volumetric flasks for preparing standards. 6. Analytical balance. 7. Syringe, 10 L. SPECIAL PRECAUTIONS: none SAMPLING: 1. Immediately before sampling, remove the samplers from the sealed containers and clip on lapel of worker. 2. Sample for an accurately measured period from 15 min to 8 hours. 3. Separate the front and back sections, cap with plastic lids provided with samplers, return to original containers, and pack securely for shipping. The samples are stable at room temperature for at least 7 days. SAMPLE PREPARATION: 4. Add 1.5 mL extraction solvent to each section of the samplers and cap immediately. 5. Allow to stand 30 min with occasional agitation. CALIBRATION AND QUALITY CONTROL: 6. Calibrate daily with at least 4 working standards of propylene oxide over the range of 4 to 500 g/mL. 7. Prepare calibration curve (ratio of peak area of propylene oxide to peak area of n-heptane vs. concentration of propylene oxide.) 8. Determine the desorption efficiency at least once for each lot of badge used. The method was validated using 3M lot No. 4122 009. Prepare three badges at each of three levels plus three media blanks. a. Spiking standards must be made from a batch of solvent that does not contain the internal standard. Otherwise, prepare as above. b. Inject a known amount of the appropriate standard directly onto the charcoal strip of a blank sampler with a microliter syringe. c. Extract and analyze together with working standards. d. Prepare a graph of DE vs. mg of propylene oxide recovered. MEASUREMENT: 9. Set gas chromatograph according to manufacturers recommendations and to conditions given above. Inject aliquot manually or with auto sampler. NOTE: If peak area is above highest standard, dilute an aliquot of the sample with the extraction solvent, reanalyze, and apply the appropriate dilution factor in the calculations. 10. Measure the peak areas. Divide the area of the propylene oxide peak by the area of the n-heptane peak on the same chromatogram. CALCULATIONS: 11. Determine the mass, g (corrected for DE) of propylene oxide found in sample front (Wf) and sample back (Wb) sorbent sections and determine the average mass found in the media blanks. NOTE: If Wb >Wf /2, report breakthrough and possible sample loss.

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AC C - F U N D E D M E T H O D P A S S I V E D O S I M E T E R

14. Calculate concentration, C, of propylene oxide. (Wf + Wb Bf Bb ) C, mg/m3 = __________________ V

EVALUATION OF METHOD: This method was validated at 0.4, 1.0, 2.2, 9.7 and 37.6 ppm. Test atmospheres were generated by delivering propylene oxide from a syringe pump to an airstream which was diluted in a sampling chamber with humidified air. The concentration was verified by collecting charcoal tube samples. Twelve samples were collected (8 hours) at each level on 3M 3520 charcoal badges, lot no. 4122 009. Four were analyzed to evaluate the accuracy and precision of the method, four were analyzed after storage for seven days at room temperature and four after storage for seven days at 4C. The average recoveries were 113.6, 111.8, 104.8, 106.5, and 99.9% at 0.4, 1.0, 2.2, 9.7 and 37.6 ppm respectively. Relative standard deviations for the four levels were 5.3%, @.0%, 2.1%, 0.15% 0.15, and 4.7%. There was no detectable sample loss upon storage for seven days under either condition. The desorption efficiencies were 87.8, 77.0, 80.3, and 75.3% at 10, 41, 413, and 2082 g, respectively.

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APPENDIX VI REFERENCES
ACGIH
American Conference of Governmental Industrial Hygienists 6500 Glenway Avenue, Bldg. D-7 Cincinnati, OH 45211-4438 ACGIH; Threshold Limit Values and Biological Exposure Indices

ANSI
American National Standards Institute 11 West 42nd Street New York, New York 10036 ANSI B16.21; Nonmetallic Flat Gasket for Pipe Flanges ANSI B31; American National Standard Code for Pressure Piping ANSI Z41.1; Safety Toe Footwear ANSI Z87.1; Occupational and Educational Eye and Face Protection ANSI Z88.2; Practices for Respiratory Protection ANSI Z89.1; Protective Headwear for Industrial Workers ANSI Z129.1; Hazardous Industrial Chemicals - Precautionary Labeling ANSI Z358.1; Emergency Eye Wash and Shower Equipment

API
American Petroleum Institute 1220 L Street, N.W. Washington, DC 20005 API RP-520; Recommended Practice for the Design and Installation of Pressure-Relieving System in Refineries Part I - Design API RP-520; Sizing, Selection and Installation of Pressure-Relieving Devices in Refineries Part II - Installation API 610; Centrifugal Pumps for General Refinery Service API 620; Recommended Rules for the Design and Construction of Large Welded, Low-Pressure Storage Tanks API 650; Welded Steel Tanks for Oil Storage API RP-2000; Venting Atmospheric and Low-Pressure Storage Tanks API RP-2028; Flame Arresters in Piping System API RP-2210; Flame Arresters for Vents of Tanks Storing Petroleum Product

ASME
American Society of Mechanical Engineers United Engineering Center 345 East 47th Street New York, New York 10017 ASME Code, Section VIII, Division 1; Boiler and Pressure Vessel Code ASME/ANSI B31; American National Standard Code for Pressure Piping 71

REFERENCES

DOT
Department of Transportation 400 Seventh Street, S.W. Washington, DC 20590 49 CFR 107; Hazardous Materials Program Procedures 49 CFR 171; General Information, Regulations and Definitions 49 CFR 171.8; Definitions and Abbreviations 49 CFR 171.14; Transitional Provisions for Implementing Requirements Based on UN Recommendation 49 CFR Part 172; Hazardous Materials Table, Special Provisions, Hazardous Materials Communication Requirements and Emergency Response Information Requirements 49 CFR 172, Subpart C; Shipping Papers 49 CFR 172, Subpart D; Markings 49 CFR 172, Subpart E; Labeling 49 CFR 172, Subpart F; Placarding 49 CFR 172, Subpart G; Emergency Response Information 49 CFR 173; Shippers - General Requirements for Shipments and Packaging 49 CFR 173.11; Shippers Registration Statement; Flammable Cryogenic Liquids 49 CFR 174; Carriage by Rail 49 CFR 176; Carriage by Vessel 49 CFR 178; Specifications for Packagings 49 CFR 179; Specifications for Tank Car Tanks 49 CFR 180, Subpart E; Qualifications and Maintenance of Cargo Tanks

EPA
United States Environmental Protection Agency 401 M Street, S.W. Washington, DC 20460 40 CFR 261; Identification and Listing of Hazardous Waste 40 CFR 262; Standards Applicable to Generators of Hazardous Waste 40 CFR 302; Designation, Reportable Quantities and Notification 40 CFR 355; Emergency Planning and Notification 40 CFR 370; Hazardous Chemical Reporting: Community Right-to-Know 40 CFR 403; General Pretreatment Regulations for Existing and New Sources of Pollution 40 CFR 707; Chemicals Imports and Exports 40 CFR 716; Health and Safety Data Reporting 40 CFR 799; Identification of Specific Chemical Substance and Mixture Testing Requirements

FR

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Office of the Federal Register National Archives and Records Administration Washington, DC 20408

REFERENCES

IARC
International Agency for Research on Cancer 49 Sheridan Street Albany, New York 12210

IATA
International Air Transport Association 1155 Mansfield Street Montreal 113, P.Q., Canada IATA; Dangerous Goods Regulations

ICAO
International Civil Aviation Organization 1000 Sherbrooke Street West Suite 400 Montreal, Quebec, Canada H3A, 2R2 ICAO; Technical Instructions for Safe Transport of Dangerous Goods, By Air

IMO
International Maritime Organization Albert Embankment London SE, 1 England IMDG; International Maritime Dangerous Goods Codes, Volumes I, II, III, IV, Supplement IMO; International Code for the Construction and Equipment of Ships Carrying Dangerous Chemicals in Bulk, IBC Code. IMO; International Code for the Construction and Equipment of ships Carrying Liquefied Gases in Bulk, IGC Code.

MSHA
Mine Safety and Health Administration 5012 Mountaineer Mall Morgantown, West Virginia 26505

NFPA
National Fire Protection Agency Batterymarch Park Quincy, Massachusetts 02269 NFPA 10; Portable Fire Extinguishers NFPA 11; Foam Extinguishing Systems, Low Expansion and Combined Agent NFPA 14; Standpipe and Hose Systems NFPA 30; Flammable and Combustible Liquids Code NFPA 70; National Electrical Code, Article 500 - Hazardous (Classified) Locations NFPA 77; Static Electricity NFPA 80; Fire Doors and Windows NFPA 704; Standard System for the Identification of the Fire Hazards of Materials 73

REFERENCES

NIOSH
National Fire Protection Association Batterymarch Park Quincy, Massachusetts 02269

NTP
National Toxicology Program P.O. Box 12233 Research Triangle Park, North Carolina 27709

OSHA
Occupational Safety and Health Administration 200 Constitution Avenue, N.W. Washington, DC 20210 29 CFR 1910.106; Flammable and Combustible Liquids 29 CFR 1910.107; Spray Finishing Using Flammable and Combustible Materials 29 CFR 1910.120; Hazardous Waste Operations and Emergency Response (HAZWOPER) 29 CFR 1910.134; Respiratory Protection 29 CFR 1910.147; Sources of Standards 29 CFR 1910.151; Medical Services and First Aid 29 CFR 1910.156; Fire Brigades 29 CFR 1910.1000; Air Contaminants 29 CFR 1910.1200; Hazard Communication

State of California
California Health and Welfare Agency Office of the Secretary 1600 Ninth Street, Room 450 Sacramento, CA 95814 Proposition 65; Californias Safe Drinking Water and Toxic Enforcement Act of 1986

State of New Jersey

New Jersey Department of Environmental Protection Division of Occupational and Environmental Health Department of Health, CN 368 Trenton, NJ 08625 New Jersey Administrative Code, Title 8, Department of Health, Chapter 59; Worker and Community Right to Know Act

State of Pennsylvania
Commonwealth of Pennsylvania Department of Labor and Industry Harrisburg, PA Commonwealth of Pennsylvania Act 1984-159; Worker and Community Right to Know Regulation

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REFERENCES

UL
Underwriters Laboratories 333 Pfingston Road Northbrook, IL 60062 UL 525; Flame Arresters for Use on Vents of Storage Tanks for Petroleum Oil and Gasoline

UN
United Nations First Avenue and Forty-second Street New York, NY 10017 Recommendations on the Transport of Dangerous Goods

US COAST GUARD
US Coast Guard, Headquarters 2100 Second Street, S.W. Washington, DC 20093-0001 46 CFR 153; Ships Carrying Bulk Liquid, Liquified Gas, or Compressed Gas Hazardous Materials

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APPENDIX VII REGULATORY SUMMARY PROPYLENE OXIDE

The following summary presents some of the federal, state and international laws and enabling regulations that require review prior to handling, storage or distribution of propylene oxide. This overview is not and should not be construed as an all inclusive source of information. In addition, other international, federal, state, and local laws and regulations may be applicable.

Federal
Clean Air Act

The Clean Air Act required the EPA to set national ambient air quality standards for pollutants determined to be injurious to health or welfare. Propylene oxide is listed as a potential human health hazard under Section 111. Specific control technologies are defined for such hazardous chemicals (40 CFR 60.489). Amendments to the Clean Air Act enacted in 1990 required EPA to establish technology standards applicable to the sources of listed pollutants. Listing under Title III, Section 112 requires automatic spill reporting under CERCLA (see below), 42 U.S.C. 9601(14)). Propylene oxide is one of the listed pollutants. Hazardous Organic NESHAP (HON) Synthetic Organic Chemicals (40 CFR 63.100-106) Under a final rule effective 4/22/94, propylene oxide is listed as a Group I chemical (Table 1). Existing sources of chemicals in Group I must be in compliance with equipment leak rules (40 CFR 63.160-183) as of 4/24/95. Propylene oxide also is listed as an organic hazardous air pollutant (Table 2) emitted from synthetic organic chemical manufacturing industry (SOCMI) processes. Emissions are regulated by 40 CFR 63.100-.182 (subparts F, G, and H). Clean Air Act Section 112(r) Risk Management Program for Accidental Release Prevention (40 CFR 68.130). Propylene oxide is one of the chemicals regulated under this program with a threshold quantity of 10,000 lbs. Propylene oxide also is on the EHS list if the vapor pressure is 10 mmHg or greater.
Clean Water Act

The Clean Water Act was enacted to ensure the chemical, physical and biological integrity of the nations waters by setting national water standards for publicly owned treatment works and industry and by creating the national Pollutant Discharge Elimination System (NPDES) permit program. The following sections of the law may be of interest to the user of propylene oxide: Section 307 Priority Pollutants (40 CFR 401.15) - not listed. Section 311 (40 CFR 116.4) List of Chemicals considered hazardous if spilled in navigable waters. Regulations specify spill procedures to be followed in the event of accidental spillage. Propylene oxide is listed.
Comprehensive Environmental Response, Compensation, & Liability Act (CERCLA)

CERCLA, more commonly known as Superfund, established a list of more than 700 hazardous substances that, when released in quantities equal to or exceeding a specified reportable quantity (RQ) must be reported to the National Response Center. Most CERCLA hazardous substances are subject not only to CERCLA regulations but also to Superfund Amendments & Reauthorization Act (SARA) Title III, Section 304, emergency notification requirements (see below). The final RQ for propylene oxide is 100 lbs. or 45.4 kgs. (40 CFR 302).

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R E G U L AT O R Y S U M M A R Y

The National Response Center hotline for reporting spills is 1-800/424-8802. EPA maintains a RCRA/Superfund hotline for information. This number is 1-800/424-9346; in Washington, D.C., the number is 202/382-3000.
Resource Conservation and Recovery Act (RCRA)

The major objectives of RCRA are to protect human health and the environment while conserving valuable material and energy resources. The Act is concerned with all stages in the hazardous waste management cycle - generation, storage, transportation, and disposal - and requires notification to EPA within 90 days by anyone who generates, transports, treats, stores, or disposes of the specific covered wastes. Process waste streams from propylene oxide manufacturing are not specifically identified as hazardous wastes (40 CFR 261.31 and 40 CFR 261.32). Off specification, discarded commercial chemicals product, spill cleanup residue, and containers containing propylene oxide are not considered listed hazardous wastes (40 CFR 261.33). Mixtures of propylene oxide and propylene oxide solutions may exhibit flash points less than 140F. and would be considered ignitable hazardous wastes (40 CFR 261.21). Under the 1984 Hazardous and Solid Waste Amendments to RCRA, prohibitions were mandated on the land disposal of hazardous waste and EPA issued a schedule for making land disposal restrictions. Propylene oxide is not specifically listed as a hazardous waste.
Safe Drinking Water Act (SDWA)

The 1986 amendments to the Safe Drinking Water Act required EPA to establish a priority list of contaminants which are known or anticipated to occur in public water systems and which may require regulation under the SDWA. Propylene oxide does not appear on the priority list of contaminants established by EPA under this law (56 FR 1473, 1/14/91). EPAs Safe Drinking Water hotline is 1-800/426-4791; in the Washington, D.C. area, the number is 202/382-5533.
Department of Transportation (DOT)

The Hazardous Materials Transportation Act of 1974 gave the Department of Transportation authority to regulate the transportation of hazardous materials in interstate commerce. DOT regulates such matters as classification, packaging, and hazard communication (labeling). DOT also has established spill notification requirements. Regulations governing the transport of hazardous materials can be found at 49 CFR 106, 107, 116, 130, 171-180, and 397. Propylene oxide is listed as a DOT hazardous material (49 CFR 172.102), identification #UN1280. It requires a Flammable Liquid label. In June 1994, the Research & Special Programs Administration (RSPA), in an action mandated by CERCLA, revised the List of Hazardous Substances and Reportable Quantities (49 CFR 172.101, Appendix A). The final rule became effective 8/29/94. Listed substances require bill of lading annotation so that shippers and carriers can identify CERCLA hazardous substances and submit required notifications if a discharge/spill occurs. Propylene oxide is listed with a reportable quantity (RQ) of 100 pounds.
Occupational Safety & Health Administration (OSHA)

The following OSHA regulations apply to propylene oxide and, where appropriate, are described in more detail in various sections of this document. 29 CFR 1910.106, Subpart H - Storage of flammable and combustible liquids.

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29 CFR 1910.155, Subpart I - Fire protection relative to flammable or combustible liquids. 29 CFR 1910.164 - Fire detection systems required when propylene oxide is in use. 29 CFR 1910.1000, Subpart Z, Permissible Exposure Limits

R E G U L AT O R Y S U M M A R Y

Table Z-1 PEL: 100 ppm; 240 mg/m3 Table Z-1-A TWA: 20 ppm; 50 mg/m3 OSHA revoked the exposure levels listed in Tables Z-1 and Z-1-A on June 30, 1993 (58 FR 35338) as a result of a court decision. They remain in this document since the following OSHA state plan states continue to enforce them and it is Lyondell Chemical Companys intent to abide by either these levels or the ACGIH levels where the latter provide more protection. Table Z-1: Arizona, Indiana, Iowa, Kentucky, Nevada, New York, North Carolina, Oregon, South Carolina, Tennessee, Utah, Virginia, Wyoming, and Puerto Rico. Table Z-1-A: Alaska, California, Connecticut, Maryland, Michigan, Minnesota, New Mexico, Vermont, Washington, and the Virgin Islands. 29 CFR 1910.1200, Hazard Communication Standard. Propylene oxide appears on one of the lists specifically cited at 29 CFR 1910.1200 (d)(3). Chemicals on these lists automatically are considered as hazardous and are subject to HCR requirements.
Superfund Amendments & Reauthorization Act (SARA)

Sections 302/304 of SARA detail emergency planning and emergency notification requirements under which facilities must report releases of extremely hazardous substances and CERCLA listed hazardous substances in excess of threshold planning quantities (TPQ) and reportable quantities (RQs). Facilities also must submit copies of MSDSs (Sections 311/312) and report emissions of toxic chemicals (Section 313). Propylene oxide is listed as an extremely hazardous substance (Section 302; 40 CFR 355) with a threshold planning quantity (TPQ) of 10,000 pounds and a reportable quantity (RQ) of 100 lbs. Lyondell Chemical has classified Propylene oxide as an immediate (acute) health hazard; a delayed (chronic) health hazard; a fire hazard; and reactive (Sections 311/312). Propylene oxide is listed as a toxic chemical (Section 313; 40 CFR 372) with a de minimus concentration level of 0.1%.
Toxic Substances Control Act (TSCA)

The Toxic Substances Control Act gives EPA authority to regulate production, use, labeling, distribution, and/or disposal of chemical substances and mixtures; to delay production; to ban or restrict manufacturing or marketing of existing or new chemical substances which present an unreasonable risk of injury to health or the environment; to require testing, recordkeeping, and reporting. All manufacturers, importers, processors, distributors, and disposers of chemical substances subject to the law are affected by its provisions and implementing regulations. Section 4 Test Rules (40 CFR 799.3450) - Propylene oxide testing has been required for health effects. Section 8(b) Chemical Substances Inventory - Propylene oxide is listed (Vol. 1., page 6, 1985 Edition) Section 8(d) Health & Safety Data Reporting (40 CFR 716) - Propylene oxide was listed by rule effective 10/4/82; reporting requirements expired 10/4/92. Section 12(b) Export Notification (40 CFR 707, Subpart D) - propylene oxide is listed and notice to EPA is required for the first export or intended export to a particular country (40 CFR 707.65(a)(2)(ii)). Effective June 19, 1995 (60 FR 31917), the EPA removed propylene oxide from the list of chemicals for which export notice is required since the required Section 4 testing has been completed. The list of removed chemicals will be codified at 40 CFR 799.18. Information on TSCA regulations can be obtained from the TSCA Assistance Office at EPA; 202/554-1404.

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State
California

California Safe Drinking Water & Toxic Enforcement Act of 1986 (Proposition 65) Prop. 65 prohibits discharge into drinking water supplies of chemicals known to the State to cause cancer or reproductive toxicity. An employer must notify all workers of possible exposure to a listed chemical. Facilities also must provide the state and local agencies with information regarding spills or releases of these chemicals to the environment. Propylene oxide was listed as a carcinogen as of 10/1/88. Based on U.S. EPA cancer potency value calculations, California also established no significant risk levels of 3 micrograms/day (oral) and 60 micrograms/day (inhalation). Additional information about Prop. 65 can be obtained from the Health and Welfare Agency, State of California, Office of the Secretary, 1600 Ninth Street, Room 450, Sacramento, CA 95814.
Connecticut

Connecticut Manufacturing Employer Hazardous Materials Notification Act This law requires any manufacturing employer who uses, produces, or stores any hazardous material to complete a survey. Hazardous materials are defined by reference to the federal Department of Transportation hazardous material table. Also included as hazardous materials are federal RCRA hazardous wastes and federal CERCLA hazardous substances. Propylene oxide is listed. The authority for these regulations is Connecticut Gen. Stat. Ann., Section 29-307a.
Florida

Florida Employee Right-to-Know Law Provisions of this law require employers to give local fire departments a list of plant areas containing toxic substances. Toxic substances are those recommended by the states Toxic Substances Advisory Council. Propylene oxide is listed. The authority for this list is Florida Statutes Annotated, Section 442.101.
Illinois

Illinois Toxic Substances Disclosure to Employees Act While some provisions of this law have been preempted, Illinois is enforcing certain requirements relative to MSDSs for defined toxic substances. Propylene oxide is defined as a toxic substance. The authority for this list is the Illinois Rev. Statute, Chapter 48, paragraph 1403. Questions may be directed to the Illinois Department of Labor, Toxic Substances Division, #1 W. Old State Capitol Plaza, Room 300, Springfield, IL. 62701. Illinois Chemical Safety Act Under this law, covered businesses using, storing, or manufacturing defined chemical substances must have a written Chemical Safety Contingency Plan. Propylene oxide is a covered substance. The authority for these regulations is Illinois Rev. Statute, Chapter 111 1/2, Paragraph 951.
Louisiana

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Louisiana Hazardous Materials Information, Development, Preparedness and Response Act This law subjects covered facilities to two separate reporting requirements: inventory reporting and release reporting. Covered materials include federal SARA extremely hazardous substances and any hazardous chemicals as defined under the federal OSHA standard. The inventory form must be submitted annually if the covered substances were present on site in amounts exceeding the specified threshold quantities (TQs) on any single day.

R E G U L AT O R Y S U M M A R Y

Propylene oxide is a listed substance (code number 04109); the TQ for inventory reporting is 500 pounds. The authority for these regulations is Louisiana Admin. Code, Title 33, Part V, Section 10101. Louisiana Spill Reporting Louisiana has established reportable quantities (RQs) to determine the need for notification for unauthorized discharges. The notification requirements are in addition to notification requirements established under the Louisiana right-to-know requirements. Unauthorized discharges of listed substances (any quantity) which cause an emergency condition must be reported to the Department of Public Safety by telephone immediately (504) 925-6595 and to the Department of Environmental Quality in writing within seven days. Unauthorized discharges of listed substances in excess of applicable reportable quantities (RQs) which do not cause an emergency condition must be reported to the Department of Environmental Quality by telephone within 24 hours (504) 342-1234 and in writing within seven days. The RQ for propylene oxide is 100 lbs. into/onto all media within any 24 hours.
Massachusetts

Massachusetts Right-to-Know Law This law established reporting, labeling, MSDS, recordkeeping, and related regulations for certain toxic or hazardous substances. Propylene oxide is listed as a carcinogen and an extraordinary hazardous substance with a 1 ppm threshold. The authority for this listing is Massachusetts General Laws Annotated, Chapter 11F and Title 105 Massachusetts Regulations Code, Section 670.000, Appendix A. Questions about the regulations can be directed to The Commonwealth of Massachusetts, Executive Office of Human Services, Department of Public Health, 150 Tremont Street, Boston, MA 02111. Massachusetts Spill Reporting The Oil and Hazardous Materials List establishes reportable quantities (RQs) for substances which require reporting of unauthorized discharges. Propylene oxide is listed with a reportable quantity (RQ) of 10 pounds. The authority for these regulations is Title 310 Massachusetts Regulations Code Sections 40.30 and 40.900 Appendix I, Department of Environmental Quality Engineering.
Michigan

Michigan Critical Materials All Michigan businesses discharging wastewater must file certain required reports with the State. When wastewater discharge is required to be reported, the use or manufacture of designated critical materials also is required to be reported. Propylene oxide has not been designated as a critical material. Authority for these requirements is contained in Michigan Act 293, P.A. 1972, and 1990 Michigan Public Acts 19, Section 6B; Michigan Administrative Code r.323.1231.
New Jersey

New Jersey Right-to-Know Act This law requires facilities containing, distributing or handling a hazardous substance to complete a Right-to-Know survey. The survey provides workers and the community with information pertaining to the specific hazardous substance. Propylene oxide is listed on the New Jersey Hazardous Substance List. The New Jersey identification number is 1615; the New Jersey hazardous material (DOT) number is 1280. Propylene oxide also is designated by New Jersey as a special health hazard subject to restriction of trade secret claims. The Hazard Codes are MU (mutagen); F4 (flammable, 4th degree); and R2 (reactive, 2nd degree). Regulations are codified in the New Jersey Administrative Code, Title 8, Department of Health Chapter 59. Additional information about the New Jersey Hazardous Substance List is available from the New Jersey Department of Environmental Protection, Division of Environmental Quality, Bureau of Hazardous Substances Information, 401 E. State

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Street, CN 405, Trenton, N. J. 08625-0405. Information about labeling regulations is available from the State of New Jersey Department of Health, CN 360, Trenton, NJ 0625-0360. New Jersey Spill Tax New Jersey has established a list of substances defined as hazardous according to the Spill Compensation and Control Tax Act (N.J. Statutes, Annotated, Section 58:10-23.11h). Propylene oxide is a listed substance. The authority for the listing is N.J. Administrative Code, Section 7:1E-1.3. Propylene oxide also is listed on New Jerseys Hazardous Substance Sub-List, the New Jersey CERCLA Substance Sub-List, the New Jersey Environmental Hazard Sub-List, and carries a registration quantity of 7700 lbs. under the New Jersey Toxic Catastrophe Prevention Act (N.J. Admin. Code Section 7:31-1).
New York

New York Bulk Storage Registration/Release Reporting New York requires the registration of bulk storage tanks and notification of releases of listed hazardous substances under the Substances Hazardous or Acutely Hazardous to Public Health, Safety or the Environment Act and the Hazardous Substances Bulk Storage Act. Propylene oxide is listed with a reportable quantity (RQ) of 100 lbs. for releases both to air and to land/water. Authority is found in New York Comp. Codes R & Regulations, Parts 595, 596, and 597.
Pennsylvania

Pennsylvania Worker & Community Right-to-Know Act This law creates the states system for communicating information about hazardous substances. A hazardous substance is defined and listed by Pennsylvania through reference to a number of source lists. The state also classifies certain substances as environmental hazards and/or special hazardous substances. The law established MSDS, labeling, and recordkeeping requirements and requires facilities or distributors handling hazardous substances to complete a Hazardous Substance Survey Form (HSSF) annually, before April 1, for the previous calendar year. Propylene oxide is listed as a special hazardous substance with a threshold of 0.01% and an environmental hazard subject to release reporting. The authority for these regulations is Pennsylvania Code, Title 34, Labor and Industry, Chapter 301-323.
Rhode Island

Rhode Island Hazardous Substance Right-to-Know Act This law requires employers who use, transport, store, or in any other manner expose employees to toxic or hazardous substances, as defined by the state, to provide notice, labeling, and training. Propylene oxide is listed with the hazard code TF (toxic and flammable).

International
Australia

Listed on Australian Inventory

Canada

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Canadian Workplace Hazardous Materials Information System (WHMIS) WHMIS established requirements for classifying hazardous substances that will be used in the workplace and for preparing MSDSs and container warning labels. Substances are classified by the manufacturer or importer to determine whether or not they are controlled products. When a product has been evaluated and is found to be a controlled product, the ingredient disclosure list (IDL) must be consulted and any ingredient present in a concentration greater than that specified must be disclosed on the MSDS.

R E G U L AT O R Y S U M M A R Y

Lyondell Chemical has classified propylene oxide as B (flammable) and D2 (toxic). Propylene oxide is listed on the IDL as a substance which must be disclosed if the weight-to-weight concentration in the product is 1% or greater. The WHMIS IDL number is 1365. Canadian Domestic Substances List Propylene oxide is listed under the name oxirane, methyl-. Canadian National Pollutant Release Inventory Established under Section 16 of the Canadian Environmental Protection Act (CEPA), the National Pollutant Release Inventory (NPRI) established a list of substances required to be reported for toxic release purposes. Supplier notification is required. Propylene oxide is listed (127 C. Gaz. 839 Part I (3/27/93).
European Union

European Inventory of Existing Commercial Chemical Substances (EINECS) Propylene Oxide is listed on EINECS under the name methyloxirane - Vol. 1, pg. 14; #200 879 2. Listing on EINECS is accepted by certain other European countries which have adopted EINECS as their base inventory; i.e., Switzerland. However, other registration requirements may apply in those countries. The EU classification number for propylene oxide under EU Directive 67/548/EEC (classification, packaging, and labeling of dangerous substances), Annex I, is 603-055-00-4. The risk phrases are: 45 (may cause cancer), 12 (extremely flammable), 20/21/22 (harmful by inhalation, in contact with skin and if swallowed), and 36/37/38 (irritating to eyes, respiratory system and skin). Safety phrases are: 53 (avoid exposure) and 45 (in case of accident or if you feel unwell, seek medical advice immediately [show the label where possible]). Symbols required are F+ (extremely flammable) and T (toxic). Under the EU Dangerous Preparations Directive, propylene oxide is classified as C2 (carcinogen category 2); the danger classifications are F+ (extremely flammable), Xn (harmful), and Xi (irritant). Under the EU Directive 90/128/EEC (2/23/90) relating to plastics materials and articles intended to come into contact with foodstuffs, propylene oxide is listed as an authorized monomer or other starting substance. The PM/Ref number is 24010; some restrictions apply.
Japan

Japanese List of Existing & New Chemical Substances (ENCS) Propylene oxide is listed under the chemical name oxirane, methyl-. The ENCS I.D. number is (2)-219.
Korea

Korean List of Existing Chemicals Propylene oxide is listed. The Korean listing number is 2-389.
Philippines

Philippines List of Existing Chemicals (Draft) Propylene oxide has been located on the draft chemical substances inventory in the Philippines. Please note that this listing has not been finalized.

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Miscellaneous
National Fire Protection Association (NFPA) Hazard Rating

The NFPA ratings assign a numeric value to specific aspects of each hazard. For propylene oxide, these ratings are as follows: Health: 2. Material hazardous to health, but areas may be entered freely with full-faced mask self-contained breathing apparatus which provides eye protection. Flammability: 4. Very flammable gases or very volatile liquids. Shut off flow and keep cooling water streams on exposed tanks or containers. Reactivity: 2. Materials which (in themselves) are normally unstable and readily undergo violent chemical change but do not detonate. Includes materials which can undergo chemical change with rapid release of energy at normal temperatures and pressures or which can undergo violent chemical change at elevated temperatures and pressures. Also includes those materials which may react violently with water or which may form potentially explosive mixtures with water. In advanced or massive fires, fire fighting should be done from a safe distance or from a protected location. Additional information on the NFPA hazard rating system can be obtained from the National Fire Protection Association, Batterymarch Park, Quincy, MA. 02269; phone 800/344-3555.

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APPENDIX VIII GLOSSARY PROPYLENE OXIDE

ACGIH Acute American Conference of Governmental Industrial Hygienists. A single or multiple exposure occurring within a short timeframe (less than 24 hours). American Industrial Hygienists Association American National Standards Institute American Petroleum Institute American Society of Mechanical Engineers American Society for Testing and Materials Transformation of non nutrient compounds through the normal metabolism of an organism. Biochemical oxygen demand The connection of two or more conductive objects by means of a conductor (most commonly a wire or metal plate). Clean Air Act Amendments Comprehensive Environmental Response, Compensation, and Liability Act Code of Federal Regulations Chemical Transportation Emergency Center A wedge or block for steadying a body or to prevent movement of a wheel. Long-term exposure to a chemical. Chemical Manufacturing Association Chemical Oxygen Demand IARC IATA ICAO Half-life HAP HazWOpER Humectant DOT EPA Flash point Dipole Moment Confined Space An area that by design has limited openings for entry and exit. A confined space has unfavorable natural ventilation and is not intended for continuous worker occupancy. CPC CPR Detoxification Chemical Protective Clothing Cardiopulmonary resuscitation Chemical transformation of a toxic chemical into a nontoxic chemical. Molecules that are arranged so that one part of the molecule has a positive electrical charge and the other part is negatively charged. Department of Transportation Environmental Protection Agency The minimum temperature at which a liquid gives off vapor in sufficient concentrations to form an ignitable mixture with air near the surface of a liquid. Granular Activated Carbon The connection of one or more conductive objects to the ground; a specific form of bonding. Grounding is also referred to as earthing. The time required for one half of the quantity of a substance to be removed. Hazardous Air Pollutant Hazardous Waste Operations and Emergency Response. Substance that promotes retention of moisture. International Agency for Research on Cancer International Air Transportation Association International Civil Aviation Organization

AIHA ANSI API ASME ASTM Biotransformation BOD Bonding

GAC Grounding

CAAA CERCLA

CFR CHEMTREC Chock

Chronic CMA COD

Combined Agent A fire protection system employing a System combination of firefighting methods (i.e., water and foam).

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GLOSSARY

IDLH

Immediately Dangerous to Life and Health: The airborne concentration of a toxic material from which one could escape within 30 minutes without any escape-impairing symptoms or any irreversible health effects. Intermodal International Maritime Dangerous Goods International Maritime Organization Isolated from the living organism and artificially maintained, as in a test tube International Organization of Standardization Soil adsorption/mobility; The partitioning of a chemical between soil or sediment, usually expressed as K (the concentration of a chemical in soil (g/g) to that in water (g/ml) or as Koc (which is divided by the organic carbon content of the soil or sediment. Lethal concentration that will kill 50 percent of the test animals within a specified time. Dose required to produce the death in 50 percent of the exposed species within a specified time. Local emergency planning committee Lower Flammability Limit Maximum achievable control technology Material Safety Data Sheet Mine Safety and Health Administration A chemical that, with exposure, causes changes in the genetic material of the nucleus of a cell in a way that can be transmitted during cell division. National Electrical Code National Fire Protection Association National Institute for Occupational Safety and Health

NPDES

National Pollutant Discharge Elimination System

Olfactory Fatigue The temporary decrease or total inability to smell a substance due to the over stimulation of the sensory receptors. OPPSD OSHA Outage OVA PEL Permeation Rate Organic Peroxide Producers Safety Division Occupational Safety and Health Administration Amount by which a packaging falls short of being liquid full. Organic vapor analyzer Permissible Exposure Level The rate , usually defined as centimeters per second, at which a liquid, vapor or gas travels through a material. Publicly owned treatment works Personal Protective Equipment

IM IMDG IMO In vitro

ISO Koc

POTW PPE

Protected Storage Facilities that have sprinkler systems Facilities installed for fire protection. ppm PSIG RCRA RQ SARA SCBA SIP SS STEL TOC TPQ Parts per million Pounds per square inch gauge. Resource Conservation and Recovery Act Reportable Quantity Superfund Amendment and Reauthorization Act Self-contained breathing apparatus State Implementation plan Stainless Steel Short term exposure limit Total Organic Carbon Threshold Planning Quantity - under the Superfund Amendments Reauthorization Act (SARA Title III) Section 302, 304, 311/312, a chemical specific quantity, in pounds, that triggers certain reporting requirements. Treatment, Storage and Disposal Facility

LC50

LD50

LEPC LFL MACT MSDS MSHA Mutagen

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NEC NFPA NIOSH

TSD

GLOSSARY

TWA UL Ullage UN

Time-weighted average Underwriters Laboratory Amount by which a packaging falls short of being liquid full. United Nations

VOC VZ-STEL

Volatile organic compound Lyondell Chemicals established estimate of concentration of a substance to which nearly all individuals can be exposed for a period and suffer no irreversible health effects.

Vapor Pressure The pressure exerted by a volatile liquid while under defined equilibrium conditions; vapor pressure is usually measured in millimeters of mercury (mm Hg).

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INDEX
ACC-funded method passive dosimeter........................67 air sampling and analysis ..............................................22 bulk storage .......................................................23, 35, 82 chemical compatibility ............................................14, 24 chemical protective clothing ..............................20-21, 85 classification......................................................53, 78, 83 confined space entry................................................19, 51 container disposal ..........................................................34 control of hazardous energy ..........................................51 conversion factors ....................................................57-58 direct reading instruments..................................21-22, 29 electrical area classification...........................................23 engineering.......................................19, 23-24, 35, 51, 71 environmental ................29-30, 33-35, 38, 56, 72, 74, 77, 81-83, 85 equipment cleanout........................................................51 fire and explosion hazard ........................................25, 33 fire fighting......................................20, 27, 35, 39, 61, 84 fire prevention ...............................................................25 fire safety..................................................................25-27 fire suppression..............................................................26 first aid .........................................................16-17, 19, 31 general information ....................................................1-14 glossary ....................................................................85-87 hazard assessment..........................................................15 hazard communication............................29-32, 74, 78-79 hygiene practices ...........................................................19 instability hazards....................................................14, 24 instrumentation........................................................23, 38 ISO tanks .................................................................49, 55 leak detection devices....................................................23 maintenance and inspection...........................................51 marking, labeling and placarding ..................................53 material requirements ....................................................23 tank cars .................................................38, 41, 45, 54-55 tank cleaning and equipment repair...............................51 tank trucks ...................................................38, 42, 46, 54 transfer operations....................................................41-49 transportation emergencies............................................55 transportation regulatory requirements ....................53-56 typical values.................................................................14 vapor containment system .............................................24 waste disposal................................................................34 work preparation ................................................41-42, 51 workplace location ........................................................38 worldwide occupational exposure limits.......................59 medical management.....................................................17 names and addresses of manufacturers ....................61-62 NIOSH method 1612 ...............................................63-65 occupational exposure limits ...................................16, 59 occupational health ..................................................15-17 off-loading station .........................................................38 OSHA hazard communication .................................29-30 packaging....................................53-55, 72, 78, 83, 86-87 personal safety and health ........................................19-22 physical properties...........................................................5 piping ....................................23, 38, 41-42, 44, 46-48, 71 product identification ......................................................1 product storage ..............................................................35 pump specifications.......................................................23 reactivity hazards...........................................................14 references .................................................................71-75 regulatory summary .................................................77-84 relief requirements.........................................................23 respiratory protection .............................19-20, 51, 71, 74 SARA title III ....................................................30, 77, 86 spills and leaks.........................................................20, 33 state regulations.................................................30, 34, 80 storage tanks ..........................................23, 33, 35, 71, 75

LCC-OP188-9510

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