CN115215722A - Co-production preparation method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene - Google Patents
Co-production preparation method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene Download PDFInfo
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- CN115215722A CN115215722A CN202110404614.6A CN202110404614A CN115215722A CN 115215722 A CN115215722 A CN 115215722A CN 202110404614 A CN202110404614 A CN 202110404614A CN 115215722 A CN115215722 A CN 115215722A
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- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 28
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 22
- 230000009471 action Effects 0.000 claims abstract description 17
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005695 dehalogenation reaction Methods 0.000 claims abstract description 16
- 238000005796 dehydrofluorination reaction Methods 0.000 claims abstract description 11
- NIFDMQJMUQOKJU-UHFFFAOYSA-N fluoromethane hydrochloride Chemical compound Cl.CF NIFDMQJMUQOKJU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000007033 dehydrochlorination reaction Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 229910007926 ZrCl Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 3
- 229910018287 SbF 5 Inorganic materials 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 28
- 239000002994 raw material Substances 0.000 description 20
- 239000006227 byproduct Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 10
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 9
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 8
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 6
- DSFRTDXWEXEMJT-UHFFFAOYSA-N F.[H]CCl Chemical compound F.[H]CCl DSFRTDXWEXEMJT-UHFFFAOYSA-N 0.000 description 6
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 6
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- ZDCWZRQSHBQRGN-UHFFFAOYSA-N 1,1,1,2,3-pentafluoropropane Chemical compound FCC(F)C(F)(F)F ZDCWZRQSHBQRGN-UHFFFAOYSA-N 0.000 description 5
- UMGQVBVEWTXECF-UHFFFAOYSA-N 1,1,2,3-tetrachloroprop-1-ene Chemical compound ClCC(Cl)=C(Cl)Cl UMGQVBVEWTXECF-UHFFFAOYSA-N 0.000 description 5
- SMCNZLDHTZESTK-UHFFFAOYSA-N 2-chloro-1,1,1,2-tetrafluoropropane Chemical compound CC(F)(Cl)C(F)(F)F SMCNZLDHTZESTK-UHFFFAOYSA-N 0.000 description 5
- 238000003682 fluorination reaction Methods 0.000 description 5
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 3
- OQISUJXQFPPARX-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Cl)=C OQISUJXQFPPARX-UHFFFAOYSA-N 0.000 description 3
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- GVVUPGXFVJLPDE-OWOJBTEDSA-N (e)-1,3,3,3-tetrachloroprop-1-ene Chemical compound Cl\C=C\C(Cl)(Cl)Cl GVVUPGXFVJLPDE-OWOJBTEDSA-N 0.000 description 2
- FYIRUPZTYPILDH-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoropropane Chemical compound FC(F)C(F)C(F)(F)F FYIRUPZTYPILDH-UHFFFAOYSA-N 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 2
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001026 inconel Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZXPCCXXSNUIVNK-UHFFFAOYSA-N 1,1,1,2,3-pentachloropropane Chemical compound ClCC(Cl)C(Cl)(Cl)Cl ZXPCCXXSNUIVNK-UHFFFAOYSA-N 0.000 description 1
- VVWFZKBKXPXGBH-UHFFFAOYSA-N 1,1,1,3,3-pentachloropropane Chemical compound ClC(Cl)CC(Cl)(Cl)Cl VVWFZKBKXPXGBH-UHFFFAOYSA-N 0.000 description 1
- LAKXDZKIXFNBES-UHFFFAOYSA-N 1,3,3-trichloro-1,1-difluoropropane Chemical compound FC(F)(Cl)CC(Cl)Cl LAKXDZKIXFNBES-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- ZGOMEYREADWKLC-UHFFFAOYSA-N 3-chloro-1,1,1,3-tetrafluoropropane Chemical compound FC(Cl)CC(F)(F)F ZGOMEYREADWKLC-UHFFFAOYSA-N 0.000 description 1
- 102100040359 Angiomotin-like protein 2 Human genes 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101100342039 Halobacterium salinarum (strain ATCC 29341 / DSM 671 / R1) kdpQ gene Proteins 0.000 description 1
- 101000891151 Homo sapiens Angiomotin-like protein 2 Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- -1 cis-1-chloro-3 Chemical compound 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
- 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
- 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
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A co-production process of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, the co-production process comprising: A1. and (3) telomerization: under the action of telomerization catalyst, the monofluoromethane chloride and trifluoroethylene are subjected to pressure telomerization reaction to prepare 3-chloro-1, 2-tetrafluoropropane; the telomerization catalyst is a Lewis acid catalyst or a mixed catalyst of the Lewis acid catalyst and dichloromethane; A2. dehydrohalogenation: the 3-chloro-1, 2-tetrafluoropropane simultaneously performs dehydrochlorination reaction and dehydrofluorination reaction under the action of a compound dehalogenation catalyst to obtain 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, and the compound dehalogenation catalyst is prepared from an oxide or a fluoride of at least one of Al, mg or Cr and activated carbon powder. The method has the advantages of simple process, mild reaction conditions, high total yield of target products and the like.
Description
Technical Field
The invention relates to the preparation of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, in particular to a method for preparing a compound by using trifluoroethylene as a raw material, a method for coproducing 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene through liquid-phase pressure telomerization and dehydrohalogenation.
Background
2,3,3,3-tetrafluoropropene (HFO-1234 yf) ODP is zero, GWP value is 4, life-time climate performance (LCCP) is lower than that of traditional refrigerant HFC-134a, system refrigeration performance is better than that of HFC-134a, and atmospheric decomposition products are the same as HFC-134a, are considered as the most potential automobile refrigerant substitute at present and are accepted by a plurality of mainstream automobile manufacturers. The preparation route comprises the following steps:
scheme (I) for hexafluoropropylene:
the preparation of 2, 3-tetrafluoropropene by using hexafluoropropylene as a raw material comprises four steps of reactions: (1) Hexafluoropropylene and hydrogen are subjected to hydrogenation reaction to prepare 1,2, 3-hexafluoropropane (HFC-236 ea); (2) The HFC-236ea is subjected to dehydrofluorination reaction under the action of a catalyst to prepare 1,2, 3-pentafluoropropene (HFO-1225 ye); (3) HFO-1225ye is further hydrogenated with hydrogen to prepare 1,2, 3-pentafluoropropane (HFC-245 eb); (4) HFC-245eb takes dehydrofluorination reaction under the action of catalyst to prepare 2, 3-tetrafluoropropene.
U.S. Pat. No. 5,000,9324A, chinese patent CN101544536A, CN102267869A, CN102026947A and the like all disclose a method for preparing 2,3,3,3-tetrafluoropropene by taking hexafluoropropylene as a raw material and carrying out four-step reactions of hydrogenation, dehydrofluorination, re-hydrogenation and re-dehydrofluorination, and the method has the characteristics of simple process, mature technology and the like, but has the problems of more reaction steps, separation and purification of various intermediate products, complex process steps, large equipment investment, low reaction yield, high separation cost, high energy consumption and the like.
In order to solve the defects of the prior art, chinese patent No. 103449963B discloses a method for synthesizing 2, 3-tetrafluoropropene by using hexafluoropropylene as a raw material through multi-step continuous reaction, which can realize continuous production in which intermediate products such as HFC-236ea, HFO-1225ye and HFC-245eb directly react without separation. However, the fact that the intermediate product is not separated and purified means that impurities are continuously accumulated and increased in the reaction materials, the yield of the target product 2, 3-tetrafluoropropene is finally influenced, and the difficulty in rectifying and separating the 2, 3-tetrafluoropropene product is increased.
(II) Tetrachloropropene (TCP) route:
patent CN101395108B discloses a method for preparing 2,3,3,3-tetrafluoropropene by using 1,1,2,3-tetrachloropropene as a raw material through three steps of reactions, which comprises the following steps: (1) 1,2, 3-tetrachloropropene and HF are subjected to gas phase fluorination to prepare 2-chloro-3, 3-trifluoropropene (HCFO-1233 xf) with a selectivity of 80-96%, when Cr is used 2 O 3 And FeCl 3 When the catalyst is used in the presence of a catalyst/C, the selectivity reaches 96 percent, and the conversion rate is only 20 percent; (2) The addition reaction of HCFO-1233xf and HF generates 2-chloro-1, 2-tetrafluoropropane (HCFC-244 bb) with the catalyst of SbCl 5 (ii) a (3) HCFC-244bb is subject to gas phase dehydrochlorination reaction under the action of activated carbon catalyst to prepare the target product 2, 3-tetrafluoropropene. The process has the problems of complicated reaction steps, low conversion rate, high reaction temperature and the like, and is unfavorable for industrial production.
U.S. Pat. No. 20090099396 discloses a process for preparing 2,3,3,3-tetrafluoropropene using 1,1,2,3-tetrachloropropene as a raw material by a two-step reaction comprising: (1) 1,2, 3-tetrachloropropene and HF are subjected to liquid phase fluorination reaction to prepare 1,2, 3-pentafluoropropane (HFC-245 eb) with SbCl as catalyst 5 The TCP conversion rate can reach 100%, but the HFC-245eb selectivity is only 53-59%, and more byproducts are generated; (2) HFC-245eb generates liquid phase dehydrofluorination reaction under the action of alkali metal hydroxide to generate the target product 2, 3-tetrafluoropropene. The process has the advantages of few reaction steps and low equipment investment, but the intermediate product HFC-245eb has low selectivity and the separation difficulty of byproducts is high.
(III) trifluoropropene route:
patent CN101979364A discloses a process for preparing 2, 3-tetrafluoropropene using 3, 3-trifluoropropene as a starting material, the reaction being carried out in four steps: (1) 3, 3-trifluoropropene and chlorine are subjected to addition reaction under photocatalysis to generate 1, 2-dichloro-3, 3-trifluoropropane, the conversion rate of the raw materials reaches 95%, and the selectivity reaches 90%; (2) The 1, 2-dichloro-3, 3-trifluoropropane is subjected to liquid-phase dehydrochlorination reaction under the action of alkali metal hydroxide to generate 2-chloro-3, 3-trifluoropropene (HCFO-1233 xf), and the conversion rate and the selectivity both reach 90 percent; (3) HCFO-1233xf and HF undergo the addition reaction to produce 2-chloro-1, 2-tetrafluoropropane (HCFC-244 bb) with the catalyst of SnCl 4 、TiCl 4 The conversion rate of the raw materials reaches 95 percent, and the selectivity is 90 to 96 percent; (4) HCFC-244bb is subjected to liquid phase dehydrochlorination reaction under the action of alkali metal catalyst to prepare target product CF 3 CF＝CH 2 The conversion rate of raw materials is 95 percent, and the selectivity is 90 to 95 percent. The process has long synthesis route, higher requirements on equipment in the first step of chlorination reaction, more waste liquid generated in the two-step dehalogenation reaction, low total reaction yield and high synthesis cost.
(IV) other routes:
the asahi glass patent WO2011162341A discloses a method for preparing 2,3,3,3-tetrafluoropropene by using 1,1-dichloro-2,3,3-tetrafluoropropene (CFO-1214 ya) as a raw material and performing hydrogenation reduction under the action of a palladium catalyst. But the hydrogenation reduction reaction degree of the method is difficult to control, easily generate intermediates or over-reduction products such as 1-chloro-2, 3-tetrafluoropropene (HCFO-1224 yd), 1-chloro-2, 3-tetrafluoropropane (HCFC-244 eb) and 2, 3-tetrafluoropropane (HFC-254 eb), the product selectivity is low, the post-treatment operation is complicated, and the byproduct HFC-254eb is easy to generate further dehydrofluorination reaction in the alkali washing treatment process to generate 3, 3-trifluoropropene (HFO-1243 zf) with the boiling point close to that of HFO-1234yf, thereby further increasing the difficulty of impurity separation. Although the problems can be improved by controlling the reaction temperature of the catalyst bed and the alkali washing absorption temperature, the improvement degree is not obvious, and the control difficulty of the process conditions is large, so that the method is not suitable for industrial amplification.
1-chloro-3, 3-trifluoropropene (HCFO-1233 zd), boiling point 19 deg.C, atmospheric lifetime 26 days, ODP value about zero, GWP value less than 5, it is the first choice of new generation environment-friendly foaming agent, it is suitable for foaming polyurethane heat insulating material in the fields of household electrical appliances, building heat preservation, cold chain transportation and industrial heat preservation, etc., it is the best substitute of CFC, HCFC, HFC and other non-fluorocarbon foaming agents. Compared with the existing foaming agent system (HFC-245 fa and cyclopentane), the foaming agent system has more excellent heat release thermal conductivity and complete machine energy consumption level, and is respectively reduced by 7 percent and 12 percent in the aspect of thermal conductivity and 3 percent and 7 percent in the aspect of complete machine energy consumption compared with the refrigerator of HFC-245fa and cyclopentane systems of the same type.
PCT patent WO9724307A1 discloses a method for preparing HCFO-1233zd from 1,1,3,3-pentachloropropane (HCC-240 fa) by using hydrogen fluoride gas phase fluorination reaction, the route is simple and is the current main commercial production method, but various byproducts such as HCFC-242fa, HCFC-244fa and the like are generated in the reaction process, and the yield of HCFO-1233zd is low.
In the US6844475A, a process for preparing HCFO-1233zd by liquid phase catalytic fluorination of HCC 240fa with HF was developed for the aforementioned problem of low HCFO-1233zd product yield, but in the process, heavy byproducts, oligomers and tar are generated in a large amount, and as the reaction time is increased, the catalyst is deactivated, thereby affecting the catalytic reaction efficiency.
Patent CN108383679A discloses a method for coproducing HCFO-1233zd and HFO-1234yf, which uses 1,1,1,3,3-pentachloropropane and 1,1,1,2,3-pentachloropropane as raw materials, firstly, under the action of catalyst A, the raw materials and hydrogen fluoride undergo fluorination reaction to obtain trans-1-chloro-3,3,3-trifluoropropene, cis-1-chloro-3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene, the above-mentioned products, hydrogen chloride and hydrogen fluoride directly enter a second reactor without separation, and continue to react under the action of catalyst B, so as to coproduce trans-1-chloro-3,3,3-trifluoropropene and 2,3,3,3-tetrafluoropropene. The method has simple process, high efficiency and energy conservation, but has the defect that the raw material 1,2, 3-pentachloropropane is not easy to obtain.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene by co-production, which has the advantages of simple process, mild reaction conditions and suitability for industrial production.
The purpose of the invention is realized by the following technical scheme:
a co-production preparation method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene is characterized by comprising the following steps: the co-production preparation method comprises the following steps:
A1. and (3) telomerization: under the action of telomerization catalyst, the monofluoromethane chloride and trifluoroethylene are subjected to pressure telomerization reaction to prepare 3-chloro-1, 2-tetrafluoropropane; the telomerization catalyst is a Lewis acid catalyst or a mixed catalyst of the Lewis acid catalyst and dichloromethane;
A2. dehydrohalogenation: the 3-chloro-1, 2-tetrafluoropropane simultaneously performs dehydrochlorination reaction and dehydrofluorination reaction under the action of a compound dehalogenation catalyst to obtain 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, and the compound dehalogenation catalyst is prepared from an oxide or a fluoride of at least one of Al, mg or Cr and activated carbon powder.
The oxide or fluoride of at least one of Al, mg or Cr is selected from Al 2 O 3 、AlF 3 、MgF 2 And Cr 2 O 3 At least one of (1); the activated carbon powder is selected from shell activated carbon, coal activated carbon or wood activated carbon.
The reaction equation of the co-production preparation process is as follows:
the Lewis acid catalyst is selected from at least one halide of Al, sb, ti, zr and Hf. Preferably, the Lewis acid catalyst is selected from ZrCl 4 、HfCl 4 、TiCl 4 、AlF 3 、AlCl 3 、SbF 5 At least one of them. More preferably, the Lewis acid catalyst is ZrCl 4 Or HfCl 4 。
The telomerization of the raw materials of monofluoromethane chloride and trifluoroethylene is carried out under a pressurized condition, and the raw materials of monofluoromethane chloride partially or completely form liquid under the reaction condition. In addition, since 3-chloro-1, 2-tetrafluoropropane produced by telomerization is liquid, the A1 step of the present invention preferably employs a solvent-free reaction to reduce the separation steps of intermediates and/or products.
The telomerization catalyst can adopt a single Lewis acid catalyst, and can also adopt a mixed catalyst of the Lewis acid catalyst and dichloromethane. When a mixed catalyst is used, the Lewis acid catalyst dissociates and activates the monofluoromethane to form F - 、CH 2 Cl + 、Cl - 、CH 2 F + Plasma; inhibition of dissociation of F formed by methylene chloride - 、CH 2 Cl + 、Cl - 、CH 2 F + Plasma recombination, thereby ensuring F - 、CH 2 Cl + Ions and trifluoroethylene generate a directional telomerization reaction to obtain a telomerization product CF with high selectivity 3 CHFCH 2 Cl。
In chemical reactions, the ratio of raw materials to catalyst, reaction temperature, reaction time, etc. all affect the reaction result, and especially the combination of multiple variables can greatly affect the reaction result.
In the telomerization step of the invention, the molar ratio of monochloromethane fluoride to trifluoroethylene is 1.1 to 1; more preferably, the molar ratio of monochloromethane fluoride to trifluoroethylene is from 1 to 1. The dosage of the Lewis acid catalyst is 0.01 to 50 weight percent of the mass of the monofluoro-chloromethane; more preferably, the amount of Lewis acid catalyst is 0.1 to 10wt% based on the mass of monochloromethane fluoride. When a mixed catalyst of a Lewis acid catalyst and dichloromethane is adopted, the molar ratio of the dichloromethane to the monochloromethane fluoride is 1.01-1; more preferably, the molar ratio of the dichloromethane to the monochloromethane is 1.1-1.
The telomerization step is carried out under the condition of pressurization, the reaction temperature is-30-100 ℃, the reaction pressure is 0.5-5.0 MPa, and the reaction time is 1-50 h. More preferably, the reaction temperature is 0-50 ℃, the reaction pressure is 0.8-3.0 MPa, and the reaction time is 5-10 h.
In the dehydrohalogenation step, 3-chlorine is reacted under the action of a composite dehalogenation catalystWhen the-1, 2-tetrafluoropropane is adsorbed on the activated carbon, dehydrochlorination reaction is carried out; when 3-chloro-1, 2-tetrafluoropropane adsorbs on Al 2 O 3 And/or AlF 3 And/or MgF 2 And/or Cr 2 O 3 In the above, a dehydrofluorination reaction takes place, whereby 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene are obtained simultaneously.
The composite dehalogenation catalyst can be prepared by adopting a conventional method as long as the composite dehalogenation catalyst can be obtained. Preferably, the preparation method adopts a blending method and comprises the following steps:
B1. mixing: mixing Al 2 O 3 And/or AlF 3 And/or MgF 2 And/or Cr 2 O 3 Mixing the active carbon powder with the active carbon powder according to the mass ratio of (0.01-0.25) to 1 and fully mixing the active carbon powder and the active carbon powder by adopting a mechanical stirring or ball milling mode;
B2. sieving: sieving the mixed material to remove the part which is not uniformly mixed;
B3. molding: feeding the sieved material into a tablet press for tabletting and forming;
B4. drying the molded catalyst to obtain the composite dehalogenation catalyst, such as Al 2 O 3- AC、AlF 3 -AC、MgF 2 -AC and Cr 2 O 3 -AC and the like catalysts.
The B3 forming step can be made into shapes such as columns, sheets and the like, and the specific shape is not limited.
The drying treatment in the step B4 generally adopts the treatment at 90-120 ℃ for more than 12 h.
When Al is adopted in the composite dehalogenation catalyst of the invention 2 O 3 When blended with activated carbon powder, al 2 O 3 The content of the catalyst is 1.0 to 20 weight percent of the total weight of the catalyst; when AlF is used 3 When blended with activated carbon powder, alF 3 The content of the catalyst is 1.0 to 20 weight percent of the total weight of the catalyst; when MgF is used 2 When blended with activated carbon, mgF 2 The content of the catalyst is 1.0 to 20 weight percent of the total weight of the catalyst; when Cr is used 2 O 3 When blended with activated carbon, cr 2 O 3 The content of the catalyst is 1.0 to 20wt percent of the total weight of the catalyst.
The dehydrohalogenation step is a gas-solid reaction, 3-chloro-1, 2-tetrafluoropropane is carried into a catalyst bed by nitrogen after being vaporized for dehydrohalogenation, and the volume space velocity of the raw material for the dehydrohalogenation is 50-300 h -1 ，N 2 The volume ratio of the 3-chloro-1, 2-tetrafluoropropane is (0.5-3.0): 1, preferably in a volume ratio of (1.5 to 2.0): 1.
the reaction temperature in the dehydrohalogenation step is 300-500 ℃, and the preferable reaction temperature is 350-450 ℃.
The distribution of products in the dehydrohalogenation step can be adjusted within a certain range by the preparation process of the composite dehalogenation catalyst, the content of active components in the catalyst and the adjustment of reaction conditions. Generally, a dehydrohalogenation step is carried out to obtain a mixture containing 10 to 50% of 2, 3-tetrafluoropropene and 10 to 70% of 1-chloro-3, 3-trifluoropropene; preferably, the elimination step product contains 20 to 40% of 2, 3-tetrafluoropropene and 30 to 60% of 1-chloro-3, 3-trifluoropropene, with the remainder being unknown by-products.
In order to further reduce the difficulty of post-treatment, therefore: the 3-chloro-1, 2-tetrafluoropropane obtained by the telomerization step is used for the dehydrohalogenation step after rectification and separation.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts monofluoro-chloromethane and trifluoroethylene as raw materials, and obtains 3-chloro-1, 2-tetrafluoropropane by pressurization and telomerization under the action of a Lewis acid catalyst or a mixed catalyst of the Lewis acid catalyst and dichloromethane; the 3-chloro-1, 2-tetrafluoropropane simultaneously performs dehydrochlorination reaction and dehydrofluorination reaction under the catalytic action of the composite dehalogenation catalyst to coproduce 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, and the method has the advantages of simple process, mild reaction conditions, high yield of target products and the like, and is suitable for industrial production.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
1. Catalyst preparation
Preparation example 1
Preparation of Cr 2 O 3 Catalyst Cr mixed with active carbon powder 2 O 3 -AC, the preparation step comprising:
s1, mixing Cr 2 O 3 Mixing with coconut shell activated carbon powder according to the mass ratio of 1/9, and putting the mixture into a ball mill for ball milling and mixing to uniformly disperse the components;
s2, sieving the mixed materials, and screening out the uneven mixed part;
s3, feeding the sieved material into a tablet press for tabletting and forming to prepare a columnar catalyst;
s4, drying the molded catalyst at 120 ℃ for 12h to prepare Cr 2 O 3 An AC catalyst, denoted as cat1.
Preparation example 2
The procedure of this preparation is the same as that of preparation 1 except that: by using AlF 3 Substitute for Cr 2 O 3 Preparation to obtain AlF 3 An AC catalyst, denoted as cat2.
Preparation example 3
The procedure of this preparation is the same as that of preparation 1 except that: cr 2 O 3 The mass ratio of the active carbon to the Cr is changed to 1/4, and the Cr is prepared 2 O 3 -AC catalyst, denoted as cat3.
2. Preparation of 2,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene
Example 1
The example provides a co-production preparation method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, which comprises a telomerization step and a dehydrohalogenation step, and specifically comprises the following steps:
(I) telomerization step
A1. An autoclave made of an Inconel alloy material and having a volume of 250mL was used as a reactor, and 3.0g of HfCl was placed therein 4 And 20.0g of dichloromethane are respectively added into the reaction kettle, and the reaction kettle is sealedThen introducing nitrogen with the pressure of more than 1.0MPa to replace the air in the reaction kettle, and repeating the steps for three times;
A2. after the air in the reaction kettle is completely replaced, 19.9g (0.29 mol) of monofluoromethane chloride and 24.6g (0.30 mol) of trifluoroethylene are introduced in sequence;
A3. setting the reaction temperature to be 10 ℃, the stirring speed to be 300rpm, the initial reaction pressure to be 0.9MPa, gradually reducing the pressure along with the reaction, and the reaction time to be 10h;
A4. after the reaction is finished, collecting unreacted gas-phase raw materials of trifluoroethylene and/or monofluoromethyl chloride, a small amount of telomeric products and dichloromethane; solid-liquid separation treatment such as filtration or distillation is carried out on the materials in the reaction kettle, and the solid part is Lewis acid catalyst (HfCl) 4 ) The liquid phase materials are dichloromethane and telomeric products, and 3-chloro-1, 2-tetrafluoropropane with the purity of 99.9 percent is obtained by rectification and separation and is used for the dehydrohalogenation step.
The Lewis acid catalyst obtained by separating the unreacted gas-phase raw material can be returned to the telomerization step for reuse.
Gas chromatography analysis of the gas and liquid feeds gave a monochloromethane conversion of 76.5%, a 3-chloro-1, 2-tetrafluoropropane selectivity of 81.2%, a major by-product of 1-chloro-1, 2, 3-tetrafluoropropane, a selectivity of 15.3%, and small amounts of other by-products.
(II) dehydrohalogenation step
B1. The method comprises the following steps of (1) adopting a reaction tube made of Inconel alloy with the inner diameter of 19mm and the length of 800mm as a fixed bed reactor, filling 20mL of cat1 into the middle of the fixed bed reactor, connecting a reaction pipeline, introducing nitrogen for purging, wherein the nitrogen flow is 100mL/min;
B2. setting the reaction temperature to be 350 ℃, the heating rate to be 5 ℃/min, and starting heating the reaction furnace;
B3. after the catalyst bed layer reaches the reaction temperature, adjusting the nitrogen flow to 20mL/min, and simultaneously continuously introducing 3-chloro-1, 2-tetrafluoropropane with the purity of 99.9% into the fixed bed reactor at the speed of 5.0g/h to start the reaction;
B4. the gas mixture exiting the reactor was treated by holding, by on-line GC and GC/MS analysis, the conversion of 3-chloro-1, 2-tetrafluoropropane reached 88.7%, the 2, 3-tetrafluoropropene content in the product reached 24.1%, and the 1-chloro-3, 3-trifluoropropene content reached 58.7%.
Example 2
This example presents a process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, operating as in example 1, with the sole difference that: in the telomerization step, zrCl is adopted 4 Substitute for HfCl 4 The dosage is 4.0g; the amount of monochloromethane monofluoride was increased to 39.7g (0.58 mol), the amount of trifluoroethylene was increased to 71.3g (0.87 mol), and the other conditions were kept constant.
The gas and liquid feeds from the telomerization step were analyzed by gas chromatography for 99.0% conversion of monochloromethane, 89.9% selectivity for 3-chloro-1, 2-tetrafluoropropane, 5.3% selectivity for the major by-product 1-chloro-1, 2, 3-tetrafluoropropane, and a small amount of other by-products.
Example 3
This example presents a process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, operating as in example 2, with the only difference that: in the telomerization step, methylene chloride was not used, and the amount of trifluoroethylene was increased to 95.1g (1.16 mol), while the reaction temperature was increased to 30 ℃ and the initial reaction pressure was increased to 1.5MPa, and the other conditions were kept constant.
The gas and liquid phase feeds from the telomerization step were analyzed by gas chromatography for monochloromethane conversion of 99.5%, 3-chloro-1, 2-tetrafluoropropane selectivity of 88.1%, 1-chloro-1, 2, 3-tetrafluoropropane as the major by-product, and 4.1% selectivity with small amounts of other by-products.
Example 4
This example presents a process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, operating as in example 2, with the sole difference that: in the telomerization step, alCl is adopted 3 Substituted for ZrCl 4 The dosage is unchanged, and is 4.0g; while dichloromethane was not used and the amount of trifluoroethylene was reduced to 52.5g (0.64 mol), the other conditions were kept unchanged.
The gas and liquid phase feeds from the telomerization step were analyzed by gas chromatography for 99.6% conversion of monochloromethane, 75.5% selectivity for 3-chloro-1, 2-tetrafluoropropane, 15.9% selectivity for the major by-product 1-chloro-1, 2, 3-tetrafluoropropane, and a small amount of other by-products.
Example 5
This example presents a process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, operating as in example 1, with the sole difference that: in the step A2 of the telomerization step, after the monochloromethane monofluoride and the trifluoroethylene are sequentially introduced into the autoclave, high-purity high-pressure nitrogen is adopted to pressurize the autoclave, the pressure in the autoclave is increased to 3.0MPa from 0.9MPa, and other conditions are kept unchanged.
The gas and liquid phase feeds from the telomerization step were analyzed by gas chromatography for monochloromethane conversion of 99.8%, 3-chloro-1, 2-tetrafluoropropane selectivity of 88.6%, 1-chloro-1, 2, 3-tetrafluoropropane as the major by-product, and 7.6% selectivity, with minor amounts of other by-products.
Example 6
This example presents a process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, operating as in example 1, with the only difference that: in the dehydrohalogenation step, cat2 is used instead of cat1.
The chromatographic analysis of the dehydrohalogenation reaction product revealed that the conversion of 3-chloro-1, 2-tetrafluoropropane was 92.9%, the content of 2, 3-tetrafluoropropene in the product was 20.3%, and the content of 1-chloro-3, 3-trifluoropropene was 58.7%.
Example 7
This example presents a process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, operating as in example 1, with the only difference that: during the dehydrohalogenation step, the cat1 dosage was increased to 40mL.
When the product of the dehydrohalogenation reaction was subjected to chromatographic analysis, the conversion of 3-chloro-1, 2-tetrafluoropropane was over 95.9%, the content of 2, 3-tetrafluoropropene in the product was 16.1%, and the content of 1-chloro-3, 3-trifluoropropene was 44.6%.
Example 8
This example presents a process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, operating as in example 1, with the sole difference that: in the dehydrohalogenation step, the reaction temperature was 450 ℃.
The chromatographic analysis of the dehydrohalogenation reaction product revealed that the conversion of 3-chloro-1, 2-tetrafluoropropane was 98.3%, the content of 2, 3-tetrafluoropropene in the product was 15.9%, and the content of 1-chloro-3, 3-trifluoropropene was 60.0%.
Comparative example 1
This comparative example presents a process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, operating as in example 1, with the sole difference that: chloroform was used instead of dichloromethane in an amount of 20g, the other conditions being maintained.
The chromatographic analysis of the material after the reaction in the telomerization step revealed that the conversion of monofluoromethane was 86.9%, the selectivity for 3-chloro-1, 2-tetrafluoropropane was 46.1%, a large amount of disproportionation product of monofluoromethane was produced, dichloromethane was produced, the selectivity reached 40.3%, and a small amount of other telomerization by-products were present.
Comparative example 2
This comparative example presents a process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, operating as in example 1, with the only difference that: by using ZnCl 2 Substitute for HfCl 4 The amount used was 3.0g, and the other conditions were kept constant.
The chromatographic analysis of the material after the polymerization step showed that the conversion of monofluoromethane was 20.8% and no target product, 3-chloro-1, 2-tetrafluoropropane, was produced.
Comparative example 3
This comparative example presents a process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, operating as in example 1, with the only difference that: without addition of HfCl 4 And dichloromethane, other conditions remaining unchanged.
The chromatographic analysis of the material after the polymerization step revealed that the conversion of monofluoromethane chloride was 7.6%, no target product, 3-chloro-1, 2-tetrafluoropropane, was produced, and only a small amount of methylene chloride, which is a disproportionation product of monofluoromethane chloride, was produced.
Comparative example 4
This comparative example presents a process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, operating as in example 1, with the only difference that: in the dehydrohalogenation step, the pretreated coconut shell activated carbon (dried at 120 ℃ for 12 h) is used for replacing cat1, and other conditions are kept unchanged.
The chromatographic analysis of the dehydrohalogenation reaction product shows that the conversion rate of 3-chloro-1, 2-tetrafluoropropane exceeds 99.7 percent, the content of 2, 3-tetrafluoropropene in the product is 99.0 percent, and no 1-chloro-3, 3-trifluoropropene is generated.
Comparative example 5
This comparative example presents a process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene, operating as in example 1, with the only difference that: the Pd/AC catalyst (Pd loading 1 wt%) was used in place of cat1, and the other conditions were maintained.
Chromatographic analysis is carried out on the dehydrohalogenation reaction product, the conversion rate of 3-chloro-1, 2-tetrafluoropropane is 83.5 percent, the 2, 3-tetrafluoropropene content in the product was 96.4%, the 1-chloro-2, 3-tetrafluoropropene content was 1.3%, and no 1-chloro-3, 3-trifluoropropene was produced.
Claims (16)
1. A co-production preparation method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene is characterized by comprising the following steps: the co-production preparation method comprises the following steps:
A1. and (3) telomerization: under the action of telomerization catalyst, the monofluoromethane chloride and trifluoroethylene are subjected to pressure telomerization reaction to prepare 3-chloro-1, 2-tetrafluoropropane; the telomerization catalyst is a Lewis acid catalyst or a mixed catalyst of the Lewis acid catalyst and dichloromethane;
A2. dehydrohalogenation: 3-chloro-1, 2-tetrafluoropropane simultaneously undergoes dehydrochlorination reaction and dehydrofluorination reaction under the action of a composite dehalogenation catalyst to obtain 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene.
2. The co-production method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene according to claim 1, characterized in that: the Lewis acid catalyst is at least one halide selected from Al, sb, ti, zr and Hf.
3. The process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene according to claim 2, characterized in that: the Lewis acid catalyst is selected from ZrCl 4 、HfCl 4 、TiCl 4 、AlF 3 、AlCl 3 、SbF 5 At least one of them.
4. The co-production method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene according to claim 1, characterized in that: the molar ratio of the monofluoromethane chloride to the trifluoroethylene is 1.1-1.
5. The co-production method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene according to claim 1, characterized in that: the Lewis acid catalyst accounts for 0.01-50 wt% of the mass of the monochloro methane.
6. The co-production method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene according to claim 1, characterized in that: the molar ratio of the dichloromethane to the monofluoromethane chloride is as follows: 1.
7. The process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene according to claim 1, characterized in that: the pressure telomerization reaction is carried out at the temperature of minus 30 to 100 ℃ and the pressure of 0.5 to 5.0MPa, and the reaction time is 1 to 50 hours.
8. The co-production method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene according to claim 1, characterized in that: the composite dehalogenation catalyst is prepared from at least one oxide or fluoride of Al, mg or Cr and activated carbon powder.
9. The co-production method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene according to claim 8, characterized in that: at least one of Al, mg or CrThe oxide or fluoride is selected from Al 2 O 3 、AlF 3 、MgF 2 And Cr 2 O 3 At least one of them.
10. The co-production method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene according to claim 8, characterized in that: the activated carbon powder is selected from shell activated carbon, coal activated carbon or wood activated carbon.
11. The co-production method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene according to claim 9, characterized in that: al (Al) 2 O 3 The content of the catalyst is 1.0 to 20 weight percent of the total weight of the catalyst, and the AlF 3 The content of the catalyst is 1.0 to 20 weight percent of the total weight of the catalyst, mgF 2 The content of the catalyst is 1.0 to 20 weight percent of the total weight of the catalyst, and the Cr content is 2 O 3 The content of the catalyst is 1.0 to 20wt percent of the total weight of the catalyst.
12. The process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene according to claim 1, characterized in that: after the 3-chloro-1, 2-tetrafluoropropane is vaporized, nitrogen is carried into a catalyst bed layer for dehydrohalogenation reaction, and the material volume space velocity of the dehydrohalogenation reaction is 50-300 h -1 ，N 2 The volume ratio of the 3-chloro-1, 2-tetrafluoropropane is (0.5-3.0): 1.
13. the co-production process of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene according to any one of claims 1 to 12, characterized by: the 2, 3-tetrafluoropropene with 10-50% and the 1-chloro-3, 3-trifluoropropene with 10-70% are obtained through a dehydrohalogenation step.
14. The co-production method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene according to claim 1, characterized in that: the compound dehalogenation catalyst is prepared by a blending method and comprises the following steps:
B1. mixing: mixing Al 2 O 3 And/or AlF 3 And/or MgF 2 And/or Cr 2 O 3 Mixing the active carbon powder with the active carbon powder according to the mass ratio of (0.01-0.25) to 1 and fully mixing the active carbon powder and the active carbon powder by adopting a mechanical stirring or ball milling mode;
B2. sieving: sieving the mixed material to remove the part which is not uniformly mixed;
B3. molding: feeding the sieved material into a tablet press for tabletting and forming;
B4. and drying the molded catalyst to prepare the composite dehalogenation catalyst.
15. The process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene according to claim 1, characterized in that: the reaction temperature of the dehydrohalogenation step is 300-500 ℃.
16. The process for the coproduction of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene according to claim 1, characterized in that: the 3-chloro-1, 2-tetrafluoropropane obtained by the telomerization step is used for the dehydrohalogenation step after rectification and separation.
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| CN202110404614.6A CN115215722B (en) | 2021-04-15 | 2021-04-15 | Co-production preparation method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene |
| JP2023563266A JP2024515341A (en) | 2021-04-15 | 2022-04-07 | Method for Producing 2,3,3,3-Tetrafluoropropene |
| US18/286,137 US20240208887A1 (en) | 2021-04-15 | 2022-04-07 | Method for preparing 2,3,3,3-tetrafluoropropene |
| EP22787430.2A EP4324811A1 (en) | 2021-04-15 | 2022-04-07 | Method for preparing 2,3,3,3-tetrafluoropropene |
| PCT/CN2022/085539 WO2022218204A1 (en) | 2021-04-15 | 2022-04-07 | Method for preparing 2,3,3,3-tetrafluoropropene |
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