Method for preparing vinyl chloride

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of vinyl chloride by the liquid-phase dehydrochlorination process of 1,2-dichloroethane. As reagent for the liquid-phase dehydrochlorination process of 1,2-dichloroethane the method involves using alcoholic solutions of quaternary ammonium salts of the general formula: [R1-R2-R3-R4N]+OR- wherein R1-R2-R3 mean (C1-C4)-alkyl; R3-R4 mean propenyl, β- or γ-chloropropenyl; R means (C1-C4)-alkyl, benzyl synthesized by electrolysis of corresponding quaternary ammonium salts in electrolyzers with ion-exchange membranes. Invention provides the development of wasteless, highly efficient, ecologically pure technology of synthesis of vinyl chloride and simplifying a method for synthesis of vinyl chloride based on decreasing temperature and pressure in carrying out the process.

EFFECT: improved method of synthesis.

2 cl, 1 tbl, 1 dwg, 4 ex

 

The present invention relates to organic synthesis, in particular, to a method for producing vinyl chloride.

Vinyl chloride is one of the most important monomers commonly used to obtain a variety of polymeric materials. When polymerization in the presence of peroxides he gives polyvinyl chloride, which produces sheet materials and pipe (vinyl plastic), tapes, skin substitutes, perchlorovinyl resin, etc. From copolymers of vinyl chloride with vinylidenechloride and produce Acrylonitrile synthetic fiber (Saran, Vignon). He also serves as an intermediate product for the synthesis of 1,1,2-trichloroethane, vinylidenechloride, chloroform.

A known method of producing vinyl chloride from acetylene and hydrogen chloride in the presence of a catalyst of mercuric chloride (HgCl2). The catalyst is prepared by impregnation of activated carbon with an aqueous solution of mercuric chloride, followed by drying. A mixture of acetylene, hydrogen chloride is bubbled through the reaction space filled with solid catalyst. Source materials should be dry to prevent the formation of acetaldehyde and excessive corrosion of the equipment. Hydrogen chloride take in excess of 10÷15% compared to acetylene. The process is carried out at a temperature of 160÷180°With a subsequent increase up to 200÷220°C. the Degree of conversion of acetylene in one PR is the progress through the reactor reaches 97÷ 98%. The reaction gases contain up to 93% vinyl chloride, about 5% of hydrogen chloride, 0.5% acetylene, 0.3% utilitaria and about 0.3% of acetaldehyde. After the capture of mercuric chloride, hydrogen chloride and water, the reaction gases are divided into components by low temperature rectification (Lebedev N.N. Chemistry and technology of basic organic and petrochemical synthesis. - 2nd ed., Rev. - M.: Chemistry, 1975. 733 S.: ill. s-161).

The main disadvantage of this method include high toxicity of mercuric chloride and the explosion of acetylene. In addition, the implementation of this method involves a rather complicated technological scheme with a large number of different devices operating at temperatures up to 220°C and pressures of 0.5÷1 MPa.

Closest to the claimed, i.e. the prototype, is a method of producing vinyl chloride by thermal dehydrochlorination of 1,2-dichloroethane at a temperature of 250÷550°and a pressure of 20÷30 ATM with subsequent quenching of the reaction gases 5% solution in 1,2-dichloroethane bifunctional catalyst - hydrochloride amine of General formula (R)3NH+Cl-where R is alkyl, isoalkyl or aryl (U.S. Pat. 2129115 of the Russian Federation, IPC C 07 C 17/25, With 07 With 21/06, the Method of producing vinyl chloride. / Rasulev SG, Screws E.V., Zagidullin R.N., Bulgarin DS. No. 97109903/04; Claimed 10.06.1997, published 20.04.1999).

The disadvantages of the method protocapitalist the need to work at high temperatures and pressures. thermal dehydrochlorination 1,2-dichloroethane formed hydrogen chloride. All this greatly complicates the instrumentation process. In addition, in the process formed organochlorine wastes that are disposed of by burning.

The invention solves the technical problem of creating a waste-free, high-performance, environmentally friendly technologies for vinyl chloride and simplify the method of producing vinyl chloride by reducing the temperature and pressure.

This object is achieved in that the vinyl chloride is produced by dehydrochlorination of 1,2-dichloroethane, and according to the invention, the dehydrochlorination is carried out in the liquid phase, liquid-phase reagent dehydrochlorinating dichloroethane use Quaternary ammonium alkoxides of General formula [R1R2R3R4N]+OR-,

where R1R2R3- alkyl, C1-C4;

R3R4- propenyl, βor γ-chloropropanol;

R is alkyl (C1-C4, benzyl,

obtained by the electrolysis of alcohol solutions of Quaternary ammonium salts in the electrolytic cells with ion-exchange membranes.

The invention consists in the following. The anode chamber of two-chamber electrolytic cell 1 with a cation exchange membrane (see drawing) fill 50÷0% (mostly 60%) alcoholic solution of Quaternary ammonium salt. In the cathode chamber is placed 0,5÷2% alcoholic solution of the corresponding Quaternary ammonium alkoxide.

In an alcohol solution causes dissociation of molecules Quaternary ammonium salt

[R1R2R3R4N]+Cl-→[R1R2R3R4N]++Cl-

with the formation of cations R1R2R3R4N+and anions Cl-. In the electric field generated in the electrolytic cell when a voltage is applied to the electrodes, there is a migration of cations [R1R2R3R4N]+through the cation exchange membrane to the cathode. In a cathode chamber of the electrolysis is the decomposition of alcohol with evolution of hydrogen and formation of the corresponding Quaternary ammonium alkoxide

2[R1R2R3R4N]++2ROH+2E→[R1R2R3R4N]+OR-+H2↑,

and in the anode chamber, the emission of chlorine

2Cl--2nd→Cl2↑.

The electrolysis is carried out at a temperature of 20÷40°and a cathode current density of 30÷50 mA/cm2to achieve the concentration of the Quaternary ammonium alkoxide in a cathode chamber 40÷60%.

Received in the electrolyzer alcoholic solution of the Quaternary ammonium alkoxide at a temperature of 10÷30°served in the reactor 2, is equipped with heating and AC is chivalson devices. In the same reactor under stirring was added 1,2-dichloroethane based on 1 mol of 1,2-dichloroethane 1,05÷1,1 mole of alkoxide. In the result of the interaction of 1,2-dichloroethane with a Quaternary ammonium alkoxide is formed of vinyl chloride and the corresponding Quaternary ammonium salt.

[R1R2R3R4N]OR+ClCH2-CH2Cl→CH2=CHCl+[R1R2R3R4N]Cl+ROH

The vinyl chloride at room temperature is in gaseous form and, consequently, its isolation from the reaction mass is not difficult. Alcohol solution of the Quaternary ammonium salt after adjusting the concentration is supplied from the reactor 2 in the anode chamber of the electrolytic cell 1 to obtain the corresponding alkoxide.

Chlorine produced in the anode chamber of the electrolytic cell, can be used to obtain dichloroethane.

Example 1

In the anode chamber membrane of the cell, separated by cation-exchange membrane brand MK-40, pour 200 ml of 60% methanol solution of [(C2H5)3NCH2C6H5]Cl. In the cathode chamber of the electrolytic cell pour 200 ml of methanol containing 2% [(C2H5)3NCH2With6H5]Och3. As electrodes using titanium plates coated with ruthenium oxide. The process was performed at room temperature, amperage 3A, cathodic current density of 40 mA/cm2within 4 hours. The concentration of the solution during electrolysis in the anode chamber of the electrolyzer support permanent add salt crystal. At the end of the process in the cathode chamber receive a 52% solution of [(C2H5)3NCH2C6H5]OCH3containing to 103.5 g of methoxide triethylenediamine.

Obtained in a cathode chamber of a membrane electrolyzer methanol solution of methoxide triethylenediamine transferred into a reactor equipped with a heating and cooling device and a stirrer. After that, the reactor at room temperature and continuous stirring was added 34 ml of 1,2-dichloroethane. The molar ratio of methoxide of triethylenediamine to 1,2-dichloroethane is 1.1:1. Released from the reaction of the vinyl chloride catch trap, cooled with nitrogen. After 5 min after the start of the process gain of 26.5 g of vinyl chloride, 96.4 g [(C2H5)3NCH2C6H5]Cl and 93.6 g of methanol. Received 51% methanolic solution of Quaternary ammonium salt after adjusting again placed in the anode chamber membrane of the cell to obtain a methanol solution of methoxide triethylenediamine. The conversion of 1,2-dichloroethane to vinyl chloride is 99.7 per cent.

Example 2

To the anode of the membrane electrolyzer, the Department is nnow cation exchange membrane brand MK-40, pour 200 ml of 60% methanol solution of [(C2H5)3NCH2C6H5]Cl. In the cathode chamber of the electrolytic cell pour 200 ml of methanol containing 2% [(C2H5)3NCH2C6H5]OCH3. As electrodes using titanium plates coated with ruthenium oxide. The process is carried out at a temperature of 20°, amperage of 2.25 And a cathode current density of 30 mA/cm2for 5.5 hours. The concentration of the solution during electrolysis in the anode chamber of the electrolyzer support permanent add salt crystal. At the end of the process in the cathode chamber receive a 52% solution of [(C2H5)3NCH2C6H5]OCH3containing 104 g of methoxide triethylenediamine.

Obtained in a cathode chamber of a membrane electrolyzer methanol solution of methoxide triethylenediamine transferred into a reactor equipped with a heating and cooling device and a stirrer. After that, the reactor at a temperature of 10°and With continuous stirring, add 35 ml of 1,2-dichloroethane. The molar ratio of methoxide of triethylenediamine to 1,2-dichloroethane is 1.05:1. Released from the reaction of the vinyl chloride catch trap, cooled with nitrogen. After 5 min after the start of the process gain of 27.7 g of vinyl chloride, 100,9 g [(C2H5)3NCH2C6H5/sub> ]Cl and 94.2 g of methanol. Received 51,7% methanol solution of the Quaternary ammonium salt after adjusting again placed in the anode chamber membrane of the cell to obtain a methanol solution of methoxide triethylenediamine. The conversion of 1,2-dichloroethane to vinyl chloride is 99,8%.

Example 3

In the anode chamber membrane of the cell, separated by cation-exchange membrane brand MK-40, pour 200 ml of 60% methanol solution of [(C2H5)3NCH2C6H5]Cl. In the cathode chamber of the electrolytic cell pour 200 ml of methanol containing 2% [(C2H5)3NCH2C6H5]OCH3. As electrodes using titanium plates coated with ruthenium oxide. The process is carried out at a temperature of 40°, amperage of 3.75 And a cathode current density of 50 mA/cm2for 3.2 hours. The concentration of the solution during electrolysis in the anode chamber of the electrolyzer support permanent add salt crystal. At the end of the process in the cathode chamber receive a 52% solution of [(C2H5)3NCH2C6H5]OCH3containing to 103.8 g of methoxide triethylenediamine.

Obtained in a cathode chamber of a membrane electrolyzer methanol solution of methoxide triethylenediamine transferred into a reactor equipped with a thermostatic device yosakoi. After that, the reactor at a temperature of 30°and With continuous stirring, add 35 ml of 1,2-dichloroethane. The molar ratio of methoxide of triethylenediamine to 1,2-dichloroethane is 1.05:1. Released from the reaction of the vinyl chloride catch trap, cooled with nitrogen. After 5 min after the start of the process get to 26.9 g of vinyl chloride, of 99.3 g [(C2H5)3NCH2C6H5]Cl and 91.2 g of methanol. Received 52,4% methanol solution of the Quaternary ammonium salt after adjusting again placed in the anode chamber membrane of the cell to obtain a methanol solution of methoxide triethylenediamine. The conversion of 1,2-dichloroethane to vinyl chloride is 99,3%.

Example 4

In the anode chamber membrane of the cell, separated by cation-exchange membrane brand MK-40, pour 200 ml of 60% alcohol solution of Quaternary ammonium salt. In the cathode chamber of the electrolytic cell pour 200 ml of ethanol containing 2% of the corresponding alkoxide. As electrodes using titanium plates coated with ruthenium oxide. The process was performed at room temperature, amperage of 3 And a cathode current density of 40 mA/cm2within 4 hours. The concentration of the solution during electrolysis in the anode chamber of the electrolyzer support permanent add salt crystal. At the end ol the process in a cathode chamber of getting solution of an alcoholic solution of the corresponding alkoxide.

Obtained in a cathode chamber of a membrane electrolyzer alcohol alkoxide solution is transferred into a reactor equipped with a heating and cooling device and a stirrer. After that, the reactor at room temperature and continuous stirring was added 34 ml of 1,2-dichloroethane. The molar ratio of alkoxide to 1,2-dichloroethane is 1.05÷to 1.1:1. Released from the reaction of the vinyl chloride catch trap, cooled with nitrogen. The process of dehydrochlorinating 1,2-dichloroethane should be performed within 5 minutes the resulting alcoholic solution of the Quaternary ammonium salt after adjusting again placed in the anode chamber membrane of the cell to obtain an alcohol solution of the alkoxide. Experiments are performed with different Quaternary ammonium salts and alcohols. The results of the experiments, the structure of Quaternary ammonium salts and alcohols in the table.

The results presented in the examples show that vinyl chloride can be obtained by liquid-phase dehydrochlorination of 1,2-dichloroethane by Quaternary ammonium alkoxides of different patterns. The resulting reaction dehydrochlorinating Quaternary ammonium salt can be used for the electrolytic production of alkoxide.

The use of the proposed method of producing vinyl chloride compared with existing has the following advantages to the company:

a) create the possibility of organizing a virtually waste-free, high-performance, environmentally friendly technologies;

b) eliminates the need to work at high temperatures and pressures;

C) the proposed method provides for obtaining stoichiometric to vinyl chloride, the amount of chlorine that can be used for the production of 1,2-dichloroethane;

g) in addition to chlorine in the electrolysis of Quaternary ammonium salt is a trademark hydrogen;

d) low energy consumption and simple equipment allows us to provide low investment and quick payback of production.

Table
№ p/pThe structure of the Quaternary ammonium saltThe structure of alcohol : The structure of the alkoxideThe concentration of the alkoxide, %The yield of vinyl chloride, %
1[(C2H5)2N(CH2-CCL=CH2)2]ClCH3HE[(C2H5)2N(CH2-CCL=CH2)2]OCH352,199,2
2[(C2H5)2N(CH2-CH=CHCl)2]ClWith2H5HE[(C2H5)2N(CH2-CH=CHCl)2/sub> ]OC2H550,398,6
3[(C4H9)4N]ClWith2H5OH[(C4H9)4N]OC2H553,4of 99.1
4[(C4H9)4N]ClWith4H9O[(C4H9)4N]OC4H951,699,3
5[(CH3)2N(CH2-CH=CH2)2]ClWith4H9O[(CH3)2N(CH2-CH=CH2)2]OS4H949,598,4
6[(CH3)4N]ClWith6H5CH2OH[(CH3)4N]och2With6H5to 47.299,3
7[(CH3)2N(CH2-CCl=CH2)2]ClWith6H5CH2OH[(CH3)2N(CH2-CCl=CH2)2]OCH2C6H546,9the 98.9
8[(CH3)2N(CH2-CH=CHCl)2]ClWith6H5CH2OH[(CH3)2N(CH2-CH=CHCl)2]Och2With6H546,5 98,8

1. The method of producing vinyl chloride by dehydrochlorination of 1,2-dichloroethane, wherein the dehydrochlorination is carried out in the liquid phase by the interaction of 1,2-dichloroethane with alcohol solutions of alkoxides, Quaternary ammonium salts of the formula [R1R2R3R4N]+OR-where R1R2R3- alkyl, C1-C4, R3R4- propenyl, βor γ-chloropropanol, R4is benzyl, R is alkyl (C1-C4, benzil with the formation of the target product and a Quaternary ammonium salt, which is used to obtain alkoxides.

2. The method according to claim 1, characterized in that the alcoholic solutions of alkoxides, Quaternary ammonium salts obtained by electrolysis of the corresponding Quaternary ammonium salts in the electrolytic cells with ion-exchange membranes.



 

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EFFECT: improved method of synthesis.

7 cl, 1 tbl, 12 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing vinyl chloride monomer and to a catalyst sued in catalytic preparing vinyl chloride monomer from flows comprising ethylene. Method for preparing vinyl chloride from ethylene is carried out by the oxidehydrochlorination reaction. Method involves combining reagents including ethylene, the source of oxygen and chlorine in the catalyst-containing reactor at temperature 350-500°C and under pressure from atmosphere to 3.5 MPa, i. e. under conditions providing preparing the product flow comprising vinyl chloride and ethylene. Catalyst comprises one or some rare-earth elements under condition that the atomic ratio between rare-earth metal and oxidative-reductive metal (iron and copper) is above 10 in the catalyst and under the following condition: when cerium presents then the catalyst comprises additionally at least one rare-earth element distinctive from cerium. Ethylene is recirculated from the product flow inversely for using at stage for combining reagents. Invention proposes a variant for a method for preparing vinyl chloride. Also, invention proposes variants of a method for catalytic dehydrochlorination of raw comprising one or some components taken among ethyl chloride, 1,2-dichloroethane and 1,1,2-trichloroethane in the presence of catalyst. Catalyst represents the composition of the formula MOCl or MCl3 wherein M represents a rare-earth element or mixture of rare-earth elements taken among lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium. The catalytic composition has the surface area BET value from 12 m2/g to 200 m2/g. Invention provides simplifying technology and enhanced selectivity of the method.

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EFFECT: improved producing method.

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2 tbl, 4 dwg, 2 ex

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26 cl, 1 tbl

FIELD: industrial organic synthesis.

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SUBSTANCE: invention relates to a method for preparing vinyl chloride monomer and to a catalyst sued in catalytic preparing vinyl chloride monomer from flows comprising ethylene. Method for preparing vinyl chloride from ethylene is carried out by the oxidehydrochlorination reaction. Method involves combining reagents including ethylene, the source of oxygen and chlorine in the catalyst-containing reactor at temperature 350-500°C and under pressure from atmosphere to 3.5 MPa, i. e. under conditions providing preparing the product flow comprising vinyl chloride and ethylene. Catalyst comprises one or some rare-earth elements under condition that the atomic ratio between rare-earth metal and oxidative-reductive metal (iron and copper) is above 10 in the catalyst and under the following condition: when cerium presents then the catalyst comprises additionally at least one rare-earth element distinctive from cerium. Ethylene is recirculated from the product flow inversely for using at stage for combining reagents. Invention proposes a variant for a method for preparing vinyl chloride. Also, invention proposes variants of a method for catalytic dehydrochlorination of raw comprising one or some components taken among ethyl chloride, 1,2-dichloroethane and 1,1,2-trichloroethane in the presence of catalyst. Catalyst represents the composition of the formula MOCl or MCl3 wherein M represents a rare-earth element or mixture of rare-earth elements taken among lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium. The catalytic composition has the surface area BET value from 12 m2/g to 200 m2/g. Invention provides simplifying technology and enhanced selectivity of the method.

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61 cl, 8 tbl, 32 ex

FIELD: chemistry of organochlorine compounds, chemical technology.

SUBSTANCE: method involves treatment of 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane with solid calcium hydroxide or a mixture of solid calcium hydroxide and solid sodium hydroxide with the content of sodium hydroxide in mixture 30%, not above, in the molar ratio 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane to alkali = 1:(1.5-1.75) at heating in the presence of catalyst. As catalysts method involves benzyltrialkyl ammonium halides, preferably, benzyltriethyl ammonium chloride or benzyltrimethyl ammonium bromide, tetraalkyl ammonium halides, preferably, tetrabutyl ammonium bromide taken in the amount 0.0005-0.005 mole. Invention provides the development of a new method for preparing 1,1-dichloro-2,2-bis-(4-chlorophenyl)-ethylene allowing to enhance ecological safety of technological process and to improve quality of the end product.

EFFECT: improved method preparing.

2 cl, 15 ex

FIELD: industrial organic synthesis.

SUBSTANCE: gas-phase thermal dehydrochlorination of 1,2-dichloroethane is conducted in presence of hydrogen chloride as promoter dissolved in feed in concentration between 50 and 10000 ppm.

EFFECT: increased conversion of raw material and reduced yield of by-products.

4 cl, 1 tbl, 8 ex

FIELD: chemical industry, in particular method for production of value monomer such as vinylchloride.

SUBSTANCE: claimed method includes passing of reaction mixture containing dichloroethane vapor trough catalytic layer providing dehydrochlorination of dichloroethane to vinylchloride. Catalyst has active centers having in IR-spectra of adsorbed ammonia absorption band with wave numbers in region of ν = 1410-1440 cm-1, and contains one platinum group metal as active component, and glass-fiber carrier. Carrier has in NMR29Si-specrum lines with chemical shifts of -100±3 ppm (Q3-line) and -110±3 ppm (Q4-line) in integral intensity ratio Q3/Q4 from 0.7 to 1.2; in IR-specrum it has absorption band of hydroxyls with wave number of ν = 3620-3650 cm-1 and half-width of 65-75 cm-1, and has density, measured by BET-method using argon thermal desorption, SAr = 0.5-30 m2/g, and specific surface, measured by alkali titration, SNa = 10-250 m2/g in ratio of SAr/SNa = 5-30.

EFFECT: method with high conversion ratio and selectivity.

3 cl, 2 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: catalyst is prepared from allyl chloride production wastes comprising 30-50% 1,3-dichloropropenes, 30-60% 1,2-dichloropropane, and 3-5% 1,2,3-trichloropropane, which are treated at 5-10°C with 30-50% dimethylamine aqueous solution in such amount as to ensure stoichiometric ratio of dimethylamine with respect to 1,3-dichloropropenes. Resulting mixture is held at 20-25°C for 0.5-1.0 h and then 40-44 sodium hydroxide solution is added in stoichiometric amount regarding dimethylamine, after which clarified waste is added to dimethylamine at 60-70°C and stirring in amount ensuring stoichiometric ratio of dimethylamine to 1,3-dichloropropenes contained in clarified waste. Mixture is aged for 2-3 h, organic phase is separated, and remaining interaction phase is supplemented by C1-C4-alcohol or benzyl alcohol at alcohol-to-dimethylamine molar ratio 1:(1-3).

EFFECT: reduced expenses on starting materials.

2 cl, 3 ex

The invention relates to cleaning and getting 1,1-dottorato, which is used for foaming plastics or as a propellant in aerosols

FIELD: organic synthesis catalysts.

SUBSTANCE: catalyst is prepared from allyl chloride production wastes comprising 30-50% 1,3-dichloropropenes, 30-60% 1,2-dichloropropane, and 3-5% 1,2,3-trichloropropane, which are treated at 5-10°C with 30-50% dimethylamine aqueous solution in such amount as to ensure stoichiometric ratio of dimethylamine with respect to 1,3-dichloropropenes. Resulting mixture is held at 20-25°C for 0.5-1.0 h and then 40-44 sodium hydroxide solution is added in stoichiometric amount regarding dimethylamine, after which clarified waste is added to dimethylamine at 60-70°C and stirring in amount ensuring stoichiometric ratio of dimethylamine to 1,3-dichloropropenes contained in clarified waste. Mixture is aged for 2-3 h, organic phase is separated, and remaining interaction phase is supplemented by C1-C4-alcohol or benzyl alcohol at alcohol-to-dimethylamine molar ratio 1:(1-3).

EFFECT: reduced expenses on starting materials.

2 cl, 3 ex

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