RU2288909C1 - Method for preparing chlorinated derivatives of ethylene - Google Patents

Abstract

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of chlorinated ethylene derivatives, in particular, vinyl chloride, vinylidene chloride, trichloroethylene by the dehydrochlorination reaction of corresponding chlorinated ethane derivatives. The process is carried out in the presence of sodium hydroxide aqueous solution, catalyst of interphase transfer relating to polyglycols and an extractant-promoter representing mixture of chlorinated hydrocarbons of the general formula: C_nH_{2n +2-x}Cl_x wherein n = 10-30; x = 1-7 with molecular mass 250-305 Da and the chlorine content is 24-43% followed by isolation of end substances by the known procedures. As a catalyst of interfase transfer the method uses polyethylene glycols in the amount 0.0001-1% of the mass of the parent chlorinated ethane derivative. Extractant-promoter is used in the amount 1-10% of the mass of the parent ethane derivative. The mole ratio of chlorinated ethane derivative to sodium hydroxide = 1:(1.15-5) at the concentration of sodium hydroxide aqueous solution 5-35 wt.-%. Invention provides the development of the complex method for synthesis of chlorinated ethylene derivatives from chlorinated ethane derivatives, among them, from depleted reagents of the method or waste of corresponding industry, and increasing yield of end products.

EFFECT: improved method of synthesis.

7 cl, 1 tbl, 12 ex

Description

The invention relates to petrochemical synthesis, and in particular to a method for producing chlorinated derivatives of ethylene, in particular vinyl chloride, vinylidene chloride, trichlorethylene, used to produce polymer materials for various purposes.

Known methods for producing vinyl chloride by pyrolysis of dichloroethane (for example, US Pat. RF No. 2179965, 2002; No. 2184721, 2002) and catalytic high-temperature processes. So, dehydrochlorination of dichloroethane is carried out in the presence of catalysts - porous carbon-graphite material at a temperature of 350-490 ° C (US Pat. RF No. 2053991, 1996), a catalyst containing Pt and Pd on γ-Al ₂ O ₃ at a temperature of 280-400 ° C ( Pat. RF No. 2070551, 1996), a bifunctional ammonium hydrochloride catalyst of the general formula (R) ₃ NH ⁺ Cl ^- at a temperature of 250-550 ° C and a pressure of 20-30 atm (Pat. RF No. 2129115, 1999), as well as using initiator - a corona discharge of direct current with a corona cathode at a temperature of 100-400 ° C (US Pat. RF No. 1153503, 1999).

Also known are high-temperature catalytic methods for the production of vinylidene chloride, for example, the dehydrochlorination of 1,1,2-trichloroethane is carried out at a temperature of 325 ° C in the presence of a catalyst CsMgCl ₃ · 6H ₂ O and methanol (US Pat. US No. 4816609, 1989), or at a temperature of 110- 190 ° C in the presence of a catalyst containing oxides of chromium, zinc and aluminum (US Pat. RF No. 2078071, 1997).

The main disadvantages of high-temperature methods for producing chlorinated derivatives of ethylene are the harsh process conditions - this is high temperature and, as a rule, high pressure, low degree of conversion of the feedstock and the need for its special treatment when returned to recycling, the formation of significant quantities of organochlorine wastes, complicated instrumentation and the use of special materials.

Also known are liquid-phase methods for the dehydrochlorination of chlorine derivatives of ethane, carried out under mild conditions, by the action of an aqueous solution of sodium hydroxide in the presence of phase transfer catalysts (Armenian Chemical Journal, v. 34, No. 6, 1981, p. 519-522).

Among these methods, methods are known for producing vinyl chloride by dehydrochlorination of dichloroethane (DCE) with an aqueous 10-50% sodium hydroxide solution at a temperature of 40-80 ° C in the presence of a catalyst system (in the amount of 0.08-0.5 wt.%) Obtained from tertiary amines, haloalkyls and alcohols with a molar ratio of DCE: NaOH = 1: 0.25-3 (US Pat. RF No. 2024475, 1994), as well as in the presence of a catalyst obtained by the interaction of polyethylene polyamines and their alkyl derivatives with benzyl chloride (in the amount of 0.4-2 wt.%) With a molar ratio of DCE: NaOH = 1: 1.1-1.2 (Pat. RF №2149155, 2000).

There are also known methods for the production of vinylidene chloride by dehydrochlorination of 1,1,2-trichloroethane with an aqueous 28-35% sodium hydroxide solution using clarified waste products from the production of vinyl chloride obtained by gas-phase dehydrochlorination of DCE containing 50-70% 1,1,2-trichloroethane as raw materials at a temperature of 5-10 ° C (US Pat. RF No. 2167140, 2001), and clarified waste products of perchlorovinyl production with a content of 80-90% 1,1,2-trichloroethane at a temperature of 15-20 ° C (US Pat. RF No. 2167141, 2001 ), in the presence of a diethylallyl-γ-chloropropenylammonium chloride or di- β-hydroxyethylallyl-γ-chloropropenylammonium chloride in an amount of 0.8-1% to 1,1,2-trichloroethane with the addition of ROH alcohol, where R is C ₂ -C ₄ alkyl, with a molar ratio of alcohol to catalyst 1-3: 1 .

The disadvantages of the known methods of dehydrochlorination of chlorinated derivatives of ethane under mild conditions, the action of an aqueous solution of sodium hydroxide in the presence of phase transfer catalysts, is the focus of each of them on obtaining a specific chlorinated derivative of ethylene, as well as the use of expensive complex catalysts.

As a prototype, a method for producing chlorinated derivatives of ethylene, in particular vinyl chloride, by dehydrochlorination of DCE at 70-75 ° C with an aqueous 10% alkali metal hydroxide solution for 3 hours in the presence of 2-5 phase transfer catalysts was taken % wt. from the original DCE at a molar ratio of DCE: NaOH = 1: 2. A variety of quaternary ammonium and phosphonium salts, as well as hydroxyethylated cetyl alcohol (OS-20), which belongs to polyglycols, were used as phase transfer catalysts. When using OS-20, vinyl chloride was obtained with a yield of 70-79% (Armenian Chemical Journal, vol. 34, No. 6, 1981, pp. 519-522).

The disadvantage of this method is that when using the OS-20 catalyst from the class of polyglycols, vinyl chloride is obtained in a low yield (70-79%), while only a laboratory procedure for its preparation is developed, and the preparation of other chlorinated ethylene derivatives is not considered.

The objective of the invention is to develop an integrated method for producing chlorinated derivatives of ethylene (vinyl chloride, vinylidene chloride, trichlorethylene), suitable for use in an industrial environment, allowing the use of chlorinated derivatives of ethane - 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2- and 1,1,2,2-tetrachloroethane and mixtures thereof, including waste products of these products, including waste according to the claimed method, as well as allowing reuse of reagents using m closed cycle principle, which consists in obtaining salable products from waste reactants.

The problem is solved by the proposed method for producing chlorinated derivatives of ethylene - vinyl chloride, vinylidene chloride, trichlorethylene, by dehydrochlorination of the corresponding chlorinated derivatives of ethane, used as feedstock, by the action of an aqueous solution of sodium hydroxide in the presence of a phase transfer catalyst related to polyglycols. The method is characterized in that the catalyst is used in an amount of 0.0001-1% by weight of the starting chlorinated ethane derivative, and the process is carried out in the presence of an extracting promoter, which is a mixture of chlorinated hydrocarbons of the general formula C _n H _{2n + 2-x} Cl _x , where n = 10-30, x = 1-7, having a molecular weight of 250-305 and a chlorine content of 24-43%, with subsequent isolation of the target products.

Polyethylene glycols, for example, grade 115 (PEG 4000) according to TU U 6-002056601.083-2000 or grade 400 (PEG 400) according to TU 2483-167-05757587-2000, are used as a phase transfer catalyst.

The promoter-extractant is used in an amount of 1-10% by weight of the starting ethane derivative.

The molar ratio of the chlorinated derivative of ethane to sodium hydroxide is 1: (1.15-5) at a concentration of an aqueous solution of sodium hydroxide of 5-35 wt.%.

As starting materials for the preparation of chlorinated derivatives of ethylene - vinyl chloride, vinylidene chloride, trichlorethylene, the corresponding chlorinated derivatives of ethane - 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2 - and 1,1,2, are used. 2-tetrachloroethane or mixtures thereof.

As a starting material for the production of chlorinated derivatives of ethylene, waste from the production of vinyl chloride, vinylidechloride and trichlorethylene, generated in known technological processes and according to the claimed method, can be used.

As an aqueous solution of sodium hydroxide, catalyst and promoter-extractant, you can use both fresh reagents and reagents remaining after isolation of the target products according to the claimed method.

It should be noted that liquid chlorinated paraffins are used as a promoter-extractant:

- KP-250 (Parachlor 250), a mixture of chlorinated paraffins of the general formula C _n H _{2n + 2-x} Cl _x , where n = 10-16, x = 1-3, having a molecular weight of 250 and a chlorine content of 24-29% ( TU 6-01-16-90);

- CP-418, a mixture of chlorinated paraffins of the general formula C _n H _{2n + 2-x} Cl _x , where n = 10-20, x = 1-7, having a molecular weight of 305 and a chlorine content of 40-43% (TU 6-01 -16-90);

- KP-30, a mixture of chlorinated paraffins of the general formula C _n H _{2n + 2-x} Cl _x , where n = 10-16, x = 1-3, having a molecular weight of 260 and a chlorine content of 28-32%, (TU 6- 01-5-63-94).

The role of these compounds is to perform the following functions:

- as surface-active substances, they contribute to the formation of a time-stable, finely dispersed emulsion of two immiscible liquids - an aqueous solution of sodium hydroxide and chlorinated derivatives of ethane with a catalyst dissolved in them, that is, chloroparaffins promote the process of interphase catalysis;

- as an extractant, liquid chlorinated paraffins extract the residues of the starting compounds and the resulting target products, as well as the catalyst from the aqueous phase - spent alkaline solution. Due to this, organochlorine compounds and a catalyst dissolved in liquid chlorinated paraffins can be used in the future to obtain chlorinated derivatives of ethylene according to the claimed method, and the spent alkaline solution after extraction of organochlorine compounds from it - as an alkaline reagent to obtain chlorinated derivatives of ethylene according to the claimed method or for processing into target products - sodium bicarbonate, sodium hydroxide technical grade RD. Thus, the closed loop principle is implemented.

The following are specific examples of the implementation of the proposed method.

Example 1

Obtaining vinyl chloride by dehydrochlorination of 1,2-dichloroethane (1,2-DCE).

A reactor volume of 2.3 m ³ are introduced 490 kg (12.25 kmol) of sodium hydroxide as a 30% aqueous solution, 400 kg (4.04 kmole) of 1,2-DCE, 1.2 kg of catalyst PEG 400 ( 0.3% by weight of 1,2-DCE) and 12 kg of the promoter-extractant (3% by weight of 1,2-DCE). The molar ratio of 1,2-DCE: NaOH = 1: 3.03. As a promoter-extractant use KP-30.

The resulting reaction mass with stirring is heated to a temperature of 80-90 ° C and when reaching a pressure of 2.5 MPa created by the resulting vinyl chloride, the selection of the target product begins. The resulting gaseous vinyl chloride passes through an over-reactor column filled with a nozzle (Raschig rings) and two cooled heat exchangers, where it is condensed and collected in the form of a liquid in a cooled container.

As a result of the dehydrochlorination process of 1,2-DCE, 250 kg (4.0 kmol) of vinyl chloride were obtained containing 99.995% of the basic substance in 99% yield.

Example 2

Obtaining vinylidene chloride by dehydrochlorination of 1,1,2-trichloroethane.

In the reactor described in example 1, containing 330 kg (8.25 kmol) of sodium hydroxide in the form of an 18.7% solution, 1.2 kg of PEG 400 catalyst (0.28% by weight of 1,1,2-trichloroethane ) and 12 kg of the promoter-extractant (2.8% by weight of 1,1,2-trichloroethane) remaining after the synthesis of vinyl chloride according to example 1, dose 430 kg (3.22 kmol) of 1,1,2-trichloroethane. The molar ratio of 1,1,2-trichloroethane: NaOH = 1: 2.56. As a promoter-extractant use KP-250.

The dehydrochlorination process is carried out at a temperature of 40-80 ° C and a pressure of 0.7 MPa. The vapors of the resulting vinylidene chloride pass through the over-reactor column and two cooled heat exchangers, where they are condensed and collected in the form of a liquid in a cooled container.

The dehydrochlorination process of 1,1,2-trichloroethane yielded 305 kg (3.14 kmol) of vinylidene chloride containing 98.6% of the basic substance in 96% yield.

Example 3

Preparation of trichlorethylene by dehydrochlorination of 1,1,2,2-tetrachloroethane.

In the reactor described in example 1, containing 200 kg (5 kmol) of sodium hydroxide in the form of an 11% solution, 1.2 kg of PEG 400 catalyst (0.29% by weight of charged 1,1,2,2-tetrachloroethane) and 12 kg of the promoter-extractant (2.9% by weight of the charged 1,1,2,2-tetrachloroethane) remaining after the process of obtaining vinylidene chloride in example 2, dose 420 kg (2.5 kmol) of 1,1,2, 2-tetrachloroethane. The molar ratio of 1,1,2,2-tetrachloroethane: NaOH = 1: 2. As a promoter-extractant use CP-418.

The dehydrochlorination process is carried out with stirring at a temperature of 70-90 ° C, which is supported by supplying a coolant in the jacket of the reactor and hot steam into the reaction mass, and at a pressure of 0.7 atm. Vapors of trichlorethylene formed in the form of an azeotrope with water pass through the overreactor column and two cooled heat exchangers, where they condense and are sent to the phase separator as a liquid, where the aqueous phase is separated from the target product. The target product trichlorethylene is sent to the collection.

As a result of the process, 313 kg (2.38 kmol) of trichlorethylene containing 98.7% of the basic substance with a yield of 94% were obtained.

At the end of the process, the catalyst and the promoter-extractant are separated from the aqueous phase, which does not contain impurities of organochlorine products. The aqueous phase is sent without further treatment to the existing wastewater treatment system.

Example 4

Preparation of trichlorethylene by dehydrochlorination of 1,1,2,2-tetrachloroethane.

In a reactor with a volume of 2.3 m ³ containing 85 kg (2.125 kmol) of a 5% sodium hydroxide solution, 0.12 kg of PEG 115 catalyst (0.04% by weight of charged 1,1,2,2-tetrachloroethane) was charged ), 12 kg of promoter-extractant (4% by weight of charged 1,1,2,2-tetrachloroethane) and 310 kg (1,85 kmol) of 1,1,2,2-tetrachloroethane. The molar ratio of 1,1,2,2-tetrachloroethane: NaOH = 1: 1.15. As a promoter-extractant use CP-418.

The dehydrochlorination process is carried out at a temperature of 85-95 ° C and a pressure of 0.7 atm for 6 hours. At the end of the process, the reaction mass is cooled to 25 ° C and the aqueous phase is separated from the organic phase. The aqueous phase is directed to feed the acid gas neutralization system of 1,1,2-trichloroethane production.

The organic phase is distilled, selecting a fraction of the target product of trichlorethylene in an amount of 228 kg (1.73 mol) containing 99% of the basic substance with a yield of 93%.

A bottoms residue in an amount of 14 kg containing a catalyst, an extractant promoter, and high-boiling organochlorine compounds was used in the manufacture of PVC compound for the manufacture of shoes in an amount of up to 5% by weight of plasticizers used in this process.

Example 5

Obtaining vinylidene chloride by dehydrochlorination of 1,1,2-trichloroethane.

In a 0.01 m ³ stainless steel reactor, 1200 g (30 mol) of a 30% aqueous sodium hydroxide solution, 13.4 g of PEG 115 catalyst are loaded (1% by weight of charged 1,1,2- trichloroethane), 134 g of a promoter-extractant (10% by weight of charged 1,1,2-trichloroethane) and 1335 g (10 mol) of 1,1,2-trichloroethane. The molar ratio of 1,1,2-trichloroethane: NaOH = 1: 3. As a promoter-extractant use KP-250.

The dehydrochlorination process is carried out with vigorous stirring at a temperature of 15-25 ° C and atmospheric pressure for 3 hours. At the end of the process, the aqueous phase is separated from the organic phase. The aqueous phase is used for the dehydrochlorination process described in example 6.

The organic phase is distilled at a bottom temperature not higher than 65 ° C, collecting 931 g (9.5 mol) of vinylidene chloride with a basic substance content of 99%. The yield of vinylidene chloride is 95%.

VAT residue containing 13.4 g of catalyst brand PEG 115 and 134 g of the promoter-extractant used in the dehydrochlorination process described in example 6.

Example 6

Obtaining vinylidene chloride by dehydrochlorination of a mixture of 1,1,2-trichloroethane and 1,2-dichloroethane.

In the 0.01 m ³ stainless steel reactor, the aqueous phase is charged after the process described in Example 5 containing 740 g (18.5 mol) of an 18.8% aqueous sodium hydroxide solution and the bottom residue after isolation vinylidene chloride by distillation according to example 5, containing 13.4 g of PEG 115 catalyst and 134 g of extractor promoter, as well as a mixture of 1670 g (12.5 mol) of 1,1,2-trichloroethane and 335 g (3.4 mol) 1 , 2-DCE, a waste product of vinyl chloride production. The molar ratio of 1,1,2-trichloroethane: NaOH = 1: 1.48. As a promoter-extractant use KP-30.

The dehydrochlorination process is carried out with vigorous stirring at a temperature of 15-25 ° C and atmospheric pressure for 6 hours. At the end of the process, the aqueous phase is separated from the organic phase. From the organic phase by distillation at a vapor temperature of 32 ° C, 1135 g (11.7 mol) of vinylidene chloride containing 99.2% of the basic substance are isolated in 94% yield.

The bottoms containing 335 g (3.4 mol) of 1,2-DCE, 13.4 g of the PEG 115 catalyst, 134 g of the extractor promoter are used in the process of producing vinyl chloride described in example 7.

After filtration, the aqueous phase was concentrated at a temperature of 90-115 ° C and a pressure of 300 mm Hg. to the content of sodium hydroxide in a solution of 45%, corresponding to the requirements of GOST 2263-79.

Example 7

Obtaining vinyl chloride by dehydrochlorination of 1,2-DCE.

In a reactor with a volume of 0.01 m ³ made of stainless steel, 1200 g (30 mol) of a 30% aqueous solution of sodium hydroxide, 3 g of PEG 115 type catalyst (0.3% by weight of charged 1.2-DCE) are charged 30 g of the promoter-extractant (3% by weight of the loaded 1,2-DCE) and 990 g (10 mol) of 1,2-DCE. The required amount of organic reagents - catalyst, promoter-extractant and 1,2-DCE is obtained by mixing 1 g of catalyst in 10 g of promoter-extractant and 940 g of 1,2-DCE with 72 g of bottoms from the stage of vinylidene chloride distillation rectification according to example 6, which contain 20 g of the promoter extractant, 2 g of catalyst and 50 g of 1,2-DCE. The molar ratio of 1,2-DCE: NaOH = 1: 3. As a promoter-extractant use CP-418.

The resulting reaction mass with stirring is heated to a temperature of 85-90 ° C and when reaching a pressure of 2.5 MPa created by the resulting vinyl chloride vapors, the selection of the target product begins. The resulting gaseous vinyl chloride passes through the over-reactor column and two cooled heat exchangers, where it is condensed and collected in the form of a liquid in a cooled tank. After 4 hours of the reaction, the end of which was recorded by the pressure drop in the reactor to atmospheric pressure, 613 g (9.8 mol) of vinyl chloride were obtained containing 99.995% of the basic substance with a yield of 98%.

At the end of the process, the catalyst and the promoter-extractant are separated from the aqueous phase and used in dehydrochlorination processes according to the claimed method described in examples 1-7.

The aqueous phase containing 20% sodium hydroxide, after filtration from a precipitate of sodium chloride, was evaporated at a temperature of 95-105 ° C and a pressure of 175-200 mm Hg to a concentration of sodium hydroxide of 45%, corresponding to GOST 2263-79.

Example 8

Obtaining vinyl chloride by dehydrochlorination of 1,2-DCE.

The process of dehydrochlorination of 1,2-DCE is carried out under conditions similar to those described in example 1, with the difference that sodium hydroxide is used in the form of a 35% aqueous solution.

Vinyl chloride was obtained in 95% yield with a basic substance content of 99.6%.

Example 9

Obtaining vinylidene chloride by dehydrochlorination of 1,1,2-trichloroethane.

The dehydrochlorination of 1,1,2-trichloroethane is carried out under conditions similar to those described in example 2, with the difference that the amount of the promoter-extractant is 1%, and the amount of PEG 400 catalyst is 0.0001% by weight of the loaded 1,1,2- trichloroethane. In addition, the temperature of the reaction mass of 70-80 ° C is maintained by supplying it with sharp steam, as well as the coolant in the reactor jacket. The yield of the desired vinylidene chloride is 96%. As a promoter-extractant use KP-250.

The aqueous phase containing 11% sodium hydroxide remaining after the production of vinylidene chloride was treated with carbon dioxide, feeding it through a bubbler under a layer of liquid at a temperature of 70-80 ° C. After 6 hours, the flow of carbon dioxide was stopped, and the resulting suspension of sodium bicarbonate in water was sent to a filter, where the precipitate was washed with water and then dried. The resulting sodium bicarbonate met the requirements of GOST 5100-85 for this brand A product.

Example 10

Obtaining vinylidene chloride by dehydrochlorination of 1,1,2-trichloroethane.

The synthesis of vinylidene chloride by dehydrochlorination of 667.5 g (5 mol) of 1,1,2-trichloroethane is carried out in the reactor described in example 5, with the difference that the process is carried out at a temperature of 5-15 ° C in the presence of a PEG 115 catalyst in an amount of 6, 7 g (1% by weight of charged 1,1,2-trichloroethane), 6.7 g of promoter-extractant (1% by weight of loaded 1,1,2-trichloroethane) and 1000 g (25 mol) of sodium hydroxide in the form of 20 % aqueous solution. As a promoter-extractant use KP-250.

The dehydrochlorination process is carried out with vigorous stirring and atmospheric pressure for 12 hours. At the end of the process, the aqueous phase is separated from the organic phase.

The organic phase is distilled at a temperature of 50-70 ° C. The yield of vinylidene chloride is 90.5%.

VAT residue containing a catalyst, a promoter-extractant and unreacted 1,1,2-trichloroethane is reused when carrying out dehydrochlorination processes according to the present method.

Example 11

Obtaining vinylidene chloride by dehydrochlorination of 1,1,2-trichloroethane.

The synthesis of vinylidene chloride by dehydrochlorination of 1410 g of 1,1,2-trichloroethane with a basic substance content of 95.36%, or 1335 g (10 mol) in terms of 100% substance, is carried out in the reactor described in example 5, in interaction with 480 g (12 mol) of sodium hydroxide in the form of an 11% aqueous solution, selected from the aqueous phase after the dehydrochlorination process described in example 10, at a temperature of 60 ° C. The molar ratio of 1,1,2-trichloroethane to sodium hydroxide is 1: 1.2. As a promoter-extractant use KP-30.

Vapors of the resulting vinylidene chloride at atmospheric pressure pass the over-reactor column, the heat exchanger and condense in a cooled collector. In 2.5 hours, 985 g of crude vinylidene chloride with a basic substance content of 96.5% were obtained. The yield of the target product is 98%.

The aqueous phase remaining in the reactor and containing 2% unreacted sodium hydroxide is used to fuel the acid gas neutralization system in the production of the starting 1,1,2-trichloroethane.

The obtained crude vinylidene chloride is subjected to rectification to obtain 936 (9.55 mol) of vinylidene chloride rectified with a basic substance content of 99%.

The yield of vinylidene chloride rectified 95.5% of 1,1,2-trichloroethane taken for saponification.

Example 12

Preparation of vinylidene chloride and trichlorethylene by dehydrochlorination of a mixture of 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane and 1,1,2,2-tetrachloroethane.

In a reactor equipped with a thermostatic device, 220 g of chlorinated derivatives of ethane, waste of the production of vinyl chloride of the following composition, wt.%, Are placed.

1,1,2-trichloroethane 69 (1.14 mol);

1,1,1,2-tetrachloroethane 19 (0.25 mol);

1,1,2,2-tetrachloroethane 12 (0.16 mol),

as well as 1.8 g of the PEG 400 catalyst (0.8% by weight of the loaded chlorinated derivatives of ethane) and at a temperature of 20 ° C, 80 g (2 mol) of sodium hydroxide are metered with stirring in the form of a 30% aqueous solution. The molar ratio of chlorinated derivatives of ethane: NaOH = 1: 1.29. As a promoter-extractant use KP-250.

Stirring is continued for 3 hours at a temperature of 20 ° C until the complete conversion of 1,1,2-trichloroethane to vinylidene chloride, and 1,1,2,2-tetrachloroethane to trichlorethylene. The dehydrochlorination process is carried out under a “nitrogen blanket” to exclude the interaction of the resulting vapors of vinylidene chloride and trichlorethylene with atmospheric oxygen, as a result of which chemical and thermal unstable products may form (“Industrial organochlorine products.” Handbook edited by L. A. Oshin, M .: "Chemistry", 1978, p.113, 151).

At the end of the process, stirring is stopped, the aqueous layer is separated from the organic. The organic layer is distilled by first selecting a fraction of vinylidene chloride with a boiling point of 31-33 ° C, a mass of 107 g (1.1 mol) containing 99% of the basic substance with a yield of 96%, and then 27 g of trichlorethylene at a temperature of 86-88 ° C. containing 99% of the basic substance (0.2 mol) with a yield of 66%.

The catalyst, extractor promoter and unreacted 1,1,1,2-tetrachloroethane remaining in the bottom residue after isolation of the desired products vinylidene chloride and trichlorethylene are used again in the dehydrochlorination processes of chlorinated ethane derivatives according to the claimed method.

The aqueous layer obtained after separation of the reaction mass is also used again in the dehydrochlorination processes of chlorinated derivatives of ethane according to the claimed method or is sent for further processing to the target commercial products - sodium hydroxide or sodium bicarbonate.

The table below shows the conditions for the process of dehydrochlorination of chlorinated derivatives of ethane with sodium hydroxide in the presence of a phase transfer catalyst and an extractant promoter according to examples 1-12.

Thus, an integrated method has been developed for producing chlorinated derivatives of ethylene suitable for industrial use by dehydrochlorination of the corresponding chlorinated derivatives of ethane by the action of an aqueous solution of sodium hydroxide, which allows the use of chlorinated derivatives of ethane and their mixtures, including waste products of these products, including waste according to the claimed method, as well as allowing reuse of reagents using the closed principle cycle, which consists in obtaining marketable products from spent reagents.

Table
Conditions for the process of dehydrochlorination of chlorine derivatives of ethane with sodium hydroxide in the presence of a phase transfer catalyst and an extractor promoter No. p / p The original chlorine derivatives of ethane The molar ratio of chlorine production. ethane: NaOH Conc. aqueous solution NaOH,% Download,% by weight of chlorine derivatives of ethane Technological parameters Target Ethylene Chloride Derivatives The yield of the target product,% Catalyst Extractor promoter Temperature ° C Pressure, ati one 2 3 four 5 6 7 8 9 10 one 1,2-dichloroethane 1: 3.03 thirty 0.30 3.0 80-90 2,5 Vinyl chloride 99 2 1,1,2-trichloroethane 1: 2.56 18.7 0.28 2,8 40-80 0.7 Vinylidene chloride 96 3 1,1,2,2-tetrachloroethane 1: 2 eleven 0.29 2.9 70-90 0.7 Trichlorethylene 94 four 1,1,2,2-tetrachloroethane 1: 1.15 5 0.04 4.0 85-95 0.7 Trichlorethylene 93 5 1,1,2-tetrachloroethane 1: 3 thirty 1,0 10 15-25 atm Vinylidene chloride 95 6 A mixture of 1,1,2-trichloroethane and 1,2-dichloroethane 1: 1.48 * 18.8 0.8 ** 8** 15-25 atm Vinylidene chloride 94 7 1,2-dichloroethane 1: 3 thirty 0.3 3.0 85-90 2,5 Vinyl chloride 98 8 1,2-dichloroethane 1: 3.03 35 0.3 3.0 80-90 2,5 Vinyl chloride 95 9 1,1,2-trichloroethane 1: 2.56 twenty 0.0001 1,0 70-80 0.7 Vinylidene chloride 96 10 1,1,2-trichloroethane 1: 5 twenty 1,0 1,0 5-15 atm Vinylidene chloride 90.5 eleven 1,1,2-trichloroethane 1: 1,2 eleven 0.0001 1,0 60 atm Vinylidene chloride 95.5 12 Mixture 1: 1.29 thirty 0.8 1,0 twenty atm 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane Vinylidene chloride 96 trichlorethylene 66 * molar ratio of 1,1,2-trichloroethane: NaOH; **% by weight of 1,1,2-trichloroethane

Claims (7)

1. The method of producing chlorinated derivatives of ethylene by dehydrochlorination of chlorinated derivatives of ethane, used as feedstock, by the action of an aqueous solution of sodium hydroxide in the presence of a phase transfer catalyst related to polyglycols, characterized in that the catalyst is used in an amount of 0.0001-1% by weight of the starting material chlorinated ethane derivative and the process is carried out in the presence of a promoter-extractant, which is a mixture of chlorinated hydrocarbons of the general formula C _n H _{2n + 2-x} Cl _x , where n = 10-30 , x = 1-7, having a molecular weight of 250-305 and a chlorine content of 24-43%, followed by the isolation of the desired products. 2. The method according to claim 1, characterized in that polyethylene glycols are used as a catalyst. 3. The method according to claim 1, characterized in that the promoter-extractant is used in an amount of 1-10% by weight of the starting chlorinated ethane derivative. 4. The method according to claim 1, characterized in that the molar ratio of the chlorinated derivative of ethane to sodium hydroxide is 1: (1.15-5) at a concentration of an aqueous solution of sodium hydroxide of 5-35 wt.%. 5. The method according to claim 1, characterized in that as the starting material for producing chlorinated derivatives of ethylene - vinyl chloride, vinylidene chloride, trichlorethylene, the corresponding chlorinated derivatives of ethane are used - 1,2-dichloroethane, 1,1,2-trichloroethane, 1, 1,1,2- and 1,1,2,2-tetrachloroethane or mixtures thereof. 6. The method according to claims 1 and 5, characterized in that the waste materials for the production of vinyl chloride, vinylidechloride and trichlorethylene formed in known technological processes and according to the claimed method are used as feedstock for producing chlorinated derivatives of ethylene. 7. The method according to claims 1 to 4, characterized in that as an aqueous solution of sodium hydroxide, catalyst and promoter-extractant using fresh reagents or reagents remaining after isolation of the target products according to the claimed method.