CN111659322A - Device and process for preparing 1,1,1, 3-tetrachloropropane - Google Patents
Device and process for preparing 1,1,1, 3-tetrachloropropane Download PDFInfo
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- UTACNSITJSJFHA-UHFFFAOYSA-N 1,1,1,3-tetrachloropropane Chemical compound ClCCC(Cl)(Cl)Cl UTACNSITJSJFHA-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 101
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000005977 Ethylene Substances 0.000 claims abstract description 94
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000605 extraction Methods 0.000 claims abstract description 12
- 238000002347 injection Methods 0.000 claims abstract description 11
- 239000007924 injection Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 11
- 238000003756 stirring Methods 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 229960002089 ferrous chloride Drugs 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 2
- FEKGWIHDBVDVSM-UHFFFAOYSA-N 1,1,1,2-tetrachloropropane Chemical compound CC(Cl)C(Cl)(Cl)Cl FEKGWIHDBVDVSM-UHFFFAOYSA-N 0.000 description 1
- LIPPKMMVZOHCIF-UHFFFAOYSA-N 1,1,2-trichloroprop-1-ene Chemical compound CC(Cl)=C(Cl)Cl LIPPKMMVZOHCIF-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- -1 tributyl phosphate Ester Chemical class 0.000 description 1
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
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Abstract
本发明公开了一种制备1,1,1,3‑四氯丙烷的反应装置，包括反应釜，反应釜外设乙烯循环系统，反应釜底部设气体分布器，乙烯循环系统包括设在反应釜上部的乙烯抽出管、设在反应釜下部的乙烯压入管、设在乙烯抽出管和压入管之间的乙烯压缩机，乙烯压入管与气体分布器连通，本发明还公开了利用该反应装置四氯化碳与乙烯反应制备1,1,1,3‑四氯丙烷的工艺，采用本发明的工艺，减少了四氯化碳与乙烯反应制备1,1,1,3‑四氯丙烷过程中胶油状副产物生成量；提高了主产物1,1,1,3‑四氯丙烷的选择性；反应釜不需要搅拌装置，在相近反应速率下降低了反应釜内乙烯的压力。
The invention discloses a reaction device for preparing 1,1,1,3-tetrachloropropane, comprising a reaction kettle, an ethylene circulation system outside the reaction kettle, a gas distributor at the bottom of the reaction kettle, and the ethylene circulation system includes The upper ethylene extraction pipe, the ethylene injection pipe arranged at the lower part of the reaction kettle, the ethylene compressor arranged between the ethylene extraction pipe and the injection pipe, the ethylene injection pipe is communicated with the gas distributor, and the invention also discloses the use of the reaction device four. The process for preparing 1,1,1,3-tetrachloropropane by the reaction of carbon tetrachloride and ethylene, by adopting the process of the present invention, the process of preparing 1,1,1,3-tetrachloropropane by the reaction of carbon tetrachloride and ethylene is reduced The amount of gelatinous by-products generated; the selectivity of the main product 1,1,1,3-tetrachloropropane is improved; the reaction kettle does not need a stirring device, and the pressure of ethylene in the reaction kettle is reduced at a similar reaction rate.
Description
技术领域technical field
本发明涉及有机卤化物制备领域，特别是制备1,1,1,3-四氯丙烷的装置及工艺。The invention relates to the field of organic halide preparation, in particular to a device and a process for preparing 1,1,1,3-tetrachloropropane.
背景技术Background technique
1,1,1,3-四氯丙烷是合成三氯丙烯、三氟丙烯的关键原料，其本身也可用于去漆剂、脱脂剂和溶剂。1,1,1,3-四氯丙烷合成方法主要包括过氧化物法(CA691213A)、电磁辐射法(CA807638A)、金属络合物和助催化剂法，其中过氧化物法和电磁辐射法因合成效率低或反应条件苛刻不适用于工业生产，金属络合物和助催化剂法则因为反应条件温和、合成效率高而适用于工业化，但不可避免的生成胶油状物粘附于反应釜内壁和搅拌器件上，非常不利于长时间的连续化生产。1,1,1,3-Tetrachloropropane is the key raw material for synthesizing trichloropropene and trifluoropropene, and it can also be used as paint remover, degreaser and solvent. The synthesis methods of 1,1,1,3-tetrachloropropane mainly include peroxide method (CA691213A), electromagnetic radiation method (CA807638A), metal complex and cocatalyst method, among which peroxide method and electromagnetic radiation method are synthesized Low efficiency or harsh reaction conditions are not suitable for industrial production. The rules of metal complexes and co-catalysts are suitable for industrialization because of mild reaction conditions and high synthesis efficiency, but the inevitable formation of glue and oil-like substances adheres to the inner wall of the reactor and the stirring device. It is very unfavorable for long-term continuous production.
US4605802A公开了四氯化碳与乙烯反应制备1,1,1,3-四氯丙烷的方法，催化剂为亚磷酸酯和铁粉，优选是额外添加氯化铁，在95℃,758kPa下反应5.5～22.6小时，转化率45～88.5％，选择性94.9～96.3％。铁粉在反应结束后留在反应器中，用于下一次反应使用；优选的在下一次反应进行之前，反应器用溶剂进行清洗，所述的溶剂为二氯甲烷、丙酮。US4605802A discloses a method for preparing 1,1,1,3-tetrachloropropane by the reaction of carbon tetrachloride and ethylene. The catalyst is phosphite and iron powder, preferably additionally adding iron chloride, and the reaction is carried out at 95°C and 758kPa for 5.5 ~22.6 hours, conversion 45-88.5%, selectivity 94.9-96.3%. The iron powder is left in the reactor after the reaction and is used for the next reaction; preferably, before the next reaction is carried out, the reactor is cleaned with a solvent, and the solvent is dichloromethane and acetone.
CN106146247A公开了在催化剂制备罐中加入四氯化碳、磷酸三丁酯和氯化亚铁，搅拌均匀后制得均匀混合物，混合物中各组分的摩尔比为：四氯化碳/磷酸三丁酯/氯化亚铁＝1/0.01/0.01，将制备好的均匀混合物通过计量泵加入带搅拌的高压釜中，维持反应温度90℃，连续通入乙烯维持反应压力1.1MPa，停留时间1h，反应粗品连续采出经色谱分析，CCl4转化率为80％，产物1,1,1,3-四氯丙烷选择性为93％。CN106146247A discloses that carbon tetrachloride, tributyl phosphate and ferrous chloride are added into the catalyst preparation tank, and a uniform mixture is prepared after stirring evenly. The molar ratio of each component in the mixture is: carbon tetrachloride/tributyl phosphate Ester/ferrous chloride=1/0.01/0.01, put the prepared homogeneous mixture into a stirred autoclave through a metering pump, maintain the reaction temperature at 90°C, continuously feed ethylene to maintain the reaction pressure at 1.1MPa, and keep the residence time 1h. The crude reaction product was continuously collected and analyzed by chromatography. The conversion rate of CCl 4 was 80%, and the selectivity of the
JP2017137263A公开了金属络合物催化剂溶解在液相中，乙烯和四氯化碳加成反应，得到含1,1,1,3-四氯丙烷的反应液，该反应液经高速离心分离产生相分离，金属络合物催化剂在轻相、1,1,1,3-四氯丙烷在重相。催化剂的分离使得反应产物在蒸馏工序不会发生副反应，保证了其高纯度。相对于100mol四氯化碳，催化剂为0.55mol铁和0.1mol二甲基乙酰胺，在130℃和0.6MPa下反应，期间连续加入二甲基乙酰胺2.5hr，直至总量为0.636mol，继续反应5hr，CCl4转化率为94％，产物选择性98％。JP2017137263A discloses that a metal complex catalyst is dissolved in a liquid phase, and ethylene and carbon tetrachloride undergo an addition reaction to obtain a reaction solution containing 1,1,1,3-tetrachloropropane, and the reaction solution is separated by high-speed centrifugation to produce a phase In separation, the metal complex catalyst is in the light phase and 1,1,1,3-tetrachloropropane is in the heavy phase. The separation of the catalyst ensures that the reaction product will not undergo side reactions in the distillation process, ensuring its high purity. Relative to 100mol carbon tetrachloride, the catalyst is 0.55mol iron and 0.1mol dimethylacetamide, the reaction is carried out at 130 ° C and 0.6MPa, during which dimethylacetamide is continuously added for 2.5hr, until the total amount is 0.636mol, continue After 5hr of reaction, the conversion rate of CCl 4 was 94%, and the product selectivity was 98%.
现有技术通过催化剂改进、后处理工艺变化提高了原料的转化率、产物选择性、以及装置的可操作性，但都没有根本解决反应生成胶油状物的问题。The prior art improves the conversion rate of raw materials, the selectivity of products, and the operability of the device through catalyst improvement and post-treatment process changes, but none of them have fundamentally solved the problem of generating a rubbery oil in the reaction.
发明内容SUMMARY OF THE INVENTION
针对现有技术四氯化碳与乙烯反应制备1,1,1,3-四氯丙烷的过程中生成胶油状物的问题，本发明通过改进反应装置，降低了胶油状物生成量。Aiming at the problem of generating gum oil in the process of preparing 1,1,1,3-tetrachloropropane by reacting carbon tetrachloride and ethylene in the prior art, the present invention reduces the amount of gum oil by improving the reaction device.
四氯化碳与乙烯反应制备1,1,1,3-四氯丙烷的反应式如下：The reaction formula of carbon tetrachloride and ethylene to prepare 1,1,1,3-tetrachloropropane is as follows:
由于乙烯在高温、高压下容易发生聚合反应，除了上述主反应外，还有系列副反应，生成胶油状副产物：Since ethylene is prone to polymerization under high temperature and high pressure, in addition to the above-mentioned main reaction, there are also a series of side reactions, resulting in a rubber-like by-product:
在相同的催化剂下，过量的乙烯或较高的乙烯浓度是导致副反应发生的主要原因，降低反应体系中乙烯浓度或乙烯的压力是减少副反应的关键。Under the same catalyst, excess ethylene or higher ethylene concentration is the main cause of side reactions, and reducing the ethylene concentration or ethylene pressure in the reaction system is the key to reducing side reactions.
本发明提供了一种四氯化碳与乙烯反应制备1,1,1,3-四氯丙烷的装置，包括反应釜，所述的反应釜外设乙烯循环系统，反应釜内底部设气体分布器，所述的乙烯循环系统包括设在反应釜上部的乙烯抽出管、设在反应釜下部的乙烯压入管、设在乙烯抽出管和压入管之间的乙烯压缩机，乙烯压入管与所述的气体分布器连通；反应釜还设有四氯化碳、催化剂加料口和反应液出料口；所述的乙烯抽出管上设有乙烯加料口。The invention provides a device for preparing 1,1,1,3-tetrachloropropane by reacting carbon tetrachloride and ethylene, comprising a reaction kettle, an ethylene circulation system is arranged outside the reaction kettle, and a gas distribution system is arranged at the inner bottom of the reaction kettle The ethylene circulation system includes an ethylene extraction pipe located at the upper part of the reaction kettle, an ethylene injection pipe located at the lower part of the reaction kettle, and an ethylene compressor located between the ethylene extraction pipe and the injection pipe. The gas distributor is connected; the reaction kettle is also provided with a carbon tetrachloride, a catalyst feed port and a reaction liquid discharge port; the ethylene extraction pipe is provided with an ethylene feed port.
优选的，所述的反应釜长径比为1.5～60，进一步优选为2～15；长径比过小的矮胖型反应釜，气液相接触时间短，不利于气液反应，反之，过大的长径比，气泡在长距离上升过程中发生聚集，使气液相接触面积减小，降低了反应效率。Preferably, the length-diameter ratio of the reaction kettle is 1.5-60, more preferably 2-15; the squat type reaction kettle with too small length-diameter ratio has a short gas-liquid contact time, which is not conducive to the gas-liquid reaction, otherwise, If the length-diameter ratio is too large, the bubbles will aggregate during the long-distance rise, which will reduce the contact area between the gas and the liquid phase and reduce the reaction efficiency.
优选的，所述的气体分布器采用烧结金属多孔材料制成，进一步优选所述的气体分布器为烧结金属多孔网板，网板面积为反应釜横截面积的30～90％，不仅保证气体的均匀分布，还能使反应液在反应釜内充分循环；Preferably, the gas distributor is made of sintered metal porous material, and further preferably, the gas distributor is a sintered metal porous mesh plate, and the area of the mesh plate is 30-90% of the cross-sectional area of the reactor, which not only ensures the gas uniform distribution, and the reaction liquid can be fully circulated in the reactor;
所述的反应釜通过来自气体分布器的乙烯鼓泡就能使液相充分搅动，不需要额外的搅拌装置，既能避免搅拌装置高速动摩擦带来的安全风险，还能避免搅拌引起金属催化剂与反应釜壁碰撞，而且大幅降低反应釜制造成本。The reaction kettle can fully agitate the liquid phase by bubbling ethylene from the gas distributor, without the need for an additional stirring device, which can not only avoid the safety risk brought by the high-speed dynamic friction of the stirring device, but also avoid the metal catalyst and the metal catalyst caused by stirring. The reactor wall collides, and the manufacturing cost of the reactor is greatly reduced.
优选的，所述的乙烯压缩机为无油压缩机，以免润滑油对反应造成不良影响；所述的乙烯压缩机的排气口与吸气口压力差为0.1～3.0MPa，排气量为每立方米反应釜体积0.4～18Nm3/min；乙烯压缩机仅需要提供克服反应釜中液位差的压力就能使乙烯在反应釜中循环，所需的动力很小；乙烯压缩机的排气量是乙烯循环能力的体现，过小的排气量无法提供足够的乙烯与液相接触反应，而过大的排气量会导致液相过度沸腾，使反应体系不稳定。Preferably, the ethylene compressor is an oil-free compressor to avoid adverse effects of lubricating oil on the reaction; the pressure difference between the exhaust port and the suction port of the ethylene compressor is 0.1-3.0MPa, and the exhaust volume is The volume of the reaction kettle per cubic meter is 0.4-18Nm 3 /min; the ethylene compressor only needs to provide the pressure to overcome the liquid level difference in the reaction kettle to make the ethylene circulate in the reaction kettle, and the required power is very small; the discharge of the ethylene compressor The gas volume is the embodiment of the ethylene circulation capacity. Too small exhaust volume cannot provide enough ethylene to react with the liquid phase, and too large exhaust volume will cause excessive boiling of the liquid phase and make the reaction system unstable.
所述的外设乙烯循环系统使乙烯在气相和液相之间充分交换，即使反应釜内乙烯压力较低，溶入反应液或与反应液接触的乙烯量也能得到保证，从而确保四氯化碳与乙烯的反应顺利进行。The described peripheral ethylene circulation system enables the ethylene to be fully exchanged between the gas phase and the liquid phase. Even if the ethylene pressure in the reactor is low, the amount of ethylene dissolved into the reaction solution or in contact with the reaction solution can be guaranteed, thereby ensuring that the tetrachloride The reaction of carbon and ethylene proceeded smoothly.
利用所述的制备1,1,1,3-四氯丙烷的反应装置制备1,1,1,3-四氯丙烷的工艺，包括：先将反应釜排出空气，然后加入催化剂、四氯化碳，通入乙烯后，启动乙烯压缩机，乙烯从反应釜上部抽出，通过乙烯压缩机加压后，又从反应釜下部压入反应釜，压入反应釜的乙烯通过气体分布器进行分布后进入反应体系，控制反应釜内乙烯压力为0.15～0.50MPa，升温至80～130℃反应，当反应液中四氯化碳的转化率为60～85％时停止反应。The process for preparing 1,1,1,3-tetrachloropropane using the reaction device for preparing 1,1,1,3-tetrachloropropane includes: firstly discharging air from the reactor, then adding catalyst, tetrachloride After the carbon is introduced into the ethylene, the ethylene compressor is started, and the ethylene is extracted from the upper part of the reaction kettle. After being pressurized by the ethylene compressor, it is pressed into the reaction kettle from the lower part of the reaction kettle, and the ethylene pressed into the reaction kettle is distributed through the gas distributor. Enter the reaction system, control the ethylene pressure in the reaction kettle to be 0.15-0.50MPa, heat up to 80-130 DEG C to react, and stop the reaction when the conversion rate of carbon tetrachloride in the reaction solution is 60-85%.
所述的催化剂为常规的四氯化碳、乙烯调聚催化剂。催化剂可选用氯化铁、氯化亚铁、氯化亚铜等，助催化剂可选用亚磷酸三丙酯、亚磷酸三丁酯等。Described catalyst is conventional carbon tetrachloride, ethylene telomerization catalyst. The catalyst can be selected from ferric chloride, ferrous chloride, cuprous chloride, etc., and the co-catalyst can be selected from tripropyl phosphite, tributyl phosphite and the like.
与现有技术相比，本发明具有如下优点：1、减少了四氯化碳与乙烯反应制备1,1,1,3-四氯丙烷过程中胶油状副产物生成量；2、提高了主产物1,1,1,3-四氯丙烷的选择性；3、反应釜不需要搅拌装置；4、在相近反应速率下降低了反应釜内乙烯的压力。Compared with the prior art, the present invention has the following advantages: 1. It reduces the amount of oil-like by-products generated during the reaction of carbon tetrachloride and ethylene to prepare 1,1,1,3-tetrachloropropane; 2. The selectivity of the
附图说明Description of drawings
图1为本发明制备1,1,1,3-四氯丙烷的装置结构示意图。Figure 1 is a schematic diagram of the structure of the device for preparing 1,1,1,3-tetrachloropropane according to the present invention.
图1中，1为反应釜，2为四氯化碳、催化剂加料口，3为乙烯抽出管，4为乙烯加料口，5为乙烯压缩机，6为乙烯压入管，7为出料口，8为气体分布器In Fig. 1, 1 is reactor, 2 is carbon tetrachloride, catalyst charging port, 3 is ethylene extraction pipe, 4 is ethylene charging port, 5 is ethylene compressor, 6 is ethylene press-in pipe, 7 is discharge port, 8 is the gas distributor
具体实施方式Detailed ways
如图1所示，一种制备1,1,1,3-四氯丙烷的装置，包括反应釜，反应釜外设乙烯循环系统，反应釜底部设气体分布器；乙烯循环系统包括设在反应釜1上部的乙烯抽出管3、设在反应釜1下部的乙烯压入管6、设在乙烯抽出管3和压入管6之间的乙烯压缩机5，乙烯压入管与气体分布器8连通；反应釜上部设有四氯化碳、催化剂加料口2，反应釜下部设有反应液出料口7，乙烯抽出管上设有乙烯加料口4；所述的反应釜为不锈钢材质，所述的气体分布器为多层烧结金属网板，平均孔径为0.3-50μm，孔隙率25％-45％，气体分布器面积为反应釜横截面积的30％-90％，所述的乙烯压缩机为无油乙烯压缩机，排气口与进气口压力差0.1～3.0MPa。As shown in Figure 1, a device for preparing 1,1,1,3-tetrachloropropane includes a reaction kettle, an ethylene circulation system is arranged outside the reaction kettle, and a gas distributor is arranged at the bottom of the reaction kettle; The
下面采用所述的反应装置，结合实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。The present invention is further described below by using the reaction device and in conjunction with the examples. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention.
实施例1Example 1
不锈钢材质的5000L反应釜，长径比为3，排出空气，加入催化剂氯化铁5kg、还原铁粉32kg，助催化剂亚磷酸三丁酯25kg，四氯化碳3750kg，从乙烯加料口通入乙烯，使反应釜内乙烯压力达到0.20MPa；启动无油乙烯压缩机，排气口与进气口压力差小于等于1.2MPa，乙烯压缩机的排气量为17.5Nm3/min，乙烯从反应釜上部抽出，通过乙烯压缩机加压后，从反应釜下部压入反应釜，压入反应釜的乙烯通过气体分布器分布进入反应体系，气体分布器为多层烧结金属网板，平均孔径0.45μm，孔隙率38％，气体分布器面积为反应釜横截面积的65％；升温至95℃反应，补充乙烯，控制反应釜内乙烯压力为0.18～0.22MPa，反应7.5小时，取样进行气相色谱分析，1,1,1,3-四氯丙烷76.2％，四氯化碳23.4％，二次加成副产物0.4％，折合四氯化碳转化率为73.4％，1,1,1,3-四氯丙烷选择性99.5％，停止反应。Stainless steel 5000L reactor with an aspect ratio of 3, exhaust air, add catalyst ferric chloride 5kg, reduced iron powder 32kg, co-catalyst tributyl phosphite 25kg, carbon tetrachloride 3750kg, feed ethylene from the ethylene feed port , make the ethylene pressure in the reaction kettle reach 0.20MPa; start the oil-free ethylene compressor, the pressure difference between the exhaust port and the air inlet is less than or equal to 1.2MPa, the exhaust volume of the ethylene compressor is 17.5Nm 3 /min, and the ethylene is discharged from the reaction kettle. The upper part is drawn out, and after being pressurized by an ethylene compressor, it is pressed into the reaction kettle from the lower part of the reaction kettle, and the ethylene pressed into the reaction kettle is distributed into the reaction system through a gas distributor. , the porosity is 38%, and the area of the gas distributor is 65% of the cross-sectional area of the reaction kettle; the temperature is raised to 95 ° C for the reaction, ethylene is added, the ethylene pressure in the reaction kettle is controlled to be 0.18 to 0.22 MPa, the reaction is 7.5 hours, and sampling is carried out for gas chromatographic analysis. , 1,1,1,3-tetrachloropropane 76.2%, carbon tetrachloride 23.4%, secondary addition by-product 0.4%, the conversion rate of carbon tetrachloride is 73.4%, 1,1,1,3- The selectivity of tetrachloropropane was 99.5%, and the reaction was stopped.
实施例2Example 2
控制反应釜内乙烯压力为0.46～0.50MPa，其他与实施例1相同，取样进行气相色谱分析，1,1,1,3-四氯丙烷85.4％，四氯化碳13.9％，二次加成副产物0.7％，折合四氯化碳转化率为84.0％，1,1,1,3-四氯丙烷选择性99.3％。The ethylene pressure in the reaction kettle was controlled to be 0.46-0.50 MPa, and the others were the same as in Example 1. Samples were taken for gas chromatographic analysis, 1,1,1,3-tetrachloropropane 85.4%, carbon tetrachloride 13.9%, secondary addition The by-product is 0.7%, the conversion rate of carbon tetrachloride is 84.0%, and the selectivity of 1,1,1,3-tetrachloropropane is 99.3%.
对比例1Comparative Example 1
反应釜没有乙烯循环系统，通过机械搅拌装置搅动反应液，控制反应釜内乙烯压力为0.78～0.82MPa，反应时间11小时，其他与实施例1相同，取样进行气相色谱分析，1,1,1,3-四氯丙烷75.9％，四氯化碳21.2％，二次加成副产物2.4％，其他0.5％，折合四氯化碳转化率为79.0％，1,1,1,3-四氯丙烷选择性96.3％。The reaction kettle did not have an ethylene circulation system. The reaction solution was stirred by a mechanical stirring device, and the ethylene pressure in the reaction kettle was controlled to be 0.78 to 0.82 MPa, and the reaction time was 11 hours. ,3-tetrachloropropane 75.9%, carbon tetrachloride 21.2%, secondary addition by-product 2.4%, other 0.5%, equivalent to carbon tetrachloride conversion rate of 79.0%, 1,1,1,3-tetrachloro Propane selectivity 96.3%.
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