• 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:
    Gaseous 1,2-dichloroethane which has been produced in a variety of ways is heated indirectly by the hot, vinyl chloride-containing gases which are led away from the radiation zone of the pyrolysis furnace. This allows the heat of the pyrolysis gases to be utilised in a favourable manner, pyrolysis rates to be increased, and operation times of the pyrolysis furnace to be prolonged. <IMAGE>
    公开号:SU1665874A3
    申请号:SU4355075
    申请日:1988-01-27
    公开日:1991-07-23
    发明作者:Линк Герхард；Фрелих Вальтер；Крумбек Райнхард；Прантль Георг；Шаффельхофер Иво
    申请人:Хехст Аг (Фирма)；Уде Гмбх (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for producing vinyl chloride by thermally cleaving 1,2-dichloroethane, which finds use as a monomer in the preparation of polymeric materials.
    The aim of the invention is to increase the degree of cleavage of 1,2-dichloroethane and reduce energy consumption,
    Figures 1-4 are a schematic representation of an apparatus for carrying out the method.
    EXAMPLE 1 From the collection for pumping (pumping) 1 (Fig. 1), 826 kg of a liquid product with a content of 1,2-dichloroethane of 99.3 wt.% With a temperature of 130 ° C and with the help of pump 2 at 125 ° C is pumped into the convection zone 3 of the reaction furnace. At 260 ° C, the product containing 1,2-dichloroethane is completely evaporated,
    gaseous gas is removed from the convection zone through conduit 4, outside the furnace in heat exchanger 5, it is heated to 350 ° C and introduced through conduit b into the radiation zone of the reaction furnace. The radiation zone 7 is heated due to four rows of burners arranged one above the other, to which 0.0876 nm of fuel (methane) per 1 kg of vinyl chloride produced is fed through pipe 8. In the radiation zone 7, most of the 1,2-dichloroethane is thermally split to vinyl chloride and hydrogen chloride. A hot, with a temperature of 518 ° C, a gas mixture containing vinyl chloride, which leaves the cleavage zones 7, is fed through conduit 9 to heat exchanger 5 and leaves it through conduit 10c with a temperature of 433 ° C. Pipeline 10 gas,
    Os 0
    00 XI
    four
     W
    containing vinyl chloride, enters the next heat exchanger 11, from which it exits at a temperature of 220 ° C through pipe 12. Then, as usual, it is cooled and distilled. The pressure with which the hot gas containing vimnilchloride leaves pipeline 9 from radiation zone 7 is 1.8 MPa. It enters the head of the column in which hydrogen chloride is distilled. In the heat exchanger 11, the feedwater of the boiler with a temperature of 100 ° C is supplied through the pipeline 13, and 90 kg / h of water vapor with a pressure of 0.9 MPa and a temperature of 175 ° C is obtained from it, which corresponds to the amount of heat of 679.5 kJ / kg Nilchloride or 0,0191 nm3 of fuel (methane) per 1 kg of vinyl chloride obtained. The effective fuel consumption (methane) is thus reduced to 0.0685 Nm3 of methane per kg of vinyl chloride produced. Water vapor leaves the heat exchanger 11 through line 14. The vinyl chloride chloride content is obtained at 313 kg / h, the splitting degree is 60%, the service life of the reaction furnace is 6 months. Comparative experience is similar to example 1. From the collection for pumping pump 1 using pump 2 (FIG. 2) s convection zone 3 of the reaction furnace serves 904 kg / h of a product with a content of 1,2-dichloroethane 99.3 wt,% with a temperature of 125 ° C, there the dichloro ethane is evaporated and gaseous is fed into the oven further through conduit 15 to zone 7 of radiation . From zone 7, the hot gas containing vinyl chloride with a temperature of 530 ° C is introduced through conduit 16 into the heat exchanger 11 and exits it at a temperature of 220 ° С via conduit 12. Feed water from the boiler with a temperature of 100 ° C to the heat exchanger 11 it is discharged 142 kg / h in a single steam with a pressure of 0.9 MPa and a temperature of 175 ° C through line 14. This corresponds to a heat of 1100 kJ / kg of vinyl chloride, respectively, to the amount of fuel 0.03 nm3 of methane per 1 kg of vinyl chloride obtained. Four rows of burners in the reaction furnace are supplied through a pipeline of 8 0.109 nm3 of methane per kg of vinyl chloride produced. The effective fuel consumption is 0.079 nm of methane per 1 kg of vinyl chloride obtained, which is 15.3% more than in Example 1. 313 kg / h of vinyl chloride is obtained, the degree of decomposition is 55%, the service life of the reaction furnace is 4 months. This comparative experiment was carried out in a manner similar to the known method.
    PRI mme R 2. From the collection for delivery by pump 1 (FIG. 3), 798.5 kg of 1,2-dichloroethane are discharged hourly and, by pump 2,
    125 ° C is pumped into sub-region 3 of the conventional zone of the reaction furnace. In subregion 3, 1,2-dichloroethane is heated to 240 ° C and liquid is supplied via conduit 4 to the evaporator 5, from which it enters the descending conduits 6 to apparatus 7 and from it via the ascending conduits 8 in a circular process again enters the evaporator 5. A gaseous product with a content of 1,2-dichloroethane and 95.8 wt.% Leaves the evaporator 5 with a temperature of 260 ° C and is fed through conduit 9 to the heat exchanger 10, which it leaves with a temperature of 367 ° C via conduit 11 and is introduced into zone
    5 12 radiation from the reaction furnace. Through the branch 13, which contains a control valve, adjustable by the height of the liquid in the evaporator 5, gaseous 1,2-dichloroethane from the evaporator 5 can
    0 are directly introduced into the radiation zone 12 of the reaction furnace. The amount of gaseous 1,2-dichloroethane, compared with the amount that is introduced through the heat exchanger 10, is insignificant and only serves to equalize the energy during process fluctuations. From the radiation zone 12, a hot gas containing vinyl chloride with a temperature of 523 ° C is fed through conduit 13 to heat exchanger 10 and leaves it with a temperature of 422 ° C.
    0 through conduit 14, which goes to apparatus 7, where the liquid 1,2-dichloroethane, which circulates from the evaporator 5, is indirectly heated by the hot gas containing vinyl chloride until boiling. Soder's
    The gas sticking to vinyl chloride through conduit 15 leaves apparatus 7 with a temperature of 265 ° C, then is cooled and processed as usual by distillation, and in the head of a distillation column in which hydrogen chloride is distilled off, the vinyl chloride containing mountains What gases leave the radiation zone 12 of the reaction furnace through the pipeline 13 with pressure
    5 1.9 MPa.
    Pipeline 16 from apparatus 7 removes hourly 28 kg of 1,2-dichloroethane, which contains particles of solid matter, elsewhere in the process it takes up solids and is used again. Through pipe 17 to the four rows of burners of the reaction furnace, a total of 0.075 nm of fuel (methane) is supplied per kg of vinyl chloride produced. In the upper part 18 of the convection zone of the reaction furnace (in a water heater) 475 dm3 / h of boiler feedwater (pressure 2.5 MPa), which is fed through conduit 19 with a temperature of 100 ° G, is heated to 150 ° C, TC through line 19 and used elsewhere in the process. Thus, 317.7 kJ / kg of vinyl chloride energy is recovered, respectively, according to the amount of fuel (methane) 0.009 Nm3 per 1 kg of vinyl chloride produced. The effective fuel consumption is thus reduced to 0.066 Nm3 per kg of vinyl chloride produced.
    330 kg / h of vinyl chloride is obtained, the degree of conversion upon splitting is 68%, the service life of the reaction furnace is 12 months.
    Comparative experience is analogous to example 2. 834 kg of 1,2-dichloroethane are discharged hourly from the collection for pump 1 (Fig. 4) and, using a pump 2 with a temperature of 125 ° C, through a heat exchanger 3 and pipe 4 are transported to an evaporator 5. The heat exchanger 3 is heated with 25 kg / h of high-pressure steam (2.1 MPa) through line 6. Through measuring the height of the level of liquid 1,2-dichloroethane in the evaporator 5, the flow of high-pressure steam into the heat exchanger 3 is regulated as a controlled quantity. 2-Dichloroethane leaves the heat exchanger 3 with a temperature of 161 ° C.
    The hot, containing vinyl chloride gas leaves the radiation zone 7 of the reaction furnace through pipeline 8 with a temperature of 533 ° C, passes apparatus 9 and leaves it with a temperature of 245 ° C through pipeline 10. Then the gas containing vinyl chloride is cooled in the usual way hydrogen chloride is distilled off. The pressure at the head of this column is set so that the hot, vinyl chloride-containing gas leaves the radiation zone 7 of the reaction furnace at a pressure of 1.9 MPa. In pipelines 11 and 12, liquid 1,2-dichloroethane, as described in Example 2, is introduced into the circulation. A gaseous product containing 95.8% by weight of 1,2-dichloroethane through conduit 13 from the evaporator 5 is fed to the emission zone 7 of the reaction furnace.
    From apparatus 9, 30 kg / h of liquid 1,2-dichloroethane is discharged through pipe 14, freed from solids and used again at a different place in the process. Four rows of burners of the reaction furnace arranged one above the other are supplied via pipeline 15 with a total of 0.1074 nm3 of fuel (methane) per kg of vinyl chloride produced. In the upper part 16 of the convection zone of the reaction furnace, in a water heater, 330 dm3 / h of boiler feedwater (pressure 2.5 MPa), which is supplied through pipeline 17 with a temperature of 80 ° C, is heated to 150 ° C and partially through pipeline 18 are introduced into the boiler 19, partly according to
    conduit 20 is again used elsewhere in the vinyl chloride production process. The liquid from the boiler 19 is supplied via conduit 21 to the lower part 22 of the convection zone of the reaction furnace, where it is heated and supplied via conduit 23 to the boiler 19. Part of the steam produced in boiler 19 is used to heat the heat exchanger 3. Most of this steam, 0 167 kg / h, is led through conduit 24 and is used elsewhere in the vinyl chloride production process. Thus, 1236.2 kJ / kg of vinyl chloride energy is recovered. The pipeline supplies 136 dm / h 5 of boiler feedwater with a temperature of 150 ° C for further use, whereby 121 kJ / kg of vinyl chloride energy is regenerated. The total regenerated amount of energy is 0 1236.2 + 121 1357.2 kJ / kg vinyl chloride, which corresponds to the amount of fuel (methane) 0.038 Nm3 / kg vinyl chloride. The effective consumption of combustible gas is thus reduced to 0.0694 Nm3 / kg, which is 5 to 5% more than that required in Example 2. The service life of the reaction furnace is 9 months, 330 kg / h of vinyl chloride are obtained, the degree of conversion upon splitting is 1, 2-dichloroethane is 65%. 0 In all examples and comparative experiments, technical 1,2-dichloroethane is used, which contains 99.7% by weight of pure 1,2-dichloroethane, the rest is common by-products, like 5 trichloroethane, benzene, 1,1-dichloroethane , trichloroethylene, tetrachlorethylene, chloroform, carbon tetrachloride, chloroprene.
    PRI me R 3. From the pump collection 1 (Fig. 3), 785 kg of 1,2-0 dichloroethane is pumped out every hour and pumped through pump 2 with a temperature of 100 ° C through section 3 of the convection zone of the reaction furnace. In this section 3, 1,2-dichloroethane is heated to 265 ° C and is fed through pipe 4 5 in liquid form to the evaporator 5. From the evaporator, the product goes through the descending pipe 6 to the device 7, from it through the ascending pipelines 8 - into the circulation circuit and again in the evaporator 5.
    The gaseous product, containing 97.5% by weight of 1,2-dichloroethane, leaves the evaporator 5 with a temperature of 275 ° C and is fed through pipe 9 to the heat exchanger 5 10, from which it is sent to pipe 11c with a temperature of 330 ° C and enters the zone 12 radiation reaction furnace. With the aid of an auxiliary tap 13, which has a control valve, with which the level
    liquids in the evaporator 5; gaseous 1,2-dichloroethane from the evaporator 5 can be directly supplied to the radiation zone 12 of the reaction furnace. The amount of this gaseous 1,2-dichloroethane compared to the amount that is directed through the heat exchanger 5 is very small and serves solely to compensate for the energy during process oscillations.
    From the radiation zone 12, hot gas containing vinyl chloride with a temperature of 480 ° C enters the heat exchanger 10 through conduit 13, from where it exits at 415 ° C through conduit 14, which enters apparatus 7, where liquid 1,2-dmchloroethane circulates from the evaporator 5, indirectly heated by gas containing hot aryl chloride, until boiling. The vinyl chloride-containing gas exits the apparatus 7 at a temperature of 290 ° C through pipe 15, after which it is cooled in the usual way and undergoes distillation, and the pressure in the head of the distillation column, in which hydrogen chloride is distilled, is set in such a way that hot gases leave radiation zone 12 of the reaction furnace through the pipeline 13 with a pressure of 2.1 MPa.
    Through the conduit 16, 25 kg of 1,2-dichloroethane, which contains particles of solids, will be removed from the apparatus 7 every hour, it will be cleaned of these solid particles in another part of the process, and then reintroduced. A total of 0.075 Nm3 of combustible substances (methane) for every 1 kg of vinyl chloride produced are fed through pipe 17 to the reaction furnace for four rows of burners,
    In the upper part 18 of the convection zone of the reaction furnace, there is an economizer to which 400 dm3 / h of feedwater for the boilers is fed through line 19 with a temperature of 100 ° C, where the water is heated to 155 ° C and discharged through the pipeline for use in other parts of the process. Due to this, a secondary energy of 296 kJ / kg of vinyl chloride is used, which in terms of the amount of combustible substances (methane) is 0.008 Nm3 per kilogram of vinyl chloride produced. Due to this, the effective consumption of combustible substances is reduced by 0.067 Nm3 per 1 kg of vinyl chloride produced. 311.9 kg / h of methyl chloride are obtained, the yield for splitting is 65%, the service life of the reaction furnace is about 15 months.
    EXAMPLE 4 Liquid 1,2-dichloroethane is heated at station 3 of the reaction furnace to 192 ° C. Gaseous product containing 98.7 May. % 1,2-dichloroethane, leaves the evaporator 5 with a temperature of 202 ° C and is fed through a pipeline to the heat exchanger 10, from which it leaves with a temperature of 290 ° C through pipe 11.
    From the radiation zone 12, the gas containing hot vinyl chloride with a temperature of 500 ° C is fed through pipe 13 to the heat exchanger, Yun leaves it with a temperature of 440 ° C. Vinyl chloride-containing gas through the pipe 15 passes through the apparatus 7 and out of it with a temperature of 217 ° C,
    5 At the head of the distillation column, where hydrogen chloride is distilled off, the pressure is set in such a way that the hot vinyl chloride-containing gases leave the radiation zone 12
    0 reaction furnace through line 13 with a pressure of 0.63 MPZ.
    A total of 0.064nm combustible substances (methane) per 1 are fed through line 17 to the reaction furnace for four rows of burners.
    5 kg of vinyl chloride produced. In the upper part of the convection zone of the reaction furnace, the water for feeding the boilers is not heated (the flue gas temperature for this purpose is insufficient) /. Get
    0 316.8 kg / h of vinyl chloride, the yield with splitting is 66%, the service life of the reaction furnace is about 13 months.
    The proposed method allows to obtain a higher degree of cleavage.
    5 1,2-dichloroethane, as well as increase the service life of the pyrolysis furnace. The use of heat contained in hot vinyl chloride-containing gases leads to a significant reduction in energy consumption.
    权利要求:
    Claims (3)
    [1]
    1. A method for producing vinyl chloride, including evaporation of liquid 1,2-dichloroethane at 202-275 ° C, supplying evaporated 1,2-dichloroethane for thermal removal of hydrogen chloride to a pyrolysis oven having a convection and radiation zone from which hot vinyl chloride-containing gas is released, characterized in that, in order to increase the degree of 1,2-dichloroethane and reduce energy consumption, evaporated 1,2-dichloroethane, containing at least 95 wt.% 1,2-dichloroethane, is additionally heated to 290 indirectly -367 ° C hot vinyl with Lorid-containing gas with temperature of 480 523 ° С and pressure of 0.63-2.1 MPa in the heat exchanger.
    [2]
    2, the method according to claim 1, characterized in that a evaporated containing at least 95% by weight 1,2-dichloroethane is obtained
    from liquid 1,2-dichloroethane in the convective zone of the pyrolysis furnace due to indirect contact with flue gases.
    [3]
    3. The method according to claim 1, characterized in that the hot gas containing vinyl chloride after the stage of indirect heating of the evaporated 1,2-dichloroethane containing at least 95% by weight of 1,2-dichloroethane is used to heat the liquid 1,2- in the evaporator dichloroethane to produce vaporized gas containing 95 wt.% 1,2-dichloroethane.
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    同族专利:
    公开号 | 公开日
    PL270315A1|1988-11-24|
    HUT45727A|1988-08-29|
    CA1326687C|1994-02-01|
    DD267485A5|1989-05-03|
    JP2593905B2|1997-03-26|
    BG48808A3|1991-05-15|
    MX167604B|1993-03-31|
    EP0276775B1|1993-03-03|
    EP0276775A3|1989-04-19|
    PL157275B1|1992-05-29|
    ES2054710T3|1994-08-16|
    JPS63192729A|1988-08-10|
    IN170519B|1992-04-04|
    EP0276775A2|1988-08-03|
    DE3702438A1|1988-08-11|
    BR8800317A|1988-09-06|
    KR880008966A|1988-09-13|
    DE3878701D1|1993-04-08|
    HU201722B|1990-12-28|
    KR950008273B1|1995-07-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE2907066A1|1979-02-23|1980-09-04|Hoechst Ag|Vinyl chloride mfr. - by cleavage of 1,2-di:chloroethane, with recovery of heat from the hot cleavage gases by indirect heat exchange|
    EP0014920B1|1979-02-23|1982-12-08|Hoechst Aktiengesellschaft|Process for the recovery of pyrolysis energy in the preparation of vinyl chloride by incomplete thermal splitting of 1,2-dichloroethane|
    DE2913030A1|1979-03-31|1980-10-16|Hoechst Ag|Vinyl chloride mfr. - by cleavage of 1,2-di:chloroethane, with recovery of heat from the hot cleavage gases by indirect heat exchange|
    DE2925720A1|1979-06-26|1981-01-22|Hoechst Ag|METHOD FOR PRODUCING VINYL CHLORIDE BY THERMAL CLEAVING 1,2-DICHLORETHANE|
    JPS6013006B2|1981-02-26|1985-04-04|Hitachi Shipbuilding Eng Co|
    DE3440685A1|1984-11-07|1986-05-07|Wacker-Chemie GmbH, 8000 München|METHOD FOR PRODUCING VINYL CHLORIDE BY THERMAL CLEAVING OF PURIFIED 1,2-DICHLORETHANE|
    DE3441080A1|1984-11-09|1986-05-15|Wacker-Chemie GmbH, 8000 München|METHOD FOR PROCESSING THE PYROLYSIS PRODUCT FROM THE 1.2 DICHLORETHANE CLEAVAGE WITH HEAT RECOVERY|
    GB2179938B|1986-08-29|1989-08-16|Snam Progetti|Production of monomeric vinyl chloride|
    JPH0692328B2|1986-11-29|1994-11-16|東ソー株式会社|Process for producing vinyl chloride monomer by thermal decomposition of 1,2-dichloroethane|US5707592A|1991-07-18|1998-01-13|Someus; Edward|Method and apparatus for treatment of waste materials including nuclear contaminated materials|
    DE19859262A1|1998-12-22|2000-07-06|Krupp Uhde Gmbh|Process for the evaporation of 1,2-dichloroethane |
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    法律状态:
    2005-01-10| REG| Reference to a code of a succession state|Ref country code: RU Ref legal event code: MM4A Effective date: 20030128 |
    优先权:
    申请号 | 申请日 | 专利标题
    DE19873702438|DE3702438A1|1987-01-28|1987-01-28|METHOD FOR PRODUCING VINYL CHLORIDE BY THERMAL CLEAVING 1,2-DICHLORETHANE|
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