WO2022218204A1 - 制备2,3,3,3-四氟丙烯的方法 - Google Patents

制备2,3,3,3-四氟丙烯的方法 Download PDF

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WO2022218204A1
WO2022218204A1 PCT/CN2022/085539 CN2022085539W WO2022218204A1 WO 2022218204 A1 WO2022218204 A1 WO 2022218204A1 CN 2022085539 W CN2022085539 W CN 2022085539W WO 2022218204 A1 WO2022218204 A1 WO 2022218204A1
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tetrafluoropropene
chloro
catalyst
telomerization
reaction
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PCT/CN2022/085539
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English (en)
French (fr)
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刘敏洋
于万金
林胜达
肖新宝
罗霞
刘武灿
张建君
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浙江省化工研究院有限公司
中化蓝天集团有限公司
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Priority claimed from CN202110404625.4A external-priority patent/CN115215724B/zh
Priority claimed from CN202110404614.6A external-priority patent/CN115215722B/zh
Priority claimed from CN202110404622.0A external-priority patent/CN115215723B/zh
Application filed by 浙江省化工研究院有限公司, 中化蓝天集团有限公司 filed Critical 浙江省化工研究院有限公司
Priority to EP22787430.2A priority Critical patent/EP4324811A1/en
Priority to JP2023563266A priority patent/JP2024515341A/ja
Publication of WO2022218204A1 publication Critical patent/WO2022218204A1/zh

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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
    • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/12—Fluorides
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons

Definitions

  • the invention relates to the preparation of 2,3,3,3-tetrafluoropropene, in particular to a kind of preparation of 2,3,3,3-tetrafluoropropene using trifluoroethylene as a raw material, and preparing through two-step reactions of telomerization and removal (dehydrochlorination, dehydrofluorination, dehydrogenation, etc.).
  • a method for 2,3,3,3-tetrafluoropropene is a method for 2,3,3,3-tetrafluoropropene.
  • the ODP of 2,3,3,3-tetrafluoropropene is zero, the GWP value is less than 1, the lifetime climate performance (LCCP) is lower than that of the traditional refrigerant HFC-134a, and the system refrigeration performance is better than that of HFC-134a.
  • LCCP lifetime climate performance
  • HFC-134a it is considered to be the most potential automotive refrigerant alternative and has been accepted by many mainstream automobile manufacturers.
  • preparation routes of 2,3,3,3-tetrafluoropropene include the following:
  • the preparation of 2,3,3,3-tetrafluoropropene from hexafluoropropene is divided into four steps: (1) Hydrogenation of hexafluoropropene and hydrogen to prepare 1,1,1,2,3,3- Hexafluoropropane (HFC-236ea); (2) Dehydrofluorination of HFC-236ea under the action of a catalyst to prepare 1,1,1,2,3-pentafluoropropene (HFO-1225ye); (3) HFO-1225ye Hydrogenation with hydrogen to prepare 1,1,1,2,3-pentafluoropropane (HFC-245eb); (4) HFC-245eb undergoes dehydrofluorination under the action of a catalyst to prepare 2,3,3,3 - Tetrafluoropropylene.
  • Chinese patent CN103449963B discloses a method for synthesizing 2,3,3,3-tetrafluoropropene by using hexafluoropropene as a raw material in a multi-step continuous reaction, which can realize HFC-236ea, HFO-1225ye
  • the continuous production of intermediate products such as HFC-245eb and HFC-245eb is directly carried out without separation.
  • the intermediate products are not separated and purified, which means that impurities will continue to accumulate and increase in the reaction materials, which will ultimately affect the yield of the target product 2,3,3,3-tetrafluoropropene, and will also increase the 2,3,3,3 - Difficulty in rectifying separation of tetrafluoropropylene products.
  • Patent CN101395108B discloses a method for preparing 2,3,3,3-tetrafluoropropene by using 1,1,2,3-tetrachloropropene as raw material through three-step reaction, the reaction steps include: (1) 1,1,2, Gas-phase fluorination of 3-tetrachloropropene and HF to prepare 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) with selectivity of 80-96%, when using Cr 2 O 3 and FeCl 3 / When AC catalyst is used, the selectivity reaches 96% and the conversion rate is only 20%; (2) HCFO-1233xf undergoes addition reaction with HF to generate 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) , the catalyst is SbCl 5 ; (3) HCFC-244bb is prepared by gas-phase dehydrochlorination reaction under the action of activated carbon catalyst to obtain the target product 2,3,3,3-tetrafluoro
  • US Patent US20090099396 discloses a method for preparing 2,3,3,3-tetrafluoropropene by two-step reaction using 1,1,2,3-tetrachloropropene as raw material.
  • the reaction steps include: (1) 1,1,2 ,3-Tetrachloropropene and HF were subjected to liquid-phase fluorination to prepare 1,1,1,2,3-pentafluoropropane (HFC-245eb), the catalyst was SbCl 5 , and the TCP conversion rate could reach 100%, but HFC- The selectivity of 245eb is only 53-59%, and many by-products are generated; (2) HFC-245eb undergoes liquid-phase dehydrofluorination reaction under the action of alkali metal hydroxide to generate the target product 2,3,3,3-tetra Fluoropropene. This process has the advantages of less reaction steps and less equipment investment, but the selectivity of the intermediate product HFC-245eb is low, and the separation of by-
  • Patent CN101979364A discloses a method for preparing 2,3,3,3-tetrafluoropropene by using 3,3,3-trifluoropropene as raw material.
  • the reaction is carried out in four steps: (1) 3,3,3-trifluoropropene and Chlorine undergoes an addition reaction under photocatalysis to generate 1,2-dichloro-3,3,3-trifluoropropane, the conversion rate of raw materials reaches 95%, and the selectivity reaches 90%; (2) 1,2-dichloro- 3,3,3-trifluoropropane undergoes liquid-phase dehydrochlorination under the action of alkali metal hydroxide to produce 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) with good conversion and selectivity.
  • HCFC-244bb 2-chloro-1,1,1,2-tetrafluoropropane
  • the catalysts are SnCl 4 , TiCl 4 , fluorosulfonic acid
  • the conversion rate of raw materials reaches 95%, and the selectivity is 90-96%
  • the selectivity is 90 to 95%.
  • the process has a long synthesis route, the first-step chlorination reaction requires higher equipment, the two-step dehalogenation reaction produces more waste liquid, the total reaction yield is low, and the synthesis cost is high.
  • the degree of hydrogenation reduction reaction in this method is difficult to control, and it is easy to generate 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd), 1-chloro-2,3,3,3-tetrafluoropropane (HCFC-244eb) and 2,3,3,3-tetrafluoropropane (HFC-254eb) and other intermediates or over-reduced products, the product selectivity is low, the post-treatment operation is complicated, and the by-product HFC-254eb is treated by alkali washing.
  • HCFO-1224yd 1-chloro-2,3,3,3-tetrafluoropropane
  • HFC-244eb 1-chloro-2,3,3,3-tetrafluoropropane
  • HFC-254eb 2,3,3,3-tetrafluoropropane
  • HFO-1243zf 3,3,3-trifluoropropene
  • HFO-1234yf 3,3,3-trifluoropropene
  • the present invention proposes a two-step method for preparing 2,3,3,3-tetrafluoropropene with simple process, mild reaction conditions, high product selectivity and suitable for industrial production.
  • the present invention provides a two-step method for preparing 2,3,3,3-tetrafluoropropene, the method comprising:
  • Telomerization step 3-chloro-1,1,1,2-tetrafluoropropane is prepared by pressure telomerization reaction between monofluoro-chloromethane and trifluoroethylene under the action of a telomerization catalyst;
  • the telomerization catalyst It is a Lewis acid catalyst or a mixed catalyst of Lewis acid catalyst and dichloromethane;
  • Dehydrochlorination step 3-chloro-1,1,1,2-tetrafluoropropane is dehydrochlorinated under the catalysis of activated carbon to obtain 2,3,3,3-tetrafluoropropene.
  • reaction equation for preparing 2,3,3,3-tetrafluoropropene by the two-step method of the present invention is as follows:
  • the Lewis acid catalyst of the present invention is selected from at least one halide of Al, Sb, Ti, Zr and Hf.
  • the Lewis acid catalyst is selected from at least one of ZrCl 4 , HfCl 4 , TiCl 4 , AlCl 3 , AlF 3 and SbF 5 . More preferably, the Lewis acid catalyst is ZrCl 4 or HfCl 4 .
  • the telomerization reaction of the raw material monofluoro-chloromethane and trifluoroethylene of the present invention is carried out under pressure conditions, and the raw material monofluoro-chloromethane is partially or completely liquid under the reaction conditions.
  • the 3-chloro-1,1,1,2-tetrafluoropropane produced by the telomerization reaction is liquid, therefore, the A1 step of the present invention preferably adopts a solvent-free reaction to reduce the separation steps of intermediates and/or products.
  • the telomerization catalyst of the present invention can be a single Lewis acid catalyst, or a mixed catalyst of Lewis acid catalyst and dichloromethane.
  • the Lewis acid catalyst dissociates and activates monofluorochloromethane to form F - , CH 2 Cl + , Cl - , CH 2 F + plasma; dichloromethane inhibits the dissociation of F - , CH 2 Cl + , Cl - , CH 2 F + plasma recombination, thereby ensuring the directional telomerization reaction of F - , CH 2 Cl + ions and trifluoroethylene, and the telomerization product CF 3 CHFCH 2 Cl is obtained with high selectivity.
  • the molar ratio of monofluorochloromethane to trifluoroethylene is 1:0.1 to 1:10; more preferably, the molar ratio of monofluorochloromethane to trifluoroethylene is 1 :1 to 1:5.
  • the dosage of the Lewis acid catalyst is 0.01-50 wt % of the mass of monofluoro-chloromethane; more preferably, the dosage of the Lewis acid catalyst is 0.1-10 wt % of the mass of monofluoro-chloromethane.
  • the molar ratio of dichloromethane and monofluoro-chloromethane is 1:0.01 to 1:10; more preferably, dichloromethane and monofluoro-chloromethane The molar ratio is 1:0.1 ⁇ 1:5.
  • the telomerization step of the present invention is carried out under pressurized conditions, the reaction temperature is -30 to 100° C., the reaction pressure is 0.5 to 5.0 MPa, and the reaction time is 1 to 50 h. More preferably, the reaction temperature is 0-50° C., the reaction pressure is 0.8-3.0 MPa, and the reaction time is 5-10 h.
  • the dehydrochlorination step of the present invention is carried out under the catalysis of activated carbon, and the activated carbon is selected from nutshell activated carbon, coal activated carbon or wood activated carbon, preferably nutshell activated carbon.
  • the reaction temperature of the dehydrochlorination step is 200-500°C, preferably the reaction temperature is 300-350°C.
  • the 3-chloro-1,1,1,2-tetrafluoropropane obtained through the telomerization step is separated by rectification used in the dehydrochlorination step.
  • the present invention provides a co-production preparation method of 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene, the co-production preparation method comprising:
  • Telomerization step 3-chloro-1,1,1,2-tetrafluoropropane is prepared by pressure telomerization reaction between monofluoro-chloromethane and trifluoroethylene under the action of a telomerization catalyst;
  • the telomerization catalyst It is a Lewis acid catalyst or a mixed catalyst of Lewis acid catalyst and dichloromethane;
  • reaction equation of the co-production preparation process of the present invention is as follows:
  • the Lewis acid catalyst of the present invention is selected from at least one halide of Al, Sb, Ti, Zr and Hf.
  • the Lewis acid catalyst is selected from at least one of ZrCl 4 , HfCl 4 , TiCl 4 , AlF 3 , AlCl 3 , and SbF 5 . More preferably, the Lewis acid catalyst is ZrCl 4 or HfCl 4 .
  • the telomerization reaction of the raw material monofluoro-chloromethane and trifluoroethylene of the present invention is carried out under pressure conditions, and the raw material monofluoro-chloromethane is partially or completely liquid under the reaction conditions.
  • the 3-chloro-1,1,1,2-tetrafluoropropane produced by the telomerization reaction is liquid, therefore, the A1 step of the present invention preferably adopts a solvent-free reaction to reduce the separation steps of intermediates and/or products.
  • the telomerization catalyst of the present invention can be a single Lewis acid catalyst, or a mixed catalyst of Lewis acid catalyst and dichloromethane.
  • the Lewis acid catalyst dissociates and activates monofluorochloromethane to form F - , CH 2 Cl + , Cl - , CH 2 F + plasma; dichloromethane inhibits the dissociation of F - , CH 2 Cl + , Cl - , CH 2 F + plasma recombination, thereby ensuring the directional telomerization reaction of F - , CH 2 Cl + ions and trifluoroethylene, and the telomerization product CF 3 CHFCH 2 Cl is obtained with high selectivity.
  • the molar ratio of monofluorochloromethane to trifluoroethylene is 1:0.1 to 1:10; more preferably, the molar ratio of monofluorochloromethane to trifluoroethylene is 1 :1 to 1:5.
  • the dosage of the Lewis acid catalyst is 0.01-50 wt % of the mass of monofluoro-chloromethane; more preferably, the dosage of the Lewis acid catalyst is 0.1-10 wt % of the mass of monofluoro-chloromethane.
  • the molar ratio of dichloromethane and monofluoro-chloromethane is 1:0.01 to 1:10; more preferably, dichloromethane and monofluoro-chloromethane The molar ratio is 1:0.1 ⁇ 1:5.
  • the telomerization step of the present invention is carried out under pressurized conditions, the reaction temperature is -30 to 100° C., the reaction pressure is 0.5 to 5.0 MPa, and the reaction time is 1 to 50 h. More preferably, the reaction temperature is 0-50° C., the reaction pressure is 0.8-3.0 MPa, and the reaction time is 5-10 h.
  • the activated carbon-supported precious metal catalyst can be prepared by conventional methods, as long as the activated carbon-supported precious metal catalyst of the present invention can be obtained.
  • the present invention adopts the impregnation method to prepare, comprises the following steps:
  • activated carbon is dried at 90 ⁇ 120°C for more than 12h;
  • the pretreated activated carbon is impregnated with a soluble salt solution of Pd or Pt under vacuum or normal pressure conditions;
  • drying temperature is 90-120°C, and the drying time is more than 12h;
  • the activated carbon after the drying treatment is subjected to reduction treatment with a hydrogen-nitrogen mixture to obtain the activated carbon-supported noble metal catalyst; the volume ratio of hydrogen in the hydrogen-nitrogen mixture is 5-50%, and the reduction temperature is 150-300°C.
  • the loadings of Pd and Pt are 0.1-5.0 wt%, preferably 0.5-1.5 wt%.
  • the removal step of the present invention is a gas-solid phase reaction. After 3-chloro-1,1,1,2-tetrafluoropropane is vaporized, nitrogen is loaded into the catalyst bed for removal reaction. The volume of the material in the removal reaction is carried out. The space velocity is 50 ⁇ 300h -1 , the volume ratio of N 2 /3-chloro-1,1,1,2-tetrafluoropropane is (0.5 ⁇ 3.0):1, preferably the volume ratio is (1.5 ⁇ 2.0):1 .
  • the reaction temperature of the removing step of the present invention is 300-600°C, preferably the reaction temperature is 400-450°C.
  • the product distribution of the A2 removal step can be adjusted within a certain range by adjusting the preparation process of the activated carbon-supported noble metal catalyst, the noble metal loading in the catalyst, and the reaction conditions.
  • 30-90% of 2,3,3,3-tetrafluoropropene and 10-50% of 1-chloro-2,3,3,3-tetrafluoropropene are obtained through the A2 removal step;
  • the product of the removal step contains 50-60% of 2,3,3,3-tetrafluoropropene and 30-50% of 1-chloro-2,3,3,3-tetrafluoropropene, and the rest are by-products, Such as 1-chloro-3,3,3-trifluoropropene.
  • the 3-chloro-1,1,1,2-tetrafluoropropane obtained by the telomerization step is used for the removal step after being separated by rectification.
  • the present invention also provides a co-production preparation method of 2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene, the co-production preparation method comprising:
  • Telomerization step 3-chloro-1,1,1,2-tetrafluoropropane is prepared by pressure telomerization reaction between monofluoro-chloromethane and trifluoroethylene under the action of a telomerization catalyst;
  • the telomerization catalyst It is a Lewis acid catalyst or a mixed catalyst of Lewis acid catalyst and dichloromethane;
  • Dehydrohalogenation step 3-chloro-1,1,1,2-tetrafluoropropane undergoes simultaneous dehydrochlorination and dehydrofluorination under the action of a composite dehalogenation catalyst to obtain 2,3,3,3-tetrafluoropropane Fluoropropene and 1-chloro-3,3,3-trifluoropropene, the composite dehalogenation catalyst is prepared from at least one oxide or fluoride of Al, Mg or Cr and activated carbon powder.
  • the oxide or fluoride of at least one of the Al, Mg or Cr is selected from at least one of Al 2 O 3 , AlF 3 , MgF 2 and Cr 2 O 3 ;
  • the activated carbon powder is selected from nutshell activated carbon , coal-based activated carbon or wood-based activated carbon.
  • reaction equation of the co-production preparation process of the present invention is as follows:
  • the Lewis acid catalyst of the present invention is selected from at least one halide of Al, Sb, Ti, Zr and Hf.
  • the Lewis acid catalyst is selected from at least one of ZrCl 4 , HfCl 4 , TiCl 4 , AlF 3 , AlCl 3 , and SbF 5 . More preferably, the Lewis acid catalyst is ZrCl 4 or HfCl 4 .
  • the telomerization reaction of the raw material monofluoro-chloromethane and trifluoroethylene of the present invention is carried out under pressure conditions, and the raw material monofluoro-chloromethane is partially or completely liquid under the reaction conditions.
  • the 3-chloro-1,1,1,2-tetrafluoropropane produced by the telomerization reaction is liquid, therefore, the A1 step of the present invention preferably adopts a solvent-free reaction to reduce the separation steps of intermediates and/or products.
  • the telomerization catalyst of the present invention can be a single Lewis acid catalyst, or a mixed catalyst of Lewis acid catalyst and dichloromethane.
  • the Lewis acid catalyst dissociates and activates monofluorochloromethane to form F - , CH 2 Cl + , Cl - , CH 2 F + plasma; dichloromethane inhibits the dissociation of F - , CH 2 Cl + , Cl - , CH 2 F + plasma recombination, thereby ensuring the directional telomerization reaction of F - , CH 2 Cl + ions and trifluoroethylene, and the telomerization product CF 3 CHFCH 2 Cl is obtained with high selectivity.
  • the molar ratio of monofluorochloromethane to trifluoroethylene is 1:0.1 to 1:10; more preferably, the molar ratio of monofluorochloromethane to trifluoroethylene is 1 :1 to 1:5.
  • the dosage of the Lewis acid catalyst is 0.01-50 wt % of the mass of monofluoro-chloromethane; more preferably, the dosage of the Lewis acid catalyst is 0.1-10 wt % of the mass of monofluoro-chloromethane.
  • the molar ratio of dichloromethane and monofluoro-chloromethane is 1:0.01 to 1:10; more preferably, dichloromethane and monofluoro-chloromethane The molar ratio is 1:0.1 ⁇ 1:5.
  • the telomerization step of the present invention is carried out under pressurized conditions, the reaction temperature is -30 to 100° C., the reaction pressure is 0.5 to 5.0 MPa, and the reaction time is 1 to 50 h. More preferably, the reaction temperature is 0-50° C., the reaction pressure is 0.8-3.0 MPa, and the reaction time is 5-10 h.
  • the dehydrohalogenation step of the present invention under the action of a composite dehalogenation catalyst, when 3-chloro-1,1,1,2-tetrafluoropropane is adsorbed on the activated carbon, a dehydrochlorination reaction occurs; - When 1,1,1,2-tetrafluoropropane is adsorbed on Al 2 O 3 and/or AlF 3 and/or MgF 2 and/or Cr 2 O 3 , a dehydrofluorination reaction occurs, thereby simultaneously obtaining 2,3, 3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene.
  • the composite dehalogenation catalyst of the present invention can be prepared by conventional methods, as long as the composite dehalogenation catalyst of the present invention can be obtained.
  • adopt co-mixing method to prepare comprise the steps:
  • the B3 molding step can be made into a column shape, a sheet shape, etc., and the specific shape is not limited.
  • the drying treatment is generally carried out at 90° C. to 120° C. for more than 12 hours.
  • the content of Al 2 O 3 when Al 2 O 3 is used for blending with activated carbon powder, the content of Al 2 O 3 is 1.0-20 wt % of the total catalyst; when AlF 3 is used for blending with activated carbon powder, The content of AlF 3 is 1.0-20 wt % of the total catalyst; when MgF 2 is used to blend with activated carbon, the content of MgF 2 is 1.0 to 20 wt % of the total catalyst; when Cr 2 O 3 is used to blend with activated carbon, The content of Cr 2 O 3 is 1.0-20 wt % of the total amount of the catalyst.
  • the dehydrohalogenation step of the present invention is a gas-solid phase reaction. After the 3-chloro-1,1,1,2-tetrafluoropropane is vaporized, nitrogen is loaded into the catalyst bed for dehydrohalogenation reaction.
  • the volume of the raw materials for the dehydrohalogenation reaction is The space velocity is 50 ⁇ 300h -1 , the volume ratio of N 2 /3-chloro-1,1,1,2-tetrafluoropropane is (0.5 ⁇ 3.0):1, preferably the volume ratio is (1.5 ⁇ 2.0):1 .
  • the reaction temperature of the dehydrohalogenation step of the present invention is 300-500°C, preferably the reaction temperature is 350-450°C.
  • the product distribution of the dehydrohalogenation step can be adjusted within a certain range.
  • 10-50% of 2,3,3,3-tetrafluoropropene and 10-70% of 1-chloro-3,3,3-trifluoropropene are obtained through a dehydrohalogenation step; preferably, the elimination
  • the step product contains 20-40% of 2,3,3,3-tetrafluoropropene and 30-60% of 1-chloro-3,3,3-trifluoropropene, and the rest are unknown by-products.
  • the 3-chloro-1,1,1,2-tetrafluoropropane obtained by the telomerization step is used for the dehydrohalogenation step after being separated by rectification.
  • the present invention has the following beneficial effects:
  • the method adopts monofluoro-chloromethane and trifluoroethylene as raw materials, and under the action of Lewis acid catalyst or Lewis acid catalyst and dichloromethane mixed catalyst, 3-chloro-1,1,1,2 is obtained by pressure telomerization. - Tetrafluoropropane.
  • 3-Chloro-1,1,1,2-tetrafluoropropane was prepared under the catalysis of activated carbon to obtain 2,3,3,3-tetrafluoropropene; or, 3-chloro-1,1,1,2-tetrafluoropropane Propane undergoes simultaneous dehydrochlorination and dehydrogenation reactions under the catalysis of activated carbon supported noble metal catalysts, and co-produces 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene Propylene; or, under the catalysis of composite dehalogenation catalyst, 3-chloro-1,1,1,2-tetrafluoropropane simultaneously undergoes dehydrochlorination and dehydrofluorination, and co-produces 2,3,3, 3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene.
  • the first aspect of the embodiments of the present invention provides a method for preparing 2,3,3,3-tetrafluoropropene by a two-step method.
  • the present embodiment proposes a two-step method for preparing 2,3,3,3-tetrafluoropropene, including a telomerization step and a dehydrochlorination step, as follows:
  • reaction temperature 10°C
  • stirring rate 300rpm
  • initial reaction pressure 0.9MPa
  • pressure to gradually decrease as the reaction proceeds
  • reaction time 10h
  • the unreacted gas-phase raw materials and the separated Lewis acid catalyst can be returned to the telomerization step for reuse.
  • the gas phase and liquid phase materials were analyzed by gas chromatography, the conversion rate of monofluoro-chloromethane was 76.5%, the selectivity of 3-chloro-1,1,1,2-tetrafluoropropane was 81.2%, and the main by-product was 1-chloro- 1,1,2,3-Tetrafluoropropane with 15.3% selectivity and small amounts of other by-products.
  • a reaction tube made of Inconel alloy with an inner diameter of 19 mm and a length of 800 mm was used as the fixed bed reactor, and coconut shell-type activated carbon with a volume of 20 mL and a particle size of 10 to 20 meshes was filled into the middle of the fixed bed reactor, and the reaction was connected.
  • the pipeline was purged with nitrogen, and the nitrogen flow was 100 mL/min;
  • This example proposes a method for preparing 2,3,3,3-tetrafluoropropene.
  • the operation is the same as that in Example 1.1, except that: in the telomerization step, ZrCl 4 is used instead of HfCl 4 , and the amount is 4.0 g;
  • the amount of fluoro-chloromethane was increased to 39.7g (0.58mol), the amount of trifluoroethylene was increased to 71.3g (0.87mol), and other conditions remained unchanged.
  • the gas phase and liquid phase materials in the telomerization step were analyzed by gas chromatography.
  • the conversion rate of monofluorochloromethane was 99.0%
  • the selectivity of 3-chloro-1,1,1,2-tetrafluoropropane was 89.9%
  • the main by-products were: 1-Chloro-1,1,2,3-tetrafluoropropane with 5.3% selectivity and small amounts of other by-products.
  • This example proposes a method for preparing 2,3,3,3-tetrafluoropropene.
  • the operation is the same as that in Example 1.2, except that in the telomerization step, dichloromethane is not used, and the amount of trifluoroethylene is increased to 95.1 g (1.16 mol), while the reaction temperature was increased to 30 °C, the initial reaction pressure was increased to 1.5 MPa, and other conditions remained unchanged.
  • the gas phase and liquid phase materials in the telomerization step were analyzed by gas chromatography.
  • the conversion rate of monofluorochloromethane was 99.5%
  • the selectivity of 3-chloro-1,1,1,2-tetrafluoropropane was 88.1%
  • the main by-products were: 1-Chloro-1,1,2,3-tetrafluoropropane with 4.1% selectivity and small amounts of other by-products.
  • This example proposes a preparation method of 2,3,3,3-tetrafluoropropene, the operation is the same as that of Example 1.2, the only difference is: in the telomerization step, AlCl 3 is used instead of ZrCl 4 , and the amount is unchanged, which is also 4.0g; at the same time, dichloromethane was not used, and the amount of trifluoroethylene was reduced to 52.5g (0.64mol), and other conditions remained unchanged.
  • the gas phase and liquid phase materials in the telomerization step were analyzed by gas chromatography.
  • the conversion rate of monofluoro-chloromethane was 99.6%
  • the selectivity of 3-chloro-1,1,1,2-tetrafluoropropane was 75.5%
  • the main by-products were: 1-Chloro-1,1,2,3-tetrafluoropropane with 15.9% selectivity and small amounts of other by-products.
  • This example proposes a method for preparing 2,3,3,3-tetrafluoropropene.
  • the operation is the same as that in Example 1.1, except that in step A2 of the telomerization step, monofluorine is successively introduced into the autoclave. After monochloromethane and trifluoroethylene, high-purity high-pressure nitrogen is used to pressurize the autoclave, and the pressure in the autoclave is increased from 0.9 MPa to 3.0 MPa, and other conditions remain unchanged.
  • the gas phase and liquid phase materials in the telomerization step were analyzed by gas chromatography.
  • the conversion rate of monofluorochloromethane was 99.8%
  • the selectivity of 3-chloro-1,1,1,2-tetrafluoropropane was 88.6%
  • the main by-products were: 1-Chloro-1,1,2,3-tetrafluoropropane with 7.6% selectivity and small amounts of other by-products.
  • This example proposes a method for preparing 2,3,3,3-tetrafluoropropene.
  • the operation steps are the same as those in Example 1.1, except that in the dehydrochlorination step, 10-20 mesh coal-based activated carbon is used instead of coconut shell. type of activated carbon.
  • This example proposes a method for preparing 2,3,3,3-tetrafluoropropene, and the operation is the same as that in Example 1.1, except that in the dehydrochlorination step, the reaction temperature is reduced to 300°C.
  • This example proposes a method for preparing 2,3,3,3-tetrafluoropropene, the operation is the same as that of Example 1.1, the only difference is that in the dehydrochlorination step, the reaction temperature is reduced to 320°C.
  • This comparative example proposes a preparation method of 2,3,3,3-tetrafluoropropene.
  • the operation is the same as that of Example 1.1, except that chloroform is used instead of dichloromethane, and the dosage is 20.0g, and other conditions remain unchanged. Change.
  • This comparative example proposes a preparation method of 2,3,3,3-tetrafluoropropene.
  • the operation is the same as that of Example 1.1, except that ZnCl 2 is used instead of HfCl 4 , and the amount is 3.0 g, and other conditions remain unchanged.
  • This comparative example proposes a preparation method of 2,3,3,3-tetrafluoropropene, the operation is the same as that of Example 1.1, the only difference is that HfCl 4 and dichloromethane are not added, and other conditions remain unchanged.
  • This embodiment proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene, including a telomerization step and a removal step, as follows :
  • reaction temperature 10°C
  • stirring rate 300rpm
  • initial reaction pressure 0.9MPa
  • pressure to gradually decrease as the reaction proceeds
  • reaction time 10h
  • the unreacted gas-phase raw materials and the separated Lewis acid catalyst can be returned to the telomerization step for reuse.
  • the gas phase and liquid phase materials were analyzed by gas chromatography, the conversion rate of monofluoro-chloromethane was 76.5%, the selectivity of 3-chloro-1,1,1,2-tetrafluoropropane was 81.2%, and the main by-product was 1-chloro- 1,1,2,3-Tetrafluoropropane with 15.3% selectivity and small amounts of other by-products.
  • a reaction tube made of Inconel alloy material with an inner diameter of 19 mm and a length of 800 mm was used as the fixed bed reactor, and the cat 2.1 with a volume of 20 mL was filled into the middle of the fixed bed reactor, connected to the reaction pipeline, and purged with nitrogen gas.
  • the nitrogen flow is 100mL/min;
  • reaction temperature 450°C
  • heating rate 5°C/min
  • reaction furnace to start heating up
  • the nitrogen flow rate is adjusted to 20mL/min, and the 3-chloro-1,1,1,2-tetrafluoropropane with a purity of 99.9% is pumped by a peristaltic pump at a rate of 5.0g/h Continuously feed into the fixed bed reactor to start the reaction;
  • This example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene.
  • the operation is the same as that in Example 2.1, except that: In the polymerization step, ZrCl 4 was used instead of HfCl 4 , and the amount was 4.0 g; the amount of monofluorochloromethane was increased to 39.7 g (0.58 mol), the amount of trifluoroethylene was increased to 71.3 g (0.87 mol), and other conditions remained unchanged.
  • the gas phase and liquid phase materials in the telomerization step were analyzed by gas chromatography.
  • the conversion rate of monofluorochloromethane was 99.0%
  • the selectivity of 3-chloro-1,1,1,2-tetrafluoropropane was 89.9%
  • the main by-products were: 1-Chloro-1,1,2,3-tetrafluoropropane with 5.3% selectivity and small amounts of other by-products.
  • This example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene.
  • the operation is the same as that in Example 2.2, except that: In the polymerization step, dichloromethane was not used, the amount of trifluoroethylene was increased to 95.1 g (1.16 mol), the reaction temperature was increased to 30° C., the initial reaction pressure was increased to 1.5 MPa, and other conditions remained unchanged.
  • the gas phase and liquid phase materials in the telomerization step were analyzed by gas chromatography.
  • the conversion rate of monofluorochloromethane was 99.5%
  • the selectivity of 3-chloro-1,1,1,2-tetrafluoropropane was 88.1%
  • the main by-products were: 1-Chloro-1,1,2,3-tetrafluoropropane with 4.1% selectivity and small amounts of other by-products.
  • This example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene.
  • the operation is the same as that in Example 2.2, except that: In the polymerization step, AlCl 3 was used instead of ZrCl 4 , and the amount was unchanged, which was also 4 g; at the same time, dichloromethane was not used, and the amount of trifluoroethylene was reduced to 52.5 g (0.64 mol), and other conditions remained unchanged.
  • the gas phase and liquid phase materials in the telomerization step were analyzed by gas chromatography.
  • the conversion rate of monofluoro-chloromethane was 99.6%
  • the selectivity of 3-chloro-1,1,1,2-tetrafluoropropane was 75.5%
  • the main by-products were: 1-Chloro-1,1,2,3-tetrafluoropropane with 15.9% selectivity and small amounts of other by-products.
  • This example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene.
  • the operation is the same as in Example 2.1, except that: in the A2 step of the telomerization step, monofluoro-chloromethane and trifluoroethylene were introduced into the autoclave in advance, and high-purity high-pressure nitrogen was used to pressurize the autoclave, and the pressure in the autoclave was raised from 0.9MPa to 3.0MPa , other conditions remain unchanged.
  • the gas phase and liquid phase materials in the telomerization step were analyzed by gas chromatography.
  • the conversion rate of monofluorochloromethane was 99.8%
  • the selectivity of 3-chloro-1,1,1,2-tetrafluoropropane was 88.6%
  • the main by-products were: 1-Chloro-1,1,2,3-tetrafluoropropane with 7.6% selectivity and small amounts of other by-products.
  • This example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene.
  • the operation is the same as that in Example 2.1, except that: In the removal step, use cat2.3 instead of cat 2.1.
  • This example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene.
  • the operation is the same as that in Example 2.1, except that: In the removal step, the amount of cat 2.1 was increased to 40 mL.
  • This example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene.
  • the operation is the same as that in Example 2.1, except that: In the removal step, use cat 2.2 instead of cat 2.1.
  • the chromatographic analysis of the removal reaction product showed that the conversion rate of 3-chloro-1,1,1,2-tetrafluoropropane was 70.1%, and the content of 2,3,3,3-tetrafluoropropene in the product was 39.2%, and 1- The chloro-2,3,3,3-tetrafluoropropene content was 28.5%.
  • This example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene.
  • the operation is the same as that in Example 2.1, except that: In the removal step, the reaction temperature was 400°C.
  • This comparative example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene.
  • the operation is the same as that in Example 2.1, except that: Trichloromethane replaces dichloromethane, the dosage is 20.0g, and other conditions remain unchanged.
  • This comparative example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene.
  • the operation is the same as that in Example 2.1, except that: ZnCl 2 replaces HfCl 4 , the dosage is 3.0 g, and other conditions remain unchanged.
  • This comparative example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene.
  • the operation is the same as that in Example 2.1, except that: no HfCl4 and dichloromethane were added and other conditions were kept constant.
  • This comparative example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene.
  • the operation is the same as that in Example 2.1, except that: Except in the step, activated carbon after pretreatment (120 °C drying for 12 h) was used to replace cat 2.1, and other conditions remained unchanged.
  • This comparative example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene.
  • the operation is the same as that in Example 2.1, except that: Al 2 O 3 replaces cat 2.1, other conditions remain the same.
  • the chromatographic analysis of the removal reaction product showed that the conversion rate of 3-chloro-1,1,1,2-tetrafluoropropane was 50.1%, the content of 2,3,3,3-tetrafluoropropene in the product was 3.1%, and the 1- The content of chloro-3,3,3-trifluoropropene was 62.2%, and no 1-chloro-2,3,3,3-tetrafluoropropene was produced.
  • This preparation example prepares Cr 2 O 3 and activated carbon powder blended catalyst Cr 2 O 3 -AC, and the preparation steps include:
  • the material is sent to a tableting machine for tableting and molding, and a columnar catalyst is made;
  • the formed catalyst was dried at 120° C. for 12 h to prepare a Cr 2 O 3 -AC catalyst, which was denoted as cat 3.1.
  • this preparation example is the same as that of preparation example 3.1, except that AlF 3 is used instead of Cr 2 O 3 to prepare an AlF 3 -AC catalyst, which is denoted as cat 3.2.
  • this preparation example is the same as that of preparation example 3.1, except that the mass ratio of Cr 2 O 3 and activated carbon is changed to 1/4, and a Cr 2 O 3 -AC catalyst is prepared, which is denoted as cat 3.3.
  • This embodiment proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene, including a telomerization step and a dehydrohalogenation step, as follows:
  • reaction temperature 10°C
  • stirring rate 300rpm
  • initial reaction pressure 0.9MPa
  • pressure to gradually decrease as the reaction proceeds
  • reaction time 10h
  • the unreacted gas-phase raw materials and the separated Lewis acid catalyst can be returned to the telomerization step for reuse.
  • the gas phase and liquid phase materials were analyzed by gas chromatography, the conversion rate of monofluoro-chloromethane was 76.5%, the selectivity of 3-chloro-1,1,1,2-tetrafluoropropane was 81.2%, and the main by-product was 1-chloro- 1,1,2,3-Tetrafluoropropane with 15.3% selectivity and small amounts of other by-products.
  • reaction tube of Inconel alloy material with an inner diameter of 19mm and a length of 800mm as the fixed bed reactor, filling the cat 3.1 with a volume of 20mL into the middle of the fixed bed reactor, connecting the reaction pipeline, and introducing nitrogen for purging, The nitrogen flow is 100mL/min;
  • This example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene, the operation is the same as that in Example 3.1, the only difference is: the telomerization step In the experiment, ZrCl 4 was used instead of HfCl 4 , and the amount was 4.0 g; the amount of monofluorochloromethane was increased to 39.7 g (0.58 mol), the amount of trifluoroethylene was increased to 71.3 g (0.87 mol), and other conditions remained unchanged.
  • the gas phase and liquid phase materials in the telomerization step were analyzed by gas chromatography.
  • the conversion rate of monofluorochloromethane was 99.0%
  • the selectivity of 3-chloro-1,1,1,2-tetrafluoropropane was 89.9%
  • the main by-products were: 1-Chloro-1,1,2,3-tetrafluoropropane with 5.3% selectivity and small amounts of other by-products.
  • This example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene, the operation is the same as that in Example 3.2, the only difference is: the telomerization step In the experiment, dichloromethane was not used, and the amount of trifluoroethylene was increased to 95.1 g (1.16 mol), the reaction temperature was increased to 30 °C, the initial reaction pressure was increased to 1.5 MPa, and other conditions remained unchanged.
  • the gas phase and liquid phase materials in the telomerization step were analyzed by gas chromatography.
  • the conversion rate of monofluorochloromethane was 99.5%
  • the selectivity of 3-chloro-1,1,1,2-tetrafluoropropane was 88.1%
  • the main by-products were: 1-Chloro-1,1,2,3-tetrafluoropropane with 4.1% selectivity and small amounts of other by-products.
  • This example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene, the operation is the same as that in Example 3.2, the only difference is: the telomerization step
  • AlCl 3 was used instead of ZrCl 4 , and the amount was unchanged, which was also 4.0 g; at the same time, dichloromethane was not used, and the amount of trifluoroethylene was reduced to 52.5 g (0.64 mol), and other conditions remained unchanged.
  • the gas phase and liquid phase materials in the telomerization step were analyzed by gas chromatography.
  • the conversion rate of monofluoro-chloromethane was 99.6%
  • the selectivity of 3-chloro-1,1,1,2-tetrafluoropropane was 75.5%
  • the main by-products were: 1-Chloro-1,1,2,3-tetrafluoropropane with 15.9% selectivity and small amounts of other by-products.
  • This example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene.
  • the operation is the same as in Example 3.1, except that:
  • step A2 of the step after successively feeding monofluoro-chloromethane and trifluoroethylene into the autoclave, high-purity high-pressure nitrogen is used to pressurize the autoclave, and the pressure in the autoclave is increased from 0.9MPa to 3.0MPa, Other conditions remain unchanged.
  • the gas phase and liquid phase materials in the telomerization step were analyzed by gas chromatography.
  • the conversion rate of monofluorochloromethane was 99.8%
  • the selectivity of 3-chloro-1,1,1,2-tetrafluoropropane was 88.6%
  • the main by-products were: 1-Chloro-1,1,2,3-tetrafluoropropane with 7.6% selectivity and small amounts of other by-products.
  • This example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene, the operation is the same as that in Example 3.1, the only difference is: dehydrohalogenation In the steps, use cat 3.2 instead of cat 3.1.
  • This example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene, the operation is the same as that in Example 3.1, the only difference is: dehydrohalogenation In the step, the amount of cat 3.1 was increased to 40 mL.
  • This example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene, the operation is the same as that in Example 3.1, the only difference is: dehydrohalogenation In the step, the reaction temperature was 450°C.
  • This comparative example proposes a co-production preparation method of 2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene. Methane was used instead of dichloromethane, and the dosage was 20 g, and other conditions remained unchanged.
  • This comparative example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene.
  • the operation is the same as that in Example 3.1, except that ZnCl 2 Instead of HfCl 4 , the dosage is 3.0 g, and other conditions remain unchanged.
  • This comparative example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene.
  • the operation is the same as that in Example 3.1, except that HfCl is not added. 4 and dichloromethane, other conditions were kept the same.
  • This comparative example proposes a co-production preparation method of 2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene.
  • the operation is the same as that in Example 3.1, except that: dehydrohalogenation
  • the coconut shell activated carbon after pretreatment drying at 120 °C for 12 h was used to replace cat 3.1, and other conditions remained unchanged.
  • the chromatographic analysis of the dehydrohalogenation reaction product shows that the conversion rate of 3-chloro-1,1,1,2-tetrafluoropropane exceeds 99.7%, and the content of 2,3,3,3-tetrafluoropropene in the product is 99.0%, and no 1-Chloro-3,3,3-trifluoropropene is formed.
  • This comparative example proposes a preparation method for co-production of 2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene.
  • the operation is the same as that in Example 3.1, except that Pd/ AC catalyst (Pd loading of 1 wt%) replaced cat 3.1, and other conditions remained unchanged.
  • the chromatographic analysis of the dehydrohalogenation reaction product showed that the conversion rate of 3-chloro-1,1,1,2-tetrafluoropropane was 83.5%, and the content of 2,3,3,3-tetrafluoropropene in the product was 96.4%, 1 - Chloro-2,3,3,3-tetrafluoropropene content is 1.3%, no 1-chloro-3,3,3-trifluoropropene is produced.

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Abstract

本发明公开了制备2,3,3,3-四氟丙烯的方法，包括两步法制备2,3,3,3-四氟丙烯的方法，2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯的联产制备方法，以及2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法。所述两步法制备2,3,3,3-四氟丙烯的方法包括：A1.调聚步骤：一氟一氯甲烷和三氟乙烯在调聚催化剂作用下经加压调聚反应制备获得3-氯-1,1,1,2-四氟丙烷；所述调聚催化剂为Lewis酸催化剂或Lewis酸催化剂和二氯甲烷的混合催化剂；A2.脱氯化氢步骤：3-氯-1,1,1,2-四氟丙烷在活性炭的催化作用下脱氯化氢获得2,3,3,3-四氟丙烯。本发明具有工艺简单、产物选择性高、反应条件温和等优点。

Description

制备2,3,3,3-四氟丙烯的方法 技术领域
本发明涉及2,3,3,3-四氟丙烯的制备，特别涉及一种采用三氟乙烯为原料，经调聚、脱除(脱氯化氢、脱氟化氢、脱氢等)两步反应制备获得2,3,3,3-四氟丙烯的方法。
背景技术
2,3,3,3-四氟丙烯的ODP为零，GWP值＜1，寿命期气候性能(LCCP)低于传统制冷剂HFC-134a，系统制冷性能优于HFC-134a，大气分解物与HFC-134a相同，被认为是目前最具潜力的汽车制冷剂替代品，已被多家主流汽车生产商所接受。目前，2,3,3,3-四氟丙烯的制备路线包括以下几种：
一、六氟丙烯路线：
以六氟丙烯为原料制备2,3,3,3-四氟丙烯，分为四步反应：(1)六氟丙烯和氢气发生加氢反应制备1,1,1,2,3,3-六氟丙烷(HFC-236ea)；(2)HFC-236ea在催化剂的作用下发生脱氟化氢反应制备1,1,1,2,3-五氟丙烯(HFO-1225ye)；(3)HFO-1225ye再和氢气发生加氢反应制备1,1,1,2,3-五氟丙烷(HFC-245eb)；(4)HFC-245eb在催化剂的作用下发生脱氟化氢反应制备2,3,3,3-四氟丙烯。
美国专利US20070179324A、中国专利CN101544536A、CN102267869A和CN102026947A等都公开了以六氟丙烯为原料经过加氢、脱氟化氢、再加氢和再脱氟化氢四步反应制备2,3,3,3-四氟丙烯的方法，具有工艺简单、技术成熟等特点，但是反应步骤多，多种中间产物需要分离提纯，存在工艺步骤复杂、设备投资大、反应收率低、分离成本高、能耗大等问题。
为了解决上述专利技术存在的不足，中国专利CN103449963B公开了一种由六氟丙烯为原料多步连续反应合成2,3,3,3-四氟丙烯的方法，能够实现HFC-236ea、HFO-1225ye和HFC-245eb等中间产物不经过分离直接进行反应的连续化生产。但是中间产物不分离提纯意味着杂质会在反应物料中不断累积和新增，最终影响目标产物2,3,3,3-四氟丙烯的收率，同时还会增加2,3,3,3-四氟丙烯产品精馏分离的难度。
二、四氯丙烯(TCP)路线：
专利CN101395108B公开了采用1,1,2,3-四氯丙烯为原料通过三步反应制备2,3,3,3-四氟丙烯的方法，反应步骤包括：(1)1,1,2,3-四氯丙烯和HF进行气相氟化反应制备2-氯-3,3,3-三氟丙烯(HCFO-1233xf)，选择性为80～96％，当使用Cr 2O 3和FeCl 3/AC催化剂时，选择性达到96％，转化率仅为20％；(2)HCFO-1233xf与HF进行加成反应生成2-氯-1,1,1,2-四氟丙烷(HCFC-244bb)，催化剂为SbCl 5；(3)HCFC-244bb在活性炭催化剂作用下进行气相脱氯化氢反应制备得到目标产物2,3,3,3-四氟丙烯。该工艺反应步骤复杂，对工业生产不利，并且存在转化率低、反应温度高等问题。
美国专利US20090099396公开了采用1,1,2,3-四氯丙烯为原料通过两步反应制备2,3,3,3-四氟丙烯的方法，反应步骤包括：(1)1,1,2,3-四氯丙烯和HF进行液相氟化反应制备1,1,1,2,3-五氟丙烷(HFC-245eb)，催化剂为SbCl 5，TCP转化率能达到100％，但是HFC-245eb选择性仅为53～59％，有较多副产物生成；(2)HFC-245eb在碱金属氢氧化物的作用下发生液相脱氟化氢反应生成目标产物2,3,3,3-四氟丙烯。该工艺具有反应步骤少，设备投资少的优点，但是中间产物HFC-245eb选择性较低，副产物分离难度较大。
三、三氟丙烯路线：
专利CN101979364A公开了采用3,3,3-三氟丙烯为原料制备2,3,3,3-四氟丙烯的方法，反应分四步进行：(1)3,3,3-三氟丙烯与氯气在光催化下发生加成反应生成1,2-二氯-3,3,3-三氟丙烷，原料转化率达到95％，选择性达到90％；(2)1,2-二氯-3,3,3-三氟丙烷在碱金属氢氧化物的作用下发生液相脱氯化氢反应生成2-氯-3,3,3-三氟丙烯(HCFO-1233xf)，转化率和选择性均达到90％；(3)HCFO-1233xf与HF进行加成反应生成2-氯-1,1,1,2-四氟丙烷(HCFC-244bb)，催化剂为SnCl 4、TiCl 4、氟磺酸，原料转化率达到95％，选择性为90～96％；(4)HCFC-244bb在碱金属催化剂作用下进行液相脱氯化氢反应制备得到目标产物CF 3CF＝CH 2，原料转化率为95％，选择性为90～95％。该工艺合成路线长，第一步氯化反应对设备要求较高，两步脱卤反应产生较多废液，反应总收率低，合成成本高。
四、其他路线：
旭硝子专利WO2011162341A公开了以1,1-二氯-2,3,3,3-四氟丙烯 (CFO-1214ya)为原料，在钯催化剂的作用下经加氢还原制备2,3,3,3-四氟丙烯的方法。但该方法加氢还原反应程度较难控制，容易生成1-氯-2,3,3,3-四氟丙烯(HCFO-1224yd)、1-氯-2,3,3,3-四氟丙烷(HCFC-244eb)和2,3,3,3-四氟丙烷(HFC-254eb)等中间体或过度还原产物，产物选择性低，后处理操作繁杂，且副产物HFC-254eb在碱洗处理过程中容易发生进一步脱氟化氢反应生成与HFO-1234yf沸点接近的3,3,3-三氟丙烯(HFO-1243zf)，进一步增加了杂质分离难度。虽然可以通过控制催化剂床层反应温度和碱洗吸收温度来改善上述问题，但改善程度不明显，且工艺条件控制难度大，不适于产业化放大。
发明内容
为了解决上述技术问题，本发明提出了一种工艺简单、反应条件温和、产物选择性高、适合产业化生产的两步法制备2,3,3,3-四氟丙烯的方法。
本发明的目的是通过以下技术方案实现的：
第一方面，本发明提供一种两步法制备2,3,3,3-四氟丙烯的方法，所述方法包括：
A1.调聚步骤：一氟一氯甲烷和三氟乙烯在调聚催化剂作用下经加压调聚反应制备获得3-氯-1,1,1,2-四氟丙烷；所述调聚催化剂为Lewis酸催化剂或Lewis酸催化剂和二氯甲烷的混合催化剂；
A2.脱氯化氢步骤：3-氯-1,1,1,2-四氟丙烷在活性炭的催化作用下脱氯化氢获得2,3,3,3-四氟丙烯。
本发明两步法制备2,3,3,3-四氟丙烯的反应方程式如下：
CH 2FCl+CF 2＝CHF→CF 3CHFCH 2Cl→CF 3CF＝CH 2
本发明所述Lewis酸催化剂选自Al、Sb、Ti、Zr、Hf中的至少一种卤化物。作为优选，所述Lewis酸催化剂选自ZrCl 4、HfCl 4、TiCl 4、AlCl 3、AlF 3、SbF 5中至少一种。更为优选地，所述Lewis酸催化剂为ZrCl 4或HfCl 4。
本发明原料一氟一氯甲烷和三氟乙烯的调聚反应在加压条件下进行，原料一氟一氯甲烷在反应条件下，部分或全部形成液体。加之调聚反应产生的3-氯-1,1,1,2-四氟丙烷为液体，故，本发明的A1步骤优选采用无溶剂反应，以减少中间体和/或产品的分离步骤。
本发明所述调聚催化剂可采用单一的Lewis酸催化剂，也可采用Lewis酸催化剂和二氯甲烷的混合催化剂。当采用混合催化剂时，Lewis酸催化剂解离活化一氟一氯甲烷，形成F -、CH 2Cl +、Cl -、CH 2F +等离子；二氯甲烷抑制解离形成的F -、CH 2Cl +、Cl -、CH 2F +等离子重新结合，从而确保F -、CH 2Cl +离子与三氟乙烯发生定向调聚反应，高选择性地得到调聚产物CF 3CHFCH 2Cl。
在化学反应中，原料之间的配比、原料与催化剂的配比、反应温度、反应时间等均会影响反应结果，尤其是多变量的结合，会对反应结果造成很大的影响。
在本发明所述调聚步骤中，一氟一氯甲烷与三氟乙烯的摩尔比为1:0.1～1:10；更为优选地，一氟一氯甲烷与三氟乙烯的摩尔比为1:1～1:5。所述Lewis酸催化剂用量为一氟一氯甲烷质量的0.01～50wt％；更为优选地，Lewis酸催化剂用量为一氟一氯甲烷质量的0.1～10wt％。当采用Lewis酸催化剂和二氯甲烷的混合催化剂时，二氯甲烷与一氟一氯甲烷的摩尔配比为1:0.01～1:10；更为优选地，二氯甲烷与一氟一氯甲烷的摩尔配比为1:0.1～1:5。
本发明所述调聚步骤在加压条件下进行，反应温度为-30～100℃，反应压力为0.5～5.0MPa，反应时间为1～50h。更为优选地，反应温度为0～50℃，反应压力为0.8～3.0MPa，反应时间为5～10h。
本发明所述脱氯化氢步骤在活性炭的催化作用下进行，所述活性炭选自果壳类活性炭、煤质类活性炭或木质类活性炭，优选果壳类活性炭。
脱氯化氢步骤反应温度为200～500℃，优选反应温度为300～350℃。
为进一步提高2,3,3,3-四氟丙烯的产品纯度，降低后处理难度，故：经调聚步骤获得的3-氯-1,1,1,2-四氟丙烷经精馏分离后用于脱氯化氢步骤。
第二方面，本发明提供一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯的联产制备方法，所述联产制备方法包括：
A1.调聚步骤：一氟一氯甲烷和三氟乙烯在调聚催化剂作用下经加压调聚反应制备获得3-氯-1,1,1,2-四氟丙烷；所述调聚催化剂为Lewis酸催化剂或Lewis酸催化剂和二氯甲烷的混合催化剂；
A2.脱除步骤：3-氯-1,1,1,2-四氟丙烷在活性炭负载贵金属催化剂作用下，同时发生脱氯化氢反应和脱氢反应获得2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯， 所述活性炭负载贵金属催化剂为Pd/AC、Pt/AC中的至少一种。
本发明联产制备工艺的反应方程式如下：
Figure PCTCN2022085539-appb-000001
本发明所述Lewis酸催化剂选自Al、Sb、Ti、Zr、Hf中的至少一种卤化物。作为优选，所述Lewis酸催化剂选自ZrCl 4、HfCl 4、TiCl 4、AlF 3、AlCl 3、SbF 5中至少一种。更为优选地，所述Lewis酸催化剂为ZrCl 4或HfCl 4。
本发明原料一氟一氯甲烷和三氟乙烯的调聚反应在加压条件下进行，原料一氟一氯甲烷在反应条件下，部分或全部形成液体。加之调聚反应产生的3-氯-1,1,1,2-四氟丙烷为液体，故，本发明的A1步骤优选采用无溶剂反应，以减少中间体和/或产品的分离步骤。
本发明所述调聚催化剂可采用单一的Lewis酸催化剂，也可采用Lewis酸催化剂和二氯甲烷的混合催化剂。当采用混合催化剂时，Lewis酸催化剂解离活化一氟一氯甲烷，形成F -、CH 2Cl +、Cl -、CH 2F +等离子；二氯甲烷抑制解离形成的F -、CH 2Cl +、Cl -、CH 2F +等离子重新结合，从而确保F -、CH 2Cl +离子与三氟乙烯发生定向调聚反应，高选择性地得到调聚产物CF 3CHFCH 2Cl。
在化学反应中，原料之间的配比、原料与催化剂的配比、反应温度、反应时间等均会影响反应结果，尤其是多变量的结合，会对反应结果造成很大的影响。
在本发明所述调聚步骤中，一氟一氯甲烷与三氟乙烯的摩尔比为1:0.1～1:10；更为优选地，一氟一氯甲烷与三氟乙烯的摩尔比为1:1～1:5。所述Lewis酸催化剂用量为一氟一氯甲烷质量的0.01～50wt％；更为优选地，Lewis酸催化剂用量为一氟一氯甲烷质量的0.1～10wt％。当采用Lewis酸催化剂和二氯甲烷的混合催化剂时，二氯甲烷与一氟一氯甲烷的摩尔配比为1:0.01～1:10；更为优选地，二氯甲烷与一氟一氯甲烷的摩尔配比为1:0.1～1:5。
本发明所述调聚步骤在加压条件下进行，反应温度为-30～100℃，反应压力为0.5～5.0MPa，反应时间为1～50h。更为优选地，反应温度为0～50℃，反应压力为0.8～3.0MPa，反应时间为5～10h。
本发明所述脱除步骤，在活性炭负载贵金属催化剂的作用下，当原料3-氯 -1,1,1,2-四氟丙烷吸附在活性炭上时，发生脱氯化氢反应；当原料3-氯-1,1,1,2-四氟丙烷吸附在活性炭上的贵金属位点时，发生脱氢反应，从而同时获得2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯。
所述活性炭负载贵金属催化剂可采用常规方法进行制备，只要能获得本发明所述活性炭负载贵金属催化剂即可。作为优选，本发明采用浸渍法制备，包括如下步骤：
B1.载体预处理：活性炭在90～120℃中干燥处理12h以上；
B2.金属盐浸渍：采用Pd或Pt的可溶性盐溶液在真空或常压条件下浸渍预处理后的活性炭；
B3.将浸渍后的活性炭进行干燥处理，干燥温度90～120℃，干燥时间12h以上；
B4.将干燥处理后的活性炭用氢氮混合气进行还原处理得到所述活性炭负载贵金属催化剂；所述氢氮混合气中氢气的体积比为5～50％，还原温度为150～300℃。
所述活性炭负载贵金属催化剂中，Pd、Pt的负载量为0.1～5.0wt％，优选负载量为0.5～1.5wt％。
本发明所述脱除步骤为气固相反应，3-氯-1,1,1,2-四氟丙烷汽化后由氮气载入催化剂床层进行脱除反应，所述脱除反应的物料体积空速为50～300h -1，N 2/3-氯-1,1,1,2-四氟丙烷的体积比为(0.5～3.0)：1，优选体积比为(1.5～2.0)：1。
本发明所述脱除步骤的反应温度为300～600℃，优选反应温度为400～450℃。
通过活性炭负载贵金属催化剂制备工艺、催化剂中贵金属负载量以及反应条件的调整，可在一定范围内调节A2脱除步骤的产物分布。一般地，经A2脱除步骤获得含30～90％的2,3,3,3-四氟丙烯和10～50％的1-氯-2,3,3,3-四氟丙烯；优选地，脱除步骤产物中含有50～60％的2,3,3,3-四氟丙烯和30～50％的1-氯-2,3,3,3-四氟丙烯，其余为副产物，如1-氯-3,3,3-三氟丙烯。
为进一步降低后处理难度，故：经调聚步骤获得的3-氯-1,1,1,2-四氟丙烷经 精馏分离后用于脱除步骤。
第三方面，本发明还提供一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，所述联产制备方法包括：
A1.调聚步骤：一氟一氯甲烷和三氟乙烯在调聚催化剂作用下经加压调聚反应制备获得3-氯-1,1,1,2-四氟丙烷；所述调聚催化剂为Lewis酸催化剂或Lewis酸催化剂和二氯甲烷的混合催化剂；
A2.脱卤化氢步骤：3-氯-1,1,1,2-四氟丙烷在复合型脱卤催化剂作用下，同时发生脱氯化氢反应和脱氟化氢反应获得2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯，所述复合型脱卤催化剂由Al、Mg或Cr中的至少一种的氧化物或氟化物与活性炭粉末制备获得。
所述Al、Mg或Cr中的至少一种的氧化物或氟化物选自Al 2O 3、AlF 3、MgF 2和Cr 2O 3中至少一种；所述活性炭粉末选自果壳类活性炭、煤质类活性炭或木质类活性炭。
本发明联产制备工艺的反应方程式如下：
Figure PCTCN2022085539-appb-000002
本发明所述Lewis酸催化剂选自Al、Sb、Ti、Zr、Hf中的至少一种卤化物。作为优选，所述Lewis酸催化剂选自ZrCl 4、HfCl 4、TiCl 4、AlF 3、AlCl 3、SbF 5中至少一种。更为优选地，所述Lewis酸催化剂为ZrCl 4或HfCl 4。
本发明原料一氟一氯甲烷和三氟乙烯的调聚反应在加压条件下进行，原料一氟一氯甲烷在反应条件下，部分或全部形成液体。加之调聚反应产生的3-氯-1,1,1,2-四氟丙烷为液体，故，本发明的A1步骤优选采用无溶剂反应，以减少中间体和/或产品的分离步骤。
本发明所述调聚催化剂可采用单一的Lewis酸催化剂，也可采用Lewis酸催化剂和二氯甲烷的混合催化剂。当采用混合催化剂时，Lewis酸催化剂解离活化一氟一氯甲烷，形成F -、CH 2Cl +、Cl -、CH 2F +等离子；二氯甲烷抑制解离形成的F -、CH 2Cl +、Cl -、CH 2F +等离子重新结合，从而确保F -、CH 2Cl +离子与三氟乙烯发生定向调聚反应，高选择性地得到调聚产物CF 3CHFCH 2Cl。
在化学反应中，原料之间的配比、原料与催化剂的配比、反应温度、反应时间等均会影响反应结果，尤其是多变量的结合，会对反应结果造成很大的影响。
在本发明所述调聚步骤中，一氟一氯甲烷与三氟乙烯的摩尔比为1:0.1～1:10；更为优选地，一氟一氯甲烷与三氟乙烯的摩尔比为1:1～1:5。所述Lewis酸催化剂用量为一氟一氯甲烷质量的0.01～50wt％；更为优选地，Lewis酸催化剂用量为一氟一氯甲烷质量的0.1～10wt％。当采用Lewis酸催化剂和二氯甲烷的混合催化剂时，二氯甲烷与一氟一氯甲烷的摩尔配比为1:0.01～1:10；更为优选地，二氯甲烷与一氟一氯甲烷的摩尔配比为1:0.1～1:5。
本发明所述调聚步骤在加压条件下进行，反应温度为-30～100℃，反应压力为0.5～5.0MPa，反应时间为1～50h。更为优选地，反应温度为0～50℃，反应压力为0.8～3.0MPa，反应时间为5～10h。
本发明所述脱卤化氢步骤，在复合型脱卤催化剂的作用下，当3-氯-1,1,1,2-四氟丙烷吸附在活性炭上时，发生脱氯化氢反应；当3-氯-1,1,1,2-四氟丙烷吸附在Al 2O 3和/或AlF 3和/或MgF 2和/或Cr 2O 3上时，发生脱氟化氢反应，从而同时获得2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯。
本发明所述复合型脱卤催化剂可采用常规方法制备，只要能获得本发明所述复合型脱卤催化剂即可。作为优选，采用共混合法制备，包括如下步骤：
B1.混合：将Al 2O 3和/或AlF 3和/或MgF 2和/或Cr 2O 3与活性炭粉末以(0.01～0.25):1的质量比配料并采用机械搅拌或球磨的方式充分混合；
B2.过筛：对混合物料进行过筛处理，将混合不均匀部分筛除；
B3.成型：将过筛后物料送入压片机进行压片成型；
B4.对成型后催化剂进行干燥处理，制备得到所述复合型脱卤催化剂，如Al 2O 3-AC、AlF 3-AC、MgF 2-AC和Cr 2O 3-AC等催化剂。
所述B3成型步骤，可制成柱状、片状等形状，对具体形状不做限制。
所述B4步骤中干燥处理一般采用90℃～120℃处理12h以上。
本发明所述复合型脱卤催化剂，当采用Al 2O 3与活性炭粉末共混时，Al 2O 3的含量为催化剂总量的1.0～20wt％；当采用AlF 3与活性炭粉末共混时，AlF 3的含量为催化剂总量的1.0～20wt％；当采用MgF 2与活性炭共混时，MgF 2的含 量为催化剂总量的1.0～20wt％；当采用Cr 2O 3与活性炭共混时，Cr 2O 3的含量为催化剂总量的1.0～20wt％。
本发明所述脱卤化氢步骤为气固相反应，3-氯-1,1,1,2-四氟丙烷汽化后由氮气载入催化剂床层进行脱卤化氢反应，脱卤化氢反应原料体积空速为50～300h -1，N 2/3-氯-1,1,1,2-四氟丙烷的体积比为(0.5～3.0)：1，优选体积比为(1.5～2.0)：1。
本发明所述脱卤化氢步骤的反应温度为300～500℃，优选反应温度为350～450℃。
通过复合型脱卤催化剂的制备工艺、催化剂中活性组分含量以及反应条件的调整，可在一定范围内调节脱卤化氢步骤的产物分布。一般地，经脱卤化氢步骤获得含10～50％的2,3,3,3-四氟丙烯和10～70％的1-氯-3,3,3-三氟丙烯；优选地，消除步骤产物中含有20～40％的2,3,3,3-四氟丙烯和30～60％的1-氯-3,3,3-三氟丙烯，其余为未知副产物。
为进一步降低后处理难度，故：经调聚步骤获得的3-氯-1,1,1,2-四氟丙烷经精馏分离后用于脱卤化氢步骤。
与现有技术相比，本发明具有的有益效果为：
本发明采用一氟一氯甲烷和三氟乙烯为原料，在Lewis酸催化剂或Lewis酸催化剂和二氯甲烷混合催化剂的作用下，经加压调聚获得3-氯-1,1,1,2-四氟丙烷。3-氯-1,1,1,2-四氟丙烷在活性炭催化作用下制备获得2,3,3,3-四氟丙烯；或者，3-氯-1,1,1,2-四氟丙烷在活性炭负载贵金属催化剂的催化作用下，同时发生脱氯化氢反应和脱氢反应，联产获得2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯；更或者，3-氯-1,1,1,2-四氟丙烷在复合型脱卤催化剂的催化作用下，同时发生脱氯化氢反应和脱氟化氢反应，联产获得2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯。本发明提供的三种制备获得2,3,3,3-四氟丙烯的方法，具有工艺简单、反应条件温和、调聚产物及目标产物选择性高等优点，适用于产业化放大。
具体实施方式
下面结合具体实施例来对本发明进行进一步说明，但并不将本发明局限于这些具体实施方式。本领域技术人员应该认识到，本发明涵盖了权利要求书范围内 所可能包括的所有备选方案、改进方案和等效方案。
本发明实施例的第一方面，提供一种两步法制备2,3,3,3-四氟丙烯的方法。
实施例1.1
本实施例提出了一种两步法制备2,3,3,3-四氟丙烯的方法，包括调聚步骤和脱氯化氢步骤，具体如下：
一、调聚步骤
A1.采用容积为250mL的Inconel合金材质的高压釜作为反应器，将3.0g HfCl 4和20.0g二氯甲烷分别加入反应釜中，密封反应釜后通1.0MPa氮气置换反应釜内空气，重复进行三次；
A2.反应釜内空气置换完全后先后通入一氟一氯甲烷19.9g(0.29mol)和三氟乙烯24.6g(0.30mol)；
A3.设定反应温度为10℃，搅拌速率为300rpm，反应初始压力为0.9MPa，随着反应的进行压力逐渐降低，反应时间为10h；
A4.反应结束，收集未反应的气相原料三氟乙烯和/或一氟一氯甲烷，以及少量调聚产物和二氯甲烷；对反应釜内物料进行过滤或蒸馏等固液分离处理，固体部分为Lewis酸催化剂(HfCl 4)，液相物料为二氯甲烷和调聚产物，经精馏分离获得纯度为99.9％的3-氯-1,1,1,2-四氟丙烷，用于脱氯化氢反应。
未反应的气相原料、分离得到的Lewis酸催化剂可返回调聚步骤重新利用。
采用气相色谱分析气相和液相物料，一氟一氯甲烷转化率为76.5％，3-氯-1,1,1,2-四氟丙烷选择性为81.2％，主要副产物为1-氯-1,1,2,3-四氟丙烷，选择性为15.3％，还有少量其他副产物。
二、脱氯化氢步骤
B1.采用内径为19mm、长度为800mm的Inconel合金材质的反应管作为固定床反应器，将体积为20mL、颗粒大小为10～20目的椰壳型活性炭装填入固定床反应器中部，连接反应管线，通入氮气进行吹扫，氮气流量为100mL/min；
B2.设定反应温度为350℃，升温速率为5℃/min，反应炉开始升温；
B3.催化剂床层到达反应温度后将氮气流量调整至20mL/min，同时将纯度为99.9％的3-氯-1,1,1,2-四氟丙烷以5.0g/h的速度连续通入固定床反应器中，开 始反应；
B4.流出反应器的气体混合物在线GC和GC/MS分析，3-氯-1,1,1,2-四氟丙烷转化率为99.6％，产物2,3,3,3-四氟丙烯选择性为99.3％。
实施例1.2
本实施例提出了一种2,3,3,3-四氟丙烯的制备方法，操作同实施例1.1，区别仅在于：调聚步骤中，采用ZrCl 4代替HfCl 4，用量为4.0g；一氟一氯甲烷用量增加至39.7g(0.58mol)，三氟乙烯用量增加至71.3g(0.87mol)，其他条件保持不变。
采用气相色谱分析调聚步骤的气相和液相物料，一氟一氯甲烷转化率为99.0％，3-氯-1,1,1,2-四氟丙烷选择性为89.9％，主要副产物为1-氯-1,1,2,3-四氟丙烷，选择性为5.3％，还有少量其他副产物。
实施例1.3
本实施例提出了一种2,3,3,3-四氟丙烯的制备方法，操作同实施例1.2，区别仅在于：调聚步骤中，不采用二氯甲烷，且三氟乙烯用量增加至95.1g(1.16mol)，同时反应温度增加至30℃，初始反应压力增加至1.5MPa，其他条件保持不变。
采用气相色谱分析调聚步骤的气相和液相物料，一氟一氯甲烷转化率为99.5％，3-氯-1,1,1,2-四氟丙烷选择性为88.1％，主要副产物为1-氯-1,1,2,3-四氟丙烷，选择性为4.1％，还有少量其他副产物。
实施例1.4
本实施例提出了一种2,3,3,3-四氟丙烯的制备方法，操作同实施例1.2，区别仅在于：调聚步骤中，采用AlCl 3代替ZrCl 4，用量不变，同样为4.0g；同时不采用二氯甲烷，且三氟乙烯用量减少至52.5g(0.64mol)，其他条件保持不变。
采用气相色谱分析调聚步骤的气相和液相物料，一氟一氯甲烷转化率为99.6％，3-氯-1,1,1,2-四氟丙烷选择性为75.5％，主要副产物为1-氯-1,1,2,3-四氟丙烷，选择性为15.9％，还有少量其他副产物。
实施例1.5
本实施例提出了一种2,3,3,3-四氟丙烯的制备方法，操作同实施例1.1，区 别仅在于：在调聚步骤的A2步骤中，在高压釜中先后通入一氟一氯甲烷和三氟乙烯后，采用高纯高压氮气对高压釜进行加压处理，将高压釜内压力由0.9MPa提升至3.0MPa，其他条件保持不变。
采用气相色谱分析调聚步骤的气相和液相物料，一氟一氯甲烷转化率为99.8％，3-氯-1,1,1,2-四氟丙烷选择性为88.6％，主要副产物为1-氯-1,1,2,3-四氟丙烷，选择性为7.6％，还有少量其他副产物。
实施例1.6
本实施例提出了一种2,3,3,3-四氟丙烯的制备方法，操作步骤同实施例1.1，区别仅在于：脱氯化氢步骤中，采用10～20目煤质类活性炭代替椰壳类活性炭。
对脱氯化氢产物进行色谱分析，3-氯-1,1,1,2-四氟丙烷转化率为99.2％，产物2,3,3,3-四氟丙烯选择性达到95.1％。
实施例1.7
本实施例提出了一种2,3,3,3-四氟丙烯的制备方法，操作同实施例1.1，区别仅在于：脱氯化氢步骤中，反应温度降低为300℃。
对脱氯化氢产物进行色谱分析，3-氯-1,1,1,2-四氟丙烷转化率为75.8％，产物2,3,3,3-四氟丙烯选择性为99.2％。
实施例1.8
本实施例提出了一种2,3,3,3-四氟丙烯的制备方法，操作同实施例1.1，区别仅在于：脱氯化氢步骤中，反应温度降低为320℃。
对脱氯化氢产物进行色谱分析，3-氯-1,1,1,2-四氟丙烷转化率为86.9％，产物2,3,3,3-四氟丙烯选择性为99.1％。
对比例1.1
本对比例提出了一种2,3,3,3-四氟丙烯的制备方法，操作同实施例1.1，区别仅在于：采用三氯甲烷代替二氯甲烷，用量为20.0g，其他条件保持不变。
对调聚步骤反应后的物料进行色谱分析，一氟一氯甲烷转化率为86.9％，3-氯-1,1,1,2-四氟丙烷选择性为46.2％，有大量一氟一氯甲烷的歧化产物二氯甲烷产生，选择性达到40.3％，还有少量其他调聚副产物。
对比例1.2
本对比例提出了一种2,3,3,3-四氟丙烯的制备方法，操作同实施例1.1，区别仅在于：采用ZnCl 2代替HfCl 4，用量为3.0g，其他条件保持不变。
对调聚步骤反应后的物料进行色谱分析，一氟一氯甲烷转化率为20.8％，无目标产物3-氯-1,1,1,2-四氟丙烷产生。
对比例1.3
本对比例提出了一种2,3,3,3-四氟丙烯的制备方法，操作同实施例1.1，区别仅在于：不加入HfCl 4和二氯甲烷，其他条件保持不变。
对调聚步骤反应后的物料进行色谱分析，一氟一氯甲烷转化率为7.7％，无目标产物3-氯-1,1,1,2-四氟丙烷产生，仅有少量一氟一氯甲烷的歧化产物二氯甲烷产生。
本发明实施例的第二方面，提供一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯的联产制备方法。
制备例2.1
取6.0mL氯钯酸溶液(浓度为0.033g Pd/mL)，并加入80.0mL蒸馏水稀释均匀，取经预处理(120℃干燥12h)的活性炭20.0g，加入上述浸渍液，浸渍12h以上，然后120℃干燥12h，即得到1％wt.Pd/AC催化剂，记为cat2.1。
制备例2.2
取9.2mL氯钯酸溶液(浓度为0.033g Pd/mL)，并加入80.0mL蒸馏水稀释均匀，取经预处理(120℃干燥12h)的活性炭20.0g，加入上述浸渍液，浸渍12h以上，然后120℃干燥12h，即得到1.5wt.％Pd/AC催化剂，记为cat2.2。
制备例2.3
取0.35g PtCl 4，溶于80.0mL蒸馏水中，取经预处理(120℃干燥12h)的活性炭20.0g，加入上述浸渍液，浸渍12h以上，然后120℃干燥12h，即得到1wt.％Pt/AC催化剂，记为cat2.3。
制备例2.4
取0.52g PtCl 4，溶于80.0mL蒸馏水中，取经预处理(120℃干燥12h)的活性炭20.0g，加入上述浸渍液，浸渍12h以上，然后120℃干燥12h，即得到1.5wt.％Pt/AC催化剂，记为cat2.4。
实施例2.1
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯联产制备方法，包括调聚步骤和脱除步骤，具体如下：
一、调聚步骤
A1.采用容积为250mL的Inconel合金材质的高压釜作为反应器，将3.0g HfCl 4和20.0g二氯甲烷分别加入反应釜中，密封反应釜后通入1.0MPa以上氮气置换反应釜内空气，重复进行三次；
A2.反应釜内空气置换完全后先后通入一氟一氯甲烷19.9g(0.29mol)和三氟乙烯24.6g(0.30mol)；
A3.设定反应温度为10℃，搅拌速率为300rpm，反应初始压力为0.9MPa，随着反应的进行压力逐渐降低，反应时间为10h；
A4.反应结束，收集未反应的气相原料三氟乙烯和/或一氟一氯甲烷，以及少量调聚产物和二氯甲烷；对反应釜内物料进行过滤或蒸馏等固液分离处理，固体部分为Lewis酸催化剂(HfCl 4)，液相物料为二氯甲烷和调聚产物，经精馏分离获得纯度为99.9％的3-氯-1,1,1,2-四氟丙烷，用于脱除步骤。
未反应的气相原料、分离得到的Lewis酸催化剂可返回调聚步骤重新利用。
采用气相色谱分析气相和液相物料，一氟一氯甲烷转化率为76.5％，3-氯-1,1,1,2-四氟丙烷选择性为81.2％，主要副产物为1-氯-1,1,2,3-四氟丙烷，选择性为15.3％，还有少量其他副产物。
二、脱除步骤
B1.采用内径为19mm、长度为800mm的Inconel合金材质的反应管作为固定床反应器，将体积为20mL的cat 2.1装填入固定床反应器中部，连接反应管线，通入氮气进行吹扫，氮气流量为100mL/min；
B2.设定反应温度为450℃，升温速率为5℃/min，反应炉开始升温；
B3.催化剂床层到达反应温度后将氮气流量调整至20mL/min，同时采用蠕动泵将纯度为99.9％的3-氯-1,1,1,2-四氟丙烷以5.0g/h的速度连续通入固定床反应器中，开始反应；
B4.流出反应器的气体混合物通过保温处理，由在线GC和GC/MS分析，3- 氯-1,1,1,2-四氟丙烷转化率为96.8％，产物中2,3,3,3-四氟丙烯含量为56.3％，1-氯-2,3,3,3-四氟丙烯含量为31.4％。
实施例2.2
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯联产制备方法，操作同实施例2.1，区别仅在于：调聚步骤中，采用ZrCl 4代替HfCl 4，用量为4.0g；一氟一氯甲烷用量增加至39.7g(0.58mol)，三氟乙烯用量增加至71.3g(0.87mol)，其他条件保持不变。
采用气相色谱分析调聚步骤的气相和液相物料，一氟一氯甲烷转化率为99.0％，3-氯-1,1,1,2-四氟丙烷选择性为89.9％，主要副产物为1-氯-1,1,2,3-四氟丙烷，选择性为5.3％，还有少量其他副产物。
实施例2.3
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯联产制备方法，操作同实施例2.2，区别仅在于：调聚步骤中，不采用二氯甲烷，且三氟乙烯用量增加至95.1g(1.16mol)，同时反应温度增加至30℃，初始反应压力增加至1.5MPa，其他条件保持不变。
采用气相色谱分析调聚步骤的气相和液相物料，一氟一氯甲烷转化率为99.5％，3-氯-1,1,1,2-四氟丙烷选择性为88.1％，主要副产物为1-氯-1,1,2,3-四氟丙烷，选择性为4.1％，还有少量其他副产物。
实施例2.4
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯联产制备方法，操作同实施例2.2，区别仅在于：调聚步骤中，采用AlCl 3代替ZrCl 4，用量不变，同样为4g；同时不采用二氯甲烷，且三氟乙烯用量减少至52.5g(0.64mol)，其他条件保持不变。
采用气相色谱分析调聚步骤的气相和液相物料，一氟一氯甲烷转化率为99.6％，3-氯-1,1,1,2-四氟丙烷选择性为75.5％，主要副产物为1-氯-1,1,2,3-四氟丙烷，选择性为15.9％，还有少量其他副产物。
实施例2.5
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯联产制备方 法，操作同实施例2.1，区别仅在于：在调聚步骤的A2步骤中，在高压釜中事先通入一氟一氯甲烷和三氟乙烯，采用高纯高压氮气对高压釜进行加压处理，将高压釜内压力由0.9MPa提升至3.0MPa，其他条件保持不变。
采用气相色谱分析调聚步骤的气相和液相物料，一氟一氯甲烷转化率为99.8％，3-氯-1,1,1,2-四氟丙烷选择性为88.6％，主要副产物为1-氯-1,1,2,3-四氟丙烷，选择性为7.6％，还有少量其他副产物。
实施例2.6
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯联产制备方法，操作同实施例2.1，区别仅在于：脱除步骤中，采用cat2.3代替cat 2.1。
对脱除反应产物进行色谱分析，3-氯-1,1,1,2-四氟丙烷转化率为89.3％，产物中2,3,3,3-四氟丙烯含量为90.3％，1-氯-2,3,3,3-四氟丙烯含量为7.7％。
实施例2.7
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯联产制备方法，操作同实施例2.1，区别仅在于：脱除步骤中，cat 2.1用量增加至40mL。
对脱除反应产物进行色谱分析，3-氯-1,1,1,2-四氟丙烷转化率为95.8％，产物中2,3,3,3-四氟丙烯含量为65.7％，1-氯-2,3,3,3-四氟丙烯含量为26.8％。
实施例2.8
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯联产制备方法，操作同实施例2.1，区别仅在于：脱除步骤中，采用cat 2.2代替cat 2.1。
对脱除反应产物进行色谱分析，3-氯-1,1,1,2-四氟丙烷转化率为70.1％，产物中2,3,3,3-四氟丙烯含量为39.2％，1-氯-2,3,3,3-四氟丙烯含量为28.5％。
实施例2.9
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯联产制备方法，操作同实施例2.1，区别仅在于：脱除步骤中，反应温度为400℃。
对脱除反应产物进行色谱分析，3-氯-1,1,1,2-四氟丙烷转化率为96.7％，产物中2,3,3,3-四氟丙烯含量为85.2％，1-氯-2,3,3,3-四氟丙烯含量为10.3％。
对比例2.1
本对比例提出了一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯联产制备方法， 操作同实施例2.1，区别仅在于：采用三氯甲烷代替二氯甲烷，用量为20.0g，其他条件保持不变。
对调聚步骤反应后的物料进行色谱分析，一氟一氯甲烷转化率为86.9％，3-氯-1,1,1,2-四氟丙烷选择性为46.2％，有大量一氟一氯甲烷的歧化产物二氯甲烷产生，选择性达到40.3％，还有少量其他调聚副产物。
对比例2.2
本对比例提出了一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯联产制备方法，操作同实施例2.1，区别仅在于：采用ZnCl 2代替HfCl 4，用量为3.0g，其他条件保持不变。
对调聚步骤反应后的物料进行色谱分析，一氟一氯甲烷转化率为20.8％，无目标产物3-氯-1,1,1,2-四氟丙烷产生。
对比例2.3
本对比例提出了一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯联产制备方法，操作同实施例2.1，区别仅在于：不加入HfCl 4和二氯甲烷，其他条件保持不变。
对调聚步骤反应后的物料进行色谱分析，一氟一氯甲烷转化率为7.7％，无目标产物3-氯-1,1,1,2-四氟丙烷产生，仅有少量一氟一氯甲烷的歧化产物二氯甲烷产生。
对比例2.4
本对比例提出了一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯联产制备方法，操作同实施例2.1，区别仅在于：脱除步骤中，采用预处理后(120℃干燥12h)的活性炭代替cat 2.1，其他条件保持不变。
对脱除反应产物进行色谱分析，3-氯-1,1,1,2-四氟丙烷转化率为99.7％，产物中2,3,3,3-四氟丙烯含量为99.0％，无1-氯-2,3,3,3-四氟丙烯生成。
对比例2.5
本对比例提出了一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯联产制备方法，操作同实施例2.1，区别仅在于：采用Al 2O 3代替cat 2.1，其他条件保持不变。
对脱除反应产物进行色谱分析，3-氯-1,1,1,2-四氟丙烷转化率为50.1％，产物中2,3,3,3-四氟丙烯含量为3.1％，1-氯-3,3,3-三氟丙烯含量为62.2％，无1-氯 -2,3,3,3-四氟丙烯产生。
本发明实施例的第三方面，提供一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法。
制备例3.1
本制备例制备Cr 2O 3与活性炭粉末共混催化剂Cr 2O 3-AC，制备步骤包括：
S1.将Cr 2O 3和椰壳类活性炭粉末按质量配比为1/9进行配料，并将配料放入球磨机中进行球磨混合，使各组分均匀分散；
S2.混合后物料过筛，筛除混合不均匀部分；
S3.过筛后物料送入压片机进行压片成型，制成柱状型催化剂；
S4.对成型后催化剂在120℃干燥处理12h，制备得到Cr 2O 3-AC催化剂，记为cat 3.1。
制备例3.2
本制备例的操作同制备例3.1，区别仅在于：采用AlF 3替代Cr 2O 3，制备得到AlF 3-AC催化剂，记为cat 3.2。
制备例3.3
本制备例的操作同制备例3.1，区别仅在于：Cr 2O 3与活性炭的质量配比改为1/4，制备得到Cr 2O 3-AC催化剂，记为cat 3.3。
实施例3.1
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯联产制备方法，包括调聚步骤和脱卤化氢步骤，具体如下：
一、调聚步骤
A1.采用容积为250mL的Inconel合金材质的高压釜作为反应器，将3.0g HfCl 4和20.0g二氯甲烷分别加入反应釜中，密封反应釜后通入1.0MPa以上氮气置换反应釜内空气，重复进行三次；
A2.反应釜内空气置换完全后先后通入一氟一氯甲烷19.9g(0.29mol)和三氟乙烯24.6g(0.30mol)；
A3.设定反应温度为10℃，搅拌速率为300rpm，反应初始压力为0.9MPa，随着反应的进行压力逐渐降低，反应时间为10h；
A4.反应结束，收集未反应的气相原料三氟乙烯和/或一氟一氯甲烷，以及少量调聚产物和二氯甲烷；对反应釜内物料进行过滤或蒸馏等固液分离处理，固体部分为Lewis酸催化剂(HfCl 4)，液相物料为二氯甲烷和调聚产物，经精馏分离获得纯度为99.9％的3-氯-1,1,1,2-四氟丙烷，用于脱卤化氢步骤。
未反应的气相原料，分离得到的Lewis酸催化剂可返回调聚步骤重新利用。
采用气相色谱分析气相和液相物料，一氟一氯甲烷转化率为76.5％，3-氯-1,1,1,2-四氟丙烷选择性为81.2％，主要副产物为1-氯-1,1,2,3-四氟丙烷，选择性为15.3％，还有少量其他副产物。
二、脱卤化氢步骤
B1.采用内径为19mm、长度为800mm的Inconel合金材质的反应管作为固定床反应器，将体积为20mL的cat 3.1装填入固定床反应器中部，连接反应管线，通入氮气进行吹扫，氮气流量为100mL/min；
B2.设定反应温度为350℃，升温速率为5℃/min，反应炉开始升温；
B3.催化剂床层到达反应温度后将氮气流量调整至20mL/min，同时将纯度为99.9％的3-氯-1,1,1,2-四氟丙烷以5.0g/h的速度连续通入固定床反应器中，开始反应；
B4.流出反应器的气体混合物通过保温处理，由在线GC和GC/MS分析，3-氯-1,1,1,2-四氟丙烷转化率达88.7％，产物中2,3,3,3-四氟丙烯含量达24.1％，1-氯-3,3,3-三氟丙烯含量达58.7％。
实施例3.2
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯联产制备方法，操作同实施例3.1，区别仅在于：调聚步骤中，采用ZrCl 4代替HfCl 4，用量为4.0g；一氟一氯甲烷用量增加至39.7g(0.58mol)，三氟乙烯用量增加至71.3g(0.87mol)，其他条件保持不变。
采用气相色谱分析调聚步骤的气相和液相物料，一氟一氯甲烷转化率为99.0％，3-氯-1,1,1,2-四氟丙烷选择性为89.9％，主要副产物为1-氯-1,1,2,3-四氟丙烷，选择性为5.3％，还有少量其他副产物。
实施例3.3
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯联产制备方法，操作同实施例3.2，区别仅在于：调聚步骤中，不采用二氯甲烷，且三氟乙烯用量增加至95.1g(1.16mol)，同时反应温度增加至30℃，初始反应压力增加至1.5MPa，其他条件保持不变。
采用气相色谱分析调聚步骤的气相和液相物料，一氟一氯甲烷转化率为99.5％，3-氯-1,1,1,2-四氟丙烷选择性为88.1％，主要副产物为1-氯-1,1,2,3-四氟丙烷，选择性为4.1％，还有少量其他副产物。
实施例3.4
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯联产制备方法，操作同实施例3.2，区别仅在于：调聚步骤中，采用AlCl 3代替ZrCl 4，用量不变，同样为4.0g；同时不采用二氯甲烷，且三氟乙烯用量减少至52.5g(0.64mol)，其他条件保持不变。
采用气相色谱分析调聚步骤的气相和液相物料，一氟一氯甲烷转化率为99.6％，3-氯-1,1,1,2-四氟丙烷选择性为75.5％，主要副产物为1-氯-1,1,2,3-四氟丙烷，选择性为15.9％，还有少量其他副产物。
实施例3.5
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯联产制备方法，操作同实施例3.1，区别仅在于：在调聚步骤的A2步骤中，在高压釜中依次通入一氟一氯甲烷和三氟乙烯后，采用高纯高压氮气对高压釜进行加压处理，将高压釜内压力由0.9MPa提升至3.0MPa，其他条件保持不变。
采用气相色谱分析调聚步骤的气相和液相物料，一氟一氯甲烷转化率为99.8％，3-氯-1,1,1,2-四氟丙烷选择性为88.6％，主要副产物为1-氯-1,1,2,3-四氟丙烷，选择性为7.6％，还有少量其他副产物。
实施例3.6
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯联产制备方法，操作同实施例3.1，区别仅在于：脱卤化氢步骤中，采用cat 3.2代替cat 3.1。
对脱卤化氢反应产物进行色谱分析，3-氯-1,1,1,2-四氟丙烷转化率为92.9％，产物中2,3,3,3-四氟丙烯含量为20.3％，1-氯-3,3,3-三氟丙烯含量为58.7％。
实施例3.7
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯联产制备方法，操作同实施例3.1，区别仅在于：脱卤化氢步骤中，cat 3.1用量增加至40mL。
对脱卤化氢反应产物进行色谱分析，3-氯-1,1,1,2-四氟丙烷转化率超过95.9％，产物中2,3,3,3-四氟丙烯含量为16.1％，1-氯-3,3,3-三氟丙烯含量为44.6％。
实施例3.8
本实施例提出了一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯联产制备方法，操作同实施例3.1，区别仅在于：脱卤化氢步骤中，反应温度为450℃。
对脱卤化氢反应产物进行色谱分析，3-氯-1,1,1,2-四氟丙烷转化率为98.3％，产物中2,3,3,3-四氟丙烯含量为15.9％，1-氯-3,3,3-三氟丙烯含量为60.0％。
对比例3.1
本对比例提出了一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯联产制备方法，操作同实施例3.1，区别仅在于：采用三氯甲烷代替二氯甲烷，用量为20g，其他条件保持不变。
对调聚步骤反应后的物料进行色谱分析，一氟一氯甲烷转化率为86.9％，3-氯-1,1,1,2-四氟丙烷选择性为46.1％，有大量一氟一氯甲烷的歧化产物二氯甲烷产生，选择性达到40.3％，还有少量其他调聚副产物。
对比例3.2
本对比例提出了一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯联产制备方法，操作同实施例3.1，区别仅在于：采用ZnCl 2代替HfCl 4，用量为3.0g，其他条件保持不变。
对调聚步骤反应后的物料进行色谱分析，一氟一氯甲烷转化率为20.8％，无目标产物3-氯-1,1,1,2-四氟丙烷产生。
对比例3.3
本对比例提出了一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯联产制备方法，操作同实施例3.1，区别仅在于：不加入HfCl 4和二氯甲烷，其他条件保持不变。
对调聚步骤反应后的物料进行色谱分析，一氟一氯甲烷转化率为7.6％，无目标产物3-氯-1,1,1,2-四氟丙烷产生，仅有少量一氟一氯甲烷的歧化产物二氯甲 烷产生。
对比例3.4
本对比例提出了一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯联产制备方法，操作同实施例3.1，区别仅在于：脱卤化氢步骤中，采用预处理后(120℃干燥12h)的椰壳类活性炭代替cat 3.1，其他条件保持不变。
对脱卤化氢反应产物进行色谱分析，3-氯-1,1,1,2-四氟丙烷转化率超过99.7％，产物中2,3,3,3-四氟丙烯含量为99.0％，无1-氯-3,3,3-三氟丙烯生成。
对比例3.5
本对比例提出了一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯联产制备方法，操作同实施例3.1，区别仅在于：采用Pd/AC催化剂(Pd负载量为1wt％)代替cat 3.1，其他条件保持不变。
对脱卤化氢反应产物进行色谱分析，3-氯-1,1,1,2-四氟丙烷转化率为83.5％，产物中2,3,3,3-四氟丙烯含量为96.4％，1-氯-2,3,3,3-四氟丙烯含量为1.3％，无1-氯-3,3,3-三氟丙烯产生。

Claims (38)

  1. 一种两步法制备2,3,3,3-四氟丙烯的方法，其特征在于：所述方法包括：
    A1.调聚步骤：一氟一氯甲烷和三氟乙烯在调聚催化剂作用下经加压调聚反应制备获得3-氯-1,1,1,2-四氟丙烷；所述调聚催化剂为Lewis酸催化剂或Lewis酸催化剂和二氯甲烷的混合催化剂；
    A2.脱氯化氢步骤：3-氯-1,1,1,2-四氟丙烷在活性炭的催化作用下脱氯化氢获得2,3,3,3-四氟丙烯。
  2. 根据权利要求1所述的两步法制备2,3,3,3-四氟丙烯的方法，其特征在于：所述Lewis酸催化剂选自Al、Sb、Ti、Zr、Hf中的至少一种卤化物。
  3. 根据权利要求2所述的两步法制备2,3,3,3-四氟丙烯的方法，其特征在于：所述Lewis酸催化剂选自ZrCl 4、HfCl 4、TiCl 4、AlCl 3、AlF 3、SbF 5中至少一种。
  4. 根据权利要求1所述的两步法制备2,3,3,3-四氟丙烯的方法，其特征在于：所述一氟一氯甲烷与三氟乙烯的摩尔配比为1:0.1～1:10。
  5. 根据权利要求1所述的两步法制备2,3,3,3-四氟丙烯的方法，其特征在于：所述Lewis酸催化剂为一氟一氯甲烷质量的0.01～50wt％。
  6. 根据权利要求1所述的两步法制备2,3,3,3-四氟丙烯的方法，其特征在于：所述二氯甲烷与一氟一氯甲烷的摩尔配比为：1:0.01～1:10。
  7. 根据权利要求1所述的两步法制备2,3,3,3-四氟丙烯的方法，其特征在于：所述加压调聚反应在-30～100℃温度和0.5～5.0MPa压力下进行，反应时间为1～50h。
  8. 根据权利要求1所述的两步法制备2,3,3,3-四氟丙烯的方法，其特征在于：所述活性炭选自果壳类活性炭、煤质类活性炭或木质类活性炭。
  9. 根据权利要求1所述的两步法制备2,3,3,3-四氟丙烯的方法，其特征在于：所述脱氯化氢步骤的反应温度为200～500℃。
  10. 根据权利要求1所述的两步法制备2,3,3,3-四氟丙烯的方法，其特征在于：经调聚步骤获得的3-氯-1,1,1,2-四氟丙烷经精馏分离后用于脱氯化氢步骤。
  11. 一种2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯的联产制备方法，其特征在于：所述联产制备方法包括：
    A1.调聚步骤：一氟一氯甲烷和三氟乙烯在调聚催化剂作用下经加压调聚反应制备获得3-氯-1,1,1,2-四氟丙烷；所述调聚催化剂为Lewis酸催化剂或Lewis 酸催化剂和二氯甲烷的混合催化剂；
    A2.脱除步骤：3-氯-1,1,1,2-四氟丙烷在活性炭负载贵金属催化剂作用下，同时发生脱氯化氢反应和脱氢反应获得2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯，所述活性炭负载贵金属催化剂为Pd/AC、Pt/AC中的至少一种。
  12. 根据权利要求11所述的2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯的联产制备方法，其特征在于：所述Lewis酸催化剂选自Al、Sb、Ti、Zr、Hf中的至少一种卤化物。
  13. 根据权利要求12所述的2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯的联产制备方法，其特征在于：所述Lewis酸催化剂选自ZrCl 4、HfCl 4、TiCl 4、AlF 3、AlCl 3、SbF 5中至少一种。
  14. 根据权利要求11所述的2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯的联产制备方法，其特征在于：所述一氟一氯甲烷与三氟乙烯的摩尔配比为1:0.1～1:10。
  15. 根据权利要求11所述的2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯的联产制备方法，其特征在于：所述Lewis酸催化剂为一氟一氯甲烷质量的0.01～50wt％。
  16. 根据权利要求11所述的2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯的联产制备方法，其特征在于：所述二氯甲烷与一氟一氯甲烷的摩尔配比为：1:0.01～1:10。
  17. 根据权利要求11所述的2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯的联产制备方法，其特征在于：所述加压调聚反应在-30～100℃温度和0.5～5.0MPa压力下进行，反应时间为1～50h。
  18. 根据权利要求11所述的2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯的联产制备方法，其特征在于：所述活性炭负载贵金属催化剂采用浸渍法制备，包括如下步骤：
    B1.载体预处理：活性炭在90～120℃中干燥处理12h以上；
    B2.金属盐浸渍：采用Pd或Pt的可溶性盐溶液在真空或常压条件下浸渍预处理后的活性炭；
    B3.将浸渍后的活性炭进行干燥处理，干燥温度90～120℃，干燥时间12h以上；
    B4.将干燥处理后的活性炭用氢氮混合气进行还原处理得到所述活性炭负载贵金属催化剂；所述氢氮混合气中氢气的体积比为5～50％，还原温度为150～300℃。
  19. 根据权利要求11所述的2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯的联产制备方法，其特征在于：活性炭负载贵金属催化剂中，Pd、Pt的负载量为0.1～5.0wt％，经A2脱除步骤获得含30～90％的2,3,3,3-四氟丙烯和10～50％的1-氯-2,3,3,3-四氟丙烯。
  20. 根据权利要求11所述的2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯的联产制备方法，其特征在于：3-氯-1,1,1,2-四氟丙烷汽化后由氮气载入催化剂床层进行脱除反应，脱除反应的物料体积空速为50～300h -1，N 2/3-氯-1,1,1,2-四氟丙烷的体积比为(0.5～3.0)：1。
  21. 根据权利要求11所述的2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯的联产制备方法，其特征在于：所述脱除步骤的反应温度为300～600℃。
  22. 根据权利要求11所述的2,3,3,3-四氟丙烯和1-氯-2,3,3,3-四氟丙烯的联产制备方法，其特征在于：经调聚步骤获得的3-氯-1,1,1,2-四氟丙烷经精馏分离后用于脱除步骤。
  23. 一种2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：所述联产制备方法包括：
    A1.调聚步骤：一氟一氯甲烷和三氟乙烯在调聚催化剂作用下经加压调聚反应制备获得3-氯-1,1,1,2-四氟丙烷；所述调聚催化剂为Lewis酸催化剂或Lewis酸催化剂和二氯甲烷的混合催化剂；
    A2.脱卤化氢步骤：3-氯-1,1,1,2-四氟丙烷在复合型脱卤催化剂作用下，同时发生脱氯化氢反应和脱氟化氢反应获得2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯。
  24. 根据权利要求23所述的2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：所述Lewis酸催化剂选自Al、Sb、Ti、Zr、Hf中的至少一种卤化物。
  25. 根据权利要求24所述的2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：所述Lewis酸催化剂选自ZrCl 4、HfCl 4、TiCl 4、AlF 3、 AlCl 3、SbF 5中至少一种。
  26. 根据权利要求23所述的2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：所述一氟一氯甲烷与三氟乙烯的摩尔配比为1:0.1～1:10。
  27. 根据权利要求23所述的2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：所述Lewis酸催化剂为一氟一氯甲烷质量的0.01～50wt％。
  28. 根据权利要求23所述的2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：所述二氯甲烷与一氟一氯甲烷的摩尔配比为：1:0.01～1:10。
  29. 根据权利要求23所述的2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：所述加压调聚反应在-30～100℃温度和0.5～5.0MPa压力下进行，反应时间为1～50h。
  30. 根据权利要求23所述的2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：所述复合型脱卤催化剂由Al、Mg或Cr中的至少一种的氧化物或氟化物与活性炭粉末制备获得。
  31. 根据权利要求30所述的2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：所述Al、Mg或Cr中的至少一种的氧化物或氟化物选自Al 2O 3、AlF 3、MgF 2和Cr 2O 3中至少一种。
  32. 根据权利要求30所述的2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：所述活性炭粉末选自果壳类活性炭、煤质类活性炭或木质类活性炭。
  33. 根据权利要求31所述的2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：Al 2O 3的含量为催化剂总量的1.0～20wt％，AlF 3的含量为催化剂总量的1.0～20wt％，MgF 2的含量为催化剂总量的1.0～20wt％，Cr 2O 3的含量为催化剂总量的1.0～20wt％。
  34. 根据权利要求23所述的2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：3-氯-1,1,1,2-四氟丙烷汽化后由氮气载入催化剂床层进行脱卤化氢反应，所述脱卤化氢反应的物料体积空速为50～300h -1，N 2/3-氯-1,1,1,2-四氟丙烷的体积配比为(0.5～3.0)：1。
  35. 根据权利要求23-34任一所述的2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：经脱卤化氢步骤获得含10～50％的2,3,3,3-四氟丙烯和10～70％的1-氯-3,3,3-三氟丙烯。
  36. 根据权利要求23所述的2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：所述复合型脱卤催化剂采用共混合法制备，包括如下步骤：
    B1.混合：将Al 2O 3和/或AlF 3和/或MgF 2和/或Cr 2O 3与活性炭粉末以(0.01～0.25):1的质量比配料并采用机械搅拌或球磨的方式充分混合；
    B2.过筛：对混合物料进行过筛处理，将混合不均匀部分筛除；
    B3.成型：将过筛后物料送入压片机进行压片成型；
    B4.对成型后催化剂进行干燥处理，制备得到所述复合型脱卤催化剂。
  37. 根据权利要求23所述的2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：所述脱卤化氢步骤的反应温度为300～500℃。
  38. 根据权利要求23所述的2,3,3,3-四氟丙烯和1-氯-3,3,3-三氟丙烯的联产制备方法，其特征在于：经调聚步骤获得的3-氯-1,1,1,2-四氟丙烷经精馏分离后用于脱卤化氢步骤。
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