WO2023108788A1 - 用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂、其制备方法与应用 - Google Patents
用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂、其制备方法与应用 Download PDFInfo
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- WO2023108788A1 WO2023108788A1 PCT/CN2021/141027 CN2021141027W WO2023108788A1 WO 2023108788 A1 WO2023108788 A1 WO 2023108788A1 CN 2021141027 W CN2021141027 W CN 2021141027W WO 2023108788 A1 WO2023108788 A1 WO 2023108788A1
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- catalyst
- tetrachloropropane
- gas
- solid phase
- continuous production
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- UTACNSITJSJFHA-UHFFFAOYSA-N 1,1,1,3-tetrachloropropane Chemical compound ClCCC(Cl)(Cl)Cl UTACNSITJSJFHA-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000010924 continuous production Methods 0.000 title claims abstract description 39
- 238000003746 solid phase reaction Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 57
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 52
- 239000011574 phosphorus Substances 0.000 claims abstract description 52
- -1 phosphorus co-modified carbon Chemical class 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000007790 solid phase Substances 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 26
- 239000005977 Ethylene Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 16
- 150000002505 iron Chemical class 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 10
- 150000001721 carbon Chemical class 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 claims description 5
- 238000006384 oligomerization reaction Methods 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- QJIMTLTYXBDJFC-UHFFFAOYSA-N (4-methylphenyl)-diphenylphosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QJIMTLTYXBDJFC-UHFFFAOYSA-N 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- ZXKWUYWWVSKKQZ-UHFFFAOYSA-N cyclohexyl(diphenyl)phosphane Chemical compound C1CCCCC1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZXKWUYWWVSKKQZ-UHFFFAOYSA-N 0.000 claims description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 159000000014 iron salts Chemical class 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 2
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000012043 crude product Substances 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 238000000921 elemental analysis Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- 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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- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
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Definitions
- the main purpose of this application is to provide a catalyst for the continuous production of 1,1,1,3-tetrachloropropane by gas-solid phase reaction and its preparation method, so as to overcome the deficiencies in the prior art.
- the embodiment of the present application also provides the preparation method of the catalyst for the continuous production of 1,1,1,3-tetrachloropropane by gas-solid phase reaction, which includes: co-modifying the carbon material with iron salt and organic phosphorus , to obtain a catalyst for the continuous production of 1,1,1,3-tetrachloropropane by gas-solid phase reaction.
- the preparation method specifically includes:
- the preparation method specifically includes:
- the embodiment of the present application also provides a method for continuously producing 1,1,1,3-tetrachloropropane by gas-solid phase reaction, which includes:
- Feed carbon tetrachloride and ethylene reaction raw material gas continuously into the catalyst bed increase the inlet pressure of the reaction raw material gas to 0.8-1.2MPa, heat the temperature of the catalyst bed to 80-120°C, and undergo a catalytic oligomerization reaction 1,1,1,3-Tetrachloropropane is obtained.
- the catalyst provided by this application uses carbon material as a carrier, on which the active component zero-valent iron is loaded to replace the main catalyst iron powder in the existing kettle reaction; the auxiliary component phosphate functional group is formed on the surface of the carbon material through phosphorus modification , to replace the cocatalyst alkyl phosphate in the existing tank reaction, and get rid of the dependence of the traditional batch reaction on the liquid catalyst.
- the application integrates the main catalyst (zero-valent iron) and the co-catalyst (phosphate functional group) on the carbon material, which can be directly used for the synthesis of 1,1,1,3-tetrachloropropane as a single solid catalyst, because no longer Using a liquid co-catalyst, the catalyst can be directly packaged into a gas-solid phase fixed-bed reactor, and carbon tetrachloride and ethylene raw materials can be fed continuously, and the 1,1,1,3-tetrachloro Continuous synthesis of propane.
- the main catalyst zero-valent iron
- the co-catalyst phosphate functional group
- Figure 1 is a microscopic morphology diagram of the zero-valent iron and phosphorus co-modified activated carbon catalyst prepared in Example 1 of the present application.
- One aspect of the embodiments of the present application provides a catalyst for the continuous production of 1,1,1,3-tetrachloropropane by gas-solid phase reaction is zero-valent iron and phosphorus co-modified carbon materials, the zero-valent iron and phosphorus
- the phosphorus co-modified carbon material includes a carbon material as a carrier, zero-valent iron as an active component loaded on the carrier, and a phosphate functional group formed on the surface of the carbon material.
- the mass content of iron in the catalyst is 1-10 wt%, and the mass content of phosphorus is 1-10 wt%.
- the particle size of the zero-valent iron in the catalyst is 2-100 nm.
- the carbon material includes at least one of activated carbon, carbon nanotubes, graphene, etc., but is not limited thereto.
- Another aspect of the embodiment of the present application also provides a method for preparing a catalyst for the continuous production of 1,1,1,3-tetrachloropropane by gas-solid phase reaction, which includes: treating carbon materials with iron salt and organic phosphorus Co-modification is carried out to obtain a catalyst for continuous production of 1,1,1,3-tetrachloropropane by gas-solid phase reaction.
- the synthesis method of the catalyst is specifically as follows:
- a synthesis step of the catalyst is as follows:
- step (2) Mix the zero-valent iron-modified carbon material obtained in step (1) with organic phosphorus, heat up to 600-1000°C in an inert atmosphere, calcinate for 1-4 hours, and cool down to room temperature to obtain the catalyst.
- another synthesis method of the catalyst is as follows:
- the reducing agent includes sodium borohydride (NaBH 4 ), potassium borohydride (KBH 4 ), etc., but is not limited thereto.
- step (2) The phosphorus-modified carbon material obtained in step (1) is immersed in an iron salt solution, and sodium borohydride or potassium borohydride is added in an inert atmosphere to reduce iron ions to zero-valent iron.
- the concentration of reducing agents such as sodium borohydride or potassium borohydride in the reaction system of step (2) is 0.2 mol/L-0.4 mol/L.
- the carbon material includes at least one of activated carbon, carbon nanotubes, graphene, etc., but is not limited thereto.
- the iron salt includes at least one of ferrous chloride, ferrous nitrate, ferrous sulfate, ferric nitrate nonahydrate, ferric chloride, etc., but is not limited thereto.
- the molar ratio of the carbon element in the carbon material or the zero-valent iron-modified carbon material to the phosphorus element in the organic phosphorus is 3:1 ⁇ 7:1.
- the concentration of the iron salt in the solution containing the iron salt is 0.1 mol/L ⁇ 1.8 mol/L.
- the organic phosphorus includes at least one of phenylphosphine dichloride, diphenylphosphine, triphenylphosphine, diphenyl-p-tolylphosphine and diphenylcyclohexylphosphine species, but not limited to this.
- Another aspect of the embodiments of the present application also provides a catalyst for the continuous production of 1,1,1,3-tetrachloropropane prepared by the aforementioned method for gas-solid phase reaction.
- Another aspect of the embodiment of the present application also provides the aforementioned catalyst for the continuous production of 1,1,1,3-tetrachloropropane in the gas-solid phase reaction for the continuous production of 1,1,1,3-tetrachloropropane Application of chloropropane.
- another aspect of the embodiment of the present application also provides a method for continuous production of 1,1,1,3-tetrachloropropane by gas-solid phase reaction, which mainly includes: encapsulating the catalyst in a gas-solid phase fixed-bed reaction In the container, carbon tetrachloride and ethylene raw material gas are continuously fed under a certain pressure and a certain temperature, and 1,1,1,3-tetrachloropropane product is obtained through catalytic oligomerization.
- the method specifically includes:
- Feed carbon tetrachloride and ethylene reaction raw material gas continuously into the catalyst bed increase the inlet pressure of the reaction raw material gas to 0.8-1.2MPa, heat the temperature of the catalyst bed to 80-120°C, and undergo a catalytic oligomerization reaction 1,1,1,3-tetrachloropropane is obtained and the 1,1,1,3-tetrachloropropane product is collected at the end of the fixed bed.
- volume ratio of carbon tetrachloride to ethylene is 1:2 ⁇ 2:1.
- the catalyst of the present application integrates the active component zero-valent iron and co-component phosphate functional groups on the carbon material carrier, which gets rid of the dependence of the traditional batch reaction on the liquid catalytic co-catalyst and realizes 1,1 , Continuous production of 1,3-tetrachloropropane in a gas-solid phase fixed-bed reactor.
- the gas-solid phase fixed-bed reactor adopts an electrically heated tubular reactor with a pipe diameter of 10 mm and a length of 0.5 m.
- the reaction process is as follows:
- the gas-solid phase fixed-bed reactor adopts an electrically heated tubular reactor with a pipe diameter of 10 mm and a length of 0.5 m.
- the reaction process is as follows:
- the gas-solid phase fixed-bed reactor adopts an electrically heated tubular reactor with a pipe diameter of 10 mm and a length of 0.5 m.
- the reaction process is as follows:
- the product obtained in this example was analyzed by gas chromatography, the conversion rate of carbon tetrachloride was 71%, and the selectivity of 1,1,1,3-tetrachloropropane was 98.8%.
- the product obtained in this example was analyzed by gas chromatography, the conversion rate of carbon tetrachloride was 45%, and the selectivity of 1,1,1,3-tetrachloropropane was 97%.
- the product obtained in this example was analyzed by gas chromatography, the conversion rate of carbon tetrachloride was 52%, and the selectivity of 1,1,1,3-tetrachloropropane was 98%.
- This embodiment utilizes the fixed-bed reactor of embodiment 8, and the reaction process is:
- the product obtained in this example was analyzed by gas chromatography, the conversion rate of carbon tetrachloride was 52%, and the selectivity of 1,1,1,3-tetrachloropropane was 98%.
- this comparative example is different in that: no ferric nitrate nonahydrate was added, and only phosphorus-modified activated carbon catalyst was obtained.
- the phosphorus-modified activated carbon catalyst prepared in this comparative example was used in Example 8, the conversion rate of carbon tetrachloride was 27%, and the selectivity of 1,1,1,3-tetrachloropropane was 41%.
- this comparative example is different in that: no triphenylphosphine is added, and only zero-valent iron modified activated carbon catalyst is prepared.
- the zero-valent iron modified activated carbon catalyst prepared in this comparative example was used in Example 8, the conversion rate of carbon tetrachloride was 54%, and the selectivity of 1,1,1,3-tetrachloropropane was 67%.
- this comparative example is different in that: only phosphorus-modified carbon nanotube catalyst is prepared without adding ferrous chloride.
- the phosphorus-modified carbon nanotube catalyst prepared in this comparative example was used in Example 13, the conversion rate of carbon tetrachloride was 25%, and the selectivity of 1,1,1,3-tetrachloropropane was 56%.
- this comparative example is different in that: no phenylphosphine dichloride is added, and only a zero-valent iron-modified carbon nanotube catalyst is prepared.
- the zero-valent iron modified carbon nanotube catalyst prepared in this comparative example was used in Example 13, the conversion rate of carbon tetrachloride was 37%, and the selectivity of 1,1,1,3-tetrachloropropane was 60%. %.
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Abstract
一种用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂、其制备方法与应用。所述催化剂包括零价铁和磷共改性碳材料,其包括作为载体的碳材料、负载于载体上的作为活性组分的零价铁,以及形成于碳材料表面的磷酸酯官能团。所述制备方法包括:以亚铁盐和有机磷对碳材料进行共同改性,获得用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂。还提供了一种气固相反应连续生产1,1,1,3-四氯丙烷的方法。该催化剂在碳材料载体上集成了活性组分零价铁和助组分磷酸酯官能团,摆脱了传统间歇釜式反应对液态催化助剂的依赖,实现了1,1,1,3-四氯丙烷在气固相固定床反应器上的连续生产。
Description
本申请基于并要求于2021年12月17日递交的申请号为202111550988.5、发明名称为“用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂、其制备方法与应用”的中国专利申请的优先权。
本申请涉及一种用于生产1,1,1,3-四氯丙烷的催化剂,具体涉及一种用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂及其制备方法与应用,属于化工技术领域。
1,1,1,3-四氯丙烷是一种重要的精细化学品,是合成去漆剂、脱脂剂和各类氟硅产品的重要原料,市场潜力巨大。该化学品以四氯化碳和乙烯为原料,通过催化低聚反应得到。常用的催化体系包括:铁粉-氯化(亚)铁-烷基(亚)磷酸酯、铁粉-烷基(亚)磷酸酯、烷基(亚)磷酸酯-氯化(亚)铁-烷基腈、铜粉-烷基腈等。在这些体系中,助催化剂烷基(亚)磷酸酯或烷基腈均为液态物质,在反应中不可或缺。所以,目前的1,1,1,3-四氯丙烷的合成只能采取间歇釜式反应。但间歇釜式反应存在催化剂分离困难、生产时间长,单釜产量有限以及升温降温过程中能耗浪费等问题,生产效率低,不适合产品的工业化大批量生产。因此,本技术领域尚缺乏一种气固相反应连续生产1,1,1,3-四氯丙烷的固体催化剂及方法。
发明内容
本申请的主要目的在于提供一种用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂及其制备方法,从而克服现有技术中的不足。
本申请的另一目的还在于提供一种气固相反应连续生产1,1,1,3-四氯丙烷的方法。
为实现前述发明目的,本申请采用的技术方案包括:
本申请实施例提供了一种用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂,所述催化剂包括零价铁和磷共改性碳材料,所述零价铁和磷共改性碳材料包括作为载体的碳材料、负载于所述载体上的作为活性组分的零价铁,以及形成于所述碳材料表面的磷酸酯官能团。
本申请实施例还提供了所述用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂的制备方法,其包括:以铁盐和有机磷对碳材料进行共同改性,获得用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂。
在一些实施例中,所述制备方法具体包括:
在惰性气氛中,对包含碳材料与铁盐的第一混合物加热,并以5℃/min~10℃/min的升温速率升温至600~1000℃进行焙烧1~4h,得到零价铁改性碳材料;
以及,在惰性气氛中,对包含所述零价铁改性碳材料与有机磷的第二混合物加热,升温至600~1000℃进行焙烧1~4h,获得所述用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂。
在另一些实施例中,所述制备方法具体包括:
在惰性气氛中,对包含碳材料与有机磷的第三混合物加热,并以5℃/min~10℃/min的升温速率升温至600~1000℃进行焙烧1~4h,得到磷改性碳材料;
以及,将所述磷改性碳材料与含有铁盐的溶液充分接触4~6h,并在惰性气氛中加入还原剂,至少将铁离子还原成零价铁,获得所述用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂。
本申请实施例还提供了所述用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂于气固相反应连续生产1,1,1,3-四氯丙烷中的应用。
相应的,本申请实施例还提供了一种气固相反应连续生产1,1,1,3-四氯丙烷的方法,其包括:
将所述用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂封装于气固相固定床反应装置中,形成催化剂床层;
将四氯化碳和乙烯反应原料气连续通入所述催化剂床层,将反应原料气进气压力提升至0.8~1.2MPa,加热催化剂床层的温度至80~120℃,经催化低聚反应获得1,1,1,3-四氯丙烷。
与现有技术相比,本申请的有益效果至少在于:
本申请提供的催化剂以碳材料为载体,在其上负载活性组分零价铁,替代现有釜式反应中的主催化剂铁粉;通过磷改性在碳材料表面形成助组分磷酸酯官能团,替代现有釜式反应中的助催化剂烷基磷酸酯,摆脱了传统间歇釜式反应对液态催化助剂的依赖。因此,本申请在碳材料上集成了主催化剂(零价铁)和助催化剂(磷酸酯官能团),可作为单一固体催化剂直接用于1,1,1,3-四氯丙烷合成,由于不再使用液态助催化剂,可以将该催化剂直接封装到气固相固定床反应器内,连续通入四氯化碳和乙烯原料,在加压加热条件下可以实现1,1,1,3-四氯丙烷的连续合成。
为了更清楚地说明本申请实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本申请中记载的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是本申请实施例1中制得的零价铁和磷共改性活性炭催化剂的微观形貌图。
鉴于现有技术中的不足,本案发明人经长期研究和大量实践,得以提出本申请的技术方案。如下将对该技术方案、其实施过程及原理等作进一步的解释说明。
本申请实施例的一个方面提供的一种用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂为零价铁和磷共改性碳材料,所述零价铁和磷共改性碳材料包括作为载体的碳材料、负载于所述载体上的作为活性组分的零价铁,以及形成于所述碳材料表面的磷酸酯官能团。
在一些实施方案中,所述催化剂中铁的质量含量为1~10wt%,磷的质量含量为1~10wt%。
在一些实施方案中,所述催化剂中零价铁的颗粒尺寸为2~100nm。
在一些实施方案中,所述碳材料包括活性炭、碳纳米管、石墨烯等中的至少一种,但不限于此。
本申请实施例的另一个方面还提供了一种用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂的制备方法,其包括:以铁盐和有机磷对碳材料进行共同改性,获得用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂。
在一些实施方式中,所述催化剂的合成方法具体如下:
在惰性气氛中,对包含碳材料与铁盐的第一混合物加热,并以5℃/min~10℃/min的升温速率升温至600~1000℃进行焙烧1~4h,得到零价铁改性碳材料;
以及,在惰性气氛中,对包含所述零价铁改性碳材料与有机磷的第二混合物加热,升温至600~1000℃进行焙烧1~4h,获得所述用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂。
在一些具体实施方式中,所述催化剂的一种合成步骤如下:
(1)将碳材料与铁盐混合,在惰性气氛下加热,以5℃/min~10℃/min的升温速率升至600~1000℃,焙烧1~4小时,降至室温得到零价铁改性碳材料;
(2)将步骤(1)所得零价铁改性碳材料与有机磷混合,在惰性气氛下加热升至 600~1000℃,焙烧1~4小时,降至室温得到所述催化剂。
在一些实施方式中,所述催化剂的另一种合成方法具体如下:
在惰性气氛中,对包含碳材料与有机磷的第三混合物加热,并以5℃/min~10℃/min的升温速率升温至600~1000℃进行焙烧1~4h,得到磷改性碳材料;
以及,将所述磷改性碳材料与含有铁盐的溶液充分接触,并在惰性气氛中加入还原剂,至少将铁离子还原成零价铁,获得所述用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂。
进一步地,所述还原剂包括硼氢化钠(NaBH
4)、硼氢化钾(KBH
4)等,但不限于此。
在另一些具体实施方式中,所述催化剂的另一种合成步骤如下:
(1)将碳材料与有机磷混合,在惰性气氛下加热,以5℃/min~10℃/min的升温速率升至600~1000℃,焙烧1~4小时,降至室温得到磷改性碳材料;
(2)将步骤(1)所得磷改性碳材料浸入铁盐溶液,在惰性气氛中加入硼氢酸钠或硼氢化钾将铁离子还原成零价铁。
(3)过滤、洗涤、干燥得到所述催化剂。
进一步地,步骤(2)的反应体系中硼氢酸钠或硼氢化钾等还原剂的浓度为0.2mol/L~0.4mol/L。
在一些实施方案中,所述碳材料包括活性炭、碳纳米管、石墨烯等中的至少一种,但不限于此。
在一些较为具体的实施例中,所述铁盐包括氯化亚铁、硝酸亚铁、硫酸亚铁、九水合硝酸铁、氯化铁等中的至少一种,但不限于此。
进一步地,所述碳材料与铁盐的摩尔比为11:1~112:1。
进一步地,所述碳材料或零价铁改性碳材料中碳元素与有机磷中磷元素的摩尔比为3:1~7:1。
进一步地,所述含有铁盐的溶液中铁盐的浓度为0.1mol/L~1.8mol/L。
在一些较为具体的实施例中,所述有机磷包括苯基二氯化膦、二苯基膦、三苯基膦、二苯基对甲苯基膦和二苯基环己基膦等中的至少一种,但不限于此。
本申请实施例的另一个方面还提供了由前述方法制备的用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂。
本申请实施例的另一个方面还提供了前述的用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂于气固相反应连续生产1,1,1,3-四氯丙烷中的应用。
相应的,本申请实施例的另一个方面还提供了一种气固相反应连续生产1,1,1,3-四氯丙烷 的方法,其主要包括:将催化剂封装在气固相固定床反应器中,在一定压力和一定温度下持续通入四氯化碳和乙烯原料气,经催化低聚反应获得1,1,1,3-四氯丙烷产品。
在一些具体实施方式中,所述方法具体包括:
将所述用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂封装于气固相固定床反应装置中,形成催化剂床层;
将四氯化碳和乙烯反应原料气连续通入所述催化剂床层,将反应原料气进气压力提升至0.8~1.2MPa,加热催化剂床层的温度至80~120℃,经催化低聚反应获得1,1,1,3-四氯丙烷,并在固定床末端收集1,1,1,3-四氯丙烷产品。
进一步地,所述四氯化碳与乙烯的体积比为1:2~2:1。
综上所述,本申请的催化剂在碳材料载体上集成了活性组分零价铁和助组分磷酸酯官能团,摆脱了传统间歇釜式反应对液态催化助剂的依赖,实现了1,1,1,3-四氯丙烷在气固相固定床反应器上的连续生产。
为更好的说明本申请的目的、技术方案和优点,下面将结合若干较佳实施例对本申请的技术方案作更为详细的解释说明。以下所述的具体实施例仅用于进一步说明和解释本申请,并非是对本申请的限制;从本申请公开的内容联想到或导出的所有变形,均认为是本申请的保护范围。
实施例1
取50g活性炭与50g九水合硝酸铁混合,在氮气气氛下以8℃/min的升温速率升温至800℃焙烧3小时,降至室温得到零价铁改性活性炭,然后与100g三苯基膦混合,在氮气气氛下900℃焙烧3小时,得到零价铁和磷共改性活性炭催化剂,元素分析得出,该催化剂中铁的质量含量为3wt%,磷的质量含量为8wt%,零价铁的颗粒尺寸为2~100nm。利用高分辨电子透射显微技术观察催化剂的微观形貌图,可以看到嵌在石墨碳层中零价铁颗粒,尺寸为13nm(如图1所示)。
实施例2
取50g石墨烯与20g氯化铁混合,在氮气气氛下以10℃/min的升温速率升温至1000℃焙烧2小时,降至室温得到零价铁改性石墨烯,然后与110g二苯基对甲苯基膦混合,在氮气气氛下900℃焙烧3小时,得到零价铁和磷共改性石墨烯催化剂,元素分析得出,该催化剂中铁的质量含量为2wt%,磷的质量含量为4wt%。
实施例3
取50g碳纳米管与200g苯基二氯化膦混合,在氮气气氛下以6℃/min的升温速率升温至 1000℃焙烧1小时,得到磷改性碳纳米管,然后浸入含50g氯化亚铁的1升水溶液,盐酸调节pH<3,通入氮气,边搅拌边滴加含50g硼氢化钠的1升水溶液,然后搅拌4小时,过滤、洗涤、干燥,得到零价铁和磷共改性碳纳米管催化剂,元素分析得出,该催化剂中铁的质量含量为8wt%,磷的质量含量为5wt%。
实施例4
取50g活性炭与50g硝酸亚铁混合,在氮气气氛下以5℃/min的升温速率升温至600℃焙烧1小时,降至室温得到零价铁改性活性炭,然后与100g二苯基膦混合,在氮气气氛下900℃焙烧3小时,得到零价铁和磷共改性活性炭催化剂,元素分析得出,该催化剂中铁的质量含量为3wt%,磷的质量含量为7wt%。
实施例5
取50g石墨烯与20g氯化亚铁混合,在氮气气氛下以8℃/min的升温速率升温至1000℃焙烧2小时,降至室温得到零价铁改性石墨烯,然后与110g二苯基环己基膦混合,在氮气气氛下1000℃焙烧1小时,得到零价铁和磷共改性石墨烯催化剂,元素分析得出,该催化剂中铁的质量含量为2wt%,磷的质量含量为3wt%。
实施例6
取50g碳纳米管与200g苯基二氯化膦混合,在氮气气氛下以5℃/min的升温速率升温至600℃焙烧4小时,得到磷改性碳纳米管,然后浸入含50g硝酸亚铁的1升水溶液,盐酸调节pH<3,通入氮气,边搅拌边滴加含50g硼氢化钾的1升水溶液,然后搅拌6小时,过滤、洗涤、干燥,得到零价铁和磷共改性碳纳米管催化剂,元素分析得出,该催化剂中铁的质量含量为8wt%,磷的质量含量为6wt%。
实施例7
取50g石墨烯与20g硫酸亚铁混合,在氮气气氛下以10℃/min的升温速率升温至1000℃焙烧2小时,降至室温得到零价铁改性石墨烯,然后与110g二苯基对甲苯基膦混合,在氮气气氛下600℃焙烧4小时,得到零价铁和磷共改性石墨烯催化剂,元素分析得出,该催化剂中铁的质量含量为2wt%,磷的质量含量为5wt%。
实施例8
本实施例中气固相固定床反应器采用管径为10毫米、长度0.5米的电加热管式反应器,反应过程为:
(1)将20g实施例1所制备的零价铁和磷共改性活性炭催化剂装入反应管;
(2)将四氯化碳85℃预热后与乙烯同时连续通入反应管,四氯化碳与乙烯体积比为1:1, 总流量为20mL/min;
(3)进气压力调节至0.9MPa;
(4)加热催化剂床层温度至100℃;
(5)在固定床末端收集1,1,1,3-四氯丙烷粗品;
对本实施例所获产品进行气相色谱分析,四氯化碳的转化率为70%,1,1,1,3-四氯丙烷的选择性为99%。
实施例9
本实施例中气固相固定床反应器采用管径为10毫米、长度0.5米的电加热管式反应器,反应过程为:
(1)将20g实施例1所制备的零价铁和磷共改性活性炭催化剂装入反应管;
(2)将四氯化碳85℃预热后与乙烯同时连续通入反应管,四氯化碳与乙烯体积比为1:2,总流量为20mL/min;
(3)进气压力调节至0.8MPa;
(4)加热催化剂床层温度至100℃;
(5)在固定床末端收集1,1,1,3-四氯丙烷粗品;
对本实施例所获产品进行气相色谱分析,四氯化碳的转化率为68%,1,1,1,3-四氯丙烷的选择性为98.9%。
实施例10
本实施例中气固相固定床反应器采用管径为10毫米、长度0.5米的电加热管式反应器,反应过程为:
(1)将20g实施例1所制备的零价铁和磷共改性活性炭催化剂装入反应管;
(2)将四氯化碳85℃预热后与乙烯同时连续通入反应管,四氯化碳与乙烯体积比为2:1,总流量为20mL/min;
(3)进气压力调节至1.2MPa;
(4)加热催化剂床层温度至100℃;
(5)在固定床末端收集1,1,1,3-四氯丙烷粗品;
对本实施例所获产品进行气相色谱分析,四氯化碳的转化率为72%,1,1,1,3-四氯丙烷的选择性为99.3%。
实施例11
本实施例中气固相固定床反应器采用管径为10毫米、长度0.5米的电加热管式反应器, 反应过程为:
(1)将20g实施例1所制备的零价铁和磷共改性活性炭催化剂装入反应管;
(2)将四氯化碳85℃预热后与乙烯同时连续通入反应管,四氯化碳与乙烯体积比为1:1,总流量为20mL/min;
(3)进气压力调节至0.9MPa;
(4)加热催化剂床层温度至80℃;
(5)在固定床末端收集1,1,1,3-四氯丙烷粗品;
对本实施例所获产品进行气相色谱分析,四氯化碳的转化率为67%,1,1,1,3-四氯丙烷的选择性为98.4%。
实施例12
本实施例中气固相固定床反应器采用管径为10毫米、长度0.5米的电加热管式反应器,反应过程为:
(1)将20g实施例1所制备的零价铁和磷共改性活性炭催化剂装入反应管;
(2)将四氯化碳85℃预热后与乙烯同时连续通入反应管,四氯化碳与乙烯体积比为1:1,总流量为20mL/min;
(3)进气压力调节至0.9MPa;
(4)加热催化剂床层温度至120℃;
(5)在固定床末端收集1,1,1,3-四氯丙烷粗品;
对本实施例所获产品进行气相色谱分析,四氯化碳的转化率为71%,1,1,1,3-四氯丙烷的选择性为98.8%。
实施例13
利用实施例8的固定床反应器,反应过程为:
(1)将20g实施例3所制备的零价铁和磷共改性碳纳米管催化剂装入反应管;
(2)将四氯化碳85℃预热后与乙烯同时连续通入反应管,四氯化碳与乙烯体积比为1:1,总流量为20mL/min;
(3)进气压力调节至1MPa;
(4)加热催化剂床层温度至110℃;
(5)在固定床末端收集1,1,1,3-四氯丙烷粗品;
对本实施例所获产品进行气相色谱分析,四氯化碳的转化率为45%,1,1,1,3-四氯丙烷的选择性为97%。
实施例14
本实施例利用实施例8的固定床反应器,反应过程为:
(1)将20g实施例4所制备的零价铁和磷共改性活性炭催化剂装入反应管;
(2)将四氯化碳85℃预热后与乙烯同时连续通入反应管,四氯化碳与乙烯体积比为1:2,总流量为20mL/min;
(3)进气压力调节至0.8MPa;
(4)加热催化剂床层温度至90℃;
(5)在固定床末端收集1,1,1,3-四氯丙烷粗品;
对本实施例所获产品进行气相色谱分析,四氯化碳的转化率为65%,1,1,1,3-四氯丙烷的选择性为96%。
实施例15
本实施例利用实施例8的固定床反应器,反应过程为:
(1)将20g实施例6所制备的零价铁和磷共改性碳纳米管催化剂装入反应管;
(2)将四氯化碳85℃预热后与乙烯同时连续通入反应管,四氯化碳与乙烯体积比为1:1,总流量为20mL/min;
(3)进气压力调节至1.2MPa;
(4)加热催化剂床层温度至120℃;
(5)在固定床末端收集1,1,1,3-四氯丙烷粗品;
对本实施例所获产品进行气相色谱分析,四氯化碳的转化率为52%,1,1,1,3-四氯丙烷的选择性为98%。
实施例16
本实施例利用实施例8的固定床反应器,反应过程为:
(1)将20g实施例6所制备的零价铁和磷共改性碳纳米管催化剂装入反应管;
(2)将四氯化碳85℃预热后与乙烯同时连续通入反应管,四氯化碳与乙烯体积比为2:1,总流量为20mL/min;
(3)进气压力调节至1.2MPa;
(4)加热催化剂床层温度至120℃;
(5)在固定床末端收集1,1,1,3-四氯丙烷粗品;
对本实施例所获产品进行气相色谱分析,四氯化碳的转化率为52%,1,1,1,3-四氯丙烷的选择性为98%。
此外,本案发明人还参照前述实施例,以本说明书述及的其它原料、工艺操作、工艺条件进行了试验,并均获得了较为理想的结果。
对照例1
本对照例与实施例1相比,不同之处在于:未加入九水合硝酸铁,仅制得磷改性活性炭催化剂。
将本对照例制得的磷改性活性炭催化剂用于实施例8中,四氯化碳的转化率为27%,1,1,1,3-四氯丙烷的选择性为41%。
对照例2
本对照例与实施例1相比,不同之处在于:未加入三苯基膦,仅制得零价铁改性活性炭催化剂。
将本对照例制得的零价铁改性活性炭催化剂用于实施例8中,四氯化碳的转化率为54%,1,1,1,3-四氯丙烷的选择性为67%。
对照例3
本对照例与实施例3相比,不同之处在于:未加入氯化亚铁,仅制得磷改性碳纳米管催化剂。
将本对照例制得的磷改性碳纳米管催化剂用于实施例13中,四氯化碳的转化率为25%,1,1,1,3-四氯丙烷的选择性为56%。
对照例4
本对照例与实施例3相比,不同之处在于:未加入苯基二氯化膦,仅制得零价铁改性碳纳米管催化剂。
将本对照例制得的零价铁改性碳纳米管催化剂用于实施例13中,四氯化碳的转化率为37%,1,1,1,3-四氯丙烷的选择性为60%。
以上所述,仅是本申请的几个实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (10)
- 一种用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂,其特征在于,包括零价铁和磷共改性碳材料,所述零价铁和磷共改性碳材料包括作为载体的碳材料、负载于所述载体上的作为活性组分的零价铁,以及形成于所述碳材料表面的磷酸酯官能团。
- 根据权利要求1所述的用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂,其特征在于:所述催化剂中铁的含量为1~10wt%,磷的含量为1~10wt%。
- 根据权利要求1所述的用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂,其特征在于:所述催化剂中零价铁的颗粒尺寸为2~100nm。
- 根据权利要求1所述的用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂,其特征在于:所述碳材料包括活性炭、碳纳米管、石墨烯中的至少一种。
- 如权利要求1-4中任一项所述用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂的制备方法,其特征在于,包括:以铁盐和有机磷对碳材料进行共同改性,获得用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂。
- 根据权利要求5所述的制备方法,其特征在于,具体包括:在惰性气氛中,对包含碳材料与铁盐的第一混合物加热,并以5℃/min~10℃/min的升温速率升温至600~1000℃进行焙烧1~4h,得到零价铁改性碳材料;以及,在惰性气氛中,对包含所述零价铁改性碳材料与有机磷的第二混合物加热,升温至600~1000℃进行焙烧1~4h,获得所述用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂。
- 根据权利要求5所述的制备方法,其特征在于,具体包括:在惰性气氛中,对包含碳材料与有机磷的第三混合物加热,并以5℃/min~10℃/min的升温速率升温至600~1000℃进行焙烧1~4h,得到磷改性碳材料;以及,将所述磷改性碳材料与含有铁盐的溶液充分接触4~6h,并在惰性气氛中加入还原剂,至少将铁离子还原成零价铁,获得所述用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂;优选的,所述还原剂包括硼氢化钠和/或硼氢化钾。
- 根据权利要求6或7所述的制备方法,其特征在于:所述碳材料与铁盐的摩尔比为11:1~112:1;和/或,所述碳材料或零价铁改性碳材料中碳元素与有机磷中磷元素的摩尔比为3:1~7:1;和/或,所述碳材料包括活性炭、碳纳米管、石墨烯中的至少一种;和/或,所述铁盐包括氯化亚铁、硝酸亚铁、硫酸亚铁、硝酸铁、氯化铁中的至少一种;和/或,所述含有铁盐的溶液中铁盐的浓度为0.1mol/L~1.8mol/L;和/或,所述有机磷包括苯基二氯化膦、二苯基膦、三苯基膦、二苯基对甲苯基膦和二苯基环己基膦中的至少一种。
- 权利要求1-4中任一项所述用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂于气固相反应连续生产1,1,1,3-四氯丙烷中的应用。
- 一种气固相反应连续生产1,1,1,3-四氯丙烷的方法,其特征在于包括:将权利要求1-4中任一项所述用于气固相反应连续生产1,1,1,3-四氯丙烷的催化剂封装于气固相固定床反应装置中,形成催化剂床层;将四氯化碳和乙烯反应原料气连续通入所述催化剂床层,将反应原料气进气压力提升至0.8~1.2MPa,加热催化剂床层的温度至80~120℃,经催化低聚反应获得1,1,1,3-四氯丙烷;优选的,所述四氯化碳与乙烯的体积比为1:2~2:1。
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WO2016128763A1 (en) * | 2015-02-13 | 2016-08-18 | Mexichem Fluor S.A. De C.V. | Production of 1,1,1 -trifluoro-2,3-dichloropropane (243bd) by catalytic chlorination of 3,3,3-trifluoropropene (1243zf) |
WO2018022500A1 (en) * | 2016-07-27 | 2018-02-01 | The Chemours Company Fc, Llc | Process for producing halogenated olefins |
US20210009490A1 (en) * | 2018-04-03 | 2021-01-14 | Blue Cube Ip Llc | Method for recycling catalyst in the production of chlorinated alkanes |
WO2020133554A1 (zh) * | 2018-12-29 | 2020-07-02 | 吕杨 | 一种2,3,3,3-四氟丙烯的连续制备方法 |
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CN111056913A (zh) * | 2019-12-09 | 2020-04-24 | 宁波巨化化工科技有限公司 | 一种1,1,1,3-四氯丙烷的连续生产方法 |
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