CN116139890A - Boron element-made high specific surface area chromium-based catalyst and preparation method of high-proportion Z-fluoroolefin/E-fluoroolefin - Google Patents

Boron element-made high specific surface area chromium-based catalyst and preparation method of high-proportion Z-fluoroolefin/E-fluoroolefin Download PDF

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CN116139890A
CN116139890A CN202310443788.2A CN202310443788A CN116139890A CN 116139890 A CN116139890 A CN 116139890A CN 202310443788 A CN202310443788 A CN 202310443788A CN 116139890 A CN116139890 A CN 116139890A
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examples
chromium
catalyst
salt
containing compound
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权恒道
张呈平
庆飞要
董利
郭勤
贾晓卿
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Quanzhou Yuji New Material Technology Co ltd
Beijing Yuji Science and Technology Co Ltd
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Quanzhou Yuji New Material Technology Co ltd
Beijing Yuji Science and Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • B01J35/615—
    • 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
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers

Abstract

A boron-containing chromium-based catalyst for the preparation of fluorine-containing olefins is disclosed, wherein the catalyst comprises a chromium salt and a boron-containing compound, or wherein the catalyst comprises a chromium salt, a second metal salt other than chromium, and a boron-containing compound. The application also discloses a preparation method of the high-proportion Z-fluoroolefin/E-fluoroolefin, and under the action of the boron-containing chromium-based catalyst, the chlorine-containing compound and anhydrous hydrogen fluoride undergo fluorine-chlorine exchange reaction to prepare the high-proportion Z-fluoroolefin/E-fluoroolefin.

Description

Boron element-made high specific surface area chromium-based catalyst and preparation method of high-proportion Z-fluoroolefin/E-fluoroolefin
Technical Field
The application relates to the field of chemical synthesis, in particular to a preparation method and application of a catalyst, and a preparation method of high-proportion Z-fluoroolefin/E-fluoroolefin.
Background
E-1-chloro-3, 3-trifluoropropene (HCFO-1233 zd (E)) Z-1-chloro-3, 3-trifluoropropene (HCFO-1233 zd (Z)) E-1, 3-tetrafluoropropene (HFO-1234 ze (E)), Z-1, 3-tetrafluoropropene (HFO-1234 ze (Z)), and E-1, 3-hexafluoro-2-butene (HFO-1336) mzz (E)) and Z-1, 3-hexafluoro-2-butene (HFO-1336 mzz (Z)) is an important species in fourth chlorofluorocarbon (CFCs) substitutes. Wherein the GWP of HCFO-1233zd (E) 100 (GWP value based on 100 years) of 7, boiling point of 19 ℃, and is widely used as a foaming agent, a refrigerant, etc. for replacing the refrigerants HCFC-123 and HFC-134a, and the substitute foaming agent HFC-245fa. The KB value of HCFO-1233zd (Z) is 34, the boiling point is 39 ℃, and the HCFO-1233zd (Z) can be used as a cleaning agent to replace HCFC-141b which is widely used. HFO-1234ze (E) is used primarily as a refrigerant, blowing agent and propellant, while HFO-1234ze (Z) is used primarily as a key heat transfer fluid for 5G base stations, high temperature heat pumps. HFO-1336mzz (E) is mainly used as a refrigerant, a foaming agent, a heat pump heat transfer working medium, etc., while HFO-1336mzz (Z) is mainly used as a foaming agent, a heat pump heat transfer working medium, etc. The main synthetic route of the fluorine-containing olefin is as follows
Synthetic route for simultaneous preparation of HCFO-1233zd (E) and HCFO-1233zd (Z)
The main synthesis route reported at present is to take 1, 3-pentachloropropane (HCC-240 fa) as raw material, and take gas-phase fluorine-chlorine exchange reaction with HF in the presence of fluorination catalyst to obtain HCFO-1233zd (E), while the content of HCFO-1233zd (Z) is generally lower.
Patent document PCT/JP2009/066528 reports that activated carbon is used for catalyzing HCC-240fa to perform a gas phase fluorine-chlorine exchange reaction at a higher reaction pressure (0.8 MPa) under the reaction conditions of: n (HF) to n (HCC-240 fa) =19.7:1, at a reaction temperature of 250 ℃, at a reaction pressure of 0.8MPa, and for a contact time of 10.2 s; the reaction result was that the conversion of HCC-240fa was 99.8%, the selectivity for HCFO-1233zd (E) was 84.8%, and the selectivity for HCFO-1233zd (Z) was 11.7%.
Patent document PCT/US2011024483 reports that when a chromium oxyfluoride catalyst is used for the vapor phase fluorine-chlorine exchange reaction of HCC-240fa, the conversion rate of CC-240fa is 100%, the selectivity of HCFO-1233zd (E) is 83.0% and the selectivity of HCFO-1233zd (Z) is 9.0% under the conditions of "n (HF): n (HCC-240 fa) =9:1, the reaction temperature is 328 to 332 ℃, the reaction pressure is 0.014MPa, and the contact time is 9.2 s".
Patent document US20200039902A1 reports Zn/Cr 2 O 3 (3% by mass of Zn) when the catalyst was used in the vapor phase fluorine-chlorine exchange reaction of HCC-240fa, under the conditions of "n (HF): n (HCC-240 fa) =15:1, reaction temperature 200 ℃, reaction pressure 0.5MPa, and contact time 12 s", the HCC-240fa conversion rate was 100%, the HCFO-1233zd (E) selectivity was 81.4%, and the HCFO-1233zd (Z) selectivity was 11.7%.
Patent document CN108383679A reports that HCFO-1233zd (E) can be obtained by two-step gas-phase fluorine-chlorine exchange reaction using a mixture of HCC-240fa and HCC-240db as a raw material, by the following method in which a chromium-based catalyst Co+Ni/Cr is packed 2 O 3 +A l2 O 3 In a reaction (mass fractions of Co and Ni are 5% and 10%, respectively), HF, HCC-240fa and HCC-240db with the mass ratio of 70:6:1 are introduced, the reaction temperature is 350 ℃, and the contact time is 7.2 s; the reacted outlet material is directly fed into catalyst Ga/Cr without separation 2 O 3 (mass fraction of Ga: 6%) was used, the reaction temperature of the two reactions was 280 ℃, 40 h was continuously run, the GC peak area percentage content of HCFO-1233zd (E) in the organic phase of the two-reaction stream was 76.2%, the HCFO-1233zd (Z) content was 0, and the HFO-1234yf content was 23.8%.
Patent document CN112723985B reports SbF 5 Tungsten oxyfluoride is used in the vapor phase fluorine-chlorine exchange reaction of HCC-240fa, under the conditions of "n (HF): n (HCC-240 fa) =15:1, reaction temperature 250 ℃, reaction pressure 0.1MPa, contact time 30 s", HCC-240fa conversion rate 100%, HCFO-1233zd (E) selectivity 95.4%, HCFO-1233zd (Z) selectivity 4.5%.
In the prior art route of fluorine-chlorine exchange reaction, the content of HCFO-1233zd (Z) obtained by synthesis is lower than that of HCFO-1233zd (E), the ratio of HCFO-1233zd (Z)/HCFO-1233 zd (E) is less than 14.4%, and few reports that the ratio of HCFO-1233zd (Z)/HCFO-1233 zd (E) exceeds 20% are found. Thus, it is difficult to prepare both HCFO-1233zd (Z)/HCFO-1233 zd (E) in proportions equal to 20% HCFO-1233zd (E) and HCFO-1233zd (Z) simultaneously using prior art routes.
(II) synthetic route for simultaneously preparing HFO-1234ze (E) and HFO-1234ze (Z)
The synthesis route of HFO-1234ze (E) mainly uses E-1-chloro-3, 3-trifluoropropene (HCFO-1233 zd (E)) or Z-1-chloro-3, 3-trifluoropropene (HCFO-1233 zd (Z)) as raw materials, and the raw materials are subjected to gas-phase fluorine-chlorine exchange reaction with HF in the presence of a fluorination catalyst to obtain the HFO-1234ze (E), wherein the HFO-1234ze (Z) content is very low. Among the documents currently disclosing the E-1-chloro-3, 3-trifluoropropene (HCFO-1233 zd (E)) or Z-1-chloro-3, 3-trifluoropropene (HCFO-1233 zd (Z)) fluorination routes, most do not disclose the specific content of HFO-1234ze (E) and HFO-1234ze (Z) in the product, but will both be HFO-1234ze, e.g., US5895825A, PCT/JP1996002942, PCT/FR2015/051653, etc., and few reports on the selectivity data for both HFO-1234ze (E) and HFO-1234ze (Z), respectively.
Patent documents PCT/JP2013/061591 and PCT/JP2011/071947 report 1200mL CrF 3 /AlF 3 When the catalyst was used in the gas phase fluorine-chlorine exchange reaction of HCFO-1233zd, the conversion of HCFO-1233zd was 59.2%, the HFO-1234ze (E) selectivity was 58.1% and the HFO-1234ze (Z) selectivity was 12.7% under the conditions of "n (HF): n (HCFO-1233 zd) =19:1, reaction temperature 360℃and contact time 3.44 s".
Patent document CN105727929a reports CrF 3 /GaF 3 When the catalyst is used in the gas phase fluorine-chlorine exchange reaction of HCFO-1233zd, the catalyst is prepared by the reaction of' n (HF): n (O) 2 ) Under the conditions of n (HCFO-1233 zd) =10:0.08:1, reaction temperature of 390 ℃, reaction pressure of 0.7-1.0MPa and contact time of 3.25 s', HCFO-1233zd conversion rate of 41.20%, HFO-1234ze (E) selectivity of 70.32% and HFO-1234ze (Z) selectivity of 12.31%.
Patent document CN112723983a reports 20% sbf 5 Tungsten oxyfluoride catalyst for gas phase of E-HCFO-1233zdIn the case of fluorine-chlorine exchange reaction, the ratio of "n (HF): n (O) 2 ) Under the conditions that the reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, and the contact time is 6 s', the conversion rate of HCFO-1233zd is 100%, the selectivity of HFO-1234ze (E) is 96.7% and the selectivity of HFO-1234ze (Z) is 3.2%, and the ratio of n (E-HCFO-1233 zd) =10:1.
Patent document CN114644546a reports CrF 3 /MgF 2 When the catalyst was used in the gas phase fluorine-chlorine exchange reaction of HCFO-1233zd, the conversion of HCFO-1233zd was 90%, the HFO-1234ze (E) selectivity was 93% and the HFO-1234ze (Z) selectivity was 6% under the conditions of "n (HF): n (HCFO-1233 zd) =6.1:1, reaction temperature 400 ℃, reaction pressure 0.8MPa and contact time 9.4 s".
In the above-described prior art route to the fluorine-chlorine exchange reaction, there is the problem that (1) when the conversion of HCFO-1233zd is high, the HFO-1234ze (Z) selectivity is very low, and at this time the HFO-1234ze (Z)/HFO-1234 ze (E) is at most 6.5% (see CN 114644546A); (2) At lower HCFO-1233zd conversion, HFO-1234ze (Z) selectivity is relatively high, at which time the ratio HFO-1234ze (Z)/HFO-1234 ze (E) is up to 21.8% (see WO2013161692A1 and WO2012063566A 1). From literature studies, we have concluded that it is difficult to produce both HFO-1234ze (Z)/HFO-1234 ze (E) in proportions equal to 25% HFO-1234ze (E) and HFO-1234ze (Z) simultaneously with high efficiency using prior art routes.
(III) synthetic route for simultaneously preparing HFO-1336mzz (E) and HFO-1336mzz (Z)
At present, the main synthetic route reported in the literature for HFO-1336mzz (E) is to take 1, 3-trichloro-4, 4-trifluoro-but-1-ene (HCFC-343-jfd) or 1,2, 4-pentachlorobut-1, 3-diene (HCO-2320 az) as a raw material, gas phase fluoro-chloro exchange with HF in the presence of a fluorination catalyst yields E-1, 3-hexafluoro-2-butene (HFO-1336 mzz (E)), with very low HFO-1336mzz (Z) content.
PCT/US2020/026570 reports the gas phase fluorine-chlorine exchange reaction of 1,2, 4-pentachlorobutane-1, 3-diene (HCO-2320 az) catalyzed by chromium oxide under the conditions of N (HF) to N (HCO-2320 az) to N (N) 2 ) =23.5:1:11.1, reaction temperature 325 ℃, reaction pressure 11 KPa, contact time 48.4 s; the reaction result was 100% HCO-2320az conversion and 7 HFO-1336mzz (E) selectivity1.7% HFO-1336mzz (Z) selectivity of 0.7%.
Patent document PCT/US 2018/063125 reports that chromium oxyfluoride catalyzes 1, 3-tetrachloro-4, 4-trifluorobutane (HCFC-343, jfd) to undergo a gas phase fluoro-chloro exchange reaction at a reaction temperature of 300 ℃, a reaction pressure of 0-1.03 MPa, and a contact time of 18 s, n (HF): n (HCFC-343 jfd) =22.6:1; the reaction results were 100% HCFC-343jfd conversion with HFO-1336mzz (E) selectivity greater than 85% and HFO-1336mzz (Z) selectivity not disclosed, inferred to be less than 15%. In addition, it has been reported that chromium oxyfluoride catalyzes 1, 3-trichloro-4, 4-trifluoro-1-butene (HCFO-1333 azd) to undergo a gas phase fluoro-chloro exchange reaction under the reaction conditions of n (HF) to n (HCFO-1333 azd) =21.6:1, a reaction temperature of 275 ℃, a reaction pressure of 0-1.03 MPa, and a contact time of 18 s; the reaction results were that HCFO-1333azd conversion was not disclosed, HFO-1336mzz (E) selectivity was greater than 90%, HFO-1336mzz (Z) selectivity was not disclosed, and less than 10% was inferred.
Patent document PCT/CN2015/072307 reports that a fluorination catalyst catalyzes HCFC-343jfd to carry out gas-phase fluorine-chlorine exchange reaction under the reaction conditions of n (HF) to n (HCFC-343 jfd) =6:1, the reaction temperature is 400 ℃, the contact time is 6.9 s, and the operation is 20 hours; the reaction result was 100% conversion of HCFC-343jfd, 96.8% HFO-1336mzz (E) selectivity, and 3.2% or less was inferred without revealing HFO-1336mzz (Z) selectivity.
Patent document CN109553506a reports that aluminium fluoride catalyzes HCFC-343jfd to undergo a gas phase fluoro-chloro exchange reaction under the reaction conditions of n (HF) to n (HCFC-343 jfd) =10:1, a reaction temperature of 280 ℃, a contact time of 6 s, run 24 h; the reaction result was 100% conversion of HCFC-343jfd, 97.9% HFO-1336mzz (E) selectivity, and no HFO-1336mzz (Z) selectivity was disclosed, inferred to be less than 2.1%.
In the technical route of the prior fluorine-chlorine exchange reaction, the following problems are that (1) the content of HFO-1336mzz (Z) obtained by synthesis is far lower than that of HFO-1336mzz (E), and the highest value of the ratio of HFO-1336mzz (Z)/HFO-1336 mzz (E) is 0.97% in the literature which clearly distinguishes the percentages of HFO-1336mzz (Z) and HFO-1336mzz (E) (see CN 113661156A); (2) Some documents explicitly disclose the percentage of HFO-1336mzz (Z), but do not explicitly disclose the percentage of HFO-1336mzz (E), it can be inferred that the upper limit of the ratio HFO-1336mzz (Z)/HFO-1336 mzz (E) is 17.6% (see CN 111433177A). Thus, it is difficult to prepare both HFO-1336mzz (Z)/HFO-1336 mzz (E) ratios equal to 18% or greater of HFO-1336mzz (E) and HFO-1336mzz (Z) with high efficiency using the prior art routes.
In summary, in the above technical route for synthesizing fluoroolefins, there is a problem that in the process of preparing E-fluoroolefins and Z-fluoroolefins simultaneously by catalyzing chlorine-containing compounds with conventional fluorination catalysts, it is difficult to prepare high-proportion Z-fluoroolefins/E-fluoroolefins, so that the prior art is difficult to meet the increasing important demands of the market on Z-fluoroolefin products.
Disclosure of Invention
In view of the above problems, the present application proposes a process for producing a high proportion of Z-fluoroolefins/E-fluoroolefins, and also provides a highly active fluorination catalyst and a process for producing the same, which are necessary for realizing such a production process.
Specifically, the technical proposal of the application is as follows
1. A high specific surface area chromium-based catalyst for boron element pore formation for the preparation of fluoroolefins, wherein the catalyst comprises a chromium salt and a boron-containing compound or the catalyst comprises a chromium salt, a second metal salt other than chromium and a boron-containing compound.
2. The catalyst according to item 1, wherein the boron-containing compound is contained in a chromium salt, and the boron-containing compound is contained in a chromium salt and a second metal salt other than chromium.
3. The catalyst according to item 1 or 2, wherein the second metal salt other than chromium is selected from any one or two or more of cobalt salt, iron salt, zinc salt, magnesium salt, aluminum salt, nickel salt, indium salt, and antimony salt.
4. The catalyst according to item 1 or 2, wherein the boron-containing compound is any one or two or more selected from the following compounds or metal salts thereof 2 O 3 ) Fluoroboric acid (HBF) 4 ) Boric acid (H) 3 BO 3 ) Diboric acid (H) 4 B 2 O 4 ) Triboric acid (H) 3 B 3 O 6 ) Tetraboric acid (H) 2 B 4 O 7 ) Pentaboric acid (H) 4 B 5 O 8 ) Or hexaboric acid (H) 4 B 6 O 11 )。
5. The method according to item 1 or 2, wherein in the catalyst, the mass percentage of the chromium element contained in the chromium salt, the second metal element contained in the second metal salt, and the boron element contained in the boron-containing compound is (70 to 99%) to (0 to 20%) to (1 to 10%), and the sum of the mass percentages of the three elements is 100%.
6. The catalyst according to item 1 or 2, wherein the catalyst is activated by hydrogen fluoride.
7. The catalyst according to item 1 or 2, wherein the catalyst is prepared by a coprecipitation method, an impregnation method or a direct mixing method.
8. The catalyst according to item 1 or 2, wherein the catalyst has a specific surface area of 100m 2 /g～600m 2 /g。
9. The method for producing a catalyst according to any one of items 1 to 8, comprising,
dissolving chromium salt and a boron-containing compound in water, or dissolving chromium salt, a second metal salt and a boron-containing compound in water, wherein the chromium salt and the second metal salt are any one or more of chloride salt, nitrate and acetate;
precipitating the mixture system by adopting a precipitating agent until the pH value is 7.5-8.5, and then filtering to obtain a filter cake;
Washing the filter cake until the filtrate is neutral, drying the obtained filter cake in a baking oven at 60-150 ℃, and roasting the filter cake at 300-500 ℃ for 6-15 hours in a nitrogen atmosphere;
crushing and tabletting the roasted material to obtain a catalyst precursor;
activating the precursor at 200-400 deg.c and with mixed gas of nitrogen and hydrogen fluoride in the molar ratio of 10 to 1 for 6-24 hr to obtain the catalyst.
10. Use of the catalyst of any one of items 1-8 or the catalyst prepared in item 9 in the preparation of a fluoroolefin.
11. Use of the catalyst of any one of items 1-8 or the catalyst prepared in item 9 in the preparation of a high ratio Z-fluoroolefin/E-fluoroolefin.
12. A process for preparing high-proportion Z-fluoroolefin/E-fluoroolefin includes such steps as exchange reaction of chlorine-containing compound with anhydrous hydrogen fluoride to obtain high-proportion Z-fluoroolefin/E-fluoroolefin.
13. The process of item 12, wherein the chlorine-containing compound is a chlorinated alkane and/or chlorinated alkene.
14. The method according to item 13, wherein, the chloralkane is 1, 3-pentachloropropane 1, 3-tetrachloro-4, 4-trifluorobutane or 1,3,4 one or more than two of heptachlorobutanes.
15. The method according to item 13, wherein, the chlorinated alkene is 1, 3-tetrachloropropene, 1, 3-tetrachloropropene, E-1-chloro-3, 3-trifluoropropene Z-1-chloro-3, 3-trifluoropropene, E-1, 3-dichloro-3, 3-difluoropropene one or more than two of Z-1, 3-dichloro-3, 3-difluoropropene, 1, 3-trichloro-4, 4-trifluorobut-1-ene or 1,2, 4-pentachlorobut-1, 3-diene.
16. The method of item 12 or 13, wherein, when the chlorine-containing compound is 1, 3-pentachloropropane when one or more of 1, 3-tetrachloropropene or 1, 3-tetrachloropropene, the reaction conditions are that the reaction pressure is 0.1-2.0 Ma, the mol ratio of the hydrogen fluoride to the chlorine-containing compound is (5-25) to 1, the contact time is 2-200 seconds, and the reaction temperature is 180-400 ℃.
17. The method of item 16, wherein the contact time is 2 to 60 seconds.
18. The process according to item 16 or 17, wherein the resulting products are E-1-chloro-3, 3-trifluoropropene and Z-1-chloro-3, 3-trifluoropropene/E-1-chloro-3, 3-trifluoropropene is not less than 20%.
19. The method of item 12 or 13, wherein, when the chlorine-containing compound is 1, 3-tetrachloro-4, 4-trifluorobutane, 1,3, 4-heptachlorobutane when any one or more of 1, 3-trichloro-4, 4-trifluorobut-1-ene or 1,2, 4-pentachlorobut-1, 3-diene, the reaction conditions are that the reaction pressure is 0.1-2.0 Ma, the mol ratio of the hydrogen fluoride to the chlorine-containing compound is (2-20) to 1, the contact time is 2-100 seconds, and the reaction temperature is 300-500 ℃.
20. The method of claim 19, wherein the contact time is 2 to 60 seconds.
21. The process according to item 18 or 19, wherein the resulting products are E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene, and Z-1, 3-tetrafluoropropene/E-1, 3-tetrafluoropropene is more than or equal to 25%.
22. The process according to item 12 or 13, wherein, when the chlorine-containing compound is any one or more of E-1-chloro-3, 3-trifluoropropene, Z-1-chloro-3, 3-trifluoropropene, E-1, 3-dichloro-3, 3-difluoropropene or Z-1, 3-dichloro-3, 3-difluoropropene, the reaction condition is that the reaction pressure is 0.1 to 2.0Ma, the molar ratio of hydrogen fluoride to chlorine-containing compound is (5 to 25):1, the contact time is 2 to 200 seconds, and the reaction temperature is 200 to 450 ℃.
23. The method of item 22, wherein the contact time is 2 to 60 seconds.
24. The method of item 22 or 23, wherein, the obtained product is E-1, 3-hexafluoro-2 butene and Z-1, 3-hexafluoro-2-butene, and Z-1, 3-hexafluoro-2-butene/E-1, 3-hexafluoro-2-butene is more than or equal to 25 percent.
Effects of the invention
1. The application provides a catalyst applied to preparing fluorine-containing olefin, which is characterized in that boron is introduced into the catalyst, and part of boron is converted into high-volatility boron trifluoride in the activation process and escapes from the surface of the catalyst, so that the catalyst is subjected to pore-forming, the catalyst has abundant micropores and high specific surface area, and the catalyst has high catalytic activity.
2. According to the preparation method of the high-proportion Z-fluoroolefin/E-fluoroolefin, the conversion rate of fluorine-chlorine exchange reaction is remarkably improved by using the catalyst containing boron; meanwhile, boron element remained in the catalyst can enhance the acidity of the catalyst, thereby being beneficial to improving the selectivity of Z-fluoroolefin and increasing the ratio of Z-fluoroolefin/E-fluoroolefin.
3. The composition of the products HFO-1234ze (E) and HFO-1234ze (Z) in the fluorine-chlorine exchange reaction is regulated by regulating the content of boron element in the catalyst, so that the purposes of green process and energy conservation are achieved.
Detailed Description
Exemplary embodiments of the present application are described below, including various details of embodiments of the present application to facilitate understanding, which should be considered as merely exemplary. Accordingly, one of ordinary skill in the art will recognize that various changes and modifications of the embodiments described herein can be made without departing from the scope and spirit of the present application. Also, descriptions of well-known functions and constructions are omitted in the following description for clarity and conciseness.
The application provides a boron element pore-forming high specific surface area chromium-based catalyst for preparing fluorine-containing olefin, which comprises chromium salt and boron-containing compound.
The application also provides a high specific surface area chromium-based catalyst for boron element pore formation for preparing fluorine-containing olefins, comprising a chromium salt, a second metal salt other than chromium, and a boron-containing compound.
The above-mentioned boron element-porous high specific surface area chromium-based catalyst is hereinafter referred to as boron-containing chromium-based catalyst.
According to the method, the boron element is introduced into the chromium-based catalyst, part of the boron element is converted into high-volatility boron trifluoride in the activation process and escapes from the surface of the catalyst, so that the chromium-based catalyst is subjected to pore forming, the catalyst has abundant micropores and high specific surface area, and the catalyst has high catalytic activity.
In the boron-containing chromium-based catalysts of the present application, the chromium salt may be one or more organic or inorganic chromium salts, wherein the oxidation state of the chromium is from 0 to 6. In the present application, the definition of chromium salts includes chromium metals. Generally the chromium salt has the formula CrX n Wherein X may be the same or different organic or inorganic groups and n is an integer of 1 to 6. Examples of organic groups are groups having from about 1 to about 20 carbon atoms selected from alkoxy groups, esters, ketones and/or amine groups. The organic group may beA branched, cyclic or acyclic, aromatic or aliphatic group, and may be a mixture of aliphatic, aromatic and/or aliphatic groups. Examples of inorganic groups include, but are not limited to, halides, sulfates, and/or oxides. In the present application, the chromium salt is not limited, and preferred chromium salts include chromium nitrate, chromium sulfate, chromium acetate, chromium formate, chromium oxalate, chromium phosphate, chromium bromide, chromium iodide, chromium fluoride, chromium chloride, and mixtures thereof.
In the boron-containing chromium-based catalyst of the present application, the second metal salt other than chromium is not limited, and is preferably selected from any one, two, three or four or more of cobalt salt, iron salt, zinc salt, magnesium salt, aluminum salt, nickel salt, indium salt and antimony salt.
In the boron-containing chromium-based catalyst of the present application, the boron-containing compound is not limited, and is preferably selected from any one or two or more of the following compounds or metal salts thereof 2 O 3 ) Fluoroboric acid (HBF) 4 ) Boric acid (H) 3 BO 3 ) Diboric acid (H) 4 B 2 O 4 ) Triboric acid (H) 3 B 3 O 6 ) Tetraboric acid (H) 2 B 4 O 7 ) Pentaboric acid (H) 4 B 5 O 8 ) Or hexaboric acid (H) 4 B 6 O 11 )。
In the boron-containing chromium-based catalyst of the present application, the ratio between the chromium salt and the boron-containing compound, or the ratio between the chromium salt, the second metal salt other than chromium, and the boron-containing compound is not limited. Preferably, the mass percentage of the chromium element contained in the chromium salt, the mass percentage of the second metal element contained in the second metal salt and the mass percentage of the boron element contained in the boron-containing compound are (70-99%) to (0-20%) to (1-10%), and the sum of the mass percentages of the three elements is 100%. For example, the catalyst comprises chromium salt and boron-containing compound, wherein the mass percentage of chromium element contained in the chromium salt and boron element contained in the boron-containing compound can be 90 percent to 10 percent, 91 percent to 9 percent, 92 percent to 8 percent, 93 percent to 7 percent, 94 percent to 6 percent, 95 percent to 5 percent, 96 percent to 4 percent, 97 percent to 3 percent, 98 percent to 2 percent and 99 percent to 1 percent, and the sum of the mass percentages of the two elements is 100 percent; for example, the catalyst includes a chromium salt, a second metal salt other than chromium, and a boron-containing compound, the mass percentage of the chromium element contained in the chromium salt, the mass percentage of the second metal element contained in the second metal salt and the mass percentage of the boron element contained in the boron-containing compound are 70:20:10%, 75:15:10%, 80:10:10%, 85:5:10%, 71:20:9%, 76:15:9%, 81:10:9%, 86:5:9%, 72:20:8%, 77:15:8%, 82:10:8%, 87:5:8:73:20:7:77:15:7:83:10:7:88:5:7:7:74:20:6 70:6:6:84:10:6:89:5:75:20:5:80:15:5:85:10:5:90:5:76:20:4:81:15:4:86:10:4:3:82:15:3:3:87:10:3:92:5:3:78:20:2:83:15:2:88:10:93:5:2:79:20:1:84:1:89:10:1:94:1:3:82:3:20:20:2:3:15:2:88:10:2:93:5:2:20:1:1:9:1:1:9:1:9:1:2:2:2:2:2:2:2:2:2:2:2:10:10:10:1:1:10:10:10:10:10:10:10:10:10:10:2:2:2:2:2:2:2:2:2:2:2:10:10:10:10:10:10:10:10:10:10:10:10:10:10:10:10:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5:5).5 5)5 5)5 5 to the sum of the mass percentages of the three elements is 100 percent.
In a preferred embodiment, the boron-containing chromium-based catalyst of the present application is activated by hydrogen fluoride.
The present application further provides a boron-containing chromium-based catalyst activated by hydrogen fluoride, which is any one of the boron-containing chromium-based catalysts described above.
The boron-containing chromium-based catalyst provided by the application has a high specific surface area, and the specific surface area of the catalyst can reach 100m 2 /g～600m 2 /g, for example, may be 120m 2 /g、140m 2 /g、160m 2 /g、180m 2 /g、200m 2 /g、250m 2 /g、300m 2 /g、350m 2 /g、400m 2 /g、450m 2 /g、500m 2 /g、520m 2 /g、540m 2 /g、560m 2 /g、580m 2 /g、600m 2 /g。
The preparation method of the boron-containing chromium-based catalyst provided by the application is not limited, any preparation method in the field can be used for preparation, and a specific implementation mode is that chromium salt, second metal salt and boron-containing compound are mixed according to a certain proportion of chromium element, second metal element and boron element, and the boron-containing chromium-based catalyst is prepared by a series of chemical reactions or material operations, wherein the preferred preparation method is a coprecipitation method, an impregnation method or a direct mixing method, and the chromium salt and the second metal salt are any one or more of chloride salt, nitrate salt and acetate salt.
The boron-containing chromium-based catalyst is characterized in that a filter cake mainly containing a mixture of chromium hydroxide, second metal hydroxide and boric acid is obtained in the preparation process, and the mixture is converted into chromium trioxide, second metal oxide and boron oxide through drying and roasting, so that a catalyst precursor is obtained; the precursor is roasted at high temperature and then enters into the activation stage of mixed gas composed of nitrogen and hydrogen fluoride, chromium trioxide and second metal oxide are both converted into chromium fluoride and second metal fluoride, boron oxide reacts with hydrogen fluoride to obtain boron trifluoride with lower boiling point, and most of boron trifluoride is separated from the catalyst structure in a gas mode, so that a pore channel can be provided for the catalyst, the specific surface area and the pore channel of the catalyst are increased, the activity of the catalyst is improved, boron elements which are not converted into boron trifluoride are mainly remained in the catalyst in the form of oxides or small amount of fluoride, carbon deposition of the catalyst at high temperature can be effectively inhibited, and meanwhile, the conversion of unstable Z-fluorine-containing olefin in fluorine-chlorine exchange reaction into E-fluorine-containing olefin is also facilitated to be inhibited, and the ratio of Z-fluorine-containing olefin to E-fluorine-containing olefin in fluorine-chlorine exchange products is improved.
The application further provides a preparation method of the catalyst, which comprises the following steps of
Dissolving a chromium salt and a boron-containing compound in water, or dissolving a chromium salt, a second metal salt and a boron-containing compound in water;
precipitating the mixture system by adopting a precipitant until the pH value is 7.5-8.5, such as 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3 and 8.4, and filtering to obtain a filter cake;
washing the filter cake with water until the filtrate is neutral, and drying the obtained filter cake in an oven at 60-150 ℃, wherein the temperature of the oven can be 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃ and 140; then, the mixture is baked at 300 to 500 ℃ for 6 to 15 hours under nitrogen atmosphere, wherein the baking temperature can be 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃ and the baking time can be 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours
Crushing and tabletting the roasted material to obtain a catalyst precursor;
the catalyst is prepared by activating a precursor at 200 to 400℃such as 210℃220℃240℃260℃280℃300℃320℃340℃360℃380℃for 6 to 24 hours in a mixed gas of nitrogen and hydrogen fluoride in a molar ratio of 10:1 for 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours.
The boron-containing chromium-based catalysts of the present application may be used to prepare fluoroolefins, and more preferably, may be used to prepare high proportions of Z-fluoroolefins/E-fluoroolefins. The boron-containing chromium-based catalyst has high catalytic activity and long service life, and simultaneously prepares the E-fluoroolefin and the Z-fluoroolefin with high efficiency, and the ratio of the Z-fluoroolefin to the E-fluoroolefin is higher.
A process for preparing high-proportion Z-fluoroolefin/E-fluoroolefin includes such steps as exchange reaction of chlorine-containing compound with anhydrous hydrogen fluoride to obtain high-proportion Z-fluoroolefin/E-fluoroolefin.
The application further provides a preparation method of the high-proportion Z-fluoroolefin/E-fluoroolefin, which comprises the step of carrying out fluorine-chlorine exchange reaction on a chlorine-containing compound and anhydrous hydrogen fluoride under the action of a boron-containing chromium-based catalyst to prepare the high-proportion Z-fluoroolefin/E-fluoroolefin.
The boron-containing chromium-based catalyst may be any of the boron-containing chromium-based catalyst catalysts described above.
In the method for producing a high-ratio Z-fluoroolefin/E-fluoroolefin provided in the present application, the chlorine-containing compound is not limited, and may be one chlorine-containing compound or a mixture of a plurality of chlorine-containing compounds, the chlorine-containing compound may for example be a chlorinated alkane, examples of preferred chlorinated alkanes include, but are not limited to, 1, 3-pentachloropropane 1, 3-tetrachloro-4, 4-trifluorobutane or 1,3, 4-heptachlorobutane. The chlorine-containing compound may be for example a chlorinated alkene, examples of preferred chlorinated olefins include, but are not limited to, 1, 3-tetrachloropropene, 1, 3-tetrachloropropene E-1-chloro-3, 3-trifluoropropene, Z-1-chloro-3, 3-trifluoropropene E-1, 3-dichloro-3, 3-difluoropropene, Z-1, 3-dichloro-3, 3-difluoropropene, 1, 3-trichloro-4, 4-trifluorobut-1-ene or 1,2, 4-pentachlorobut-1, 3-diene.
In a preferred embodiment of the present invention, the chlorinated compound is selected from 1, 3-pentachloropropane, 1, 3-tetrachloro-4, 4-trifluorobutane or 1,3, 4-heptachlorobutane the chlorinated alkene is 1, 3-tetrachloropropene, 1, 3-tetrachloropropene, E-1-chloro-3, 3-trifluoropropene one, two, three or more than four of Z-1-chloro-3, 3-trifluoropropene, E-1, 3-dichloro-3, 3-difluoropropene, Z-1, 3-dichloro-3, 3-difluoropropene, 1, 3-trichloro-4, 4-trifluorobut-1-ene or 1,2, 4-pentachlorobut-1, 3-diene.
In the process for producing a high-ratio Z-fluoroolefin/E-fluoroolefin of the present application, the type of reactor used for the fluorine-chlorine exchange reaction is not critical, and a tubular reactor, a fluidized bed reactor or the like may be used. Alternatively, adiabatic reactors or isothermal reactors may be used.
In the process for preparing a high ratio Z-fluoroolefin/E-fluoroolefin of the present application, the reaction conditions are not limited, and in a preferred embodiment, when the chlorine-containing compound is 1, 3-pentachloropropane when one or more of 1, 3-tetrachloropropene or 1, 3-tetrachloropropene, the reaction conditions are that the reaction pressure is 0.1-2.0 Ma, for example, 0.2Ma, 0.3Ma, 0.4Ma, 0.5Ma, 1.0Ma, 1.5Ma, 1.6Ma, 1.7Ma, 1.8Ma and 1.9Ma; wherein the molar ratio of hydrogen fluoride to chlorine-containing compound (5-25) to 1, for example, may be 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 15:1, 20:1, 22:1, 23:1, 24:1; the contact time is 2 to 200 seconds, and may be, for example, 3 seconds, 4 seconds, 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 15 seconds, 20 seconds, 30 seconds, 50 seconds, 60 seconds, 80 seconds, 100 seconds, 150 seconds, 160 seconds, 170 seconds, 180 seconds, 190 seconds, preferably 2 to 100 seconds, more preferably 2 to 60 seconds, and even more preferably 2 to 30 seconds; the reaction temperature is 180 to 400℃and may be 190℃200℃210℃220℃250℃260℃280℃300℃340℃360℃380 ℃. The products obtained are E-1-chloro-3, 3-trifluoropropene and Z-1-chloro-3, 3-trifluoropropene, and Z-1-chloro-3, 3-trifluoropropene/E-1-chloro-3, 3-trifluoropropene may be 20%, for example 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 150%, 200%, 250%, 300%, 350%, 400%, 450%, 500%.
In the process for preparing a high ratio Z-fluoroolefin/E-fluoroolefin of the present application, the reaction conditions are not limited, and in a preferred embodiment, when the chlorine-containing compound is 1, 3-tetrachloro-4, 4-trifluorobutane, 1,3, 4-heptachlorobutane when any one or more of 1, 3-trichloro-4, 4-trifluorobut-1-ene or 1,2, 4-pentachlorobut-1, 3-diene, the reaction conditions are that the reaction pressure is 0.1-2.0 Ma, for example, 0.2Ma, 0.3Ma, 0.4Ma, 0.5Ma, 1.0Ma, 1.5Ma, 1.6Ma, 1.7Ma, 1.8Ma and 1.9Ma; the molar ratio of hydrogen fluoride to chlorine-containing compound is (2-20) to 1, and may be, for example, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 15:1, 16:1, 17:1, 18:1, 19:1; the contact time is 2 to 100 seconds, and may be, for example, 3 seconds, 4 seconds, 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 15 seconds, 20 seconds, 30 seconds, 50 seconds, 60 seconds, 65 seconds, 70 seconds, 75 seconds, 80 seconds, 85 seconds, 90 seconds, 95 seconds, preferably 2 to 80 seconds, more preferably 2 to 60 seconds, and even more preferably 2 to 30 seconds; the reaction temperature is 300 to 500 ℃, and may be 310 ℃, 320 ℃, 330 ℃, 350 ℃, 400 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, for example. The obtained products are E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene, and Z-1, 3-tetrafluoropropene/E-1, 3-tetrafluoropropene is more than or equal to 25 percent, for example, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 150%, 200%, 250%, 300%, 350%, 400%, 450%, 500% may be used.
In the method for producing a high-ratio Z-fluoroolefin/E-fluoroolefin of the present invention, the reaction conditions are not limited, and in a preferred embodiment, when the chlorine-containing compound is any one or more of E-1-chloro-3, 3-trifluoropropene, Z-1-chloro-3, 3-trifluoropropene, E-1, 3-dichloro-3, 3-difluoropropene or Z-1, 3-dichloro-3, 3-difluoropropene, the reaction conditions are such that the reaction pressure is 0.1 to 2.0Ma, for example, 0.2Ma, 0.3Ma, 0.4Ma, 0.5Ma, 1.0Ma, 1.5Ma, 1.6Ma, 1.7Ma, 1.8Ma, 1.9Ma; the molar ratio of hydrogen fluoride to chlorine-containing compound is (5-25) to 1, and may be, for example, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 15:1, 20:1, 22:1, 23:1, 24:1; the contact time is 2 to 200 seconds, and may be, for example, 3 seconds, 4 seconds, 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 15 seconds, 20 seconds, 30 seconds, 50 seconds, 60 seconds, 80 seconds, 100 seconds, 150 seconds, 160 seconds, 170 seconds, 180 seconds, 190 seconds, preferably 2 to 100 seconds, more preferably 2 to 60 seconds, and even more preferably 2 to 30 seconds; the reaction temperature is 200 to 450 ℃, and may be 210 ℃, 220 ℃, 250 ℃, 260 ℃, 280 ℃, 300 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 440 ℃, for example. And Z-1, 3-hexa fluorine-2-butene/E-and Z-1, 3-hexafluoro-2-butene/E-1, 3-hexafluoro-2-butene not less than 25%, for example, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 150%, 200%, 250%, 300%, 350%, 400%, 450%, 500% may be used.
According to the preparation method of the high-proportion Z-fluoroolefin/E-fluoroolefin, the boron-containing chromium-based catalyst is used as the catalyst, and by introducing boron element into the chromium-based catalyst, part of boron element is converted into high-volatility boron trifluoride in the hydrogen fluoride activation process and escapes from the surface of the catalyst, so that the catalyst is subjected to pore forming, the catalyst has abundant micropores and high specific surface area, the catalyst has high catalytic activity, and the conversion rate of fluorine-chlorine exchange reaction is remarkably improved; meanwhile, boron element remained in the catalyst can enhance the acidity of the catalyst, thereby being beneficial to improving the selectivity of Z-fluoroolefin and increasing the ratio of Z-fluoroolefin/E-fluoroolefin.
Examples
Gas chromatography method: (1) analytical instrument: shimadzu GC-2010, column DB-VRX capillary column (i.d. 0.32 mm; length 30M; J & M Scientific Inc.); (2) analysis conditions: the temperature of the detector is 280 ℃, the temperature of the vaporization chamber is 280 ℃, the initial temperature of the column is 40 ℃, the temperature is kept for 8 minutes, the temperature is increased to 230 ℃ at 15 ℃/min, and the temperature is kept for 20 minutes.
Example 1 preparation of catalyst
Example 1-1
According to the mass percentage ratio of 85 percent to 10 percent to 5 percent of chromium element, magnesium element and boron element, dissolving chromium nitrate, magnesium chloride and sodium borate in water, adding precipitator ammonia water at 60 ℃, controlling the pH value of the solution to be between 7.5 and 8.5, fully precipitating the solution under the stirring condition, filtering the formed slurry, washing the solution with deionized water until the filtrate is neutral to obtain a filter cake, drying the filter cake at 120 ℃ for 12 hours, roasting the filter cake at 400 ℃ for 10 hours under the nitrogen atmosphere, crushing the roasted material, and tabletting to obtain a catalyst precursor; the precursor is activated for 12 hours at 350 ℃ in the mixed gas composed of nitrogen and hydrogen fluoride with the mol ratio of 10:1, and the fluorinated boron-containing chromium-based catalyst is prepared.
Examples 1 to 2
Examples 1-2 differ from examples 1-1 only in that the mass ratio of chromium element, magnesium element, and boron element was 90% to 5%, with the other conditions being the same.
Examples 1 to 3
Examples 1 to 3 differ from examples 1 to 1 only in that the mass ratio of chromium element, magnesium element and boron element was 99% to 0% to 1%, and the other conditions were the same.
Examples 1 to 4
Examples 1 to 4 differ from examples 1 to 1 only in that the mass ratio of chromium element, magnesium element and boron element was 80% to 15% to 5%, and the other conditions were the same.
Examples 1 to 5
Examples 1 to 5 differ from examples 1 to 1 only in that the mass ratio of chromium element, magnesium element and boron element was 70% to 20% to 10%, and the other conditions were the same.
Examples 1 to 6
Examples 1 to 6 differ from examples 1 to 1 only in that the composition of the chromium element, the magnesium element and the boron element was 90% to 0:10% by mass, and the other conditions were the same.
Examples 1 to 7
Example 7 differs from example 1-1 only in that the mass ratio of chromium element, magnesium element, and boron element is 95% to 0:5%, and the other conditions are the same.
Examples 1 to 8
Examples 1-8 differ from examples 1-1 only in that the magnesium element was changed to cobalt element, the magnesium chloride was changed to cobalt chloride, and the remaining conditions were the same.
Examples 1 to 9
Examples 1-9 differ from examples 1-1 only in that the magnesium element was changed to nickel element, the magnesium chloride was changed to nickel chloride, and the remaining conditions were the same.
Examples 1 to 10
Examples 1-10 differ from examples 1-1 only in that the magnesium element was changed to iron element, the magnesium chloride was changed to ferric chloride, and the remaining conditions were the same.
Examples 1 to 11
Examples 1-11 differ from examples 1-1 only in that the magnesium element was changed to aluminum element, the magnesium chloride was changed to aluminum nitrate, and the remaining conditions were the same.
Examples 1 to 12
Examples 1-12 differ from examples 1-1 only in that the magnesium element was changed to zinc element, the magnesium chloride was changed to zinc chloride, and the remaining conditions were the same.
Comparative examples 1 to 1
Comparative example 1-1 differs from example 1-1 only in that the mass ratio composition of chromium element, magnesium element, boron element is 100% to 0:0, and the other conditions are the same.
The catalyst prepared in examples and comparative examples was prepared with the respective component substances and contents shown in Table 1.
TABLE 1
Figure SMS_1
。
EXAMPLE 2 preparation of fluoroolefins
1. Preparation of high proportions of HCFO-1233zd (Z)/HCFO-1233 zd (E) (examples 2-1-examples 2-32)
Example 2-1
A tubular reactor of Inconel having an inner diameter of 1/2 inch and a length of 30cm was charged with 10 ml of the fluorination catalyst prepared in example 1. The reactor was warmed to 180℃and was then charged with anhydrous hydrogen fluoride and 1, 3-pentachloropropane (HCC-240 fa) to react, the molar ratio of hydrogen fluoride to HCC-240fa was controlled at 10:1, the contact time was 30 seconds, the reaction pressure was 0.1MPa, after 20 hours of reaction, the reaction product was washed with water, alkali, and the organic matter was separated, dried to remove water, and the composition of the organic matter was analyzed by gas chromatography, and the results were shown in Table 2.
Example 2-2
The same operation as in example 2-1 was conducted except that the reaction temperature was changed to 200℃and the results were shown in Table 2.
Examples 2 to 3
The same operation as in example 2-1 was conducted except that the reaction temperature was changed to 250℃and the results were shown in Table 2.
Examples 2 to 4
The same operation as in example 2-1 was conducted except that the reaction temperature was changed to 300℃and the results were shown in Table 2.
Examples 2 to 5
The same operation as in example 2-1 was conducted except that the reaction temperature was changed to 350℃and the results were shown in Table 2.
Examples 2 to 6
The same operation as in example 2-1 was conducted except that the reaction temperature was changed to 400℃and the results were shown in Table 2.
Examples 2 to 7
The same operations as in examples 2-3 were conducted except that the contact time was changed to 2 seconds, and the results are shown in Table 2.
Examples 2 to 8
The same operations as in examples 2-3 were conducted except that the contact time was changed to 10 seconds, and the results are shown in Table 2.
Examples 2 to 9
The same operations as in examples 2-3 were conducted except that the contact time was changed to 60 seconds, and the results are shown in Table 2.
Examples 2 to 10
The same operations as in examples 2-3 were conducted except that the contact time was changed to 100 seconds, and the results are shown in Table 2.
Examples 2 to 11
The same operations as in examples 2-3 were conducted except that the contact time was changed to 200 seconds, and the results are shown in Table 2.
Examples 2 to 12
The same operations as in examples 2-3 were conducted except that the molar ratio of hydrogen fluoride to HCC-240fa was changed to 5:1, and the results are shown in Table 2.
Examples 2 to 13
The same operations as in examples 2-3 were conducted except that the molar ratio of hydrogen fluoride to HCC-240fa was changed to 15:1, and the results are shown in Table 2.
Examples 2 to 14
The same operations as in examples 2-3 were conducted except that the molar ratio of hydrogen fluoride to HCC-240fa was changed to 20:1, and the results are shown in Table 2.
Examples 2 to 15
The same operations as in examples 2-3 were conducted except that the molar ratio of hydrogen fluoride to HCC-240fa was changed to 25:1, and the results are shown in Table 2.
Examples 2 to 16
The same operations as in examples 2-3 were conducted except that the reaction pressure was changed to 0.5MPa, and the results are shown in Table 2.
Examples 2 to 17
The same operations as in examples 2-3 were conducted except that the reaction pressure was changed to 1MPa, and the results are shown in Table 2.
Examples 2 to 18
The same operations as in examples 2-3 were conducted except that the reaction pressure was changed to 1.5MPa, and the results are shown in Table 2.
Examples 2 to 19
The same operations as in examples 2-3 were conducted except that the reaction pressure was changed to 2.0MPa, and the results are shown in Table 2.
Examples 2 to 20
The same operations as in examples 2-3 were conducted except that the fluorination catalyst prepared in example 2 was used, and the results are shown in Table 2.
Examples 2 to 21
The same operations as in examples 2-3 were conducted except that the fluorination catalyst prepared in example 3 was used, and the results are shown in Table 2.
Examples 2 to 22
The same operations as in examples 2-3 were conducted except that the fluorination catalyst prepared in example 4 was used, and the results are shown in Table 2.
Examples 2 to 23
The same operations as in examples 2-3 were conducted except that the fluorination catalyst prepared in example 5 was used, and the results are shown in Table 2.
Examples 2 to 24
The same operations as in examples 2-3 were conducted except that the fluorination catalyst prepared in example 6 was used, and the results are shown in Table 2.
Examples 2 to 25
The same operations as in examples 2-3 were conducted except that the fluorination catalyst prepared in example 7 was used, and the results are shown in Table 2.
Examples 2 to 26
The same operations as in examples 2-3 were conducted except that the fluorination catalyst prepared in example 8 was used, and the results are shown in Table 2.
Examples 2 to 27
The same operations as in examples 2-3 were conducted except that the fluorination catalyst prepared in example 9 was used, and the results are shown in Table 2.
Examples 2 to 28
The same operations as in examples 2-3 were conducted except that the fluorination catalyst prepared in example 10 was used, and the results are shown in Table 2.
Examples 2 to 29
The same operations as in examples 2-3 were conducted except that the fluorination catalyst prepared in example 11 was used, and the results are shown in Table 2.
Examples 2 to 30
The same operations as in examples 2-3 were conducted except that the fluorination catalyst prepared in example 12 was used, and the results are shown in Table 2.
Examples 2 to 31
The same operations as in examples 2-3 were conducted except that HCC-240fa was replaced with 1, 3-tetrachloropropene, and the results are shown in Table 2.
Examples 2 to 32
The same operations as in Experimental example 3 were conducted except that HCC-240fa was replaced with 1, 3-tetrachloropropene, and the results are shown in Table 2.
Comparative example 2-1
The same operation as in example 2-3 was conducted except that the fluorination catalyst prepared in comparative example 1-1 was used, and the results are shown in Table 2.
TABLE 2 preparation of high proportions of HCFO-1233zd (Z)/HCFO-1233 zd (E)
Figure SMS_2
。
2. Processes for preparing high proportions of HFO-1234ze (Z)/HFO-1234 ze (E) (examples 2-33 to 2-65)
Examples 2 to 33
A tubular reactor of Inconel having an inner diameter of 1/2 inch and a length of 30cm was charged with 10 ml of the fluorination catalyst prepared in example 1. The reactor was heated to 300℃and was then reacted with anhydrous hydrogen fluoride and E-1-chloro-3, 3-trifluoropropene (HCFO-1233 zd (E)), the molar ratio of hydrogen fluoride to HCFO-1233zd (E) was controlled to 10:1, the contact time was 10 seconds, the reaction pressure was 0.1MPa, after 20 hours of reaction, the reaction product was washed with water and with alkali, the organic matter was separated, and after drying to remove water, the composition of the organic matter was analyzed by gas chromatography, and the results were shown in Table 3.
Examples 2 to 34
The same operations as in examples 2 to 33 were conducted except that the reaction temperature was changed to 350℃and the results are shown in Table 3.
Examples 2 to 35
The same operations as in examples 2 to 33 were conducted except that the reaction temperature was changed to 375℃and the results are shown in Table 3.
Examples 2 to 36
The same operations as in examples 2 to 33 were conducted except that the reaction temperature was changed to 400℃and the results are shown in Table 3.
Examples 2 to 37
The same operations as in examples 2 to 33 were conducted except that the reaction temperature was changed to 450℃and the results were shown in Table 3.
Examples 2 to 38
The same operations as in examples 2 to 33 were conducted except that the reaction temperature was changed to 500℃and the results are shown in Table 3.
Examples 2 to 39
The same operations as in examples 2 to 35 were conducted except that the contact time was changed to 2 seconds, and the results are shown in Table 3.
Examples 2 to 40
The same operations as in examples 2 to 35 were conducted except that the contact time was changed to 5 seconds, and the results are shown in Table 3.
Examples 2 to 41
The same operations as in examples 2 to 35 were conducted except that the contact time was changed to 30 seconds, and the results are shown in Table 3.
Examples 2 to 42
The same operations as in examples 2 to 35 were conducted except that the contact time was changed to 50 seconds, and the results are shown in Table 3.
Examples 2 to 43
The same operations as in examples 2 to 35 were conducted except that the contact time was changed to 100 seconds, and the results are shown in Table 3.
Examples 2 to 44
The same operations as in examples 2-35 were conducted except that the molar ratio of hydrogen fluoride to HCFO-1233zd (E) was changed to 2:1, and the results are shown in Table 3.
Examples 2 to 45
The same operations as in examples 2-35 were conducted except that the molar ratio of hydrogen fluoride to HCFO-1233zd (E) was changed to 5:1, and the results are shown in Table 3.
Examples 2 to 46
The same operations as in examples 2-35 were conducted except that the molar ratio of hydrogen fluoride to HCFO-1233zd (E) was changed to 15:1, and the results are shown in Table 3.
Examples 2 to 47
The same operations as in examples 2-35 were conducted except that the molar ratio of hydrogen fluoride to HCFO-1233zd (E) was changed to 20:1, and the results are shown in Table 3.
Examples 2 to 48
The same operations as in examples 2 to 35 were conducted except that the reaction pressure was changed to 0.5MPa, and the results are shown in Table 3.
Examples 2 to 49
The same operations as in examples 2 to 35 were conducted except that the reaction pressure was changed to 1MPa, and the results are shown in Table 3.
Examples 2 to 50
The same operations as in examples 2 to 35 were conducted except that the reaction pressure was changed to 1.5MPa, and the results are shown in Table 3.
Examples 2 to 51
The same operations as in examples 2 to 35 were conducted except that the reaction pressure was changed to 2.0MPa, and the results are shown in Table 3.
Examples 2 to 52
The same operations as in examples 2 to 35 were conducted except that the fluorination catalyst prepared in example 2 was used, and the results are shown in Table 3.
Examples 2 to 53
The same operations as in examples 2 to 35 were conducted except that the fluorination catalyst prepared in example 3 was used, and the results are shown in Table 3.
Examples 2 to 54
The same operations as in examples 2 to 35 were conducted except that the fluorination catalyst prepared in example 4 was used, and the results are shown in Table 3.
Examples 2 to 55
The same operations as in examples 2 to 35 were conducted except that the fluorination catalyst prepared in example 5 was used, and the results are shown in Table 3.
Examples 2 to 56
The same operations as in examples 2 to 35 were conducted except that the fluorination catalyst prepared in example 6 was used, and the results are shown in Table 3.
Examples 2 to 57
The same operations as in examples 2 to 35 were conducted except that the fluorination catalyst prepared in example 7 was used, and the results are shown in Table 3.
Examples 2 to 58
The same operations as in examples 2 to 35 were conducted except that the fluorination catalyst prepared in example 8 was used, and the results are shown in Table 3.
Examples 2 to 59
The same operations as in examples 2 to 35 were conducted except that the fluorination catalyst prepared in example 9 was used, and the results are shown in Table 3.
Examples 2 to 60
The same operations as in examples 2 to 35 were conducted except that the fluorination catalyst prepared in example 10 was used, and the results are shown in Table 3.
Examples 2 to 61
The same operations as in examples 2 to 35 were conducted except that the fluorination catalyst prepared in example 11 was used, and the results are shown in Table 3.
Examples 2 to 62
The same operations as in examples 2 to 35 were conducted except that the fluorination catalyst prepared in example 12 was used, and the results are shown in Table 3.
Examples 2 to 63
The same operations as in examples 2-35 were conducted except that HCFO-1233zd (E) was replaced with Z-1-chloro-3, 3-trifluoropropene (HCFO-1233 zd (Z)), and the results are shown in Table 3.
Examples 2 to 64
The same operations as in examples 2-35 were conducted except that HCFO-1233zd (E) was replaced with E-1, 2-dichloro-3, 3-difluoropropene (HCFO-1232 zd (E)), and the results are shown in Table 3.
Examples 2 to 65
The same operations as in examples 2-35 were conducted except that HCFO-1233zd (Z) was replaced with Z-1, 2-dichloro-3, 3-difluoropropene (HCFO-1232 zd (Z)), and the results are shown in Table 3.
Comparative examples 2 to 2
The same operations as in examples 2 to 35 were conducted except that the fluorination catalyst prepared in comparative example 1-1 was used, and the results are shown in Table 3.
TABLE 3 preparation of high proportions of HFO-1234ze (Z)/HFO-1234 ze (E)
Figure SMS_3
。
3. Preparation of high ratio HFO-1336mzz (Z)/HFO-1336 mzz (E) (examples 2-66 through 2-98)
Examples 2 to 66
A tubular reactor of Inconel having an inner diameter of 1/2 inch and a length of 30cm was charged with 10 ml of the fluorination catalyst prepared in example 1. The temperature of the reactor was raised to 200 ℃, anhydrous hydrogen fluoride and 1, 3-tetrachloro-4, 4-trifluorobutane (HCFC-343-jfd) were introduced to react, the molar ratio of hydrogen fluoride to HCFC-343-jfd was controlled to be 10:1, the contact time was 30 seconds, the reaction pressure was 0.1MPa, after 20 hours of reaction, the reaction product was washed with water and alkali, the organic matter was obtained by separation, and after drying and water removal, the composition of the organic matter was analyzed by gas chromatography, and the results are shown in Table 4.
Examples 2 to 67
The same operations as in examples 2 to 66 were conducted except that the reaction temperature was changed to 250℃and the results are shown in Table 4.
Examples 2 to 68
The same operations as in examples 2 to 66 were conducted except that the reaction temperature was changed to 300℃and the results are shown in Table 4.
Examples 2 to 69
The same operations as in examples 2 to 66 were conducted except that the reaction temperature was changed to 350℃and the results are shown in Table 4.
Examples 2 to 70
The same operations as in examples 2 to 66 were conducted except that the reaction temperature was changed to 400℃and the results are shown in Table 4.
Examples 2 to 71
The same operations as in examples 2 to 66 were conducted except that the reaction temperature was changed to 450℃and the results are shown in Table 4.
Examples 2 to 72
The same operations as in examples 2 to 69 were conducted except that the contact time was changed to 2 seconds, and the results are shown in Table 4.
Examples 2 to 73
The same operations as in examples 2 to 69 were conducted except that the contact time was changed to 10 seconds, and the results are shown in Table 4.
Examples 2 to 74
The same operations as in examples 2 to 69 were conducted except that the contact time was changed to 60 seconds, and the results are shown in Table 4.
Examples 2 to 75
The same operations as in examples 2 to 69 were conducted except that the contact time was changed to 100 seconds, and the results are shown in Table 4.
Examples 2 to 76
The same operations as in examples 2 to 69 were conducted except that the contact time was changed to 200 seconds, and the results are shown in Table 4.
Examples 2 to 77
The same operations as in examples 2 to 69 were conducted except that the molar ratio of hydrogen fluoride to HCFC-343-jfd was changed to 5:1, and the results are shown in Table 4.
Examples 2 to 78
The same operations as in examples 2 to 69 were conducted except that the molar ratio of hydrogen fluoride to HCFC-343-jfd was changed to 15:1, and the results are shown in Table 4.
Examples 2 to 79
The same operations as in examples 2 to 69 were conducted except that the molar ratio of hydrogen fluoride to HCFC-343jfd was changed to 20:1, and the results are shown in Table 4.
Examples 2 to 80
The same operations as in examples 2 to 69 were conducted except that the molar ratio of hydrogen fluoride to HCFC-343-jfd was changed to 25:1, and the results are shown in Table 4.
Examples 2 to 81
The same operations as in examples 2 to 69 were conducted except that the reaction pressure was changed to 0.5MPa, and the results are shown in Table 4.
Examples 2 to 82
The same operations as in examples 2 to 69 were conducted except that the reaction pressure was changed to 1MPa, and the results are shown in Table 4.
Examples 2 to 83
The same operations as in examples 2 to 69 were conducted except that the reaction pressure was changed to 1.5MPa, and the results are shown in Table 4.
Examples 2 to 84
The same operations as in examples 2 to 69 were conducted except that the reaction pressure was changed to 2.0MPa, and the results are shown in Table 4.
Examples 2 to 85
The same operations as in examples 2 to 69 were conducted except that the fluorination catalyst prepared in example 2 was used, and the results are shown in Table 4.
Examples 2 to 86
The same operations as in examples 2 to 69 were conducted except that the fluorination catalyst prepared in example 3 was used, and the results are shown in Table 4.
Examples 2 to 87
The same operations as in examples 2 to 69 were conducted except that the fluorination catalyst prepared in example 4 was used, and the results are shown in Table 4.
Examples 2 to 88
The same operations as in examples 2 to 69 were conducted except that the fluorination catalyst prepared in example 5 was used, and the results are shown in Table 4.
Examples 2 to 89
The same operations as in examples 2 to 69 were conducted except that the fluorination catalyst prepared in example 6 was used, and the results are shown in Table 4.
Examples 2 to 90
The same operations as in examples 2 to 69 were conducted except that the fluorination catalyst prepared in example 7 was used, and the results are shown in Table 4.
Examples 2 to 91
The same operations as in examples 2 to 69 were conducted except that the fluorination catalyst prepared in example 8 was used, and the results are shown in Table 4.
Examples 2 to 92
The same operations as in examples 2 to 69 were conducted except that the fluorination catalyst prepared in example 9 was used, and the results are shown in Table 4.
Examples 2 to 93
The same operations as in examples 2 to 69 were conducted except that the fluorination catalyst prepared in example 10 was used, and the results are shown in Table 4.
Examples 2 to 94
The same operations as in examples 2 to 69 were conducted except that the fluorination catalyst prepared in example 11 was used, and the results are shown in Table 4.
Examples 2 to 95
The same operations as in examples 2 to 69 were conducted except that the fluorination catalyst prepared in example 12 was used, and the results are shown in Table 4.
Examples 2 to 96
The same operations as in examples 2-69 were conducted except that HCFC-343jfd was replaced with 1,3, 4-heptachlorobutane, and the results are shown in Table 4.
Examples 2 to 97
The same operations as in examples 2-69 were conducted except that HCFC-343jfd was replaced with 1, 3-trichloro-4, 4-trifluoro-1-butene and the results are shown in Table 4.
Experiment 98
The same operations as in examples 2-69 were conducted except that HCFC-343jfd was replaced with 1,2, 4-pentachlorobutane-1, 3-diene, and the results are shown in Table 4.
Comparative examples 2 to 3
The same operations as in examples 2 to 69 were conducted except that the fluorination catalyst prepared in comparative example 1-1 was used, and the results are shown in Table 4.
TABLE 4 preparation of high ratio HFO-1336mzz (Z)/HFO-1336 mzz (E)
Figure SMS_4
。
Although described above in connection with the embodiments of the present application, the present application is not limited to the specific embodiments and fields of application described above, which are intended to be illustrative, instructive, and not limiting. Those skilled in the art, having the benefit of this disclosure, may make numerous forms, and equivalents thereof, without departing from the scope of the invention as defined by the claims.

Claims (18)

1. A high specific surface area chromium-based catalyst for boron element pore formation for the preparation of fluoroolefins, wherein the catalyst comprises a chromium salt and a boron-containing compound or the catalyst comprises a chromium salt, a second metal salt other than chromium and a boron-containing compound.
2. The catalyst according to claim 1, wherein the boron-containing compound is contained in a chromium salt and a second metal salt other than chromium.
3. The catalyst according to claim 1 or 2, wherein the second metal salt other than chromium is selected from any one or two or more of cobalt salt, iron salt, zinc salt, magnesium salt, aluminum salt, nickel salt, indium salt, and antimony salt; or alternatively
The boron-containing compound is any one or more selected from the following compounds or metal salts thereof 2 O 3 ) Fluoroboric acid (HBF) 4 ) Boric acid (H) 3 BO 3 ) Diboric acid (H) 4 B 2 O 4 ) Triboric acid (H) 3 B 3 O 6 ) Tetraboric acid (H) 2 B 4 O 7 ) Pentaboric acid (H) 4 B 5 O 8 ) Or hexaboric acid (H) 4 B 6 O 11 )。
4. The method according to claim 1 or 2, wherein in the catalyst, the mass percentage of the chromium element contained in the chromium salt, the second metal element contained in the second metal salt, and the boron element contained in the boron-containing compound is (70-99%) to (0-20%) to (1-10%), and the sum of the mass percentages of the three elements is 100%.
5. The catalyst of claim 1 or 2, wherein the catalyst is activated by hydrogen fluoride.
6. The catalyst according to claim 1 or 2, wherein the specific surface area of the catalyst is 100m 2 /g～600m 2 /g。
7. A process for preparing a catalyst as claimed in claim 1 to 6, comprising,
dissolving chromium salt and a boron-containing compound in water, or dissolving chromium salt, a second metal salt and a boron-containing compound in water, wherein the chromium salt and the second metal salt are any one or more of chloride salt, nitrate and acetate;
precipitating the mixture system by adopting a precipitating agent until the pH value is 7.5-8.5, and then filtering to obtain a filter cake;
washing the filter cake until the filtrate is neutral, drying the obtained filter cake in a baking oven at 60-150 ℃, and roasting the filter cake at 300-500 ℃ for 6-15 hours in a nitrogen atmosphere;
crushing and tabletting the roasted material to obtain a catalyst precursor;
activating the precursor at 200-400 deg.c and with mixed gas of nitrogen and hydrogen fluoride in the molar ratio of 10 to 1 for 6-24 hr to obtain the catalyst.
8. Use of the catalyst of any one of claims 1 to 6 or the catalyst prepared according to claim 10 for the preparation of high proportions of Z-fluoroolefins/E-fluoroolefins.
9. A process for preparing high-proportion Z-fluoroolefin/E-fluoroolefin includes such steps as exchange reaction of chlorine-containing compound with anhydrous hydrogen fluoride to obtain high-proportion Z-fluoroolefin/E-fluoroolefin.
10. The process of claim 9, wherein the chlorine-containing compound is a chlorinated alkane and/or chlorinated alkene.
11. The method of claim 10, wherein, the chloralkane is 1, 3-pentachloropropane 1, 3-tetrachloro-4, 4-trifluorobutane or 1,3,4 one or more than two of heptachlorobutanes.
12. The method of claim 10, wherein, the chlorinated alkene is 1, 3-tetrachloropropene, 1, 3-tetrachloropropene, E-1-chloro-3, 3-trifluoropropene Z-1-chloro-3, 3-trifluoropropene, E-1, 3-dichloro-3, 3-difluoropropene one or more than two of Z-1, 3-dichloro-3, 3-difluoropropene, 1, 3-trichloro-4, 4-trifluorobut-1-ene or 1,2, 4-pentachlorobut-1, 3-diene.
13. The method according to claim 9 or 10, wherein, when the chlorine-containing compound is 1, 3-pentachloropropane when one or more of 1, 3-tetrachloropropene or 1, 3-tetrachloropropene, the reaction conditions are that the reaction pressure is 0.1-2.0 Ma, the mol ratio of the hydrogen fluoride to the chlorine-containing compound is (5-25) to 1, the contact time is 2-200 seconds, and the reaction temperature is 180-400 ℃.
14. The process according to claim 13, wherein the products obtained are E-1-chloro-3, 3-trifluoropropene and Z-1-chloro-3, 3-trifluoropropene/E-1-chloro-3, 3-trifluoropropene is ≡20%.
15. The method according to claim 9 or 10, wherein, when the chlorine-containing compound is 1, 3-tetrachloro-4, 4-trifluorobutane, 1,3, 4-heptachlorobutane when any one or more of 1, 3-trichloro-4, 4-trifluorobut-1-ene or 1,2, 4-pentachlorobut-1, 3-diene, the reaction conditions are that the reaction pressure is 0.1-2.0 Ma, the mol ratio of the hydrogen fluoride to the chlorine-containing compound is (2-20) to 1, the contact time is 2-100 seconds, and the reaction temperature is 300-500 ℃.
16. The process according to claim 15, wherein the products obtained are E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene, and Z-1, 3-tetrafluoropropene/E-1, 3-tetrafluoropropene is more than or equal to 25%.
17. The process according to claim 9 or 10, wherein when the chlorine-containing compound is any one or more of E-1-chloro-3, 3-trifluoropropene, Z-1-chloro-3, 3-trifluoropropene, E-1, 3-dichloro-3, 3-difluoropropene or Z-1, 3-dichloro-3, 3-difluoropropene, the reaction conditions are such that the reaction pressure is 0.1 to 2.0Ma, the molar ratio of hydrogen fluoride to chlorine-containing compound is (5 to 25) to 1, the contact time is 2 to 200 seconds, and the reaction temperature is 200 to 450 ℃.
18. The method of claim 17, wherein, the obtained product is E-1, 3-hexafluoro-2 butene and Z-1, 3-hexafluoro-2-butene, and Z-1, 3-hexafluoro-2-butene/E-1, 3-hexafluoro-2-butene is more than or equal to 25 percent.
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WO2006052232A1 (en) * 2004-11-04 2006-05-18 Chevron Phillips Chemical Company, L.P. Organochromium/ metallocene combination catalyst for producing bimodal resins
CN102674704A (en) * 2011-03-11 2012-09-19 北京市太阳能研究所有限公司 Preparation method of porous nano silicon dioxide anti-reflection film
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