Ethylene dichloroethane

Chlorination of Ethylene. Dichloroethane, produced by chlorination of ethylene, can be further chlorinated to trichloroethylene and... 

Mixed-gas method. In this method [148], naphtha is thermally cracked to form acetylene and ethylene. Dichloroethane is formed by reacting ethylene with chlorine, and vinyl chloride is obtained by thermal decomposition of dichloroethane with simultaneous formation of hydrogen chloride. Further, the reaction between hydrogen chloride and acetylene also gives vinyl chloride. 

Acetylation of Alkenes. Alkenes, on treatment with AcCl/AlCls under standard Friedel-Crafts conditions, are transformed into mixtures of /3-chloroalkyl methyl ketones, allyl methyl ketones, and vinyl methyl ketones, but the reaction is not generally preparatively useful because both the products and the starting alkenes are unstable under the hyperacidic reaction conditions. Preparatively useful yields have been reported only with electron poor alkenes such as ethylene (dichloroethane, 5-10 °C >80% yield of 4-chloro-2-butanone) and allyl chlo-... 

Consider vinyl chloride production (see Example 2.1). In the oxychlorination reaction step of the process, ethylene, hydrogen chloride, and oxygen are reacted to form dichloroethane ... 

A fiowsheet for this part of the vinyl chloride process is shown in Fig. 10.5. The reactants, ethylene and chlorine, dissolve in circulating liquid dichloroethane and react in solution to form more dichloroethane. Temperature is maintained between 45 and 65°C, and a small amount of ferric chloride is present to catalyze the reaction. The reaction generates considerable heat. 

This problem is solved in the reactor shown in Fig. 10.6. Ethylene and chlorine are introduced into circulating liquid dichloroethane. They dissolve and react to form more dichloroethane. No boiling takes place in the zone where the reactants are introduced or in the zone of reaction. As shown in Fig. 10.6, the reactor has a U-leg in which dichloroethane circulates as a result of gas lift and thermosyphon effects. Ethylene and chlorine are introduced at the bottom of the up-leg, which is under sufficient hydrostatic head to prevent boiling. 

The reactants dissolve and immediately begin to react to form further dichloroethane. The reaction is essentially complete at a point only two-thirds up the rising leg. As the liquid continues to rise, boiling begins, and finally, the vapor-liquid mixture enters the disengagement drum. A very slight excess of ethylene ensures essentially 100 percent conversion of chlorine. 

Acetylene and hydrogen chloride historically were used to make chloroprene [126-99-8]. The olefin reaction is used to make ethyl chloride from ethylene and to make 1,1-dichloroethane from vinyl chloride. 1,1-Dichloroethane is an intermediate to produce 1,1,1-trichloroethane by thermal (26) or photochemical chlorination (27) routes. 

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). 

By-products from EDC pyrolysis typically include acetjiene, ethylene, methyl chloride, ethyl chloride, 1,3-butadiene, vinylacetylene, benzene, chloroprene, vinyUdene chloride, 1,1-dichloroethane, chloroform, carbon tetrachloride, 1,1,1-trichloroethane [71-55-6] and other chlorinated hydrocarbons (78). Most of these impurities remain with the unconverted EDC, and are subsequendy removed in EDC purification as light and heavy ends. The lightest compounds, ethylene and acetylene, are taken off with the HCl and end up in the oxychlorination reactor feed. The acetylene can be selectively hydrogenated to ethylene. The compounds that have boiling points near that of vinyl chloride, ie, methyl chloride and 1,3-butadiene, will codistiU with the vinyl chloride product. Chlorine or carbon tetrachloride addition to the pyrolysis reactor feed has been used to suppress methyl chloride formation, whereas 1,3-butadiene, which interferes with PVC polymerization, can be removed by treatment with chlorine or HCl, or by selective hydrogenation. 

When catalysts are used in a highly exothermic reaction, an active phase may be diluted with an inert material to help dissipate heat and moderate the reaction. This technique is practiced in the commercial oxychlorination of ethylene to dichloroethane, where an alumina-supported copper haUde catalyst is mixed with a low surface area inert diluent. 

Oxychlorination of Ethylene to Dichloroethane. Ethylene (qv) is converted to dichloroethane in very high yield in fixed-bed, multitubular reactors and fluid-bed reactors by reaction with oxygen and hydrogen chloride over potassium-promoted copper(II) chloride supported on high surface area, porous alumina (84) ... 

Oxychlorination of ethylene to dichloroethane is the first reaction performed in an integrated vinyl chloride plant. In the second stage, dichloroethane is cracked thermally over alumina to give vinyl chloride and hydrogen chloride. The hydrogen chloride produced is recycled back to the oxychlorination reactor. 

Chlorination of various hydrocarbon feedstocks produces many usehil chlorinated solvents, intermediates, and chemical products. The chlorinated derivatives provide a primary method of upgrading the value of industrial chlorine. The principal chlorinated hydrocarbons produced industrially include chloromethane (methyl chloride), dichloromethane (methylene chloride), trichloromethane (chloroform), tetrachloromethane (carbon tetrachloride), chloroethene (vinyl chloride monomer, VCM), 1,1-dichloroethene (vinylidene chloride), 1,1,2-trichloroethene (trichloroethylene), 1,1,2,2-tetrachloroethene (perchloroethylene), mono- and dichloroben2enes, 1,1,1-trichloroethane (methyl chloroform), 1,1,2-trichloroethane, and 1,2-dichloroethane (ethylene dichloride [540-59-0], EDC). 

Dichloroethane, an important intermediate for vinyl chloride production, is produced by catalytic chlorination of ethylene in either vapor or Hquid phase or by oxychlorination of ethylene. Thermal dehydrochlorination of 1,2-dichloroethane produces vinyl chloride and coproduct hydrogen chloride. Hydrogen chloride is commonly recycled to an oxychlorination unit to produce 1,2-dichloroethane or is processed into sales-grade anhydrous or aqueous hydrogen chloride. 

Addition Chlorination. Chlorination of olefins such as ethylene, by the addition of chlorine, is a commercially important process and can be carried out either as a catalytic vapor- or Hquid-phase process (16). The reaction is influenced by light, the walls of the reactor vessel, and inhibitors such as oxygen, and proceeds by a radical-chain mechanism. Ionic addition mechanisms can be maximized and accelerated by the use of a Lewis acid such as ferric chloride, aluminum chloride, antimony pentachloride, or cupric chloride. A typical commercial process for the preparation of 1,2-dichloroethane is the chlorination of ethylene at 40—50°C in the presence of ferric chloride (17). The introduction of 5% air to the chlorine feed prevents unwanted substitution chlorination of the 1,2-dichloroethane to generate by-product l,l,2-trichloroethane. The addition of chlorine to tetrachloroethylene using photochemical conditions has been investigated (18). This chlorination, which is strongly inhibited by oxygen, probably proceeds by a radical-chain mechanism as shown in equations 9—13. 

Oxychlorination. This is an important process for the production of 1,2-dichloroethane which is mainly produced as an intermediate for the production of vinyl chloride. The reaction consists of combining hydrogen chloride, ethylene, and oxygen (air) in the presence of a cupric chloride catalyst to produce 1,2-dichloroethane (eq. 24). The hydrogen chloride produced from thermal dehydrochlorination of 1,2-dichloroethane to produce vinyl chloride (eq. 25) is usually recycled back to the oxychlorination reactor. The oxychlorination process has been reviewed (31). 

The first large-scale commercial oxychlorination process for vinyl chloride was put on-stream in 1958 by The Dow Chemical Company. This plant, employing a fixed-tube reactor containing a catalyst of cupric chloride on an active carrier, produced 1,2-dichloroethane from ethylene. The high temperatures involved in the reaction were moderated by a suitable diluent. The average heat output from the reaction is 116 kJ/mol (50,000 Btu/lb mol). 

Significant quantities of ethyl chloride are also produced as a by-product of the catalytic hydrochlorination over a copper chloride catalyst, of ethylene and hydrogen chloride to produce 1,2-dichloroethane, which is used as feedstock in the manufacture of vinyl choride (see Vinyl polymers). This ethyl chloride can be recovered for sale or it can be concentrated and catalyticaHy cracked back to ethylene and hydrogen chloride (25). As the market for ethyl chloride declines, recovery as an intermediate by-product of vinyl chloride manufacture may become a predominant method of manufacture of ethyl chloride. 

Other Proeesses For Ethyl Chloride. 1,2-Dichloroethane and ethylene, after at least 3 min in the presence of anhydrous calcium sulfate at 250—350°C and pressures of 0.69—2.76 MPa (100—400 psi), yield a mixture of ethyl chloride and vinyl chloride (35). 

Dichloroethane [107-06-2] ethylene chloride, ethylene dichloride, CH2CICH2CI, is a colorless, volatile Hquid with a pleasant odor, stable at ordinary temperatures. It is miscible with other chlorinated solvents and soluble in common organic solvents as well as having high solvency for fats, greases, and waxes. It is most commonly used in the production of vinyl chloride monomer. 

Dichloroethane is produced by the vapor- (28) or Hquid-phase chlorination of ethylene. Most Hquid-phase processes use small amounts of ferric chloride as the catalyst. Other catalysts claimed in the patent Hterature include aluminum chloride, antimony pentachloride, and cupric chloride and an ammonium, alkaU, or alkaline-earth tetrachloroferrate (29). The chlorination is carried out at 40—50°C with 5% air or other free-radical inhibitors (30) added to prevent substitution chlorination of the product. Selectivities under these conditions are nearly stoichiometric to the desired product. The exothermic heat of reaction vapori2es the 1,2-dichloroethane product, which is purified by distillation. 

Oxychl orin ation of ethylene has become the second important process for 1,2-dichloroethane. The process is usually incorporated into an integrated vinyl chloride plant in which hydrogen chloride, recovered from the dehydrochlorination or cracking of 1,2-dichloroethane to vinyl chloride, is recycled to an oxychl orin a tion unit. The hydrogen chloride by-product is used as the chlorine source in the chlorination of ethylene in the presence of oxygen and copper chloride catalyst ... 

Trichloroethane is produced in the United States directly or indirectly from ethylene, for example, by chlorination of 1,2-dichloroethane, a product... 

Tetrachloroethane is produced by direct chlorination or oxychlorination utilizing ethylene as a feedstock. In most cases, 1,1,2,2-tetrachloroethane is not isolated, but immediately thermally cracked at 454°C to give the desired trichloroethylene and tetrachloroethylene products (122). A two-stage chlorination of 1,2-dichloroethane to give 1,1,2,2-tetrachloroethane has been patented (126). High purity 1,1,2,2-tetrachloroethane is made by chlorinating acetylene. 

As late as 1968, 85% of the production capacity in the United States was based on acetylene, but rising acetylene [74-86-2] costs reduced this figure to 8% by 1976 (23), and now most trichloroethylene is made from ethylene [74-85-1] or 1,2-dichloroethane [107-06-2]. 

Oxychlorination of Ethylene or Dichloroethane. Ethylene or dichloroethane can be chlorinated to a mixture of tetrachoroethylene and trichloroethylene in the presence of oxygen and catalysts. The reaction is carried out in a fluidized-bed reactor at 425°C and 138—207 kPa (20—30 psi). The most common catalysts ate mixtures of potassium and cupric chlorides. Conversion to chlotocatbons ranges from 85—90%, with 10—15% lost as carbon monoxide and carbon dioxide (24). Temperature control is critical. Below 425°C, tetrachloroethane becomes the dominant product, 57.3 wt % of cmde product at 330°C (30). Above 480°C, excessive burning and decomposition reactions occur. Product ratios can be controlled but less readily than in the chlorination process. Reaction vessels must be constmcted of corrosion-resistant alloys. 

Other Routes. A unique process that produces vinyl chloride, trichloroethylene, dichloroethane, and trichloroethane simultaneously has been developed by Produits Chemiques Pechiney-Saint-Gobain in France (31). Dichloroethylene is chlorinated directly at low temperature to tetrachloroethane, which is then thermally cracked to give trichloroethylene and hydrochloric acid. The dichloroethylene feed is coproduced with vinyl chloride in a hot chlorination reactor, using chlorine and ethylene as feedstocks. 

The reaction is carried out over a supported metallic silver catalyst at 250—300°C and 1—2 MPa (10—20 bar). A few parts per million (ppm) of 1,2-dichloroethane are added to the ethylene to inhibit further oxidation to carbon dioxide and water. This results ia chlorine generation, which deactivates the surface of the catalyst. Chem Systems of the United States has developed a process that produces ethylene glycol monoacetate as an iatermediate, which on thermal decomposition yields ethylene oxide [75-21-8]. 

Chlorohydrin Process. Ethylene oxide is produced from ethylene chlorohydrin by dehydrochlorination using either sodium or calcium hydroxide (160). The by-products include calcium chloride, dichloroethane, bis(2-chloroethyl) ether, and acetaldehyde. Although the chlorohydrin process appears simpler, its capital costs are higher, largely due to material of constmction considerations (197). 

Di-(/)-chlorophenyl)-acetic acid has been made by the action of alcoholic potassium hydroxide on l,l-di-(/>-chlorophenyl)-2,2-dichloroethane by the action of barium hydroxide on DDT in ethylene glycol and by the condensation of chlorobenzene with glyoxylic acid. ... 

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