CN103936548A - Method for producing 1,1, 2-trichloroethane by chlorination of 1, 2-dichloroethane - Google Patents
Method for producing 1,1, 2-trichloroethane by chlorination of 1, 2-dichloroethane Download PDFInfo
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 title abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 39
- 238000000066 reactive distillation Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000007791 liquid phase Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 3
- 238000007086 side reaction Methods 0.000 claims 15
- 230000035484 reaction time Effects 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 15
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000010354 integration Effects 0.000 abstract 1
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 22
- 239000012808 vapor phase Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical compound ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- GSNJPCNTXZRBRA-UHFFFAOYSA-N chloroethane;1,1,2-trichloroethane Chemical compound CCCl.ClCC(Cl)Cl GSNJPCNTXZRBRA-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种1,2-二氯乙烷氯化生产1,1,2-三氯乙烷的方法，该方法采用主要由精馏塔和侧反应器耦合组成的反应精馏集成装置，以1,2-二氯乙烷和氯气为原料，将1,2-二氯乙烷直接通入侧反应器，与氯气在光催化条件下发生氯化反应。侧反应器中反应后的物料返回精馏塔，再将精馏塔塔板液相物料采出进入下一级侧反应器继续氯化反应，从精馏塔釜得到所需要的产物。本发明方法工艺流程简单、操作灵活，生产成本低，经济效益高；既能保持反应精馏集成技术的优势，同时又可以使反应器操作条件与精馏塔操作条件保持独立，反应器体积和反应量可以自由调整，实现了反应能力与分离能力的最佳匹配，有利于实现大规模化工业生产。
The invention discloses a method for producing 1,1,2-trichloroethane by chlorination of 1,2-dichloroethane. The method adopts a reactive distillation integrated device mainly composed of a rectification tower and a side reactor coupled , with 1,2-dichloroethane and chlorine gas as raw materials, 1,2-dichloroethane is directly passed into the side reactor, and chlorination reaction occurs with chlorine gas under photocatalytic conditions. The reacted material in the side reactor is returned to the rectification tower, and then the liquid phase material on the rectification tower tray is taken out and sent to the next side reactor to continue the chlorination reaction, and the desired product is obtained from the rectification tower kettle. The method of the invention has simple technological process, flexible operation, low production cost and high economic benefit; it can not only maintain the advantages of reactive distillation integration technology, but also make the operating conditions of the reactor and the operating conditions of the rectifying tower independent, and the reactor volume and The reaction volume can be adjusted freely, which realizes the best matching of reaction capacity and separation capacity, and is conducive to the realization of large-scale industrial production.
Description
技术领域technical field
本发明属于化工领域，涉及一种生产1,1,2-三氯乙烷的工艺，具体是一种以1,2-二氯乙烷为原料生产1,1,2-三氯乙烷的工艺。The invention belongs to the field of chemical industry and relates to a process for producing 1,1,2-trichloroethane, in particular to a process for producing 1,1,2-trichloroethane with 1,2-dichloroethane as raw material craft.
背景技术Background technique
1,1,2-三氯乙烷是一种重要的有机中间体，可用于生产偏二氯乙烯单体。工业化制备1,1,2-三氯乙烷的方法主要有氯乙烯氯化法和1,2-二氯乙烷氯化法。氯乙烯氯化法工艺成熟，并且反应条件温和；但是随着国际油价持续走高，氯乙烯氯化法生产成本较高，1,2-二氯乙烷氯化法凭借其原料成本优势倍受关注。1,1,2-Trichloroethane is an important organic intermediate that can be used in the production of vinylidene chloride monomer. The industrial production methods of 1,1,2-trichloroethane mainly include vinyl chloride chlorination method and 1,2-dichloroethane chlorination method. The vinyl chloride chlorination process is mature and the reaction conditions are mild; however, as the international oil price continues to rise, the production cost of the vinyl chloride chlorination process is relatively high, and the 1,2-dichloroethane chlorination process has attracted much attention due to its raw material cost advantage .
1,2-二氯乙烷氯化反应是一个多步连串反应过程，随着氯化深度的不同，反应可生成1,1,2-三氯乙烷、1,1,1,2-四氯乙烷(简称偏四氯乙烷)、1,1,2,2-四氯乙烷(简称正四氯乙烷)、五氯乙烷、六氯乙烷等多氯代化合物，除了六氯乙烷是所有的氢均被氯取代的最终氯化产物，其他的多氯代产物均是氯化连串反应的中间产物。The chlorination reaction of 1,2-dichloroethane is a multi-step series reaction process. With the different chlorination depth, the reaction can generate 1,1,2-trichloroethane, 1,1,1,2- Tetrachloroethane (referred to as partial tetrachloroethane), 1,1,2,2-tetrachloroethane (referred to as n-tetrachloroethane), pentachloroethane, hexachloroethane and other polychlorinated compounds, except six Ethyl chloride is the final chlorination product in which all hydrogens are replaced by chlorine, and other polychlorinated products are intermediate products of the chlorination chain reaction.
专利US2174737介绍了1,2-二氯乙烷与氯气在光催化条件下生成1,1,2-三氯乙烷，专利US2140549中报道将气相1,2-二氯乙烷和氯气通过熔融的金属氯化物(如铁、纳、锌、铝等)生产1,1,2-三氯乙烷，专利US3919337介绍了一种不使用光照和任何催化剂，在较高的温度和压力下(120～150℃，3～5atm)由1,2-二氯乙烷直接氯化生成1,1,2-三氯乙烷的方法，专利CN101921167介绍了一种多釜串联生产1,1,2-三氯乙烷的方法。以上这些方法的缺点是反应条件复杂，反应的选择性较差、多氯代副产物多，造成后续分离的困难和高成本。Patent US2174737 introduced 1,2-dichloroethane and chlorine to generate 1,1,2-trichloroethane under photocatalytic conditions, and reported in patent US2140549 that gas phase 1,2-dichloroethane and chlorine were passed through a molten Metal chlorides (such as iron, sodium, zinc, aluminum, etc.) produce 1,1,2-trichloroethane, and the patent US3919337 introduces a method that does not use light and any catalyst, under higher temperature and pressure (120～ 150°C, 3～5atm) to generate 1,1,2-trichloroethane by direct chlorination of 1,2-dichloroethane, the patent CN101921167 introduces a multi-pot serial production of 1,1,2-trichloroethane Chloroethane method. The disadvantages of the above methods are that the reaction conditions are complex, the selectivity of the reaction is poor, and there are many polychlorinated by-products, resulting in difficulties and high costs for subsequent separation.
为克服1,2-二氯乙烷氯化的反应产物复杂、很难高选择性地得到目标产物的缺点，采用反应精馏集成技术不仅可以缩减反应工艺流程，而且可将反应物与产物原位分离，有利于提高转化率和选择性。吴化冰等人(吴化冰，袁向前，宋宏宇.1,2-二氯乙烷反应精馏制备1,1,2-三氯乙烷.化学反应工程与工艺.2008,24(4):381-384)采用反应精馏技术，以二1,2-氯乙烷和氯气为原料，在反应精馏塔中制备1,1,2-三氯乙烷，在反应压力0.2MPa、反应温度110℃的条件下，1,1,2-三氯乙烷的选择性最大可达到96％，但是反应温度和压力较高。然而，将反应与精馏在塔内耦合的传统方式，反应能力取决于精馏塔塔板或填料上的持液量，因此装置生产能力受到了很大的限制，只有采取加压、提高温度的方式强化反应来提升装置能力，不适合用于大规模的工业化生产。In order to overcome the shortcomings of the complex reaction products of 1,2-dichloroethane chlorination and the difficulty of obtaining the target product with high selectivity, the integrated technology of reactive distillation can not only reduce the reaction process, but also combine the reactants and products Bit separation is beneficial to improve conversion rate and selectivity. Wu Huabing et al. (Wu Huabing, Yuan Xiangqian, Song Hongyu. Preparation of 1,1,2-trichloroethane by reactive distillation of 1,2-dichloroethane. Chemical Reaction Engineering and Technology. 2008,24(4):381-384) Using reactive distillation technology, di-1,2-chloroethane and chlorine are used as raw materials to prepare 1,1,2-trichloroethane in a reactive distillation tower under the conditions of reaction pressure 0.2MPa and reaction temperature 110°C The maximum selectivity of 1,1,2-trichloroethane can reach 96%, but the reaction temperature and pressure are relatively high. However, in the traditional way of coupling reaction and rectification in the column, the reaction capacity depends on the liquid holdup on the tray or packing of the rectification column, so the production capacity of the device is greatly limited, and the only way to increase the pressure and increase the temperature The way to strengthen the reaction to improve the capacity of the device is not suitable for large-scale industrial production.
发明内容Contents of the invention
本发明的目的就是针对现有1,2-二氯乙烷氯化生产1,1,2-三氯乙烷技术的不足，提供一种在由精馏塔和侧反应器耦合组成的反应精馏集成装置内，由1,2-二氯乙烷和氯气反应生产1,1,2-三氯乙烷的方法。The purpose of the present invention is exactly to aim at the deficiencies of existing 1,2-dichloroethane chlorination production 1,1,2-trichloroethane technology, provide a kind of reaction refiner that is formed by the coupling of rectification column and side reactor A method for producing 1,1,2-trichloroethane from 1,2-dichloroethane and chlorine in a distillation integrated device.
本发明的目的可以通过以下措施来达到：The object of the present invention can be achieved through the following measures:
一种以1,2-二氯乙烷为原料生产1,1,2-三氯乙烷的方法，该方法采用主要由精馏塔和侧反应器耦合组成的反应精馏集成装置，以1,2-二氯乙烷和氯气为原料，将1,2-二氯乙烷直接通入与精馏塔耦合的第一台侧反应器，氯气连续通入与精馏塔连接的各台侧反应器，在第一台侧反应器中，在光催化条件下发生氯化反应，侧反应器中反应得到的液相物料进入精馏塔，从精馏塔釜得到所需要的产物；或者当侧反应器为两台以上时，将精馏塔的液相物料采出后进入下一级侧反应器继续氯化反应，再返回至采出的下一块塔板，从精馏塔釜得到所需要的产物；其中，氯气的总通入量与1,2-二氯乙烷的进料量摩尔比为1:1。A method for producing 1,1,2-trichloroethane using 1,2-dichloroethane as a raw material, the method adopts a reactive distillation integrated device mainly composed of a rectification column and a side reactor coupled, with 1 , 2-dichloroethane and chlorine gas are used as raw materials, 1,2-dichloroethane is directly fed into the first side reactor coupled with the rectification tower, and chlorine gas is continuously fed into each side reactor connected to the rectification tower Reactor, in the first side reactor, a chlorination reaction occurs under photocatalytic conditions, the liquid phase material obtained from the reaction in the side reactor enters the rectification tower, and the required product is obtained from the rectification tower tank; or when When there are more than two side reactors, the liquid phase material of the rectification tower is extracted and then enters the next side reactor to continue the chlorination reaction, and then returns to the next extracted tray to obtain all the The desired product; wherein the molar ratio of the total feed amount of chlorine to the feed amount of 1,2-dichloroethane is 1:1.
所述的精馏塔操作压力控制在常压；各台侧反应器中的反应温度在20～80℃，反应压力控制在常压，反应停留时间控制在0.1～5h。精馏塔的塔顶温度为80～90℃，精馏塔塔釜温度为110～115℃。The operating pressure of the rectification tower is controlled at normal pressure; the reaction temperature in each side reactor is 20-80°C, the reaction pressure is controlled at normal pressure, and the reaction residence time is controlled at 0.1-5h. The temperature at the top of the rectifying tower is 80-90°C, and the temperature at the bottom of the rectifying tower is 110-115°C.
优选各台侧反应器中的反应温度在50～70℃。Preferably, the reaction temperature in each side reactor is 50-70°C.
优选各台侧反应器中的反应停留时间控制在0.5～2h。Preferably, the reaction residence time in each side reactor is controlled at 0.5-2 h.
精馏塔由上至下分为反应精馏区和提馏区，所述的侧反应器通过进、出物料管道与反应精馏区连接耦合；提馏区塔板数在5～50块，优选10～20块；反应精馏区塔板数在1～20块，优选5～15块。相邻侧反应器之间间隔的反应精馏区塔板数在1～5块。氯气按一定比例连续通入与精馏塔连接的各台侧反应器；塔顶轻组分全采出后进入第一台侧反应器，与氯气发生氯化反应后，再回到反应精馏区精馏塔第一块塔板，反应精馏区塔板液相物料全采出分别进入与之相连的各台侧反应器进行氯化反应，反应后再回到反应精馏区采出塔板的下一块塔板；氯化反应产物在精馏塔的提馏区进行提馏，所得反应产物由塔底采出。The rectification tower is divided into a reactive distillation zone and a stripping zone from top to bottom, and the side reactor is connected and coupled with the reactive distillation zone through inlet and outlet material pipelines; the number of trays in the stripping zone is 5 to 50, Preferably 10-20; the number of trays in the reactive distillation zone is 1-20, preferably 5-15. The number of trays in the reactive distillation zone spaced between adjacent side reactors is 1-5. Chlorine gas is continuously fed into the side reactors connected to the rectification tower in a certain proportion; after all the light components at the top of the tower are extracted, it enters the first side reactor, and after chlorination reaction with chlorine gas, it returns to the reactive distillation The first tray of the rectification tower in the rectification zone, the liquid phase materials of the trays in the reactive distillation zone are all extracted and enter the side reactors connected to it for chlorination reaction, and then return to the extraction tower in the reactive distillation zone The next tray of the plate; the chlorination reaction product is stripped in the stripping zone of the rectification tower, and the resulting reaction product is extracted from the bottom of the tower.
本发明侧反应器的进出物料均与精馏塔相连，侧反应器台数1～5台，优选2～4台。当侧反应器台数为多台时，1,2-二氯乙烷直接通入第一台侧反应器，氯气按一定比例分配到各台侧反应器，通入各侧反应器的氯气占总通入量的比例为1～99％，优选20～80％。The incoming and outgoing materials of the side reactors of the present invention are all connected to the rectification tower, and the number of side reactors is 1-5, preferably 2-4. When there are multiple side reactors, 1,2-dichloroethane is directly passed into the first side reactor, and chlorine gas is distributed to each side reactor in a certain proportion, and the chlorine gas passed into each side reactor accounts for the total The ratio of the feeding amount is 1-99%, preferably 20-80%.
所述的侧反应器采用釜式反应器，反应在光催化条件下进行，光的波长范围为可见光。The side reactor adopts a tank reactor, and the reaction is carried out under photocatalytic conditions, and the wavelength range of light is visible light.
本发明反应精馏装置的塔底连续采出富含1,1,2-三氯乙烷的氯化产物。The chlorination product rich in 1,1,2-trichloroethane is continuously extracted from the tower bottom of the reactive distillation device of the present invention.
本发明具体是以1,2-二氯乙烷为原料生产1,1,2-三氯乙烷的方法，采用主要由精馏塔和侧反应器耦合组成的反应精馏集成装置，1,2-二氯乙烷直接通入与塔顶冷凝液相连的侧反应器，与氯气在光催化条件下发生氯化反应，侧反应器中反应后的物料返回精馏塔第一块塔板；然后再将精馏塔塔板液相物料全部采出进入下一级侧反应器继续氯化反应，氯化反应液再返回至采出塔板的下一块塔板，依此配置不同的侧反应器台数，从精馏塔釜得到1,1,2-三氯乙烷粗产品。Specifically, the present invention uses 1,2-dichloroethane as a raw material to produce 1,1,2-trichloroethane, and adopts a reactive distillation integrated device mainly composed of a rectification tower and a side reactor. 1, 2-Dichloroethane is directly passed into the side reactor connected to the condensate at the top of the tower, and chlorination reaction occurs with chlorine gas under photocatalytic conditions, and the reacted material in the side reactor is returned to the first tray of the rectification tower ; Then all the liquid phase materials on the rectification column tray are extracted and enter the next-stage side reactor to continue the chlorination reaction, and the chlorination reaction solution is returned to the next tray of the extraction tray, and different side reactors are configured according to this The number of reactors, the crude product of 1,1,2-trichloroethane is obtained from the still of the rectification column.
本发明的优点是：The advantages of the present invention are:
本发明将侧反应器置于精馏塔的外部，侧反应器中的物料来自于其上方的塔板，经反应后进入其下方的塔板，侧反应器与精馏塔之间既相互联系又相互独立。这种耦合方式既可以保持反应精馏集成技术的优势，同时又可以使反应器操作条件与精馏塔操作条件保持独立。本发明采用的侧反应器与精馏塔耦合的方式，由1,2-二氯乙烷氯化生产1,1,2-三氯乙烷，可以达到高转化率，而且使得塔底产品中1,1,2-三氯乙烷的摩尔分数高达0.98，四氯乙烷生成量的摩尔分数在0.02以下，工艺流程短，操作控制灵活，生产成本低，经济效益高，同时反应器体积和反应量可以自由调整，实现了反应能力与分离能力的最佳匹配，有利于实现大规模工业化生产。In the present invention, the side reactor is placed outside the rectification tower, and the material in the side reactor comes from the tray above it, and enters the tray below it after reaction, and the side reactor and the rectification tower are connected to each other and independent of each other. This coupling method can not only maintain the advantages of the integrated technology of reactive distillation, but also make the operating conditions of the reactor and the operating conditions of the rectification column independent. The side reactor that the present invention adopts is coupled with the mode of rectifying tower, produces 1,1,2-trichloroethane by chlorination of 1,2-dichloroethane, can reach high transformation rate, and makes the tower bottom product The molar fraction of 1,1,2-trichloroethane is as high as 0.98, and the molar fraction of tetrachloroethane is less than 0.02. The process flow is short, the operation control is flexible, the production cost is low, and the economic benefit is high. At the same time, the reactor volume and The reaction volume can be adjusted freely, which realizes the best match between the reaction capacity and the separation capacity, and is conducive to the realization of large-scale industrial production.
附图说明Description of drawings
图1是反应精馏耦合生产1,1,2-三氯乙烷的工艺流程示意图。Figure 1 is a schematic diagram of the process flow for the coupled production of 1,1,2-trichloroethane by reactive distillation.
图1中标号为：1-精馏塔反应精馏区，2-精馏塔提馏区，3-精馏塔塔顶汽相管线，4-精馏塔塔顶冷凝器，5-精馏塔塔顶回流管线，全冷凝的物料进入第1台侧反应器，6-第1侧台反应器的氯化氢气体出料管线，7-第1台侧反应器的1,2-二氯乙烷进料管线，8-第1台侧反应器，9-从第1台侧反应器返回精馏塔的液相管线，反应产物通过该管线返回精馏塔反应精馏区，10-第1台侧反应器的氯气进料管线，11-从精馏塔到第2台侧反应器的液相进料管线，12-第2侧台反应器的氯化氢气体出料管线，13-第2台侧反应器，14-从第2台侧反应器返回精馏塔的液相管线，15-第2台侧反应器的氯气进料管线，16-第n侧台反应器的氯化氢气体出料管线，17-从精馏塔到第n台侧反应器的液相进料管线，18-第n台侧反应器，19-从第n台侧反应器返回精馏塔的液相管线，20-第n台侧反应器的氯气进料管线，21-精馏塔塔釜再沸器汽相循环管线，22-精馏塔塔釜再沸器，23-精馏塔塔釜再沸器液相循环管线，24-精馏塔塔釜产品采出管线。The labels in Fig. 1 are: 1-reaction rectification zone of rectification tower, 2-rectification tower stripping zone, 3-rectification tower overhead vapor phase pipeline, 4-rectification tower overhead condenser, 5-rectification The reflux line at the top of the tower, the fully condensed material enters the first side reactor, 6- the hydrogen chloride gas discharge line of the first side reactor, 7- the 1,2-dichloroethane of the first side reactor Feed pipeline, 8-the first side reactor, 9-the liquid phase pipeline returning from the first side reactor to the rectification tower, and the reaction product returns to the rectification column through this pipeline, 10-the first Chlorine gas feed line of side reactor, 11-liquid phase feed line from rectification tower to the second side reactor, 12-hydrogen chloride gas discharge line of the second side reactor, 13-second side reactor Reactor, 14-returns the liquid phase pipeline of the rectifying tower from the 2nd side reactor, 15-the chlorine feed pipeline of the 2nd side reactor, the hydrogen chloride gas discharge pipeline of the 16th n side reactor, 17-from the rectification tower to the liquid phase feed line of the nth side reactor, 18-the nth side reactor, 19-from the nth side reactor to return the liquid phase pipeline of the rectification tower, 20-the nth side reactor Chlorine gas feed line for n sets of side reactors, 21-distillation tower kettle reboiler vapor phase circulation pipeline, 22-distillation tower tower kettle reboiler, 23 rectification tower tower kettle reboiler liquid phase circulation Pipeline, 24-rectification tower bottom product extraction pipeline.
具体实施方式Detailed ways
下面结合实施例进一步描述本发明，本发明的范围不限于这些实施例。Further describe the present invention below in conjunction with embodiment, the scope of the present invention is not limited to these embodiment.
实施例1：Example 1:
在直径0.8m，塔板数为15块塔板的精馏塔中(反应精馏区塔板数1块，提馏区塔板数14块)，与1台体积5m3的釜式反应器相连，其中塔顶汽相物料冷凝后全部进入第1台侧反应器，侧反应器出口物料返回精馏塔第1块塔板(塔板数从上向下数)，精馏塔与侧反应器之间的物料通过泵输送。In a rectification tower with a diameter of 0.8m and 15 trays (the number of trays in the reactive distillation area is 1, and the number of trays in the stripping area is 14), with a tank reactor with a volume of 5m3 The vapor phase materials at the top of the tower are all condensed into the first side reactor, and the outlet materials of the side reactor are returned to the first tray of the rectification tower (the number of trays is counted from top to bottom), and the rectification tower reacts with the side reactor. The material between the containers is transported by the pump.
侧反应器内装有蓝光光源。1,2-二氯乙烷向侧反应器的进料流率为4kmol/h，氯气向侧反应器的进料流率为4kmol/h。反应温度80℃，侧反应器压力为0.1MPa，由侧反应器返回精馏塔的液相流率为65kmol/h，各组分摩尔分数为：1,2-二氯乙烷0.908、1,1,2-三氯乙烷0.090、四氯乙烷0.002。精馏塔操作压力为0.1MPa，塔底采出量为4kmol/h。反应精馏装置稳定后，精馏塔塔顶温度85.2℃，塔釜温度113.1℃。塔底产品中1,1,2-三氯乙烷的摩尔分数为0.950，1,2-二氯乙烷与四氯乙烷的摩尔分数分别为0.03、0.02。The side reactor is equipped with a blue light source. The feed flow rate of 1,2-dichloroethane to the side reactor is 4 kmol/h, and the feed flow rate of chlorine gas to the side reactor is 4 kmol/h. The reaction temperature is 80°C, the side reactor pressure is 0.1 MPa, the liquid phase flow rate from the side reactor to the rectification tower is 65 kmol/h, and the mole fraction of each component is: 1,2-dichloroethane 0.908, 1, 1,2-trichloroethane 0.090, tetrachloroethane 0.002. The operating pressure of the rectification tower is 0.1 MPa, and the output at the bottom of the tower is 4 kmol/h. After the reactive distillation unit stabilized, the temperature at the top of the distillation column was 85.2°C, and the temperature at the bottom of the column was 113.1°C. The molar fraction of 1,1,2-trichloroethane in the bottom product was 0.950, and the molar fractions of 1,2-dichloroethane and tetrachloroethane were 0.03 and 0.02, respectively.
注：四氯乙烷有两种同分异构体，但是考虑到本工艺中四氯乙烷生成量非常少，而且产物中两种异构体生成量相当，故统称四氯乙烷，下同。Note: tetrachloroethane has two isomers, but considering that the amount of tetrachloroethane generated in this process is very small, and the amount of the two isomers in the product is equivalent, so it is collectively called tetrachloroethane, the following same.
实施例2：Example 2:
在直径0.8m，塔板数为15块塔板的精馏塔中(反应精馏区塔板数7块，提馏区塔板数8块)，与2台体积3m3的釜式反应器相连，反应器之间间隔塔板数为5块，其中塔顶汽相物料冷凝后全部进入第1台侧反应器，侧反应器出口物料返回精馏塔第1块塔板(塔板数从上向下数)；从第6块精馏塔板出来的物料进入第2台反应器，侧反应器出口物料返回精馏塔第7块塔板，精馏塔与侧反应器之间的物料通过泵输送。In a rectification tower with a diameter of 0.8m and 15 trays (the number of trays in the reactive distillation area is 7, and the number of trays in the stripping area is 8), with two tank reactors with a volume of 3m3 The number of trays between the reactors is 5, wherein the vapor phase material at the top of the tower is condensed and all enters the first side reactor, and the outlet material of the side reactor returns to the first tray of the rectification tower (the number of trays starts from counting from top to bottom); the material from the 6th rectification tray enters the second reactor, the outlet material of the side reactor returns to the 7th tray of the rectification tower, and the material between the rectification tower and the side reactor Delivered by pump.
每台侧反应器内装有白光光源，反应采用光催化。1,2-二氯乙烷向侧反应器的进料流率为4kmol/h，氯气向第1、2台侧反应器的进料流率分别为2.4、1.6kmol/h。反应温度70℃，各台侧反应器压力为0.1MPa，由侧反应器返回精馏塔的液相流率及组成如表1。精馏塔操作压力为0.1MPa，塔底采出量为4kmol/h，塔板液相物料全采出进入与之相连的侧反应器。反应精馏装置稳定后，精馏塔塔顶温度84.2℃，塔釜温度113.3℃。塔底产品中1,1,2-三氯乙烷的摩尔分数为0.970，1,2-二氯乙烷与四氯乙烷的摩尔分数分别为0.014、0.016。Each side reactor is equipped with a white light source, and the reaction adopts photocatalysis. The feed flow rate of 1,2-dichloroethane to the side reactor is 4 kmol/h, and the feed flow rate of chlorine gas to the first and second side reactors is 2.4 and 1.6 kmol/h, respectively. The reaction temperature is 70°C, the pressure of each side reactor is 0.1 MPa, and the flow rate and composition of the liquid phase returned from the side reactor to the rectification tower are shown in Table 1. The operating pressure of the rectification tower is 0.1 MPa, the extraction volume at the bottom of the tower is 4 kmol/h, and all the liquid phase materials on the trays are extracted into the side reactor connected to it. After the reaction rectification device stabilized, the temperature at the top of the rectification tower was 84.2°C, and the temperature at the bottom of the tower was 113.3°C. The molar fraction of 1,1,2-trichloroethane in the bottom product was 0.970, and the molar fractions of 1,2-dichloroethane and tetrachloroethane were 0.014 and 0.016, respectively.
表1侧反应器出口液相流率及组成Table 1 Liquid phase flow rate and composition at the outlet of the side reactor
实施例3：Example 3:
在直径0.8m，塔板数为30块塔板的精馏塔中(反应精馏区塔板数11块，提馏区塔板数19块)，与3台体积3m3的釜式反应器相连，反应器之间间隔塔板数为4块，其中塔顶汽相物料冷凝后全部进入第1台侧反应器，侧反应器出口物料返回精馏塔第1块塔板(塔板数从上向下数)；从第5块精馏塔板出来的物料进入第2台反应器，侧反应器出口物料返回精馏塔第6块塔板；从第10块精馏塔板出来的物料进入第3台反应器，侧反应器出口物料返回精馏塔第11块塔板，精馏塔与侧反应器之间的物料通过泵输送。In a rectification tower with a diameter of 0.8m and 30 trays (the number of trays in the reactive distillation area is 11, and the number of trays in the stripping area is 19), with 3 tank reactors with a volume of 3m3 The number of trays between the reactors is 4, wherein the vapor phase material at the top of the tower is condensed and all enters the first side reactor, and the outlet material of the side reactor returns to the first tray of the rectification tower (the number of trays starts from counting from top to bottom); the material from the 5th rectification tray enters the second reactor, and the material from the outlet of the side reactor returns to the 6th tray of the rectification tower; the material from the 10th rectification tray After entering the third reactor, the material at the outlet of the side reactor returns to the 11th tray of the rectification tower, and the material between the rectification tower and the side reactor is transported by a pump.
每台侧反应器内装有黄光光源，反应采用光催化。1,2-二氯乙烷向侧反应器的进料流率为3kmol/h，氯气向各台侧反应器的进料流率分别为1.8、0.9、0.3kmol/h。反应温度60℃，各台侧反应器压力为0.1MPa，由侧反应器返回精馏塔的液相流率及组成如表2。精馏塔操作压力为0.1MPa，塔底采出量为3kmol/h，塔板液相物料全采出进入与之相连的侧反应器。反应精馏装置稳定后，精馏塔塔顶温度83.9℃，塔釜温度113.5℃。塔底产品中1,1,2-三氯乙烷的摩尔分数为0.980，1,2-二氯乙烷与四氯乙烷的摩尔分数分别为0.009、0.011。Each side reactor is equipped with a yellow light source, and the reaction adopts photocatalysis. The feed flow rate of 1,2-dichloroethane to the side reactors is 3 kmol/h, and the feed flow rates of chlorine gas to each side reactor are 1.8, 0.9, and 0.3 kmol/h, respectively. The reaction temperature is 60°C, the pressure of each side reactor is 0.1MPa, and the flow rate and composition of the liquid phase returned from the side reactor to the rectification tower are shown in Table 2. The operating pressure of the rectification tower is 0.1 MPa, the output at the bottom of the tower is 3 kmol/h, and all the liquid phase materials on the trays are extracted into the side reactor connected to it. After the reactive distillation device stabilized, the temperature at the top of the distillation column was 83.9°C, and the temperature at the bottom of the column was 113.5°C. The molar fraction of 1,1,2-trichloroethane in the bottom product was 0.980, and the molar fractions of 1,2-dichloroethane and tetrachloroethane were 0.009 and 0.011, respectively.
表2侧反应器出口液相流率及组成Table 2 The flow rate and composition of the liquid phase at the outlet of the side reactor
实施例4：Example 4:
在直径0.8m，塔板数为30块塔板的精馏塔中(反应精馏区塔板数13块，提馏区塔板数17块)，与5台体积2m3的釜式反应器相连，反应器之间间隔塔板数为2块，其中塔顶汽相物料冷凝后全部进入第1台侧反应器，侧反应器出口物料返回精馏塔第1块塔板(塔板数从上向下数)；从第3块精馏塔板出来的物料进入第2台反应器，侧反应器出口物料返回精馏塔第4块塔板；以此类推，相邻侧反应器之间间隔的塔板数为2，与侧反应器相连接的进出物料在精馏塔上为相邻塔板。精馏塔与侧反应器之间的物料通过泵输送。In a rectification tower with a diameter of 0.8m and 30 trays (the number of trays in the reactive distillation area is 13, and the number of trays in the stripping area is 17), with 5 tank reactors with a volume of 2m3 The number of trays between the reactors is 2, wherein the vapor phase material at the top of the tower is condensed and all enters the first side reactor, and the outlet material of the side reactor returns to the first tray of the rectification tower (the number of trays starts from counting from top to bottom); the material from the third rectification tray enters the second reactor, and the outlet material of the side reactor returns to the fourth tray of the rectification tower; and so on, between adjacent side reactors The number of separated trays is 2, and the incoming and outgoing materials connected with the side reactors are adjacent trays on the rectification column. The materials between the rectification column and the side reactors are transported by pumps.
每台侧反应器内装有蓝光光源，反应采用光催化。1,2-二氯乙烷向侧反应器的进料流率为4kmol/h，氯气向各台侧反应器的进料流率均为0.8kmol/h。反应温度80℃，各台侧反应器压力为0.1MPa，由侧反应器返回精馏塔的液相流率及组成如表4。精馏塔操作压力为0.1MPa，塔底采出量为4kmol/h，塔板液相物料全采出进入与之相连的侧反应器。反应精馏装置稳定后，精馏塔塔顶温度83.7℃，塔釜温度113.2℃。塔底产品中1,1,2-三氯乙烷的摩尔分数为0.965，1,2-二氯乙烷与四氯乙烷是的摩尔分数均为0.019、0.016。Each side reactor is equipped with a blue light source, and the reaction adopts photocatalysis. The feed flow rate of 1,2-dichloroethane to the side reactors is 4 kmol/h, and the feed flow rate of chlorine gas to each side reactor is 0.8 kmol/h. The reaction temperature is 80°C, the pressure of each side reactor is 0.1 MPa, and the flow rate and composition of the liquid phase returned from the side reactor to the rectification tower are shown in Table 4. The operating pressure of the rectification tower is 0.1 MPa, the extraction volume at the bottom of the tower is 4 kmol/h, and all the liquid phase materials on the trays are extracted into the side reactor connected to it. After the reaction rectification device is stabilized, the temperature at the top of the rectification tower is 83.7°C, and the temperature at the bottom of the tower is 113.2°C. The molar fraction of 1,1,2-trichloroethane in the bottom product is 0.965, and the molar fractions of 1,2-dichloroethane and tetrachloroethane are both 0.019 and 0.016.
表3侧反应器出口液相流率及组成Table 3 side reactor outlet liquid phase flow rate and composition
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| CN115055144A (en) * | 2022-07-15 | 2022-09-16 | 常州新东化工发展有限公司 | System and process for producing o-chlorotrifluoromethylene |
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