Method for preparing chlorinated derivatives of ethylene

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: CnH2n +2-xClx 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

 

The invention relates to petrochemical synthesis, namely the method of production of chlorinated derivatives of ethylene, in particular vinyl chloride, vinylidenechloride, trichloroethylene, used to produce polymeric materials for various purposes.

Known methods for producing vinyl chloride by pyrolysis of dichloroethane (for example, U.S. Pat. RF№2179965, 2002; №2184721, 2002) and high-temperature catalytic processes. So, the dehydrochlorination of dichloroethane is carried out in the presence of catalysts - porous graphitic carbon material at a temperature 350-490° (U.S. Pat. Of the Russian Federation No. 2053991, 1996), the catalyst containing Pt and Pd on γ-Al2O3at a temperature of 280-400° (U.S. Pat. Of the Russian Federation No. 2070551, 1996), bifunctional catalyst hydrochloride ammonium General formula (R)3NH+Cl-at a temperature of 250-550°and a pressure of 20-30 bar (U.S. Pat. Of the Russian Federation No. 2129115, 1999), as well as using initiator - corona discharge, direct current discharge cathode at a temperature of 100-400° (U.S. Pat. Of the Russian Federation No. 1153503, 1999).

Also known high-temperature catalytic methods of obtaining vinylidenechloride, for example, the dehydrochlorination 1,1,2-trichloroethane is carried out at a temperature of 325°in the presence of a catalyst CsMgCl3·6H2O and methanol (U.S. Pat. U.S. No. 4816609, 1989), or at a temperature of 110-190°in the presence of a catalyst containing hydroxy what s chromium, zinc and aluminum (U.S. Pat. Of the Russian Federation No. 2078071, 1997).

The main disadvantages of high-temperature methods of obtaining chlorinated derivatives of ethylene are hard conditions and processes high temperature and, as a rule, high pressure, low degree of conversion of the feedstock and the need for special cleaning upon return to recycling, the formation of significant quantities of chlorinated organic wastes, complex instrumentation and the use of special materials.

Also known liquid-phase methods dehydrochlorinating chlorinated ethane carried out under mild conditions, by the action of an aqueous solution of sodium hydroxide in the presence of phase transfer catalysts (Armenian chem. journal C, No. 6, 1981, s-522).

Among these methods, known methods for producing vinyl chloride by dehydrochlorination of dichloroethane (EDC) water 10-50%sodium hydroxide solution at a temperature of 40-80°in the presence of catalytic systems (0.08 to 0.5 wt.%), derived from tertiary amines, haloalkyl and alcohols in a molar ratio of EDC:NaOH=1:0.25 to 3 (U.S. Pat. Of the Russian Federation No. 2024475, 1994)and in the presence of a catalyst obtained by the interaction of polyethylenepolyamines and their alkyl derivatives with benzyl chloride (in an amount of 0.4-2 wt.%) when the molar ratio of EDC:NaOH=1:1.1 to 1.2 (U.S. Pat. RF is 2149155, 2000).

There are also known methods of obtaining vinylidenechloride the dehydrochlorination 1,1,2-trichloroethane water 28-35%sodium hydroxide solution, using as raw material the clarified waste of vinyl chloride, the obtained gas-phase dehydrochlorination EDC with the content of 50-70% of 1,1,2-trichloroethane at a temperature of 5-10° (U.S. Pat. Of the Russian Federation No. 2167140, 2001), and the clarified waste of perchlorovinyl with the content of 80-90% of 1,1,2-trichloroethane at a temperature of 15-20° (U.S. Pat. Of the Russian Federation No. 2167141, 2001), in the presence of catalyst diethylether-γ-chloropropylamine chloride or di-β-oxicillin-γ-chloropropylamine chloride at 0.8-1% of 1,1,2-trichloroethane with the addition of the alcohol ROH, where R is alkyl With2-C4when the molar ratio of alcohol to catalyst 1-3:1.

The disadvantages of the known methods dehydrochlorinating chlorinated derivatives of ethane under mild conditions, by the action of an aqueous solution of sodium hydroxide in the presence of phase transfer catalysts, is the focus of each of them to receive specific chlorinated derivative of ethylene, and the use of expensive catalysts of complex composition.

As the prototype was taken way to obtain chlorinated derivatives of ethylene, in particular, vinyl chloride by dehydrochlorination EDC at a temperature of 70-75° With aqueous 10%solution of alkali metal hydroxide for 3 hours in the presence of phase transfer catalysts in the amount of 2-5% by weight. from the original EDC at a molar ratio of EDC:NaOH=1:2. As phase transfer catalysts has been used a number of Quaternary ammonium and fofanah salts, and ethoxylated cetyl alcohol (OS-20)related to the polyglycols. When using OS-20 vinyl chloride obtained with the yield 70-79% (Armenian chem. journal C, No. 6, 1981, s-522).

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

The task of the invention is to develop an integrated method of producing chlorinated derivatives of ethylene (vinyl chloride, vinylidenechloride, trichloroethylene), suitable for use in industrial environments, allowing you to apply as a feedstock chlorinated derivatives of ethane - 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2 - and 1,1,2,2-tetrachlorethane and mixtures thereof, including waste of these products, including waste according to the claimed method, as well as allowing multiple use is the development of reagents with the application of the principle of a closed loop, who is getting products from waste chemicals.

The problem is solved by the proposed method of obtaining chlorinated derivatives of ethylene - vinyl chloride, vinylidenechloride, trichloroethylene, by dehydrochlorination of the corresponding chlorinated derivatives of ethane used as raw material by the action of an aqueous solution of sodium hydroxide in the presence of a phase transfer catalyst, related to the polyglycols. The method differs in that the catalyst is used in amounts of 0.0001-1% by weight of the original chlorinated derivative of ethane, and the process is carried out in the presence of promoter-extractant, which is a mixture of chlorinated hydrocarbons with the General formula CnH2n+2-xClxwhere n=10-30, x=1-7, having a molecular weight of 250-305 and chlorine 24-43%, followed by separation of the desired products.

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

The promoter-extragent used in the amount of 1-10% by weight of the original derived ethane.

The molar ratio of chlorinated derivative of ethane to sodium hydroxide is 1:(1,15-5) when the concentration of the aqueous solution of sodium hydroxide 5-35 wt.%.

As a source with the earth with the total amount to obtain the chlorinated derivatives of ethylene - vinyl chloride, vinylidenechloride, trichloroethylene use the corresponding chlorinated derivatives of ethane - 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2 - and 1,1,2,2-tetrachlorethane or mixtures thereof.

As a source of raw material for producing chlorinated derivatives of ethylene possible to use a waste production of vinyl chloride, vinylidenechloride and trichloroethylene, which is formed in known processes and by the claimed method.

As an aqueous solution of sodium hydroxide, catalyst and promoter-extractant can be used as fresh reagents, and reagents remaining after selection of the target products by the claimed method.

It should be noted that, as a promoter of extractant used liquid chlorinated paraffins:

- CP-250 (Perchlor 250), a mixture of chlorinated paraffins General formula CnH2n+2-xClxwhere 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 General formula CnH2n+2-xClxwhere n=10-20, x=1-7, having a molecular weight of 305 and the chlorine content of 40-43% (TU 6-01-16-90);

- CP-30, a mixture of chlorinated paraffins General formula CnH2n+2-xClxwhere 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 the functions:

as surface-active substances they contribute to the formation of stable time-dispersed emulsion of two immiscible liquids - aqueous solution of sodium hydroxide and chlorinated derivatives of ethane with diluted catalyst, i.e., the chlorinated paraffin wax promotirovat the process of interphase catalysis;

as extractant liquid chlorinated paraffins extracted residues of parent compounds and the resulting target products and catalyst from the aqueous phase is spent alkaline solution. Thanks to organochlorine compounds and the catalyst dissolved in the 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 the extraction from it of organochlorine compounds as an alkaline reagent to obtain a chlorinated derivatives of ethylene according to the claimed method or for processing into end products, sodium bicarbonate, sodium hydroxide technical grade RD. Thus, is the principle of closed loop.

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

Example 1.

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

In a reactor with a volume of 2.3 m3enter 490 kg (12,25 to the ol) of sodium hydroxide in the form of a 30%aqueous solution, 400 kg (4.04 KMOL) 1,2-EDC, 1.2 kg of catalyst PEG 400 (of 0.3% by weight of 1,2-EDC) and 12 kg promoter-extractant (3% by weight of 1,2-EDC). The molar ratio of 1,2-EDC:NaOH=1:3,03. As a promoter of extractant used CP-30.

The resulting reaction mass with stirring is heated to a temperature of 80-90°and when the pressure of 2.5 MPa, created formed by vinyl chloride, begin by selecting the target product. The resulting gaseous vinyl chloride passes adreactor column filled with nozzle (ring process) and two cooled heat exchanger where it condenses and the liquid is collected in a cooled container.

In the process dehydrochlorinating 1,2-EDC received 250 kg (4.0 KMOL) of vinyl chloride, containing 99,995% of the basic substance with a yield of 99%.

Example 2.

Getting vinylidenechloride the dehydrochlorination 1,1,2-trichloroethane.

In the reactor described in example 1, containing 330 kg (8.25 KMOL) of sodium hydroxide in the form of 18.7%solution, 1.2 kg of catalyst PEG 400 (0,28% by weight of 1,1,2-trichloroethane) and 12 kg promoter-extractant (2,8% by weight of 1,1,2-trichloroethane), remaining after carrying out the synthesis of vinyl chloride in example 1, dispense 430 kg (3,22 KMOL) 1,1,2-trichloroethane. The molar ratio of 1,1,2-trichloroethane:NaOH=1:2,56. As a promoter of extractant used CP-250.

The process of dehydrochlorinating carried out at tempera is ur 40-80° C and a pressure of 0.7 MPa. The pair formed vinylidenechloride are adreactor column and two-cooled heat exchanger, where it is condensed and the liquid is collected in a cooled container.

In the process dehydrochlorinating 1,1,2-trichloroethane received 305 kg (3.14 KMOL) vinylidenechloride containing 98.6% of the basic substance with a yield of 96%.

Example 3.

Getting trichloroethylene by dehydrochlorination 1,1,2,2-tetrachlorethane.

In the reactor described in example 1, containing 200 kg (5 KMOL) of sodium hydroxide in the form of a 11%solution, 1.2 kg of catalyst PEG 400 (0.29% of the mass loaded 1,1,2,2-tetrachlorethane) and 12 kg promoter-extractant (2.9% of the weight of the loaded 1,1,2,2-tetrachlorethane), remaining after the process of obtaining vinylidenechloride in example 2, dispense 420 kg (2.5 KMOL) 1,1,2,2-tetrachlorethane. The molar ratio of 1,1,2,2-tetrachlorethane:NaOH=1:2. As a promoter of extractant used CP-418.

The process of dehydrochlorinating carried out under stirring at a temperature of 70-90°, which is supported by the supply of the heating fluid in the jacket of the reactor and steam in the reaction mass, and at a pressure of 0.7 MPa. The pair formed of trichloroethylene in the form of an azeotrope with water, are adreactor column and two-cooled heat exchanger, where it is condensed and the liquid is sent to razorscale is l, where separating the aqueous phase from the target product. The target product of trichloroethylene is sent to the collection.

In the process the received 313 kg (2,38 KMOL) of trichloroethylene containing 98,7% of the basic substance with a yield of 94%.

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

Example 4.

Getting trichloroethylene by dehydrochlorination 1,1,2,2-tetrachlorethane.

In a reactor with a volume of 2.3 m3containing 85 kg (2,125 KMOL) of a 5%solution of sodium hydroxide, download 0,12 kg of catalyst brand PEG 115 (0.04% of the weight of the loaded 1,1,2,2-tetrachlorethane), 12 kg promoter-extractant (4% by weight of loaded 1,1,2,2-tetrachlorethane) and 310 kg (1,85 KMOL) 1,1,2,2-tetrachlorethane. The molar ratio of 1,1,2,2-tetrachlorethane:NaOH=1:1,15. As a promoter of extractant used CP-418.

The process of dehydrochlorinating carried out at a temperature of 85-95°and the pressure of 0.7 MPa for 6 hours. At the end of the process the reaction mass is cooled to 25°and carry out the separation of the aqueous phase from the organic. The aqueous phase is sent to backfeed the neutralisation of acid gases production of 1,1,2-trichloroethane.

The organic phase is distilled, selecting a fraction of the price is avago product of trichloroethylene in the amount of 228 kg (1,73 mol), containing 99% of the basic substance with a yield of 93%.

VAT residue of 14 kg, containing the catalyst, the extractant-promoter and the high-boiling chlorinated organic compounds used in the manufacture of PVC compound for the manufacture of shoes in an amount up to 5% by weight used in the process of plastification.

Example 5.

Getting vinylidenechloride the dehydrochlorination 1,1,2-trichloroethane.

In a reactor with a volume of 0.01 m3made of stainless steel, load of 1200 g (30 mol) of 30%aqueous sodium hydroxide solution, and 13.4 g of the catalyst of the brand PEG 115 (1% by weight of loaded 1,1,2-trichloroethane), 134 g of promoter-extractant (10% by weight of loaded 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 of extractant used CP-250.

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

The organic phase is distilled at a temperature of the cube above 65°collecting 931 g (9.5 mol) of vinylidenechloride with the content of the main substance of 99%. The output vinylidenechloride 95%.

VAT residue containing a 13.4 g of catalysis is ora brand PEG 115 and 134 g of promoter-extractant, use when carrying out the process dihydrochloride described in example 6.

Example 6.

Getting vinylidenechloride the dehydrochlorination mixture of 1,1,2-trichloroethane and 1,2-dichloroethane.

In a reactor with a volume of 0.01 m3made of stainless steel, download the aqueous phase after the process described in example 5, containing 740 g (18.5 mol) 18,8%aqueous sodium hydroxide solution, and the VAT residue after extraction of vinylidenechloride by distillation in example 5, containing a 13.4 g of the catalyst of the brand PEG 115 and 134 g of promoter-extractant, and the mixture 1670 g (12.5 mol) of 1,1,2-trichloroethane and 335 g (3.4 mol) of 1,2-EDC, representing a departure from the production of vinyl chloride. The molar ratio of 1,1,2-trichloroethane:NaOH=1:1,48. As a promoter of extractant used CP-30.

The process of dehydrochlorinating carried out with vigorous stirring at a temperature of 15-25°and atmospheric pressure for 6 hours. At the end of the process, separating the aqueous phase from the organic. From the organic phase by distillation at a temperature of vapor 32°allocate 1135 g (11.7 mol) vinylidenechloride containing 99.2% of the basic substance with a yield of 94%.

VAT residue, containing 335 g (3.4 mol) of 1,2-EDC, and 13.4 g of catalyst PEG 115, 134 g of promoter-extractant used in the process of obtaining vinyl chloride in example 7.

The aq is the phase after filtration 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 requirements of GOST 2263-79.

Example 7.

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

In a reactor with a volume of 0.01 m3made of stainless steel, load of 1200 g (30 mol) of 30%aqueous sodium hydroxide solution, 3 g of the catalyst of the brand PEG 115 (0.3% of the mass loaded 1,2-EDC), 30 g of promoter-extractant (3% by weight of loaded 1,2-EDC) and 990 g (10 mol) of 1,2-EDC. The required amount of organic reagents, catalyst, promoter-extractant and 1,2-EDC prepared by mixing 1 g of catalyst in 10 g of promoter-extractant and 940 g of 1,2-EDC with 72 g of distillation residue from the stage of selection of vinylidenechloride by distillation in example 6, which contained 20 g of promoter-extractant, 2 g of catalyst and 50 g of 1,2-EDC. The molar ratio of 1,2-EDC:NaOH=1:3. As a promoter of extractant used CP-418.

The resulting reaction mass with stirring is heated to a temperature of 85-90°and when the pressure of 2.5 MPa, the generated pairs formed of vinyl chloride, begin by selecting the target product. The resulting gaseous vinyl chloride passes adreactor column and two-cooled heat exchanger where it condenses and the liquid is collected in a cooled container. 4 hours of reaction, after which fiksirovalis pressure drop in the reactor to atmospheric, received 613 g (9.8 mol) of vinyl chloride, containing 99,995% of the basic substance with a yield of 98%.

At the end of the process the catalyst and the promoter-extractant is separated from the aqueous phase and used in the processes of dehydrocorydaline stated in the method described in examples 1-7.

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

Example 8.

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

The process of dehydrochlorinating 1,2-EDC conducted 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.

The vinyl chloride is obtained with a yield of 95% when the content of the basic substance to 99.6%.

Example 9.

Getting vinylidenechloride the dehydrochlorination 1,1,2-trichloroethane.

The dehydrochlorination 1,1,2-trichloroethane is carried out in conditions similar to those described in example 2, with the difference that the number of promoter-extradata is 1%, and the amount of catalyst PEG 400 is 0.0001% by weight of loaded 1,1,2-trichloroethane. In addition, the temperature of the reaction mass 70-80°supported by feeding it with a sharp pair and the coolant jacket. The yield of the target VI is redenchilada is 96%. As a promoter of extractant used CP-250.

The aqueous phase containing 11% of sodium hydroxide, the remainder after receiving vinylidenechloride, was treated with carbon dioxide, giving her the 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 sediment was rinsed with water, and then dried. Received sodium bicarbonate comply with the requirements of GOST 5100-85 on this product brand A.

Example 10.

Getting vinylidenechloride the dehydrochlorination 1,1,2-trichloroethane.

Synthesis of vinylidenechloride the dehydrochlorination 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 conducted at a temperature of 5-15°in the presence of a catalyst PEG 115 in the amount of 6.7 g (1% by weight of loaded 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 a 20%aqueous solution. As a promoter of extractant used CP-250.

The process of dehydrochlorinating carried out under vigorous stirring and atmospheric pressure for 12 hours. At the end of the process, separating the aqueous phase from the organic.

The organic phase is distilled at a temperature of 50-70°C. the Output of vinylidene the reed 90,5%.

VAT residue containing the catalyst, the promoter-extractant and unreacted 1,1,2-trichloroethane used again during dehydrochlorination by the present method.

Example 11.

Getting vinylidenechloride the dehydrochlorination 1,1,2-trichloroethane.

Synthesis of vinylidenechloride the dehydrochlorination 1410 g of 1,1,2-trichloroethane with the content of the basic substance 95,36%, or 1335 g (10 mol) in terms of 100%substance is carried out in the reactor described in example 5, when interacting with 480 g (12 mol) of sodium hydroxide in the form of an 11%aqueous solution selected from aqueous phase after dihydrochloride described in example 10, at a temperature of 60°C. the Molar ratio of 1,1,2-trichloroethane to the sodium hydroxide is 1:1,2. As a promoter of extractant used CP-30.

The pair formed vinylidenechloride at atmospheric pressure are adreactor column, heat exchanger and is condensed in the cooled collection. 2.5 hours received 985 g vinylidenechloride raw content of the basic substance of 96.5%. The yield of the target product was 98%.

The aqueous phase remaining in the reactor and containing 2% of unreacted sodium hydroxide, used to feed the system of neutralization of the acid gases in the production of the original 1,1,2-trichloroethane.

The resulting vinylidenechloride raw all Laut rectification, getting 936 (of 9.55 mol) vinylidenechloride-rectified with the content of the main substance of 99%.

The output vinylidenechloride-rectified to 95.5% from the saponification 1,1,2-trichloroethane.

Example 12.

Getting vinylidene chloride trichloroethylene by dehydrochlorination mixture of 1,1,2-trichloroethane, 1,1,1,2-tetrachlorethane and 1,1,2,2-tetrachlorethane.

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

1,1,2-trichloroethane 69 (1,14 mol);

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

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

and 1.8 g of catalyst PEG 400 (0.8% of the mass loaded chlorinated derivatives of ethane) and at a temperature of 20°With metered with stirring to 80 g (2 mol) of sodium hydroxide in the form of a 30%aqueous solution. The molar ratio of chlorinated derivatives of ethane:NaOH=1:1,29. As a promoter of extractant used CP-250.

The stirring is continued for 3 hours at a temperature of 20°until complete conversion of 1,1,2-trichloroethane in vinylidenechloride, and 1,1,2,2-tetrachlorethane in trichloroethylene. The process of dehydrochlorinating carried out under a nitrogen blanket to avoid interaction of the generated vapor of vinylidene chloride trichloroethylene with oxygen, which can form chemical and thermal n is stable products (Industrial organochlorine products. Handbook edited Laushine, M.: Chemistry, 1978, p.113, 151).

At the end of the process the stop stirring, the aqueous layer was separated from the organic. The organic layer is distilled, selecting first fraction vinylidenechloride with a boiling point 31-33°, weight 107 g (1.1 mol), containing 99% of the basic substance with a yield of 96%, and then 27 g of trichloroethylene at a temperature 86-88°containing 99% of the basic substance (0.2 mol) to yield 66%.

Catalyst, promoter-extractant and unreacted 1,1,1,2-tetrachlorethane left as residue after extraction of target products - vinylidene chloride trichloroethylene, are used again in the process of dehydrochlorinating chlorinated derivatives of ethane according to the claimed method.

The aqueous layer obtained after separation of the reaction mass, is also used again in the process of dehydrochlorinating chlorinated derivatives of ethane according to the claimed method or sent for further processing in the target commodity products - caustic soda or sodium bicarbonate.

The table lists the process conditions of dehydrocorydaline chlorinated derivatives of ethane sodium hydroxide in the presence of a phase transfer catalyst and promoter of the extractant in examples 1-12.

Thus, we have developed an integrated method of obtaining chlorinated p is ossadnik ethylene, suitable for use in industrial environments, by dehydrochlorination of the corresponding chlorinated derivatives of ethane by the action of aqueous sodium hydroxide solution, allowing you to apply as a feedstock chlorinated derivatives of ethane and mixtures thereof, including waste of these products, including waste according to the claimed method, and allows reuse of reagents by application of the principle of a closed loop, which consists in obtaining marketable products from waste chemicals.

Table

The process conditions of dehydrocorydaline chlorinated ethane sodium hydroxide in the presence of a phase transfer catalyst and promoter-extractant
№ p/pThe source of chlorinated ethaneThe molar ratio of chlorproma. Ethan:NaOHConc. water rest. NaOH, %Download, % by weight of chlorinated ethaneTechnological parametersTarget chlorinated ethyleneThe yield of the target product, %
CatalystPromoter-extractantTemperature, �B0; CPressure, MPa
12345678910
11,2-dichloroethane1:3,03300,303,080-902,5The vinyl chloride99
21,1,2-trichloroethane1:2,5618,70,282,840-800,7Vinylidenechloride96
31,1,2,2-tetrachlorethane1:2110,292,970-900,7Trichloroethylene94
41,1,2,2-tetrachlorethane1:1,1550,044,085-950,7Trichloroethylene93
51,1,2-tetrachlorethane1:3301,01015-25ATMVinylidenechloride95
6A mixture of 1,1,2-trichloroethane and 1,2-dichloroethane1:1,48*18,80,8**8**15-25 ATMVinylidenechloride94
71,2-dichloroethane1:3300,33,085-902,5The vinyl chloride98
81,2-dichloroethane1:3,03350,33,080-902,5The vinyl chloride95
91,1,2-trichloroethane1:2,56200,00011,070-800,7Vinylidenechloride96
101,1,2-trichloroethane1:5201,01,05-15ATMVinylidenechloride90,5
111,1,2-trichloroethane1:1,2110,00011,060ATMVinylidenechloride95,5
12Mixture1:1,29300,81,020ATM
1,1,2-trichloroethane, 1,1,1,2-tetrachlorethane, 1,1,2,2-tetrachloro the Tana Vinylidenechloride96
trichloroethylene66
* the molar ratio of 1,1,2-trichloroethane:Nahon; ** % by weight of 1,1,2-trichloroethane

1. The method of obtaining chlorinated derivatives of ethylene by the dehydrochlorination of chlorinated derivatives of ethane used as raw material by the action of an aqueous solution of sodium hydroxide in the presence of a phase transfer catalyst, related to the polyglycols, characterized in that the catalyst is used in amounts of 0.0001-1% by weight of the original chlorinated derivative of ethane and the process is carried out in the presence of promoter-extractant, which is a mixture of chlorinated hydrocarbons with the General formula CnH2n+2-xClxwhere n=10-30, x=1-7, having a molecular weight of 250-305 and chlorine 24-43%, followed by separation of the desired products.

2. The method according to claim 1, characterized in that the catalyst used glycols.

3. The method according to claim 1, characterized in that the promoter-extractant used in the amount of 1-10% by weight of the original chlorinated derivative of ethane.

4. The method according to claim 1, characterized in that the molar ratio of chlorinated derivative of ethane to sodium hydroxide is 1:(1,15-5) when the concentration of the aqueous solution of hydroc the IDA sodium 5-35 wt.%.

5. The method according to claim 1, characterized in that as a source of raw material for producing chlorinated derivatives of ethylene - vinyl chloride, vinylidenechloride, trichloroethylene, use the corresponding chlorinated derivatives of ethane - 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2 - and 1,1,2,2-tetrachlorethane or mixtures thereof.

6. The method according to claims 1 and 5, characterized in that as a source of raw material for producing chlorinated derivatives of ethylene using waste products of vinyl chloride, vinylidenechloride and trichloroethylene, which is formed in known processes and by the claimed method.

7. The method according to claims 1 to 4, characterized in that an aqueous solution of sodium hydroxide, catalyst and promoter-extractant use fresh reagents or reagents remaining after selection of the target products by the claimed method.



 

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The invention relates to a method for vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane in the presence of a catalyst and an alcohol additive
The invention relates to a method for vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane by the action of aqueous NaOH in the presence of a catalyst

The invention relates to organic synthesis, in particular, to a catalytic process for the production of vinylidenechloride, which is the raw material for plastics, composite materials, paints, adhesives and other valuable products

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.

EFFECT: improved conversion method.

61 cl, 8 tbl, 32 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing vinyl chloride monomer from ethane and ethylene. Method involves generating the outlet flow from reactor by catalytic interaction in common of ethane, ethylene, oxygen and at least one chlorine source taken among hydrogen chloride, chlorine or chlorohydrocarbon wherein the mole ratio of indicated ethane to indicated ethylene is in the range from 0.02 to 50. At the indicated stage of catalytic interaction method involves using a catalyst comprising component of rare-earth material under condition that catalyst doesn't comprise iron and copper practically and under additional condition that when component of rare-earth material represents cerium then catalyst comprises additionally at least one more rare-earth material but not cerium. Indicated outlet flow from reactor is cooled and condensed to form flow of crude product comprising the first part of hydrogen chloride and flow of crude cooled hydrogen chloride comprising the second part of indicated hydrogen chloride. Then method involves separation of indicated flow of crude product for vinyl chloride monomer as the flow product and flow of light fractions comprising the indicated first part of indicated hydrogen chloride. Then indicated flow of light fractions is recycled for catalytic interaction in common with indicated ethane, indicated ethylene, indicated oxygen and indicated chlorine source at indicated generating stage. Also, invention proposes variants of a method for producing vinyl chloride from ethane and ethylene. Invention provides preparing vinyl (chloride) from ethane and ethylene by the complete extraction of hydrogen chloride from the reactor outlet flow.

EFFECT: improved producing method.

40, 9 tbl, 3 dwg, 31 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing vinyl chloride monomer. Method involves generating outlet flow from reactor by catalytic interaction in common ethane, ethylene, oxygen and at least one source of chlorine taken among hydrogen chloride, chlorine or chlorohydrocarbon wherein the mole ratio of indicated ethane to indicated ethylene is in the range from 0.02 to 50. At this stage of catalytic interaction method involves using a catalyst comprising component of rare-earth material under condition that catalyst has no iron and copper practically and under additional condition that when component of rare-earth material represents cerium then catalyst comprises additionally at least one more component of rare-earth material being except for cerium. Indicated outlet flow from reactor is quenched to form flow of crude product that doesn't comprise hydrogen chloride practically. Flow of crude product is separated for vinyl chloride monomer flow and light fractions flow and the latter flow is recycled for catalytic interaction in common with indicated ethane, indicated ethylene, indicated oxygen and indicated chlorine source at the indicated generating stage. Also, invention proposes variants of a method in producing vinyl chloride. Invention provides the complete extraction of hydrogen chloride from the reactor outlet flow after conversion of ethane/ethylene to vinyl (chloride).

EFFECT: improved producing method.

30 cl, 5 dwg, 9 tbl, 30 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 technology, in particular method for vinylchloride production.

SUBSTANCE: claimed method includes fast gas cooling in quenching column followed by separation of pyrolysis products. Quenching and separation are carried out by barbotage through the layer of liquid concentrated by-products of these gases in quenching column cube. Then steam/gas mixture is brought into contact with returning condensate in regular filling layer of rectification tower with simultaneous purification of steam/gas mixture in rectification zone upstream. Liquid concentrated by-products are additionally rectified in vacuum with isolating and recovery of products having boiling point higher than the same for dichloroethane and distillate recycling. Method of present invention also makes it possible to produce perchloroethylene and tricloroethylene.

EFFECT: vinylchloride of high quality; reduced effort and energy consumption.

2 tbl, 4 dwg, 2 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: chemical industry, in particular method for production of value products from lower alkanes.

SUBSTANCE: claimed method includes passing of gaseous reaction mixture containing at least one lower alkane and elementary chlorine through catalytic layer. Used catalyst represents geometrically structured system comprising microfiber with diameter of 5-20 mum. 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 of increased yield.

3 cl, 4 ex

The invention relates to the production of parameningeal by alkylation of phenol, alpha-methylstyrene and the catalyst for this process
The invention relates to a technology for chlorohydrocarbons by the chlorination of olefins and subsequent separation of the products of chlorination on target and by-products, in particular to a method of rectification of a mixture of chlorinated propylene with obtaining allyl chloride of high purity
The invention relates to a technology for chlorohydrocarbons by the chlorination of olefins and subsequent separation of the products of chlorination on target and by-products, in particular to a method of rectification of a mixture of chlorinated propylene with obtaining allyl chloride of high purity

FIELD: petrochemical processes.

SUBSTANCE: invention relates to oxidative halogenation processes to obtain halogenated products, in particular allyl chloride and optionally propylene. Process comprises interaction of hydrocarbon having between 3 and 10 carbon atoms or halogenated derivative thereof with halogen source and optionally oxygen source in presence of catalyst at temperature above 100°C and below 600°C and pressure above 97 kPa and below 1034 kPa. Resulting olefin containing at least 3 carbon atoms and halogenated hydrocarbon containing at least 3 carbon atoms and larger number of halogen atoms than in reactant. Catalyst contains essentially iron and copper-free rare-earth metal halide or oxyhalide. Atomic ratio of rare-earth metal to iron or copper is superior to 10:1. In case of cerium-containing catalyst, catalyst has at least one more rare-earth element, amount of cerium present being less than 10 atomic % of the total amount of rare-earth elements. Advantageously, process is conducted at volumetric alkane, halogen, and oxygen supply rate above 0.1 and below 1.0 h-1, while diluent selected from group including nitrogen, helium, argon, carbon monoxide or dioxide or mixture thereof is additionally used. Halogenated product is recycled while being converted into supplementary olefin product and olefin product is recycled in order to be converted into halogenated hydrocarbon product. Optionally, allyl chloride and ethylene are obtained via interaction of propane with chlorine source in presence of catalyst.

EFFECT: increased productivity of process and improved economical characteristics.

26 cl, 1 tbl

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to perfluoroolefins production technology, notably to heaxafluorobutadiene CF2=CF-CF=CF2. Process comprises reaction of 1,2,3,4-tetrachlorohexafluorobutane with zinc in aqueous medium at 30 to 90°C. Reaction is carried out by metering 1,2,3,4-tetrachlorohexafluorobutane into reaction vessel containing zinc and water, while simultaneously desired product formed is recovered. Advantageously, process is conducted in presence of promoter selected from acids such as sulfuric acid and hydrochloric acid, soluble weak base salts such as zinc and ammonium halides, interphase transfer catalysts such as quaternary ammonium salts, quaternary phosphonium salts, tetrakis(dialkylamino)phosphonium salts, and N,N',N"-hexaalkyl-substituted guanidinium salts, or mixtures of indicated substances.

EFFECT: increased purity of heaxafluorobutadiene and simplified technology.

4 cl, 7 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.

EFFECT: improved conversion method.

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

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