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Styrene Monomer

PRODUCT SAFETY BULLETIN

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 Company, environmentally sound operations, like environmentally sound products, make good business sense. Lyondell Chemical Company Product Safety Bulletins are prepared by our Product Stewardship Team. The data reflects 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.

December 2007

Lyondell Chemical Company, headquartered in Houston, Texas, is North America's third-largest independent, publicly traded chemical company. Lyondell is a leading global manufacturer of chemicals and plastics, a refiner of heavy, high-sulfur crude oil and a significant producer of fuel products. Key products include ethylene, polyethylene, styrene monomer, propylene, propylene oxide, gasoline, ultra low-sulfur diesel, MTBE and ETBE.

Product Safety Bulletin

IN CASE OF A TRANSPORTATION EMERGENCY, CALL:


CHEMTREC (800) 424-9300 International (call collect) (202) 483-7616 or CANUTEC (in Canada) (613) 996-6666 or SETIQ (in the Mexican Republic) (800) 002-1400 (Calls originating in Mexico City or the Metropolitan Area) (5) 559-1588 (Calls originating elsewhere) (52-555) 559-1588 or Lyondell SCDI (Serious Chemical Distribution Incident) Reporting Hotline (800) 245-4532 FOR MORE INFORMATION ABOUT OUR PRODUCT, CALL: Lyondell Chemical Company Customer Service (888) 777-0232 (USA) (33-3) 4424-9205 (Europe, Middle East, Asia) (55-11) 5185-9300 (South America) or visit www.lyondell.com
We are pleased to provide you with the most recently revised Styrene Monomer Product Safety Bulletin. Please discard any previous versions of this document. 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 and 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 are provided as a matter of convenience, and are not an endorsement or recommendation of a particular brand or company. In addition, the information 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 from our web site at www.lyondell.com.
ii Product Safety Bulletin

TABLE OF CONTENTS
1.
1.1 1.2 1.3 1.4 1.5 1.6 1.7

GENERAL INFORMATION . . . . . . . . . . . . . . . .1
Product identification Physical Properties typical Values instability Hazards reactivity Hazards Self-Polymerization Precautions When Handling tBc

7.
7.1 7.2 7.3

ENVIRONMENTAL . . . . . . . . . . . . . . . . . . . . .29
air Quality considerations clean Water act Waste Management

8.
8.1 8.2 8.3 8.4

PRODUCT STORAGE . . . . . . . . . . . . . . . . . . .33


drum Storage Storage tanks unloading installations Workplace location

2.
2.1 2.2 2.3 2.4

OCCUPATIONAL HEALTH . . . . . . . . . . . . . . .13


Hazard assessment occupational exposure limits first aid Medical Management

9.
9.1 9.2 9.3 9.4 9.5 9.6

TRANSFER OPERATIONS . . . . . . . . . . . . . . .39


Work Preparation tank cars dot 111a tank cars dot 105J tank trucks iSo tanks Marine transport

3.
3.1 3.2 3.3 3.4 3.5

PERSONAL SAFETY AND HEALTH . . . . . . .19


Site facilities Hygiene Practices Personal Protective equipment (PPe) respiratory Protection direct reading instruments air Sampling and analysis

10. TANK CLEANING AND EQUIPMENT REPAIR . . . . . . . . . . . . . . . . . . .51


10.1 10.2 10.3 10.4 10.5 Work Preparation control of Hazardous energy confined Space entry equipment cleanout Maintenance and inspection

4.

ENGINEERING . . . . . . . . . . . . . . . . . . . . . . . .21
Bulk Storage Piping electrical area classification Pump Specifications instrumentation relief requirements leak detection devices Material requirements Vapor containment System chemical compatibility fire and explosion Hazard fire Prevention fire Suppression fire fighting

4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10

11. TRANSPORTATION REGULATORY REQUIREMENTS . . . . . . . . . . . . . . . . . . . . . .53


11.1 11.2 11.3 11.4 a1. a2. a3. a4. a5. a6. a7. classification Marking, labeling and Placarding Packaging transportation emergencies conversion factors Worldwide occupational exposure limits names and addresses of Manufacturers references regulatory Summary Visual Quick test Glossary

APPENDICES . . . . . . . . . . . . . . . . . . . . . . . . . . . . .57

5.
5.1 5.2 5.3 5.4

FIRE SAFETY . . . . . . . . . . . . . . . . . . . . . . . . .23

6.
6.1 6.2 6.3

HAZARD COMMUNICATION. . . . . . . . . . . . . .25


oSHa Hazard communication Sara title iii State regulations

Product Safety Bulletin iii

1. GENERAL INFORMATION
1.1 Product Identification
Ethenylbenzene Aromatic Hydrocarbon Styrene monomer Vinylbenzene Vinylbenzol Phenylethylene Phenethylene Phenylethene Cinnamol Cinnamene Styrol Styrole Styrolene 100-42-5 C8H8

1.1.2

Applications

Chemical Name Chemical Family Common Names

CAS# Formula

1.1.1

Chemistry

The conventional method of producing styrene monomer involves the alkylation of benzene with ethylene to produce ethylbenzene, which is followed by dehydrogenation to produce styrene monomer. This process accounts for over 80 percent (CMAI, 2004) of the worlds total styrene monomer production (see Figure 1.1). Lyondell Chemical Company uses an alternative process, a proprietary technology, to manufacture styrene monomer. Ethylbenzene is oxidized to form ethylbenzene hydroperoxide, which reacts with propylene to form propylene oxide and methyl benzyl alcohol. Methyl benzyl alcohol is then dehydrated to form styrene monomer (see Figure 1.2).

Styrene monomer is a basic building block of the plastic industry. It is used to make a host of downstream derivative products that go into millions of consumer goods. Primary derivatives of styrene monomer, in order of demand, include: polystyrene, expandable polystyrene (EPS) and acrylonitrilebutadiene-styrene (ABS)/styrene-acrylonitrile (SAN) resins, styrene butadiene (SB) latex, SB Rubber (SBR), unsaturated polyester resins (UPR), specialty polymers, co-polymers and styrene thermoplastic elastomers (TPE) (see Figures 1.3 and 1.4). Polystyrene is one of the easiest plastics to use to produce commodity packages and consumer goods. It is primarily used in insulation, packaging, appliances, furniture, toys and cassettes. It consumed 49 percent of the world production of styrene monomer based on 2004 data. Expandable polystyrene (EPS) beads are produced from styrene monomer and non-CFC (chlorinated fluorocarbons) blowing agents. It is primarily used in food packaging, insulation and cushion packaging. Resins of ABS/SAN are used in construction materials, appliances, business machines and transportation. Expandable polystyrene and ABS/SAN resins accounted for 30 percent of the world production based on 2004 data. Other applications include paper and textile coatings and carpet backing (SB latex), production of tires (SBR), construction and marine applications (UPR), adhesives and polymer modification (TPEs), etc. Polystyrene products are recyclable. In the past, polystyrene companies routinely recycled plant scraps to make their manufacturing processes as efficient as possible. More recently, with growing concerns about how it disposes of its wastes, the polystyrene industry has started recycling post consumer polystyrene packaging. Polystyrene is being recycled back into packaging, as well as durable goods such as office supplies, house and garden products, construction materials, video cassettes and other useful products.

Product Safety Bulletin 1

General Information
Figure 1.1 Conventional Technology
CH2 CH3
ALKYLATION

C2H4
Ethylene

+
Benzene Ethylbenzene

CH2 CH3
DEHYDROGENATION
Ethylbenzene

CH = CH2 +
Styrene Monomer

H2
Hydrogen

Figure 1.2 Lyondell Chemical Company Technology


CH2 CH3
OXIDATION
Ethylbenzene

O OH CH CH3 + O2
Ethylbenzene Hydroperoxide

O OH
EPOXIDATION

CH CH3

OH CH2 CH CH3 + O
Propylene Oxide

+ CH3 CH = CH2
Propylene

CH CH3
Methyl Benzyl Alcohol

Ethylbenzene Hydroperoxide

OH
DEHYDRATION

CH CH3
Methyl Benzyl Alcohol

CH = CH2 +
Styrene Monomer

H 2O

Product Safety Bulletin

General Information
Figure 1.3 Major Uses of Syrene Monomer

MAJOR USES FOR STYRENE MONOMER


STYRENE MONOMER

POLYSTYRENE (PS) Commodity Packages Consumer Goods Insulation Appliances Furniture Toys Cassettes

EXPANDABLE POLYSTYRENE (EPS)

Food Packaging Insulation Cushion Packaging

ACRYLONITRILE-BUTADIENE-STYRENE (ABS) STYRENE-ACRYLONITRILE (SAN) RESINS

Construction Materials Appliances Business Machines Transportation Material

STYRENE BUTADIENE RUBBER (SBR) Tires

STYRENE BUTADIENE LATEX (SB LATEX)

UNSATURATED POLYESTER RESINS (UPR RESINS) Construction Marine Applications

Paper and Textile Coatings Carpet Backing

Figure 1.4 Additional Styrene Monomer Derivatives

ADDITIONAL STYRENE DERIVATIVES


STYRENE MONOMER

STYRENE BUTADIENE C0-POLYMER (K-RESIN)

METHYL METHACRYLATE BUTADIENE, STYRENE CO-POLYMER (MBS)

STYRENE AND MALEIC ANHYDRIDE CO-POLYMER (SMA)

Stronger Packaging Products

Impact Modifier for PVC Resins

Automotive Interior Parts

THERMOPLASTIC ELASTOMERS (TPE)

OTHER DERIVATIVES

Adhesives Polymer Modification

Coatings Esters Polymer Polyols Polystyrene Latex Terpine Resins XT Polymer by CYRP

Product Safety Bulletin 3

General Information 1.2 Physical Properties


VALUE Liquid Colorless 145.2C (293.4F) 104.152 -30.6C (-23.1F) 0.9011 g/ml See Figure 1.5 and Table 1.2 See Figure 1.6 See Table 1.3 See Figure 1.7 See Figure 1.8 1.54682 1.54395 0.000971C 1 363C (685F) 3.84 MPa 557.0 psia 3.38 cc/g 0.0541 ft3/lb 0.256 0.2971 -1019 Kcal/mol 35.23 Kcal/mol PROPERTY Heat/Formation, Liquid @ 25C Heat/Fusion @ -30.6C Heat/Vaporization Heat Capacity of Satd Liquid Enthalpy of Satd Liquid Heat Capacity of Vapor Enthalpy of Satd Vapor Surface Tension Thermal Conductivity of Satd Liquid Thermal Conductivity of Vapor Flash Point (TCC) Auto Ignition Upper Flam. Limit Lower Flam. Limit Solubility @ 20C VALUE 24.84 Kcal/mol 2617 cal/mol 4711 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 31.9C (90F) 490C (914F) 6.1 vol% 1.1 vol% Water: 0.032 wt% Alcohol: Ether: 0.81 mol% 2.84 wt% 4.33 x 10-31 Cm 16.68 Kcal/mol 9.0%

Table 1.1. Styrene Monomer Physical Properties


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

Sat. Conc. in Air @ 25C Dipole Moment Heat/Polymerization @25C Minimum Oxygen for Combustion (MOC)

Product Safety Bulletin

General Information
Figure 1.5 Styrene Monomer Density of Saturated Liquid as a Function of Temperature
0.95 0.94 0.93 0.92

Density of Saturated Liquid (g/cc)

0.91 0.90 0.89 0.88 0.87 0.86 0.85 0.84 0.83 0.82 0.81 0.80 0.79 0.78 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140

Temperature (C)

Table 1.2

Styrene Monomer Density as a Function of Temperature


Lbs. Per U.S. Gallon 7.665 7.661 7.657 7.653 7.649 7.645 7.641 7.637 7.633 7.629 7.624 7.620 7.616 7.612 7.608 7.604 7.600 7.596 7.592 7.588 7.584 7.580 7.575 7.571 7.567 7.563 7.559 7.555 7.551 7.547 7.543 7.538 7.534 7.530 Sp. Gr. to 60F 1.0107 1.0102 1.0097 1.0091 1.0086 1.0081 1.0075 1.0070 1.0065 1.0059 1.0054 1.0048 1.0043 1.0038 1.0032 1.0027 1.0022 1.0016 1.0011 1.0005 1.0000 0.9995 0.9989 0.9984 0.9978 0.9973 0.9968 0.9962 0.9957 0.9951 0.9946 0.9940 0.9935 0.9930 Temperature C F 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 35.6 36.1 36.7 37.2 37.8 38.3 38.9 39.4 40.0 40.6 41.1 41.7 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 99 100 101 102 103 104 105 106 107 Lbs. Per U.S. Gallon 7.526 7.522 7.518 7.514 7.510 7.505 7.501 7.497 7.493 7.489 7.485 7.481 7.476 7.472 7.468 7.464 7.460 7.456 7.451 7.447 7.443 7.439 7.435 7.430 7.426 7.422 7.418 7.414 7.409 7.405 7.401 7.397 7.393 7.388 Sp. Gr. to 60F 0.9924 0.9919 0.9913 0.9908 0.9902 0.9897 0.9891 0.9886 0.9880 0.9875 0.9869 0.9864 0.9859 0.9853 0.9848 0.9842 0.9837 0.9831 0.9826 0.9820 0.9815 0.9809 0.9804 0.9798 0.9792 0.9787 0.9781 0.9776 0.9770 0.9765 0.9759 0.9754 0.9748 0.9743 Temperature C F 42.2 42.8 43.3 43.9 44.4 45.0 45.6 46.1 46.7 47.2 47.8 48.3 48.9 49.4 50.0 50.6 51.1 51.7 52.2 52.8 53.3 53.9 54.4 55.0 55.6 56.1 56.7 57.2 57.8 58.3 58.9 59.4 60.0 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 Lbs. Per U.S. Gallon 7.384 7.380 7.376 7.372 7.367 7.363 7.359 7.355 7.350 7.346 7.342 7.338 7.333 7.329 7.325 7.321 7.316 7.312 7.308 7.304 7.299 7.295 7.291 7.287 7.282 7.278 7.274 7.269 7.265 7.261 7.256 7.252 7.248 Sp. Gr. to 60F 0.9737 0.9731 0.9726 0.9720 0.9715 0.9709 0.9704 0.9698 0.9692 0.9687 0.9681 0.9676 0.9670 0.9664 0.9659 0.9653 0.9648 0.9642 0.9636 0.9631 0.9625 0.9619 0.9614 0.9608 0.9603 0.9597 0.9591 0.9586 0.9580 0.9574 0.9569 0.9563 0.9557

Temperature C F 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 21.7 22.2 22.8 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 71 72 73

Product Safety Bulletin 5

General Information
Figure 1.6 Styrene Monomer Density of Vapor @ 1 Atmosphere as a Function of Temperature
4.7 4.6 4.5 4.4 4.3

Density of Vapor x 103 (g/cc)

4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140

Temperature (C)

Table 1.3.

Styrene Monomer Vapor Pressure as a Function of Temperature


mm Hg 0.08 0.14 0.22 0.34 0.52 0.77 1.13 1.64 2.33 3.26 4.50 6.12 8.24 10.96 14.40 18.74 24.13 30.78 38.91 48.78 60.64 74.81 91.61 111.41 Vapor Pressure psia 0.00 0.00 0.00 0.01 0.01 0.01 0.02 0.03 0.04 0.06 0.09 0.12 0.16 0.21 0.28 0.36 0.47 0.60 0.75 0.94 1.17 1.45 1.77 2.15 psig Temperature C F 90.00 95.00 100.00 105.00 110.00 115.00 120.00 125.00 130.00 135.00 140.00 145.00 145.45 150.00 155.00 160.00 165.00 170.00 175.00 180.00 185.00 190.00 195.00 200.00 194.00 203.00 212.00 221.00 230.00 239.00 248.00 257.00 266.00 275.00 284.00 293.00 293.81 302.00 311.00 320.00 329.00 338.00 347.00 356.00 365.00 374.00 383.00 392.00 mm Hg 134.58 161.55 192.76 228.67 269.80 316.65 369.80 429.81 497.30 572.90 657.25 751.05 760.00 854.98 969.78 1096.19 1234.98 1386.95 1552.89 1733.66 1930.10 2143.09 2373.53 2622.35 Vapor Pressure psia 2.60 3.12 3.73 4.42 5.22 6.12 7.15 8.31 9.62 11.08 12.71 14.52 14.70 16.53 18.75 21.20 23.88 26.82 30.03 33.52 37.32 41.44 45.90 50.71 0.00 1.84 4.06 6.50 9.18 12.12 15.33 18.83 22.63 26.74 31.20 36.01 psig

Temperature C F -30.00 -25.00 -20.00 -15.00 -10.00 -5.00 0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00 70.00 75.00 80.00 85.00 -22.00 -13.00 -4.00 5.00 14.00 23.00 32.00 41.00 50.00 59.00 68.00 77.00 86.00 95.00 104.00 113.00 122.00 131.00 140.00 149.00 158.00 167.00 176.00 185.00

Product Safety Bulletin

General Information
Figure 1.7 Styrene Monomer Viscosity of Saturated Liquid as a Function of Temperature
1.9 1.8 1.7 1.6

Viscosity of Saturated Liquid (cps)

1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140

Temperature (C)

Figure 1.8 Styrene Monomer Viscosity of Vapor @ 1 Atmosphere as a Function of Temperature


9.0 8.8 8.6 8.4 8.2 8.0

Viscosity of Vapor x 103 (cps)

7.8 7.6 7.4 7.2 7.0 6.8 6.6 6.4 6.2 6.0 5.8 5.6 5.4 5.2 5.0 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140

Temperature (C)

Product Safety Bulletin 7

General Information
Figure 1.9 Styrene Monomer Heat of Vaporization as a Function of Temperature
110 108 106 104

Heat of Vaporization (cal/g)

102 100 98 96 94 92 90 88 86

-30

-20

-10

10

20

30

40

50

60

70

80

90

100

110

120

130

140

Temperature (C)

Figure 1.10 Styrene Monomer Heat Capacity of Saturated Liquid as a Function of Temperature
0.52 0.51 0.50 0.49 0.48 0.47 0.46 0.45 0.44 0.43 0.42 0.41 0.40 0.39 0.38 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140

Heat Capacity of Saturated Liquid (cal/gC)

Temperature (C)

Product Safety Bulletin

General Information
Figure 1.11 Styrene Monomer Enthalpy of Saturated Liquid as a Function of Temperature
70 65 60 55

Enthalpy of Saturated Liquid (cal/g)

50 45 40 35 30 25 20 15 10 5 0 -5 -10 -15 -20 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140

Reference: Saturated Liquid Styrene Monomer at 0C

Temperature (C)

Figure 1.12 Styrene Monomer Heat Capacity of Vapor (Ideal Gas) as a Function of Temperature
0.38 0.37 0.36 0.35

Heat Capacity of Vapor (cal/gC)

0.34 0.33 0.32 0.31 0.30 0.29 0.28 0.27 0.26 0.25 0.24 0.23

-30

-20

-10

10

20

30

Temperature (C)

40

50

60

70

80

90

100

110

120

130

140

Product Safety Bulletin 9

General Information
Figure 1.13 Styrene Monomer Enthalpy of Saturated Vapor as a Function of Temperature
150 145 140 135 130 125 120 115 110 105 100 95

Enthalpy of Saturated Vapor (cal/g)

-30

-20

-10

10

20

30

Reference: Saturated Liquid Styrene Monomer at 0C

Temperature (C)

40

50

60

70

80

90

100

110

120

130

140

Figure 1.14 Styrene Monomer Surface Tension as a Function of Temperature


32.5 32.0 31.5 31.0 30.5

Surface Tension (dynes/cm)

30.0 29.5 29.0 28.5 28.0 27.5 27.0 26.5 26.0 25.5 25.0

10

20

30

40

50

60

70

80

90

100

110

120

130

140

Temperature (C)

10

Product Safety Bulletin

General Information
Figure 1.15 Styrene Monomer Thermal Conductivity of Saturated Liquid as a Function of Temperature
1.30 1.28 1.26 1.24 1.22 1.20 1.18 1.16 1.14 1.12 1.10 1.08 1.06 1.04 1.02 1.00 0.98 0.96 0.94 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140

Thermal Conductivity of Saturated Liquid [Cal / (hr cm C)]

Temperature (C)

Figure 1.16 Styrene Monomer Thermal Conductivity of Vapor @ 1 Atmosphere as a Function of Temperature
Thermal Conductivity of Saturated Liquid [Cal / (hr cm C)]
0.200 0.195 0.190 0.185 0.180 0.175 0.170 0.165 0.160 0.155 0.150

150

155

160

165

170

175

180

185

190

195

200

Temperature (C)

Product Safety Bulletin 11

General Information 1.3 Typical Values


should also be conducted. At the first sign of uncontrolled polymerization, TBC should be added and product temperature should be reduced. TBC inhibitor should be added as an 85 percent solution in methanol. Add TBC to an initial concentration of 50-100 ppm TBC in styrene monomer. Circulate tank contents to mix the TBC in styrene monomer. If circulation is not possible, agitate by bubbling air into tank bottom. (Caution: The air/styrene monomer vapor mixture may be within the flammability envelope). If runaway polymerization continues, add TBC up to a 0.5 wt% concentration. Dilution with toluene, xylene or ethylbenzene will slow the polymerization. Lowering product temperature will also slow polymerization. Tanks can be cooled by refrigeration, circulation and water spray. When tank temperatures are stable and polymerization has stopped, product should be removed from tank before it becomes solid. If products viscosity prohibits removal, dilute with toluene, xylene or ethylbenzene before emptying the tank.

Lyondell styrene monomer meets the requirements of ASTM D 2827-04: Purity, wt% min . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .99.8 Ethylbenzene, ppm max . . . . . . . . . . . . . . . . . . . . . . . . 500 Benzene, ppm max. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 Aldehydes (as Benzaldehyde), ppm max . . . . . . . . . . . . 100 Peroxides (as H2O2), ppm max . . . . . . . . . . . . . . . . . . . . 50 Polymer, ppm max . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 4-tert-Butylcatechol, ppm min . . . . . . . . . . . . . . . . . 10-15 Color, Pt-Co (ASTM D-1209), max . . . . . . . . . . . . . . . 10 OR Color, Pt-Co (ASTM D-5386), max . . . . . . . . . . . . . . . 15

1.4

Instability Hazards

Styrene monomer can self-react and polymerize unless properly inhibited. Polymerization will release heat and results in temperature and pressure increases. The most commonly used inhibitor is 4-tert-Butylcatechol (TBC). Maintaining the storage temperature below 21C (70F) and the dissolved oxygen content of the liquid at 15 to 20 ppm will help inhibit polymerization (See Section 8.2.4).

1.7

Precautions When Handling TBC

1.5

Reactivity Hazards

Styrene monomer reacts with oxidizers, peroxides, strong acids and alkali metal-graphite compounds. Avoid copper and copper containing alloys. Styrene monomer will dissolve many natural and synthetic rubbers. Storage vessels must be free of rust and scale which can promote polymerization. Styrene monomer emits acrid vapors on thermal decomposition. Incomplete combustion can produce carbon monoxide.

TBC and solutions of TBC are corrosive and can cause severe burns to the skin and eyes. TBC may cause allergic reactions in certain individuals. Consult the manufacturers Material Safety Data Sheet for additional information. When handling TBC, personnel should prevent exposure to the skin by wearing chemical protective gloves, apron and boots. Prevent eye contact by wearing chemical splash goggles or face shield.

1.6

Self-Polymerization

Styrene monomer is inhibited with TBC to reduce and control self-polymerization. Styrene monomer undergoes polymerization slowly at ambient temperatures, but polymerization will become rapid at elevated temperatures. Styrene monomer may experience rapid polymerization if TBC inhibitor and dissolved oxygen are depleted at elevated temperatures or if product is contaminated with incompatible materials. Styrene monomer polymerization is exothermic evolving 290 BTU/lb (16.7 Kcal/mol). If excess heat is not adequately dissipated, the product temperature will rise with a subsequent rise in the rate of polymerization. At temperatures above 65C (149F), runaway polymerization is possible. When a runaway polymerization occurs, temperatures can quickly exceed the boiling point of styrene monomer. Vapors may erupt violently from tank vents or, if vents become plugged with polymer, excessive pressure can be generated that may rupture the containment vessel. Styrene monomer should be monitored regularly for TBC content. During excessive transit times, monitoring 12 Product Safety Bulletin

2.
2.1

OCCUPATIONAL HEALTH
Hazard Assessment
2.1.1 Acute Effects of Over Exposure

Styrene monomer is a highly volatile liquid with a low odor threshold. The odor of styrene monomer has been described as sweet and pleasant at low concentrations but disagreeable at high concentrations. Styrene monomer has a low to moderate order of acute toxicity. The major hazard from acute exposure to styrene monomer is the irritant effect on the eyes, skin and mucous membranes of the respiratory system. High inhalation exposure may cause dizziness and central nervous system depression, while ingestion may be fatal if aspiration into the lungs occurs. Styrene monomer may also increase the sensitivity of the heart to endogenous neurotransmitters leading to potentially fatal cardiac sensitization. Repeat inhalation studies demonstrate that mouse nose and lung are highly sensitive to styrene monomer vapor, while responses in the rat are much less pronounced. Sensory and behavioral effects have also been reported with repeated styrene monomer exposure. Mild, but permanent, hearing loss was reported in rats after repeated exposure to high concentrations of vapor. Minor impairment of color discrimination and equivocal effects on behavior responses have been identified in some studies of workers exposed to styrene monomer. The available animal and human data demonstrate that styrene monomer is not selectively toxic toward the fetus, nor does it adversely impact reproduction. Results from genotoxicity studies are generally negative with no consistent or conclusive evidence of genetic damage in exposed worker populations. Chronic inhalation to styrene monomer vapor resulted in an increased incidence of pathology and late onset tumors in the lungs of mice, which are believed to have arisen through a nongenotoxic mechanism. Tumor incidence in rats was unaffected after chronic inhalation exposure. The available evidence from mechanistic studies and human epidemiology studies indicate that humans are at low risk for cancer from styrene monomer exposure.

Styrene monomer is of low to moderate toxicity following acute (single dose) exposure. Single oral doses that produced lethality (LD50) in laboratory animals ranged from 316 mg/kg in mice to approximately 5000 mg/kg in rats. Inhalation exposure also produced variable acute toxicity with mice that were apparently more sensitive. Lethality was observed in mice administered 500 ppm styrene monomer vapor for six hours (LDLo), whereas, a four-hour exposure to 2770 ppm styrene monomer vapor was lethal (LD50) to rats. Acute toxicity associated with dermal contact to styrene monomer has not been reported. However, adverse systemic health effects are not expected following accidental or incidental contact with styrene monomer liquid. Styrene monomer liquid is moderately irritating to the skin and eyes. The predominant clinical signs and symptoms that may be anticipated with over exposure to styrene monomer are irritation to contact surfaces and central nervous system effects. Ingestion of styrene monomer liquid may cause discomfort and irritation of the gastrointestinal tract, and high vapor concentrations may cause irritation of the eyes, nose and throat. High oral and inhalation exposure to styrene monomer may cause central nervous system depression as evidenced by fatigue, dizziness and loss of concentration, with collapse, coma and death in cases of severe exposure. Over exposure may also increase the sensitivity of the heart to endogenous catecholamines leading to potentially fatal cardiac sensitization. As with other hydrocarbons, styrene monomer may be aspirated into the lungs and cause chemical pneumonitis, which can be fatal. A controlled exposure study of human volunteers to styrene monomer vapor confirms that surface tissue contact and the nervous system are targets of acute high-dose exposure. Exposure of volunteers to 800 ppm styrene monomer produced immediate symptoms of eye, nose and throat irritation with drowsiness, listlessness and muscular weakness. At approximately 200 ppm, nasal irritation was produced after 20 minutes of exposure. Exposure to 200 to 380 ppm styrene monomer for 30 to 90 minutes reportedly produced altered neurological effects (slightly impaired performance in neurobehavioral tests). Upon removal from the styrene monomer atmosphere, all of these symptoms readily reversed with complete recovery. No symptoms of irritation or toxicity were reported by volunteers exposed to 50 to 100 ppm styrene monomer for one to two hours.

Product Safety Bulletin 13

Occupational Health
2.1.2 Repeated Exposures
magnitude and hence unlikely to be of clinical significance. Variable and inconsistent results have been reported in laboratory animal and human neurobehavioral studies. In studies conducted in rats, high vapor concentrations (500 ppm and greater) produced transient reversible decreases in visual response time and operant behavior but no effects on grip strength, spontaneous activity and peripheral nerve conduction. These findings may have been due to acute CNS depression from the styrene monomer exposure. A number of human workplace studies assessing potential long-term neurobehavioral effects of repeated exposure to vapor have been reported. Some of these investigations reported effects while others found no change in workers exposed to similar or higher levels of styrene monomer vapor. Overall, there is no consistency within or between studies, and critical confounding factors were unaddressed in the majority of the studies. Therefore, no definite conclusion can presently be made on styrene monomers potential for neurobehavioral decrements.

Results from repeat-dose toxicity studies demonstrate that the mouse is highly sensitive to styrene monomer-induced respiratory toxicity, while toxicological responses in the rat are less marked. Mechanistic studies demonstrate greater formation of locally-toxic products in mouse nose and lung, and provide a metabolic basis for these species differences in susceptibility. Negligible metabolism in humans suggests that humans are less susceptible than the mouse to styrene monomer-induced respiratory tract toxicity. Sensory and behavioral effects have also been reported with repeated styrene monomer exposure.. Mice that were exposed for two years to styrene monomer vapor at concentrations ranging from 20 to 160 ppm exhibited an increased incidence of hyperplasia and fibrosis in lung tissue and atrophy and degeneration of nasal olfactory epithelium. In a shorter-term (13 week) study, higher exposure concentrations (150 to 200 ppm) produced abnormal liver histopathology in mice; however, these effects were not apparent in the two-year exposure study. In a companion rat two-year exposure study, styrene monomer vapor concentrations ranging from 50 to 1000 ppm produced only mild nasal tissue changes with no other treatment-related tissue effects noted. The olfactory portion of the nasal mucosa in rats and mice has been consistently reported to exhibit changes after inhalation of styrene monomer vapor, with the most pronounced changes seen in the mouse. Nasal lesions, however, have not been reported for any species following exposure via other routes. Uptake of styrene monomer in the respiratory tract is dependent partly on the concentration of styrene monomer in air and partly on the rate and extent of styrene monomer metabolism in respiratory tissue. Metabolic investigations support differences in rodent respiratory metabolism of styrene monomer which is thought to account for the differential sensitivity of rat and mice to styrene monomer- induced nasal and pulmonary toxicity. Human metabolism of styrene monomer in nasal and pulmonary tissue is expected to be very low, suggesting that styrene monomer is unlikely to be toxic to human nasal epithelium or lungs. Effects on hearing, color vision and behavior have been reported for styrene monomer. Exposure of rats to 600 ppm styrene monomer vapor produced a mild (1-3 dB) increase in auditory brainstem response and loss of outer hair cells in regions of the organ of Corti. Combined exposure to noise and styrene monomer gave a greater increase in auditory brainstem response that was produced by either noise or styrene monomer alone. There is some evidence of a minor effect on hearing in human worker populations exposed to styrene monomer. However, these studies had confounding factors (such as age and co-exposure to noise) which preclude a definitive determination. Decreased color discrimination (dyschromoatopsia) has been reported in some workers following occupational exposure to styrene monomer. Color vision measurements (Desat D-15 test) found poorer color discrimination in workers exposed to styrene monomer vapors in the range of approximately 30 to 50 ppm. These changes, although statistically significant, were small in 14 Product Safety Bulletin

2.1.3

Reproductive and Developmental Toxicity

The potential for styrene monomer to induce toxicity to reproduction and development has been studied in several mammalian species. There is no convincing evidence that styrene monomer will affect reproduction or development at doses which are not parentally toxic. Results from reproductive toxicity studies in rats exposed via drinking water or inhalation have shown that styrene monomer is not selectively toxic to the gonads, nor does it adversely affect fertility or litter parameters. A three-generation study in rats conducted using dose levels of up to 250 ppm (equivalent to daily doses for males of 14 mg/kg and females of 21 mg/kg) found no effect on reproductive parameters. The highest dose that could be tested in this study was limited by the low solubility of styrene monomer in water. A recent two-generation study has been conducted in rats exposed to up to 500 ppm styrene monomer. The dams also received oral equivalent doses (up to 300 mg/kg) between postnatal day 1 and 4 to assure continuous exposure to the pups (inhalation exposure normally suspended during postnatal day 1 to 4, as pup separation during this period is deleterious). Parental mating and fertility indices (including sperm, ovary and estrus parameters), mean live litter size and postnatal survival were unaffected by styrene monomer treatment. Body weight, body weight gain and feed consumption were decreased at various times during the study in adult and pups of both sexes exposed to 500 ppm, with less pronounced but significant reductions also present in the 150 ppm groups. Overall, these results provide no indication that styrene monomer adversely affected reproductive performance in male and female rats exposed to 500 ppm over two generations. Results from 13-week and two-year inhalation studies in rats and mice also found no evidence of any adverse structural effect on ovaries, testes, adrenals or uterus (mice only). Several studies have examined reproductive function in male workers occupationally exposed to styrene monomer. Overall, these studies provide no

Occupational Health
evidence of a link between internal body burden and reproduction function. Results from laboratory animal studies demonstrate that styrene monomer is not a teratogen, nor is it fetotoxic at sub-maternally toxic treatment levels. Styrene monomer has been studied in a number of conventional developmental toxicity studies conducted in rats, rabbits and hamsters using inhalation or oral exposure. These studies did not find adverse effects on embryo/fetal development at doses that did not produce maternal toxicity. At high doses (300 ppm and greater), there were some indications of fetal toxicity. However, these occurred in the presence of maternal toxicity. A recent developmental neurotoxicity study has been conducted in rats as an adjunct to the two-generation reproductive toxicity study. This study found some evidence of developmental delay (prolonged acquisition of pinnal detachment and balanopreputial separation), altered locomotor activity (decreased, then increased) and neurobehavioral deficits (increased escape time from a Biel maze, reduced forelimb/ hindlimb grip strength) in F2 litters exposed to 500 ppm (300 mg/kg) styrene monomer. However, these findings were attributed to decreased body weight, rather than a direct/ selective response of the offspring to styrene monomer exposure. In an earlier study, decreases in brain neurotransmitter levels were observed in pups from dams exposed to 300 ppm styrene monomer but not at 50 or 60 ppm styrene monomer. The significance of these brain chemical changes is unknown but doubtful as they occurred at levels below which measurable behavioral changes have been found in other studies. A number of human epidemiological studies, focusing on developmental effects, have been conducted but most of these have too few subjects to be conclusive. There is limited evidence from one study that styrene monomer may increase the rate of spontaneous abortions in female workers. However, the majority of studies have been generally negative and provide no reliable evidence of styrene monomer exposure-related effects in relation to spontaneous abortion, congenital abnormalities or birth weight reductions. the studies indicates increased chromosomal aberrations or micronuclei in peripheral lymphocytes following occupational exposure. These findings, however, did not show an apparent dose response relationship and were probably confounded by previous or concurrent exposure of subjects to other genotoxic substances, such that definitive conclusions cannot be drawn for styrene monomer exposure. Overall, the available investigations of genetic damage in exposed worker populations provide no consistent or conclusive evidence for the genotoxicity of styrene monomer in workers.

2.1.5

Carcinogenicity

2.1.4

Genetic Toxicity

The genotoxic potential of styrene monomer has been investigated extensively. Results from in vitro tests are mostly negative, although occasional positive findings have been reported in some test systems, presumably reflecting conversion of styrene monomer to styrene monomer oxide (a demonstrated mutagen). In vivo studies in rats, mice and hamsters generally show no increase in chromosomal aberrations or micronuclei after single or repeated inhalation, oral or intraperitoneal exposure. However, simultaneous assessment of sister chromatid exchanges resulted in a weakly positive result in some of these same studies. The significance of these findings to styrene monomer mutagenicity is unclear. A number of studies have been performed that examine the genotoxic potential of styrene monomer in workers. The results from these studies are generally negative, although a minority of

The carcinogenic potential of styrene monomer has been investigated in rats and mice after long-term inhalation or oral exposure. Results for the rat provide no evidence of carcinogenicity, whereas data from the mouse indicate an increase in late-onset tumors in the lung (no other organ affected). The mouse lung tumors occurred in the presence of hyperplasia and inflammatory changes which were not present in the rat lungs. In rats, while individual studies have shown isolated increases in various tumor types, these findings have typically fallen within the historical background range for the tissue in question, were not reproduced between studies, were not doserelated, or occurred at sites which have shown no other signs of styrene monomer-related toxicity or morphological change. A recent inhalation study that administered rats for two years to up to 1000 ppm styrene monomer vapor found no increases in tumor incidence. Overall, based on the results from eight long-term carcinogenicity studies, there is no compelling evidence that styrene monomer is carcinogenic in the rat. In mice, the available data indicate that styrene monomer produces an increase in lung tumors following lifetime exposure. This is based on the findings from three oral gavage administrations and a recent inhalation study, all of which reported varying but increased incidences of pulmonary adenoma and/or carcinoma. In the inhalation study, there were no treatment-related neoplastic findings noted at the first interim sacrifice at week 53. At the second interim sacrifice at week 79, the occurrence of pulmonary bronchiolar-alveolar adenoma was increased in some of the male and female treatment groups. The observed increases in lung tumor incidence occurred in conjunction with chronic inflammation. At terminal sacrifice, a statistically significant dose-related increase in pulmonary-bronchiolar adenomas was observed in males at 40 ppm and above and in females at 20 ppm and above. The incidence of bronchiolar-alveolar carcinomas was significantly increased in females and increased, but not significantly, in males. There were no significant differences between styrene monomer-exposed and control animals for tumors at other sites. The tumor profile for styrene monomer is suggestive of a nongenotoxic mode of action. Supporting information includes the species- and tissue specificity of the late onset lung tumors in mice and the presence of concurrent non-neoplastic Product Safety Bulletin 15

Occupational Health
inflammatory changes in the tumor bearing tissue. Mechanistic studies suggest that a styrene monomer metabolite(s) may be responsible for the lung toxicity and tumor development, and differences in species metabolism may explain differences in species sensitivity to tumors. Metabolism studies have shown that mouse lung is more efficient at metabolizing styrene monomer, whereas pulmonary metabolism is negligible in rat lung and virtually undetectable in human lung. Several epidemiology studies of workers exposed to styrene monomer during production of styrene/polystyrene, styrenebutadiene rubber and reinforced plastics and composites have been reported. Of these studies, the studies in the reinforced plastics and composites industry provide the most confident assessment of cancer in light of higher exposure to styrene monomer and less confounding from other chemical exposures. In the reinforced plastics and composites industry studies, there is no clear evidence that exposure to styrene monomer increased the risk of cancer. In the other two manufacturing industries, exposures to styrene monomer are much lower and are confounded by a variety of other chemicals, a number of which are suspected carcinogens. While several studies of workers in these two industries have shown increases in certain types of cancer, the data either strongly implicate other chemicals present, or show no pattern consistent with a role of styrene monomer. Overall, the combined weight of evidence from studies from all industry segments supports a low concern for cancer in humans from styrene monomer exposure. The carcinogenicity of styrene monomer has been reevaluated by IARC and the classification maintained as possibly carcinogenic in humans Group 2B. The IARC working group concluded that there was limited evidence in humans for the carcinogenicity of styrene monomer and also limited evidence in animals.

2.2.1

Warning Properties

Styrene monomer is a highly volatile liquid with a low odor detection threshold of 0.14 ppm. Styrene monomer has a sharp, sweet, pleasant odor at low concentrations, but is disagreeable at high concentrations. Styrene monomer is considered to have good warning properties.

2.3

First Aid

When an emergency arises, employees should approach the accident site with caution. Do not become a casualty. Employees should understand emergency procedures and know where rescue equipment and emergency contact numbers are located before the need arises. Personnel providing assistance to a victim must be cautious not to contaminate themselves by touching the victims clothing unless wearing protective equipment such as gloves. The removal of clothing from the victim, however, is important to minimize continued skin contact and to prevent continued volatilization of styrene monomer 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 a burning or irritating sensation.

2.3.1

Eye Contact

For eye contact, flush eyes immediately with copious amounts of clean water for at least 15 minutes, periodically lifting the lower and upper lids to enhance flushing. Individuals splashed with styrene monomer may require assistance in locating emergency eyewash stations and flushing the eyes. Medical attention should be provided as soon as possible. An ophthalmologist should be available for consultation.

2.2

Occupational Exposure Limits

2.3.2

Skin Contact

The American Conference of Governmental Industrial Hygienists (ACGIH) in the United States of America has established a Threshold Limit Value (TLV) for styrene monomer monomer. The TLV is 20 ppm as an 8-hour Time-Weighted Average (TWA8) and 40 ppm as a 15-minute Short-Term Exposure Limit (STEL). Some world-wide occupational exposure limits are shown in Appendix 2. The U.S. Department of Labor, Occupational Safety and Health Administration (OSHA) has a Permissible Exposure Limit (PEL) for styrene monomer which is less conservative than the TLV. This value is listed in 29 CFR 1910.1000. The U.S. National Institute for Occupational Safety and Health (NIOSH) has classified 700 ppm of styrene monomer as immediately dangerous to life and health (IDLH). This limit represents the maximum concentration from which, in the event of respirator failure, workers could escape within 30 minutes from the contaminated workplace without experiencing any escape impairing (for example, severe eye irritation) or irreversible health effects. 16 Product Safety Bulletin

Anyone splashed by liquid styrene monomer should flush affected areas thoroughly with water from a safety shower or other running stream of water. While under the shower, the exposed person should remove all contaminated clothing, rings, watches, shoes or anything else that would prevent complete flushing. All skin areas exposed to liquid styrene monomer should then be washed with soap and water. If skin reddening is noted, the exposed person should seek medical attention. Clothing should not be reused before laundering.

2.3.3

Inhalation

If overcome from inhalation of styrene monomer, move victim from contaminated atmosphere into fresh air at once. Treat for shock if necessary. If victim has stopped breathing, administer cardiopulmonary resuscitation (CPR) immediately. First aidtrained individuals, or equivalent, should administer CPR. The victim should be monitored for respiratory distress. If cough or difficulty in breathing develops, administer 100 percent humidified supplementary oxygen with assisted ventilation, if required. Seek prompt medical attention.

Occupational Health
2.3.4 Ingestion
substances, special consideration should be given to those with impaired renal function. Since styrene monomer exposure may effect the respiratory system, special consideration should be given to this when pre-screening employees. A specific targeted protocol for the initial medical examination developed by an occupational health physician should be established before employing individuals who may be exposed to styrene monomer.

Anyone who has swallowed styrene monomer should be given a pint or more of warm water, but only if the exposed person is completely conscious and alert. Vomiting should not be induced; the risk of lung damage exceeds other hazards. If vomiting occurs, have the person position their head below waist level to minimize the risk of aspiration into the lungs. Otherwise, chemical pneumonitis or bronchitis can result. Seek prompt medical attention.

2.4.2

Periodic Screening

2.4

Medical Management

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 persons on site 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 and hospital emergency room to plan for medical emergencies. Hospital selection should be based upon proximity and the hospitals ability to handle chemical emergencies. Copies of the MSDS and the Product Safety Bulletin for styrene monomer should be provided to, and reviewed with, medical personnel.

Employees potentially exposed to styrene monomer should receive routine medical evaluations. Periodic medical screening is an effective tool for the identification and prevention of occupational disease. In the United States, the ACGIH has established a Biological Exposure Index (BEI) for styrene monomer. Biological monitoring provides the occupational physician with a method for assessing worker exposure. Biological monitoring can be accomplished by determining styrene monomer in blood or styrene monomer metabolites in urine. Employers should consult with their occupational health physicians to determine the specific targeted protocol to be followed.

2.4.1

Initial Medical Screening

Prospective employees who may be potentially exposed to styrene monomer should be physically able to work with styrene monomer and, with reasonable accommodations, the personal protective equipment which may be required. An employee who will be working with or around styrene monomer should have an initial medical screening for preexisting conditions that may be aggravated by styrene monomer exposures. The individual may be stressed by wearing personal protective equipment, which may include respiratory protection and chemical protective clothing (see Sections 3.3 and 3.4). Some employees are claustrophobic when placed in full-face piece respiratory protection or full containment suits, or simply when entering confined spaces. Styrene monomer can cause skin irritation and blistering. Persons with pre-existing skin disorders may be more susceptible to the effects of this chemical. For persons with impaired pulmonary function, especially those with obstructive airway diseases, breathing styrene monomer may exacerbate symptoms. Styrene monomer may affect the CNS, aggravating pre-existing central nervous system disorders. Although styrene monomer is not known as a liver toxin in humans, the importance of the organ in the biotransformation and detoxification of foreign substances should be considered before exposing persons with impaired liver function. Similarly, styrene monomer is not known as a kidney toxin. However, due to the importance of this organ in the elimination of toxic

Product Safety Bulletin 17

3. PERSONAL SAFETY AND HEALTH


3.1 Site Facilities 3.3 Personal Protective Equipment (PPE) Respiratory Protection

If a potential for contact with styrene monomer 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 4 for citations). Workers should be familiar with the location and operation of this safety equipment. Workers should be provided with washing facilities for cleaning before consuming food or beverages and before using tobacco or cosmetics. Properly ventilated areas should be provided where workers can take breaks and eat meals. Such areas should be separate from those in which styrene monomer or other chemicals are handled or stored. Where the potential for exposure exists under normal operating conditions, it would be prudent to have shower facilities available for use at the end of the shift. There should be provisions to separate work clothing from street clothing. If contaminated clothing is laundered, appropriate facilities should be provided. Styrene monomer will evaporate from clothing potentially increasing the risk of worker exposure. Site facilities should include closed containers for clothing storage and engineering controls to limit worker 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.

Good industrial hygiene practice requires that engineering controls be used to reduce employee workplace airborne concentrations to below the ACGIH TLV of 20 ppm or other local regulatory limits. However, if engineering controls are not feasible, are being installed, or fail to control exposures and need to be supplemented, respiratory protection should be provided for workers. Respirators may also be needed for operations that require confined-space entry into tanks or closed vessels and in emergency situations resulting from spills/leaks and fire/ explosions involving styrene monomer. If respirators are used, a complete respiratory protection program should be implemented that includes training, inspection, medical surveillance, fit testing, cleaning and maintenance. Respiratory protection programs should meet the requirements of OSHA Respiratory Protection Standard (29 CFR 1910.134) and ANSI Z88.2. When worker exposure exceeds established limits, NIOSHapproved respirators should be used. Table 3.1 provides guidance for selecting respiratory protection.

3.3.1

Eye Protection

Chemical safety goggles should be worn whenever the potential for exposure to vapor or 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.

3.2

Hygiene Practices

3.3.2

Foot Protection

Proper personal hygiene practices should be used while working with and around styrene monomer. Employees should be familiar with good work practices to avoid direct contact with styrene monomer. Personal hygiene practices that should be considered while working with and around styrene monomer include prohibiting consumption and storage of food, use and storage of tobacco products and application and storage of cosmetics. Styrene monomer should not be handled or stored in areas where workers take breaks (such as lunch rooms) or in areas that are not designed for styrene monomer storage. After handling styrene monomer and prior to eating, smoking, drinking, applying cosmetics or using toilet facilities, workers should thoroughly wash their hands and faces with warm water and mild soap/detergent. Protective clothing and equipment used during the handling of styrene monomer, including gloves, aprons, protective suits and respirators, should be properly decontaminated using mild soap/detergent and water. To prevent exposure, contaminated clothing should be sealed in containers until laundered or disposed of properly.

Heavy overboots should be provided and worn over leather shoes or boots to protect the leather from contamination. Rubber boots should be worn under trouser legs to prevent styrene monomer from entering the boot.

3.3.3

Skin Protection

Impervious protective clothing suitable for a particular task or work activity should always be worn where chemical contact is possible. Protective equipment can include an ensemble of chemicalresistant gloves and a chemical apron to full-body chemical-resistant coveralls, chemical gloves and a face-shield for protection. Productspecific styrene monomer permeation and degradation data should be evaluated prior to specifying any personal protective equipment (PPE). Protective clothing web sites such as www.dupont.com are an excellent source of information for making clothing selections based on the task. Glove manufacturers web sites such as www.bestglove.com or www.ansell.com provide chemical permeation and degradation data on their specific gloves to many chemicals including styrene monomer. Product Safety Bulletin 19

Personal Safety and Health


Where the potential for exposure to styrene monomer liquid exists, as in the case of a spill clean-up, or during materials transfers/handling, employees should increase their level of protection to liquid-tight coveralls as well as appropriate face and hand protection. Liquid-tight PPE is designed to protect employees from skin contact with styrene monomer liquid. All PPE including chemical-resistant suits, gloves, boots, etc, should be inspected prior to each use so as to identify any damage, excessive wear or situations that may compromise worker safety and health. If PPE is torn, damaged or is contaminated with styrene monomer, then it should be collected and properly disposed of in accordance with local, state and federal regulations.

3.5

Air Sampling and Analysis

3.4

Direct Reading Instruments

Styrene monomer can be readily analyzed by a variety of directreading instruments. The advantage of using direct-reading instruments is that real-time analysis and instantaneous air concentrations can be determined. 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 styrene monomer are combustible gas indicators, infrared spectrophotometers, flame ionization detectors, photoionization detectors and colorimetric detector tubes. Appendix 3 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 an industrial hygienist or other trained professional.

When assessing worker exposure to styrene monomer, an extended sampling period is required. The accepted method of air sampling is collection of the material on a sorbent media over an extended period of time. Air is drawn at a measured rate by a sampling pump into a charcoal tube. Passive samplers, which use the diffusion characteristics of the material instead of an active sampling pump, are also available. These methods have been extensively developed and evaluated for use with styrene monomer. When considering the use of these methods for determining employee exposure, it is important that a monitoring program be developed by professional industrial hygienists. This program should include sampling strategy, quality assurance and statistical analysis of results.

Table 3.1

Styrene Monomer Respiratory Protection Selection Guide


Minimum Respiratory Protection* Required Above 20 ppm A half-face negative pressure chemical cartridge respirator with organic vapor cartridge.** A full-face negative pressure chemical cartridge respirator with organic vapor cartridge.** Any half-face supplied air respirator (SAR) in continuous flow mode. Any full-face SAR in positive pressure or pressure demand mode. Requires an appropriately-sized escape bottle to be used in conjunction with the SAR. SCBA with full-face piece in pressure demand or positive pressure mode. SCBA with full-face piece in pressure demand or positive pressure mode. any escape ScBa. any full-face chemical cartridge respirator with organic vapor cartridges. any full-face gas mask with an organic vapor canister/cartridge.

Condition (Vapor Concentration) 20 ppm - 200 ppm 200 ppm - 500 ppm 500 ppm - 700 ppm

Greater than 700 ppm or unknown concentration Fire Fighting Escape

* Only approved/certified equipment should be used. ** If potential for eye irritation, recommend utilization of full-face respirator 20 Product Safety Bulletin

4.

ENGINEERING
4.3 Electrical Area Classification

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 styrene monomer will require additional engineering studies to determine the applicability of the enclosed information.

All electrical equipment should be suitable for flammable organic liquids, be constructed and installed to recognized, appropriate engineering codes of practice and conform to the appropriate area classification.

4.4

Pump Specifications

4.1

Bulk Storage

The construction of low-pressure styrene monomer storage should be according to API-620 and 650 (see Appendix 4 for citations). Higher-pressure storage vessels should comply with ASME Code Section VIII, Division 1 or equivalent. All internal surfaces should be kept clean and rust-free and should be internally lined with inorganic zinc such as Carbozinc II or a baked phenolic to prevent polymerization problems. Liquid styrene monomer should enter through the bottom of the tank. Incoming liquid should be prevented from free-falling through the tank vapor space (see Section 8). Tanks should have a minimum of internal beams, pipes and projections that can provide places for condensed styrene monomer vapors to accumulate and polymerize. Refrigeration by external chillers may be required to maintain the monomer temperature below 21C (70F). All above-ground storage tanks should be insulated and designed with a means of styrene monomer agitation. For a complete discussion on storage conditions, see Section 8.

Centrifugal pumps: any carbon steel or stainless steel type designed with closed impellers and mechanical seals. Secondary seals should be of Kalrez 6375 or Chemraz 505. Rotary pumps: any type made for hydrocarbon service with mechanical seals. Check pump regularly for gear wear. Positive displacement pumps: any type made for hydrocarbon service with mechanical seals. Check pump regularly for wear. Drum pumps: should be regularly checked for leakage and cleaned thoroughly after each use. When pumps are installed, care should be taken to avoid the possibility of allowing a pump to run against closed valves. Deadheading the pump will cause heat buildup and lead to polymerization of the monomer; therefore, a minimum flow line should be used. The line should have a cooler to keep the styrene monomer below its polymerization temperature. The pump design should also allow for complete drainage and recirculation.

4.5

Instrumentation

4.2

Piping

Piping and piping components should comply with the latest edition of ASME/ANSI B31.3 or the appropriate equivalent. Carbon steel is an acceptable material of construction although, to prevent increased polymerization and color problems, stainless steel is preferred. One and one half inch pipe or smaller can use threaded, threaded and backwelded or socket welded connections. Butt-welded fittings and flanged connections are preferred. Piping should be laid out to facilitate complete draining or permit nitrogen purging back to the styrene monomer storage tank or other common collection points. If lines are to be used infrequently, complete draining is crucial. These lines should be buried or shaded to minimize the potential for polymerization due to temperature increases. For extended storage, all lines should be designed to allow recirculation and chilling.

Independent high-level alarms and/or shutdowns should be provided for storage tanks. Storage tanks should be equipped with temperature and level indicators. All instrumentation should be designed, manufactured and installed to appropriate engineering codes and conform to the appropriate area classification. Avoid TFE coated-construction. TFE seals are acceptable.

4.6

Relief Requirements

The requirements of API RP-2000 should be followed for low-pressure vertical storage tanks. Pressure-relieving systems for pressure vessels are defined in API RP-520, Parts 1 and 2. Flame arresters, when required, should follow the requirements of API R-2028 and 2210. Pressure-relief valves in styrene monomer service should be regularly inspected for polymer formation. A nitrogen purge under the seat of the relief valve can be used to minimize polymer buildup. Avoid composite rupture disks with TFE seals. A nitrogen purge under the seal of the relief valve can be used to minimize polymer buildup.

Product Safety Bulletin 21

Engineering 4.7 Leak Detection Devices


4.8.5 Valve Packing

Secondary containment areas in confined spaces should be monitored with instrumentation able to detect the lower flammability limit of styrene monomer in air. Instruments that have been successfully used to measure styrene monomer are combustible gas indicators, infrared spectrophotometers, flame ionization detectors and photoionization detectors (see Section 3.4).

Die-formed rings: graphite-based Bonnet gaskets: metal-reinforced, flexible graphite.

4.8.6

Hoses

All hoses should be flexible stainless steel, have suitable pressure/ temperature ratings and should be grounded to discharge static electricity. All hoses should be tested on a regular basis.

4.8

Material Requirements

4.9

Vapor Containment System

Styrene monomer, like other aromatics, is not compatible with most elastomers and rubber materials. It is not compatible with copper and copper alloys. Care should be taken when selecting materials that will contact styrene monomer. Consult with individual manufacturers about the specific needs of your facility.

Vapor containment systems for pressure vessels are defined in API RP-520, Parts 1 and 2.

4.10 Chemical Compatibility


Styrene monomer is highly reactive, especially with oxidizers, peroxides, strong acids, metal halides and metal alkyls. Copper and copper alloys should be avoided because their use can discolor styrene monomer.

4.8.1

Gaskets

Flat-ring (sheet): Durable nitrile, compressed fiber or Grafoil GHE with dimensions according to ANSI B 16.21. Spiral-wound: Flexitallic CG or 100 percent graphite-filled with dimensions according to API 601. Avoid TFE piping gaskets. Teflon gaskets used for truck or other transport applications should be inspected regularly and replaced as needed.

4.8.2

O-Rings

Kalrez, Viton, Teflon, Fluorel or equivalent. Avoid TFEencapsulated O-rings.

4.8.3

Pipe Thread Sealant

Teflon paste or tape. The continuity across connections should be checked to ensure grounding.

4.8.4

Pump Seals

Component materials for mechanical seals should include: Stationary Faces: tungsten carbide Rotating Faces: carbon Elastomers: Kalrez 6375 or Chemraz 505

Grafoil is a registered trademark of Graphtech Inc. Kalrez and Viton are registered trademarks of DuPont Performance Elastomers. Fluorel is a registered trademark of Dyneon, LLC. Chemraz 505 is a registered trademark of Green Tweed Company. Teflon is a registered trademark of E.I. du Pont de Nemours and Company.

22

Product Safety Bulletin

5.
5.1

FIRE SAFETY
Fire and Explosion Hazard 5.2 Fire Prevention

Styrene monomer is classified by OSHA 29 CFR 1910.106 (see Appendix 4 for citations) as a Class IC flammable liquid. The National Fire Protection Association (NFPA) Code 30 also defines styrene monomer as a Class IC flammable liquid. For application of the National Electric Code (NFPA 70), styrene monomer is a Class I, Group D. Styrene monomer has a flash point of 31.9C (90F). Styrene monomer vapors are explosive in air at concentrations between 1.1 and 6.1 percent by volume if an ignition source is present (see Figure 5.1). Styrene monomer vapor is heavier than air and may travel a considerable distance to a source of ignition and then flashback. All precautions necessary for the safe handling and storage of a volatile flammable liquid or vapor should be strictly observed with styrene monomer. Uncontrolled polymerization should not occur if TBC inhibitor levels, temperatures and dissolved oxygen are controlled. However, if polymerization does occur, it causes heat and pressure to increase. The resultant increase in heat and pressure can cause storage containers to rupture and, if ignited, explode. Polymer formation can lead to plugging of the relief vents or equipment with an increase in fire and explosion risk. Storage areas should be designed to prevent exposure of styrene monomer to fire (see Section 8). Inhibitor levels should be checked daily if styrene monomer is stored at temperatures above 27C (80F). Section 8 contains further information on TBC monitoring. If styrene monomer is involved in a fire, unauthorized individuals should be prevented from entering the area, and the area downwind of the fire should be evacuated. All fires should be fought from a safe distance upwind of the fire. Styrene monomer fires produce carbon dioxide and may produce carbon monoxide upon incomplete combustion. As it decomposes, styrene monomer will emit acrid vapors and may produce a powerful lacrimator (tear producing agent) upon reaction with chlorine or bromine. Heat may build pressure and rupture closed containers. A water fog should be used to cool the containers. Water may be ineffective as an extinguishing agent due to styrene monomers low solubility. The flow of styrene monomer should be stopped before trying to extinguish a fire. Liquid should be kept from entering water sources and sewers by building dikes as necessary to contain the flow. Proper authorities should be notified if styrene monomer enters sewers or public water systems.

Styrene monomer can form explosive mixtures. Sources of ignition including heat, sparks, flames and sources of static electricity should be avoided. Each facility handling styrene monomer should adopt a comprehensive program for fire prevention. The following management systems contribute to an effective fire prevention program: no smoking policy where styrene monomer is used the use of non-sparking tools while working with or near equipment containing styrene monomer grounding metallic containers/vessels in which styrene monomer is stored bonding and grounding metallic containers stringent welding, cutting and burning permit systems implementation of inside and outside storage methods that comply with regulatory requirements and good industry practice

5.2.1

Static Electricity

As with other flammable liquids, the transfer of styrene monomer can create static electricity charges, which can act as an ignition source for 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 1910.106), building and fire codes (NFPA 30, 70 and 77 and API RP-2003) and industry practice. Bonding provides a low-resistance path to current flow between surfaces that are physically separated or become separated. According to NFPA 77, a maximum of one megaohm is acceptable, but generally much lower values are possible. Grounding connects the containment vessels and pipes to a grounding electrode (ground) in the earth by means of conductors welded or attached to both the equipment and the grounding electrode. A 10-ohm maximum is the recommended value for the resistance of the cable and ground.

Product Safety Bulletin 23

Fire Safety 5.3 Fire Suppression 5.4 Fire Fighting

Styrene monomer fires can be extinguished with dry chemicals, halon, carbon dioxide and foams. For large fires, water spray or fog may be effective. However, fixed-foam protection using an application rate of 0.1 gallons per minute per square surface is recommended. Several types of foam are effective. Manufacturers should be contacted for specific recommendations. Water may be ineffective in fighting styrene monomer fires. Water can sometimes be used to extinguish styrene monomer fires when several coordinated hose streams are used to sweep the flames from the surface of the burning liquid. This approach should be used only by experienced firefighters working under favorable conditions. Water spray can also be used to disperse vapors, protect firefighters, absorb heat and protect exposed structures and adjacent storage areas. Portable fire extinguishers should be placed near styrene monomer storage and handling areas. Workers should be trained in the use of portable fire extinguishers (29 CFR 1910.157). Class B dry chemical or foam extinguishers should be used to fight styrene monomer fires. Information on how to select, use, distribute, inspect, maintain and recharge portable fire extinguishers can be found in NFPA 10.

Facilities that rely on local fire authorities should provide them with information on styrene monomer operations and storage, including an illustration of storage locations and quantities of styrene monomer present. Drills should be conducted periodically with the local fire authority, and facility information should be updated regularly. Facilities using internal fire brigades should follow the OSHA Fire Brigade Standard 29 CFR 1910.156. This standard includes information on fire brigade organization, personnel qualification, firefighting equipment and training requirements. Firefighters should use full protective clothing and equipment, including approved self-contained breathing apparatus (see Section 3). If a fire is controllable or styrene monomer 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 styrene monomer containers are exposed to direct flame, an evacuation zone with a minimum radius of 3,000 feet may be required. After a fire has been extinguished, any residual styrene monomer should be cleaned up to prevent another fire or environmental contamination. Individuals involved in a cleanup should be thoroughly trained in proper techniques according to the OSHA Hazardous Waste Operations and Emergency Response (HazWOpER) Standard 29 CFR 1910.120. Refer to Section 7 for additional information on environmental considerations.

Figure 5.1 Flammability Region* for Styrene Monomer Storage


10 9

Concentration in Air (Volume %)

8 7 6 5 4 3 2 1 0

Upper Flammability Limit

Lower Flammability Limit


0 10 20 30

Storage Temperature (C)

40

50

60

70

80

Minimum Oxygen for Combustion (MOC) 9.0 percent *This is the region where flammable vapors exist over styrene monomer liquid at atmospheric pressure. 24 Product Safety Bulletin

6.
6.1

HAZARD COMMUNICATION
OSHA Hazard Communication
good warning properties. Styrene monomer has a sweet, aromatic odor. To determine worker exposure to styrene monomer in air, measurements can be made using air-sampling equipment. A variety of instruments are available to provide instantaneous or continuous monitoring of styrene monomer concentrations in air. Direct-reading instruments including combustible gas indicators, infrared spectrophotometers, flame and photoionization detectors and colorimetric detector tubes can be used to monitor for styrene monomer (see Section 3.4). When assessing worker exposure to styrene monomer, personal breathing zone samples should be collected to determine compliance with the established exposure limits (see Section 3.5). 6.1.1.3 Methods of Protection Hazard communication training must include information on methods of protection that can be used by workers handling styrene monomer. This should include the engineering and administrative controls employed, as well as the PPE to be worn (see Sections 3.3 and 3.4).

Under Hazard Communication and Right to Know Laws, workers and communities should be informed of the potential hazards of styrene monomer. At the federal level, the OSHA Hazard Communication Standard 29 CFR 1910.1200 (see Appendix 4 for citations) requires that employers who use hazardous chemicals, including styrene monomer, in their workplace develop written programs and train workers on the potential hazards and protective measures.

6.1.1

Worker Training

As a user of styrene monomer, an employer must provide information and training on its hazards for workers, the methods for detecting releases and methods of protection from exposure. This information should be included in the Hazard Communication Training Program required by OSHA 29 CFR 1910.1200. To assist in this effort, the following summary information is provided. 6.1.1.1 Hazards Styrene monomer is a highly flammable liquid with a moderately high boiling point and a low vapor pressure. The vapors of styrene monomer are heavier than air and may travel long distances along the ground. These vapors are flammable and will burn or explode. Styrene monomer is very reactive and may self polymerize producing heat and pressure. Avoid contact with heat, flame, oxidizers, peroxides, strong acids, aluminum chloride, metal halides and metal alkyl. It is corrosive to copper and copper alloys and will dissolve many natural and synthetic rubbers. The major hazard associated with repeated daily exposure to low levels of styrene monomer is related to styrene monomers effect on the CNS causing drowsiness, listlessness, nausea and loss of appetite. Skin contact, depending on concentration and duration of exposure, may cause moderate irritation and dermatitis. Eye contact with liquid styrene monomer may cause moderate irritation, including a burning sensation and tears. High vapor concentrations may also cause eye irritation. The International Agency for Research on Cancer (IARC) classified styrene monomer as a possible human carcinogen (Class 2B). The EPA has not classified styrene monomer, and OSHA has determined that there is insufficient evidence to classify this product. For a complete discussion of the health effects of styrene monomer, see Section 2. 6.1.1.2 Methods of Detection Because styrene monomer can be detected via odor at concentrations as low as 0.14 ppm, it is considered to have

6.1.2

Labeling

All incoming containers of styrene monomer are accompanied by a product label providing health and safety information. The product label is a primary source of information for safe handling of this material. Lyondell Chemical Company product labels contain the material identification, principal hazards and Companys name, address and telephone number (see Figure 6.1). Containers of styrene monomer or mixtures containing styrene monomer in concentrations greater than or equal to 0.1 percent must be labeled according to the OSHA Hazard Communication Standard. The DOT labeling requirements for styrene monomer are presented in Section 11.2. Each vessel into which styrene monomer is transferred should be clearly identified as to its contents and the hazards of the materials it contains. Many firms elect to employ the United States National Fire Protection Association (NFPA) 704 Standard System for the Identification of the Fire Hazards of Materials (Hazard Diamond) as a means of in-plant communication to workers, contractors and firefighters. The appropriate numerical hazard classifications for styrene monomer are as follows: Health (Blue): 2 Fire (Red): 3 Reactivity (Yellow): 2

Product Safety Bulletin 25

Hazard Communication
6.1.3 Material Safety Data Sheets

6.2

SARA Title III

Operational Excellence and legislation in most countries, (e.g. Directive 91/155/EEC) require that customers, transporters, etc. should be given the appropriate, necessary information on a chemicals hazards and the precautions/ remedial actions required. This is done through the MSDS, and Lyondell Chemical Company ensures that, as a minimum, provision of such data complies with the requirements of the countries in which they operate. A Lyondell Chemical Company MSDS is provided with the first order and after any change or revision to the MSDS. In some regions, an additional issue is also undertaken with the first delivery of a new year. The MSDS is a primary means of providing information regarding the safe storage, handling, use and ultimate disposal of Lyondell 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 your local Lyondell sales representative, regional sales office or call Customer Service at (888) 777-0232. Lyondell Chemical Company MSDSs are available in several languages and formats. While the additional downstream sales of styrene monomer or materials containing styrene monomer are the responsibility of the distributor, Lyondell Chemical Company will support your hazard communication efforts.

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 that use or store styrene monomer to notify their state emergency response commissions and work with local authorities to develop emergency response plans. Users of styrene monomer should read the SARA Title III regulations and familiarize themselves with its requirements. Because styrene monomer is a potentially hazardous chemical, facilities should submit a copy of their MSDS or their chemical inventory list to their local emergency planning committee (LEPC). This inventory listing should include all mixtures of styrene monomer in excess of 0.1 percent concentration. Lyondell Chemical Company uses values known as Emergency Response Planning Guidelines (ERPGs) to assist in developing strategies for protecting workers and the general public against the harmful effects of styrene monomer. The proposed ERPG values are: ERPG 1 = 50 ppm, EPRG 2 = 100 ppm and ERPG 3 = 1000 ppm. It is believed that all individuals could be exposed to up to 50 ppm for nearly an hour without experiencing any mild or adverse health effects, while 250 ppm is a level in which nearly all individuals could be exposed for up to one hour without experiencing or developing any irreversible health effects that could impair ones ability to take action. At 1000 ppm, individuals could be exposed for up to an hour without developing life-threatening effects.

6.3

State Regulations

State or local regulations are based on the federal legislation, but may have different or more stringent requirements. Facilities should review specific state regulations to assess their applicability to the use of styrene monomer (see Appendix 5).

26

Product Safety Bulletin

Hazard Communication
Figure 6.1 Styrene Monomer Label Information
Manufacturer: LYONDELL CHEMICAL COMPANY 1221 McKinney Houston, TX 77010 Telephone Numbers EMERGENCY (800) 424-9300 Chemtrec (713) 652-7200 CUSTOMER SERVICE (888) 777-0232 Info Only SCID (800) 245-4532

Use Statement: For industrial use only. Keep out of the reach of children. Signal Word: Danger. Physical Hazards: Highly flammable. Reactive, unstable unless inhibited. Health Hazards: Mucous membrane irritant. Skin and eye irritant. Ingestion hazard. Precautionary Measures: Avoid high temperature and shocks. Material is unstable, and hazardous polymerization may occur. Do not handle near heat, sparks or open flame. Keep containers closed when not in use. Do not store near combustible materials. Avoid contact with eyes, skin and clothing. Avoid prolonged or repeated breathing of vapor. Use only with adequate ventilation/personal protection. Prevent contact with food, chewing or smoking materials. DOT Information: UN/NA ID Number - UN 2055 Hazard Class: Flammable Liquid Proper Shipping: Styrene Monomer, Inhibited (RQ 1000 lbs/454 Kg) Component Name: Styrene (CAS Number 100-42-5) 4-tert-Butylcatechol (CAS Number 98-29-3) In case of fire: Dry chemical, CO2, foam FIRST AID Inhalation: 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: For even minor eye contact, immediately rinse with clean water for 2030 minutes. Retract eyelid often. Obtain emergency medical attention. Prompt action is essential. Skin Contact: Immediately remove contaminated clothing. Flush with lukewarm water for 15 minutes. Wash skin thoroughly with mild soap and water. Seek medical attention if ill effect or irritation develops. Ingestion: If a large quantity is swallowed, give lukewarm water (pint) if victim is completely conscious/ alert. Do not induce vomiting, as risk of damage to lungs exceeds poisoning risk. Obtain emergency medical attention. In case of spill: Release can cause a fire and/or explosion hazard. May polymerize and release heat and gases. Extinguish all ignition sources. Blanket with firefighting foam. Impound and recover large land spills if safely possible. Soak up small spills. On water, contain, minimize dispersion and collect if safely possible. Report per regulatory requirements. PROTECTIVE EQUIPMENT Respiratory apparatus: Use NIOSH/MSHA-approved air-purifying or supplied air respirator as appropriate. Eye: Chemical splash goggles and/or face shield. Skin: Protective clothing including gloves, apron, sleeves, boots and full head/face protection.

Product Safety Bulletin 27

7.

ENVIRONMENTAL
emit 10 tons per year of any single air toxic or 25 tons per year of any combinations of air toxics.)

Styrene monomer is an extremely flammable and slightly volatile liquid at ambient temperatures. Spills and leaks require prompt response to minimize the risk of fire and/or explosion, as well as fugitive air emissions. Styrene monomer has a reportable quantity (RQ) of 1,000 pounds. for spills under the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA), and annual reporting is required under 40 CFR 372 (Toxic Chemical Release Reporting: Community Right-to-Know see Appendix 4 for citations). Styrene monomer is slightly soluble in water and is soluble in most organic solvents. It is biodegradable by acclimatised bacterial populations, but surface waters and wastewater treatment plants should be protected from spills. The primary removal mechanism of styrene monomer from water is most likely volatilization, as indicated by its relatively high Henrys Law Constant (2.83 x 10-3 atm/molm3). The primary mechanisms for styrene monomer removal from soils are biodegradation, solubilization by infiltrating water and, in shallow soils, volatilization. Based on its low water solubility and the magnitude of its organic carbon partitioning coefficient (calculated KOC= 260-550), styrene monomers mobility in soil is considered to be moderate to low. Limited bioconcentration experiments indicate that styrene monomer has a relatively low bioconcentration factor, suggesting that it should not bioaccumulate in animals and plants to any significant extent.

7.1.2

Toxic Chemical Release Inventory

Styrene monomer is among the chemicals listed in the Superfund Amendments and Reauthorization Act (SARA) Title III, Section 313 (40 CFR 372). Facilities subject to these regulations are required to submit annual reports listing the quantities of styrene monomer emitted from point sources and as fugitive emissions.

7.1.3

State Requirements

All states which contain National Ambient Air Quality Standards (NAAQS) non-attainment areas are required to revise their State Implementation Plans (SIPs) under the CAAA. Styrene monomer will thus be regulated by individual states to meet the requirements of CAAA. In addition, states may enforce more stringent air emission requirements than the federal standards.

7.2

Clean Water Act

7.1
7.1.1

Air Quality Considerations


Clean Air Act

Styrene monomer is classified as a Volatile Organic Compound (VOC) under the Clean Air Act (CAA). In addition, styrene monomer has been listed as a Hazardous Air Pollutant (HAP) under the Clean Air Act Amendments of 1990 (CAAA). These two classifications are the principal areas under which air emissions of styrene monomer will be regulated. Facilities with the potential to emit styrene monomer may be subject to the CAAA. (Consult with federal, state and local officials to determine other air regulations that may apply.) The EPA has designated various Air Quality Control Regions (AQCR) of the country as either Attainment, Nonattainment or Unclassified for ozone. As a VOC, styrene monomer is subject to the new regulations for ozone nonattainment areas. These regulations require emission controls on industrial sources of VOCs. As a HAP, styrene monomer is subject to regulations by industrial category rather than as an individual compound. Major source facilities in the regulated categories will be required to install Maximum Achievable Control Technology (MACT) and may also be required to adopt process, material or work practice changes to minimize emissions. (Major sources

The discharge of wastes containing styrene monomer to waters of the United States is regulated under the National Pollutant Discharge Elimination System (NPDES) permit program of the Clean Water Act (CWA). Styrene monomer is listed as a hazardous substance under Section 311 (b)(4). Federal Water Quality Criteria for the protection of human health and/or aquatic organisms have not been developed for this compound. Styrene monomer is thus subject to case-by-case determination of NPDES permit limits. Styrene monomer is a regulated organic contaminant under the Safe Drinking Water Act. It has a maximum Containment Level (MCL) of 100 g/L and is subject to regulation in public water systems.

7.2.1

State and Local Water Quality Criteria

The direct and indirect discharge of toxic pollutants to waters of a state may be regulated by state surface water quality criteria and/or effluent limitations, as well as local publicly owned treatment works (POTW) pretreatment requirements. Pretreatment requirements are mandated under federal law to prevent the discharge of pollutants that may create a fire or explosion hazard in sewers or at the POTW that may pass through the POTW or interfere with its normal operations. Applicable state and local regulations should be consulted.

Product Safety Bulletin 29

Environmental
7.2.2 Categorical Standards 7.3.2 Waste Classification

Styrene monomer is not specifically regulated under categorical effluent standards, but may be regulated as a component of chemical or biochemical oxygen demand (COD or BOD) or total organic carbon (TOC).

7.3
7.3.1

Waste Management
Spills and Leaks

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. In the event of a styrene monomer release of 1,000 pounds or more to the environment, the National Response Center must be notified. The telephone number of the National Response Center is (800) 424-8802. The reporting requirement is due to the listing of styrene monomer as a hazardous substance under CERCLA Section 302. Styrene monomer users should also be familiar with any state and local reporting requirements for styrene monomer. Accidental discharges of styrene monomer or process waste containing styrene monomer into the public sewer system or waterways should be immediately evaluated and, if required, reported to local authorities. The discharge should be diluted with copious quantities of water to reduce the fire and explosion hazard. In the event of a spill of styrene monomer, all non-essential personnel should be evacuated and all ignition sources extinguished immediately. After donning the appropriate personal protective equipment (see Section 3), the spill can be covered with firefighting foam (see Section 5.3) to minimize emissions and the potential fire hazard. Depending on the volume and location of the spill, it can be recovered by vacuum truck or adsorbed with solid sorbent and placed in appropriate containers for disposal. Spills into surface water may be cleaned up using a skimmer or vacuum system. Styrene monomer floats on water and also tends to polymerize to form a surface glaze. All power equipment used in cleanup must meet National Electrical Code (NFPA 70) requirements of Class I, Group D areas. The use of water for cleanup should be minimized, but residual styrene monomer should be flushed with water into sump or collection area for subsequent treatment or disposal. Soil contaminated with styrene monomer that exhibits one or more of the hazardous characteristics of 40 CFR 261 should be excavated and transported to an authorized, secure hazardous waste treatment or disposal facility. Other materials contaminated with styrene monomer may be ignitable and should be treated as hazardous until proven otherwise.

Wastes containing styrene monomer are not listed hazardous wastes under the RCRA, but styrene monomer-containing materials may be hazardous under RCRA by virtue of the characteristics of ignitability. Styrene monomer wastes are considered characteristically hazardous if the flash point of the material is below 140F. Hazardous wastes may include, but are not limited to, process wastes containing styrene monomer, styrene monomercontaminated water, soil and debris and empty containers (see 40 CFR 261).

7.3.3

Waste Handling and Storage

The handling and storage of hazardous materials are regulated by OSHA and EPA. OSHA regulation 29 CFR 1910.120 Hazardous Waste Operations and Emergency Response (HazWOpER) applies to the handling of spills of styrene monomer. This regulation applies to personnel engaged in hazardous waste storage, hazardous waste sites and emergency response. EPA regulations 40 CFR 260-272 apply to the storage, handling, transportation and disposal of hazardous wastes. Users of styrene monomer who generate, store, reclaim or tender for transportation and disposal any hazardous waste should review these regulations. Hazardous waste may be held on site for up to 90 days (for generators of small quantities up to 180 days and under certain circumstances 270 days) without a RCRA permit provided that the waste is placed in approved containers and stored in clearly identified areas. Exceptions for generators of small quantities (100-1000kg) are found in 40 CFR 262. Hazardous waste storage areas must be designated so that any spillage of waste is collected. Containers stored in such facilities must be clearly labeled, dated and checked at least weekly (see 40 CFR 264 and 265) for deterioration of containers and containment system caused by corrosion or other factors. If the facility is not exempt as a small-quantity generator, detailed records must be kept. State regulations may specify additional design requirements for temporary hazardous and nonhazardous waste accumulation areas.

30

Product Safety Bulletin

Environmental
7.3.4 Waste Treatment and Disposal

Styrene monomer wastes are not hazardous by (RCRA) definition and may be disposed of either by burning as fuel or by transfer to a permitted disposal facility. Solid wastes may be landfilled or incinerated. Liquid wastes may be treated in an on-site wastewater treatment plant if this will not cause plant upset or violate the NPDES permit limits. They may also be sent to a POTW with local authority approval. Dilute styrene monomer has been shown to be biodegradable under aerobic conditions in a number of studies. Characteristic hazardous wastes containing styrene monomer require disposal at permitted facilities in accordance with RCRA requirements. Hazardous wastes must be treated as specified in the Land Disposal Restrictions (40 CFR 268) prior to their management in a land-based system (e.g. landfill or surface impoundment). Liquid wastes should be collected for incineration, burning as fuels or other treatment. All burning of hazardous waste fuels containing styrene monomer must be in accordance with RCRA and 40 CFR 266. Water contaminated with styrene monomer may be treated by air stripping, chemical oxidation or granular activated carbon (GAC). Vented styrene monomer vapors should be captured by a condenser. Containers used to hold styrene monomer must be drained and then thoroughly rinsed to be considered nonhazardous. Rinsate generated by this washing should be collected and properly disposed. Although not required, it may be desirable to complete a certificate of cleaning, which documents that the containers have been appropriately cleaned and can be reused. Any container that has not been completely water-washed should be considered a potential fire or explosion risk and should not be burned, soldered or welded.

Product Safety Bulletin 31

8.

PRODUCT STORAGE
8.1 Drum Storage

Considerations in the design and construction of styrene monomer storage and handling facilities are flammability, potential to polymerize, environmental contamination and worker exposure. The specific requirements for storing and handling styrene monomer depend on several factors, including volumes stored or handled, container type, mode of transportation, processes used at the facility and the proximity to other hazardous materials. The proper design and construction of storage and handling facilities requires consultation with competent professional engineers. Additional requirements may be imposed by the OSHA Process Safety Management of Highly Hazardous Chemicals 29 CFR 1910.119 (see Appendix 4 for citations). The standard applies to processes involving flammable liquids in quantities of 10,000 pounds or more. Styrene monomer is highly reactive and, therefore, different from other common aromatic compounds in that it will polymerize. Styrene monomer polymerizes slowly at room temperature and more rapidly at elevated temperatures. Polymer formation may be accelerated by any of the following: depleted inhibitor concentration high temperatures acids peroxides oxidizers other catalysts such as dirt and scale insufficient dissolved oxygen levels The rate of polymerization can become uncontrollable. This can lead to hardening and plugging of equipment or, in the worst cases, a fire or explosion. To prevent polymer formation in styrene monomer, TBC inhibitor is typically added at a concentration of 10-15 ppm. In addition to using TBC, temperature control and proper selection of a storage environment should ensure shelf life with the necessary quality specifications.

Indoor storage of styrene monomer should typically be constrained to drum-sized or smaller packagings. Storage should follow the regulations and guidelines for storage of flammable liquids, such as NFPA 30 and 29 CFR 1910. The two most significant considerations for storage of drums containing styrene monomer are temperature and time. Drums of styrene monomer should be kept out of direct sunlight and away from any sources of heat. Preferably, the styrene monomer drums will be kept in an air-conditioned warehouse or even a chilled room. Even where such precautions are possible and especially where they are not, the time duration that styrene monomer is held in inventory must be closely monitored (see Table 8.1). Styrene monomer may be safely stored in steel drums. However, to minimize the risk of premature polymerization, the drums should be lined with a compatible impervious lining. Rust and scale from an unlined drum may promote polymerization of the styrene monomer. If drums containing styrene monomer are observed to be warmer than ambient air temperature, then styrene monomer polymerization may be occurring. The drums should be immediately cooled using a water spray until the temperature of the drums has stabilized. Drum temperatures should then be closely monitored until the material can be used or disposed.

8.2

Storage Tanks

When designing bulk storage facilities for styrene monomer, certain factors should be considered. In addition to normal precautions taken for flammable liquids against fire and explosion hazards, care must be taken to avoid conditions that could cause polymerization and oxidation. Tanks and distribution systems should be designed to eliminate excessive temperatures and contamination from polymer residue left in infrequently used lines and pumps. Additional design features should include inhibitor addition, tank content sampling and recirculation, tank breathing and control of vapor emissions.

Product Safety Bulletin 33

Product Storage
8.2.1 Tank Construction
Circulation is recommended for all styrene monomer storage tanks to facilitate thorough mixing when new monomer or inhibitor is added, to help control monomer temperature and to maintain the required dissolved oxygen in the system. Circulation of tank contents may be achieved by using a swing pipe design or an eductor. For the swing pipe design, the outlet line operates through a floating swing pipe adjusted so the monomer is always withdrawn a few inches below the surface. Warm monomer is withdrawn from the top, circulated and discharged at the bottom of the tank. The other mixing option is to install an eductor inside the tank on the discharge end of the recirculation line. Mixing improves temperature uniformity of the monomer and ensures that samples are representative of the tanks content. The inlet line and outlet line should be at opposite ends of the tank. Valves located below liquid level must be designed to prevent breakage from freezing, heat shock or mechanical stress. Lubricated plug cocks and non-lubricated ball valves lined with Viton are satisfactory. Stainless steel ball valves have been used for styrene monomer service. All valves require routine maintenance to prevent plugging. Considerations in site selection and tank spacing include proximity to other flammable material storage facilities, nearby sources of ignition, accessibility for firefighting and the impact of a vapor cloud explosion on nearby areas. Bulk storage tanks should have fire monitors to provide cooling in the event of an external fire. Article 500 of NFPA 70 (NEX) outlines electrical requirements for handling, transport and storage of styrene monomer and other Class IC 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. Storage tanks should be situated within containment systems that are capable of providing detection and control of an accidental release of styrene monomer from any tank surface and from piping to and from the tank. Containment-system design and operation should conform with NFPA 30. Tanks must also be designed to provide complete drainage. Separate drain lines, a small built-in sump with a bottom drain and floors sloped to the drains are important for complete drainage.

Atmospheric styrene monomer storage tanks should be designed and constructed according to NFPA 30 as it applies to Class IC liquids and API 650 as a minimum. API 620 is also acceptable. This API standard is intended to ensure that tanks possess sufficient structural strength and pressure-relief systems to prevent catastrophic loss of contents either in normal service or under fire conditions. A typical storage tank for styrene monomer can be seen in Figure 8.1. Proper storage conditions are essential to ensure good styrene monomer quality with minimal polymer formation. The storage tank should be clean, constructed of steel with a selfsupporting dome roof for vertical storage tanks. Styrene monomer vapors are not inhibited and can form polymer. The ceiling of the storage tank should be smooth and free of internal superstructure to eliminate sites for polymer formation. Keep an absolute minimum of internal beams, pipes, projections and crevices that can provide places for condensed styrene monomer vapors to accumulate and polymerize. In addition, it is recommended that all internal structural connections be welded. Tank cleanliness is important, as dirt and scale may act as catalysts for polymer formation. Copper and copper-bearing alloys such as brass, bronze and Monel should be avoided because copper will react with the TBC and impart a bluishgreen color to the styrene monomer. Openings in the roof and sidewalls above normal liquid levels should be of large diameter, and the number should be kept to a minimum. Large-diameter openings facilitate easy cleaning and dual-purpose use, where feasible. Tank openings such as vents, arrester plates and man-ways should be inspected every six months for polymer buildup. If polymer buildup occurs, it is a good indication that more serious polymer formation in the form of stalactites on the tank roof may be occurring. The polymer buildup should be removed. Tank linings have proven quite successful in controlling polymerization problems in styrene monomer storage. Liners will cover any scale and oxidation and prevent future scale. A tight, nonporous, non-wettable smooth surface allows the uninhibited styrene monomer vapor condensate to return quickly to the inhibited liquid monomer before polymerization can take place. Baked phenolic, carbon-zinc, modified epoxy and catalyzed epoxy linings have all been used for this type of service. However, these lining are all nonconductive and, at a minimum, the lower portion of the storage tank should be lined with a conductive coating that provides electrical grounding. Inorganic zinc silicate linings have been used for years in styrene monomer service, giving both the conductivity and smooth surface desired. Other comparable linings are available, and the manufacturers of the coating should be consulted for performance and application information. Rubber-based coatings should not be used. The styrene monomer storage tank can be filled from the bottom or top. When using a top-fill line, the line should be extended inside the tank to the bottom so as to prevent static electric discharge. The fill outlet should be below minimal operating level. 34 Product Safety Bulletin

8.2.2

Tank Breather Vents

Tank breather systems should be designed to minimize the emission of vapors. Unloading piping should include an equalization or vapor return line to exchange displaced vapors between the storage tank and the unloading vehicle. Tankventing and emergency relief should comply with API 2000. When designing large storage tanks, it should be noted that it is impractical to install sufficient relief capacity in the event of a runaway polymerization. Therefore, it is critical to maintain the correct inhibitor and oxygen concentrations, control tank temperature and provide tank circulation.
Monel is a registered trademark of Special Metals Corporation.

VAPOR CONTROL SYSTEM See Section 8.2.3

BREATHER AND VENT SYSTEM See Section 8.2.2

TI
FOAM

15

SEE N.F.P.A. 11 STANDARD FOR LOW { FOAM AND COMBINE AGENT SYSTEMEXPANSION

H 4 6 TI LT 2 7 M
Sloped STYRENE Liquid Level

L 9 14 6 TI H TS 8 10 TT 12 6 TI 1 11 13 TA H

LA

LS

REFRIGERATION SYSTEM

OR BARGE

RECYCLE

FROM IMO TANK (Fig. 9-8) TANK TRUCK (Fig. 9-6) TANK CAR (Fig. 9-1)

LI 3

19 M 16 17
INHIBITOR ADDITION POINT

PI

18

20 17

Figure 8.1 Typical Atmosphereic Storage Tank Configuration*


TO PROCESS

See Section 8.2.4

1. CONTAINMENT DIKE . NFPA IDENTIFICATION CODE 8. MANWAY 9. SUCTION LINE AND FLOAT 10. SWING JOINT

6. TEMPERATURE INDICATOR

11. MIXING EDUCTOR/S 12. TEMPERATURE TRANSMITTER 13. TEMPERATURE SWITCH HIGH 14. TEMPERATURE ALARM HIGH 15. FOAM CHAMBER/FOAM MAKER

16. STRAINER 17. GROUND WIRE 18. PUMP 19. PRESSURE INDICATOR W/SEAL 20. CHECK VALVE

2. LEVEL TRANSMITTE

3. LEVEL INDICATOR

4. LEVEL SWITCH HIGH/LOW

5. LEVEL ALARM HIGH/LOW

Product Safety Bulletin 35

Product Storage

*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 the applicable requirements.

Product Storage
Figure 8.2 Decrease of TBC Concentration in Styrene Monomer
20

Initial Concentration 10 ppm 15 ppm 20 ppm

18

16

TBC Concentration (ppm)

14

12

10

DO NOT ALLOW TO FALL BELOW THIS LIMIT

10

12

14

Weeks at Room Temperature 19 C (68 F)

8.2.3

Control of Vapor Emissions

Table 8.1

Styrene Monomer Storage Time*


Frequency of TBC Monitoring Daily Daily Twice a week Weekly Storage Time 3 days 2 weeks 5 weeks 3 months

Bulk storage tanks should be vented to a vapor collection and containment system that effectively eliminates discharges of styrene monomer vapors to the atmosphere. The exchange of vapors between the bulk delivery vehicle and the storage tank through an equalization line may be used. Different types of vapor recovery systems are available. These include carbon adsorption beds, condensers, incinerators, flares and thermal oxidizers. Emission reductions may be achieved by reducing tank temperatures. The venting or collection system should be designed to prevent the passage of a flame or explosion from one container to another.

Temperature 35C/95F 29C/85F 24C/75F 18C/65F

*TBC levels maintained at 15 ppm The levels of 4-tert-Butylcatechol should be monitored on a routine basis (see Table 8.1 and Appendix 6). Polymer and color analyses should be conducted at the same frequency as the TBC analysis. The preferred method for 4-tert-Butylcatechol analysis is the ASTM Method D-4590. A Visual Quick Test Method is provided in Appendix 6 for use when rapid test results are justified. If TBC levels fall below 10 ppm, inhibitor should be added to bring the level up to 10-15 ppm. The 4-tert-Butylcatechol concentrations should never fall below 4 ppm. Depending on tank conditions, incipient polymerization may occur at this level. This is evidenced by a slight increase in styrene monomer viscosity and/or temperature. Polymer formation is shown by diluting one part of styrene monomer with 10 parts methanol and observing a cloudy solution. The exact polymer level can be determined using ASTM Method D-2121, Method A.

8.2.4

Inhibitor Control

Lyondell Chemical Company adds 4-tert-Butylcatechol to all styrene monomer. It acts as an inhibitor to prevent polymer formation. The standard addition rate is 10-15 ppm. This level of inhibitor permits the use of styrene monomer in most applications while still providing good shelf life. Higher levels of TBC may be added to meet customer specifications. Another important factor for product stability is the effect of TBC depletion over time in styrene monomer. Table 8.1 shows maximum recommended storage times as a function of tank contents temperature. This table should be considered only a guideline, as other factors will also influence stability.

36

Product Safety Bulletin

Product Storage
The 4-tert-Butylcatechol levels will be depleted if tank temperatures are too high (see Figure 8.2). Tank temperatures should generally be maintained below 21C (70F). Lower temperatures are recommended if styrene monomer will be stored for extended periods. Tank temperatures can be reduced in warmer climates by tank insulation, reflective painting and circulation. Refrigeration should be provided when no other means exist to maintain tank temperatures below 21C. Tanks should be equipped with recirculation lines and pumps to aid in cooling, in addition to providing mixing and dissolved oxygen requirements. Recirculation of process and offloading lines should be considered where there is a potential for extended holdup of material. Temperature indicators should be provided at various levels in the tank. If infrequent temperature checks are made, a temperature alarm system may also be provided. The 4-tert-Butylcatechol inhibitor requires dissolved oxygen to work effectively. The minimum required dissolved oxygen level in styrene monomer is approximately 20 ppm. This can be maintained easily by recirculation of the styrene monomer in an air blanketed storage tank at least three to four times per week. If oxygen is totally removed from a storage tank by using a nitrogen blanket, dissolved oxygen will be removed and TBC becomes ineffective, leading to polymerization. Nitrogen blanketing is only recommended for short-term storage. If an inert gas is used as a blanket for extended storage, the oxygen content in the vapor phase should be controlled between 2 and 6 volume percent. This oxygen content will provide sufficient dissolved oxygen for TBC as well as prevent flammability. An oxygen analyzer may be useful to maintain proper oxygen content under this storage condition. When TBC addition is needed, it can be made most easily by adding a TBC solution of 85 percent TBC and 15 percent methanol supplied directly by the manufacturer. It may be added through the suction line of the recirculation pump. Each 20,000 liter increment of styrene monomer should have 210 gm of TBC solution added to an approximate 10 ppm TBC concentration. The TBC will only be effective when the tank is circulated and thoroughly mixed. Lyondell Chemical Company has TBC available at all terminal facilities to adjust the level to specific customer requirements. According to API 2350, instrumentation at the loading station should warn the operator of the potential for overfilling and shut off flow whenever overfill is imminent. Neither device is to be used as a regular operating tool for determining tank level. Styrene monomer collection systems should be large enough to contain the worst credible accidental release of styrene monomer, 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 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 with an impermeable membrane or ballast installed over an impermeable barrier suitable for the retention of styrene monomer. The drainage surfaces should be pitched with a grade of at least 1 percent toward the collection basin or sump. The sump or catch-basin should have fire seals and should be equipped with instruments that will reliably detect liquid levels and the presence of styrene monomer vapor. Rain water and spills trapped inside the containment area are to be disposed of through the sump or catch-basin. Discharge valves from the collection area should be closed under normal conditions. Accumulated liquids should be disposed of only by a trained operator after determining the liquids composition. Lighting adequate for nighttime unloading operations should be provided, unless all unloading will be done during daylight. A suitable method of discharging container contents should be provided. Acceptable methods include gravity flow, pumping from the top through a dip pipe or pressurization with nitrogen. If nitrogen pressurization is used, the facility should be designed to avoid over-pressurization of the vessel. Furthermore, a means of collection and environmentally acceptable treatment of the vapor (e.g., flaring or scrubbing) should be provided. Vapor containment systems should be designed to remove or recover vapor (see Section 4). Additionally, nitrogen containing 2 to 6 vol% oxygen should be used (see Section 8.2.4). The location of tank car loading and unloading should be distant from general activity, ignition sources and traffic. The ground should be sloped toward a containment area to permit recovery or disposal of any spills. An automatic deluge sprinkler system should protect the loading facility and rail tank car. A fire-water monitor nozzle should be located within 40 feet of the tank car and should have an unobstructed path to the target. Dry-powder or carbon dioxide fire extinguishers should also be present.

8.3

Unloading Installations

The installation for unloading rail tank cars and tank trucks of styrene monomer should be designed, maintained and operated to meet current standards for fire protection, worker safety and environmental safety. Loading racks should be located at least 150 feet from all equipment and tanks according to NFPA 30. Electrical wiring and devices should comply with NFPA 70. Piping throughout the installation should comply with NFPA 30 or with ASME/ ANSI B31.3. Piping systems for tank trucks and tank cars should be connected to a common earth ground and bonded to the discharge system. Continuity to ground should be checked prior to unloading.

Product Safety Bulletin 37

Product Storage 8.4 Workplace Location

Processing operations using styrene monomer should be located and operated to minimize the potential risk of fire and explosion and any possible consequence. The minimum distance of a processing vessel to any adjoining property or building is based on the stability of the chemical (see NFPA 30). These distance requirements do not apply where a vessel is located in a building and the exterior blank wall facing the vessel is more than 25 feet away and has a two-hour fire rating and is explosion-resistant. When a blank wall with a four-hour or greater fire resistance rating is provided, there are no distance requirements. In the case of styrene monomer, the wall must be explosion-resistant. According to NFPA 30, 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 that has a two-hour fire rating and is explosion-resistant. The operating facility should be accessible from at least one side for firefighting. For appropriate fire extinguisher types, refer to Section 5.3. Facilities storing or using styrene monomer should use either a gravity or continuous mechanical-exhaust ventilation system. If styrene monomer is dispensed within the room, mechanical ventilation is required. Dispensing of styrene monomer in the warehouse is not recommended unless the dispensing area is suitably separated from the other combustible or styrene monomer storage area.

38

Product Safety Bulletin

9.

TRANSFER OPERATIONS
9.2 Tank Cars DOT 111A

Styrene monomer should be transferred and handled according to written operating procedures developed for the specific facility. This section includes guidelines used by Lyondell Chemical Company in its handling of styrene monomer. Operating procedures should address the hazards associated with this material (see Section 6), the selection of personal protective clothing and equipment (see Section 3) and fireprevention methods (see Section 5). Only workers trained in proper operating procedures should handle styrene monomer. Dedicated unloading lines are recommended for styrene monomer service. All unloading lines should be purged with an inert gas before and after use to prevent air from entering the storage system or to prevent spilling of liquid styrene monomer.

Lyondell Chemical Company ships styrene monomer in DOT 111A tank cars (see Figure 9.1). Refer to 49 CFR 174 Subparts C and G (see Appendix 4 for citations) for DOT unloading regulations. The following procedures are comparable to those used by Lyondell Chemical Company for unloading tanks cars and can be used as a basis for site-specific procedures. A suggested unloading checklist is provided in Figure 9.2.

9.2.1

Unloading Procedures

9.1

Work Preparation

When unloading vessels or containers, workers should have the following equipment and supplies available: Functional local eyewash stations and safety showers Non-sparking tools Unloading block valve Stainless steel double-braided accordion-type hose Grounding connectors Nitrogen supply with pressure regulator and check valve The consignee should determine that tank ullage (sufficient capacity) is available to accept the shipment. Ensure that all high-level warning devices are activated and functioning. Verify that the material is styrene monomer by confirming that the identification number is UN 2055 and by review of the shipping documents and delivery schedule. In certain circumstances and conditions, a second person should verify proper valve positioning to confirm that the piping is routed to the correct receiving tank. This may be advisable in multi-tank bulk storage tank farms that have complicated piping runs and contain other incompatible strong acids, bases or oxidizers (see Sections 1.4 and 1.5). Visually inspect containers for structural damage or tampering in transit. Wet spots may be an indication of leaks. Look for evidence of discharge from pressure relief valves. Styrene monomer is supplied with an inhibitor to prevent self-polymerization. Inhibitor depletion can occur during extended transportation delays and exposure to high temperatures. If product is received at high temperature or pressure, a self-polymerization reaction may be occurring. For more information on polymerization hazards, see Section 1.6.

The unloading procedures for rail/tank cars are as follows: 1. Gather all necessary equipment. For tank car unloading, also include: wheel chocks DOT-approved STOP signs derailer 2. Position the tank car correctly with respect to the unloading station, then set its brake and chock one wheel on both sides. 3. Place DOT-approved, blue rectangular STOP signs at both ends of the car between rails. Place an additional sign at the rail siding switch. 4. Place a derailer on the rail siding between the car and the siding switch. Lock derailer, if possible. 5. Be sure that the receiving tanks ullage (available space) is sufficient to receive the full load with room to spare after the transfer is complete. 6. Identify all pipelines so proper valve alignment can be made. 7. Connect ground cable to car and check for continuity. 8. Remove and read the Lyondell Chemical Company label attached to the cars outlet valve. Make sure that it identifies the cars contents as styrene monomer. Also, remove the one-eighth inch wire cable seal and verify the seal number with the paperwork. 9. Determine that the unloading stations spill collection sump drain is closed and that the sump is substantially free of accumulated liquid. 10. A sample can be taken, if needed, by using the three-fourths inch sample valve at the top of the car. 11. Some tank cars may contain equipment for optional nitrogen padding during off-loading. Tank car should be unloaded with air only if the product temperature is below the lower flammable limit (see Figure 5.1). If product temperature is above lower flammable limit, unload under nitrogen. Connect the nitrogen or dry air line to the one inch threaded air line valve at the top of the car and open the valve. The recommended psig is 20-30 for unloading if not using a pump. If using a pump, you must feed nitrogen or air in at a rate that will displace the liquid as the car is being unloaded to prevent the tank from implosion. Product Safety Bulletin 39

Transfer Operations
12. Attach flexible unloading hose to the cars bottom outlet valve after ensuring that all parts including gaskets and O-rings are in good condition. 13. Set valves in fixed piping to begin transfer. 14. Open cars external (lower) bottom valve. 15. Open cars internal bottom valve. Check carefully for leakage. If any is noted, take remedial action. 16. Start transfer pump. 17. Immediately make a visual check for leaks, especially at places where seals and O-rings are present; shut down immediately and take remedial action if leaks are observed. 18. Check that receiving tanks level is rising at the expected rate for the transfer system. 19. Monitor the transfer. When the tank car is empty, close pump discharge valve and immediately shut off pump. 20. Close valves connecting transfer line and pump to receiving tank. 21. Close tanks internal and external bottom outlet valves. 22. Disconnect unloading hose, taking precautions to catch residual styrene monomer for proper disposal. 23. Close and secure manway latch.

9.2.2

Release of Empty Car

The following steps complete the process of unloading tank cars: 1. Disconnect the ground cable. 2. Remove the wheel chocks, derailer, blue flag and caution signs. Leave the car brakes engaged for railroad crew to release. 3. Make sure placards are affixed for return trip. 4. If there were any mechanical problems with the tank car, advise Lyondell Chemical Company Customer Service at (888) 777-0232.

Figure 9.1 Typical Tank Car 111A-100W Configuration*


11 10 10 8 TO 7 5 6 12 10 9 TO 4 5 16 13 10 15 ATM 14 NITROGEN SUPPLY 17 10 18 16 FROM SHUTDOWN INTERLOCKS 19 10 13 10 TO STORAGE (Figure 8-1)

M 10

STYRENE MONOMER STABILIZED


21 3 39 2055 2 20 22

TO PUMP 23

1. WHEEL CHOCKS (BOTH SIDES OF WHEEL) 3. HAZARD INDICATION PLACARD 2. LABEL (FLAMMABLE LIQUID)

9. DRY DISCONNECT & FLEX. HOSE 10. ISOLATING VALVE

ASSEMBLY (FOR TOP UNLOADING)

16. APPROVED GROUND 17. STRAINER 18. PUMP

4. DRY DISCONNECT & FLEX. HOSE 5. SAFETY VALVE

ASSEMBLY (FOR BOTTOM UNLOADING)

12. NITROGEN HIGH POINT PURGE 14. PRESSURE SAFETY VALVE 13. CHECK VALVE

11. PRESSURE GAUGE

19. PRESSURE GAUGE W/DIAPHRAGM SEAL 21. HAND BRAKE WHEEL 23. APPROVED GROUND CLAMP 22. DERAILER 20. HANDRAIL

6. MANWAY

8. FLEX. HOSE ASSEMBLY

7. VAPOR RETURN/AIR/NITROGEN CONNECTION

15. PRESSURE CONTROL VALVE

*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 the applicable requirements.

40

Product Safety Bulletin

Transfer Operations
Figure 9.2 Styrene Monomer Unloading Checklist DOT 111A

Tank Car Number: Operator:


Prior to Unloading Tank Car

Date: Time:
AM/PM
Yes No

Wheels chocked and hand brakes engaged ................................................................. Blue ag and derailer in place ........................................................................................ Metal caution signs located in front of and behind tank car .......................................... Storage tank capacity and tank car liquid level determined before lling...................... Proper piping alignment made and checked ................................................................. Product hose and ttings visually inspected prior to use ............................................... Eyebath and safety shower ushed and ready............................................................... Ground cable to car connected and checked for continuity .......................................... N2 hose hooked up to vapor valve ................................................................................. Transfer started and system visually checked for leaks ................................................. Qualied operator in attendance during transfer............................................................ After Unloading Tank Car Yes No

When tank car is empty, shut down the pump................................................................ Unloading line valve closed to the storage tank ............................................................. Tank car liquid unloading valve closed .......................................................................... N2 valve closed .............................................................................................................. Transfer line disconnected and residual liquid collected ............................................... Manway cover secured................................................................................................... Ground cable disconnected ........................................................................................... Are placards afxed and in good condition?.................................................................. Blue ag and derailer device removed........................................................................... Wheel chocks removed................................................................................................... Car brake left engaged for railway crew.........................................................................
Advise Lyondell Chemical Company of any mechanical problems at (888) 777-0232.

Product Safety Bulletin 41

Transfer Operations 9.3 Tank Cars DOT 105J


2. Position the tank car correctly with respect to the unloading station, then set its brake and chock one wheel on both sides. 3. Place DOT-approved, blue rectangular STOP signs at both ends of the car between rails. Place an additional sign at the rail-siding switch. 4. Place a derailer on the rail siding between the car and the siding switch. 5. Connect ground cable to car and check for continuity. 6. Remove the one-eighth inch wire cable seal and verify the seal number with the paperwork. 7. 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 9.5).

Lyondell Chemical Company also ships styrene monomer in DOT 105J tank cars (see Figure 9.3). These tank cars are top unloaded by pressure or pumping. Refer to 49 CFR 174 for DOT unloading regulations. The following procedures are comparable to those used by Lyondell Chemical Company for unloading tanks cars and can be used as a basis for site-specific procedures. A suggested unloading checklist is provided in Figure 9.4.

9.3.1

Unloading Procedures

The unloading procedures for tank cars are as follows: 1. Gather all necessary equipment. For tank car unloading, also include: wheel chocks DOT-approved STOP sign derailer

8. 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, tighten fittings and recheck.

Figure 9.3 Typical Tank Car 105-J Configuration*

STYRENE MONOMER STABILIZED

WHEEL CHOCKS (Both Sides of Wheel)

*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 the applicable requirements.

42

Product Safety Bulletin

Transfer Operations
Figure 9.4 Styrene Monomer Unloading Checklist DOT 105J

Tank Car Number: Operator:


Prior to Unloading Tank Car

Date: Time:
AM/PM
Yes No

Wheels chocked and hand brakes engaged ................................................................. Blue ag and derailer in place ........................................................................................ Metal caution signs located in front of and behind tank car .......................................... Eyebath and safety shower ushed and ready............................................................... Ground cable to car connected and checked for continuity .......................................... Pressure dome inspected for leakage around valves and ttings.................................. Bill of lading checked and sample veried..................................................................... Cericate of analysis and placards checked.................................................................. Storage tank capacity and tank car liquid level determined before lling...................... Load and vent-back lines connected, purged and tested for leaks............................... Proper piping alignment made and checked ................................................................. Open transfer lines and monitor liquid level ................................................................... Qualied operator in attendance during transfer............................................................ After Unloading Tank Car Yes No

When tank car is empty, shut down the pump................................................................ Transfer line blown clear of styrene monomer ................................................................ Unloading line valve closed to the storage tank and the storage tank vent ................... Tank car vapor valve and liquid unloading valve closed................................................ Transfer line vented of pressure .................................................................................... Transfer, nitrogen and storage tank vent lines disconnected ........................................ Test for leakage and secure dome cover ....................................................................... Ground cable disconnected ........................................................................................... Are placards afxed and in good condition?.................................................................. Blue ag, metal caution signs and derailer device removed.......................................... Wheel chocks removed................................................................................................... Car brake left engaged for railroad crew........................................................................
Advise Lyondell Chemical Company of any mechanical problems at (888) 777-0232.

Product Safety Bulletin 43

Transfer Operations
Figure 9.5 Typical Tank Car Dome Configuration*

*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 the applicable requirements.

44

Product Safety Bulletin

Transfer Operations
9. If a sample from the tank car is required to confirm its contents, the following procedure may be used: Sample tank car through the sample line, which is located in the pressure dome area. Fill the sample bottle leaving approximately 20 percent vapor space to allow for expansion. If closed sampling system is not employed, proper personal protective equipment should be used. 10. Determine the receiving tank ullage (available space) and the liquid level in the tank car before transfer. 11. Attach nitrogen or vapor return line to the vapor valve. 12. Attach flexible hose to the liquid unloading (eduction) valve. 13. Open vapor valve. If product will be unloaded under nitrogen pressure, open vapor valve and use a regulator to adjust the nitrogen pressure to equalize that of the tank car. This will force liquid styrene monomer into unloading hose. Nitrogen should be supplied in nominal pressures to equalize the tank and ensure the pressure supply is compatible with unloading system. 14. Open liquid unloading valve and allow styrene monomer to fill the pump by opening the liquid line block valves. These valves must be opened slowly to avoid activating the excess flow valve. Start pump and begin pumping styrene monomer to the storage tank. A positive pressure should be maintained on the tank car to keep the pump from pulling a vacuum on the car. Monitor this closely. 15. Check that the receiving tanks level is rising at the expected rate for the transfer system. 16. Monitor the transfer. When the tank car is empty, immediately shut off pump. 17. Clear the transfer line. 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. Disconnect transfer, nitrogen and storage tank vent lines. 18. Test for leakage by pouring soapy water over the valves. If bubbles are present, retighten all valves and retest. If leaks are still detected, contact Lyondell Chemical Company Customer Service before shipping.

figure 9.6

typical tank truck configuration*

TO PART NO. 7 19

STYRENE MONOMER STABILIZED

DOT 407 DOT 412

17 4
CHEMTREC 800/424-9300

ATM AIR SUPPLY OR VAPOR BALANCE LINE

12

13

20 18

21

1 10 To Part 11 2 2 14 11 14

M 15 14 16

17 TO STORAGE (Figure 8-1)

1. REAR END PROTECTION 2. WHEEL CHOCKS (BOTH SIDES OF WHEEL) 3. CHEMTREC EMERGENCY NUMBER (800) 424-9300 4. DOT PLACARD (Figure 11.2) (ALL 4 SIDES) 5. MANHOLE ASSY. & OVERTURN PROTECTION 6. CUSTOMER VENT 7. AIR INLET ASSEMBLY 8. PRESSURE VENT

9. VACUUM BEAKER 10. OUTLET VALVE 11. FLEX. HOSE ASSEMBLY 12. GAUGING DEVICE 13. CERTIFICATION PLATE 14. GROUND WIRE 15. STRAINER 16. PUMP

17. CHECK VALVE 18. PRESSURE GAUGE 19. FLEX. HOSE ASSEMBLY 20. PRESSURE RELIEF VALVE 21. PRESSURE CONTROL VALVE 22. DOT CLASSIFICATION NUMBER

*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 the applicable requirements.

Product Safety Bulletin 45

Transfer Operations
9.3.2 Release of Empty Car
11. Trucks are equipped for nitrogen unloading. Attach N2 line and open valve. Tank cars should be unloaded with air only if the product temperature is below the lower flammable limit. If product temperature is above lower flammable limit, unload under nitrogen. 12. Connect a flexible unloading hose to bottom discharge valve connector. 13. Set valves in fixed piping to begin the transfer. 14. Open tank trucks external (lower) outlet valve. 15. Open tank trucks internal bottom valve. Check carefully for leakage. If any is noted, take remedial action. 16. Start transfer pump. 17. Immediately make a visual check for leaks, especially at places where seals and O-rings are present. If leaks are observed, shut down immediately and take remedial action. 18. Check that the receiving tanks level is rising at the expected rate for the transfer system. 19. Monitor the transfer. When the tank truck is empty, close pump-discharge valve and immediately shut off pump. 20. Close valves connecting transfer line and pump to receiving tank. 21. Close the trailers internal and external bottom outlet valves. 22. Disconnect unloading hose, taking precautions to catch residual styrene monomer for proper disposal. Store hose in a protected location. 23. Close and secure the manway cover. 24. Pad with N2.

The following steps complete the process of unloading tank cars: 1. Ensure that all valves are closed, and caps/plugs are in place and are tightened. 2. Disconnect the ground cable. 3. Remove the wheel chocks, derailer, blue flag and caution signs. Leave the car brakes engaged for railroad crew to release. 4. Make sure placards are affixed and in good condition. 5. If there were any mechanical problems with the tank car, advise Lyondell Chemical Company Customer Service.

9.4

Tank Trucks

Lyondell Chemical Company ships styrene monomer in DOT 407 stainless steel tank trucks with approximate capacity of 5,500 to 6,500 gallons. DOT 412 tank trucks are also acceptable. They are normally bottom unloaded by gravity or pumped through a valve located at the bottom of the truck (see Figure 9.6). Refer to 49 CFR 177 for information on unloading regulations. The following procedures are comparable to those used by Lyondell Chemical Company for unloading tank trucks and can be used as a basis for developing site-specific procedures for unloading styrene monomer. A suggested unloading checklist is provided in Figure 9.7.

9.4.1

Unloading Procedures

The unloading procedures for tank trucks are as follows: 1. Gather all necessary equipment. For tank truck unloading, also include: road barriers wheel chocks 2. Instruct driver to position tank truck for unloading at designated station, then set brakes, shut off engine and leave cab. The driver should remain in a designated area. 3. Safeguard truck from nearby traffic by putting up road barriers or warning lights. 4. Chock both sides of one tank truck wheel. 5. Attach ground connectors and ensure continuity to ground. 6. Remove and read the label attached to the tank trucks outlet valve to confirm that its contents are styrene monomer. 7. Visually inspect hoses and fittings prior to use. 8. Determine that the receiving storage tank has sufficient capacity to hold the entire contents of the tank truck. 9. Identify all pipelines so that proper valve alignment can be made. 10. Determine that the unloading stations spill-collection sump drain is closed and substantially free of accumulated liquid.

9.4.2

Release of Empty Truck

The following steps complete the process of unloading tank trucks: 1. Ensure that all valves are closed, and caps/plugs are in place and are tightened. 2. Disconnect the ground cable. Remove the wheel chocks and traffic-control devices. 3. Ensure that tank truck placards for the return trip meet DOT requirements. Ensure truck has been resealed. 4. Release the vehicle to the driver. 5. If there were any mechanical problems with the tank truck, advise Lyondell Chemical Company Customer Service.

46

Product Safety Bulletin

Transfer Operations
Figure 9.7 Styrene Monomer Unloading Checklist DOT 407

Tank Car Number: Operator:


Prior to Unloading Tank Truck

Date: Time:
AM/PM
Yes No

Trailer safeguarded with road barriers/warning lights .................................................... Wheels chocked and parking brakes engaged.............................................................. Ground cable to truck connected and checked for continuity ....................................... Storage tank capacity checked ...................................................................................... Proper piping alignment made and checked ................................................................. Product hose and ttings visually inspected prior to use ............................................... Eyebath and safety shower ushed and ready............................................................... N2 hooked up to vapor connection ................................................................................ Transfer started and system visually checked for leaks ................................................. Qualied operator in attendance during transfer............................................................ After Unloading Tank Truck Yes No

When tank truck is empty, shut down the pump............................................................. Unloading line valve closed to the storage tank ............................................................. Tank trucks internal and external bottom outlet valves closed ...................................... Transfer line disconnected and residual liquid collected ............................................... Manway cover secured................................................................................................... Ground cable disconnected ........................................................................................... Placards proper for shipment ......................................................................................... Wheel chocks removed...................................................................................................
Advise Lyondell Chemical Company of any mechanical problems at (888) 777-0232.

Product Safety Bulletin 47

Transfer Operations 9.5 ISO Tanks

Lyondell Chemical Company ships styrene momomer in intermodal bulk transport tanks meeting IM 101 (T2 tank container) specifications. These tanks contain up to 4,800 gallons of styrene monomer and are shipped at atmospheric pressure. The unloading valve is located at the rear bottom end of the tank (see Figure 9.8). International Organization for Standardization (ISO) tank work preparation and unloading procedures are essentially the same as those in this section.

Figure 9.8 Typical T2 Tank Configuration


ATM 24 16 AIR SUPPLY OR VAPOR BALANCE LINE

17 14 15 13 10 STYRENE MONOMER STABILIZED 25 9 (2) 11 12 1

6 IM-101 23 5

FROM SHUTDOWN INTERLOCKS

27 7 CHEMTREC (800) 424-9300

20 8 22 4 18 19 21 21 15 M TO STORAGE See Figure 8-1

21

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 STYRENE SERVICE) 8. THERMOMETER

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

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

19. 20. 21. 22. 23. 24. 25.

PUMP PRESSURE GAUGE W/DIAPHRAGM SEAL GROUND WIRE FLEXIBLE HOSE ASSEMBLY DOT CLASSIFICATION NO. PRESSURE GAUGE DOT PLACARD (Figure 11.2) ALL 4 SIDES 26. CHEMTREC EMERGENCY NUMBER (800) 424-9300 27. CARRIERS NAME CONTAINER OWNER/LESSORS NAME CERTIFICATION DECALS

*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 the applicable requirements.

48

Product Safety Bulletin

Transfer Operations 9.6 Marine Transport


Independent inspectors or surveyors take quality and quantity measurements to ensure that styrene monomer is loaded only into uncontaminated tanks. Tanks or compartments should be in dedicated service for styrene monomer. Where tanks or compartments are not in dedicated service, a cleaning certificate along with a list of the last three cargos will be required prior to loading. In addition, all tanks and compartments receive an additional check at the one foot fill level to insure product quality. Lyondell Chemical Company has detailed guidelines available for inspectors. Styrene monomer is normally loaded at a temperature less than 21C (70F), with a TBC inhibitor content of between 10-15 ppm and a dissolved oxygen content of approximately 20 ppm. For short duration trips (approximately 10 days), no additional precautions are usually needed to prevent polymerization. If extended delays are expected or incurred, daily product temperature checks should be conducted. An increase in product temperature may be an indication of polymerization. To reduce and control polymerization, additional TBC can be added. For extended trips, lower product temperature and higher TBC content can be arranged. Chemical container ships used for long hauls may require refrigeration of styrene monomer. Daily temperature checks may be required. 4-tert-Butylcatechol inhibitor, in solution, should be available for addition in case of polymerization. Styrene monomer should not be stored adjacent to tanks or compartments that are heated. Shifting of the styrene monomer to other tanks or compartments should be avoided. Styrene monomer quality and reactivity can be adversely affected by low levels of any contaminant present. As with other handling operations, the unloading of barges or ships that contain hazardous materials such as styrene monomer must only be carried out by fully trained personnel equipped with all necessary information, PPE and suitable equipment, following correct operating procedures. In the event of any problems that may affect product, or any indications of polymerization, contact Lyondell Chemical Company Customer Service immediately.

A customer considering receipt of styrene monomer by water for the first time should contact Lyondell Chemical Company Customer Service for specific requirements. Styrene monomer handling in marine transport is similar to that required for other flammable liquid hydrocarbons. However, a number of areas may be different and should be evaluated before handling styrene monomer. These areas are: 1. Materials Compatibility As discussed in Section 4, materials requirements for styrene monomer should be reviewed. Specifically, check compatibility of loading hoses and tank and compartment liners or coatings. 2. Water Solubility Styrene monomer is minimally soluble in and somewhat lighter than water. Contact with water should be avoided to maintain product quality. Also, any water contaminated with styrene monomer should be evaluated for waste classification (Section 7) and proper disposal. 3. Fire Foams As discussed in Section 5, fire foams should be evaluated to determine if alcohol resistant foams are required. 4. Exposure Any vented marine transfer operations should be monitored to insure that vapor exposure is below the limits discussed in Section 3. Exposure to high levels of styrene monomer can result in eye, skin and respiratory irritation and anesthetic-like effects (see Section 2). Although styrene monomer has low atmospheric reactivity, vapor recovery during marine loading operations may be utilized, particularly in ozone-containment areas. In the event that vapor recovery is utilized, Coast Guard regulations require that the Maximum Experimental Safe Gap (MESG) be evaluated to determine proper fire protection equipment. The MESG for styrene monomer is .95 mm. All barges to be loaded at Lyondell Chemical Companys Houston facility must be Coast Guard certified. Certification will require the installation of a vapor recovery system. In the case of a marine spill, styrene monomer should form a slick which will slowly volatilize. Because of styrene monomers low water solubility, little of the spilled styrene monomer will dissolve into the water. The amount that dissolves will depend on a number of factors including air and water temperatures and turbulence. General spill handling guidelines are given in Section 7.

Product Safety Bulletin 49

10. TANK CLEANING AND EQUIPMENT REPAIR


10.1 Work Preparation
Proper preparation for cleaning or maintaining styrene monomer storage vessels and equipment is necessary to prevent fire or harm to workers or the environment. Only fully trained and properly equipped workers should clean or repair styrene monomer tanks and equipment. A hazardous work permit system should be established before any maintenance or inspection activities involving hot work, line breaking or confined-space entry are performed. A permit should identify all job-related hazards and include a work plan to address them. Facilities should use engineering controls and appropriate personal protective equipment. Before opening, tanks and equipment that contained styrene monomer should be emptied of all liquid by draining at low points. Tanks and equipment should then be purged with an inert gas, then air, to a vapor management system, or they should be flushed with water. Eyewash and safety showers should be located near the work area. Appropriate fire extinguishing equipment should be present (see Section 5.3). Permit Required Confined Space (PRCS) program requirements include: 1. Written program 2. Identify and classify spaces 3. Establish hazard control measures Prevent unauthorized entry Establish acceptable conditions Isolation Ventilation Coordinate entry by multiple workers Periodic re-evaluation for change of conditions 4. Develop permit system Preparation Issuance Implementation Cancellation Returning space to service 5. Provide specialized equipment Atmospheric monitoring Ventilation PPE Lighting Communication Emergency 6. Designate key personnel Entrants Attendants Entry supervisor Qualified atmospheric tester Emergency response 7. Perform testing and monitoring Prior to entry and periodically during entry and work 8. Establish rescue and emergency procedures 9. Procedures for contractors multi-employer work sites 10. Provide information and training 11. Conduct program review

10.2 Control of Hazardous Energy


A facilitys procedures for controlling hazardous energy sources should comply with the requirements of 29 CFR 1910.147 (see Appendix 4 for citations). These procedures should be used to protect workers in areas where styrene monomer vessels or equipment are cleaned, maintained or entered. After styrene monomer has been purged, positive measures should be taken to ensure that all potential sources of styrene monomer or hazardous energy are physically tagged or locked out and affected persons notified. Personal protective equipment should be worn by workers who might be exposed to styrene monomer residue.

10.3 Confined Space Entry


The OSHA standard (29 CFR 1910.146) establishes requirements for entry into confined spaces. An OSHA confined space is defined as a work zone large enough and so configured to permit entry and work, has limited openings for entry or exit and is not designed for continuous human occupancy. A confined space may present one or more of the following characteristics: a toxic, oxygen-deficient, flammable and/or explosive atmosphere, an engulfment hazard and sidewalls that could trap a worker. Tanks and other process equipment that require worker entry may be considered confined spaces.

Product Safety Bulletin 51

Tank Cleaning and Equipment Repair


Training is required for three categories of workers involved in confined space work: those entering the confined space, attendants or standby/safety persons and the person authorizing the permit. Workers should not enter confined spaces where the styrene monomer vapor concentrations exceed 10 percent of its lower flammable limit of 1.1 percent by volume without a proper permit. Respiratory protection should be worn whenever the styrene monomer concentration exceeds the TLV of 50 ppm or the oxygen concentration is less than 19.5 percent (see Section 3). An employee entering a confined space should be able to readily and continuously communicate with a standby person trained to provide emergency rescue.

10.5 Maintenance and Inspection


Facilities should conduct preventive maintenance and inspection of containers, hoses, pumps, fittings, fire protection equipment and refrigeration units used for styrene monomer. An adequate supply of spare parts for refrigeration units should be maintained. Maintenance and inspection schedules should be established that are appropriate for the device or equipment. Inspectors should be trained how to identify abnormal situations and conduct a proper inspection. A checklist or guide should be used to conduct inspections, and all findings and work carried out should be recorded. Styrene monomer bulk storage tanks should be emptied and visually inspected regularly, such as every two years. The inspection frequency should be increased if polymer formation occurs. Inspections should include lining, roof, vents, seals, relief valves piping and tank openings. Preventive maintenance schedules should be developed for critical equipment such as fire fighting equipment, combustible gas detectors, tank instruments and gauges, pumps, safety-relief valves, isolating valves, gaskets and emissioncontrol equipment.

10.4 Equipment Cleanout


Cleaning styrene monomer equipment is a hazardous operation and should be conducted by experienced and trained workers in compliance with a written, approved procedure. A job safety analysis (JSA) or hazards analysis should be used to identify hazards and necessary protective measures. The emptying of styrene monomer vessels or storage tanks presents a danger of ignition, toxic vapors and environmental contamination. Vessels, lines and equipment should be emptied from low-point drains and repeatedly rinsed with water until the styrene monomer concentration is less than 1 percent. Residual styrene monomer can be removed by purging with inert gas such as nitrogen. Acidic cleaning solutions should not be used because their residues can cause polymerization. To protect product quality vessels, lines and equipment should be clean and dry before being placed into service initially or after repair. Polymerized styrene monomer should be removed from interior surfaces. Polymer usually forms around internal tank supports, openings, valves, flanges and vents. If a vessel is to be entered for cleaning, the guidelines for control of hazardous energy and confined space entry in this section should be followed.

52

Product Safety Bulletin

11. TRANSPORTATION REGULATORY REQUIREMENTS


The Distribution Safety Program of Lyondell Chemical Company has been implemented in accordance with the companys Operational Excellence Standards. 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. This bulletin is written is accordance with the Code of Federal Regulation, Title 49 issued Jan. 29, 2003. 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. Lyondell Chemical Company recommends that those offering hazardous materials for transport be trained in the proper application of these regulations.

11.2 Marking, Labeling and Placarding


Identification numbers are required on each side and each end if the packaging capacity is 1000 gallons or more; on two opposing sides if the packaging capacity is greater than 119 gallons, but less than 1000 gallons. Markings for non-bulk packaging (119 gallons or less) include the proper shipping name, identification number preceded by UN or NA, the technical name, if applicable, and the consignors name and address. Labels are required on non-bulk packages and must be located on the same surface and near the marking. Placards are required on each side and each end of bulk packaging. Requirements concerning marking, labeling, placarding and the preparation of shipping papers vary somewhat depending on the transport mode, packaging configuration and quantity of hazardous material being transported. Marking, labeling and placarding requirements are explained in detail in 49 CFR 172 Subparts D, E and F, respectively. Labels and placards applicable to flammable liquids are required for styrene monomer (see Figures 11.1 and 11.2). Bulk containers should remain placarded when emptied unless the special requirements of Subpart F are met.

11.1 Classification
Styrene monomer is listed in the Hazardous Materials Table (49 CFR 172-101). Therefore, it is classified as a hazardous material for transportation purposes. The table gives the following designation for styrene monomer: Proper shipping name Styrene monomer, stabilized Hazard Class 3 Identification Number UN 2055 Packing Group III Label Required Flammable Liquid Appendix A to HMT RQ is 454 kg, 1000 lbs. The following description is required on the bill of lading for styrene monomer under DOT regulations (49 CFR 172 Subpart C): Styrene monomer, stabilized 3, UN 2055, PG III. RQ (454 kg, 1000 lbs.)

11.3 Packaging
Packaging exceptions are permitted. Limited quantity shipments with inner packagings not exceeding 5.0 liters net capacity each, are authorized (49 CFR 173 Subpart D). Non-bulk packaging is explained in 49 CFR 173 Subpart E, and bulk packaging is described in Subpart F. In bulk packagings, liquids must be loaded so that the outage is at least 1 percent of the total capacity of a cargo or portable tank, or compartment thereof, or at least 1 percent of the total capacity of the tank and dome for tank car and multi-unit tank car tanks at the reference temperature of 46C (115F) for uninsulated tanks and 41C (105F) for insulated tanks. Hazardous materials may not be loaded into the dome of a tank car. If the dome of the tank car does not provide sufficient outage, vacant space must be left in the shell to provide the required outage (49 CFR 173 Subpart B). The outage for an IM portable tank may not be less than 2 percent at a temperature of 50C (122F). The maximum volume of styrene monomer in various bulk packaging may be calculated for the referenced temperature using Table 1.2, Styrene Monomer Density as a Function of Temperature.

Product Safety Bulletin 53

Transportation Regulatory Requirements


Figure 11.1 Figure 11.2

11.3.1 Tank Cars


In accordance with 49 CFR 173, DOT 111A tank cars are authorized to carry styrene monomer. Lyondell Chemical Company prefers to ship styrene monomer by rail in tank cars meeting DOT Specification 105J300W. Such cars are of mild steel construction and have capacities of 26,000 gallons. These are pressure cars with no bottom outlets. The DOT 105J300W cars are preferred because their probability of consequential product release is lower than the general purpose car. Styrene monomer should be transported by rail only if it is consigned to a party having a private track (49 CFR 171.8) or to a party using railroad siding facilities that are equipped for piping styrene monomer from the tank car to permanent storage. Tank cars loaded with styrene monomer should be placarded with FLAMMABLE placards according to 49 CFR 172 Subpart F (see Figure 11.2).

11.3.3 ISO Tanks


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 ships styrene monomer in ISO tanks constructed of either steel or stainless steel that meets IM-101 (T2 tank container) specifications (1.5 bar minimum test pressure) and Chapter 13 of the International Maritime Dangerous Goods (IMDG) Code. Such tanks must be at least 80 percent full during transport. When ISO tanks are transported by road, they must be on dropchassis trailers only.

11.3.4 Canadian Transborder Highway Shipments


With the exception of retro reflective placarding, the origin countrys hazardous material regulations govern. Reciprocal agreements are found in the respective regulations. Retro reflective placards are required in both directions. Intra Canadian shipments are governed by Transport Dangerous Goods regulations exclusively.

11.3.2 Tank Trucks


Lyondell Chemical Company ships styrene monomer in DOT 407 stainless-steel tank trucks with capacities ranging from 5,500 to 6,600 gallons. They are equipped for unloading from bottom outlet valves. See 49 CFR 173 Subpart F for special requirements concerning the pressure relief system and bottom outlets. Refer to 49 CFR 180 Subpart E for information on requirements for testing and inspection of cargo tanks, minimum qualification for inspectors and testers, tests and inspection markings and reporting and records-retention requirements. These regulations should be reviewed in detail to establish inspection protocols for tank trucks used in the transport of styrene monomer. A suggested tank truck unloading procedure is provided in Section 9.4. 54 Product Safety Bulletin

11.3.5 Marine Transportation


The transport of styrene monomer on cargo and passenger vessels is permitted for on-deck and under-deck stowage. For cargo vessels, the United States DOT specification and UN Standard packaging is constructed of materials that will not react dangerously with or be decomposed by the styrene monomer (see Section 1.5). The requirements for shipment of poisonous and flammable liquids such as styrene monomer over water are defined in 49 CFR 176. Lyondell Chemical Company transports styrene monomer in ISO tanks on container ships or barges. Vessel/barge owners should comply with 46 CFR 153, Code for the Construction and Equipment of Ships Carrying Dangerous Chemicals in Bulk (BCH Code) and

Transportation Regulatory Requirements


Regulations for the Control of Pollution by Noxious Liquid Substances in Bulk. These are Coast Guard and IMO regulations governing vessel/barge operation and construction. The application and maintenance of a nitrogen blanket for styrene monomer in an ISO tank is detailed in 46 CFR 153.500. An independent inspector is employed for quality and quantity measurements to ensure that the styrene monomer is loaded in uncontaminated tanks (see Section 9.6).

11.4.1 CANUTEC
If an emergency involving a Lyondell Chemical Company product occurs in Canada, you may call CANadian Transport Emergency Centre (CANUTEC) collect at (613) 996-6666. CANUTEC is the national bilingual advisory service provided by Transport Canada to assist emergency response personnel in handling dangerous goods emergencies. CANUTEC should be called first, with a follow-up call to SCDI.

11.3.6 Air Transportation


Styrene monomer may be transported domestically and internationally by air in specific packagings and quantities which comply with ICAO technical instructions. These regulations have been generally incorporated in DOT regulations (49 CFR 175) cited in this section. A package shall not contain more than 220 liters on a cargo-only aircraft. Inner packagings not over 5.0 liters net capacity each, packed in strong outer packagings, are authorized by exception in limited quantities. The entire package cannot exceed 66 pounds gross weight (CFR Part 173, Subpart D). Applicable regulations should be reviewed thoroughly prior to shipping styrene monomer by air.

11.4.2 SETIQ
If an emergency accident/incident occurs in Mexico, you may elect to call SETIQ (in the Mexican Republic) at (800) 002-1400; (Calls originating in Mexico City or in the Metropolitan Area) (5) 559-1588; (Calls originating elsewhere) (52-555) 559-1588.

11.4.3 Reporting Requirements


A transportation incident involving styrene monomer may necessitate the notification of federal authorities. Refer to 49 CFR 171 for detailed response and reporting requirements.

11.4 Transportation Emergencies


Lyondell Chemical Company markets its products in a manner which takes into consideration the health and safety of customers, transporters and the general public. However, emergencies can occur in spite of best precautions. Lyondell Chemical Company has made provisions to respond to all emergencies. All Lyondell Chemical Company Material Safety Data Sheets (MSDS) include telephone numbers for CHEMical TRansportion Emergency Center (CHEMTREC). The CHEMTREC numbers are (800) 424-9300, and you can call collect at (202) 483-7616. The number for Lyondell Serious Chemical Distribution Incident Response System (SCDI) is (800) 245-4532. These numbers are staffed 24 hours a day. If the event of a transportation emergency, CHEMTREC should be called first, with a follow-up call to SCDI. SCDI was established to minimize the effects of any out-ofplant incidents by providing an efficient and responsible means of emergency assistance. It covers incidents such as transportation accidents (e.g., collisions, rollovers or derailments), shipping container damage or leaks, difficulties at customer facilities, leaks or spills in distribution terminals or toll processors facilities and exposure under all circumstances. When notification of an SCDI emergency is received at Lyondell Chemical Company Channelview, Texas plant, the call is immediately directed to a group of trained coordinators. The coordinator who receives the emergency call will immediately contact the person originally requesting assistance (according to 49 CFR 172 Subpart G) to confirm receipt of the notification, obtain details and agree upon the course of action.

11.4.4 Transport of Styrene Monomer Residue


If a discharge of styrene monomer occurs during transport, an official of the federal, state or local government may require its immediate removal to prevent further consequences, according to DOT regulations (49 CFR). The removal may be made without preparing a manifest. The EPA does not require the freight carrier to have an EPA identification number (see EPA regulations, 40 CFR) under such circumstances. If a hazardous waste transporter removes the residue, EPA regulations require that an EPA identification number be used.

Product Safety Bulletin 55

APPENDIX 1. CONVERSION FACTORS


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

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
1 kg 1g 1 metric ton 1 ton (US) 1 lb 1 oz kg 1 1x10 3 1000. 907.1847 0.45359237 0.02834952 g 1000. 1 1x10 6 9.071847x10 5 453.59237 28.34952 metric ton 1x10 3 1x10 6 1 0.9071847 4.5359237x10 4 2.834952x10 5 ton (US) 1.102311x10 3 1.102311x10 6 1.102311 1 0.0005 3.125x10 5 lb 2.204623 2.204623x10 3 2204.623 2000. 1 0.0625 oz 35.27396 0.03527396 35273.96 32000. 16. 1 (1 Liter = 1 dm 3)

Units of Volume
1m 1 dm 3 1 cm 3 1 yd 3 1 ft 3 1 in 3 1 gal 1 bbl
3

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

m3 1 1x10 3 1x10 6 0.7645549 0.02831685 1.638706x10 5 3.785412x10 3 0.1589873 in 3 6.102374x10 4 61.02374 0.06102374 46656. 1728 1 231. 9702.

dm 3 1000. 1 1x10 3 764.5549 28.31685 0.01638706 3.785412 158.9873 gal 264.1721 0.2641721 2.641721x10 4 201.9740 7.480519 4.329004x10 3 0.02380952 42.

cm 3 1x10 6 1000. 1 7.645549x10 5 28.31685x10 3 16.38706 3785.412 1.589873x10 5 bbl 6.289812 6.289812x10 3 6.289812x10 6 4.808905 0.1781076 1.030715x10 4 1

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

ft 3 35.31467 0.03531467 3.531467x10 5 27 1 5.787037x10 4 0.1336806 5.614558

(1 Liter = 1 dm 3)

Product Safety Bulletin 57

Appendix 1. Conversion Factors Units of Density


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

kg m 3 1 1000. 16.01847 27679.91 119.8264

g cm 3 0.001 1 0.01601847 27.67991 0.1198264

lb ft 3 0.06242795 62.42795 1 1728. 7.480519

lb in 3 3.612728x10 5 0.03612728 5.7870370x10 4 1 4.3290043x10 3

lb gal 1 8.345403x10 3 8.345403 0.1336806 231. 1 (1 g dm 3= 1 kg m 3)

Units of Pressure
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 cm2 1 kg(wt) cm2 1 atm 1 torr 1 lb in2 1 in Hg(60F) 1 in H2O(60F) Pa 1 1x10 5 0.1 98066.5 101325.0 133.3224 6894.757 3376.85 248.835 torr 7.500617x10 3 750.0617 7.500617x10 4 735.5592 760. 1 51.71493 25.3285 1.86642 bar 1x10 5 1 1x10 6 0.980665 1.013250 1.333224x10 3 0.06894757 0.0337685 2.48835x10 3 lb in -2 1.450377x10 4 14.50377 1.450377x10 5 14.22334 14.69595 0.01933678 1 0.489757 0.0360895 dyne cm 2 10. 1 x10 6 1 980665. 1013250. 1333.224 68947.57 33768.5 2488.35 in Hg(60F) 2.961340x10 4 29.61340 2.961340x10 5 29.0408 30.0058 0.0394812 2.04183 1 0.0736885 kg(wt) cm 2 1.019716x10 5 1.019716 1.019716x10 6 1 1.033227 1.359510x10 3 0.07030696 0.0344343 2.53741x10 3 in H2O(60F) 4.01872x10 3 401.872 4.01872x10 4 394.103 407.197 0.535786 27.7089 13.5706 1 atm 9.869233x10 6 0.9869233 0.9869233x10 8 0.9678411 1 1.315789x10 3 0.06804596 0.0333269 2.45581x10 3

Units of Dynamic Viscosity


1 Pa s 1 kgf s m 2 1 poise 1 cP 1 lbf s in 2 1 lbf s ft 2 Pa s 1 9.80665 0.1 0.001 6894.758 47.88026 kgf s m 2 0.1019716 1 0.01019716 1.019716x10 4 703.0697 4.882428 poise 10 98.0665 1 0.01 68947.58 478.8026 cP 1000. 9806.65 100. 1 6894758. 47880.26 lbf s in 2 1.450377x10 4 1.422334x10 3 1.450377x10 5 1.450377x10 7 1 6.944444x10 3 lbf s ft 2 0.02088543 0.2048161 2.085543x10 3 2.088543x10 5 144. 1

Units of Thermal Conductivity


1 W m 1 K 1 1 cal s 1 cm 1 K 1 1 cal hr 1cm 1K 1 1 Btu s 1 ft 1 R 1 1 Btu hr 1 ft 1 R 1 W m 1K 1 1 418.4 0.1162222 6230.646 1.730735 cal s 1cm 1K 1 2.390057x10 3 1 2.777778x10 4 14.89160 4.136555x10 3 cal hr 1cm 1K 1 8.604205 3600. 1 53609.77 14.89160 Btu s 1ft 1R 1 1.604970x10 4 0.06715194 1.865332x10 5 1 2.777778x10 4 Btu hr 1ft 1R 1 0.5777892 241.7471 0.06715197 3600. 1

58

Product Safety Bulletin

APPENDIX 2. WORLDWIDE OCCUPATIONAL EXPOSURE LIMITS


Styrene Monomer
Country ACGIH TLV3 Belgium British Columbia Canada China Finland Germany Japan Mexico Netherlands Spain Sweden United Kingdom USA NIOSH REL4 TWA81 (ppm) 20 50 50 50 20 20 20 50 25 20 20 100 50 STEL2 (ppm) 40 100 75 100 100 40 100 40 50 250 100

Reference: 2006 ACGIH [American Conference of Governmental Industrial Hygienists] TWA8 is the eight-hour Time Weighted Average. STEL is the Short Term (15 minute) Exposure Limit. 3 TVL is the Threshold Value Limit. 4 NIOSH REL is the National Institute for Occupational Safety and Health Recommended Exposure Limit
1 2

Product Safety Bulletin 59

APPENDIX 3. NAMES AND ADDRESSES OF MANUFACTURERS


Combustible Gas Detectors TLV Sniffer Bacharach, Inc. 621 Hunt Valley Circle New Kensington, PA 15068-7074 (724) 334-5000 MSA P.O. Box 426 Pittsburgh, Pennsylvania 15230 (800) MSA-2222 Invensys/Foxboro 33 Commercial Street Foxboro, MA 02035 (866) 746-6477 (US & Canada) (508) 549-2424 (International) OVM Badge System TraceAir Morphix Technologies 2557 Production Road Virginia Beach, VA 23454 (800) 808-2234 Sensidyne 16333 Bay Vista Drive Clearwater, FL 34620 (727) 530-3602 Draeger Safety Inc. 101 Technology Drive Pittsburgh, PA 15275-1057 (800) 858-1737 Ansell Edmont Industrial 200 Schultz Dr. Red Bank, NJ 07701 (800) 800-0444 Best Manufacturing Company 579 Edison Street Menlo, GA 30731 (800) 241-0323 Comasec Safety Inc. P.O. Box 1219 8 Niblick Road Enfield, CT 06082 (800) 333-0219 Chem-Tex Corp. P.O. Box 5878 550 West Ingham Ave. Trenton, NJ 08638 (609) 392-6770 (800) 875-6770

Explosimeter

Colorimetric Detector Tubes Styrene (Nos. 124 or 124L)

Infrared Spectrophotometers MIRAN 1B2 MIRAN 1BX MIRAN 101 MIRAN 103 MIRAN 1B MIRAN 1A Century OVA 128 Century OVA 108

Styrene

Chemical Protective Clothing

Flame Ionization Detectors Invensys/Foxboro 33 Commercial Street Foxboro, MA 02035 (866) 746-6477 (US & Canada) (508) 549-2424 (International) Photovac Inc. 176 Second Avenue Waltham, MA 02451 (781) 290-0777 HNU Process Analyzers 25 Walpole Park South Drive Walpole, MA 02081 (800) 743-6826 (US & Canada) (508) 660-5001 (International)

Photoionization Detectors Photovacs TIP

HNU Model PI01

TraceAir is a registered trademark of Morphix Technologies.

Product Safety Bulletin 61

APPENDIX 4. REFERENCES
STYRENE MONOMER
ACGIH
American Conference of Governmental Industrial Hygienists 6500 Glenway Avenue, Bldg. D-7 Cincinnati, OH 45211-4438 ACGIH; Threshold Limit Values and Biological Exposures Indices

ASME
American Society of Mechanical Engineers, United Engineering Center 45 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

AIHA
American Industrial Hygiene Association 2700 Prosperity Avenue, Ste. 250 Fairfax, VA 22031

DOT
Department of Transportation 400 Seventh Street, S.W. Washington, DC 20590 49 CFR 171; General Information, Regulations and Definitions 49 CFR Part 172; Hazardous Materials Table, Special Provisions, Hazardous Materials Communication Requirements and Emergency Response Requirements 49 CFR 173; Shippers General Requirements for Shipments and Packaging 49 CFR 174; Carriage by Rail 49 CFR 176; Carriage by Vessel Carriage by Public Highway 49 CFR 178; Shipping Containers Specifications 49 CFR 179; Specifications for Tank Car 49 CFR 180; Qualification and Maintenance of Cargo Tanks continues next page

ANSI
American National Standards Institute 1819 L Street, NW Washington, DC 20036 ANSI Z358.1; Emergency Eye Wash and Shower Equipment ANSI Z88.2; American National Standard for Respiratory Protection ANSI Z87.1; Occupational and Eductional Personal Eye and Face Protection Devices

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 PressureRelieving Devices in Refineries Part II Installation API 601; Metallic Gaskets for Raised-Face Pipe Flanges and Flanged Connections (Double-Jacketed Corrugated and Spiral-Wound) 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-2003; Protection Against Ignition Arising Out of Static, Lightning, and Stray Currents API RP-2028; Flame Arresters in Piping System API RP-2210; Flame Arresters for Vents of Tanks Storing Petroleum Product API RP-2350; Protection for Petroleum Storage Tanks, First Edition

Product Safety Bulletin 63

Appendix 4. References
EPA
United States Environmental Protection Agency 401 M Street, S.W. Washington, DC 20460 40 CFR 260; Hazardous Waste Management System: General 40 CFR 261; Identification and Listing of Hazardous Waste 40 CFR 262; Standards Applicable to Generators of Hazardous Waste 40 CFR 263; Standards Applicable to Transporters of Hazardous Waste 40 CFR 264; Standards for Owners and Operators of Hazardous Waste Treatment, Storage and Disposal Facilities 40 CFR 265; Interim Status Standards for Owners and Operators of Hazardous Waste Treatment, Storage and Disposal Facilities 40 CFR 266; Standards for the Management of Specific Hazardous Waste and Specific Types of Hazardous Waste Management Facilities 40 CFR 267; Interim Standards for Owners and Operators of New Hazardous Waste Treatment, Storage and Disposal Facilities 40 CFR 268; Land Disposal Restrictions 40 CFR 270; EPA Administered Permit Programs: The Hazardous Waste Permit Program 40 CFR 271; Requirements for Authorization of State Hazardous Waste Programs 40 CFR 272; Approved State Hazardous Waste Management Programs 40 CFR 372; Toxic Chemical Release Reporting: Community Right-to-Know

IMO
International Maritime Organization Albert Embankment London SE,1 England IMDG; International Maritime Dangerous Goods Codes

NFPA
National Fire Protection Association Batterymarch Park Quincy, Massachusetts 02269 NFPA 10; Portable Fire Extinguishers NFPA 11; Foam Extinguishing Systems, Low Expansion and Combined Agent NFPA 30; Flammable and Combustible Liquids Code NFPA 70; National Electrical Code NFPA 77; Static Electricity NFPA 704; Standard System for the Identification of the Fire Hazards of Materials

NIOSH
National Institute for Occupational Safety and Health US Department of Health, Education and Welfare 4676 Columbia Parkway Cincinnati, Ohio 45226

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

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

OCCUPATIONAL HEALTH REFERENCES (FOR SECTION 2)


K.M. Bodner, G.G. Bond, R.R. Cook. Review of Recent Epidemiological Studies. Prepared for Styrene Information & Research Center (SIRC), 1987. N. Cherry. The Effects of Occupational Exposure to Styrene on the Nervous System in Man. Prepared for SIRC. J. Orr, R. Brillinger, I.C. Munroe and R.F. Willes. Review of Styrene Pharmacokinetics and Carcinogenicity. Prepared for SIRC, 1989. The SIRC Review, vol. 1, No. 1. 1990. Ibid. vol. 1, No. 2. 1990. H.C. Spencer, D.D. Irish, E.M. Adams and V.K. Rowe. J. Ind. Hyg. Toxicol. 24, 295, 1942. USEPA Drinking Water Criteria Document, PB86-1180556, 1985. M.A. Wolfe, V.K. Rowe, D.D. McCollister, R.C. Hollingsworth, F. Oyen. Am. Med. Assoc. Arch. Ind. Health 14, 387, 1956. (The SIRC documents and the EPA document contain complete listings of all pertinent articles and have been used extensively in preparing this Bulletin.)

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

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Appendix 4. References
OSHA
Occupational Safety and Health Administration United States Department of Labor 200 Constitution Avenue, N.W. Washington, DC 20210 29 CFR 1910.106; Flammable and Combustible Liquids 29 CFR 1910.119; Process Safety Management of Highly Hazardous Chemicals 29 CFR 1910.120; Hazardous Waste Operations and Emergency Response (HazWOpER) 29 CFR 1910.134; Respiratory Protection 29 CFR 1910.146; Permit-Required Confined Space 29 CFR 1910.147; Sources of Standards 29 CFR 1910.151; Medical Services and First Aid 29 CFR 1910.156; Fire Brigades 29 CFR 1910.157; Portable Fire Extinguishers 29 CFR 1910.252; Welding, Cutting, and Brazing 29 CFR 1910.1000; Air Contaminants 29 CFR 1910.1200; Hazard Communication

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 42nd 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, Liquefied Gas, or Compressed Gas Hazardous Material

Product Safety Bulletin 65

APPENDIX 5. REGULATORY SUMMARY


Styrene Monomer
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 styrene (or styrene monomer). 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.

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 the Superfund Amendments & Reauthorization Act (SARA) Title III, Section 304, emergency notification requirements (see below). Styrene is a listed hazardous substance. The RQ is 1,000 pounds (40 CFR 302.4). The National Response Center hotline for reporting spills is (800) 424-8802. EPA also maintains a RCRA/Superfund hotline for information. This number is (800) 424-9346; in Washington, D.C., the number is (703) 412-9810.

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. Styrene 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 the EPA to establish technology standards applicable to the sources of listed pollutants. Styrene is listed as a hazardous air pollutant in Section 112(b). As a result, facilities that manufacture styrene will be subject to Maximum Achievable Control Technology standards. This listing also may require additional emission controls at facilities that use styrene as a solvent or reactant. Hazardous Organic NESHAP (HON) Synthetic Organic Chemicals (40 CFR 63. 100-106, Table 1). Under a final rule effective 4/22/94, styrene is listed as a Group I chemical. Existing sources of chemicals in Group I must comply with equipment leak rules (40 CFR 63.160182) by 10/24/94.

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. For styrene, discarded off specification product, spill cleanup residue and empty styrene containers are not considered listed hazardous waste (40 CFR 261.33). However, liquid waste material should be evaluated for the characteristics of ignitability (40 CFR 261.21). Mixtures of styrene and styrene solutions destined for disposal which exhibit flash points less than 140F are also considered ignitable hazardous waste (40 CFR 261.21). Styrene is included in the list Hazardous Constituents Subject to Groundwater Monitoring (40 CFR 264, Appendix IX). This requirement pertains only to facilities that have obtained a permit for storage, treatment or disposal of hazardous waste and are subject to groundwater monitoring requirements.

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 styrene: Section 307 Priority Pollutants (40 CFR 401.15) styrene is 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. Styrene is listed. Section 311 (40 CFR 117.3) Reportable Quantities of Designated Hazardous Substances. Styrene has a reportable quantity of 1000 pounds (reportable quantity category B).

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Appendix 5. Regulatory Summary


Safe Drinking Water Act (SDWA)
The 1974 SDWA directed the EPA to promulgate primary drinking water regulations which specify contaminants which may have an adverse effect on human health and to specify either maximum contaminant levels (MCLs) or treatment techniques. A MCL of 0.1 mg/l applies to styrene. Under Section 1445(a)(1) of the SDWA, the EPA issued regulations requiring public water systems to conduct monitoring for specified contaminants. Styrene is a listed chemical for which monitoring is required (40 CFR 141.40). The 1986 amendments to the SDWA required the 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. Under these amendments, the EPA also was required to publish maximum contaminant level goals (MCLGs) for the listed substances. Styrene is listed as one of the substances which the EPA substituted for a Congressionally mandated substance on the list of Statutory Contaminants (53 FR 1892, 1/22/88). The MCLGs for styrene is 0.1 mg/l. EPAs Safe Drinking Water hotline is (800) 426-4791. 29 CFR 1910.146 - Permit-required confined spaces. (Effective 4/15/93) 29 CFR 1910.155, Subpart I - Fire protection relative to flammable or combustible liquids. 29 CFR 1910.164 - Fire detection systems required when styrene is in use. 29 CFR 1910.1000, Subpart Z, Permissible Exposure Limits. Table Z-1-A TWA: 50 ppm; 215 mg/m3 STEL: 100 ppm; 425 mg/m3 OSHA revoked these levels on June 30, 1993 (58 FR 35338) as a result of a court decision. They remain in this document since the following OSHA state plans continue to enforce them: Alaska, California, Connecticut, Maryland, Michigan, Minnesota, New Mexico, Vermont and Washington. The Virgin Islands also are enforcing the 1989 PELs. It also is Lyondell Chemical Companys intent to abide by either these levels or the ACGIH levels where the latter provide more protection. Table Z-2 8-Hour TWA: 100 ppm. Acceptable Ceiling Concentration: 200 ppm. Acceptable Maximum peak above the acceptable ceiling concentration for an 8-hour shift: 600 ppm. Maximum duration of acceptable maximum peak: five minutes in any three hours 29 CFR 1910.1200, Hazard Communication Standard. Styrene 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.

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 (labelling). DOT also has established spill notification requirements. Regulations governing the transport of hazardous materials can be found at 49 CFR 172 and 173. Styrene is listed as Hazard Class 3; the proper shipping name is Styrene Monomer, Inhibited; the identification number assigned to the proper shipping name is UN 2055; packing group III. The hazard label required is Flammable Liquid. On November 5, 1992, DOT issued a final rule (57 FR 52930) which amended the Hazardous Material Regulations to list materials identified as marine pollutants by the International Maritime Organization. Styrene Monomer, Inhibited, is cited on the list of marine pollutants (49 CFR 172.101, Appendix B).

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 (TPQs) and RQs. Facilities also must submit copies of MSDSs (Sections 311/312) and report emissions of toxic chemicals (Section 313). Styrene is not listed as an extremely hazardous substance (Section 302; 40 CFR). Lyondell Chemical Company has classified styrene as an immediate (acute) health hazard; as a delayed (chronic) health hazard; as a fire hazard; and as reactive (Sections 311/312). Styrene is listed as a toxic chemical (Section 313; 40 CFR 372) and is subject to Toxic Release Inventory Reporting. The de minimis concentration level of 0.1 percent; supplier notification is required.

Occupational Safety & Health Administration (OSHA)


The following OSHA regulations may apply to styrene 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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Appendix 5. Regulatory Summary


Toxic Substances Control Act (TSCA)
The Toxic Substances Control Act gives the 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 8(b) Chemical Substances Inventory - Styrene is listed. Section 12(b) Export Notification (40 CFR 707, Subpart D) - Styrene is not listed. Information on TSCA regulations can be obtained from the TSCA Assistance Office at the EPA (202) 554-1404.

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. Styrene is designated as a toxic substance. The authority for this list is Florida Statutes Annotated, Section 442.101.

Illinois
Illinois Toxic Substances Disclosure to Employees Act Under the Illinois Right to Know Law, known as the Toxic Substances Disclosure to Employees Act, employees are required to inform workers of potential hazards, safety precautions and emergency procedures concerning exposure to toxic substances in the workplace. Styrene is defined as a toxic substance. Illinois Chemical Safety Act Under this law, covered businesses using, storing or manufacturing defined chemical substances must have a written Chemical Safety Contingency Plan. Styrene is a covered substance. The authority for these requirements is Illinois Rev. Statute, Chapter 111 1/2, Paragraph 951.

STATE
California
California Safe Drinking Water & Toxic Enforcement Act of 1986 (Prop. 65) Prop. 65 prohibits discharge of chemicals known to the state to cause cancer or reproductive toxicity into drinking water supplies. An employer must notify all workers of possible exposure to a chemical. Facilities must also provide the state and local agencies with information regarding spills or releases of these chemicals to the environment. Styrene is not listed. Additional information about Prop. 65 can be obtained from the Office of Environmental Health Hazard Assessments Proposition 65 Implementation Office at (916) 445-6900.

Louisiana
Louisiana Hazardous Materials Information, Development, Preparedness and Response Act This law subjects covered facilities to right-to-know type requirements. Covered materials include federal SARA extremely hazardous substances and any hazardous chemicals as defined under the federal OSHA standard. Styrene is listed with a reportable quantity of 1000 pounds. The authority for these regulations is Louisiana Admin. Code, Title 33, Chapter 39.

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. Styrene is listed. The authority for these regulations is Connecticut Gen. Stat. Ann., Section 29-307a.

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Appendix 5. Regulatory Summary


Massachusetts
Massachusetts Right-to-Know Law This law established reporting, labeling, MSDS, recordkeeping and related regulations for certain toxic or hazardous substances. Styrene is listed on the Massachusetts Substance List as an extraordinarily hazardous substance with a one ppm threshold and as a carcinogen. Questions about the regulations can be directed to The Commonwealth of Massachusetts, Executive Office of Human Services, Department of Public Health, Bureau of Environmental Health Assessment, 250 Washington Street, Boston, MA 02108-4619, (617) 624-6000. Massachusetts Spill Reporting The Oil and Hazardous Materials List establishes reportable quantities (RQs) for substances which require reporting of unauthorized discharges. Styrene is listed with an RQ of 50 pounds.

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. Styrene is listed with an RQ for releases to air of 1000 pounds; and an RQ for releases to land/water of 1 pound. Authority is found in New York Comp. Codes R & Regulations, Parts 595 through 599.

Pennsylvania
Pennsylvania Worker & Community Right-to-Know Act This law requires facilities or distributors handling hazardous substances to complete a Hazardous Substances Survey Form (HSSF) annually for the previous calendar year. The HSSF lists chemicals as an environmental hazard or special hazard. Styrene is listed as an environmental hazard with a threshold of 1 percent. Additional information is available from the Pennsylvania Department of Labor and Industry, Bureau of Penn. Safe.

New Jersey
New Jersey Worker & Community 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. Styrene is listed on the New Jersey Hazardous Substance List. The New Jersey I.D. number is 1748; the New Jersey hazardous material number is 2055. Styrene is listed as an environmental hazard subject to state release reporting and with a zero inventory reporting threshold. Styrene also is designated as a New Jersey special hazard subject to restriction of trade secrecy claims. Regulations are codified in the New Jersey Administrative Code, Title 8, Department of Health and Senior Services, Chapter 59. Additional information is available from the State of New Jersey Department of Health and Senior Services, CN 360, Trenton, NJ 08625-0360. New Jersey Spill Tax New Jersey has established a list of substances defined as hazardous according to the Spill Compensation and Control Act (N.J. Statutes, Annotated, Section 58:10-23.11 et seq.). Styrene is a listed substance. The authorities for the listing are New Jersey Administrative Code, Section 7:1E-1.3.

Rhode Island
Rhode Island Hazardous Substances 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. Styrene is listed with the hazard code CTF = Carcinogenic; Toxic; Flammable. The authority for these regulations is Rhode Island General Laws 28-21-1.

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Appendix 5. Regulatory Summary International Australia


Australian Inventory of Chemical Substances (AICS) Styrene is listed.

Philippines
Philippine Inventory of Chemicals and Chemical Substances (PICCS) Styrene is listed.

MISCELLANEOUS
National Fire Protection Association (NFPA) Hazard Rating The NFPA ratings assign a numeric value to specific aspects of each hazard. Ratings for styrene are as follows: Health: 2. Materials hazardous to health, but areas may be entered freely with full-faced mask self-contained breathing apparatus which provides eye protection. Flammability: 3. Materials which can be ignited under almost all normal temperature conditions. Water may be ineffective because of the low flash point. Reactivity: 2. Materials which (in themselves) are normally unstable and readily undergo violent chemical change but do not detonate. Includes materials which can undergo violent chemical change at elevated temperatures and pressures. Also includes these 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, (800) 344-3555.

Canada
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. Lyondell Chemical Company has classified styrene as Class B2 (Flammable Liquids); Class D2A (Very Toxic Material); and Class F (Dangerously Reactive Material). Styrene is listed on the IDL as a substance which must be disclosed if the weight-to-weight concentration in the product is 0.1 percent or greater. The WHMIS number is 1473. Canadian Domestic Substances List Styrene is listed.

China
Chinese Inventory of Existing Chemical Substances Styrene is listed.

European Economic Community


European Inventory of Existing Commercial Chemical Substances (EINECS) Styrene is listed on EINECS - number 202 851 5. Listing on EINECS is accepted by certain other European countries which have adopted EINECS as their base inventory; i.e., Austria, Finland, Switzerland. However, other registration requirements may apply in those countries.

Japan
Japanese List of Existing & New Chemical Substances (ENCS) Styrene is listed. The ENCS number is (3)-4.

Korea
Korean List of Existing Chemicals (ECL) Styrene is listed; the Korean listing number is KE-35342.

Product Safety Bulletin 71

APPENDIX 6. VISUAL QUICK TEST


To Determine ppm of TBC Inhibitor Present in Styrene Monomer
This is a visual method. Analytical methods are available on request. Visual Method
Standard solutions Prepare a series of solutions containing 5, 10, 15, 20 and 25 ppm (and others as necessary) 4-tert-Butylcatechol in uninhibited styrene. Prepare the uninhibited styrene by extracting inhibited styrene with successive portions of 4 percent potassium hydroxide until no pink color is produced in the caustic layer. These standards must be prepared at the time of each analysis. Procedure 1. Add 50 ml. of the sample and of each standard to respective 125 ml. separatory funnels by means of suitable graduates. 2. Add 25 ml. of 4 percent potassium hydroxide to each funnel and shake for five minutes. 3. Allow the layers to separate and filter the lower layer through fluted filter paper into respective 50 ml. nessler tubes. 4. Allow the filtrates to stand for 15 minutes. 5. Compare the pink color of the sample solution with the standards. 6. Report the 4-tert-Butylcatechol content of the sample as the concentration of the standard which matches the sample. If the color of the sample is between two of the standards, report the content of the sample as between the concentrations of these standards.

Product Safety Bulletin 73

APPENDIX 7. GLOSSARY
ACGIH American Conference of Governmental Industrial Hygienists AFFF-AR aqueous film-forming foam, alcohol resistant AIHA American Industrial Hygienists Association ANSI American National Standards Institute API American Petroleum Institute ASME American Society of Mechanical Engineers ASTM American Society for Testing and Materials BOD biochemical oxygen demand Bonding the connection of two or more conductive objects by means of a conductor (most commonly a wire or metal plate) CAAA Clean Air Act Amendments CANUTEC Canadian Transport Emergency Centre CERCLA Comprehensive Environmental Response, Compensation, and Liability Act CFR Code of Federal Regulations CGI combustible gas indicators CHEMTREC Chemical Transportation Emergency Center COD chemical oxygen demand 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 chemical protective clothing DOT Department of Transportation, United States of America EPA Environmental Protection Agency, United States of America Flash point 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 GAC granular activated carbon Grounding the connection of one or more conductive objects to the ground; a specific form of bonding. Grounding is also referred to as earthing. HAP hazardous air pollutant HazWOpEWR Hazardous Waste Operations and Emergency Response IARC International Agency for Research on Cancer IATA International Air Transport Association ICAO International Civil Aviation Organization 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 IM intermodal IMDG International Maritime Dangerous Goods IMO International Maritime Organization ISO International Standards Organization KOC 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 K divided by the organic carbon content of the soil or sediment) LEPC local emergency planning committee LFL lower flammability limit MACT maximum achievable control technology MSDS material safety data sheet MSHA Mine Safety and Health Administration NEC National Electric Code NFPA National Fire Protection Association NIOSH National Institute for Occupational Safety and Health NPDES National Pollutant Discharge Elimination System OSHA Occupational Safety and Health Administration Outage amount by which a packing falls short of being liquid full POTW publicly owned treatment works PPE personal protective equipment ppm parts per million RCRA Resource Conservation and Recovery Act RQ reportable quantity SARA Superfund Amendment and Reauthorization Act SCBA self-contained breathing apparatus SIP state implementation plan STEL short-term exposure limit TOC total organic carbon TPQ 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 TWA time-weighted average UL Underwriters Laboratory Ullage amount by which a packaging falls short of being liquid full UN United Nations 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), pounds per square inch, bar or Pascal. VOC volatile organic compound

Product Safety Bulletin 75

World Headquarters Lyondell Chemical Company 1221 McKinney Houston, TX 77010 Tel (713) 652-7200 Toll-free (888) 777-0232 European Headquarters Lyondell Chemical Europe, Inc. P. O. Box 2416 3000 CK Rotterdam The Netherlands Tel (31-10) 275-5500 Tel (33-3) 4424-9205 (tech service) Lyondell South America Av Roque Petroni Jr, 999, cj 123 Sao Paulo, SP 04707-910 Brazil Tel (55-11) 5184-8400 Asian Headquarters Lyondell Asia Pacific, Ltd. 41st Floor The Lee Gardens 33 Hysan Avenue Causeway Bay, Hong Kong Tel (85-2) 2882-2668 Tel (33-3) 4424-9205 (tech service) www.lyondell.com

the information in this document is, to our knowledge, true and accurate. However, because the particular uses and actual conditions of use of our products are beyond our control, it is the customers responsibility to determine whether a product is appropriate and suitable for the customers specific use. all uses of lyondell products and any written or oral information, suggestions, or technical advice from lyondell is without warranty, express or implied, and is not an inducement to use any process or product in conflict with any patent. More detailed safety and disposal information on our products is contained in the Material Safety data Sheet (MSdS). all users of our products are urged to retain and use the MSdS. you may request a copy by going to our Web site: www.lyondell.com. you can also obtain an MSdS by calling (800) 700-0946 or (713) 309-7513. 3284-V3-1207 Supersedes July 2004 version

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