CN116037117A - Initiator, fluorination catalyst and preparation method of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene - Google Patents
Initiator, fluorination catalyst and preparation method of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene Download PDFInfo
- Publication number
- CN116037117A CN116037117A CN202310334212.2A CN202310334212A CN116037117A CN 116037117 A CN116037117 A CN 116037117A CN 202310334212 A CN202310334212 A CN 202310334212A CN 116037117 A CN116037117 A CN 116037117A
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- China
- Prior art keywords
- initiator
- ccl
- tetrafluoropropene
- hours
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- 239000003999 initiator Substances 0.000 title claims abstract description 100
- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 150000001336 alkenes Chemical class 0.000 claims abstract description 46
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 claims abstract description 44
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 4
- 239000010439 graphite Substances 0.000 claims abstract description 4
- 239000002808 molecular sieve Substances 0.000 claims abstract description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 172
- 230000004913 activation Effects 0.000 claims description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 44
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 239000012018 catalyst precursor Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 20
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 15
- 150000001845 chromium compounds Chemical class 0.000 claims description 15
- 230000003213 activating effect Effects 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- 150000001350 alkyl halides Chemical class 0.000 claims description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 13
- FPBWSPZHCJXUBL-UHFFFAOYSA-N 1-chloro-1-fluoroethene Chemical group FC(Cl)=C FPBWSPZHCJXUBL-UHFFFAOYSA-N 0.000 claims description 11
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 11
- 235000019404 dichlorodifluoromethane Nutrition 0.000 claims description 11
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 10
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 239000012320 chlorinating reagent Substances 0.000 claims description 9
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 9
- 150000001408 amides Chemical class 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 5
- 229940029284 trichlorofluoromethane Drugs 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- OMAWWKIPXLIPDE-UHFFFAOYSA-N (ethyldiselanyl)ethane Chemical compound CC[Se][Se]CC OMAWWKIPXLIPDE-UHFFFAOYSA-N 0.000 claims description 4
- JVPGYYNQTPWXGE-UHFFFAOYSA-N 2-(4-methylphenyl)-1,3-benzothiazole Chemical compound C1=CC(C)=CC=C1C1=NC2=CC=CC=C2S1 JVPGYYNQTPWXGE-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 239000004338 Dichlorodifluoromethane Substances 0.000 claims description 4
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 4
- QLTKZXWDJGMCAR-UHFFFAOYSA-N dioxido(dioxo)tungsten;nickel(2+) Chemical compound [Ni+2].[O-][W]([O-])(=O)=O QLTKZXWDJGMCAR-UHFFFAOYSA-N 0.000 claims description 4
- DJZHPOJZOWHJPP-UHFFFAOYSA-N magnesium;dioxido(dioxo)tungsten Chemical compound [Mg+2].[O-][W]([O-])(=O)=O DJZHPOJZOWHJPP-UHFFFAOYSA-N 0.000 claims description 4
- NZMAJUHVSZBJHL-UHFFFAOYSA-N n,n-dibutylformamide Chemical compound CCCCN(C=O)CCCC NZMAJUHVSZBJHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000004334 fluoridation Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 28
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010808 liquid waste Substances 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 description 42
- 239000000047 product Substances 0.000 description 24
- 238000002474 experimental method Methods 0.000 description 18
- 239000012071 phase Substances 0.000 description 18
- 238000000926 separation method Methods 0.000 description 18
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 16
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical group F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000007791 liquid phase Substances 0.000 description 13
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical group [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- 229910052721 tungsten Inorganic materials 0.000 description 9
- 239000010937 tungsten Substances 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 description 4
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 150000008282 halocarbons Chemical class 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229950005499 carbon tetrachloride Drugs 0.000 description 3
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 3
- 229940042935 dichlorodifluoromethane Drugs 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910001026 inconel Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 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 2
- ZEJBFBYYCVJWCZ-UHFFFAOYSA-N 1,1,1,3-tetrachloro-3-fluoropropane Chemical compound FC(Cl)CC(Cl)(Cl)Cl ZEJBFBYYCVJWCZ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- LTUTVFXOEGMHMP-UHFFFAOYSA-N dibromofluoromethane Chemical compound FC(Br)Br LTUTVFXOEGMHMP-UHFFFAOYSA-N 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- RIHYOLCRHKZJPJ-UHFFFAOYSA-N fluoro(diiodo)methane Chemical compound FC(I)I RIHYOLCRHKZJPJ-UHFFFAOYSA-N 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 2
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- MAXQCYDCBHPIAB-UHFFFAOYSA-N 1,1,2,3,3-pentachloroprop-1-ene Chemical compound ClC(Cl)C(Cl)=C(Cl)Cl MAXQCYDCBHPIAB-UHFFFAOYSA-N 0.000 description 1
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical compound FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 1
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-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
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910021564 Chromium(III) fluoride Inorganic materials 0.000 description 1
- 229910021565 Chromium(IV) fluoride Inorganic materials 0.000 description 1
- 229910021566 Chromium(V) fluoride Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- OMKYWARVLGERCK-UHFFFAOYSA-I chromium pentafluoride Chemical compound F[Cr](F)(F)(F)F OMKYWARVLGERCK-UHFFFAOYSA-I 0.000 description 1
- SYJRAUIOIRVQSW-UHFFFAOYSA-J chromium(4+);tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Cr+4] SYJRAUIOIRVQSW-UHFFFAOYSA-J 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
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- B01J27/224—Silicon carbide
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B01J37/0209—Impregnation involving a reaction between the support and a fluid
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- 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
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Abstract
The application discloses an initiator for preparing hydrochlorocarbon or hydrochlorofluorocarbon by halogenated olefin and halogenated alkane, wherein the initiator is obtained by an initiator precursor, the initiator precursor consists of iron element and a carrier, and the mass ratio of the iron element to the carrier is (5% -30%) to (70% -95%); wherein the carrier is selected from one or more than two of active carbon, molecular sieve, silicon dioxide, silicon carbide, graphite and graphene; the initiator is prepared by the following method: according to the mass ratio of the iron element to the carrier, the soluble salt of the iron element is immersed on the carrier, the initiator precursor is obtained through filtration, and then the initiator precursor is dried, roasted and activated to obtain the initiator. Also disclosed is a fluorination catalyst and a process for the preparation of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene. The preparation method has the characteristics of easily obtained raw materials, high single-pass yield, no liquid waste and solid waste, and capability of realizing gas-phase continuous zero-pollution production.
Description
Technical Field
The application relates to the technical field of chemical synthesis, in particular to an initiator, a fluorination catalyst and a preparation method of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene.
Background
At present, E-1, 3-tetrafluoropropene (HFO-1234 ze (E)) is difficult to synthesize by a simple synthetic route, and is generally prepared by a synthetic route combining telomerization with other reaction steps such as fluorine-chlorine exchange, dehydrohalogenation and the like, and mainly comprises the following steps:
(1) US2005245773A1 reports the liquid phase telomerization of vinyl fluoride with trifluoroiodomethane or trifluorobromomethane followed by dehydrohalogenation of the intermediate to give HFO-1234ze (E) and Z-1, 3-tetrafluoropropene (HFO-1234 ze (Z)). This route has the following drawbacks: (a) The raw material trifluoroiodomethane or trifluorobromomethane is expensive and difficult to obtain; (b) The use of large amounts of solvents, which produce large amounts of waste solutions, can severely pollute the environment.
(2) US2005245773A1 reports that 1, 1-difluoroethylene as a starting material is subjected to liquid phase telomerization with diiodo-monofluoromethane or dibromo-monofluoromethane, and then a synthetic route through fluorination reaction and dehydrohalogenation reaction has the defect that raw materials diiodo-monofluoromethane and dibromo-monofluoromethane are difficult to obtain.
(3) WO2013122822A1 reports a synthetic route of starting materials of fluoroethylene and carbon tetrachloride through liquid phase telomerization, fluorine-chlorine exchange (low temperature 65-70 ℃) and dehydrochlorination, and intermediates are HCFC-241fb and HCFC-244fa in sequence. The route relates to a liquid phase telomerization process, which adopts a large amount of solvents and initiators, and is easy to generate a large amount of liquid waste and solid waste.
(4) WO2010101198A1 reports the synthesis routes of starting from fluoroethylene and carbon tetrachloride by liquid phase telomerization, fluorine-chlorine exchange (high temperature 281 ℃) and fluorine-chlorine exchange, the intermediates being HCFC-241fb and HCFO-1233zd (E/Z) in sequence. The route relates to a liquid phase telomerization process, which adopts a large amount of solvents and initiators, and is easy to generate a large amount of liquid waste and solid waste.
(5) WO2013122822A1, WO2010101198A1 and JP2015120669A, CN112723985B report synthetic routes to liquid phase telomerization and two-step fluorine-chlorine exchange reactions using vinyl chloride and carbon tetrachloride as starting materials, with the intermediates HCC-240fa and HCFO-1233zd (E/Z) in sequence. The route relates to a liquid phase telomerization process, which adopts a large amount of solvents and initiators, and is easy to generate a large amount of liquid waste and solid waste.
Up to now, the route for synthesizing E-1, 3-tetrafluoropropene by using 1-chloro-1-fluoroethylene or 1, 1-dichloroethylene as a starting material through telomerization and other reaction combinations is not disclosed and reported.
Disclosure of Invention
Aiming at the problems, the application provides a preparation method of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene, which has the advantages of easily available raw materials, high single-pass yield, no liquid waste and solid waste, and capability of realizing gas-phase continuous zero-pollution production.
Specifically, the technical scheme of the application is as follows:
1. an initiator for the preparation of hydrochlorocarbons or hydrochlorofluorocarbons by means of a haloalkene and a haloalkane, wherein,
the initiator is obtained by passing an initiator precursor,
the initiator precursor consists of iron element and a carrier, wherein the mass ratio of the iron element to the carrier is (5% -30%) to (70% -95%);
wherein the carrier is selected from one or more than two of active carbon, molecular sieve, silicon dioxide, silicon carbide, graphite and graphene;
the initiator is prepared by the following method: according to the mass ratio of the iron element to the carrier, the soluble salt of the iron element is immersed on the carrier, the initiator precursor is obtained through filtration, and then the initiator precursor is dried, roasted and activated to obtain the initiator.
2. The initiator according to item 1, wherein,
the drying conditions are as follows: the drying temperature is 120-200 ℃ and the drying time is 6-15 hours.
3. The initiator according to item 1, wherein,
the roasting conditions are as follows: the roasting temperature is 300-500 ℃ and the roasting time is 6-15 hours.
4. The initiator according to item 1, wherein,
the activation comprises a first activation, a second activation and a third activation in sequence.
5. The initiator according to item 4, wherein,
in the first activation, a mixed gas of nitrogen and hydrogen is used for activation for 6-24 hours at the temperature of 250-350 ℃, and the molar ratio of the nitrogen to the hydrogen is (1-10): 1, a step of;
in the second activation, a chlorinating reagent is used for activating for 6-24 hours at 150-350 ℃, wherein the chlorinating agent is selected from the group consisting of 1, 3-pentachloropropane, 1, 3-tetrachloropropane one or more of 1, 3-tetrachloro-2-fluoropropane and 1, 3-tetrachloro-4, 4-trifluorobutane;
in the third activation, an amide reagent is used for activating for 6-24 hours at 150-350 ℃, wherein the amide reagent is selected from one or more than two of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylbutyramide, N-diethylformamide, N-dipropylcarboxamide and N, N-dibutylformamide.
6. The initiator according to item 1, wherein,
the soluble salt of the iron element is selected from one or more than two of ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate and ferrous sulfate.
7. A fluorination catalyst for the production of hydrofluoroolefins by hydrochlorocarbons or hydrochlorofluorocarbons wherein,
the fluorination catalyst is obtained by fluorinating a catalyst precursor,
The fluoridation catalyst precursor consists of trivalent chromium compound and tungstate, wherein the mass ratio of the trivalent chromium compound to the tungstate is (70% -99%) to (1% -30%),
the catalyst is prepared by the following steps: uniformly mixing a trivalent chromium compound and tungstate according to a mass ratio, pressing and forming to obtain a fluorination catalyst precursor, and drying, roasting and activating the fluorination catalyst precursor to obtain the fluorination catalyst.
8. The fluorination catalyst of item 7, wherein,
the trivalent chromium compound is chromium hydroxide or chromium oxide,
the tungstate is one or more than two of zinc tungstate, nickel tungstate, iron tungstate, cobalt tungstate, magnesium tungstate, aluminum tungstate, silicotungstic acid, ammonium tungstate, ammonium paratungstate and ammonium metatungstate.
9. The fluorination catalyst of item 7, wherein,
the drying conditions are as follows: the drying temperature is 120-200 ℃ and the drying time is 6-15 hours.
10. The fluorination catalyst of item 7, wherein,
the roasting conditions are as follows: the roasting temperature is 300-500 ℃ and the roasting time is 6-15 hours.
11. The fluorination catalyst of item 7, wherein,
in the activation, mixed gas of nitrogen and nitrogen trifluoride is used for activation for 6-24 hours at 300-500 ℃, and the molar ratio of the nitrogen to the nitrogen trifluoride is (1-10): 1.
12. Use of the initiator according to any one of items 1 to 6 and the fluorination catalyst according to any one of items 7 to 11 in the preparation of a hydrofluoroolefin by gas-phase continuous reaction.
13. A process for the preparation of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene, comprising the steps of:
reacting a haloolefin with a haloalkane in the presence of an initiator to produce cci m F n CH 2 CCl x F y Wherein 3.gtoreq.m.gtoreq.1, 2.gtoreq.n.gtoreq.0, and m+n=3, 3.gtoreq.x.gtoreq.1, 2.gtoreq.y.gtoreq.0, and x+y=3;
the CCl is m F n CH 2 CCl x F y Reacting with hydrogen fluoride in the presence of a fluorination catalyst to produce 1-chloro-1, 3-tetrafluoropropene;
the 1-chloro-1, 3-tetrafluoropropene and hydrogen exist in the presence of a hydrogenation catalyst in this case E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene are formed.
14. The production process according to item 13, wherein the halogenated olefin is one or more selected from the group consisting of 1, 1-difluoroethylene, 1-dichloroethylene and 1-chloro-1-fluoroethylene.
15. The production process according to item 13, wherein the halogenated alkane is one or more selected from the group consisting of carbon tetrachloride, trichlorofluoromethane and dichlorodifluoromethane.
16. The production method according to item 13, wherein the initiator is any one of the initiators of items 1 to 6;
The fluorination catalyst according to any one of items 7 to 11.
17. The production method according to claim 13, wherein the halogenated olefin and halogenated alkane are reacted in the presence of an auxiliary agent and an initiator at a reaction pressure of 0.1 to 1.5mpa and/or a contact time of 1 to 100s and/or a reaction temperature of 100 to 250 ℃.
18. The process according to claim 17, wherein the molar ratio of the halogenated olefin, the halogenated alkane and the auxiliary agent is (1 to 4): 1: (0.01 to 0.05).
19. The process according to item 17, wherein the auxiliary is N, N-dimethylformamide or N, N-dimethylacetamide.
20. The production method according to item 13, wherein the CCl m F n CH 2 CCl x F y Reacting with hydrogen fluoride in the presence of a fluorination catalyst, wherein the reaction pressure is 0.1-2.0 MPa, and/or the contact time is 2-200 s, and/or the reaction temperature is 200-400 ℃.
21. The production method according to item 20, wherein the hydrogen fluoride and CCl m F n CH 2 CCl x F y The molar ratio of (5-20): 1.
22. the production method according to item 13, wherein the 1-chloro-1, 3-tetrafluoropropene is reacted with hydrogen in the presence of a hydrogenation catalyst at a reaction pressure of 0.1 to 2.0mpa and/or a contact time of 2 to 200 seconds and/or a reaction temperature of 150 to 350 ℃.
23. The production method according to item 22, wherein the molar ratio of the hydrogen gas to the 1-chloro-1, 3-tetrafluoropropene is (2 to 20): 1.
24. the production process according to item 13, wherein the hydrogenation catalyst is composed of palladium element, bismuth element and porous metal fluoride,
in the hydrogenation catalyst, the mass percentage of the palladium element is 0.1% -2.0%, the mass percentage of the bismuth element is 0.5% -5.0%, and the mass percentage of the porous metal fluoride is 97.0% -99.4%.
ADVANTAGEOUS EFFECTS OF INVENTION
The preparation method of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene provided by the application is easy to obtain raw materials of 1, 1-difluoroethylene, 1-dichloroethylene or 1-chloro-1-fluoroethylene, wherein the 1, 1-difluoroethylene or 1-chloro-1-fluoroethylene can also be obtained by synthesizing the 1, 1-dichloroethylene and hydrogen fluoride through gas phase catalytic fluorine-chlorine exchange reaction; the method can realize zero-pollution production of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene, and the reaction of each step can lead the material to completely react through an independent circulating system, thereby realizing full utilization of the material, greatly reducing pollution and realizing zero pollution of production.
Drawings
The drawings are included to provide a better understanding of the present application and are not to be construed as unduly limiting the present application. Wherein:
FIG. 1 is a flow chart of the preparation process of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene.
Symbol description
1-a first reactor; 2-first distillation column: 3-a second reactor; 4-a second distillation column; a 5-phase separator; 6-a third distillation column; 7-a fourth distillation column; an 8-third reactor; 9-a fifth distillation column; 10-a sixth distillation column; 11-seventh distillation column; 12-eighth distillation column; 13-a ninth distillation column; 14-43 are all lines.
Detailed Description
The present application is described in detail below. While specific embodiments of the present application are shown, it should be understood that the present application may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
It should be noted that, throughout the specification and claims, the terms "include" and "comprising" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. The description hereinafter sets forth the preferred embodiment for carrying out the present application, but is not intended to limit the scope of the present application in general, as the description proceeds. The scope of the present application is defined by the appended claims.
The application provides an initiator for preparing hydrochlorocarbon or hydrochlorofluorocarbon by halogenated olefin and halogenated alkane, wherein the initiator is obtained by an initiator precursor, the initiator precursor consists of iron element and a carrier, and the mass ratio of the iron element to the carrier is (5% -30%): (70% -95%); wherein the carrier is one or more than two of active carbon, molecular sieve, silicon dioxide, silicon carbide, graphite and graphene; the initiator is prepared by the following method: according to the mass ratio of the iron element to the carrier, the soluble salt of the iron element is immersed on the carrier, the initiator precursor is obtained through filtration, and then the initiator precursor is dried, roasted and activated to obtain the initiator.
The traditional initiator is generally a bulk catalyst and is only used for liquid phase reaction of batch process, the initiator is difficult to recycle and reuse, and serious pollution is caused by discharging into the environment. The application belongs to a supported initiator, and is applicable to mobile phase reactions (including liquid phase reactions and gas phase reactions) of continuous processes, so that the continuous processes for synthesizing hydrochlorofluorocarbon by using the mobile phase are realized, the synthesis efficiency is greatly improved, meanwhile, the utilization efficiency of the initiator is improved, and the service life of the initiator is remarkably prolonged.
In the present application, the mass of the iron element means the mass of the iron element in the soluble salt of the iron element, for example, 1g FeCl 3 The mass of Fe in (C).
In some embodiments, the mass ratio of elemental iron to carrier may be 5%:95%, 6%:94%, 7%:93%, 8%:92%, 9%:91%, 10%:90%, 11%:89%, 12%:88%, 13%:87%, 14%:86%, 15%:85%, 16%:84%, 17%:83%, 18%:82%, 19%:81%, 20%:80%, 21%:79%, 22%:78%, 23%:77%, 24%:76%, 25%:75%, 26%:74%, 27%:73%, 28%:72%, 29%:71%, 30%:70% or any range therebetween. If the content of iron element is less than 5%, the concentration of the initiator is too low to initiate the reaction rapidly and efficiently; if the content of the iron element is more than 30%, the initiator precursor may severely block the pore volume of the carrier, thereby adversely affecting the complete activation of the initiator precursor and thus the efficient progress of the initiation reaction.
In some embodiments, in the preparation of the initiator, the drying conditions are: the drying temperature is 120-200 ℃, and the drying time is 6-15 hours, wherein the drying temperature can be 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ or any range between the two, and the drying time can be 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours or any range between the two.
In some embodiments, in the preparation of the initiator, the firing conditions are: the roasting temperature is 300-500 ℃ and the roasting time is 6-15 hours, wherein the roasting temperature can be 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃ or any range between the two, and the roasting time can be 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours or any range between the two.
In some embodiments, in the preparation of the initiator, the activation comprises a first activation, a second activation, and a third activation in sequence.
In some embodiments, in the preparation of the initiator, in the first activation, a mixed gas of nitrogen and hydrogen is used for activation at 250 ℃ to 350 ℃ for 6 to 24 hours, and the molar ratio of nitrogen to hydrogen is (1 to 10): 1, a step of; wherein the first activation temperature may be 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃ or any range therebetween, the first activation time may be 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours or any range therebetween, and the molar ratio of nitrogen and hydrogen may be 1: 1. 2: 1. 3: 1. 4: 1. 5: 1. 6: 1. 7: 1. 8: 1. 9: 1. 10:1 or any range therebetween.
In some embodiments, in the preparation of the initiator, the second activation is performed using a chlorinating agent at 150 to 350 ℃ for 6 to 24 hours, wherein the chlorinating agent is selected from the group consisting of 1, 3-pentachloropropane, 1, 3-tetrachloropropane one or more of 1, 3-tetrachloro-2-fluoropropane and 1, 3-tetrachloro-4, 4-trifluorobutane; wherein the second activation temperature may be 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, or any range therebetween, and the second activation time may be 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, or any range therebetween.
In some embodiments, in the preparation of the initiator, in the third activation, an amide reagent is used for activation at 150 ℃ to 350 ℃ for 6 to 24 hours, wherein the amide reagent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylbutyramide, N-diethylformamide, N-dipropylcarboxamide and N, N-dibutylformamide, wherein, the third activation temperature may be 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, or any range therebetween, and the third activation time may be 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, or any range therebetween.
In some embodiments, the activation includes a first activation, a second activation and a third activation sequentially, specifically, a mixed gas of nitrogen and hydrogen is used for activation at 250 ℃ to 350 ℃ for 6 to 24 hours, and the molar ratio of the nitrogen to the hydrogen is (1 to 10): 1, activating for 6-24 hours at 150-350 ℃ by using a chlorinating reagent, wherein the chlorinating agent is selected from one or more than two of 1, 3-pentachloropropane, 1, 3-tetrachloropropane, 1, 3-tetrachloro-2-fluoropropane and 1, 3-tetrachloro-4, 4-trifluorobutane, finally, an amide reagent is used for activating for 6-24 hours at the temperature of 150-350 ℃, wherein the amide reagent is selected from one or more than two of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylbutyramide, N-diethylformamide, N-dipropylcarboxamide and N, N-dibutylformamide.
In some embodiments, in the preparation of the initiator, the soluble salt of elemental iron is selected from one or more of ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate.
The initiator can be used for preparing hydrochlorocarbons or hydrochlorofluorocarbons through halogenated olefins and halogenated alkanes, and the initiator can trigger the halogenated alkanes to generate chlorine free radicals and halogenated alkyl free radicals in the whole reaction process, so that the chlorine free radicals and the halogenated alkyl free radicals are respectively added to carbon-carbon double bonds of the halogenated olefins, and the target hydrochlorocarbons or hydrochlorofluorocarbon products are generated.
The application provides a fluorination catalyst for preparing hydrofluoroolefin by hydrochlorocarbon or hydrochlorofluorocarbon, which is obtained by a fluorination catalyst precursor, wherein the fluorination catalyst precursor consists of trivalent chromium compounds and tungstate, the mass ratio of the trivalent chromium compounds to the tungstate is (70% -99%) to (1% -30%), and the catalyst is obtained by the following preparation method: uniformly mixing a trivalent chromium compound and tungstate according to a mass ratio, pressing and forming to obtain a fluorination catalyst precursor, and drying, roasting and activating the fluorination catalyst precursor to obtain the fluorination catalyst.
According to the method, a catalyst is prepared by adopting a blending method, a trivalent chromium compound and tungstate are mixed according to a certain proportion to prepare a catalyst precursor, the precursor is subjected to high-temperature roasting and then enters an activation stage of mixed gas consisting of nitrogen and nitrogen trifluoride, the nitrogen trifluoride can be pyrolyzed to obtain nitrogen and fluorine, the fluorine activates tungsten element to obtain tungsten hexafluoride with a lower boiling point, the tungsten hexafluoride is separated from a catalyst structure in a gas mode, so that a pore channel can be provided for the catalyst, the specific surface area and the pore volume of the catalyst are increased, the activity of the catalyst is improved, and tungsten element which is not converted into tungsten hexafluoride is mainly left in the catalyst in the form of oxide or a small amount of fluoride, and carbon deposition of the catalyst at a high temperature can be effectively inhibited; meanwhile, fluorine gas obtained by pyrolyzing nitrogen trifluoride can also activate most of chromium element into mixed fluoride of trivalent chromium, tetravalent chromium and pentavalent chromium, and high-valence chromium-based catalysts have been proved to have higher catalytic activity in fluorine-chlorine exchange reaction than trivalent chromium catalysts. In addition, in addition to the above reaction, the silicotungstic acid can also be reacted, fluorine gas activates silicon element to obtain silicon tetrafluoride with a lower boiling point, and most of silicon tetrafluoride is separated from the surface of the catalyst in a gas mode, so that not only can a pore canal be provided for the catalyst, but also the specific surface area and the pore volume of the catalyst are increased, the activity of the catalyst is improved, but silicon element which is not converted into silicon tetrafluoride is mainly remained in the catalyst in the form of oxide, and carbon deposition of the catalyst at a high temperature can be effectively inhibited. The whole effect is seen, the fluorination catalyst prepared by the scheme has high use temperature, high catalytic activity and long service life.
The catalyst can be suitable for mobile phase reactions (including liquid phase reactions and gas phase reactions) of continuous processes, so that the continuous processes for synthesizing the hydrofluoroolefin by the mobile phase are realized, the synthesis efficiency is greatly improved, the utilization efficiency of the catalyst is improved, and the service life of the catalyst is remarkably prolonged.
In some embodiments, the mass ratio of tungstate to trivalent chromium compound may be 1%:99%, 2%:98%, 3%:97%, 4%:96%, 5%:95%, 6%:94%, 7%:93%, 8%:92%, 9%:91%, 10%:90%, 11%:89%, 12%:88%, 13%:87%, 14%:86%, 15%:85%, 16%:84%, 17%:83%, 18%:82%, 19%:81%, 20%:80%, 21%:79%, 22%:78%, 23%:77%, 24%:76%, 25%:75%, 26%:74%, 27%:73%, 28%:72%, 29%:71%, 30%:70% or any range therebetween. If the content of tungstate is less than 1%, the concentration of tungsten element used as a pore-forming material is too low, so that the catalyst is not sufficiently subjected to effective pore-forming, the specific surface area of the catalyst is not greatly increased, and the catalytic activity of the catalyst is remarkably improved; if the content of tungstate is higher than 30%, the concentration of tungsten element serving as a pore-forming material is too high, so that more tungsten element remains in the catalyst, and other metal assistants with more content are introduced, and the active sites on the surface of the chromium-based catalyst can be covered by the tungsten element with too high content and other metal assistants, so that the catalytic activity of the catalyst is reduced.
In some embodiments, the trivalent chromium compound is chromium hydroxide or chromium oxide in the preparation of the catalyst.
In some embodiments, the catalyst is prepared by one or more of zinc tungstate, nickel tungstate, iron tungstate, cobalt tungstate, magnesium tungstate, aluminum tungstate, silicotungstic acid, ammonium tungstate, ammonium paratungstate, and ammonium metatungstate.
In some embodiments, in the preparation of the catalyst, the drying conditions are: the drying temperature is 120-200 ℃ and the drying time is 6-15 hours; the drying temperature may be 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ or any range therebetween, and the drying time may be 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours or any range therebetween.
In some embodiments, in the preparation of the catalyst, the calcination conditions are: the roasting temperature is 300-500 ℃ and the roasting time is 6-15 hours, wherein the roasting temperature can be 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃ or any range between the two, and the roasting time can be 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours or any range between the two.
In some embodiments, in the preparation of the catalyst, in the activation, a mixed gas of nitrogen and nitrogen trifluoride is used for activation for 6-24 hours at 300-500 ℃, and the molar ratio of nitrogen to nitrogen trifluoride is (1-10): 1, wherein the activation temperature may be 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃ or any range therebetween, the activation time may be 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours or any range therebetween,
the molar ratio of nitrogen to nitrogen trifluoride may be 1: 1. 2: 1. 3: 1. 4: 1. 5: 1. 6: 1. 7: 1. 8: 1. 9: 1. 10:1 or any range therebetween.
The catalyst prepared by the method is a fluorination catalyst, and the target hydrofluoroolefin product is obtained by catalyzing the hydrochlorofluorocarbon and hydrogen fluoride to generate fluorine-chlorine exchange reaction. The prepared fluorination catalyst has the advantages of high conversion rate, good selectivity and long service life.
The application also provides the application of the initiator and the fluorination catalyst in preparing hydrofluoroolefins by gas-phase continuous reaction. The initiator and the fluorination catalyst are used in the following production methods.
In the present application, the hydrofluoroolefin may be 1-chloro-1, 3-tetrafluoropropene or E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene are possible.
The application provides a preparation method of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene, which comprises the following steps:
step one: reacting a haloolefin with a haloalkane in the presence of an initiator to produce cci m F n CH 2 CCl x F y Wherein 3.gtoreq.m.gtoreq.1, 2.gtoreq.n.gtoreq.0, and m+n=3, 3.gtoreq.x.gtoreq.1, 2.gtoreq.y.gtoreq.0, and x+y=3; step two: the CCl is m F n CH 2 CCl x F y Reacting with hydrogen fluoride in the presence of a fluorination catalyst to produce 1-chloro-1, 3-tetrafluoropropene; step three: the 1-chloro-1, 3-tetrafluoropropene and hydrogen exist in the presence of a hydrogenation catalyst in this case E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene are formed.
In step one, the halogenated olefin is reacted with halogenated alkane in the presence of an auxiliary agent and an initiator to generate CF 3 CCl 2 CH 2 CCl x F y 。
Step one includes step 1.1 and step 1.2.
Step 1.1: the halogenated olefin, halogenated alkane and auxiliary agent enter a first reactor filled with an initiator for reaction. Step 1.2: separating the product obtained in the step 1.1 by a first distillation tower, wherein the tower top component is a mixture of unreacted halogenated olefin, halogenated alkane and auxiliary agent, and the tower bottom component is CCl m F n CH 2 CCl x F y The tower top component can be recycled to the first reactor for continuous reaction, and the tower bottom component is the target product of the first step.
In some embodiments, the halogenated olefin and halogenated alkane are reacted in the presence of an auxiliary agent and an initiator at a reaction pressure of 0.1-1.5 MPa for a contact time of 1-100 s at a reaction temperature of 100-250deg.C to produce CCl m F n CH 2 CCl x F y 。
In this application, the contact time refers to the time for the reaction mass to pass through the fixed bed layer, i.e. the time for a single pass reaction of the fixed bed.
Specifically, the halogenated alkane can be any one or more than two of carbon tetrachloride, trichloro-monofluoromethane or dichloro-difluoromethane. The halogenated olefin can be one or more than two of 1, 1-difluoroethylene, 1-dichloroethylene and 1-chloro-1-fluoroethylene.
The specific reaction may be:
or alternatively
Or alternatively
Specifically, the reaction pressure may be 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa, or any range therebetween.
In some embodiments, the reaction pressure is 0.1 to 0.5mpa. In some embodiments, the reaction pressure is 0.2 to 0.5mpa. In some embodiments, the reaction pressure is 0.3 to 0.5mpa. In some embodiments, the reaction pressure is 0.4 to 0.5mpa. In some embodiments, the reaction pressure is 0.5 to 0.6mpa. In some embodiments, the reaction pressure is 0.5 to 0.7mpa. In some embodiments, the reaction pressure is 0.5 to 0.8mpa. In some embodiments, the reaction pressure is 0.5 to 0.9mpa. In some embodiments, the reaction pressure is 0.5 to 1.0mpa. In some embodiments, the reaction pressure is 0.5 to 1.1mpa. In some embodiments, the reaction pressure is 0.5 to 1.2mpa. In some embodiments, the reaction pressure is 0.5 to 1.3mpa. In some embodiments, the reaction pressure is 0.5 to 1.4mpa. In some embodiments, the reaction pressure is 0.5 to 1.5mpa.
Specifically, the contact time may be 1s, 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 95s, 100s or any range therebetween.
In some embodiments, the contact time may be 10 to 60 seconds. In some embodiments, the contact time may be 10 to 55 seconds. In some embodiments, the contact time may be 10 to 50 seconds. In some embodiments, the contact time may be 10 to 40 seconds. In some embodiments, the contact time may be 10 to 30 seconds.
Specifically, the reaction temperature may be 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, or any range therebetween.
In some embodiments, the reaction temperature may be 150-200 ℃. In some embodiments, the reaction temperature may be 100-200 ℃. In some embodiments, the reaction temperature may be 150-210 ℃. In some embodiments, the reaction temperature may be 150-220 ℃. In some embodiments, the reaction temperature may be 150-230 ℃. In some embodiments, the reaction temperature may be 150 to 240 ℃. In some embodiments, the reaction temperature may be 150 to 250 ℃.
In some embodiments, the molar ratio of halogenated olefin, halogenated alkane and auxiliary agent is (1-4): 1: (0.01 to 0.05), preferably (1.5 to 2.5): 1: (0.02-0.04). In some embodiments, the molar ratio of halogenated olefin, halogenated alkane and auxiliary agent is (1-4): 1:0.01. in some embodiments, the molar ratio of halogenated olefin, halogenated alkane and auxiliary agent is (1-4): 1:0.02. in some embodiments, the molar ratio of halogenated olefin, halogenated alkane and auxiliary agent is (1-4): 1:0.03. in some embodiments, the molar ratio of halogenated olefin, halogenated alkane and auxiliary agent is (1-4): 1:0.04. in some embodiments, the molar ratio of halogenated olefin, halogenated alkane and auxiliary agent is (1-4): 1:0.05. in some embodiments, the molar ratio of halogenated olefin, halogenated alkane and auxiliary is (1.5-2.5): 1:0.01. in some embodiments, the molar ratio of halogenated olefin, halogenated alkane and auxiliary is (1.5-2.5): 1:0.02. in some embodiments, the molar ratio of halogenated olefin, halogenated alkane and auxiliary is (1.5-2.5): 1:0.03. in some embodiments, the molar ratio of halogenated olefin, halogenated alkane and auxiliary is (1.5-2.5): 1:0.04. in some embodiments, the molar ratio of halogenated olefin, halogenated alkane and auxiliary is (1.5-2.5): 1:0.05. in some embodiments, the molar ratio of halogenated olefin, halogenated alkane, and auxiliary is 1:1: (0.01 to 0.05). In some embodiments, the molar ratio of halogenated olefin, halogenated alkane, and auxiliary is 1.5:1: (0.01 to 0.05). In some embodiments, the molar ratio of halogenated olefin, halogenated alkane, and adjuvant is 2:1: (0.01 to 0.05). In some embodiments, the molar ratio of halogenated olefin, halogenated alkane, and auxiliary is 2.5:1: (0.01 to 0.05). In some embodiments, the molar ratio of halogenated olefin, halogenated alkane, and auxiliary is 3:1: (0.01 to 0.05). In some embodiments, the molar ratio of halogenated olefin, halogenated alkane, and auxiliary is 3.5:1: (0.01 to 0.05). In some embodiments, the molar ratio of halogenated olefin, halogenated alkane, and auxiliary is 4:1: (0.01 to 0.05). In some embodiments, the molar ratio of halogenated olefin, halogenated alkane, and auxiliary is 1:1: (0.02-0.04). In some embodiments, the molar ratio of halogenated olefin, halogenated alkane, and auxiliary is 1.5:1: (0.02-0.04). In some embodiments, the molar ratio of halogenated olefin, halogenated alkane, and adjuvant is 2:1: (0.02-0.04). In some embodiments, the molar ratio of halogenated olefin, halogenated alkane, and auxiliary is 2.5:1: (0.02-0.04). In some embodiments, the molar ratio of halogenated olefin, halogenated alkane, and auxiliary is 3:1: (0.02-0.04). In some embodiments, the molar ratio of halogenated olefin, halogenated alkane, and auxiliary is 3.5:1: (0.02-0.04). In some embodiments, the molar ratio of halogenated olefin, halogenated alkane, and auxiliary is 4:1: (0.02-0.04). In some embodiments, the molar ratio of halogenated olefin, halogenated alkane, and auxiliary is 1:1:0.01, 1.5:1:0.01, 2:1:0.01, 2.5:1:0.01, 3:1:0.01, 3.5:1:0.01, 4:1:0.01, 1:1:0.02, 1:1:0.03, 1:1:0.04, 1:1:0.05, 1.5:1:0.02, 1.5:1:0.03, 1.5:1:0.04, 1.5:1:0.05, 2:1:0.02, 2:1:0.03, 2:1:0.04, 2:1:0.05, 2.5:1:0.02, 2.5:1:0.03, 2.5:1:0.04, 2.5:1:0.05, 3:1:0.02, 3:1:0.03, 3:1:0.04, 3:1:0.05, 3.5:1:0.02, 3.5:1:0.03, 3.5:1:0.04, 3.5:1:0.05, 4:1:0.02, 4:1:0.03, 4:1:0.04 or 4:1:0.05.
Specifically, the auxiliary agent is N, N-dimethylformamide or N, N-dimethylacetamide.
Specifically, in the CCl m F n CH 2 CCl x F y In which x may be 1, 2 or 3 and y may be 0, 1 or 2. When m=x=1, n=y=2, ccl m F n CH 2 CCl x F y Is CClF 2 CH 2 CClF 2 The method comprises the steps of carrying out a first treatment on the surface of the When m=x=2, n=y=1, ccl m F n CH 2 CCl x F y For CCl 2 FCH 2 CCl 2 F. When m=x=3, n=y=0, ccl m F n CH 2 CCl x F y For CCl 3 CH 2 CCl 3 The method comprises the steps of carrying out a first treatment on the surface of the When m=1, x=2, n=2, y=1, ccl m F n CH 2 CCl x F y Is CClF 2 CH 2 CCl 2 F, performing the process; when m=1, x=3, n=2, y=0, ccl m F n CH 2 CCl x F y Is CClF 2 CH 2 CCl 3 The method comprises the steps of carrying out a first treatment on the surface of the When m=2, x=1, n=1, y=2, ccl m F n CH 2 CCl x F y For CCl 2 FCH 2 CClF 2 The method comprises the steps of carrying out a first treatment on the surface of the When m=2, x=3, n=1, y=0, ccl m F n CH 2 CCl x F y For CCl 2 FCH 2 CCl 3 The method comprises the steps of carrying out a first treatment on the surface of the When m=3, x=1, n=0, y=2, ccl m F n CH 2 CCl x F y For CCl 3 CH 2 CClF 2 The method comprises the steps of carrying out a first treatment on the surface of the When m=3, x=2, n=0, y=1, ccl m F n CH 2 CCl x F y For CCl 3 CH 2 CCl 2 F。
In the present application, the CCl m F n CH 2 CCl x F y May be CClF 2 CH 2 CClF 2 、CCl 2 FCH 2 CCl 2 F、CCl 3 CH 2 CCl 3 、CClF 2 CH 2 CCl 2 F、CClF 2 CH 2 CCl 3 、CCl 2 FCH 2 CClF 2 、CCl 2 FCH 2 CCl 3 、CCl 3 CH 2 CClF 2 And CCl 3 CH 2 CCl 2 F, one or more than two of F.
In the present application, step two includes step 2.1, step 2.2, step 2.3, and step 2.4.
Step 2.1: the CCl is m F n CH 2 CCl x F y And hydrogen fluoride is introduced into a second reactor filled with a fluorination catalyst for reaction. Step 2.2: after the reaction of step 2.1, the reaction product obtained in step 2.1The material flow enters a second distillation tower for separation, and the tower kettle components are 1-chloro-1, 3-tetrafluoropropene, 1, 3-pentafluoropropene, low-fluorination degree pentachloropropene, unreacted hydrogen fluoride and CCl m F n CH 2 CCl x F y The tower top component is hydrogen chloride. Step 2.3: 2.2, the tower bottom component of the second distillation tower obtained in the step 2.2 enters a phase separator for continuous separation, wherein the upper layer of the phase separator is hydrogen fluoride, and the lower layer of the phase separator is liquid phase of 1-chloro-1, 3-tetrafluoropropene, 1, 3-pentafluoropropene, low-fluorination degree pentahalopropene and CCl m F n CH 2 CCl x F y Recycling upper layer component hydrogen fluoride to the second reactor to continue the reaction, wherein the phase separation temperature of the phase separator is-10-30 ℃; step 2.4: the lower layer component of the phase separator obtained in the step 2.3 enters a third distillation tower to be continuously separated, the tower top component is 1-chloro-1, 3-tetrafluoropropene and 1, 3-pentafluoropropene, and the tower bottom component is CCl m F n CH 2 CCl x F y And the tower top component enters a fourth distillation tower to be separated, and the tower bottom component is circulated to the second reactor to continue to react, wherein the tower top component of the fourth distillation tower is 1, 3-pentafluoropropene, and the tower bottom component is the target product 1-chloro-1, 3-tetrafluoropropene in the step 2.1. The reaction conditions of step 2.1 are: the reaction pressure is 0.1-2.0 MPa, the contact time is 2-200 seconds, and the reaction temperature is 200-400 ℃.
The specific reaction can be as follows:
in some preferred embodiments, the CCl m F n CH 2 CCl x F y And hydrogen fluoride react in the presence of a fluorination catalyst, wherein the reaction pressure is 0.1-0.5 MPa, the contact time is 10-60 s, and the reaction temperature is 250-300 ℃.
In some embodiments, the reaction pressure is 0.1 to 0.5mpa. In some embodiments, the reaction pressure is 0.2 to 0.5mpa. In some embodiments, the reaction pressure is 0.3 to 0.5mpa. In some embodiments, the reaction pressure is 0.4 to 0.5mpa. In some embodiments, the reaction pressure is 0.5 to 0.6mpa. In some embodiments, the reaction pressure is 0.5 to 0.7mpa. In some embodiments, the reaction pressure is 0.5 to 0.8mpa. In some embodiments, the reaction pressure is 0.5 to 0.9mpa. In some embodiments, the reaction pressure is 0.5 to 1.0mpa. In some embodiments, the reaction pressure is 0.5 to 1.1mpa. In some embodiments, the reaction pressure is 0.5 to 1.2mpa. In some embodiments, the reaction pressure is 0.5 to 1.3mpa. In some embodiments, the reaction pressure is 0.5 to 1.4mpa. In some embodiments, the reaction pressure is 0.5 to 1.5mpa. In some embodiments, the reaction pressure is 0.5 to 1.6mpa. In some embodiments, the reaction pressure is 0.5 to 1.7mpa. In some embodiments, the reaction pressure is 0.5 to 1.8mpa. In some embodiments, the reaction pressure is 0.5 to 1.9mpa. In some embodiments, the reaction pressure is 0.5 to 2mpa.
Specifically, the reaction pressure may be 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa, 2MPa, or any range therebetween.
Specifically, the contact time may be 2s, 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 95s, 100s, 110s, 120s, 130s, 140s, 150s, 160s, 170s, 180s, 190s, 200s or any range therebetween.
In some embodiments, the reaction temperature may be 250-300 ℃. In some embodiments, the reaction temperature may be 250-310 ℃. In some embodiments, the reaction temperature may be 250-320 ℃. In some embodiments, the reaction temperature may be 250-330 ℃. In some embodiments, the reaction temperature may be 250-340 ℃. In some embodiments, the reaction temperature may be 250-350 ℃. In some embodiments, the reaction temperature may be 250-360 ℃. In some embodiments, the reaction temperature may be 250-370 ℃. In some embodiments, the reaction temperature may be 250-380 ℃. In some embodiments, the reaction temperature may be 250-390 ℃. Further, the reaction temperature may be 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, or any range therebetween.
In particular, the hydrogen fluoride and CCl m F n CH 2 CCl x F y Molar ratio (5 to 20): 1, preferably (7 to 15): 1. in some embodiments, the hydrogen fluoride and CCl m F n CH 2 CCl x F y The molar ratio of (1) to (16): 1. in some embodiments, the hydrogen fluoride and CCl m F n CH 2 CCl x F y The molar ratio of (1) to (17): 1. in some embodiments, the hydrogen fluoride and CCl m F n CH 2 CCl x F y The molar ratio of (1) to (18): 1. in some embodiments, the hydrogen fluoride and CCl m F n CH 2 CCl x F y The molar ratio of (1) to (19): 1. in some embodiments, the hydrogen fluoride and CCl m F n CH 2 CCl x F y The molar ratio of (7-20): 1.
in particular, the hydrogen fluoride and CCl m F n CH 2 CCl x F y The molar ratio of (3) may be 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1 or 20:1.
In the present application, the third step includes step 3.1, step 3.2, step 3.3, step 3.4, and step 3.5.
Step 3.1: 1-chloro-1, 3-tetrafluoropropene and hydrogen are introduced into a third reactor filled with a hydrogenation catalyst for reaction. Step 3.2: the product stream obtained in the step 3.1 enters a fifth distillation tower for separation, the tower top components are hydrogen chloride and hydrogen, the tower kettle component is E-1, 3-tetrafluoropropene, Z-1, 3-tetrafluoropropene 1, 3-tetrafluoropropane and 1-chloro-1, 3-tetrafluoropropene, the tower top component enters a sixth distillation tower for continuous separation, and the tower bottom component enters a seventh distillation tower for continuous separation; step 3.3: the tower top component of the sixth distillation tower obtained in the step 3.2 is hydrogen, the tower bottom component is hydrogen chloride, the hydrogen is circulated to the third reactor to continue the reaction, and the hydrogen chloride is extracted from the system; step 3.4: the seventh distillation column obtained in the step 3.3 has the tower top components of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene, the tower bottom components are 1-chloro-1, 3-tetrafluoropropene and 1, 3-tetrafluoropropane, the tower bottom components enter an eighth distillation tower for separation, and the tower top components enter a ninth distillation tower for separation; step 3.5: the tower top component of the eighth distillation tower obtained in the step 3.4 is 1-chloro-1, 3-tetrafluoropropene, the tower bottom component is 1, 3-tetrafluoropropane, the tower top component is circulated to a third reactor for continuous reaction, the tower bottom component is subjected to operations such as acid removal, rectification and the like to obtain a byproduct 1, 3-tetrafluoropropane, the system is extracted, the tower top component of the ninth distillation tower obtained in the step 3.4 is E-1, 3-tetrafluoropropene, the tower bottom component is Z-1, 3-tetrafluoropropene, the tower top component and the tower bottom component are used as crude products to obtain target products E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene after operations such as acid removal, rectification and the like.
The specific reaction can be as follows:
specifically, the 1-chloro-1, 3-tetrafluoropropene and hydrogen react in the presence of a hydrogenation catalyst, the reaction pressure is 0.1-2.0 MPa, the contact time is 2-200 seconds, the reaction temperature is 150-350 ℃, preferably, the reaction pressure is 0.1-0.5 MPa, the contact time is 10-60 seconds, and the reaction temperature is 200-300 ℃.
Specifically, the reaction pressure may be 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa or 2MPa.
Specifically, the contact time may be 2s, 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 110s, 120s, 130s, 140s, 150s, 160s, 170s, 180s, 190s, 200s or any value or range therebetween.
Specifically, the molar ratio of the hydrogen to the 1-chloro-1, 3-tetrafluoropropene is (2-20): 1, preferably (2 to 10): 1, for example, may be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, or 20:1.
Specifically, the hydrogenation catalyst comprises palladium element, bismuth element and porous metal fluoride, wherein in the hydrogenation catalyst, the mass percentage of the palladium element is 0.1% -2.0%, the mass percentage of the bismuth element is 0.5% -5.0%, and the mass percentage of the porous metal fluoride is 97.0% -99.4%.
In the hydrogenation catalyst, the mass percentage of the palladium element may be, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0% or any value or any range thereof.
In the hydrogenation catalyst, the mass percentage of the bismuth element may be, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5% or any value or any range therein.
In the hydrogenation catalyst, the mass percentage of the porous metal fluoride may be, for example, 97.0%, 97.1%, 97.2%, 97.3%, 97.4%, 97.5%, 97.6%, 97.7%, 97.8%, 97.9%, 98%, 98.1%, 98.2%, 98.3%, 98.4%, 98.5%, 98.6%, 98.7%, 98.8%, 98.9%, 99%, 99.1%, 99.2%, 99.3%, 99.4% or any number or any range therein.
In the present application, the hydrogenation catalyst is obtained by the following preparation method:
Step a: dissolving soluble salts of palladium and bismuth in water to prepare an impregnating solution; step b: immersing porous metal fluoride in the immersion liquid at room temperature for 3-24 hours, and then filtering to obtain a catalyst precursor; step c: drying the catalyst precursor at 120-200 ℃ for 6-15 hours; step d: roasting the dried catalyst precursor at the temperature of 200-350 ℃ for 6-15 hours; step e: activating the calcined catalyst precursor, namely, at the temperature of 150-300 ℃, the mass ratio of substances is (1-10): 1, activating for 6-24 hours in the mixed gas of nitrogen and hydrogen to prepare the hydrogenation catalyst.
In the step a, the soluble salt of palladium is at least one or more than two of palladium nitrate, palladium acetate or palladium chloride.
The soluble salt of bismuth is at least one or more than two of bismuth nitrate, bismuth acetate or bismuth chloride.
In the step b, the porous metal fluoride is at least one or more of aluminum fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, chromium fluoride, iron fluoride and zinc fluoride.
In step c, the drying temperature may be 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, or any value or any range therein. The drying time may be 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, 15h or any value or any range therein.
In the step d, the firing temperature may be 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃ or any value or any range thereof. The firing time may be 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, 15h, or any value or any range therein.
In step e, the activation temperature may be 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, or any value or any range therein.
In step e, the activation time may be 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, 15h, 15.5h, 16h, 16.5h, 17h, 17.5h, 18h, 18.5h, 19h, 19.5h, 20h, 20.5h, 21h, 21.5h, 22h, 22.5h, 23h, 23.h, 24h, or any value or range therein.
In the mixed gas, the mass ratio of the nitrogen to the hydrogen is 1: 1. 2: 1. 3: 1. 4: 1. 5: 1. 6: 1. 7: 1. 8: 1. 9:1 or 10:1.
in one embodiment, the process for the preparation of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene of the present application comprises the steps of: reacting 1-chloro-1-fluoroethylene with halogenated alkane in the presence of initiator to produce CCl m F n CH 2 CCl x F y Wherein 3.gtoreq.m.gtoreq.1, 2.gtoreq.n.gtoreq.0, and m+n=3, 3.gtoreq.x.gtoreq.1, 2.gtoreq.y.gtoreq.0, and x+y=3; the CCl is m F n CH 2 CCl x F y Reacting with hydrogen fluoride in the presence of a fluorination catalyst to produce 1-chloro-1, 3-tetrafluoropropene; the 1-chloro-1, 3-tetrafluoropropene and hydrogen exist in the presence of a hydrogenation catalyst in this case E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene are formed.
In one embodiment, the process for the preparation of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene of the present application comprises the steps of: reacting 1-chloro-1-fluoroethylene with one or more halogenated alkanes selected from carbon tetrachloride, trichloro-monofluoromethane and dichloro-difluoromethane in the presence of initiator to produce CCl m F n CH 2 CCl x F y Wherein 3.gtoreq.m.gtoreq.1, 2.gtoreq.n.gtoreq.0, and m+n=3, 3.gtoreq.x.gtoreq.1, 2.gtoreq.y.gtoreq.0, and x+y=3; the CCl is m F n CH 2 CCl x F y Reacting with hydrogen fluoride in the presence of a fluorination catalyst to produce 1-chloro-1, 3-tetrafluoropropene; the 1-chloro-1, 3-tetrafluoropropene and hydrogen exist in the presence of a hydrogenation catalyst in this case E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene are formed.
In some embodiments, the invention is described in further detail with reference to fig. 1. But not limiting the invention. Fresh C1 perhalogenated hydrocarbon, C2 halogenated olefin and auxiliary agent (any one of N, N-dimethylformamide and N, N-dimethylacetamide) are reacted through a pipeline 14 together with C1 perhalogenated hydrocarbon, C2 halogenated olefin and auxiliary agent mixture which are recycled through a pipeline 15 and enter a first reactor 1 filled with an initiator through a pipeline 16, the product flows through a pipeline 17 and enters a first distillation column 2 for separation, the tower top component is C1 perhalogenated hydrocarbon, C2 halogenated olefin and auxiliary agent mixture, and the tower bottom component is CCl m F n CH 2 CCl x F y The tower top component is recycled to the first reactor through the pipelines 15 and 16 to continue the reaction, and the tower bottom component enters the second reactor 3 through the pipeline 18 to react; fresh hydrogen fluoride is in line 19 with CCl in line 18 m F n CH 2 CCl x F y With hydrogen fluoride recycled via line 21 and CCl recycled via line 20 m F n CH 2 CCl x F y Together through line 22 into a second reactor 3 packed with fluorination catalyst, and the reaction product flows through line 23 into a second distillation column 4 for separation; the bottoms components of the second distillation column 4 are 1-chloro-1, 3-tetrafluoropropene, 1, 3-pentafluoropropene, low-fluorination-level pentafluoropropene, and unreacted hydrogen fluoride and CCl m F n CH 2 CCl x F y Wherein, the method comprises the steps of, wherein, the low-fluorinated pentahalopropene is selected from the group consisting of 1, 1-dichloro-3, 3-trifluoropropene, 1, 3-trichloro-3, 3-difluoropropene, 1, 3-tetrachloro-3-fluoropropene 1, 3-dichloro-1, 3-trifluoropropene, 1, 3-trichloro-1, 3-difluoropropene, 3-chloro-1, 3-tetrafluoropropene, 1, 3-pentachloropropene, the tower top component is hydrogen chloride, and the hydrogen chloride is extracted from the system through a pipeline 24; the bottoms fraction from the second distillation column 4 is fed via line 25 to phase separator 5 for further processingSeparating, wherein the upper layer of the phase separator is hydrogen fluoride, and the lower layer is liquid phase of 1-chloro-1, 3-tetrafluoropropene, 1, 3-pentafluoropropene, low-fluorination degree pentahalopropene and CCl m F n CH 2 CCl x F y The upper layer hydrogen fluoride is recycled to the second reactor 3 via lines 21 and 22 for further reaction; the lower layer composition of the phase separator 5 enters a third distillation column 6 through a pipeline 26 for continuous separation, the tower top composition is 1-chloro-1, 3-tetrafluoropropene and 1, 3-pentafluoropropene, and the tower bottom composition is CCl m F n CH 2 CCl x F y And low-fluorination pentahalopropene, the tower top component enters the fourth distillation tower 7 for separation through a pipeline 27, and the tower bottom component is recycled to the second reactor 3 for continuous reaction through pipelines 20 and 22; the tower top component of the fourth distillation tower 7 is 1, 3-pentafluoropropene (boiling point-21 ℃/760 mmHg), the tower bottom component is 1-chloro-1, 3-tetrafluoropropene (boiling point 17-23.5 ℃), the tower top component is withdrawn from the system through a pipeline 28, and the tower bottom component enters a third reactor 8 for reaction through pipelines 29 and 32; fresh hydrogen is passed via line 30 to a third reactor 8 packed with hydrogenation catalyst via line 32 together with 1-chloro-1, 3-tetrafluoropropene via line 29 and a mixture of hydrogen and 1-chloro-1, 3-tetrafluoropropene recycled via line 31, the product stream passing via line 33 to a fifth distillation column 9 for separation; the top components of the fifth distillation column 9 are hydrogen chloride and hydrogen, the tower kettle component is E-1, 3-tetrafluoropropene, Z-1, 3-tetrafluoropropene 1, 3-tetrafluoropropane and 1-chloro-1, 3-tetrafluoropropene, the tower top component enters the sixth distillation tower 10 through a pipeline 34 for continuous separation, and the tower bottom component enters the seventh distillation tower 11 through a pipeline 35 for continuous separation; the top component of the sixth distillation column 10 is hydrogen, the bottom component of the column is hydrogen chloride, the hydrogen is circulated to the third reactor 8 through the pipelines 36, 31 and 32 to continue the reaction, and the hydrogen chloride is extracted from the system through the pipeline 37; the top components of the seventh distillation column 11 are E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene, the tower kettle components are 1-chloro-1, 3-tetrafluoropropene and 1, 3-tetrafluoropropane, the tower bottom component enters the eighth distillation tower 13 for separation through a pipeline 39, the tower top component enters the ninth distillation tower 12 for separation through a pipeline 38, and the tower top component of the ninth distillation tower 12 is E-1, 3-tetrafluoropropene Is divided into Z-1, 3-tetrafluoropropene, and after the operations of acid removal, rectification and the like are carried out on the tower top component and the tower bottom component serving as crude products, the target products E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene are obtained by respectively extracting through a pipeline 40 and a pipeline 41; the tower top component of the eighth distillation tower 13 is 1-chloro-1, 3-tetrafluoropropene, the tower bottom component is 1, 3-tetrafluoropropane, the tower top component is circulated to the third reactor 8 through the pipelines 42, 31 and 32 for continuous reaction, the tower kettle component enters the operation steps of acid removal, rectification and the like through a pipeline 43 to obtain high-purity 1, 3-tetrafluoropropane for selling; the top component of the ninth distillation column 12 is E-1, 3-tetrafluoropropene, the bottom component of the column is Z-1, 3-tetrafluoropropene, the top component enters the operation flows of acid removal, rectification and the like through a pipeline 42, the target product E-1, 3-tetrafluoropropene is obtained, and the tower kettle component enters the operation flows of acid removal, rectification and the like through a pipeline 43 to obtain the target product Z-1, 3-tetrafluoropropene.
Gas chromatography method: (1) analytical instrument: shimadzu GC-2010, column DB-VRX capillary column (i.d. 0.32 mm; length 30 m; J & Mo Scientific Inc.); (2) analysis conditions: the temperature of the detector is 280 ℃, the temperature of the vaporization chamber is 280 ℃, the initial temperature of the column is 40 ℃, the temperature is kept for 8 minutes, the temperature is increased to 230 ℃ at 15 ℃/min, and the temperature is kept for 20 minutes.
The reactor types of the first reactor, the second reactor, the third reactor in this application are not critical, and a tubular reactor, a fluidized bed reactor, etc. may be used. Alternatively, adiabatic reactors or isothermal reactors may be used.
According to the preparation method, a blending method is adopted to prepare the fluorination catalyst, a trivalent chromium compound and tungstate are mixed according to a certain proportion to prepare a catalyst precursor, the precursor is subjected to high-temperature roasting and then enters an activation stage of mixed gas consisting of nitrogen and nitrogen trifluoride, hexavalent tungsten reacts with active fluorine generated by pyrolysis of the nitrogen trifluoride to obtain oxygen and tungsten hexafluoride with a low boiling point, most of the tungsten hexafluoride breaks away from a catalyst structure in a gas mode, so that a pore channel can be provided for the catalyst, the specific surface area and the pore volume of the catalyst are increased, the activity of the catalyst is improved, and tungsten elements which are not converted into tungsten hexafluoride are mainly left in the catalyst in the form of oxides or small amounts of fluorides, so that carbon deposition of the catalyst at a high temperature can be effectively inhibited. In addition, for ammonium salts of tungstic acid, including ammonium tungstate, ammonium paratungstate or ammonium metatungstate, when the precursor enters high-temperature roasting, the precursor is heated and decomposed, a large amount of volatile matters are generated, mainly ammonia gas is generated, so that the catalyst has the characteristics of high specific surface area, large pore volume and the like, and the catalytic activity of the catalyst is improved; for the metal salts of tungstic acid, including zinc tungstate, nickel tungstate, magnesium tungstate and aluminum tungstate, other introduced metal elements besides tungsten can play the role of an auxiliary agent; for silicotungstic acid, the precursor enters an activation stage of a mixed gas composed of nitrogen and nitrogen trifluoride after high-temperature roasting, at 300-500 ℃, tetravalent silicon can react with active fluorine generated by pyrolysis of the nitrogen trifluoride to obtain silicon tetrafluoride, and most of the silicon tetrafluoride is separated from a catalyst structure in a gas mode, so that a pore channel can be provided for the catalyst, the specific surface area and the pore volume of the catalyst are increased, the activity of the catalyst is improved, and silicon elements which are not converted into the silicon tetrafluoride are mainly remained in the catalyst in the form of oxides or small amount of fluorides, and carbon deposition of the catalyst at high temperature can be effectively inhibited. In addition, chromium element in the catalyst precursor is subjected to high-temperature roasting and then enters an activation stage of mixed gas consisting of nitrogen and nitrogen trifluoride, trivalent chromium can react with active fluorine generated by pyrolysis of the nitrogen trifluoride to obtain chromium trifluoride or/and a mixture of chromium tetrafluoride and/or chromium pentafluoride, oxygen and tungsten hexafluoride with a low boiling point, and the catalytic activity of high-valence chromium ions with the valence of 4 and 5 in the fluorine-chlorine exchange reaction is proved to be higher than that of the trivalent chromium ions. The whole effect is seen, the fluorination catalyst prepared by the scheme has high use temperature, high catalytic activity and long service life.
The preparation method is characterized in that raw materials 1, 1-difluoroethylene, 1-dichloroethylene or 1-chloro-1-fluoroethylene are easy to obtain, wherein the 1, 1-difluoroethylene or 1-chloro-1-fluoroethylene can also be synthesized by gas phase catalytic fluorine-chlorine exchange reaction of the 1, 1-dichloroethylene and hydrogen fluoride; the method can realize zero-pollution production of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene, and the reaction of each step can lead the material to completely react through an independent circulating system, thereby realizing full utilization of the material, greatly reducing pollution and realizing zero pollution of production.
According to the preparation method, the target product is prepared under specific conditions (specific temperature, pressure, contact time and specific raw material ratio), the selectivity of the target product and the raw material conversion rate are high, the energy consumption is low, and the production cost is low. When the reaction temperature is too high, unnecessary byproducts are easy to generate, the service lives of the initiator and production equipment are shortened, and when the reaction temperature is too low, the conversion rate of raw materials is low, so that the production efficiency is greatly reduced. When the reaction pressure is higher, not only the energy consumption is high, but also the requirement on production equipment is higher, and the production cost is greatly increased. When the contact time is too short, the conversion rate of the raw materials is lower, the production efficiency is greatly reduced, and when the contact time is too long, the conversion rate and the selectivity of the raw materials are both higher, but the production efficiency is also reduced due to the too long time, and the production efficiency of enterprises is greatly influenced. When the content of halogenated hydrocarbon in the raw material is too high, although the selectivity and the conversion rate of the raw material are high, the production cost is increased, the enterprise development is not facilitated, and when the content of halogenated hydrocarbon in the raw material is too low, the conversion rate of the raw material is low, and the production efficiency is greatly reduced.
Examples
The experimental methods used in the following examples are conventional methods, if no special requirements are imposed.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
Preparation of an initiator: the mass ratio of the iron element to the carrier is 20:80, impregnating a carrier with a soluble salt of iron, filtering to obtain an initiator precursor, drying the initiator precursor at 160 ℃ for 10 hours, roasting at 400 ℃ for 10 hours, and using a mass ratio of 5:1, activating the mixed gas of nitrogen and hydrogen for 15 hours, then using a solvent selected from the group consisting of 1, 3-pentachloropropane, 1, 3-tetrachloropropane activating any one chlorinating reagent of 1, 3-tetrachloro-2-fluoropropane or 1, 3-tetrachloro-4, 4-trifluorobutane at 250 ℃ for 15 hours, finally, the initiator is obtained by activating the mixture for 15 hours at 200 ℃ by using N, N-dimethylformamide. Wherein the carrier is active carbon.
Example 2 differs from example 1 only in that the mass ratio composition of elemental iron and carrier is 5:95.
example 3 differs from example 1 only in that the mass ratio composition of elemental iron to carrier is 10:90.
Example 4 differs from example 1 only in that the mass ratio composition of elemental iron to carrier is 30:70.
comparative example 1
Preparation of an initiator: the mass ratio of the iron element to the carrier is 20 percent: 80%, dipping soluble salt of iron on a carrier, filtering to obtain an initiator precursor, and drying the initiator precursor at 160 ℃ for 10 hours under the protection of nitrogen; roasting for 10 hours at 400 ℃ under the protection of nitrogen to obtain the initiator. Wherein the carrier is active carbon.
The raw materials and conditions for preparing the initiator in examples 1 to 4 and comparative example 1 are listed in the following table 1:
TABLE 1
Example 5
Preparation of the fluorination catalyst: dissolving chromium nitrate in water, adding precipitator ammonia water at 60 ℃, controlling the pH value of the solution to be within the range of 7.5-8.5, fully precipitating the solution under the stirring condition, filtering the formed slurry, washing the slurry to be neutral by deionized water, and then drying the slurry at 150 ℃ for 12 hours to obtain chromium hydroxide. The mass ratio of the obtained chromium hydroxide to tungstate is 80:20, and then drying the catalyst precursor for 10 hours at 150 ℃, and roasting for 10 hours at 400 ℃, wherein the mass ratio of substances used at 350 ℃ is 5:1 and nitrogen trifluoride for 18 hours. Wherein the tungstate is zinc tungstate.
Example 6 differs from example 5 only in that the mass ratio of chromium hydroxide to tungstate is 70:30.
example 7 differs from example 5 only in that the mass ratio of chromium hydroxide to tungstate is 90:10.
example 8 differs from example 5 only in that the mass ratio of chromium hydroxide to tungstate is 99:1.
comparative example 2
Preparation of the fluorination catalyst: dissolving chromium nitrate in water, adding precipitator ammonia water at 60 ℃, controlling the pH value of the solution to be within the range of 7.5-8.5, fully precipitating the solution under the stirring condition, filtering the formed slurry, washing the slurry to be neutral by deionized water, and then drying the slurry at 150 ℃ for 12 hours to obtain chromium hydroxide. The obtained chromium hydroxide is pressed and molded to obtain a catalyst precursor, and then the catalyst precursor is dried for 10 hours at 150 ℃, and is roasted for 10 hours at 400 ℃, and the mass ratio of substances used at 350 ℃ is 5:1 and nitrogen trifluoride for 18 hours.
The raw materials and proportions of the fluorination catalysts prepared in examples 5 to 8 and comparative example 2 are shown in the following table 2:
TABLE 2
Experimental example
Experimental example 1
A tubular reactor of Inconel having an inner diameter of 1/2 inch and a length of 30cm was charged with 10 ml of an initiator prepared from a precursor composed of 20% of Fe element and 80% of activated carbon. The first reactor is heated to 100 ℃, 1-chloro-1-fluoroethylene (HCFO-1131 a), carbon tetrachloride and N, N-Dimethylacetamide (DMAC) are introduced to react, and the molar ratio of the HCFO-1131a to the carbon tetrachloride to the DMAC is controlled to be 2:1:0.03, the contact time is 40 seconds, the reaction pressure is 0.1MPa, after the reaction is carried out for 20 hours, the reaction product is washed by water and separated to obtain organic matters, and after the organic matters are dried and dehydrated, the composition of the organic matters is analyzed by gas chromatography.
Experimental example 2 differs from Experimental example 1 only in that the reaction temperature is 150 ℃.
Experimental example 3 differs from Experimental example 1 only in that the reaction temperature is 200 ℃.
Experimental example 4 differs from Experimental example 1 only in that the reaction temperature is 250 ℃.
Experimental example 5 differs from experimental example 2 only in that the contact time was 1 second.
Experimental example 6 differs from Experimental example 2 only in that the contact time is 10 seconds.
Experimental example 7 differs from Experimental example 2 only in that the contact time is 60 seconds.
Experimental example 8 differs from experimental example 2 only in that the contact time was 100 seconds.
Experimental example 9 differs from Experimental example 2 only in that the molar ratio of HCFO-1131a, carbon tetrachloride and N, N-dimethylacetamide is 1:1:0.01.
experimental example 10 differs from Experimental example 2 only in that the molar ratio of HCFO-1131a, carbon tetrachloride and N, N-dimethylacetamide is 1.5:1:0.02.
experimental example 11 differs from Experimental example 2 only in that the molar ratio of HCFO-1131a, carbon tetrachloride and N, N-dimethylacetamide is 2.5:1:0.04.
experimental example 12 differs from Experimental example 2 only in that the molar ratio of HCFO-1131a, carbon tetrachloride and N, N-dimethylacetamide is 4:1:0.05.
experimental example 13 differs from Experimental example 2 only in that the reaction pressure is 0.5MPa.
Experimental example 14 differs from Experimental example 2 only in that the reaction pressure is 1MPa.
Experimental example 15 differs from Experimental example 2 only in that the reaction pressure is 1.5MPa.
Experimental example 16 differs from Experimental example 2 only in that HCFO-1131a is replaced with an equal amount of 1, 1-difluoroethylene (HFO-1132 a).
Experimental example 17 differs from Experimental example 2 only in that HCFO-1131a is replaced by an equal amount of 1, 1-dichloroethylene (HCO-1130 a).
Experimental example 18 differs from Experimental example 2 only in that carbon tetrachloride is replaced by trichlorofluoromethane (CFC-11) in an equivalent amount.
Experimental example 19 differs from Experimental example 2 only in that carbon tetrachloride is replaced by an equivalent amount of difluorodichloromethane (CFC-12).
Experimental example 20 differs from Experimental example 2 only in that HCFO-1131a is replaced with HCO-1130a in an equal amount of substance, and carbon tetrachloride is replaced with CFC-11 in an equal amount of substance.
Experimental example 21 differs from Experimental example 2 only in that HCFO-1131a is replaced with HCO-1130a in an equal amount of substance, and carbon tetrachloride is replaced with CFC-12 in an equal amount of substance.
Experimental example 22 differs from Experimental example 2 only in that HCFO-1131a was replaced with HFO-1132a in an equivalent amount and carbon tetrachloride was replaced with CFC-11 in an equivalent amount.
Experimental example 23 differs from Experimental example 2 only in that HCFO-1131a is replaced with HFO-1132a in an equivalent amount and carbon tetrachloride is replaced with CFC-12 in an equivalent amount.
Experiment example 24 differs from experiment example 2 only in that the initiator in this experiment example was the initiator prepared in example 2.
The experimental example 27 differs from the experimental example 2 only in that the initiator in this experimental example is the initiator prepared in comparative example 1.
The reaction conditions and experimental analysis results of the above experimental examples 1 to 27 are shown in table 3:
TABLE 3 Table 3
Note that: (1) In experimental examples 1-15, halogenated olefin is HCFO-1131a, halogenated alkane is carbon tetrachloride, and product CCl m F n CH 2 CCl x F y Is CFCl 2 CH 2 CCl 3 ；
(2) In Experimental example 16, the halogenated olefin was HFO-1132a, the halogenated alkane was carbon tetrachloride, and the product CCl m F n CH 2 CCl x F y Is CF (CF) 2 ClCH 2 CCl 3 ；
(3) In Experimental example 17, the haloalkene was HCO-1130a, the haloalkane was carbon tetrachloride, and the product CCl m F n CH 2 CCl x F y For CCl 3 CH 2 CCl 3 ；
(4) In example 18, the haloolefin was HCFO-1131a, the haloalkane was CFC-11, and the product CCl m F n CH 2 CCl x F y Is CFCl 2 CH 2 CCl 2 F；
(5) In example 19, the haloolefin was HCFO-1131a, the haloalkane was CFC-12, and the product CCl m F n CH 2 CCl x F y Is CFCl 2 CH 2 CClF 2 ；
(6) In Experimental example 20, the haloalkene was HCO-1130a, the haloalkane was CFC-11, and the product CCl m F n CH 2 CCl x F y For CCl 3 CH 2 CCl 2 F；
(7) In Experimental example 21, the haloalkene was HCO-1130a, the haloalkane was CFC-12, and the product CCl m F n CH 2 CCl x F y For CCl 3 CH 2 CClF 2 ；
(8) In example 22, the haloolefin was HFO-1132a, the haloalkane was CFC-11, and the product CCl m F n CH 2 CCl x F y Is CF (CF) 2 ClCH 2 CCl 2 F；
(9) In example 23, the haloalkene was HFO-1132a, the haloalkane was CFC-12, and the product CCl m F n CH 2 CCl x F y Is CF (CF) 2 ClCH 2 CClF 2 。
The small knot: as is clear from Table 3, the preparation method of step one of the present application is carried out under specific conditions (specific temperature, pressure, contact time and temperatureSpecific feed ratio) CCl formed from said haloalkene and haloalkane m F n CH 2 CCl x F y The selectivity and the conversion rate of raw materials are high, the energy consumption is low, and the production cost is low. When the reaction temperature is too high, unnecessary byproducts are easy to generate, the service lives of the initiator and production equipment are shortened, and when the reaction temperature is too low, the conversion rate of raw materials is low, so that the production efficiency is greatly reduced. When the reaction pressure is higher, not only the energy consumption is high, but also the requirement on production equipment is higher, and the production cost is greatly increased. When the contact time is too short, the conversion rate of the raw materials is lower, the production efficiency is greatly reduced, and when the contact time is too long, the conversion rate and the selectivity of the raw materials are both higher, but the production efficiency is also reduced due to the too long time, and the production efficiency of enterprises is greatly influenced. When the content of halogenated hydrocarbon in the raw material is too high, although the selectivity and the conversion rate of the raw material are high, the production cost is increased, the enterprise development is not facilitated, and when the content of halogenated hydrocarbon in the raw material is too low, the conversion rate of the raw material is low, and the production efficiency is greatly reduced.
Experimental example 28
A tubular reactor made of Inconel having an inner diameter of 1/2 inch and a length of 30cm was charged with 10 ml of 80% Cr (OH) 3 And 20% cobalt tungstate precursor. The temperature of the second reactor is raised to 200 ℃, anhydrous hydrogen fluoride and 1, 3-pentachloro-3-fluoropropane (HCFC-331 fa) are introduced for reaction, and the molar ratio of the hydrogen fluoride to the HCFC-331fa is controlled to be 10:1, the contact time is 30 seconds, the reaction pressure is 0.1MPa, after the reaction is carried out for 20 hours, the reaction product is washed with water and alkali, organic matters are obtained by separation, and after drying and water removal, the composition of the organic matters is analyzed by gas chromatography.
Experimental example 29 differs from experimental example 28 only in that the reaction temperature was 250 ℃.
Experimental example 30 differs from experimental example 28 only in that the reaction temperature was 300 ℃.
Experimental example 31 differs from experimental example 28 only in that the reaction temperature is 350 ℃.
Experimental example 32 differs from experimental example 28 only in that the reaction temperature is 400 ℃.
Experimental example 33 differs from experimental example 30 only in that the contact time was 2 seconds.
Experimental example 34 differs from experimental example 30 only in that the contact time was 10 seconds.
Experimental example 35 differs from experimental example 30 only in that the contact time was 60 seconds.
Experimental example 36 differs from experimental example 30 only in that the contact time was 100 seconds.
Experimental example 37 differs from experimental example 30 only in that the contact time is 200 seconds.
Experimental example 38 differs from experimental example 30 only in that the molar ratio of hydrogen fluoride to HCFC-331fa is 5:1.
experimental example 39 differs from experimental example 30 only in that the molar ratio of hydrogen fluoride to HCFC-331fa is 7:1.
experimental example 40 differs from experimental example 30 only in that the molar ratio of hydrogen fluoride to HCFC-331fa is 15:1.
experimental example 41 differs from experimental example 30 only in that the molar ratio of hydrogen fluoride to HCFC-331fa is 20:1.
experimental example 42 differs from experimental example 30 only in that the reaction pressure was 0.5MPa.
Experimental example 43 differs from experimental example 30 only in that the reaction pressure was 1MPa.
Experimental example 44 differs from experimental example 30 only in that the reaction pressure is 1.5MPa.
Experimental example 45 differs from experimental example 30 only in that the reaction pressure was 2.0MPa.
Experimental example 46 differs from experimental example 30 only in that HCFC-331fa was replaced with an equivalent amount of 1, 3-tetrachloro-1, 3-difluorobutane (HCFC-332 fa).
Experimental example 47 differs from experimental example 30 only in that HCFC-331fa was replaced with an equivalent amount of 1, 3-trichloro-1, 3-trifluorobutane (HCFC-333 fa).
Experimental example 48 differs from Experimental example 30 only in that HCFC-331fa is replaced with an equivalent amount of 1, 3-hexachlorobutane (HCC-330 fa).
Experimental example 49 differs from experimental example 30 only in that HCFC-331fa was replaced with an equivalent amount of 1, 3-tetrachloro-3, 3-difluorobutane (HCFC-332 fb).
Experimental example 50 differs from experimental example 30 only in that HCFC-331fa was replaced with an equivalent amount of 1, 3-dichloro-1, 3-tetrafluorobutane (HCFC-334 fa).
Experimental example 51 differs from experimental example 30 only in that the fluorination catalyst in this experimental example is the fluorination catalyst prepared in example 6.
Experimental example 52 differs from experimental example 30 only in that the fluorination catalyst in this experimental example is the fluorination catalyst prepared in example 7.
Experimental example 53 differs from experimental example 30 only in that the fluorination catalyst in this experimental example is the fluorination catalyst prepared in example 8.
Experimental example 54 differs from experimental example 30 only in that the fluorination catalyst in this experimental example is the fluorination catalyst prepared in comparative example 2.
The reaction conditions and experimental analysis results of the above experimental examples 28 to 54 are shown in table 4:
TABLE 4 Table 4
Note that: (1) HCFO-1224zb is an abbreviation for 1-chloro-1, 3-tetrafluoropropene;
(2) HFO-1225zc is an abbreviation for 1, 3-pentafluoropropene;
(3) The low-fluorinated pentahalopropene is selected from the group consisting of 1, 1-dichloro-3, 3-trifluoropropene, 1, 3-trichloro-3, 3-difluoropropene, 1, 3-tetrachloro-3-fluoropropene 1, 3-dichloro-1, 3-trifluoropropene, 1, 3-trichloro-1, 3-difluoropropene any one or a plurality of 3-chloro-1, 3-tetrafluoropropene and 1, 3-pentachloropropene;
(4) CCl in Experimental examples 21-38 m F n CH 2 CCl x F y HCFC-331fa;
(5) CCl in Experimental example 39 m F n CH 2 CCl x F y HCFC-332fa;
(6) CCl in Experimental example 40 m F n CH 2 CCl x F y HCFC-333fa;
(7) CCl in Experimental example 41 m F n CH 2 CCl x F y HCC-330fa;
(8) CCl in Experimental example 42 m F n CH 2 CCl x F y Is HCFC-332fb;
(9) CCl in Experimental example 43 m F n CH 2 CCl x F y Is HCFC-334fa.
The small knot: as is clear from Table 4, the preparation method of the second step of the present application is CCl under specific conditions (specific temperature, pressure, contact time and specific raw material ratio) m F n CH 2 CCl x F y The selectivity and the conversion rate of the 1-chloro-1, 3-tetrafluoropropene generated by hydrogen fluoride are high, the energy consumption is low, the production cost is low, and the by-products can be recycled to continuously generate the 1-chloro-1, 3-tetrafluoropropene.
Experimental example 55
A tubular reactor of Inconel having an inner diameter of 1/2 inch and a length of 30cm was charged with 10 ml of a catalyst composed of 1% Pd, 2.5% Bi and 96.5% AlF 3 A hydrogenation catalyst. The temperature of the third reactor is raised to 150 ℃, and hydrogen and 1-chloro-1, 3-tetrafluoropropene (HCFO-1224 zb) are introduced to react, wherein the molar ratio of the hydrogen to the HCFO-1224zb is controlled to be 5:1, the contact time is 30 seconds, the reaction pressure is 0.1MPa, after the reaction is carried out for 20 hours, the reaction product is washed with water and alkali, organic matters are obtained by separation, and after drying and water removal, the composition of the organic matters is analyzed by gas chromatography.
Experimental example 56 differs from experimental example 55 only in that the reaction temperature is 200 ℃.
Experimental example 57 differs from experimental example 55 only in that the reaction temperature was 250 ℃.
Experimental example 58 differs from experimental example 55 only in that the reaction temperature was 300 ℃.
Experiment 59 differs from experiment 55 only in that the reaction temperature was 350 ℃.
Experimental example 60 differs from experimental example 57 only in that the molar ratio of hydrogen to HCFO-1224zb is 1:1.
experimental example 61 differs from experimental example 57 only in that the molar ratio of hydrogen to HCFO-1224zb is 2:1.
experiment 62 differs from experiment 57 only in that the molar ratio of hydrogen to HCFO-1224zb is 10:1.
experimental example 63 differs from experimental example 57 only in that the molar ratio of hydrogen to HCFO-1224zb is 20:1.
experimental example 64 differs from experimental example 57 only in that the contact time was 2 seconds.
Experimental example 65 differs from experimental example 57 only in that the contact time is 10 seconds.
Experiment 66 differs from experiment 57 only in that the contact time was 60 seconds.
Experimental example 67 differs from experimental example 57 only in that the contact time was 100 seconds.
Experiment 68 differs from experiment 57 only in that the contact time was 200 seconds.
Experimental example 69 differs from experimental example 57 only in that the reaction pressure was 0.5MPa.
Experimental example 70 differs from experimental example 57 only in that the reaction pressure is 1MPa.
Experimental example 71 differs from experimental example 57 only in that the reaction pressure was 1.5MPa.
Experimental example 72 differs from experimental example 57 only in that the reaction pressure was 2.0MPa.
The reaction conditions and experimental analysis results of the above experimental examples 55 to 72 are shown in table 5:
TABLE 5
Note that: (1) HFO-1234ze (E) is an abbreviation for E-1, 3-tetrafluoropropene;
(2) HFO-1234ze (Z) is an abbreviation for Z-1, 3-tetrafluoropropene;
(3) HFC-254fb is an abbreviation for 1, 3-tetrafluoropropane.
The small knot: as can be seen from Table 5, the preparation method in step three of the present application has higher selectivity of the final products E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene under specific conditions (specific temperature, pressure, contact time and specific raw material ratio), higher raw material conversion rate, low energy consumption and lower production cost.
Although described above in connection with the embodiments of the present application, the present application is not limited to the specific embodiments and fields of application described above, which are intended to be illustrative, instructive, and not limiting. Those skilled in the art, having the benefit of this disclosure, may make numerous forms, and equivalents thereof, without departing from the scope of the invention as defined by the claims.
Claims (17)
1. An initiator for the preparation of hydrochlorocarbons or hydrochlorofluorocarbons by means of a haloalkene and a haloalkane, wherein,
the initiator is obtained by passing an initiator precursor,
the initiator precursor consists of iron element and a carrier, wherein the mass ratio of the iron element to the carrier is (5% -30%) to (70% -95%);
wherein the carrier is selected from one or more than two of active carbon, molecular sieve, silicon dioxide, silicon carbide, graphite and graphene;
the initiator is prepared by the following method: according to the mass ratio of the iron element to the carrier, the soluble salt of the iron element is immersed on the carrier, the initiator precursor is obtained through filtration, and then the initiator precursor is dried, roasted and activated to obtain the initiator.
2. The initiator according to claim 1, wherein,
the activation comprises a first activation, a second activation and a third activation in sequence;
in the first activation, a mixed gas of nitrogen and hydrogen is used for activation for 6-24 hours at the temperature of 250-350 ℃, and the molar ratio of the nitrogen to the hydrogen is (1-10): 1, a step of; or alternatively
In the second activation, a chlorinating reagent is used for activating for 6-24 hours at 150-350 ℃, wherein the chlorinating agent is selected from the group consisting of 1, 3-pentachloropropane, 1, 3-tetrachloropropane one or more of 1, 3-tetrachloro-2-fluoropropane and 1, 3-tetrachloro-4, 4-trifluorobutane; or alternatively
In the third activation, an amide reagent is used for activating for 6-24 hours at 150-350 ℃, wherein the amide reagent is selected from one or more than two of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-dimethylbutyramide, N-diethylformamide, N-dipropylcarboxamide and N, N-dibutylformamide.
3. A fluorination catalyst for the production of hydrofluoroolefins by hydrochlorocarbons or hydrochlorofluorocarbons wherein,
the fluorination catalyst is obtained by fluorinating a catalyst precursor,
the fluoridation catalyst precursor consists of trivalent chromium compound and tungstate, wherein the mass ratio of the trivalent chromium compound to the tungstate is (70% -99%) to (1% -30%),
the catalyst is prepared by the following steps: uniformly mixing a trivalent chromium compound and tungstate according to a mass ratio, pressing and forming to obtain a fluorination catalyst precursor, and drying, roasting and activating the fluorination catalyst precursor to obtain the fluorination catalyst.
4. A fluorination catalyst according to claim 3, wherein,
the trivalent chromium compound is chromium hydroxide or chromium oxide,
the tungstate is one or more than two of zinc tungstate, nickel tungstate, iron tungstate, cobalt tungstate, magnesium tungstate, aluminum tungstate, silicotungstic acid, ammonium tungstate, ammonium paratungstate and ammonium metatungstate.
5. Use of an initiator according to claim 1 or 2, a fluorination catalyst according to claim 3 or 4 for the preparation of a hydrofluoroolefin by gas phase continuous reaction.
6. A process for the preparation of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene, comprising the steps of:
reacting a haloolefin with a haloalkane in the presence of an initiator to produce cci m F n CH 2 CCl x F y Wherein 3.gtoreq.m.gtoreq.1, 2.gtoreq.n.gtoreq.0, and m+n=3, 3.gtoreq.x.gtoreq.1, 2.gtoreq.y.gtoreq.0, and x+y=3;
the CCl is m F n CH 2 CCl x F y Reacting with hydrogen fluoride in the presence of a fluorination catalyst to produce 1-chloro-1, 3-tetrafluoropropene;
the 1-chloro-1, 3-tetrafluoropropene and hydrogen exist in the presence of a hydrogenation catalyst in this case E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene are formed.
7. The process according to claim 6, wherein the halogenated olefin is one or more selected from the group consisting of 1, 1-difluoroethylene, 1-dichloroethylene and 1-chloro-1-fluoroethylene.
8. The process according to claim 6, wherein the halogenated alkane is one or more selected from the group consisting of carbon tetrachloride, trichlorofluoromethane and dichlorodifluoromethane.
9. The production method according to claim 6, wherein the initiator is the initiator according to claim 1 or 2;
The fluorination catalyst is the fluorination catalyst of claim 3 or 4.
10. The preparation method according to claim 6, wherein the halogenated olefin and halogenated alkane are reacted in the presence of an auxiliary agent and an initiator, the reaction pressure is 0.1-1.5 mpa, and/or the contact time is 1-100 s, and/or the reaction temperature is 100-250 ℃.
11. The preparation method of claim 10, wherein the molar ratio of the halogenated olefin, the halogenated alkane and the auxiliary agent is (1-4): 1: (0.01 to 0.05).
12. The preparation method according to claim 10, wherein the auxiliary agent is N, N-dimethylformamide or N, N-dimethylacetamide.
13. The preparation method according to claim 6, wherein the CCl is m F n CH 2 CCl x F y Reacting with hydrogen fluoride in the presence of a fluorination catalyst, wherein the reaction pressure is 0.1-2.0 MPa, and/or the contact time is 2-200 s, and/or the reaction temperature is 200-400 ℃.
14. The production method according to claim 13, wherein the hydrogen fluoride and CCl are m F n CH 2 CCl x F y The molar ratio of (5-20): 1.
15. the production process according to claim 6, wherein the 1-chloro-1, 3-tetrafluoropropene is reacted with hydrogen in the presence of a hydrogenation catalyst at a reaction pressure of 0.1 to 2.0mpa and/or a contact time of 2 to 200 seconds and/or a reaction temperature of 150 to 350 ℃.
16. The production method according to claim 15, wherein the molar ratio of the hydrogen gas to the 1-chloro-1, 3-tetrafluoropropene is (2 to 20): 1.
17. the process according to claim 6, wherein the hydrogenation catalyst comprises palladium, bismuth and porous metal fluoride,
in the hydrogenation catalyst, the mass percentage of the palladium element is 0.1% -2.0%, the mass percentage of the bismuth element is 0.5% -5.0%, and the mass percentage of the porous metal fluoride is 97.0% -99.4%.
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