The method of producing dichloroethane
(57) Abstract:Use: solvent. The inventive receiving dichloroethane lead by the chlorination of ethylene with an excess of 5 to 40 mol% of the latter. The content of dichlorethane in the reaction mass support 95,0 - a 99.6 wt.% when the temperature in the cube reactor 85 - 105oWith the pressure of the top combined with the reactor column 0,11 - 0,155 MPa, and tapped the top of this column of exhaust gases dechlorinate at 30 - 110oIn the environment of liquid dichlorethane with the dissolved ferric chloride, provided that the ratio of containing abasah unreacted ethylene and chlorine was close to 1 : 1, the resulting dichloroethane fed into the reactor and/or combined with it the rectification column, and the column selection boiling lead cleanup digaetano from boiling impurities and at the same time from the high-boiling impurities, for which boiling fraction of the column selection boiling serves for processing, dihloretan-rectified output from the intermediate plate and guide for feeding the reaction mass in the reactor, and CBM stream is sent for treatment in vacuum column selection high-boiling impurities. 1 table, 2 Il. The invention relates to the chemical industry in parts receive the teachings of dichloroethane by the interaction of chlorine with ethylene in the hollow reactor, in the liquid medium of the reaction mixture with the dissolved ferric chloride at the boiling temperature of the reaction mixture. Received dichloroethane is collected in the vapor phase and fed to the rectification column. The heat of reaction is used for rectification dichloroethane raw, and the reactor plays the role of the reboiler of the column. There is no need to rinse dichloroethane raw from hydrogen chloride and ferric chloride. A large part of the bottom liquid of the rectification column is returned to the reactor, and a lower portion with a bottom liquid from the reactor is sent to the column selection high-boiling products. The process is conducted with an excess of ethylene. The molar ratio of ethylene to chlorine may be in the range of 1.01-1,10. Chlorine may contain 1-10 mol. air. Dichloroethane-rectified output from the intermediate plates of the distillation column, and the top of the last stand boiling impurities  Reaction mass contains 250-500 ppm of ferric chloride catalyst. The process temperature is maintained within 85-180aboutWith due to the increased pressure of the process and composition of the circulating reaction liquid. The latter mainly consists of: 1,2-dichloroethane about 35-50 wt. 1,1,2-trichloroethane about 40-60 wt. tetrachlorethane rsii reagents and lack of high selectivity. This is a consequence of increased process temperature and a low content of dichloroethane in the reaction mass.In another process of obtaining dichloroethane  the chlorination of ethylene is conducted in the environment of the boiling reaction mixture. The molar ratio of ethylene and chlorine is 1.2:1. The heat of reaction is used for rectification of the resulting dichloroethane. This process is carried out in the apparatus, the lower part of the reaction, and the top of the distillation. Purified dichloroethane receive in the form of a side selection of the distillation zone. Thus, the share of commercial product (20about/20aboutC) is 1,2557. For comparison, 100% dichloroethane has a specific gravity of 1,2530, i.e. approximately dichloroethane-rectified receive a purity of about 98,66%
The disadvantages of this process should include a great breakthrough of unreacted ethylene and low purity of the commercial product.Developed the process of obtaining dichloroethane, conducted under similar conditions and the molar ratio of ethylene chlorine of 1.05:1. The output of dichloroethane filed on chlorine in this process is the 95.8-98.6% of
The disadvantage of this method is the relatively low selectivity of the process.Pre the Torah, consisting of a mixture of anhydrous ferric chloride and a nitrogen base or its salts, which are also inhibitors of adverse reactions. The process is carried out at a temperature below the boiling point of dichloromethane and atmospheric or elevated pressures 
The disadvantages of the process include the misuse of heat of reaction, as well as the need for a special system for the regeneration of the catalyst.A method of obtaining dichloroethane by direct liquid-phase chlorination of ethylene with 65-160aboutAnd pressure to 1.96 MPa in the presence of ferric chloride catalyst in the amount of 10-600 ppm, and inhibitor adverse reactions. As the latter can be used benzene, toluene, xylene, ethylbenzene, mesitylene, n-butylbenzoyl, cumene, chlorinated benzene and toluene, or a mixture thereof. The inhibitor is added in an amount of 0.0001-20 wt. in the calculation of the liquid phase. The selectivity of the formation of dichloroethane under these conditions reaches of 98.5-99.2 percent while in the absence of inhibitor selectivity of the formation of dichloroethane is about 97,0% 
The disadvantage of this method of producing dichloroethane is its relatively low selectivity.The method of chlorination of ethylene in idce, required for the reaction, and 90-100 mol. of ethylene. Formed and unreacted products come in the second reaction zone, in which a counter continuously served with ethylene so that the total number of the latter were 100-102% compared to chlorine 
The disadvantages of this method are the non-use of heat of reaction, and the presence of contaminated dichloroethane wastewater.Closest to the proposed technical solution is the method of producing dichloroethane in two reaction zones  the Second area is used for chlorination of ethylene, unreacted in the first zone, in which the process is conducted at the boiling temperature of the dichloride in a molar ratio of ethylene to chlorine (1,03-1,20):1. In the second zone, the process temperature is maintained within the range of 10-40aboutC, and the molar ratio of ethylene to chlorine 1:(of 1.05 to 1.50). Reacted in the second reaction zone of the chlorine dissolved in the cooled ethylene dichloride, filling the area, and the resulting solution is fed to the first reaction zone.The disadvantage of this method is the use of excess chlorine in the second reaction zone, thus reducing the selectivity of the process.The purpose of the image is raw.This goal is achieved by the fact that upon receipt of dichloroethane by the interaction of ethylene with chlorine in the environment boiling of the reaction mixture in the presence of a complex catalyst is ferric chloride and oxygen by using eye-catching in the process of heat of reaction to heat combined with the reactor column, in which the rectification dichloroethane raw, and return dichloroethane, unreacted in pyrolysis furnaces, pre-separated from the boiling impurities on the column selection boiling, high-boiling impurities are removed from the system operating under vacuum column selection storable, and exhaust gases containing ethylene, is directed to dekhlorirovanie, the process of chlorination of ethylene is carried out with an excess of the last 5-40 wt. the content of dichloroethane in the reaction mass support 95,0-a 99.6 wt. preferably 99,0-a 99.6 wt. due to the feeding level of the reaction mass side selection of the column selection boiling impurities, the temperature in the cube reactor 85-105aboutWith pressure, the top combined with the reactor column 0,11-0,155 MPa, and tapped the top of this column of exhaust gases containing unreacted ethylene, dechlorinate when 30-110aboutIn the environment of liquid dichloroethane containing the Lena and chlorine was close to 1:1, the resulting dichloroethane is fed directly into the reactor and/or combined with it the column rectification or after caustic leaching, and the column selection boiling, along with clearing of dichloroethane, and reacted by pyrolysis, they clean dichloroethane fed from the reactor and/or from a cube, combined with him or her columns, from boiling impurities and at the same time from the high-boiling impurities, for which boiling fraction from the top of the column selection boiling serves for processing, dichloroethane-rectified output from the intermediate plate and guide for feeding the reaction mass in the reactor and, if necessary, on pyrolysis, and CBM product sent for treatment in vacuum column selection high-boiling impurities.To reduce the expenditure ratio of ethylene with high selectivity process in General dekhlorirovanie abgasnorm ethylene expediently carried out at a temperature of about 30-70aboutC.Reaction heat released in the reactor in which the process is conducted at 80-140aboutWith use for rectification of dichloroethane. In case, if the heat of reaction is not enough, partly heating the distillation column, combined with reagency process can be used as one of the stages of production of vinyl chloride from ethylene or naphtha, moreover, if at the stage of ethylene oxychlorination process as the oxidant is oxygen, the exhaust gases from this stage it is advisable to submit to the reactor defloriani ethylene. Instead of ferric chloride may be used other catalyst, for example a complex of ferric chloride and dimethylformamide, are added to the reaction mass in an amount of 0.1-2.0 wt. mixed with a stabilizer with hexamethylenetetramine in an amount up to 1% by weight of the catalyst.In Fig. 1 shows one of the circuits receiving dichloroethane by chlorination of ethylene in the proposed method. The process is carried out in boiling reaction medium at a temperature in the cube reactor 85-105aboutC. the Reagents are fed through the bubblers in the lower part of the reactor 1 with a large excess (5-40 mol.) of ethylene. There also introducing oxygen in the amount of 0.5-4.0% of the amount of chlorine. Oxygen is supplied in pure form or in the form of air entering directly into the reactor or pre-mixing it with chlorine. Can be used in the process of electrolytic chlorine containing oxygen. How it was fed to the chlorination process has no effect.The reaction is exothermic chlorination of ethylene. Released as a result of formation of one mole of d is absorbed with him the rectification column 2, except as contained in the gaseous reagents inertol and unreacted ethylene, do a couple of dichloroethane and organic impurities. In this process along with the main reaction reaction accession runs a number of adverse reactions reactions substitution chlorination of ethylene and the reaction hydrochlorination of ethylene with the formation respectively of such side products, such as trichloroethane and tetrachlorethane, and ethyl chloride. In General, these compounds are organic impurities in ethylene dichloride, are qualitatively and quantitatively in the case of filing a third-party system dichloroethane.To improve the selectivity of the process contents of dichloroethane in the reaction mass is maintained at the level 95,0-a 99.6 wt. preferably 99,0-a 99.6 wt. by feeding the reaction mass cleaner dichloroethane. With the same purpose, use complex inhibitor substitution chlorination of 0,005 0,050 wt. ferric chloride and 0.2 to 1.0 wt. benzene with the addition to the reaction mass of oxygen in the ratio with benzene 1:(0-20).Ferric chloride or specifically added to the reactor or formed during the process due to the interaction of hydrogen chloride generated in the result of the factor 1 column 2 is the rectification flowing from the reactor, and, if necessary, and dichloroethane. The reactor combine constructively with the column, as shown in Fig. 1, or via ducts (Fig. 2). He performs the role of a boiler. Gas-vapor stream from the upper part of the reactor served in the cube column 2, from which derive liquid dichloroethane, enriched high-boiling impurities. Depending on the process conditions this dichloroethane or return to the reactor, either partially or fully directed to the column selection boiling 7 or column selection storable 10. From the top of column 2 facing pairs of dichloroethane, unreacted ethylene, oxygen and inert gases.The pressure of the upper combined column 2 is maintained at the level of 0.11-0,155 MPa. In the condenser 3 is the condensation of the vapors of dichloroethane. Part of the liquid returned to the column 2 in the form of phlegmy, and take part in a commercial product. The exhaust from the condenser 3, the exhaust gases contain an explosive mixture of ethylene and oxygen. To create explosion concentration of this mixture according to the optimal operation of declarator 4 exhaust gases from the combined columns diluted with 2 pairs of dichloroethane, the number of which is regulated by the flow of cooling agent in the context of mercury interval associated with the amount received in this apparatus abgasnorm ethylene. If it is not, then it is advisable to process carried out at low temperature (about 30-60aboutC). This will allow you to achieve a high selectivity of the process and not to complicate its hardware design. If the number abgasnorm ethylene is more than 300 nm3/h, it is desirable to utilize the heat of reaction received from several low selectivity. As the catalyst used dissolved in dichloroethane ferric chloride, and as an inhibitor adverse reactions ferric chloride in combination with oxygen supplied to declarator together with the exhaust gases. The ratio abgasnorm ethylene and chlorine maintain a close 1:1. In this case, the process defloriani is carried out at a temperature of 105-110aboutC. Formed in declaratory 4 dichloroethane vapor state comes combined with it in column 5, where due to the heat of reaction is its rectification. On top of the column 5 output dichloroethane-rectified. Exhaust gases leaving the condenser 6, after the removal of dichloroethane are thermoabrasion or catalytic oxidation.From the cube reactor 1 and/or combined with it column 2 the liquid phase is fed to the column selection boiling impurities 7. When using this process is Satoru 8 this column deduce boiling fraction, from the cube, heated by using a heater 9, selected dichloroethane, enriched high-boiling and intermediate plates dichloroethane-rectified. This dichloroethane can be used as a commercial product, or recycled to the pyrolysis or in the reactor 1. Boiling fraction is fed to the processing, for example in carbon tetrachloride, and dichloroethane with a high boiling point in a vacuum rectification column 10. This column is cleaned dichloroethane from the high-boiling. Purified dichloroethane from the condenser 11 of the column 10 is fed into the reactor 1 and/or combined with it the column 2. With the intermediate plates of the column output dichloroethane, enriched by 20-70% of high-boiling impurities, and sent for recycling, for example in carbon tetrachloride. From the cube vacuum column 10, the heated using the heater 12, excrete liquid waste that is sent for incineration or after special processing for processing.In Fig. 2 shows another variant of the scheme receive dichloroethane by chlorination of ethylene in the proposed method. The process is carried out in reactor 1.Combined with the reactor 1 column 2 is the rectification flowing from the reactor and, if necessary, ka. Gas-vapor stream from the upper part of the reactor 1 is served in the cube column 2, from which derive liquid dichloroethane, enriched high-boiling impurities. This dichloroethane sent to the column selection boiling 7.Column 2 is equipped with a condenser 3, from which part of the liquid returned to the column in the form of phlegmy, part of the output in the form of a commercial product. Its possible that part of the distillate is used for feeding the reactor 1 with the objective of maintaining therein the desired level of the reaction mass. The exhaust from the condenser 3, the exhaust gases are directed to declarator 4 for the chlorination of unreacted ethylene. The process is carried out at 50-70aboutWith what the main part of the heat of reaction is removed in the external heat exchanger 6. Exhaust gases from declarator 4 after the removal of dichloroethane are thermoabrasion or catalytic oxidation.In the rest of the process flow depicted in Fig. 2, a similar process scheme shown in Fig. 1.The proposed process allows you to output cycle boiling and high-boiling impurities and to produce dichloroethane required cleanliness with the lowest cost of energy.P R I m e R s. In accordance with the prototype percent is ktora 1 introducing chlorine and ethylene, and part of the chlorine is in the form of a solution in dichloroethane from declarator 4. In the reactor the process is conducted in an environment of boiling of the reaction mass at 105-110aboutC. the Heat of reaction generated in the reactor, is used for rectification dichloroethane formed in the distillation column 2. Declarator 4 made in the form of columns filled with metal nozzle. The temperature is maintained at a level of 10aboutWith due submission, in the upper part of declarator dichloroethane cooled cube from reactor 1 (not shown). In the lower part of declarator serves 4 containing unreacted in the reactor 1 ethylene exhaust gases, the exhaust from the top of the column 2, and chlorine. In declaratory 4 is almost complete conversion of ethylene and unreacted excess chlorine is dissolved in the cooled resulting ethylene dichloride and entered with him into the reactor 1. The concentration of ferric chloride in the circulating dichloroethane is about 0.02 wt. From the bottom of the reactor 1 is constantly deduce the reaction mass at 20% and is directed to the column selection high-boiling impurities 10 for removal of high-boiling impurities, resins and partially deactivated from ferric chloride. Purified dichloroethane returns to sistova of hydrogen with metal nozzle in declaratory 4. The top of the distillation column 2 selected commodity dichloroethane purity 99.97% of the Total conversion on chlorine and ethylene are close to 100%
In accordance with the proposed process in the reactor 1 serves 100 KMOL/h of ethylene, and 74,95 of KMOL/h of gaseous chlorine, in addition, there is injected 8,35 of KMOL/h of chlorine dissolved in dichlorethane 4. Total supply of chlorine is 83,30 of KMOL/h, which determines the molar ratio of ethylene to chlorine, equal to 1.2:1. The top of the distillation column 2 output exhaust gases, consisting of unreacted ethylene in the number 16,70 of KMOL/h and vapors dichloroethane. These exhaust gases are served in the lower part of declarator 4, enter 25,05 of KMOL/h of gaseous chlorine. Thus, the molar ratio of ethylene to chlorine in declaratory 4 is 1:1,5. and for the whole system is about 1:1.The source and received during the data presented in the table. The same table shows the results of the research in accordance with the claimed invention. The process is conducted in the reactor 1, is combined with a distillation column 2. In the bottom of the reactor 1 is injected chlorine and ethylene with an excess of the last 5-40 mol. The process takes place in an environment of boiling of the reaction mass at 85-110aboutC. Thepinoy column 2. The pressure of the top of the column support at the level 0,101-0,155 MPa. The temperature in declaratory 4 support level 50-110aboutWith due to the circulation of the reaction mass through the external heat exchanger 6. In the lower part of declarator serves chlorine and exhaust gases, the exhaust from the top of the column 2. The ratio of unreacted in the reactor 1 of the ethylene contained in obrazach, to chlorine maintain a close 1:1. In declaratory 4 is almost complete conversion of ethylene. The resulting dichloroethane after leaching from ferric chloride and hydrogen chloride fed into the reactor 1. The concentration of chlorine Gisela in circulating dichloroethane is about 0.02 wt. From the bottom of the reactor 1 or column 2 permanently remove the liquid phase and is sent to the column selection boiling impurities 7 for cleaning the latter. From the condenser 8 of this column deduce boiling fraction containing dichloroethane 20-30 wt. From the cube column 7, the heated using the heater 9, selected dichloroethane, enriched high-boiling 60-70 mol. and with intermediate plates dichloroethane-rectified. This dichloroethane is sent to the reactor 1 for maintaining constant the level of the reaction mass. Boiling fraction is fed to the processing of e is cleaned dichloroethane from high-boiling, resinous and partially deactivated from ferric chloride. Purified dichloroethane from the condenser 11 of the column 10 return in column 2. Intermediate plates are selected mixture of dichloroethane with high-boiling impurities. This mixture is recycled for receiving carbon tetrachloride. From the cube column 10, heated by using a heater 12, a display containing ferric chloride liquid waste that is sent for incineration. Supplementation of ferric chloride is due to the reaction resulting from side processes of hydrogen chloride with the material of the walls in declaratory 4. The top of the distillation column 2 selected commodity dichloroethane. Total conversion on chlorine and ethylene are close to 100%
The output of dichloroethane was determined based on filed in the reactor, ethylene and chlorine. The METHOD of producing DICHLOROETHANE interaction of ethylene with chlorine in the environment boiling of the reaction mixture in the presence of a complex catalyst is ferric chloride and oxygen by using eye-catching in the process of heat of reaction to heat combined with the reactor column, in which the rectification dichloroethane raw and non-dichloroethane, in particular with the stages of the oxychlorination process mausi at the stage of pyrolysis, pre-separated from the boiling impurities on the column selection boiling, high-boiling impurities are removed from the vacuum column selection storable, and exhaust gases containing ethylene, is directed to dharitvena, characterized in that, to increase the selectivity of the process and reduce the expenditure coefficients for raw materials, chlorination of ethylene is carried out with an excess of the last 5 to 40 mol.%, the content of dichloroethane in the reaction mass support 95,0 - a 99.6 wt.%, preferably 99,0 - a 99.6 wt.%, when the temperature in the cube reactor 85 - 106oAnd pressure of the top combined with the reactor column 0,11 - 0,155 MPa, and exhaust from the top of this column of exhaust gases containing unreacted ethylene, possibly after caustic leaching, dechlorinate at 30 - 110oIn the environment of liquid dichloroethane containing dissolved ferric chloride, in a ratio contained in the exhaust gases of unreacted ethylene and chlorine, close to 1 : 1, the resulting dichloroethane is fed directly to the chlorination reactor and/or combined with it the rectification column, and the column selection boiling served along with dichloroethane, and reacted at the stage of pyrolysis, also dichloroethane from the chlorination reactor and/or vydelyaut boiling impurities and submit them for processing, with the intermediate plates of the column output dichloroethane-rectified and sent it to recharge the reaction mass in the reactor chlorination or, if necessary, to the stage of pyrolysis, and CBM product is directed to the column selection high-boiling impurities.
FIELD: industrial organic synthesis.
SUBSTANCE: invention is dealing with production of chlorohydrocarbons exhibiting plasticizing properties in polymer compositions in production of synthetic building materials, varnishes and paints, artificial films and leathers, in rubber industry, and as fire-retardant additives in polymers. Process comprises chlorination of waste obtained in production of C14-C32 fraction by ethylene-α-olefin oligomerization. Chlorination is accomplished in two steps: addition chlorination at 35-55°C followed by substitution chlorination at 40-105°C. Chlorohydrocarbons thus obtained can, in particular, be used as secondary plasticizer in polyvinylchloride compositions.
EFFECT: reduced expenses due to using production waste.
4 tbl, 30 ex
FIELD: petrochemical and industrial organic synthesis.
SUBSTANCE: process comprises separating gaseous pyrolysis products to recover ethylene-containing fraction with 54-65% ethylene content and C3-C5-hydrocarbon fraction. Ethylene-containing fraction is subjected to liquid-phase catalytic chlorination. Gas phase of chlorination product is purified via adsorption and fed into furnace as fuel. C3-C5-Hydrocarbon fraction is subjected to exhaustive hydrogenation, hydrogenation product is combined with fresh raw material at weight ratio (0.05ч1):1 and sent to pyrolysis plant.
EFFECT: achieved integration of process, increased reliability thereof, and reduced expenses.
1 dwg, 1 tbl, 15 ex
FIELD: organic chemistry.
SUBSTANCE: 1,2-dichloroethane is obtained by liquid phase ethylene chlorination with discharging of reaction heat due to operation medium boiling. In claimed process nitrogen is added to chlorine and ethylene reagents. Ratio of chlorine volume consumption to nitrogen volume consumption is maintained as 1:1. Reaction is carried out at temperature lower than 1,2-dichloroethane boiling point, and discharging of reaction heat is carried out by evaporative cooling of operation medium in nitrogen.
EFFECT: process of increased selectivity; decreased yield of by-products.
1 tbl, 5 dwg
FIELD: chemical industry; designs of the bubble-type reactors for production of 1.2-dichloroethane.
SUBSTANCE: the invention is pertaining to the design of the bubble-type reactors for production of 1.2-dichloroethane by the method of the liquid-phase chlorination of ethylene with the reaction heat removal at boiling of the working medium. As the contact device the reactor uses two layers of the metallic nozzle. The liquid 1.2-dichloroethane is fed from above to the nozzle, into the space between the layers of the nozzle feed the gaseous chlorine with nitrogen, and under the lower layer of the nozzle feed the gaseous ethylene with nitrogen, that allows to reduce the diameter of the reactor in 1.5-2 times due to the increased effectiveness of stirring and formation of the developed contact surface of the phases. At that the heat of the reaction is removed by evaporation of 1.2-dichloroethane in nitrogen. At that the temperature of the liquid is maintained below the boiling temperature. The technical result of the invention is the increased selectivity of the process, reduction of the outlet of the by-products (the highest ethane chlorides) and the decreased overall dimensions of the reactor.
EFFECT: the invention ensures the increased selectivity of the process, reduction of the outlet of the by-products (the highest ethane chlorides) and the decreased overall dimensions of the reactor.
1 ex, 4 dwg
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for synthesis of 1,2-dichloroethane by method of liquid-phase chlorination of ethylene. The process is carried out by direct feeding gaseous reagents chlorine and ethylene in liquid reaction medium of reactor. Before feeding into reactor chlorine and ethylene are heated preliminary in heat-exchangers to temperature equal to that of liquid in reactor. Method provides enhancing selectivity of process and reducing formation of by-side substances representing higher chlorine-derivatives of ethane.
EFFECT: improved method of synthesis.
4 dwg, 1 ex
FIELD: chemical technology.
SUBSTANCE: invention relates to a method for synthesis of 1,2-dichloroethane by method of liquid-phase chlorination of ethylene. Method involves maintaining the optimal ratio of heat eliminated based on evaporation and heat eliminated based on cooling a liquid medium in a heat exchanger in the process. One-sixth part of heat formed in reactor is eliminated based on evaporation of synthesized compound in boiling and 5/6 part of formed heat is eliminated based on circulation of liquid working medium in external heat exchanger. The temperature gradient in the reaction zone is maintained equal 52°C. Invention provides enhancing selectivity of process and reducing amount of by-side products of reaction (higher chlorine-derivate of ethane).
EFFECT: improved method of synthesis.
3 dwg, 1 ex
FIELD: industrial organic synthesis.
SUBSTANCE: invention relates to a process of liquid-phase chlorination of ethylene wherein reaction heat is removed by means of vaporization of reaction medium. Process is conducted at vacuum-mediated reduction of reaction medium boiling temperature below 60°C, vacuum being developed because of condensation of vapors formed in external condenser accompanied by removal of non-condensed gases by vacuum pump.
EFFECT: enhanced selectivity of process and decreased yield of by-products (higher chlorine derivatives of ethane).