Ethylene dichloride Processes

Chemical Processing Intermediates and Other Applications. Monoethanolamine can be used as a raw material to produce ethylenedianiine. This technology has some advantages over the ethylene dichloride process in that salts are not a by-product. Additional reactions are requked to produce the higher ethyleneamines that are normally produced in the ethylene dichloride process. 

Cataljdic reactions performed in fluid beds are not too numerous. Among these are the oxidation of o-xylene to phthalic anhydride, the Deacon process for oxidizing HCl to CI2, producing acrylonitrile from propylene and ammonia in an oxidation, and the ethylene dichloride process. In the petroleum industry, cataljdic cracking and catalyst regeneration is done in fluid beds as well as some hydroforming reactions. 

McNaughton, K. J-, Ethylene dichloride process Chem. Engng, 90 (25) 54-58 (1983). 

Once the principal route to vinyl chloride, in all but a few percent of current U.S. capacity this has been replaced by dehydrochlorination of ethylene dichloride. A combined process in which hydrogen chloride cracked from ethylene dichloride was added to acetylene was advantageous but it is rarely used because processes to oxidize hydrogen chloride to chlorine with air or oxygen are cheaper (7) (see Vinyl polymers). 

Polyamines can also be made by reaction of ethylene dichloride with amines (18). Products of this type are sometimes formed as by-products in the manufacture of amines. A third type of polyamine is polyethyleneimine [9002-98-6] which can be made by several routes the most frequently used method is the polymeriza tion of azitidine [151 -56 ] (18,26). The process can be adjusted to vary the amount of branching (see Imines, cyclic). Polyamines are considerably lower in molecular weight compared to acrylamide polymers, and therefore their solution viscosities are much lower. They are sold commercially as viscous solutions containing 1—20% polymer, and also any by-product salts from the polymerization reaction. The charge on polyamines depends on the pH of the medium. They can be quaternized to make their charge independent of pH (18). 

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). 

Solvent Treatment. Solvent processes can be divided into two main categories, solvent extraction and solvent dewaxing. The solvent used in the extraction processes include propane and cresyHc acid, 2,2 -dichlorodiethyl ether, phenol (qv), furfural, sulfur dioxide, benzene, and nitrobenzene. In the dewaxing process (28), the principal solvents are benzene, methyl ethyl ketone, methyl isobutyl ketone, propane, petroleum naphtha, ethylene dichloride, methylene chloride, sulfur dioxide, and iV-methylpyrroHdinone. 

Chlorination of Ethylene Dichloride. Tetrachloroethylene and trichloroethylene can be produced by the noncatalytic chlorination of ethylene dichloride [107-06-2] (EDC) or other two-carbon (C2) chlorinated hydrocarbons. This process is advantageous when there is a feedstock source of mixed C2 chlorinated hydrocarbons from other processes and an outlet for the by-product HCl stream. Product ratios of tri- and tetrachloroethylene are controlled by adjusting the CI2 type="subscript">2 EDC ratio to the reactor. Partially chlorinated by-products are recycled to the chlorinator. The primary reactions are... 

The per pass ethylene conversion in the primary reactors is maintained at 20—30% in order to ensure catalyst selectivities of 70—80%. Vapor-phase oxidation inhibitors such as ethylene dichloride or vinyl chloride or other halogenated compounds are added to the inlet of the reactors in ppm concentrations to retard carbon dioxide formation (107,120,121). The process stream exiting the reactor may contain 1—3 mol % ethylene oxide. This hot effluent gas is then cooled ia a shell-and-tube heat exchanger to around 35—40°C by usiag the cold recycle reactor feed stream gas from the primary absorber. The cooled cmde product gas is then compressed ia a centrifugal blower before entering the primary absorber. 

In order to assure control of the reaction, the vapor-phase inhibitor concentration must be closely controlled in the ppm range. Although several compounds have been claimed to be useful, it is likely that commercial processes use only ethylene dichloride or some of the simpler chlorinated aromatics (102). In general, the choice between inhibitors is not based on their differences in performance, but rather on the designers preference for dealing with the type of control problems each inhibitor system imposes (102). 

The chemistry of side reactions and by-products may also offer opportunities for increasing the inherent safety of a process. For example, a process involving a caustic hydrolysis step uses ethylene dichloride (EDC 1,2-dichloroethane) as a solvent. Under the reaction conditions a side reaction between sodium hydroxide and EDC produces small but hazardous quantities of vinyl chloride ... 

Perchlor may also he produced from ethylene dichloride (1,2-dichloroethane) through an oxychlorination-oxyhydrochlorination process. Trichloroethylene (trichlor) is coproduced (Chapter 7). 

However, ethylene as a cheap raw material has replaced acetylene for obtaining vinyl chloride. The production of vinyl chloride via ethylene is a three-step process. The first step is the direct chlorination of ethylene to produce ethylene dichloride. Either a liquid- or a vapor-phase process is used ... 

Perchloro- and trichloroethylenes could he produced from ethylene dichloride hy an oxychlorination/oxyhydrochlorination process without hy-product hydrogen chloride. A special catalyst is used ... 

Important applications for titanium have been developed in processes involving acetic acid, malic acid, amines, urea, terephthalic acid, vinyl acetate, and ethylene dichloride. Some of these represent large scale use of the material in the form of pipework, heat exchangers, pumps, valves, and vessels of solid, loose lined, or explosion clad construction. In many of these the requirement for titanium is because of corrosion problems arising from the organic chemicals in the process, the use of seawater or polluted cooling waters, or from complex aggressive catalysts in the reaction. 

Bromine and chlorine add rapidly to alkenes to yield 1,2-dihalides, a process called lialogenatioii. For example, approximately 6 million tons per year of 1,2-dichloroethane (ethylene dichloride) are synthesized industrially by addition... 

Trace amounts of chlorine suppress the total oxidation. This effect was discovered inadvertently when the selectivity of the process in an industrial plant rose spontaneously from one day to the other. Analysis of the catalyst revealed traces of chlorine, originating from a newly commissioned neighboring chlorine plant. Consequently, small amounts of a chlorine-containing compound, such as ethylene dichloride, are nowadays added to the feed. 

Trichloroethylene is currently produced in the United States using ethylene dichloride (a produet of ethylene and chlorine feedstocks) (EPA 1985e). PPG Industries uses a single-step oxychlorination proeess, which yields triehloroethylene and tetraehloroethylene. In the PPG proeess, ethylene dichloride is reaeted with chlorine and/or hydrogen chloride and oxygen to form the triehloroethylene and tetraehloroethylene. DOW Chemical produces trichloroethylene by a direct chlorination process, in which ethylene dichloride is reacted with chlorine to form trichloroethylene and tetraehloroethylene. 

On November 8, 2000, U.S. EPA listed as hazardous two wastes generated by the chlorinated aliphatics industry.18 The two wastes are wastewater treatment sludges from the production of ethylene dichloride or vinyl chloride monomer (EDC/VCM), and wastewater treatment sludges from the production of vinyl chloride monomer using mercuric chloride catalyst in an acetylene-based process. 

Elsewhere in this book, White and Sandel [7] discuss the integration of chlorine and ethylene dichloride (EDC) processes. The oxygen content of the chlorine fed to an EDC unit must be kept within the process specification. This can be achieved by liquefying at least part of the chlorine in order to reject non-condensables or by acidifying the brine fed to the cells. Oxygen results from the anodic oxidation of hydroxide ions free acid in the feed brine will neutralise those ions and so reduce the amount of oxygen formed. 

A recent abstract reported an excessive mortality from non-Hodgkin s lymphoma during the 1970s and 1980s in grain millers in the grain processing industry (Alavanja et al. 1988). Such workers had been exposed to 1,2-dibromoethane as well as aluminum phosphide, ethylene dichloride, malathion, and methyl bromide. 

The original rnanufacturing route to vinyl chloride (VC) didn t involve ethylene dichloride (EDC) but was the reaction of acetylene with hydrochloric acid. This process was commercialized in the 1940s, but like most acetylene-based chemistry in the United States, it gave way to ethylene in the 1950s and 1960s. The highly reactive acetylene molecule was more sensitive, hazardous,... 

Ethylene dichloride, C2H4C12, is a petrochemical that is made so that vinyl chloride can be made out of it. The process for maldng EDC is sometimes integrated with the vinyl chloride plant. EDC is made by reacting ethylene with hydrogen chloride. 

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