Styrene Monomer

Storage & Handling Safety Guide

STYRENE MONOMER STORAGE & HANDLING SAFETY GUIDE

Table of Contents

INTRODUCTION.........................................................................................................................................................3 TYPICAL PRODUCT PROPERTIES.......................................................................................................................4 EMERGENCY RESPONSE ......................................................................................................................................7 SPILLS......................................................................................................................................................................7 SMALL SPILLS ...................................................................................................................................................7 LARGE SPILLS ...................................................................................................................................................7 FIRES .......................................................................................................................................................................7 UNCONTROLLED POLYMERIZATION ..............................................................................................................8 HEALTH HAZARDS / FIRST AID / PERSONAL PROTECTION EQUIPMENT ..............................................8 TRANSPORTATION..................................................................................................................................................9 STORAGE AND HANDLING....................................................................................................................................9 OVERVIEW..............................................................................................................................................................9 PREVENTION OF POLYMER FORMATION IN STYRENE .............................................................................9 TBC INHIBITOR in STYRENE..........................................................................................................................9 SHELF LIFE of STYRENE ..............................................................................................................................10 STORAGE TEMPERATURE...........................................................................................................................10 TBC DEPLETION and ADDITIONS ...............................................................................................................11 GENERAL STORAGE CONDITIONS................................................................................................................12 GENERAL HANDLING PRECAUTIONS ...........................................................................................................12 QUALITY IMPACTS .............................................................................................................................................13 COLOR...............................................................................................................................................................13 PARTICULATE MATTER ................................................................................................................................14 SAMPLING AND ANALYTICAL METHODS.......................................................................................................14 TANK CLEANING AND INSPECTION .................................................................................................................15 SUGGESTED INSPECTION POINTS FREQUENCY .....................................................................................15 DISPOSAL.................................................................................................................................................................15 INTERNET RESOURCES/LINKS..........................................................................................................................16 TRADE ASSOCIATIONS.....................................................................................................................................16 INDUSTRY STANDARDS ...................................................................................................................................16 GOVERNMENT/REGULATORY AGENCIES...................................................................................................16 REFERENCES..........................................................................................................................................................17

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INTRODUCTION
INEOS Styrenics LLC produces plastics and chemicals that are essential to everyday life, with a focus on two product chains: styrene and polystyrene. Styrene is one of the most important monomers produced by the chemical industry today. Styrene, also known as cinnamene, ethenylbenzene, phenylethene, phenylethylene, styrol, styrolene, vinylbenzene, is a clear, colorless, oily flammable liquid with a distinctive sweet aromatic odor. Styrene undergoes polymerization to produce a wide variety of polymers and copolymers, which are used in a wide range of consumer and industrial goods. INEOS Styrenics produces styrene at three locations: its Sarnia, Ontario facility, its Texas City, Texas facility and its Bayport, Texas facility. In addition, INEOS Styrenics supplies styrene as part of a tolling arrangement with Lyondell Chemical Company. The large volumes produced and the variety of end uses for styrene underscores the need for readily available information concerning its hazards, safe handling, and its chemical and physical properties. It has been well-demonstrated that styrene can be used, handled, and stored without difficulty when its physical and chemical properties are understood and the safeguards associated with these properties are observed. Styrenes reactivity is such that it must be handled within a range of specially prescribed conditions. This is necessary to avoid flammability and polymerization hazards and to prevent deterioration in the quality of the styrene. INEOS Styrenics works to ensure the safest possible management of chemical products throughout their life cycles; from the early stages of planning of new products through their manufacture, distribution, use and ultimate disposal. In support of this commitment, INEOS Styrenics prepared this Guide to help our customers safely handle, store and process our styrene monomer. The information provided in this Guide is believed to be accurate as of the publication date. This Guide is intended for use in conjunction with INEOS Styrenics styrene Material Safety Data Sheet (MSDS). Important precautions related to the safe handling, transport, storage and use of our styrene monomer are detailed on the MSDS. Please consult the references provided at the end of this guide for updates or more detailed information. It is important to note that government legislation/regulations and industry standards/codes must always be observed. Certain required regulatory information is summarized on the MSDS. For an up-to-date MSDS, please contact INEOS Styrenics via e-mail at psinfo@ineosstyrenics.com

INEOS STYRENICS DOES NOT WARRANT OR REPRESENT THE INFORMATION GIVEN TO BE ACCURATE OR COMPLETE, AND EXPRESSLY DISCLAIMS ALL IMPLIED WARRANTIES AND CONDITIONS INCLUDING THOSE OF MERCHANTABILITY AND FITNESS OF PRODUCT(S) FOR A PARTICULAR PURPOSE. THIS GUIDE IS PROVIDED FOR THE PURPOSE OF ASSISTANCE AND THEREFORE ANY TECHNICAL ADVICE FURNISHED OR RECOMMENDATION MADE BY INEOS STYRENICS OR ANY REPRESENTATIVE THEREOF CONCERNING ANY USE OR APPLICATION OF ANY PRODUCT IS BELIEVED TO BE RELIABLE BUT SELLER MAKES NO WARRANTY, EITHER EXPRESS OR IMPLIED, AS TO ITS ACCURACY OR COMPLETENESS OR OF THE RESULTS TO BE OBTAINED. WITH REGARD TO ANY PROCESSING OF ANY PRODUCT, CUSTOMER ASSUMES FULL RESPONSIBILITY FOR QUALITY CONTROL, TESTING AND DETERMINATION OF SUITABILITY OF PRODUCT FOR ITS INTENDED APPLICATION OR USE. THE INFORMATION CONTAINED HEREIN IS SUBJECT TO CHANGE WITHOUT NOTICE AND INEOS STYRENICS DISCLAIMS ANY OBLIGATION TO UPDATE THE INFORMATION CONTAINED HEREIN. RESPONSIBILITY FOR USE, TRANSPORTATION, STORAGE, HANDLING AND DISPOSAL OF THE PRODUCTS DESCRIBED HEREIN AFTER DELIVERY AT THE DELIVERY POINT IS THAT OF THE PURCHASER OR END USER.

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TYPICAL PRODUCT PROPERTIES 1

Property Auto ignition temperature (in air) (1) Boiling point (2,9) 760 mm Hg 100 mm Hg 30 mm Hg 10 mm Hg 1mm Hg Color Corrosivity Critical pressure (pc) (3) Critical temperature (tc) (3) Critical volume (Vc) (3) Cubical coefficient of expansion (per deg. C) ) (4) Density of liquid (4) Value 490C (914F) 145.2C (293.4F) 82.2C 54.7C 33.6C -1.6C Colorless to light yellow Non-corrosive to metals except to copper and alloys of copper 39.5 atm. (580 psia) 374.4C (706F) 0.369 1/mole 9.710x 10 4 at 20C 9.805 x 104 at 30C 9.902 x 10 4 at 40C Temperature (C) 0 20 40 60 80 100 Temperature (C) 20 40 60 82.48 cal/(gm-mole)-deg. 0.9 6.8 volume-percent 31C (87.8F) 51.10 kcal/(gm-mole) -30.628C (-23.13F) -1018.83 kcal/(gm-mole) 35.22 kcal/(gm-mole) 24.83 kcal/(g-mole) -17.8 kcal/(gm-mole) 8.82 kcal/(gm-mole) 104.14 gm/(gm-mole) Sweet, almost floral odor at low concentrations; sharp, penetrating, disagreeable at higher concentrations Liquid Density (g/cc) 0.9237 0.9059 0.8880 0.8702 0.8524 0.8345 2.4257 2.3884 2.3510

Dielectric constant of liquid (5)

Entropy of gas at 25C (S) (2) Flammable limits (in air) at atmospheric pressure (1) Flash point (6) : (Tagliabue closed cup) Free energy of formation of gas at 25C (Gf)(2) Freezing point (2) Heat of combustion, gas at const. press., 25C, to form gaseous products (H0 ) (2) Heat of formation (2) gas at 25C (Hf ) liquid at 25C (Hf) Heat of Polymerization at 90C H) (7) Heat of vaporization at 145.1C (9) Molecular weight Odor Physical state at room temperature

Superscripts refer to reference sources listed at the end of this guide.

1. The data contained in this section have been obtained or derived from published scientific and chemical literature.

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Refractive index: (4)

Solubility: Styrene in water (8)

Temperature (C) 15 20 25 30 35 Temperature (C) 0 20 40 60 80 Temperature (C) 0 20 40 60 80 Soluble in all proportions 0.906 Temperature (C) 7 17 37 57 77 97 117 Temperature (C) 0 15.6 25.0 37.8 93.0 149.0 260.0 538.0 Temperature (C) 0 20 40 60 80

Solubility: Water in styrene (8)

ND 1.5495 1.5467 1.5439 1.5410 1.5382 Solubility (gm/100 gmH20) 0.018 0.029 0.040 0.051 0.062 Solubility (gm/100 gm styrene) 0.020 0.060 0.100 0.140 0.180

Solubility in: (9) Acetone CC14 Benzene Ether n-Heptane Ethanol Specific gravity @ 68F (Water = 1) Specific heat (liquid) (7)

cp (cal/gm-C) 0.406 0.413 0.425 0.440 0.456 0.474 0.494 cp (cal/gm-C) 0.256 0.271 0.280 0.292 0.340 0.385 0.462 0.593 Surface Tension (dynes/cm) 34.5 32.3 30.0 27.8 25.6

Specific heat (vapor) (2)

Surface Tension (7)

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100 Viscosity, cps (4) Temperature (C) 0 20 40 60 80 100 120 4.5 mmHg (at 20 deg C) 17%

23.5 Viscosity (Centipoises) 1.040 0.763 0.586 0.470 0.385 0.326 0.278

Vapor pressure Volume change on polymerization (shrinkage)(7)

* Superscripts refer to reference sources listed at the end of this guide.

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EMERGENCY RESPONSE
In the event of an emergency, contact the local police and the appropriate emergency numbers listed in the styrene monomer MSDS. Ensure statutory and regulatory reporting requirements in the appropriate jurisdiction are met.

SPILLS
If conditions are safe to do so, stop the source of the leak and eliminate sources of ignition before attempting to clean up the spill. If conditions are unsafe, cleanup should not begin until all ignition sources have been eliminated. Personnel should stay upwind and not enter low areas where vapors can accumulate. Full-face, NIOSH-approved, self-contained breathing apparatus and appropriate protective clothing must be worn by all individuals required to enter the hazard area. Since styrene vapor is invisible, heavier than air and spreads along the ground, it may travel considerable distances to a source of ignition such as pilot lights, welding equipment, electrical motors or switches and then flashback. Use vaporsuppressing foam or water spray to control vapors. It is important to prevent the formation of explosive or combustible mixtures, and to take precautions to avoid the ignition of any such mixtures.

SMALL SPILLS
For small spills, the area should be isolated immediately to encompass 80 160 feet (25 50 meters) in all directions. Small spills (non-marine) may be absorbed by using a suitable inert material such as sand or another non-reactive absorbent material. Some absorbing agents, such as untreated clays and micas, may cause an exothermic reaction such as hazardous polymerization or possibly even ignite the styrene. For this reason, absorbing agents should be pre-tested under controlled conditions for compatibility and to determine their effect on polymerization of the styrene before being used on large spills. Contact local environmental or health authorities for approved disposal of the absorbing agent. Spills into surface water may be cleaned up using a skimmer or vacuum system because styrene floats on water and tends to polymerize to form a surface film.

LARGE SPILLS
For large spills, the area should be isolated immediately to encompass 1000 feet (300 meters). Personnel should stay upwind of the spill. Full-face, NIOSH-approved, self-contained breathing apparatus and appropriate protective clothing must be worn by all individuals required to enter the hazard area. Large spills may be absorbed by using a suitable inert material such as sand or another non-reactive absorbent material. If the area is unpaved, diking and water flooding may be used to float up the styrene to facilitate its recovery and prevent soaking into the ground. If the spill is on a hard surface, the area should be scrubbed with soap and water after the bulk of the styrene has been removed. Styrene should be kept out of sewage and drainage systems and waterways. If styrene has entered any of these facilities, the appropriate authorities must be informed as soon as possible.

FIRES
Styrene monomer is a highly flammable liquid when in the presence of open flames, sparks and heat. Tanks or other sealed containers containing styrene monomer that are heated by an external fire or other means pose a severe risk of bursting and explosion. Use water to cool fire-exposed containers and to protect personnel. In addition, styrene tanks or containers in the vicinity of a neighboring fire should be kept cool by spraying with a water spray. If it can be done safely, consider removing other flammable liquids in the vicinity, if this can be done safely. For fires involving styrene, do not enter any enclosed or confined fire space without proper protective equipment. Styrene fires can be extinguished using foam, dry chemical, carbon dioxide, water fog or water spray. Water jets should not be used, as these may

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spread the fire. The use of unmanned hose holders or monitor nozzles should be considered. Burning styrene may produce carbon monoxide, carbon dioxide, low molecular weight hydrocarbons, and large quantities of thick black smoke. For this reason, breathing of fumes, smoke, and gas from a styrene fire should be avoided. Personnel should stay upwind of the fire. Fullface, NIOSH-approved self-contained breathing apparatus and appropriate protective clothing must be worn by all individuals required to enter the hazard area.

UNCONTROLLED POLYMERIZATION
Styrene may undergo polymerization if the inhibitor becomes depleted, a process which, if it becomes rapid and uncontrolled, can be dangerous. This polymerization process is exothermic, evolving 288 btu/lb (17.8 kcal/gm mole). As the styrene polymerizes, it becomes more viscous, reducing the rate at which heat can be dissipated. If the evolved heat cannot be dissipated rapidly enough, the temperature of the styrene will rise, increasing the rate of polymerization and the associated rate at which heat is generated. The temperature may rise to the point where the reaction becomes very rapid and self-accelerating (runaway polymerization). During a runaway polymerization, the temperature will reach and exceed the boiling point of styrene. The vapor may then erupt violently from the tank vents. If the vents are plugged or too small, the vapor can create enough pressure to rupture the tank. When indications of rapid polymerization are observed, it is imperative that the styrene be cooled. Immediate action should be taken to clear the area of non-essential personnel and to ensure the storage vessel is adequately vented to relieve any build-up of pressure. The use of a water spray on the storage vessel to cool the reaction may help; coolers are ideal where available. If possible, the storage vessel should be circulated. Also, if possible, polymerization inhibitor (TBC, 4-tertiary butylcatechol) should be added to styrene while the tank is circulating. Diluting the monomer with a non-reactive, miscible solvent (diluent) such as ethylbenzene or toluene may also quench a runaway polymerization, but only when there is significant dilution of the styrene. If the styrene is hot, the diluting solvent may just vaporize or flash off. The appropriate action to take in response to a runaway polymerization will depend primarily on temperature. The beginning of a runaway polymerization may be identified by an increase in styrene temperature (particularly if styrene temperature exceeds ambient or rises more than 3F in one day). Decisions concerning the appropriate/necessary actions to take must be made on-site. For steps on how to halt a runaway polymerization or to deal with an advanced runaway polymerization, please refer to the Canutec or ChemTrec emergency response manuals. Uncontrolled polymerization should not occur, however, if certain factors such as TBC levels, tank temperatures, and the level of dissolved oxygen are controlled. These topics will be discussed in further detail later in this guide.

HEALTH HAZARDS / FIRST AID / PERSONAL PROTECTION EQUIPMENT

As with all chemicals, the hazardous properties of styrene must be recognized and all necessary precautions must be taken in order to avoid accidents and injury. Fundamental precautions with respect to ventilation, protective equipment, good engineering and safety practices should be observed to prevent exposures, personnel injuries and fatalities. Employees who work in areas where styrene is manufactured, handled, or stored should receive instruction in: The hazardous properties of styrene The requirements for proper protective equipment and its use First aid measures required after exposure to styrene liquid and vapor.

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Allowable exposure levels may vary and applicable regulations should be consulted to determine allowable exposure levels and personal protection requirements in your area. Please refer to the current MSDS for more information.

TRANSPORTATION
Styrene monomer is regulated nationally and internationally as a hazardous material or dangerous good in transportation. Persons intending to transport styrene, or prepare it for transportation, need to consult regulations applicable to the mode of transport, country of origin, and destination for the shipment. Please refer to the current MSDS for additional transportation information. INEOS Styrenics transports its styrene monomer in a variety of modes, utilizing different carriers within these modes, and has the capability to ship styrene via marine vessels to both domestic and international destinations. INEOS Styrenics uses tank cars and tank trucks that comply with transportation regulatory requirements to transport its styrene monomer from its facilities in U.S and Canada. When hiring a transportation service and preparing to load styrene monomer, the following elements should be considered: Vessel (truck / rail / marine) material of construction (Stainless Steel / Zinc / Mild Steels / etc.) Cleaning procedures Drying procedures Inspection capabilities Pump / gasket / valve / hose compatibility Wall washes (for testing to insure cleanliness) The above elements are only a partial listing of items that should be considered; individual customers may have their own specific requirements.

STORAGE and HANDLING

OVERVIEW
The primary concerns in the handling and storage of styrene are: prevention of polymer build-up, minimization of incident risk, and the maintenance of product quality over a period of time. Adhering to the recommended handling and storage practices is advisable for all users to avoid degradation of styrene in storage. Styrene polymerizes slowly at room temperature and more rapidly at elevated temperatures. The rate of polymerization could eventually become uncontrolled, leading to hardening and plugging of equipment, or, in the worst cases, a fire or explosion. To prevent polymer formation in styrene, an inhibitor called TBC is added. In addition to TBC use, temperature control and the selection of a proper storage environment will insure long shelf life and the needed quality specifications.

PREVENTION OF POLYMER FORMATION IN STYRENE TBC INHIBITOR in STYRENE

Styrene polymerizes slowly at normal ambient temperatures but very rapidly at elevated temperatures. The maximum acceptable polymer content according to ASTMs D2827 is a specification of 10mg/kg (ppm). The presence of more than 15mg/kg (ppm) polymer in styrene may adversely affect the color and clarity of polymer produced by some polymerization processes. Once a high level of polymer forms in styrene, the only way to lower polymer content is by distillation or by blending low-polymer styrene into the styrene with high polymer content.

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TBC is added to styrene as an inhibitor to prevent polymer formation and oxidative degradation during shipment and subsequent storage. TBC has been shown to provide protection against polymer formation even at concentrations as low as 3ppm. The recommended practice is to maintain inhibitor (TBC) levels between 10-50ppm to help reduce the risk of polymerization. Some customers may require higher levels of inhibitor because of unique storage conditions or process requirements. For TBC to effectively inhibit the formation of polymer, tank temperatures must be controlled and sufficient dissolved oxygen must be present. If tank temperatures are too high or if the styrene is stored for a long period, TBC levels will be depleted. The rate at which the TBC concentration depletes depends almost solely on temperature. Other factors which can also affect the depletion of TBC are contamination caused by an exposure to an alkali water phase, or exposure to copper / brass which may result in a similar rapid depletion of TBC.

SHELF LIFE of STYRENE

The following table shows the effect of inhibitor and oxygen concentrations on the shelf life of styrene at various temperatures. For informational purposes only, as referenced in Annex C of NFPA 69 Standard on Explosion Prevention Systems, the Limiting Oxidant Concentration (LOC) value for styrene when using nitrogen as a diluent in air is 9% oxygen (by volume). The purpose of the LOC value is to ensure sufficient inert gas (such as nitrogen) is used to dilute the oxygen concentration in air so that the mixture cannot become flammable. Styrene Temperature 60oF (16C) 85oF (28C) 110oF (42C) 12-15 ppm TBC Saturated with Oxygen 5 to 6 months 1 to 2 months 8 to 12 days Less Than 3 ppm Oxygen 10 to 15 days 4 to 5 days Less than 24 hours 50-75 ppm TBC Saturated with Oxygen More than 1 year 3 to 4 months Less than 30 days

However, assuming the TBC and dissolved oxygen concentration levels are maintained at the recommended minimum, the following table shows the maximum recommended storage times: Styrene Temperature, oF 95 85 75 65 Maximum Storage Time 3 days 2 weeks 5 weeks 3 months

Storage times decrease markedly with increasing temperatures. In order to minimize the degradation of large volumes of stored styrene, as a general practice the maximum shelf life times listed should never be exceeded. Storage times exceeding three months should normally be avoided so that quality isnt impacted from extended storage. This may also eliminate the need for expensive cooling systems. If possible, the best practice is to have the tank contents circulated continuously and chilled to maintain the product quality and uniformity. Consideration must also be given to plant shutdowns, and the affect they may have on storage periods.

STORAGE TEMPERATURE
Precautions must be taken to prevent the elevation of the temperature of styrene, as the increase in temperature may impact the quality of the material. High temperatures in the vapor space over styrene (often found in un-insulated, atmospheric storage tanks during hot weather) speed up the formation of oxygenated impurities in the uninhibited styrene condensate.

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The temperature of styrene in storage should be maintained as low as is economically feasible. While storage temperatures up to 100F (38C) are permissible for very short periods of time, it is recommended that styrene be stored below 84F (29C), and ideally, the temperature should not be allowed to exceed 65F (18C) for long-term storage. Adequate temperature indication should be provided at various levels in the tank. Necessary steps must be taken to insure adequate cooling of styrene in the storage tank. Tank temperatures can be reduced by using tank insulation or by painting the tank with a light, reflective paint. Refrigeration is recommended for large, above ground bulk-storage tanks in which the styrene temperature may exceed 75F (24C). The need to refrigerate also depends on the expected inventory turnover frequency. The recommended practice is to either periodically or continuously circulate styrene in storage along the delivery piping systems, using an in-line exchanger to keep the styrene cool. Circulating a portion of the tank contents to an external chiller also works to cool styrene. Other methods that can be used for temperature control include the use of underground tanks, water spray on the outside of tanks, and shading.

TBC DEPLETION and ADDITIONS

If styrene is to be held in storage for an extended period, the TBC level should be checked at regular intervals and additional inhibitor should be added to maintain a safe TBC level. It is a common practice to not let the TBC level fall below 10ppm. If TBC levels fall below 10ppm, additions should be made to bring it up to the 10-50ppm level. As stated before, TBC levels will be depleted if tank temperatures are too high or if the monomer is stored for long periods. When TBC additions are needed, they can easily be made by adding a TBC solution. (Note: Commercially available TBC is usually purchased as either an 80 or 85% solution in methanol, so it may first be necessary to do some calculations to correct its dilution.) Each 5000-gallon increment of styrene should have seven ounces of TBC solution added to raise the TBC concentration by 10ppm. After addition, the vessel or tank should be re-circulated until the inhibitor test results are consistent and target levels have been achieved. Styrene users are recommended to have a TBC concentrate/solution on-site to restore the TBC level once below 10ppm. If the inhibitor has been depleted and polymerization has begun, inhibitor should be added immediately. If unstable styrene is not treated promptly, a self-accelerating polymerization reaction could occur. As styrene polymerizes it gives off heat (exothermic reaction) but at an extremely low rate. As long as that heat is allowed to dissipate there is minimal concern. However, since most storage is insulated, if the heat does accumulate, then it is possible for a self-accelerating polymerization reaction to start. It is important to note that TBC inhibitor requires dissolved oxygen to work effectively. Normal levels of TBC will not effectively inhibit styrene polymerization in the absence of oxygen. Consequently, it is important to ensure adequate concentration levels of oxygen in the styrene. The recommended dissolved oxygen level in styrene is 15-20ppm. All that is typically needed to maintain the required dissolved oxygen content is re-circulation or atmospheric diffusion of oxygen and normal cycling of inventory levels as the tank is filled and emptied. Agitation of the styrene is also required in order to avoid regions of oxygen depletion. (Note: In order to avoid a potential explosive mixture, it is not advisable to inject pure oxygen or a highly concentrated oxygen mixture directly into the styrene.) Reduction of the oxygen absorbed by styrene, which normally occurs if the storage tank is nitrogenblanketed, substantially reduces the activity of the inhibitor. Complete elimination of oxygen from the vapor space will lead to depletion of dissolved oxygen from the styrene. If the dissolved oxygen is substantially reduced, the effectiveness of the TBC as a polymerization inhibitor is reduced; and depending on the storage temperature, polymer formation in the styrene can occur. If an inert gas blanket such as nitrogen is used, and the styrene inventory is expected to have a slow turnover, compressed air (instrument air quality) can be bubbled into the bottom of the tank via a seal loop. This will help maintain the oxygen content at acceptable levels. Extended storage times tend to lead to the requirement of routine testing of the styrenes dissolved oxygen. The continual filling and emptying of

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tanks in service, along with the small continuous N2 purge into the vapor space, serve to keep the partial pressure of oxygen in the vapor space low. This in turn reduces styrene oxidation and, as long as the oxygen level in the vapor space is kept below 10-11%, also removes the danger of explosion.

GENERAL STORAGE CONDITIONS

The following are recommended storage conditions that are essential for insuring good styrene quality with minimal polymer formation. The capacity of styrene storage tanks should match with production and shipping/receiving requirements. The capacity must also be able to accommodate typical shipment volumes (i.e. - railcar vs. truck) and allow for shipment transit time, as well as provide reasonable turnover time of the inventory so quality wont be adversely affected. Atmospheric styrene storage tanks should be designed and constructed according to both NFPA30 Flammable and Combustible Liquids as it applies to Class IV liquids, and API 650 Welded Steel Tanks for Oil Storage. The API standard is intended to ensure that tanks possess both sufficient structural strength and pressure-relief systems to prevent catastrophic loss of contents either in normal service or under fire conditions. If receiving styrene is not a regular occurrence, or if lines cannot be circulated or are seldom used, the piping should be drained or blown clear after receiving a shipment to avoid polymer formation. Styrene tanks may become contaminated with polymer pumped into the tank from stagnant transfer lines, particularly those that have been exposed to elevated temperatures. These lines should be periodically or continuously circulated to prevent build-up of polymer. Tanks should be equipped with re-circulation lines and pumps that will aid in cooling, in addition to, providing TBC mixing and dissolved oxygen requirements. Depending on the ambient temperature, circulation may be required as frequently as once per day. Styrene vapors are not inhibited and will have a tendency to form polymer in the upper sections of storage tanks if the styrene temperature is allowed to fluctuate with the day/night cycle (typically referred to as the diurnal cycle). During a cool night, the styrene vapors will condense on the surfaces as they cool and then will form polymer as the metal heats up during the day since TBC is not present. If these stalactite (icicle-like) formations are allowed to grow within the tank, they can create a hazard during maintenance, and their weight may damage the roof or roof supporting structure of the storage tank. If carbon steel is used in tank construction, the tank should be primed. Polymer will still form on top of primed surfaces, but liners will provide better protection because they will cover up any scale and oxidation and reduce the occurrence of future scale. They also provide a smooth surface, and the styrene vapors (when condensed) will drain more rapidly from a tank roof and reduce polymerization. Lining is also done because tank shells are typically thin and have small allowances for corrosion. Storage tanks should also be lined with an inorganic zinc primer. The zinc liner will provide protection from polymer buildup, as well as reduce the potential for a static charge in a tank transfer. (Note: The resistance characteristics of the zinc primer should be checked, and information obtained from the manufacturer on the long-term performance for styrene storage.) Tank cleanliness is also important, as dirt and scale may act as a catalyst for polymer formation. Due to the prescribed conditions necessary to insure quality styrene with minimal polymer formation, intentional storage of styrene in tank cars is discouraged.

GENERAL HANDLING PRECAUTIONS

In addition to previously discussed topics, such as the need to provide styrene circulation for mixing or refrigeration, there are also specific handling recommendations for styrene. All pipes used to transfer styrene should be sloped so they can be conveniently drained. Low spots should be avoided as styrene may polymerize. All low points should be provided with drains or some other means of removing the styrene. Pumps should be designed for easy draining of any residual styrene.

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Aboveground piping should be insulated and properly grounded. Lines should not be buried because of the difficulty of checking for leakage. If burial is preferred, the regulatory requirements to protect soil and ground water should be observed. Provisions should be made either for circulating styrene through all lines or for blowing them empty. Styrene must never be left in pipelines that are blocked at both ends. As the lines warm up in sunlight, the styrene will expand and can lead to sufficient pressure build-up and potentially to blown-out gaskets at flange connections, thus leading to spills. Great care must be taken to avoid pumping styrene against a closed valve (deadhead). The styrene in the pump will become heated and polymerize, often resulting in contamination of an entire tank. Styrene has a high volume resistivity and can pick up and hold static charge during transfer from a tank car or truck to a storage tank. In order to minimize accumulation of static electricity when pumping into airblanketed tanks, barges, or ship compartments, the initial pumping rate of styrene should conform to recommended practices. Both the tank car and transportation equipment should be well grounded. Submerged filling is recommended for all flammable liquids. When transferring styrene into a tank, submerged filling along with proper bonding and grounding should be used to dissipate static electricity. The inlet line should discharge at or near the bottom of the tank and make electrical contact with the tank to also help eliminate uncontrolled static discharge. Typically, a diffuser is installed to reduce the velocity of styrene entering a tank, thereby reducing the friction and the static created. For more information on minimizing static electricity, refer to OSHA Standard 29 CFR1910.106, Flammable and Combustible Liquids, National Fire Protection Association (NFPA) 77, Recommended Practice on Static Electricity and/or the American Petroleum Institute (API) Recommended Practice 2003, Protection Against Ignitions Arising Out of Static, Lightning, and Stray Currents.

QUALITY IMPACTS COLOR

Stored styrene occasionally develops color that can be imparted to the polymerized final product. For this reason, ASTM D2827 set the standard maximum color specification at a 10 on the Pt/Co scale using the ASTM D1209 Lumatron method, or 15 Pt/Co scale using the ASTMD5386 Hunter Tristimulus testing method. Color may develop in several ways: Copper or copper-containing alloys such as brass or bronze can form soluble copper salts when contacted by TBC inhibitor. These will impart a green or blue-green color to the styrene and will inhibit polymerization of styrene. Highly colored styrene oxidation products may form in the liquid monomer or be introduced by polymer falling or dissolving from the walls and roof. Iron, usually originating from rust in tanks or in piping, may react with TBC at the ppm level to give styrene a yellow or yellow-green color. Styrene lying stagnant in a line may develop color and, if flushed into a tank, can cause the entire tank to become off-color. Color development in storage can be minimized or reduced in several ways: Avoid copper or copper-alloyed material from coming in contact with TBC inhibitor. Similar precautions used to prevent polymer formation can prevent color development, such as: paying careful attention to the oxygen level in the styrene and the vapor space above the styrene; designing tanks properly; avoiding rust and polymer build-up on tank walls and roof; and the proper selection of metallurgies. Color in styrene can be reduced to acceptable limits by distilling the colored styrene or by blending with non-colored styrene. Caution should be used, however, since color does not always blend down proportionately.

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PARTICULATE MATTER
Styrene should be free of particulate matter when it is polymerized. Although some particulate matter in styrene originates from outside contamination via the receiving transfer system, it is also formed by the reaction of concentrated TBC solutions with iron. This happens in lines that have contained styrene but have been blown dry. All aromatic hydrocarbons have a high solubility for oxygen and water (close to ~300ppm before any free water begins to appear). When oxygen, water and warm temperatures are together, carbon steel corrosion will take place, and result in particulate matter. This is especially true when dealing with atmospheric tanks and piping systems in humid conditions. Particulate matter may be avoided by: Proper metallurgy selection, such as stainless steel Paying careful attention to cleanliness Properly coating the inside of tanks and transfer lines.

SAMPLING AND ANALYTICAL METHODS

Although INEOS Styrenics styrene monomer meets or exceeds ASTM D2827 Standard Specification for Styrene Monomer, it is essential that representative samples be taken and careful analysis be done to properly evaluate the styrene while in storage. Refer to ASTM D3437, Standard Practice for Sampling and Handling Liquid Cyclic Products for sampling information. Standard sampling practices include the following: Use clean, dry bottles for sample collection. Flush sample taps thoroughly prior to sampling. Use written sampling procedures. Analysis of samples should be completed immediately after sampling. Samples should be refrigerated if stored prior to analysis. Customers should regularly check the inhibitor level and styrene temperature. In addition, customers that have styrene in a nitrogen-blanketed storage vessel should also test the Dissolved Oxygen (DO) content. Testing for polymer and aldehyde are also good practices if the styrene has been in storage for an extended period of time. Analysis Inhibitor level (TBC) Dissolved Oxygen level (DO) Polymer Color Styrene temperature Suggested Frequency 2-3 times per week or daily if the styrene temperature is 80F (27C) or higher. Weekly, if tank is nitrogen blanketed, or if styrene turnover is slow. 2-3 times per week or daily if the styrene temperature is 80F (27C) or higher. 2-3 times weekly Daily

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Some of the recommended testing protocols are listed below: Component Aldehydes, (ppm) Polymer (ppm) Inhibitor (ppm) Method ASTM D2119 ASTM D2121 ASTM D4590

TANK CLEANING and INSPECTION

Depending on the metallurgy, tanks should be thoroughly cleaned before being put into styrene service. This may require sand blasting, vacuuming, wiping, and coating. It is critical that all openings (vents, hatches, flame arrestors, foam nozzles, etc.) leading into the vapor space of tanks be inspected at regular intervals to ensure they are not plugged with polymer. Since plugged openings could significantly hamper efforts to fight a fire, polymer should be removed whenever the buildup becomes excessive. All safety equipment should undergo regular maintenance and replacement to avoid fouling/plugging by styrene polymerization. The interior of the tank roof should also be checked periodically for polymer deposits. Since polymer is dissolved by styrene, there should not be any polymer on the floor or walls (within operating levels) unless the tank was drained and left with a heel for an extended period of time. Polymer can be removed by using a solvent that is less volatile than styrene. Tank coatings and walls are often damaged by chipping, and should be repaired before the tank is used again. Sufficient consideration must be made for tank maintenance and how it will affect production requirements. A suggested inspection schedule is provided below. More or less frequent inspections may be indicated for some installations.

SUGGESTED INSPECTION POINTS FREQUENCY

Vents, hatches, flame arrestors, etc. connected to the vapor space should be inspected periodically for polymer buildup: About every 6 months is recommended, but the exact frequency should be dictated by the individual storage conditions and the likelihood of polymer formation. Tank interior: Coated: Every 3-5 years Uncoated: Annually (Coated tanks require less frequent inspections since they are more effective in controlling polymer growth inside storage tanks than uncoated tanks.) During the cleaning or repair of tanks and other equipment used for styrene, all standard safety and industry practices applicable to volatile, flammable hydrocarbons, along with local regulatory restrictions, should be followed.

DISPOSAL
Styrene monomer, if discarded, meets the definition of a hazardous waste as per U.S. and Canadian regulations. Check local, state, federal, and provincial regulations prior to disposal. The use, mixing or processing of this material may alter this product. Contact federal, provincial/state and local authorities in order to generate or ship a waste material associated with this product to ensure materials are handled appropriately and meet all criteria for disposal of hazardous waste.

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INTERNET RESOURCES/LINKS
INEOS Styrenics www.ineosstyrenics.com The following Internet links are not owned or controlled by INEOS Styrenics which expressly disclaims all responsibility with respect to the content, accuracy, completeness or otherwise of the information available through or posted on such Internet links or of the links themselves. Use or attempted use of the Internet is the responsibility of the user.

TRADE ASSOCIATIONS
International Styrene Industry Forum (ISIF) Styrene Information and Research Center (SIRC) American Chemistry Council (ACC) European Chemical Industry Council Canadian Transport Emergency Center (CANUTEC) Chemical Transportation Emergency Center (CHEMTREC) Canadian Chemical Producers Association (CCPA) www.styrene.org www.americanchemistry.com www.cefic.org http://www.tc.gc.ca/canutec http://www.chemtrec.org/ http://www.ccpa.ca/

INDUSTRY STANDARDS
National Institute for Occupational Safety and Health (NIOSH) American Society for Testing and Materials National Fire Protection Association (NFPA) American Petroleum Institute (API) www.cdc.gov/niosh www.astm.org http://www.nfpa.org/ http://www.api.org/

GOVERNMENT/REGULATORY AGENCIES
Occupational Safety and Health Administration (OSHA) Environmental Protection Agency (EPA) Department of Transportation (DOT) Transport Dangerous Goods Directorate (TDG) Environment Canada www.osha.gov www.epa.gov www.dot.gov http://www.tc.gc.ca/tdg http://www.ec.gc.ca

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REFERENCES
Styrene and Polystyrene. Their manufacture and use. A white Paper 1990. A publication of the Polystyrene Packaging Council, Inc. Styrene. Toxicological Profile. ASTRD Public Health Service, U.S. Department of Health and Human Services, February 15, 1991. G. W. Jones, G. S. Scott, and W. E. Miller, Bureau of Mines Report of Investigations 3630. American Petroleum Institute Research Project 44, Selected Values of Properties of Hydrocarbons and Related Compounds. Physical Constants of Hydrocarbons C1 to C10, ASTM Special Technical Publication No. 109A (1963). Kirk-Othmer Encyclopedia of Chemical Technology, (2nd Ed.), Vol. 19, Interscience, New York, 1968, p. 56-57. J. Petro and C. P. Smyth, J. Amer. Chem. Soc., 80, 73 (1958). Manufacturing Chemists Association Chemical Safety Data Sheet SD-37 (Rev. 1971), p. 5. R. H. Boundy and R. F. Boyer (Eds.), Styrene: Its Polymers, Copolymers, and Derivatives, Reinhold, New York, 1952, Ch. 3. W. H. Lane, Ind. Eng. Chem. (Anal. Ed.), 18, 295, (1946). R. R. Dreisbach, Physical Properties of Chemical Compounds, Vol. 1, Am. Chem. Soc., 1955, p. 159.

INEOS Styrenics LLC | Styrenic Sales & Marketing 25846 SW Frontage Road Channahon, IL 60410 Phone +1.815.423.5541 / +1.866.890.6353 Fax +1.866.890.6362 www.ineosstyrenics.com | E-mail info@ineosstyrenics.com

INEOS Styrenics International SA Avenue de la Gare 12 CH-1700 Fribourg, Switzerland Phone +41.26.426.56.56 Fax +41.26.426.56.57

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