• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A method for producing 1,2-dichloroethane by reacting ethylene with chlorine in the presence of suspended copper chloride or a mixture of copper and iron chlorides at a temperature of 185292 s and a pressure of 0.097-0.6 MPa with the removal of heat generated throughout the reaction space by indirect cooling using a liquid or gaseous coolant, characterized in that, in order to simplify its technology, the process is carried out when chlorine is supplied at a point located height equal to 50-69% of the total reactor height, and the lower portion of reactivity. ethylene, hydrogen chloride and a mixture of nitrogen and oxygen are fed at a molar ratio of hydrogen chloride, ethylene, oxygen and chlorine 2:
    公开号:SU1147247A3
    申请号:SU802928849
    申请日:1980-05-30
    公开日:1985-03-23
    发明作者:РИДЛЬ Йозеф；Кюн Венцель；Видманн Петер
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:


    vj
    Nd The invention relates to an improved process for the preparation of 1,2-dichloroethane, which is widely used as an intermediate in the preparation of vinyl chloride and as a solvent. HsBjecTeH is a method of producing 1,2-dichloroethane by direct chlorination of ethylene in the liquid phase at 90100 G in the presence of a catalyst of ferric chloride C. Ethylene is usually used in 3-20% excess. The method provides a high yield of the target product. The disadvantage of this method is the high consumption of scarce chlorine. There is also known a method for producing 1,2-dichloroethane by oxychlorination of ethylene at 210-260 ° C in the presence of a catalyst — copper salts 1 deposited on alumina. The ratio of ethylene chloride to oxygen is 1: 1: (1.03-1.05). . The disadvantage of this method is the relatively low yield of t, 2-dichloroethane — up to 97% with a conversion of chlorine to hydrogen of 99%. The closest to the proposed results achieved is a method for producing 1, 2-d 1-chloroethane, in which ethylene is reacted with chlorine in a vertical reactor. In the lower part of the reactor, a mixture of gases containing up to 4% ethylene, chlorine, oxygen and nitrogen with a ratio of chlorine, ethylene and oxygen of 1: 1: 1.1 is given. The process is carried out in the presence of suspended catalysts — copper chloride or a mixture of copper and gel chlorides at 80–250 ° C and a pressure of 0.0970.6 MPa. The method uses ethylene that has not reacted during the pre-carried out oxychlorination stage (the parameters of the oxychlorination process are not given in the description of the method). A mixture of ethylene, oxygen and nitrogen is obtained after cooling the reaction mass of the oxychlorination process and separation of the main amount of 1,2-dichloroethane from it. In this case, the heat generated in the whole reaction space is removed by indirect cooling using a liquid or gaseous heat carrier 2} The known method allows to reduce the consumption of chlorine, since the bulk of the ethylene reacts during the oxychlorination. However, the disadvantage of the method is the complexity of the technology associated with the need for additional stages of oxychlorination, cooling and separation of the reaction mass of oxychlorination of ethylene before carrying out the chlorination process. The purpose of the invention is to simplify the technology for producing 1,2-dichloroethane. The goal is achieved by the fact that according to the method of producing 1.2-dichloroethane by the interaction of ethylene with chlorine at a temperature of 185-292 ° C in the presence of suspended copper chloride or a mixture of copper and iron chlorides at a pressure of 0.097-0.6 MPa in a vertical reactor in the presence of a nitrogen-oxygen mixture and with the removal of heat generated in the entire reaction space, by indirect cooling using a liquid or gaseous coolant, the process is carried out when chlorine is supplied at a point located at a height of Avna 50-69% of the total height of the reactor, and ethylene, hydrogen chloride and a mixture of nitrogen and oxygen are fed to the lower part of the reaction zone at a molar ratio of hydrogen chloride, ethylene, oxygen and chlorine 2: (1.23-2.07): Co , 8-1): (Oh, 18-1). All gases can be introduced into the reactor separately, but more conveniently hydrogen chloride and ethylene, on the one hand, and oxygen and nitrogen (for example, in the form of air), on the other hand, can be introduced into the mixture with one another. The catalyst must be in suspension. After leaving the reactor, the products are passed through a separator to separate solid, fine catalyst particles, then washed and partially condensed at a temperature of about 10 ° C. 1, 2-Dichloroethane is separated by distillation. The most convenient form of the reactor is a double-jacketed vertical cylinder with built-in coolant supply structures. Gases are fed through pipelines, and inlets for mixtures of ethylene with hydrogen chloride and oxygen with nitrogen 3 are expediently located at the bottom of the reactor. . The catalyst — copper (II) chloride or its mixture with iron (III) chloride — is deposited on carriers with high specific surface, for example, alumina. The gas flow rate in the reaction space is chosen as /; so that at least 95% of the catalyst particles are in suspension. Example 1 The reaction is carried out in a vertical glass cylindrical reactor with an internal diameter of 80 mm, equipped with a jacket and a coil for the heat transfer medium, which ensures that the required temperature is maintained in the reactor. A glass ball is located above the top of the cylinder for separating the solid particles of catalyst carried away by the gas stream. The gas that has passed through the ball passes on to a water cooler with a collector, for condensate and a vapor tube connected to the cooler, cooled with brine. The reaction space (cylinder interior minus the volume of embedded structures) has a volume of 4.7 l. At the bottom of the pacnonalra reactor, the inlets for air blowing and mixtures of ethylene with hydrogen chloride, equipped with porous baffles, are placed. The chlorine feed is in the middle of the reactor at a height equal to 69% of the total height of the reactor. Before starting the reaction, the reactor is flushed with hot air at a rate of 60 l / h (volume under normal conditions) for 30 minutes. Then increase the air supply rate to 90 l / h and at the same time begin to supply a mixture of ethylene (45 l / h) and hydrogen chloride (44 l / g), as well as chlorine at a rate of 22 l / h. All the above gases are heated to 60 ° C before being fed into the reactor. The temperature in the reactor gradually rises to 220 ° C, after which it is kept at a constant level. The pressure is 0.097 MPa. The gases leaving the reactor pass through a cooler with a temperature of 13. cooled by water, a scrubber for flushing uncondensed gases and a cooler cooled by brine to 15 ° C. The test was carried out for 4 hours. The composition of the condensate and exhaust gases was determined by gas chromatography. The process is conducted at an atmospheric pressure of 0.096 MPa. The molar ratio of the reactants during the reaction is HC2: CrH ,:: C6t: Ot 2: 2.05: 1: 0.86. - The degree of conversion of hydrogen chloride is 96%, chlorine is 99.99%, ethylene is 97.5%. The yield of dichloroethane is 93.9% based on ethylene missed. Example 2. The process is carried out as in Example 1, but at a temperature and for 5 hours. The degree of conversion of hydrogen chloride is 92%, chlorine 99.9%, ethylene 96%. The output of dichloroethane 92.2% in terms of the missed ethylene. Example 3. The process is carried out as in example 1, but at a temperature of 240 ° C and for 4, 5 hours. The degree of conversion of hydrogen chloride is 98%, chlorine is 100%, ethylene is 98%. The output of dichloroethane in terms of ethylene 94,7%. Example 4. The process is carried out as in example 1, but for 3 hours and at air supply rates of 90 l / h, ethylene 27 l / h, hydrogen chloride 44 l / h and chlorine 4 l / h, which corresponds to the HC: 02.2 ratio : 1.23: 0.18: 0.86. The degree of conversion of hydrogen chloride is 95.5%, the shoreline is 100%, and ethylene is 96%. The output of dichloroethane in terms of ethylene 91,8%. Example 5. A reactor similar to that described in Example 1 was used - but made of nickel and equipped with a porous glass plate instead of a glass ball. The internal diameter of the reactor is 50 mm. At the outlet, the reactor is equipped with a pressure reducing valve. The internal volume of the reactor is 1.5 liters, the volume of catalyst is 0.36 liters. The chlorine feed is at a height equal to 50% of the total height of the reactor. The process is carried out as in Example 1, but the gases are fed under pressure. By adjusting the pressure reducing valve, the pressure is maintained at 0.392 MPa; during the process, the temperature is maintained at 220 C. The process is carried out for 6 hours. I 1 The degree of conversion of hydrogen chloride is 99%, chlorine 100%, ethylene 98.5%. The yield of dichloroethane in terms of ethylene is 95.7%. Example 6. The reaction is carried out as in Example 1, but at a temperature of ZSO-C and the catalyst also contains, with 3.7% of copper oxide deposited on copper chloride, another 0.51% of iron (III) chloride. The process. Will be 5h. The degree of conversion of hydrogen chloride 92%, chlorine 99.9%, ethylene 95%. The output of dichloroethane in terms of ethylene 91,3%. Example 7, Reaction wire as in example 1, but the temperature is maintained within 285-292 0, and the ethylene feed rate is 45.5 l. The experiment lasts 4 hours. The ratio of reagents, tO 2: 2.07: 1: 0.86. The degree of conversion of hydrogen chloride 93%, chlorine 100%, ethylene 96%, the yield of dichloroethane in terms of ethylene is 92.9%. Example 8. The process is carried out as in Example 1, but instead of air, pure oxygen is introduced in the amount of 22 l / h and nitrogen in the amount of 68 l / h. The reaction temperature is 225 C. The ratio of the reactants: CEg: 02 2: 2.05: 1: 1. The degree of conversion of hydrogen chloride is 98%, chlorine is 100%, ethylene is 97%. The output of dichloroethane in terms of ethylene 95,1%. Example 9. The process is carried out as in Example 1, but the input for chlorine is located at a height equal to 50% of the total height of the reactor. The reaction temperature is 195 ° C, the pressure is 0.6 MPa. The ratio of KCf: CiE; Cf:: 0g. 2: 2.05: 1: 0.86. The degree of conversion of porous hydrogen is 96%, chlorine is 100%, ethylene is 96%. Example 10 (comparative). The process is carried out in a reactor similar to that described in Example 1, with the difference that the inlets for the mixture of ethylene with hydrogen chloride and air and the inlet for chlorine are brought together so that the distance from them is no more than 4% of the length of the reactor. Thus, ethylene is not mixed with oxygen and chlorine consistently, as in examples 1-8, but almost simultaneously. Otherwise, the conditions of the experiment coincide with the conditions of example 1. The degree of conversion of hydrogen chloride is 88%, chlorine is 100%, ethylene is 93.5%. The output of dichloroethane in terms of ethylene 90%. A comparison of the results given in examples 1 and 10 shows that the sequential interaction of ethylene with chlorine with hydrogen and oxygen and then with chlorine contributes to an increase in the degree of conversion of the reactants and the yield of dichloroethane. The proposed method for producing 1,2-dichloroethane allows the process technology to be significantly simplified by replacing two stages with one, the conversion levels of the reagents and the yields of 1,2-dichloroethane being high. The process can be carried out in continuous mode without the use of sophisticated equipment and a shortage of materials .:
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING 1,2-DICHLOROETHANE by reacting ethylene with chlorine in the presence of suspended copper chloride or a mixture of copper and iron chlorides at a temperature of 185292 ° C and a pressure of 0.097-0.6 MPa in a vertical reactor in the presence of nitrogen-oxygen mixtures and with the removal of heat generated in the entire reaction space by indirect cooling using a liquid or gaseous coolant, characterized in that, in order to simplify its technology, the process is conducted when chlorine is supplied at a point located at ote equal to 50-69% of the total height of the reactor, and ethylene, hydrogen chloride and a mixture of nitrogen and oxygen are fed to the lower part of the reaction zone at a molar ratio of hydrogen chloride, ethylene, oxygen and chlorine 2: (1.23g2.07) :( 0 , 8-1) :( 0.18-1).
    SU. 1147247
    147247 1
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    引用文献:
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    US2716140A|1948-01-15|1955-08-23|Purdue Research Foundation|Fluorine activated chlorination|
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    US3488398A|1964-04-23|1970-01-06|Goodrich Co B F|Method of preparing 1,2-dichloroethane|
    FR1483132A|1965-07-07|1967-06-02|Pittsburgh Plate Glass Co|Aliphatic hydrocarbon oxychlorination process|
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    US3992463A|1967-05-19|1976-11-16|Produits Chimiques Pechiney-Saint Gobain|Oxychlorination of ethylene with a fixed bed catalyst|
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    US3892816A|1972-12-19|1975-07-01|Shell Oil Co|Process for oxychlorination of ethylene|
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    DE2733502C3|1977-07-25|1980-09-25|Wacker-Chemie Gmbh, 8000 Muenchen|Process for the production of 1,2-dichloroethane from ethylene-containing residual gases which originate from an oxychlorination|
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    法律状态:
    优先权:
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