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Regulations (Preambles to Final Rules) - Table of Contents
• Record Type: Occupational Exposure to 1,3-Butadiene
• Section: 4
• Title: Section 4 - IV. Chemical Identification, Production and Use

IV. Chemical Identification, Production and Use

A. Monomer

The chemical 1,3-butadiene (BD) (Chemical Abstracts Registry Number 106-99-0) is a colorless, noncorrosive, flammable gas with a mild aromatic odor at standard ambient temperature and pressure. It has a chemical formula of C(4)H(6), a molecular weight of 54.1, and a boiling point of -4.7 deg. C at 760 mm Hg, a lower explosive limit of 2%, and an upper explosive limit of 11.5%. Its vapor density is almost twice that of air. It is slightly soluble in water, somewhat soluble in methanol and ethanol, and readily soluble in less polar organic solvents such as hexane, benzene, and toluene. (Ex. 17-17) It is highly reactive, dimerizes to 4-vinylcyclohexene, and polymerizes easily. Because of its low odor threshold, high flammability and explosiveness, BD has been handled with extreme care in the industry.

In the United States BD has been produced commercially by three processes: Catalytic dehydrogenation of n-butane and n-butene, oxidative dehydrogenation of n-butene, and recovery as a by-product from the C(4) co-product stream from the steam cracking process used to manufacture ethylene, which is the major product of the petrochemical industry. For economic reasons, almost all BD currently made in the U.S. is produced by the ethylene co-product process.

In the steam cracking process for ethylene, a hydrocarbon feedstock is diluted with steam then heated rapidly to a high temperature by passing it through tubes in a furnace. The output stream, containing a broad mixture of hydrocarbons from the pyrolysis reactions in the cracking tubes plus unreacted components of feedstock, is cooled and then processed through a series of distillation and other separation operations in which the various products of the cracking operation are separated for disposal, recycling or recovery.

The cracking process produces between 0.02 to 0.3 pounds of BD per pound of ethylene, depending upon the composition of the feedstock. BD is recovered from the C(4) stream by the separation operations. The C(4) stream contains from 30 to 50% BD plus butane, butenes and small fractions of other hydrocarbons. This crude BD stream from the ethylene unit may be refined in a unit on site, or transferred to another location, a monomer plant, owned by the same or a different company, to produce purified BD.

Regardless of the source of the crude BD-ethylene co-product, (dehydrogenation, or blending of C(4) streams from other sources), the processes used by different companies to refine BD for subsequent use in polymer production are similar. Extractive distillation is used to effect the basic separation of BD from butanes and butenes and fractional distillation operations are used to accomplish other related separations. A typical monomer plant process is described below.

C(3) and C(4) acetylene derivatives, present in the C(4) co-product stream, are converted to olefins by passing the stream through a hydrogenation reactor. The stream is then fed to an extractive distillation column to separate the BD from butanes and butenes. Several different solvents have been employed for this operation, including n-methylpyrrolidone, dimethylformamide, furfural, acetonitrile, dimethylacetamide, and cuprous ammonium acetate solution. The BD, extracted by the solvent, is stripped from it in the solvent recovery column, then fed to another fractionation column, the methylacetylene column, to have residual acetylene stripped out. The bottom stream from the methylacetylene column, containing the BD, is fed to the BD rerun column, from which the purified BD product is taken off overhead. The solvent, recovered in the solvent recovery column, is recycled to the extractive distillation column with part of it distilled to keep down the level of polymer. (Ex. 17-17) A stabilizer is added to the monomer to inhibit formation of polymer during storage. It is stored as a liquid under pressure, sometimes refrigerated to reduce the pressure, generally stored in a tank farm in diked spheres. It is shipped to polymer manufacturers and other users by pipeline, barge, tank car, or tank truck.

BD is a major commodity product of the petrochemical industry. Total U.S. production of BD in 1991 was 3.0 billion pounds. Although BD is a toxic flammable gas, its simple chemical structure with low molecular weight and high chemical reactivity make it a useful building block for synthesizing other products. In "1,3-Butadiene Use and Substitutes Analysis," EPA identified 140 major, minor and potential uses of BD in the chemical industry. (Ex. 17-15) Over 60% of the BD consumed in the United States is used in the manufacture of rubber, about 12% in making adiponitrile which in turn is used to make hexamethylenediamine (HMDA), a component of Nylon, approximately 8% in making styrene-butadiene copolymer latexes, approximately 7% in producing polychloroprene, and about 6% in producing acrylonitrile-butadiene-styrene (ABS) resins. Lesser amounts are consumed in the production of rocket propellants, specialty copolymer resins and latexes for paint, coatings and adhesive applications, and hydrogenated butadiene-styrene polymers used as lubricating oil additives. Some nonpolymer applications include the manufacture of the agricultural fungicides, Captan and Captofol, the industrial solvent sulfolane, and anthroquinone dyes.

B. Polymers

BD based synthetic elastomers are manufactured by polymerizing BD by itself, by polymerizing BD with other monomers to produce copolymers, and by producing mixtures of these polymers. The largest-volume product is the copolymer of styrene and BD, styrene-butadiene rubber, followed in volume by polybutadiene, polychloroprene, and nitrile rubber. Polybutadiene is the polymer of BD monomer by itself. Polychloroprene is made by polymerizing chloroprene, produced by chlorination of BD. Nitrile rubbers are copolymers of acrylonitrile and BD.

Four general types of processes are used in polymerizing BD and its copolymers: emulsion, suspension, solution and bulk polymerization. In emulsion and suspension polymerization, the monomers and the many chemicals used to control the reaction are finely dispersed or dissolved in water. In solution polymerization, the monomers are dissolved in an organic solvent such as hexane, pentane, toluene. In bulk polymerization, the monomer itself serves as solvent for the polymer. The polymer product, from which end-use products are manufactured, is produced in the form of polymer crumb (solid particles), latex (a milky suspension in water), or cement (a solution).

Emulsion polymerization is the principal process used to make synthetic rubber. A process for the manufacture of styrene-butadiene crumb is typical of emulsion processes. Styrene and BD are piped to the process area from the storage area. The BD is passed through a caustic soda scrubber to remove the inhibitors which were added to prevent premature polymerization. The fresh BD monomer streams are mixed with styrene, aqueous emulsifying agents, activator, catalyst, and modifier, and then fed to the first of a train of reactors. The reaction proceeds stepwise in the series of reactors to around 60% conversion of monomer to polymer. In the cold process, the reactants are chilled and the reactor temperature is maintained at 4 deg. C to 7 deg. C (40 deg. F to 45 deg. F) and pressure at 0 to 15 psig; in the hot rubber process, temperature and pressure are around 50 deg. C (122 deg. F) and 40 to 60 psig, respectively.

The latex from the reactor train is flashed to evaporate unreacted BD which is compressed, condensed and recycled. Uncondensed vapors are absorbed in a kerosene absorber before venting and the absorbed BD is steam stripped or recovered from the kerosene by some other operation. The latex stream is passed through a steam stripper, operated under vacuum, to remove and recover unreacted styrene. The styrene and water in the condensate are separated by decanting. The styrene phase is recycled to the process. Noncondensibles from the stripping column contain some BD and are directed through the BD recovery operations.

Stripped latex, to which an antioxidant has been added, is pumped to coagulation vessels where dilute sulfuric acid and sodium chloride solution are added. The acid and brine mixture breaks the emulsion, releasing the polymer in the form of crumb. Sometimes carbon black and oil are added during the coagulation step since better dispersion is obtained than by mixing later on.

The crumb and water slurry from the coagulation operation is screened to separate the crumb. The wet crumb is pressed in rotary presses to squeeze out most of the entrained water then dried with hot air on continuous dry belt dryers. The dried product is baled and weighed for shipment.

Production of styrene-butadiene latex by the emulsion polymerization process is similar to that for crumb but is usually carried out on a smaller scale with fewer reactors. For some but not all products, the reaction is run to near completion, monomer removal is simpler and recovery may not be practiced.

Polybutadiene rubber is usually produced by solution polymerization. Inhibitor is removed from the monomer by caustic scrubbing. Both monomer and solvent are dried by fractional distillation, mixed in the desired ratio and dried in a desiccant column. Polymerization is conducted in a series of reactors using initiators and catalysts and is terminated with a shortstop solution. The solution, called rubber cement, is pumped to storage tanks for blending. Crumb is precipitated by pumping the solution into hot water under violent agitation. Solvent and monomer are recovered by stripping and distillation similar to those previously described. The crumb is screened, dewatered, dried and baled.

Polychloroprene (neoprene) elastomers are manufactured by polymerizing chloroprene in an emulsion polymerization process similar to that used for making styrene-butadiene rubber. The monomer, chloroprene (2-chloro-BD), is made by chlorination of BD to make 3,4-dichlorobutene, and dehydrochlorination of the latter.

Nitrile rubbers, copolymers of acrylonitrile and BD, are produced by emulsion polymerization similar to that used to make styrene-butadiene rubber.

Substantial amounts of BD are used in the production of two other large volume polymers: Nylon resins and ABS resin. Dupont manufactures adiponitrile from BD and uses the product to make hexamethylenediamine which is polymerized in making Nylon resins and fibers, including Nylon 6,6. Acrylonitrile, BD and styrene are the monomers used to make ABS resin which is a major thermoplastic resin. Chemically complex emulsion, suspension and bulk polymerization processes are used by different producers to make ABS polymer.

Regulations (Preambles to Final Rules) - Table of Contents

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