Ethylene pyrolysis

Pyrolysis gasoline is a by-product of the steam cracking of hydrocarbon feeds in ethylene crackers (see Ethylene). Pyrolysis gasoline typically contains about 50—70 wt % aromatics, of which roughly 50% is benzene, 30% is toluene, and 20% is mixed xylenes (which includes EB). 

Figure 6.1.29. Py-GC/MS results for multi-arm poly(propylene-alt-ethylene). Pyrolysis done on 0.4 mg material at 60Cf C in He, with the separation on a Carbowax type...

Ethylene pyrolysis can also take place in the same way. Additionally, the presence of steam as a diluent reduces the chances of hydrocarbons coming in contact with the reactor tube-wall. The carbon deposits reduce heat transfer through the reactor tubes, but steam reduces this effect by reacting with them [12] (steam reforming reaction). 

Most of the ethylene dichloride produced is utilized for the manufacture of vinyl chloride, which may be obtained from it by pyrolysis or the action of caustic soda. Large quantities are also used in anti-knock additives for gasoline. As a solvent It has been displaced by trichloroethylene and tetrachloroelhyJene. U.S. production 1978 4-75 megatonnes. 

Vlayl fluoride [75-02-5] (VF) (fluoroethene) is a colorless gas at ambient conditions. It was first prepared by reaction of l,l-difluoro-2-bromoethane [359-07-9] with ziac (1). Most approaches to vinyl fluoride synthesis have employed reactions of acetylene [74-86-2] with hydrogen fluoride (HF) either directly (2—5) or utilizing catalysts (3,6—10). Other routes have iavolved ethylene [74-85-1] and HF (11), pyrolysis of 1,1-difluoroethane [624-72-6] (12,13) and fluorochloroethanes (14—18), reaction of 1,1-difluoroethane with acetylene (19,20), and halogen exchange of vinyl chloride [75-01-4] with HF (21—23). Physical properties of vinyl fluoride are given ia Table 1. 

Concentrations depend on severity of pyrolysis. At a high severity (- 2000° C) acetylene/ethylene ratio is 1, but at lower severity acetylene concentration is reduced and ethylene is increased. 

Hoechst HTP Process. The two-stage HTP (high temperature pyrolysis) process was operated by Farbwerke Hoechst ia Germany. The cracking stock for the HTP process can be any suitable hydrocarbon. With hydrocarbons higher than methane, the ratio of acetylene to ethylene can be varied over a range of 70 30 to 30 70. Total acetylene and ethylene yields, as wt % of the feed, are noted ia Table 11. 

Regenerative pyrolysis processing is very versatile it can handle varied feedstocks and produce a range of ethylene to acetylene. The acetylene content of the cracked gases is high and this assists purification. On the other hand, the plant is relatively expensive and requires considerable maintenance because of the wear and tear on the refractory of cycHc operation. 

Hydrogen is also a significant by-product of other industrial processes, such as steam pyrolysis (68) of hydrocarbons to produce ethylene (qv), eg,... 

Ethylene Dichlonde and Vinyl Chloride. In the United States, all ethylene dichloride [107-60-2] (EDC) is produced from ethylene, either by chlorination or oxychlorination (oxyhydrochlorination). The oxychlorination process is particularly attractive to manufacturers having a supply of by-product HCl, such as from pyrolysis of EDC to vinyl chloride [75-01-4] monomer (VCM), because this by-product HCl can be fed back to the oxychlorination reactor. EDC consumption follows demand for VCM which consumed about 87% of EDC production in 1989. VCM is, in turn, used in the manufacture of PVC resins. Essentially all HCl generated during VCM production is recycled to produce precursor EDC (see Chlorocarbons and Cm OROHYDROCARBONS ViNYLPOLYAffiRS). 

Combination techniques such as microscopy—ftir and pyrolysis—ir have helped solve some particularly difficult separations and complex identifications. Microscopy—ftir has been used to determine the composition of copolymer fibers (22) polyacrylonitrile, methyl acrylate, and a dye-receptive organic sulfonate trimer have been identified in acryHc fiber. Both normal and grazing angle modes can be used to identify components (23). Pyrolysis—ir has been used to study polymer decomposition (24) and to determine the degree of cross-linking of sulfonated divinylbenzene—styrene copolymer (25) and ethylene or propylene levels and ratios in ethylene—propylene copolymers (26). 

Propjiene [115-07-17, CH2CH=CH2, is perhaps the oldest petrochemical feedstock and is one of the principal light olefins (1) (see Feedstocks). It is used widely as an alkylation (qv) or polymer—ga soline feedstock for octane improvement (see Gasoline and other motor fuels). In addition, large quantities of propylene are used ia plastics as polypropylene, and ia chemicals, eg, acrylonitrile (qv), propylene oxide (qv), 2-propanol, and cumene (qv) (see Olefin POLYMERS,polypropylene Propyl ALCOHOLS). Propylene is produced primarily as a by-product of petroleum (qv) refining and of ethylene (qv) production by steam pyrolysis. 

In a typical balanced plant producing vinyl chloride from EDC, all the HCl produced in EDC pyrolysis is used as the feed for oxychlorination. On this basis, EDC production is about evenly spHt between direct chlorination and oxychlorination, and there is no net production or consumption of HCl. The three principal operating steps used in the balanced process for ethylene-based vinyl chloride production are shown in the block flow diagram in Eigure 1, and a schematic of the overall process for a conventional plant is shown in Eigure 2 (76). A typical material balance for this process is given in Table 2. 

Oxychlorination of Ethylene. When compared with direct chlorination, the oxychlorination process is characterized by higher capital investment, higher operating costs, and slightly less pure EDC product. However, use of the oxychlorination process is dictated by the need to consume the HCl generated in EDC pyrolysis. 

Chlorinated by-products of ethylene oxychlorination typically include 1,1,2-trichloroethane chloral [75-87-6] (trichloroacetaldehyde) trichloroethylene [7901-6]-, 1,1-dichloroethane cis- and /n j -l,2-dichloroethylenes [156-59-2 and 156-60-5]-, 1,1-dichloroethylene [75-35-4] (vinyhdene chloride) 2-chloroethanol [107-07-3]-, ethyl chloride vinyl chloride mono-, di-, tri-, and tetrachloromethanes (methyl chloride [74-87-3], methylene chloride [75-09-2], chloroform, and carbon tetrachloride [56-23-5])-, and higher boiling compounds. The production of these compounds should be minimized to lower raw material costs, lessen the task of EDC purification, prevent fouling in the pyrolysis reactor, and minimize by-product handling and disposal. Of particular concern is chloral, because it polymerizes in the presence of strong acids. Chloral must be removed to prevent the formation of soflds which can foul and clog operating lines and controls (78). 

Ethylene Dichloride Pyrolysis to Vinyl Chloride. Thermal pyrolysis or cracking of EDC to vinyl chloride and HCl occurs as a homogenous, first-order, free-radical chain reaction. The accepted general mechanism involves the four steps shown in equations 10—13 ... 

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