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3284
3284
Foreword
Lyondell Chemical Company is dedicated to continuous improvement in product, health, safety and environmental performance. Included in this eort 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 reects 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 specic 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 rener of heavy, high-sulfur crude oil and a signicant producer of fuel products. Key products include ethylene, polyethylene, styrene monomer, propylene, propylene oxide, gasoline, ultra low-sulfur diesel, MTBE and ETBE.
TABLE OF CONTENTS
1. GENERAL INFORMATION . . . . . . . . . . . . . . . . 1
1.1 1.2 1.3 1.4 1.5 1.6 1.7 2.1 2.2 2.3 2.4 3.1 3.2 3.3 3.4 3.5 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 5.1 5.2 5.3 5.4 6.1 6.2 6.3 Product Identication Physical Properties Typical Values Instability Hazards Reactivity Hazards Self-Polymerization Precautions When Handling TBC Hazard Assessment Occupational Exposure Limits First Aid Medical Management Site Facilities Hygiene Practices Personal Protective Equipment (PPE) Respiratory Protection Direct Reading Instruments Air Sampling and Analysis Bulk Storage Piping Electrical Area Classication Pump Specications Instrumentation Relief Requirements Leak Detection Devices Material Requirements Vapor Containment System Chemical Compatibility Fire and Explosion Hazard Fire Prevention Fire Suppression Fire Fighting OSHA Hazard Communication SARA Title III State Regulations
7. ENVIRONMENTAL . . . . . . . . . . . . . . . . . . . . . 29
7.1 7.2 7.3 8.1 8.2 8.3 8.4 9.1 9.2 9.3 9.4 9.5 9.6 Air Quality Considerations Clean Water Act Waste Management Drum Storage Storage Tanks Unloading Installations Workplace Location Work Preparation Tank Cars DOT 111A Tank Cars DOT 105J Tank Trucks ISO Tanks Marine Transport
8. PRODUCT STORAGE . . . . . . . . . . . . . . . . . . . 33
2. OCCUPATIONAL HEALTH . . . . . . . . . . . . . . . 13
9. TRANSFER OPERATIONS . . . . . . . . . . . . . . . 39
4. ENGINEERING . . . . . . . . . . . . . . . . . . . . . . . . 21
APPENDICES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
5. FIRE SAFETY . . . . . . . . . . . . . . . . . . . . . . . . . 23
6. HAZARD COMMUNICATION . . . . . . . . . . . . . 25
1. GENERAL INFORMATION
1.1 Product Identication
Chemical Name Chemical Family Common Names CAS# Formula Ethenylbenzene Aromatic Hydrocarbon Styrene monomer Vinylbenzene Vinylbenzol Phenylethylene Phenethylene Phenylethene Cinnamol Cinnamene Styrol Styrole Styrolene 100-42-5 C8H8
1.1.2 Applications
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 uorocarbons) 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 modication (TPEs), etc. Polystyrene products are recyclable. In the past, polystyrene companies routinely recycled plant scraps to make their manufacturing processes as ecient 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 oce supplies, house and garden products, construction materials, video cassettes and other useful products.
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).
General Information
Figure 1.1 Conventional Technology
CH2 CH3
ALKYLATION
C2H4
Ethylene
+
Benzene Ethylbenzene
CH2 CH3
DEHYDROGENATION
Ethylbenzene
CH = CH2 +
Styrene Monomer
H2
Hydrogen
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
General Information
Figure 1.3 Major Uses of Syrene Monomer
POLYSTYRENE (PS) Commodity Packages Consumer Goods Insulation Appliances Furniture Toys Cassettes
OTHER DERIVATIVES
Coatings Esters Polymer Polyols Polystyrene Latex Terpine Resins XT Polymer by CYRP
Sat. Conc. in Air @ 25C Dipole Moment Heat/Polymerization @25C Minimum Oxygen for Combustion (MOC)
General Information
Figure 1.5 Styrene Monomer Density of Saturated Liquid as a Function of Temperature
0.95 0.94 0.93 0.92
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)
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
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)
General Information
Figure 1.7 Styrene Monomer Viscosity of Saturated Liquid as a Function of Temperature
1.9 1.8 1.7 1.6
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)
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)
General Information
Figure 1.9 Styrene Monomer Heat of Vaporization as a Function of Temperature
110 108 106 104
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
Temperature (C)
General Information
Figure 1.11 Styrene Monomer Enthalpy of Saturated Liquid as a Function of Temperature
70 65 60 55
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
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
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
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
-30
-20
-10
10
20
30
Temperature (C)
40
50
60
70
80
90
100
110
120
130
140
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)
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
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)
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. OCCUPATIONAL HEALTH
2.1 Hazard Assessment
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 eect 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 eects 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 eects on behavior responses have been identied 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 unaected 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.
Occupational Health
2.1.2 Repeated Exposures
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 dierences 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 eects 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 brosis 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 eects 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 eects 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 dierences in rodent respiratory metabolism of styrene monomer which is thought to account for the dierential 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. Eects 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 eect 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 denitive 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 signicant, were small in 14 PRODUCT SAFETY BULLETIN magnitude and hence unlikely to be of clinical signicance. 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 eects on grip strength, spontaneous activity and peripheral nerve conduction. These ndings may have been due to acute CNS depression from the styrene monomer exposure. A number of human workplace studies assessing potential long-term neurobehavioral eects of repeated exposure to vapor have been reported. Some of these investigations reported eects 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 denite conclusion can presently be made on styrene monomers potential for neurobehavioral decrements.
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 nd adverse eects 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 decits (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 ndings were attributed to decreased body weight, rather than a direct/ selective response of the ospring 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 signicance 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 eects, 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 eects 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 ndings, 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 denitive 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
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 aected). The mouse lung tumors occurred in the presence of hyperplasia and inammatory changes which were not present in the rat lungs. In rats, while individual studies have shown isolated increases in various tumor types, these ndings 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 ndings 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 ndings noted at the rst interim sacrice at week 53. At the second interim sacrice 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 inammation. At terminal sacrice, a statistically signicant 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 signicantly increased in females and increased, but not signicantly, in males. There were no signicant dierences between styrene monomer-exposed and control animals for tumors at other sites. The tumor prole for styrene monomer is suggestive of a nongenotoxic mode of action. Supporting information includes the species- and tissue specicity of the late onset lung tumors in mice and the presence of concurrent non-neoplastic PRODUCT SAFETY BULLETIN 15
Occupational Health
inammatory 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 dierences in species metabolism may explain dierences in species sensitivity to tumors. Metabolism studies have shown that mouse lung is more ecient 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 condent 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 classication 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.
2.3.3 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 diculty in breathing develops, administer 100 percent humidied supplementary oxygen with assisted ventilation, if required. Seek prompt medical attention.
Occupational Health
2.3.4 Ingestion
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. substances, special consideration should be given to those with impaired renal function. Since styrene monomer exposure may eect the respiratory system, special consideration should be given to this when pre-screening employees. A specic 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.
* Only approved/certied equipment should be used. ** If potential for eye irritation, recommend utilization of full-face respirator 20 PRODUCT SAFETY BULLETIN
4. ENGINEERING
This section is included for use as a guideline. It is not intended to be a design handbook and does not relieve the user from exercising competent engineering judgment or using qualied professional personnel to meet the specic requirements. The information contained is only applicable to the specic chemical compound identied in Section 1 General Information, 1.1 Product Identication. Mixtures or compounds using styrene monomer will require additional engineering studies to determine the applicability of the enclosed information.
4.5 Instrumentation
Independent high-level alarms and/or shutdowns should be provided 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 classication. Avoid TFE coated-construction. TFE seals are acceptable.
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 ttings and anged 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.
4.8.6 Hoses
All hoses should be exible stainless steel, have suitable pressure/ temperature ratings and should be grounded to discharge static electricity. All hoses should be tested on a regular basis.
4.8.1 Gaskets
Flat-ring (sheet): Durable nitrile, compressed ber or Grafoil GHE with dimensions according to ANSI B 16.21. Spiral-wound: Flexitallic CG or 100 percent graphite-lled with dimensions according to API 601. Avoid TFE piping gaskets. Teon gaskets used for truck or other transport applications should be inspected regularly and replaced as needed.
4.8.2 O-Rings
Kalrez, Viton, Teon, Fluorel or equivalent. Avoid TFEencapsulated O-rings.
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. Teon is a registered trademark of E.I. du Pont de Nemours and Company.
5. FIRE SAFETY
5.1 Fire and Explosion Hazard
Styrene monomer is classied by OSHA 29 CFR 1910.106 (see Appendix 4 for citations) as a Class IC ammable liquid. The National Fire Protection Association (NFPA) Code 30 also denes styrene monomer as a Class IC ammable liquid. For application of the National Electric Code (NFPA 70), styrene monomer is a Class I, Group D. Styrene monomer has a ash 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 ashback. All precautions necessary for the safe handling and storage of a volatile ammable 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 re and explosion risk. Storage areas should be designed to prevent exposure of styrene monomer to re (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 re, unauthorized individuals should be prevented from entering the area, and the area downwind of the re should be evacuated. All res should be fought from a safe distance upwind of the re. Styrene monomer res 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 ineective as an extinguishing agent due to styrene monomers low solubility. The ow of styrene monomer should be stopped before trying to extinguish a re. Liquid should be kept from entering water sources and sewers by building dikes as necessary to contain the ow. Proper authorities should be notied if styrene monomer enters sewers or public water systems.
8 7 6 5 4 3 2 1 0
40
50
60
70
80
Minimum Oxygen for Combustion (MOC) 9.0 percent *This is the region where ammable vapors exist over styrene monomer liquid at atmospheric pressure. 24 PRODUCT SAFETY BULLETIN
6. HAZARD COMMUNICATION
6.1 OSHA Hazard Communication
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. 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, ame 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).
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 identication, 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 identied as to its contents and the hazards of the materials it contains. Many rms elect to employ the United States National Fire Protection Association (NFPA) 704 Standard System for the Identication of the Fire Hazards of Materials (Hazard Diamond) as a means of in-plant communication to workers, contractors and reghters. The appropriate numerical hazard classications for styrene monomer are as follows: Health (Blue): 2 Fire (Red): 3 Reactivity (Yellow): 2
Hazard Communication
6.1.3 Material Safety Data Sheets
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 rst order and after any change or revision to the MSDS. In some regions, an additional issue is also under taken with the rst 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 specic to the actual uses of the product. When the information provided does not adequately fulll your needs, contact your local Lyondell sales representative, regional sales oce 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 eorts.
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 ammable. 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 ame. 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 re: Dry chemical, CO2, foam First Aid Inhalation: If overcome by exposure, remove victim to fresh air immediately. Give oxygen or articial 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 re and/or explosion hazard. May polymerize and release heat and gases. Extinguish all ignition sources. Blanket with reghting 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.
7. ENVIRONMENTAL
Styrene monomer is an extremely ammable and slightly volatile liquid at ambient temperatures. Spills and leaks require prompt response to minimize the risk of re 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 inltrating water and, in shallow soils, volatilization. Based on its low water solubility and the magnitude of its organic carbon partitioning coecient (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 signicant extent. emit 10 tons per year of any single air toxic or 25 tons per year of any combinations of air toxics.)
Environmental
7.2.2 Categorical Standards
Styrene monomer is not specically regulated under categorical euent standards, but may be regulated as a component of chemical or biochemical oxygen demand (COD or BOD) or total organic carbon (TOC).
Environmental
7.3.4 Waste Treatment and Disposal
Styrene monomer wastes are not hazardous by (RCRA) denition and may be disposed of either by burning as fuel or by transfer to a permitted disposal facility. Solid wastes may be landlled or incinerated. Liquid wastes may be treated in an on-site waste water 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 specied in the Land Disposal Restrictions (40 CFR 268) prior to their management in a land-based system (e.g. landll 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 certicate 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 re or explosion risk and should not be burned, soldered or welded.
8. PRODUCT STORAGE
Considerations in the design and construction of styrene monomer storage and handling facilities are ammability, potential to polymerize, environmental contamination and worker exposure. The specic 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 ammable liquids in quantities of 10,000 pounds or more. Styrene monomer is highly reactive and, therefore, dierent 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 insucient 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 re 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 specications.
Product Storage
8.2.1 Tank Construction
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 sucient structural strength and pressure-relief systems to prevent catastrophic loss of contents either in normal service or under re 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, modied 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 lled from the bottom or top. When using a top-ll line, the line should be extended inside the tank to the bottom so as to prevent static electric discharge. The ll outlet should be below minimal operating level. 34 PRODUCT SAFETY BULLETIN 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 oating 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 ammable material storage facilities, nearby sources of ignition, accessibility for reghting and the impact of a vapor cloud explosion on nearby areas. Bulk storage tanks should have re monitors to provide cooling in the event of an external re. Article 500 of NFPA 70 (NEX) outlines electrical requirements for handling, transport and storage of styrene monomer and other Class IC ammable liquids. It also requires that, whenever ammable liquids are stored or transferred, their containers should be eectively 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 oors sloped to the drains are important for complete drainage.
TI
FOAM
15
SEE N.F.P.A. 11 STANDARD FOR LOW EXPANSION { FOAM AND COMBINE AGENT SYSTEM
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
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
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
18
16
14
12
10
10
12
14
*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 justied. 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.
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, reective 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 ooading 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 eectively. 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 ineective, 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 sucient dissolved oxygen for TBC as well as prevent ammability. 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 eective when the tank is circulated and thoroughly mixed. Lyondell Chemical Company has TBC available at all terminal facilities to adjust the level to specic customer requirements. According to API 2350, instrumentation at the loading station should warn the operator of the potential for overlling and shut o ow whenever overll 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 ush water and rain water. The unloading area should be curbed to divert spillage into the drainage system and prevent run-o 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 re 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 ow, 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., aring 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 trac. 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 re-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 re extinguishers should also be present.
9. TRANSFER OPERATIONS
Styrene monomer should be transferred and handled according to written operating procedures developed for the specic 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 reprevention 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.
Transfer Operations
12. Attach exible 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 xed 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 o 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.
M 10
TO PUMP 23
1. WHEEL CHOCKS (BOTH SIDES OF WHEEL) 3. HAZARD INDICATION PLACARD 2. LABEL (FLAMMABLE LIQUID)
12. NITROGEN HIGH POINT PURGE 14. PRESSURE SAFETY VALVE 13. CHECK VALVE
19. PRESSURE GAUGE W/DIAPHRAGM SEAL 21. HAND BRAKE WHEEL 23. APPROVED GROUND CLAMP 22. DERAILER 20. HANDRAIL
6. MANWAY
*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.
Transfer Operations
Figure 9.2 Styrene Monomer Unloading Checklist DOT 111A
Date: Time:
AM/PM
Yes No 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
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.
8. Inspect for leakage around valves and ttings in the pressure dome area by pouring soapy water on the connections only and checking for bubbles. If leaks are detected, tighten ttings and recheck.
*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.
Transfer Operations
Figure 9.4 Styrene Monomer Unloading Checklist DOT 105J
Date: Time:
AM/PM
Yes No 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
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.
Transfer Operations
Figure 9.5 Typical Tank Car Dome Conguration*
*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.
Transfer Operations
9. If a sample from the tank car is required to conrm 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 exible 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 ll the pump by opening the liquid line block valves. These valves must be opened slowly to avoid activating the excess ow 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 o 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.
TO PART NO. 7 19
17 4
CHEMTREC 800/424-9300
12
13
20 18
21
1 10 To Part 11 2 2 14 11 14
M 15 14 16
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.
Transfer Operations
9.3.2 Release of Empty Car
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 ag and caution signs. Leave the car brakes engaged for railroad crew to release. 4. Make sure placards are axed and in good condition. 5. If there were any mechanical problems with the tank car, advise Lyondell Chemical Company Customer Service. 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 ammable limit. If product temperature is above lower ammable limit, unload under nitrogen. 12. Connect a exible unloading hose to bottom discharge valve connector. 13. Set valves in xed 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 o 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.
Transfer Operations
Figure 9.7 Styrene Monomer Unloading Checklist DOT 407
Date: Time:
AM/PM
Yes No 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
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.
6 IM-101 23 5
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
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
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.
11.1 Classication
Styrene monomer is listed in the Hazardous Materials Table (49 CFR 172-101). Therefore, it is classied 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 Identication 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 sucient 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.
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 rst, with a follow-up call to SCDI.
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.
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 rst in each table. Factors with less than seven signicant 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
(1 Liter = 1 dm 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
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
Explosimeter
Infrared Spectrophotometers MIRAN 1B2 MIRAN 1BX MIRAN 101 MIRAN 103 MIRAN 1B MIRAN 1A Century OVA 128 Century OVA 108
Styrene
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)
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 Denitions 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 Specications 49 CFR 179; Specications for Tank Car 49 CFR 180; Qualication 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 Reneries Part I Design API RP-520; Sizing, Selection and Installation of PressureRelieving Devices in Reneries 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
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; Identication 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 Specic Hazardous Waste and Specic 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 Identication 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
IATA
International Air Transport Association 1155 Manseld 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
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 Conned 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 Pngston 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, Liqueed Gas, or Compressed Gas Hazardous Material
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. Specic control technologies are dened 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 nal rule eective 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.
Florida
Florida Employee Right-to-Know Law Provisions of this law require employers to give local re 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 dened as a toxic substance. Illinois Chemical Safety Act Under this law, covered businesses using, storing or manufacturing dened 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 Oce of Environmental Health Hazard Assessments Proposition 65 Implementation Oce 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 dened 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 Notication Act This law requires any manufacturing employer who uses, produces or stores any hazardous material to complete a survey. Hazardous materials are dened 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.
New York
New York Bulk Storage Registration/Release Reporting New York requires the registration of bulk storage tanks and notication 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 specic 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 codied 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 dened 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 dened 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.
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 specic 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 ineective because of the low ash 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 res, re ghting 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 classied 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 specied must be disclosed on the MSDS. Lyondell Chemical Company has classied 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.
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.
APPENDIX 7. GLOSSARY
ACGIH American Conference of Governmental Industrial Hygienists AFFF-AR aqueous lm-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 Conned space an area that by design has limited openings for entry and exit. A conned 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 o vapor in sucient 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 specic 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 eects 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 ammability 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 specic 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 dened equilibrium conditions. Vapor pressure is usually measured in millimeters of mercury (mm Hg), pounds per square inch, bar or Pascal. VOC volatile organic compound
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 Pacic, 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 specic 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 conict 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