The method of producing vinyl chloride

 

(57) Abstract:

Usage: vinyl chloride is the major monomer, going mainly for the production of polyvinyl chloride. The essence of the invention: balanced method of the ethylene - his catalytic chlorination and oxidation catalytic chlorination of ethylene get 1,2-dichloroethane, which is then dehydrochlorinated, share products dehydrochlorinating to the target product, unreacted 1,2-dichloroethane and organochlorine wastes; the latter is separated from the resinous products and direct on stage hydrogenolysis using a palladium catalyst, and the reaction products under hydrogenolysis is directed to phase oxidation catalytic chlorination of ethylene in the beginning of the process. This method allows to reduce the consumption of ethylene and chlorine and reduce the amount of waste to be destroyed. 1 table, 1 Il.

The invention relates to methods for organochlorine products and can be used in the chemical industry for the improvement of the production of vinyl chloride from ethylene.

Vinyl chloride is one of the most important monomers, going mainly for the production of polyvinyl chloride, neboevye acetylene in the vapor phase on the catalyst, combined method of acetylene and ethylene, a combined method of straight-run gasoline [1]

Closest to the claimed method is a balanced process of obtaining vinyl chloride from ethylene [2] consisting of six stages:

1) synthesis of 1,2-dichloroethane by direct liquid-phase chlorination of ethylene;

2) synthesis of 1,2-dichloroethane oxidative catalytic chlorination of ethylene;

3) washing, drying and distillation 1,2-dichloroethane;

4) thermal volumetric dehydrochlorination of 1,2-dichloroethane;

5) separation of the products of dehydrocorydaline 1,2-dichloroethane;

6) the distillation of vinyl chloride.

The disadvantage of this method is the formation of a large amount of waste reaching 50 110 kg per 1 t of vinyl chloride. Given that the standard production capacity is 250,0 thousand tons per year, the amount of waste in year one production is 12.5 27.5 thousand tons per year. As a result of formation of such wastes in the production of vinyl chloride in a known manner a high expense ratios.

The aim of the invention is to reduce the amount of waste and the reduction of expenditure coefficients for ethylene and chlorine.

Put apoderado catalytic hydrogenolysis, and the products of the reaction stage hydrogenolysis go on stage ethylene oxychlorination process.

The drawing shows a block diagram of the proposed method.

The essence of the proposal the applicant is as follows: organochlorine waste of vinyl chloride balanced on chlorine method consist mainly 1,2,3-trichloroethane mixed with 1,2-dichloroethane and some other substances, including resinous substance. Before applying these organochlorine wastes by hydrogenolysis, they are subjected to bleaching (separation from resin), for example, evaporation and condensation. The clarified waste consisting mainly of 1,1,2-trichloroethane and 1,2-dichloroethane is subjected to hydrogenolysis in the presence of hydrogen at a temperature of 250 350oWith catalyst MA-15, representing 0.4% of Pd on activated alumina. In the process of hydrogenolysis of organochlorine wastes receive a gaseous mixture consisting of ethylene, ethane and hydrogen chloride:

2C2H3Cl3+3H2_ C2H4+C2H6+6HCl

2C2H2Cl2+2H2_ C2H4+C2H6+4HCl

At the stage of ethylene oxychlorination process flow the following reactions

what if the products of the hydrogenolysis reactions of the stage to guide on the stage oxychlorination process, the ethylene and hydrogen chloride in the result is the raw material for the production of dichloroethane, and then and vinyl chloride. Due to this, in the proposed method achieves processing organochlorine wastes, reduction of expenditure coefficients for raw materials.

Example. Ethylene served in equal amounts into the reactor direct and oxidative chlorination. The reactor direct chlorination of ethylene filled with liquid 1,2-dichloroethane containing catalyst FeCl3equipped with a jacket for removal of heat of reaction and maintain the temperature of 60oC. Simultaneously with ethylene in the reactor serves chlorine. The amount of reagents given in the table.

The reactor for the oxychlorination process is a vertical cylindrical apparatus with fluidized bed chlorides of copper supported on a carrier (catalyst deacon). Into the reactor simultaneously with ethylene serves hydrogen chloride and air. The process is carried out at 220oC.

The washed and drained dichloroethane from the stage oxychlorination process and phases of the direct chlorination sent for rectification, where the separated impurities and purified dichloroethane sent to pyrolysis at a temperature of 490oC. Conversion per pass 50%

Received videleyt cube from the rectification column of dichloroethane. Wastes have the following average composition, wt. 1,2-dichloroethane 14; 1,1,2-trichloroethane 40; perchlorethylene 18; 1,1,2,2-tetrachlorethane 7,4; pentachloride 18; hexachlorethane 2; resinous substance 0,6.

In experiments 1-4 distillation waste sent for incineration. In experiments 5-8 these distillation waste is subjected to clarification by simple distillation: with the resin is 15% waste. As lightening carried out by simple distillation, the distillation residue after clarifying remains practically unchanged and similar to the above without regard to resinous products.

The clarified waste is evaporated and sent to the hydrogenolysis reactor filled with industrial palladium catalyst MA-15, containing 0.4% Pd on alumina. The process is carried out at a temperature of 300oC. the Supply of hydrogen is performed with 10% excess.

The reaction products of the hydrogenolysis process in addition to ethylene, ethane and hydrogen chloride contain unreacted hydrogen in the amount of 10% of the submitted response (0,046 0,088 g/h, respectively).

The cost of reagents, the amount of vinyl chloride, the amount of waste received and processed number, and other data presented in the table.

Analysis of the data, before the Hai hydrogenolysis with feed gases this stage to the stage of oxidation of ethylene reduces expenditure ratios for ethylene 459.36-472.72 to 453.64-460.12 kg/t and chlorine with 617.56-677.04 to 604.46-648.23 kg/t (experiments 1-4 and 5-8, respectively), and reduce 80-85% of the amount of waste to be destroyed. Given that the capacity of production of vinyl chloride from ethylene are usually 250 270 thousand tons per year, saving material costs several thousand tons per year.

The essential features of the proposed method of producing vinyl chloride is an introduction to balanced chlorine process stage hydrogenolysis organochlorine waste transfer reaction products of this stage to the stage oxychlorination process.

The method of producing vinyl chloride balanced method of ethylene, comprising the stage of synthesis of 1,2-dichloroethane by direct liquid-phase catalytic chlorination of ethylene oxidation catalytic chlorination of ethylene, washing, drying and distillation 1,2-dichloroethane, gas-phase dehydrochlorination 1,2-dichloroethane, separation of the products of dehydrocorydaline 1,2-dichloroethane, rectification on the target product, unreacted 1,2-dichloroethane and organochlorine wastes, characterized in that the chlorinated organic waste is separated from the resinous products and direct on stage hydrogenolysis using a palladium catalyst, and the reaction products under hydrogenolysis is directed to phase oxidant is

 

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FIELD: industrial organic synthesis.

SUBSTANCE: invention is dealing with production of chlorohydrocarbons exhibiting plasticizing properties in polymer compositions in production of synthetic building materials, varnishes and paints, artificial films and leathers, in rubber industry, and as fire-retardant additives in polymers. Process comprises chlorination of waste obtained in production of C14-C32 fraction by ethylene-α-olefin oligomerization. Chlorination is accomplished in two steps: addition chlorination at 35-55°C followed by substitution chlorination at 40-105°C. Chlorohydrocarbons thus obtained can, in particular, be used as secondary plasticizer in polyvinylchloride compositions.

EFFECT: reduced expenses due to using production waste.

4 tbl, 30 ex

FIELD: petrochemical and industrial organic synthesis.

SUBSTANCE: process comprises separating gaseous pyrolysis products to recover ethylene-containing fraction with 54-65% ethylene content and C3-C5-hydrocarbon fraction. Ethylene-containing fraction is subjected to liquid-phase catalytic chlorination. Gas phase of chlorination product is purified via adsorption and fed into furnace as fuel. C3-C5-Hydrocarbon fraction is subjected to exhaustive hydrogenation, hydrogenation product is combined with fresh raw material at weight ratio (0.05ч1):1 and sent to pyrolysis plant.

EFFECT: achieved integration of process, increased reliability thereof, and reduced expenses.

1 dwg, 1 tbl, 15 ex

FIELD: organic chemistry.

SUBSTANCE: 1,2-dichloroethane is obtained by liquid phase ethylene chlorination with discharging of reaction heat due to operation medium boiling. In claimed process nitrogen is added to chlorine and ethylene reagents. Ratio of chlorine volume consumption to nitrogen volume consumption is maintained as 1:1. Reaction is carried out at temperature lower than 1,2-dichloroethane boiling point, and discharging of reaction heat is carried out by evaporative cooling of operation medium in nitrogen.

EFFECT: process of increased selectivity; decreased yield of by-products.

1 tbl, 5 dwg

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SUBSTANCE: the invention is pertaining to the design of the bubble-type reactors for production of 1.2-dichloroethane by the method of the liquid-phase chlorination of ethylene with the reaction heat removal at boiling of the working medium. As the contact device the reactor uses two layers of the metallic nozzle. The liquid 1.2-dichloroethane is fed from above to the nozzle, into the space between the layers of the nozzle feed the gaseous chlorine with nitrogen, and under the lower layer of the nozzle feed the gaseous ethylene with nitrogen, that allows to reduce the diameter of the reactor in 1.5-2 times due to the increased effectiveness of stirring and formation of the developed contact surface of the phases. At that the heat of the reaction is removed by evaporation of 1.2-dichloroethane in nitrogen. At that the temperature of the liquid is maintained below the boiling temperature. The technical result of the invention is the increased selectivity of the process, reduction of the outlet of the by-products (the highest ethane chlorides) and the decreased overall dimensions of the reactor.

EFFECT: the invention ensures the increased selectivity of the process, reduction of the outlet of the by-products (the highest ethane chlorides) and the decreased overall dimensions of the reactor.

1 ex, 4 dwg

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of 1,2-dichloroethane by method of liquid-phase chlorination of ethylene. The process is carried out by direct feeding gaseous reagents chlorine and ethylene in liquid reaction medium of reactor. Before feeding into reactor chlorine and ethylene are heated preliminary in heat-exchangers to temperature equal to that of liquid in reactor. Method provides enhancing selectivity of process and reducing formation of by-side substances representing higher chlorine-derivatives of ethane.

EFFECT: improved method of synthesis.

4 dwg, 1 ex

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EFFECT: improved method of synthesis.

3 dwg, 1 ex

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