CN114409499A - Process for preparing 1, 1-difluoroethylene - Google Patents
Process for preparing 1, 1-difluoroethylene Download PDFInfo
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- CN114409499A CN114409499A CN202011170535.5A CN202011170535A CN114409499A CN 114409499 A CN114409499 A CN 114409499A CN 202011170535 A CN202011170535 A CN 202011170535A CN 114409499 A CN114409499 A CN 114409499A
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- rare earth
- saturated solution
- earth fluoride
- mass ratio
- alcohol
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000012047 saturated solution Substances 0.000 claims abstract description 46
- -1 rare earth fluoride Chemical class 0.000 claims abstract description 41
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 38
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000010992 reflux Methods 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 238000009833 condensation Methods 0.000 claims abstract description 14
- 230000005494 condensation Effects 0.000 claims abstract description 14
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000004480 active ingredient Substances 0.000 claims abstract description 8
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims abstract description 5
- 150000008046 alkali metal hydrides Chemical class 0.000 claims abstract description 5
- 239000004615 ingredient Substances 0.000 claims abstract description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 39
- 239000007789 gas Substances 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 239000002608 ionic liquid Substances 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 8
- 229920000223 polyglycerol Polymers 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 5
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012312 sodium hydride Substances 0.000 claims description 4
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 claims description 2
- 229940087646 methanolamine Drugs 0.000 claims description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N mono-n-propyl amine Natural products CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004888 n-propyl amino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical group [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims 1
- RVKZDIDATLDTNR-UHFFFAOYSA-N sulfanylideneeuropium Chemical compound [Eu]=S RVKZDIDATLDTNR-UHFFFAOYSA-N 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000002156 mixing Methods 0.000 description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000012043 crude product Substances 0.000 description 11
- 239000012530 fluid Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 238000005265 energy consumption Methods 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XULHFMYCBKQGEE-MRXNPFEDSA-N 2-Hexyl-1-decanol Natural products CCCCCCCC[C@H](CO)CCCCCC XULHFMYCBKQGEE-MRXNPFEDSA-N 0.000 description 7
- XULHFMYCBKQGEE-UHFFFAOYSA-N 2-hexyl-1-Decanol Chemical compound CCCCCCCCC(CO)CCCCCC XULHFMYCBKQGEE-UHFFFAOYSA-N 0.000 description 7
- 238000003379 elimination reaction Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000007530 organic bases Chemical class 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- BOTHRHRVFIZTGG-UHFFFAOYSA-K praseodymium(3+);trifluoride Chemical compound F[Pr](F)F BOTHRHRVFIZTGG-UHFFFAOYSA-K 0.000 description 3
- OJIKOZJGHCVMDC-UHFFFAOYSA-K samarium(iii) fluoride Chemical compound F[Sm](F)F OJIKOZJGHCVMDC-UHFFFAOYSA-K 0.000 description 3
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 3
- XRADHEAKQRNYQQ-UHFFFAOYSA-K trifluoroneodymium Chemical compound F[Nd](F)F XRADHEAKQRNYQQ-UHFFFAOYSA-K 0.000 description 3
- KCSRIQFDDJARDG-UHFFFAOYSA-N 1-butyl-4-chloro-2,3-dimethyl-2H-imidazole Chemical compound C(CCC)N1C(N(C(=C1)Cl)C)C KCSRIQFDDJARDG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WDEZYHHMIZHERM-UHFFFAOYSA-N 1,1-bis(fluoranyl)ethene Chemical compound FC(F)=C.FC(F)=C WDEZYHHMIZHERM-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 1
- AKIOUZFROHTEEN-UHFFFAOYSA-N 1-butyl-2,3-dimethyl-1,2-dihydroimidazol-1-ium chloride Chemical compound [Cl-].CCCC[NH+]1C=CN(C)C1C AKIOUZFROHTEEN-UHFFFAOYSA-N 0.000 description 1
- HHHYPTORQNESCU-UHFFFAOYSA-M 1-butyl-2,3-dimethylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1C HHHYPTORQNESCU-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical group 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical group 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229940105963 yttrium fluoride Drugs 0.000 description 1
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
-
- 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
Abstract
A preparation method of 1, 1-difluoroethylene comprises the following steps: i) preparing an inorganic base alcohol saturated solution; ii) placing the inorganic alkaline alcohol saturated solution and the rare earth fluoride catalyst in a reaction kettle provided with a condensation reflux device and a gas collecting pipeline, introducing 1, 1-difluoro-1-chloroethane, and collecting a vinylidene fluoride product discharged from the gas collecting pipeline. The rare earth fluoride catalyst comprises an active ingredient and an auxiliary ingredient, wherein the active ingredient comprises rare earth fluoride, acetylacetone salt and ferric chloride; the auxiliary component comprises C1‑6Alkylamine, C1‑6Alkyl alkoxides, C1‑6An alkyl alkanolamine, an alkali metal hydride, or a mixture thereof.
Description
Technical Field
The present invention relates to a process for producing 1, 1-difluoroethylene using 1, 1-difluoro-1-chloroethane (HCFC-142 b). The process of the present invention has improved HCFC-142b conversion and 1, 1-difluoroethylene (VDF) selectivity.
Background
The fluorine-containing material has excellent high temperature resistance, oil resistance, solvent resistance, weather resistance and physical and mechanical properties, is one of indispensable and alternative basic materials in modern industry, particularly in the high-tech field, is widely applied in industrial and agricultural production, and is mainly used in the fields of chemical equipment, electronics and electrics, piezoelectric materials, lithium batteries, architectural coatings and the like. In recent years, with the progress of science and technology and the development of material synthesis technology, people have higher and higher market demand and performance requirements on fluorine-containing materials, and the synthesis field of preparing monomer 1, 1-difluoroethylene is driven to develop rapidly.
1, 1-difluoroethylene, also known as vinylidene fluoride (VDF), of the formula CH2＝CF2The monomer is one of important monomers in the fluorine chemical industry, and is mainly used for producing polyvinylidene fluoride, fluororubber and fluorine-containing copolymers such as vinylidene fluoride-hexafluoropropylene, vinylidene fluoride-vinylidene fluoride, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene and the like. At present, the method for industrially producing the VDF monomer mainly adopts 1, 1-difluoro-1-chloroethane (HCFC-142b) as a raw material, and comprises the steps of cracking through an empty tube or diluting through water vapor to dehydrochlorinate (HCl), then carrying out a series of post-treatment steps including carbon removal, water washing, alkali washing, compression, cold removal and finally rectifying to obtain the VDF monomer.
For example, CN103664508A discloses a method for producing vinylidene fluoride monomer, comprising: 1) HCFC-142b is used as a raw material, and is cracked through an empty tube or diluted and cracked by steam, and light components are removed through a vinylidene fluoride lightness-removing tower; 2) obtaining a vinylidene fluoride monomer by a vinylidene fluoride rectifying tower; 3) removing impurities and high-boiling residues by a side line impurity removing tower, recovering vinylidene fluoride from a tower top kettle, collecting high-boiling residues and impurities from the bottom of the tower kettle, controlling the tower top temperature to be 35 ℃ below zero, the tower kettle temperature to be 90-95 ℃, the tower top pressure to be 2MPa, controlling the pressure drop of the whole tower to be 9KPa, and controlling the molar reflux ratio to be 80; 4) and recovering vinylidene fluoride monomer and unreacted difluoromonochloroethane.
The cracked gas obtained by the HCFC-142b cracking process all has more impurities: CH (CH)3F、CH3CHF2、C2H3F、C2H2ClF and the like, the content of the impurities is more than 3 percent, the impurities are difficult to remove by rectification, and the impurities can increase the difficulty of temperature control of the rectification tower and increase the energy consumption when being accumulated to a certain degree. In addition, the process has the defects of large equipment investment, high reaction temperature (600-900 ℃), high energy consumption, easy coking of reaction tubes, poor product selectivity and the like.
In order to solve the problems, CN105384596A discloses a preparation method of vinylidene fluoride, which comprises the steps of adding 10-70% of inorganic alkali liquor, a phase transfer agent and 1, 1-difluoro-1-chloroethane into a reaction kettle for reaction at the reaction temperature of 60-200 ℃, extracting and collecting gas-phase materials in the reaction process, controlling the pressure of the reaction kettle to be 1-5.0MPa, stopping collecting the gas-phase materials after reacting for 0.5-5h, cooling reaction liquid, relieving pressure, collecting the gas-phase materials in the reaction kettle, and mixing the collected gas-phase materials before and after mixing to obtain a crude product of the vinylidene fluoride. Although the improved method has the advantages of simple process, relatively mild reaction conditions, less equipment investment, low energy consumption and less byproducts compared with the existing cracking method, the preparation method has the following defects:
a) the reaction is carried out in an aqueous alkali solution, 1, 1-difluoro-1-chloroethane is easy to generate substitution reaction, so that the yield is low, and the elimination reaction of 1, 1-difluoro-1-chloroethane is easy to generate defluorination products, so that the product selectivity is poor;
b) the reaction is carried out under high pressure, and distillation operation is needed subsequently, so that the public engineering consumption is large, the investment of the whole equipment is still high, and the method is not suitable for industrial production;
c) there is still room for improvement in the conversion of 1, 1-difluoro-1-chloroethane and in the selectivity of vinylidene fluoride.
There is still a need in the art to develop a method for preparing vinylidene fluoride, which has the advantages of simple process, low energy consumption, low equipment investment, high product purity and convenient post-treatment, and also has improved conversion rate of 1, 1-difluoro-1-chloroethane and selectivity of vinylidene fluoride.
Disclosure of Invention
The invention aims to provide a preparation method of vinylidene fluoride, which has the advantages of simple process, low energy consumption, low equipment investment, high product purity and convenient post-treatment, and also has improved conversion rate of 1, 1-difluoro-1-chloroethane and selectivity of the vinylidene fluoride.
Accordingly, the present invention relates to a process for the preparation of 1, 1-difluoroethylene comprising the steps of:
i) preparing an alcohol saturated solution of inorganic base;
ii) placing the alcohol saturated solution of the inorganic base and the rare earth fluoride catalyst in a reaction kettle provided with a condensation reflux device and a gas collecting pipeline, introducing 1, 1-difluoro-1-chloroethane, and collecting a vinylidene fluoride product discharged from the gas collecting pipeline.
Detailed Description
The preparation method of the 1, 1-difluoroethylene comprises the following steps:
i) preparing alcohol saturated solution of inorganic base
The inorganic base suitable for the method of the present invention is not particularly limited, and may be a conventional inorganic base known in the art. For example, it may be an inorganic base as mentioned in CN105384596A (which is incorporated herein by reference as part of the present invention). In one embodiment of the invention, the inorganic base is selected from alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates or mixtures thereof. In one embodiment of the invention, the inorganic base is selected from potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate or a mixture of two or more thereof.
The alcohol suitable for the process of the present invention is not particularly limited as long as it can form an alcohol-saturated solution of an inorganic base with the inorganic base and the resulting saturated solution can be advantageously used in the process of the present invention. In one embodiment of the invention, the alcohol is C1-18Alkanols and hyperbranched polyglycerols. In one embodiment of the invention, the alcohol is selected from the group consisting of hyperbranched polyglycerol, ethanol, methanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-hexyl-1-decanol or mixtures thereof.
The hyperbranched polyglycerols used in the present invention can be obtained commercially or prepared by the method disclosed in, for example, CN 105209520A. In one example of the present invention, the hyperbranched polyglycerol is a hyperbranched polyglycerol of generation 4.
The method for preparing the saturated solution of the inorganic base alcohol is not particularly limited, and may be a conventional method known in the art. For example, the inorganic base can be added into the alcohol solvent or the alcohol solvent can be added into the inorganic base and mixed to obtain the alcohol saturated solution of the inorganic base.
In order to improve the reaction efficiency, the saturated solution of inorganic base alcohol can also optionally contain ionic liquid. In one embodiment of the present invention, the ionic liquid is selected from at least one of tetrabutylammonium bromide, tetrabutylammonium chloride, (1-butyl-3-methylimidazole) chloride, and 1-butyl-2, 3-dimethylimidazolium chloride salt. In one embodiment of the present invention, the mass ratio of the ionic liquid to the saturated solution of inorganic base alcohol is 1 (80-120), preferably 1 (85-110), more preferably 1 (90-100).
ii) placing the alcohol saturated solution of the inorganic base and the rare earth fluoride catalyst in a reaction kettle provided with a condensation reflux device and a gas collecting pipeline, introducing 1, 1-difluoro-1-chloroethane, and collecting a vinylidene fluoride product discharged from the gas collecting pipeline.
The reaction vessel suitable for use in the process of the present invention is not particularly limited and may be a conventional reaction vessel known in the art with a reflux condenser and a gas collection line fluidly connected to the reflux condenser.
The rare earth fluoride used as a catalyst in the process of the present invention may be a rare earth fluoride known in the art, for example, a rare earth fluoride obtainable by the process described in CN101348274A (which is incorporated herein by reference as part of the present invention). In one example of the present invention, the rare earth fluoride is selected from fluorides of yttrium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, or mixtures of two or more thereof.
In one example of the invention, the rare earth fluoride catalyst comprises an active ingredient and an auxiliary ingredient, wherein the active ingredient comprises rare earth fluoride, acetylacetone salt and ferric chloride, and the auxiliary ingredient comprises C1-6Alkylamine, C1-6Alkanediamine, C1-6Alkyl alkoxides, C1-6An alkyl alkanolamine, an alkali metal hydride or a mixture of two or more thereof.
In one embodiment of the present invention, the rare earth fluoride catalyst comprises an active component and an auxiliary component in a mass ratio of (3-5):1, preferably (3.2-4.8):1, more preferably (3.4-4.6):1, preferably (3.6-4.4):1, and preferably (3.8-4.2): 1.
In one embodiment of the invention, the acetylacetonate comprises copper acetylacetonate.
In one embodiment of the present invention, said C1-6The alkylamine is selected from n-propylamine, n-butylamine, n-hexylamine, or a mixture thereof; said C is1-6The alkanediamine is selected from ethylenediamine, propylenediamine or a mixture thereof; said C is1-6The alkyl alkoxide is selected from potassium tert-butyl alkoxide, sodium methoxide, sodium ethoxide, potassium methoxide or their mixture; said C is1-6The alkylalkanolamine is selected from ethanolamine, methanolamine or a mixture thereof; the alkali metal hydride is selected from potassium hydride, sodium hydride or mixtures thereof.
In one embodiment of the invention, the active ingredients are rare earth fluoride, copper acetylacetonate and ferric chloride which are mixed according to the mass ratio of 1 (2-3) to 1.
The method of the invention comprises the step of placing the alcohol saturated solution of the inorganic base and the rare earth fluoride catalyst which are prepared in the prior step into the reaction kettle. The rare earth fluoride is used in a catalytically effective amount.
In one embodiment of the invention, the mass ratio of the alcohol-saturated solution of the inorganic base to the catalyst is (8-10):0.1, preferably (8.2-9.8):0.1, more preferably (8.4-9.6):0.1, preferably (8.6-9.2):0.1, and most preferably (8.8-9.0): 0.1.
After the alcohol saturated solution of the inorganic base and the rare earth fluoride catalyst are placed in the reaction kettle, the method of the invention can also comprise a step of replacing the gas in the reaction kettle with inert gas. The inert gas to be used is not particularly limited and may be a conventional inert gas known in the art, and for example, the inert gas may be selected from any one of nitrogen, helium, neon, and argon. From the viewpoint of cost, nitrogen is preferred.
After the replacement with the inert gas, the process of the present invention comprises the step of introducing HCFC-142b into the reaction vessel. The flow rate of HCFC-142b is not particularly limited and may be a flow rate conventional in the art. In one embodiment of the invention, the HCFC-142b is introduced at a rate of from 1 to 2g/min, preferably from 1.1 to 1.9g/min, more preferably from 1.2 to 1.8g/min, preferably from 1.3 to 1.7g/min, most preferably from 1.4 to 1.6 g/min.
In one embodiment of the present invention, the reaction temperature in the reaction vessel is 60-80 deg.C, preferably 62-78 deg.C, more preferably 65-75 deg.C, preferably 68-72 deg.C, when HCFC-142b is introduced and the reaction vessel is started.
In one embodiment of the present invention, the temperature of the refrigerant liquid in the reflux condenser is from-25 to-15 deg.C, preferably from-22 to-18 deg.C. In one embodiment of the invention, the refrigerating fluid is formed by mixing ethylene glycol and water according to a mass ratio of (3-5) to 1.
After the reaction to obtain vinylidene fluoride, the method of the invention may further comprise a step of purifying the vinylidene fluoride. The applicable purification method is not particularly limited, and may be a conventional purification method known in the art. In one embodiment of the present invention, the purification step includes washing and drying the vinylidene fluoride obtained from the reaction sequentially to obtain the finished 1, 1-difluoroethylene product.
Compared with the prior art, the synthesis method of 1, 1-difluoroethylene provided by the invention has the following advantages:
(1) the preparation method of 1, 1-difluoroethylene provided by the invention can safely, quickly and efficiently convert HCFC-142b into VDF, does not need a high-temperature cracking process, does not need expensive catalysts, has simple post-treatment, does not cause environmental pollution, has convenient byproduct treatment, and has higher economic value, social value and ecological value;
(2) the preparation method of 1, 1-difluoroethylene provided by the invention overcomes the defects of large equipment investment, high reaction temperature, large energy consumption, easy coking of a reaction tube, poor product selectivity and the like in the traditional VDF production process, and has the advantages of higher production efficiency, fewer byproducts and three wastes, lower cost, higher atom utilization rate, simpler process route and post-treatment, low energy consumption, low equipment investment and suitability for continuous large-scale production;
(3) according to the preparation method of 1, 1-difluoroethylene, provided by the invention, the ionic liquid is added in the elimination reaction process, so that the dissolution selectivity can be improved, the reaction can be catalyzed, and the yield and the product purity are effectively improved. Particularly, the product selectivity and the reactant conversion rate are improved by reasonably selecting the catalyst;
(4) the preparation method of 1, 1-difluoroethylene provided by the invention has the advantages that the reaction is carried out at low temperature, the oxidation or polymerization reaction of the monomer containing unsaturated bonds is avoided, the reaction is carried out at normal pressure, the operation is simpler and safer, the subsequent distillation operation is not needed, and the energy consumption of public works and the equipment investment cost are reduced.
Examples
The present invention will be described in further detail with reference to examples.
Example 1
1. Preparation of rare earth fluoride catalyst
YF (YF) was prepared as described in example 1 of CN101348274A3) Mixing yttrium fluoride, copper acetylacetonate and ferric chloride according to the mass ratio of 1:2:1 to form an active component; the active component and n-butylamine are mixed according to the mass ratio of 3:1 to prepare the rare earth fluoride catalyst.
2. Preparing organic base alcohol saturated solution
Adding potassium hydroxide into an ethanol solvent at the temperature of 20 ℃, and preparing an ethanol saturated solution of the potassium hydroxide after uniformly mixing.
Tetrabutylammonium bromide is added to the ethanol saturated solution of potassium hydroxide in such an amount that the mass ratio of tetrabutylammonium bromide to the ethanol saturated solution of potassium hydroxide is 1: 80.
3. Elimination reaction and purification
And (3) placing the ethanol saturated solution of potassium hydroxide and the rare earth fluoride catalyst in a mass ratio of 8:0.1 into a reaction kettle with a condensation reflux device, wherein a gas collecting pipeline is arranged at the upper end of the condensation reflux device. The temperature of the refrigerating fluid of the condensing and refluxing device is-15 ℃ (the refrigerating fluid is formed by mixing ethylene glycol and water according to the mass ratio of 3: 1). Purging and replacing air in the reactor by using nitrogen, gradually introducing HCFC-142b into the solution in the reaction kettle at the flow rate of 1g/min, stirring at 65 ℃, and directly collecting gas when gas is discharged from a gas collecting pipeline to obtain a crude product.
And (3) washing and drying the crude product in sequence to obtain a finished product of the 1, 1-difluoroethylene.
Tests show that the conversion rate of HCFC-142b is 92% and the selectivity of VDF reaches 95% calculated by taking the consumption of HCFC-142b as a reference.
Example 2
1. Preparation of rare earth fluoride catalyst
Lanthanum fluoride (LaF) was prepared as described in example 2 of CN101348274A3) Mixing lanthanum fluoride, copper acetylacetonate and ferric chloride according to the mass ratio of 1:2.3:1 to form an active component; the active component and ethylenediamine are mixed according to the mass ratio of 3.5:1 to prepare the rare earth fluoride catalyst.
2. Preparing organic base alcohol saturated solution
Adding potassium carbonate into a methanol solvent at 23 ℃, and mixing uniformly to prepare a methanol saturated solution of potassium carbonate.
To the methanol saturated solution of potassium carbonate, (1-butyl-3-methylimidazole) chloride was added in an amount such that the mass ratio of (1-butyl-3-methylimidazole) chloride to the methanol saturated solution of potassium carbonate was 1: 90.
3. Elimination reaction and purification
And placing the methanol saturated solution of potassium carbonate and the rare earth fluoride catalyst in a mass ratio of 8.5:0.1 into a reaction kettle with a condensation reflux device, wherein a gas collecting pipeline is arranged at the upper end of the condensation reflux device. The temperature of the refrigerating fluid of the condensing and refluxing device is-17 ℃ (the refrigerating fluid is formed by mixing ethylene glycol and water according to the mass ratio of 3.5: 1). Purging and replacing air in the reactor by using nitrogen, gradually introducing HCFC-142b into the solution in the reaction kettle at the flow rate of 1.2g/min, stirring at 68 ℃, and directly collecting gas when gas is discharged from a gas collecting pipeline to obtain a crude product.
And (3) washing and drying the crude product in sequence to obtain a finished product of the 1, 1-difluoroethylene.
Tests show that the conversion rate of HCFC-142b is 93 percent and the selectivity of VDF reaches 91 percent based on the consumption of HCFC-142 b.
Example 3
1. Preparation of rare earth fluoride catalyst
Praseodymium fluoride (PrF) was prepared as described in example 3 of CN101348274A3) Praseodymium fluoride,Mixing copper acetylacetonate and ferric chloride according to the mass ratio of 1:2.5:1 to form an active component; the active ingredient is mixed with a mixture (1:1 mixture) of n-butylamine and potassium tert-butoxide according to the mass ratio of 4:1 to prepare the rare earth fluoride catalyst.
2. Preparing organic base alcohol saturated solution
Adding sodium carbonate into a 2-hexyl-1-decanol solvent at 25 ℃, and mixing uniformly to prepare a 2-hexyl-1-decanol saturated solution of the sodium carbonate.
To the saturated solution of sodium carbonate in 2-hexyl-1-decanol was added chloro (1-butyl-2, 3-dimethylimidazole) in such an amount that the mass ratio of chloro (1-butyl-2, 3-dimethylimidazole) to the saturated solution of sodium carbonate in 2-hexyl-1-decanol was 1: 100.
3. Elimination reaction and purification
And (2) placing the methanol saturated solution of potassium carbonate and the rare earth fluoride catalyst in a reaction kettle with a condensation reflux device according to the mass ratio of 9:0.1, wherein a gas collecting pipeline is arranged at the upper end of the condensation reflux device. The temperature of the refrigerating fluid of the condensing and refluxing device is-20 ℃ (the refrigerating fluid is formed by mixing ethylene glycol and water according to the mass ratio of 4: 1). Purging and replacing air in the reactor by using nitrogen, gradually introducing HCFC-142b into the solution in the reaction kettle at the flow rate of 1.5g/min, stirring at 70 ℃, and directly collecting gas when gas is discharged from a gas collecting pipeline to obtain a crude product.
And (3) washing and drying the crude product in sequence to obtain a finished product of the 1, 1-difluoroethylene.
Tests show that the conversion rate of HCFC-142b is 96 percent and the selectivity of VDF reaches 96 percent based on the consumption of HCFC-142 b.
Example 4
1. Preparation of rare earth fluoride catalyst
Neodymium fluoride (NdF) was obtained as described in example 4 of CN101348274A3) Mixing neodymium fluoride, copper acetylacetonate and ferric chloride according to the mass ratio of 1:2.9:1 to form an active component; n-butylamine, ethylenediamine, ethanolamine, potassium tert-butoxide, and sodium hydride are added in a ratio of 1:1: 3: 2:1 forming a mixture of auxiliary ingredients, mixing saidAnd mixing the active component and the auxiliary component mixture according to the mass ratio of 4.5:1 to prepare the rare earth fluoride catalyst.
2. Preparing organic base alcohol saturated solution
Mixing the components in a mass ratio of 1:2: 4, adding a mixture of potassium hydroxide, potassium carbonate and sodium carbonate into a mixed alcohol solvent, wherein the mixed alcohol solvent is prepared by mixing ethanol, methanol, 2-hexyl-1-decanol and hyperbranched polyglycerol in a 4 th generation mode according to a ratio of 1:1: 3: 2, and preparing an alcohol saturated solution of the inorganic base.
Adding an ionic liquid into the alcohol saturated solution, wherein the ionic liquid is prepared by mixing tetrabutylammonium bromide, 1-butyl-3-methylimidazole chloride and 1-butyl-2, 3-dimethylimidazole chloride according to the mass ratio of 1:1: 3. The mass ratio of the ionic liquid to the alcohol saturated solution is 1: 115.
3. Elimination reaction and purification
And placing the alcohol saturated solution and the rare earth fluoride catalyst in a reaction kettle with a condensation reflux device according to the mass ratio of 9.5:0.1, wherein the upper end of the condensation reflux device is provided with a gas collecting pipeline. The temperature of the refrigerating fluid of the condensing and refluxing device is-23 ℃ (the refrigerating fluid is formed by mixing ethylene glycol and water according to the mass ratio of 4.5: 1). Purging and replacing air in the reactor by using nitrogen, gradually introducing HCFC-142b into the solution in the reaction kettle at the flow rate of 1.8g/min, stirring at 73 ℃, and directly collecting gas when gas is discharged from a gas collecting pipeline to obtain a crude product.
And (3) washing and drying the crude product in sequence to obtain a finished product of the 1, 1-difluoroethylene.
Tests show that the conversion rate of HCFC-142b is 97 percent and the selectivity of VDF reaches 98 percent based on the consumption of HCFC-142 b.
Example 5
1. Preparation of rare earth fluoride catalyst
Samarium fluoride (SmF) was prepared as described in example 6 of CN101348274A3) Mixing samarium fluoride, copper acetylacetonate and ferric chloride according to the mass ratio of 1:3:1 to form an active component; mixing the active component and sodium hydride according to the mass ratio of 5:1 to prepare the fluorideA rare earth catalyst.
2. Preparing organic base alcohol saturated solution
At 30 ℃, mixing the components in a mass ratio of 3: 5, adding potassium hydroxide into a mixed alcohol solvent, wherein the mixed alcohol solvent is prepared by mixing 2-hexyl-1-decanol and hyperbranched polyglycerol 4 th generation by a ratio of 3: 5, and preparing an alcohol saturated solution of the inorganic base.
Tetrabutylammonium bromide was added to the alcohol saturated solution. The mass ratio of the tetrabutylammonium bromide to the alcohol saturated solution is 1: 120.
3. Elimination reaction and purification
And placing the alcohol saturated solution and the rare earth fluoride catalyst in a reaction kettle with a condensation reflux device according to the mass ratio of 10:0.1, wherein the upper end of the condensation reflux device is provided with a gas collecting pipeline. The temperature of the refrigerating fluid of the condensing and refluxing device is-25 ℃ (the refrigerating fluid is formed by mixing ethylene glycol and water according to the mass ratio of 5: 1). Purging and replacing air in the reactor by using nitrogen, gradually introducing HCFC-142b into the solution in the reaction kettle at the flow rate of 2g/min, stirring at 75 ℃, and directly collecting gas when gas is discharged from a gas collecting pipeline to obtain a crude product.
And (3) washing and drying the crude product in sequence to obtain a finished product of the 1, 1-difluoroethylene.
Tests show that the conversion rate of HCFC-142b is 92% and the selectivity of VDF reaches 90% calculated by taking the consumption of HCFC-142b as a reference.
Comparative example 1
Vinylidene fluoride was prepared in the same manner as in example 1 of CN 105384596A.
Tests show that the conversion rate of HCFC-142b is 75% and the selectivity of VDF reaches 52% based on the consumption of HCFC-142 b.
Comparative example 2
Vinylidene fluoride was prepared in substantially the same manner as in example 1 except that no rare earth fluoride catalyst was added.
Tests show that the conversion rate of HCFC-142b is 72 percent and the selectivity of VDF reaches 65 percent based on the consumption of HCFC-142 b.
Claims (10)
1. A preparation method of 1, 1-difluoroethylene comprises the following steps:
i) preparing an inorganic base alcohol saturated solution;
ii) placing the inorganic alkaline alcohol saturated solution and the rare earth fluoride catalyst in a reaction kettle provided with a condensation reflux device and a gas collecting pipeline, introducing 1, 1-difluoro-1-chloroethane, and collecting a vinylidene fluoride product discharged from the gas collecting pipeline.
2. The process of claim 1, wherein the inorganic base is selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, and mixtures of two or more thereof; the alcohol is selected from C1-18Alkanols and hyperbranched polyglycerols.
3. The method according to claim 1, wherein the saturated solution of inorganic base alcohol further comprises an ionic liquid selected from at least one of tetrabutylammonium bromide, tetrabutylammonium chloride, 1-butyl-3-methylimidazole chloride, and 1-butyl-2, 3-dimethylimidazolium chloride; the mass ratio of the ionic liquid to the inorganic alkaline alcohol saturated solution is 1:80-120, preferably 1:85-110, more preferably 1: 90-100.
4. The method according to any one of claims 1 to 3, wherein the rare earth fluoride catalyst comprises an active component and an auxiliary component, and the active component comprises rare earth fluoride, acetylacetonate and ferric chloride; the auxiliary component comprises C1-6Alkylamine, C1-6Alkanediamine, C1-6Alkyl alkoxides, C1-6An alkyl alkanolamine, an alkali metal hydride, or a mixture thereof.
5. The process according to claim 4, wherein the mass ratio of the active ingredient to the auxiliary ingredient is 3-5:1, preferably 3.2-4.8:1, more preferably 3.4-4.6:1, preferably 3.6-4.4:1, preferably 3.8-4.2: 1.
6. The method of claim 4, wherein the acetylacetonate comprises copper acetylacetonate; said C is1-6The alkylamine is selected from n-propylamine, n-butylamine, n-hexylamine, or a mixture thereof; said C is1-6The diamine is selected from ethylenediamine, propylenediamine or their mixture; said C is1-6The alkyl alkoxide is selected from potassium tert-butyl alkoxide, sodium methoxide, sodium ethoxide, potassium ethoxide or their mixture; said C is1-6The alkylalkanolamine is selected from ethanolamine, methanolamine or a mixture thereof; the alkali metal hydride is selected from potassium hydride, sodium hydride or mixtures thereof.
7. The preparation method according to claim 4, wherein the active ingredients are rare earth fluoride, acetylacetone salt and ferric chloride which are mixed according to the mass ratio of 1 (2-3) to 1.
8. The process according to any one of claims 1 to 3, wherein the mass ratio of the saturated solution of the inorganic base alcohol to the rare earth fluoride catalyst is from 8 to 10:0.1, preferably from 8.2 to 9.8:0.1, more preferably from 8.4 to 9.6:0.1, preferably from 8.6 to 9.2:0.1, preferably from 8.8 to 9.0: 0.1.
9. The method according to any one of claims 1 to 3, wherein after the inorganic basic alcohol saturated solution and the rare earth fluoride catalyst are placed in the reaction vessel, the method further comprises a step of replacing the gas in the reaction vessel with an inert gas.
10. A method according to any one of claims 1 to 3, wherein the reaction temperature in the reaction vessel is 60 to 80 ℃, preferably 62 to 78 ℃, more preferably 65 to 75 ℃, preferably 68 to 72 ℃; the HCFC-142b is fed at a flow rate of 1 to 2g/min, preferably 1.1 to 1.9g/min, more preferably 1.2 to 1.8g/min, still more preferably 1.3 to 1.7g/min, most preferably 1.4 to 1.6 g/min.
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Citations (4)
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|---|---|---|---|---|
| US3830856A (en) * | 1970-09-08 | 1974-08-20 | Bayer Ag | Preparation of vinylidene fluoride |
| CN104817425A (en) * | 2015-04-03 | 2015-08-05 | 常熟三爱富中昊化工新材料有限公司 | 1,1,2,3-tetrachloropropene synthesis method |
| CN105384596A (en) * | 2015-11-13 | 2016-03-09 | 巨化集团技术中心 | Preparation method of vinylidene fluoride (VDF) |
| CN109180420A (en) * | 2018-09-27 | 2019-01-11 | 浙江工业大学 | A kind of preparation method of 1,1- difluoroethylene |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5946211B2 (en) * | 1975-12-29 | 1984-11-10 | ダイキン工業株式会社 | 1-Chloro-1,1-difluoroethane matach/Oyobi 1,1,1-trifluoroethane |
| CN101348274B (en) * | 2008-08-27 | 2011-06-15 | 西南交通大学 | Method for preparing rare earth fluoride |
| CN103664508A (en) * | 2013-12-18 | 2014-03-26 | 常熟振氟新材料有限公司 | Production method of vinylidene fluoride monomer |
| CN106588563B (en) * | 2016-12-28 | 2019-02-05 | 浙江工业大学 | A kind of preparation method of 1,1- difluoroethylene |
| CN106866354B (en) * | 2017-01-18 | 2019-06-21 | 浙江工业大学 | A kind of preparation method of 1,1- difluoroethylene |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3830856A (en) * | 1970-09-08 | 1974-08-20 | Bayer Ag | Preparation of vinylidene fluoride |
| CN104817425A (en) * | 2015-04-03 | 2015-08-05 | 常熟三爱富中昊化工新材料有限公司 | 1,1,2,3-tetrachloropropene synthesis method |
| CN105384596A (en) * | 2015-11-13 | 2016-03-09 | 巨化集团技术中心 | Preparation method of vinylidene fluoride (VDF) |
| CN109180420A (en) * | 2018-09-27 | 2019-01-11 | 浙江工业大学 | A kind of preparation method of 1,1- difluoroethylene |
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