CN106902806B - High-activity molybdenum-based catalyst, preparation method and application - Google Patents
High-activity molybdenum-based catalyst, preparation method and application Download PDFInfo
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- CN106902806B CN106902806B CN201710208491.2A CN201710208491A CN106902806B CN 106902806 B CN106902806 B CN 106902806B CN 201710208491 A CN201710208491 A CN 201710208491A CN 106902806 B CN106902806 B CN 106902806B
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- molybdenum
- catalyst
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- based catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 254
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 103
- 239000011733 molybdenum Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 230000000694 effects Effects 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 204
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical group [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000004913 activation Effects 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 47
- 150000003839 salts Chemical class 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000011261 inert gas Substances 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 15
- 239000012018 catalyst precursor Substances 0.000 claims description 14
- ZSSVQAGPXAAOPV-UHFFFAOYSA-K molybdenum trichloride Chemical compound Cl[Mo](Cl)Cl ZSSVQAGPXAAOPV-UHFFFAOYSA-K 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052702 rhenium Inorganic materials 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- DBGPLCIFYUHWKA-UHFFFAOYSA-H hexachloromolybdenum Chemical compound Cl[Mo](Cl)(Cl)(Cl)(Cl)Cl DBGPLCIFYUHWKA-UHFFFAOYSA-H 0.000 claims description 6
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- OYMJNIHGVDEDFX-UHFFFAOYSA-J molybdenum tetrachloride Chemical compound Cl[Mo](Cl)(Cl)Cl OYMJNIHGVDEDFX-UHFFFAOYSA-J 0.000 claims description 4
- BQBYSLAFGRVJME-UHFFFAOYSA-L molybdenum(2+);dichloride Chemical compound Cl[Mo]Cl BQBYSLAFGRVJME-UHFFFAOYSA-L 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052716 thallium Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 159000000021 acetate salts Chemical class 0.000 claims description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 241000282326 Felis catus Species 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 66
- 230000003197 catalytic effect Effects 0.000 abstract description 56
- 229910052731 fluorine Inorganic materials 0.000 abstract description 55
- 239000011737 fluorine Substances 0.000 abstract description 53
- 238000000034 method Methods 0.000 abstract description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 24
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 12
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 abstract description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 82
- 150000002221 fluorine Chemical class 0.000 description 41
- 230000002194 synthesizing effect Effects 0.000 description 40
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- 239000011651 chromium Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 18
- 229910052804 chromium Inorganic materials 0.000 description 18
- 229910052759 nickel Inorganic materials 0.000 description 14
- 239000011701 zinc Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000001307 helium Substances 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 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 4
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 4
- OQISUJXQFPPARX-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Cl)=C OQISUJXQFPPARX-UHFFFAOYSA-N 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 4
- 206010028980 Neoplasm Diseases 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 150000001844 chromium Chemical class 0.000 description 4
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229910052754 neon Inorganic materials 0.000 description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 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 3
- -1 aluminum halide Chemical class 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 201000011510 cancer Diseases 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
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- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 3
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- CDOOAUSHHFGWSA-UPHRSURJSA-N (z)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C/C(F)(F)F CDOOAUSHHFGWSA-UPHRSURJSA-N 0.000 description 2
- FWAQVJAOVDYHAF-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethane Chemical compound FC(F)C(F)Cl FWAQVJAOVDYHAF-UHFFFAOYSA-N 0.000 description 2
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 2
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
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- 238000003682 fluorination reaction Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 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 2
- 229910052743 krypton Inorganic materials 0.000 description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
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- 241000282412 Homo Species 0.000 description 1
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- 208000012322 Raynaud phenomenon Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005796 dehydrofluorination reaction Methods 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- TZNXTUDMYCRCAP-UHFFFAOYSA-N hafnium(4+);tetranitrate Chemical compound [Hf+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O TZNXTUDMYCRCAP-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000003 human carcinogen Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910001987 mercury nitrate Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 description 1
- DRXYRSRECMWYAV-UHFFFAOYSA-N nitrooxymercury Chemical compound [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 description 1
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- FYNXQOUDSWHQQD-UHFFFAOYSA-N tantalum(5+) pentanitrate Chemical compound [Ta+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYNXQOUDSWHQQD-UHFFFAOYSA-N 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/28—Molybdenum
-
- 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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a high-activity molybdenum-based catalyst, wherein the active metal of the catalyst consists of molybdenum element and a cocatalyst; the mass percentage of the two components is 60-100% and 0-40% respectively; with the proviso that the promoter is not Cr. In addition, a preparation method of the molybdenum-based catalyst is also disclosed. The method comprises the step of introducing hydrogen fluoride gas in an activation stage to convert part of molybdenum oxide into molybdic acid fluoride and molybdic acid fluoride. The molybdenum-based catalyst disclosed by the invention is safe, environment-friendly and harmless, has high catalytic activity, high catalytic stability and long service life, and is mainly used for preparing fluorine-containing olefin by catalyzing halogenated olefin to generate fluorine-chlorine exchange reaction in a gas phase under a high-temperature condition.
Description
Technical Field
The invention belongs to the technical field of fluorine chemical industry, relates to a molybdenum-based catalyst, a preparation method and application, and particularly relates to a high-activity molybdenum-based catalyst for preparing fluorine-containing olefin by gas-phase catalysis of halogenated olefin under a high-temperature condition to generate fluorine-chlorine exchange reaction, and a preparation method and application.
Background
To fulfill the montreal protocol aimed at protecting the earth's ozone layer, Hydrofluorocarbons (HFCs) and Hydrofluoroolefins (HFOs) with zero ODP values have been introduced in countries around the world, thus eliminating chlorofluorocarbons (CFCs) and Hydrochlorofluorocarbons (HCFCs) with ODP values other than zero. At present, HFCs and HFOs have been widely used as refrigerants, cleaning agents, foaming agents, fire extinguishing agents, etching agents, and the like.
At present, most of HFCs or HFOs produced industrially adopt a method of gas phase catalysis fluorine-chlorine exchange reaction of halogenated organic matters, and the method has the advantages of simple process, easy continuous large-scale production, safe operation and the like. The fluorine-chlorine exchange catalyst plays a central role in the gas phase catalytic fluorine-chlorine exchange reaction of halogenated organic matters. The most common fluorine-chlorine exchange catalyst is a chromium-based catalyst, the major active component of which is chromium. Due to the advantages of easy availability of raw materials and high activity, the chromium-based catalyst has attracted research interest of scientists all over the world.
U.S. dupont reported in US4465786A an Al modified chromium-based catalyst for the catalytic preparation of trifluoropropene.
U.S. DuPont in US2010/0051853A1 reports that monochloro-fluoromethane and tetrafluoropropene as raw materials react under the action of aluminum halide to obtain 1-chloro-2, 2,3,3, 3-pentafluoropropane (HCFC-235cb), and then HCFC-235cb reacts with Cr2O3In the presence of the catalyst, dehydrofluorination reaction is carried out to obtain E/Z-1-chloro-2, 3,3, 3-tetrafluoropropene (E/Z-HCFC-1224yd), and finally the E/Z-HCFC-1224yd and hydrogen fluoride are subjected to gas-phase fluorine-chlorine exchange reaction under the action of a Zn element modified chromium-based catalyst to obtain the E/Z-1,1,1,2, 3-pentafluoropropene (E/Z-HFC-1225ye), wherein the content of trans-configuration and the cis-configuration is respectively 95 percent and 5 percent.
The british empire chemical industry company reported in patent US5763704A a modified chromium-based catalyst of the Zn element for the catalytic preparation of difluoromethane (HFC-32).
The uk empire chemical industry company reported in patent US5763707A a chromium-based catalyst modified with Zn element and Ni element together for the catalytic production of HFC-125.
The French Elvator chemical company reports in the patent US5811603A the production of 1-chloro-3, 3, 3-trifluoropropene (HCFO-1233zd), 1,3,3, 3-tetrafluoropropene (HFO-1234ze) and 1,1,1,3, 3-pentafluoropropane (HFC-245fa) by catalyzing HCO-1233za with a chromium-based catalyst.
The french er-vogue chemical company reported in patent US6184172A that a chromium-based catalyst modified with Al element and Ni element together was used to catalyze 1-chloro-3, 3, 3-trifluoroethane (HCFC-133a) to produce 1,1,1, 3-tetrafluoroethane (HFC-134 a).
Japanese Dajin company reported in U.S. Pat. No. 6,6300531, 6300531A that a specific surface area S is 170-300 m2The chromium-based catalyst is used for catalyzing 1,1, 1-trichloroethane to generate fluorine-chlorine exchange reaction to synthesize HFC-134a, and can also be used for catalyzing tetrachloroethylene to generate fluorine-chlorine exchange reaction to obtain pentafluoroethane (HFC-125).
Japanese Dajin company reported in U.S. Pat. No. 5,983, 0217928A1 that a chromium-based catalyst catalyzes the gas phase fluorine-chlorine exchange reaction of 2-chloro-3, 3, 3-trifluoropropene (HCFO-1233xf) with HF to give 2,3,3, 3-tetrafluoropropene (HFO-1234 yf).
The Japanese Central glass company reported in patent US5905174A that chromium-based catalysts were used to catalyze the preparation of 1,1, 1-trifluoro-3, 3-dichloroacetone from pentachloroacetone.
Japanese Raynaud and Senso-Dow company in patent CN1192995C report a fluorine-chlorine exchange catalyst prepared by impregnating Cr (NO) with Cr3)3Loaded on active carbon, dried, roasted and activated by hydrogen fluoride, and is used for catalyzing cyclo-CF at 330 DEG C2CF2CF2Preparation of cyclo-CF by fluoro-chloro exchange reaction of CCl ═ CCl and hydrogen fluoride2CF2CF2CF ═ CCl, which has very low catalytic activity, with a conversion of only 26% and a selectivity of 91%.
China Sigan gold bead modern chemical industry finite responsibility company reports that one element of Mn, Co or Zn and the other element of Mg or Ni, a chromium-based catalyst modified by two elements is used for catalyzing trichloroethylene, and HFC-134a is synthesized through a two-step gas-phase fluorine-chlorine exchange reaction through an intermediate HCFC-133 a.
China-chemical modern environmental protection chemical industry (Xian) limited company reports that a rare earth element modified chromium-based catalyst is used for catalyzing HCFC-133a and HF to perform gas-phase fluorine-exchange reaction to synthesize HFC-134a in patent CN 102580767A.
In patent CN1145275A of the national institute of chemistry of Sichuan, a cobalt and magnesium modified chromium catalyst is reported, the carrier is aluminum fluoride, which is used for catalyzing trichloroethylene to perform two-step gas-phase fluorine-chlorine exchange reaction to synthesize HFC-134a through intermediate HCFC-133 a.
However, the chromium catalyst still has the defects of low use temperature, low catalytic activity, short service life and difficult recycling, and more importantly, chromium has toxicity and can cause great harm to people, and particularly, high-valence chromium has strong carcinogenicity. Research suggests that hexavalent chromium is 100 times more toxic than trivalent chromium, is easily absorbed by the human body and accumulates in the body, and is slowly metabolized and eliminated. Under certain conditions, trivalent chromium and hexavalent chromium can be interconverted. Hexavalent chromium has been identified as a cause of respiratory cancer in humans. Hexavalent chromium, once absorbed and metabolized by the ubiquitous reducing agents in the cell, forms chromium-promoted DNA-damage cancers in the cells of the human digestive system. Hexavalent chromium is listed as a "human carcinogen" by the world health organization international agency for research on cancer (IARC).
Therefore, a non-chromium-based catalyst which is safe, environment-friendly, harmless, high in catalytic activity and long in service life is urgently needed to be found as a fluorine-chlorine exchange catalyst.
Disclosure of Invention
In order to overcome the deficiencies of the prior art, it is an object of the present invention to provide a molybdenum-based catalyst that provides both a higher olefin conversion and a higher selectivity to fluorine-containing olefins. It is another object of the present invention to provide a molybdenum-based catalyst having high catalytic stability and having a service life of more than 1000 hours. It is a further object of the present invention to provide a molybdenum-based catalyst which maintains a high catalytic activity at service temperatures in excess of 400 ℃. The molybdenum-based catalyst of the present invention has a milestone effect in finding non-chromium-based catalysts for gas-phase catalysis of fluorine-chlorine exchange reactions.
In order to achieve the purpose, on one hand, the invention adopts the following technical scheme: a high-activity molybdenum-based catalyst, the active metal of the catalyst consists of molybdenum element and a cocatalyst; the catalyst is characterized in that the mass percentages of the molybdenum element and the cocatalyst are respectively 60-100% and 0-40%; with the proviso that the promoter is not Cr.
According to the high-activity molybdenum-based catalyst, the mass percentages of molybdenum element and cocatalyst are 65-100% and 0-35% respectively; preferably, the mass percentage compositions of the molybdenum element and the cocatalyst are respectively 70-100% and 0-30%; more preferably, the mass percentage compositions of the molybdenum element and the cocatalyst are respectively 75-95% and 5-25%; and, most preferably, the mass percentage composition of the molybdenum element and the cocatalyst is 80-95% and 5-20%, respectively.
In one embodiment, the molybdenum element and the promoter are 90% and 10% by weight, respectively. In another embodiment, the molybdenum element and the promoter are 80% and 20% by weight, respectively.
The high-activity molybdenum-based catalyst is characterized In that the cocatalyst is at least one or more selected from Al, Mg, Ni, Co, Ti, Zr, V, Fe, Zn, In, Cu, Ag, Cd, Hg, Ga, Sn, Pb, Mn, Ba, Re, Sc, Sr, Ru, Nb, Ta, Ca, Ce, Sb, Tl and Hf. Preferably, the cocatalyst is selected from at least one or more of Al, Mg, Ni, Co, Ti, Fe, Zn, Cu, Cd, Mn, Ba, Re, Sc, Sr, Nb and Ca; more preferably, the cocatalyst is selected from at least one or more of Ni, Co, Fe, Zn, Cu, Mn, Re, Sc and Nb; and, most preferably, the promoter is selected from Ni and/or Co.
In one embodiment, the promoter is selected from Ni; that is, the active metal of the catalyst consists of molybdenum and Ni, the mass percentages of which are 90% and 10%, respectively. In another embodiment, the promoter is selected from Co; that is, the active metal of the catalyst consists of molybdenum and Co in the mass percentages of 90% and 10%, respectively.
The high-activity molybdenum-based catalyst according to the present invention, wherein the molybdenum-based catalyst is prepared by a preparation method comprising the steps of,
(1) according to the mass percentage composition of molybdenum element and cocatalyst, dissolving soluble salt of molybdenum and soluble salt of cocatalyst in water, then dropwise adding a precipitator to enable the precipitation to be complete, adjusting the pH value to 7.0-9.0, aging for a certain time, filtering, drying, then crushing, and performing compression molding to obtain a catalyst precursor;
(2) roasting the catalyst precursor obtained in the step (1) at 300-500 ℃ in an inert gas atmosphere; then, at the temperature of 200-400 ℃, the mass ratio of the substances is 1: 2, activating in mixed gas consisting of hydrogen fluoride and inert gas to prepare the high-activity molybdenum-based catalyst.
The high-activity molybdenum-based catalyst according to the present invention, wherein the soluble salt of molybdenum comprises, but is not limited to, at least one or more of molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum hexachloride; preferably, the soluble salt of molybdenum is selected from at least one or more of molybdenum trichloride, molybdenum pentachloride and molybdenum hexachloride; more preferably, the soluble salt of molybdenum is selected from at least one or more of molybdenum trichloride and molybdenum pentachloride; and, most preferably, the soluble salt of molybdenum is selected from molybdenum trichloride.
The high-activity molybdenum-based catalyst according to the present invention, wherein the soluble salt of the promoter includes, but is not limited to, at least one or more of nitrate, chloride or acetate of the promoter; preferably, the soluble salt of the promoter is selected from at least one or several of nitrate or acetate salts of the promoter; and, most preferably, the soluble salt of the promoter is selected from the nitrate salts of cocatalysts.
In one embodiment, the soluble salt of the promoter is selected from nickel nitrate. In another embodiment, the soluble salt of the promoter is selected from cobalt nitrate.
The high-activity molybdenum-based catalyst provided by the invention is characterized in that the precipitant comprises at least one or more of ammonia water, sodium hydroxide, potassium hydroxide, cesium hydroxide and rubidium hydroxide; preferably, the precipitant is selected from at least one or more of ammonia water, sodium hydroxide and potassium hydroxide; more preferably, the precipitant is selected from at least one or more of ammonia water and sodium hydroxide; and, most preferably, the precipitating agent is selected from aqueous ammonia.
The high-activity molybdenum-based catalyst provided by the invention has the advantages that the aging time is 1-96 hours; preferably, the aging time is 3-72 hours; more preferably, the aging time is 6-48 hours; and, most preferably, the aging time is 9 to 36 hours.
In one embodiment, the aging time is 12 hours.
The high-activity molybdenum-based catalyst according to the present invention, wherein the inert gas is selected from nitrogen, helium, neon, argon, krypton, and xenon; preferably, the inert gas is selected from nitrogen, helium, neon and argon; more preferably, the inert gas is selected from nitrogen and helium; and, most preferably, the inert gas is selected from nitrogen.
The high-activity molybdenum-based catalyst is dried for 6-96 hours at the temperature of 60-100 ℃; preferably, the drying condition is drying at 70-90 ℃ for 12-72 hours; more preferably, the drying condition is drying at 75-85 ℃ for 18-60 hours; and, most preferably, the drying condition is drying at 80 ℃ for 24-48 hours.
In one embodiment, the drying conditions are drying at 80 ℃ for 36 hours.
The high-activity molybdenum-based catalyst provided by the invention has the advantages that the roasting time is 1-48 hours; preferably, the roasting time is 2-36 hours; more preferably, the roasting time is 4-24 hours; and, most preferably, the calcination time is 6 to 15 hours.
In one embodiment, the firing time is 8 hours.
The high-activity molybdenum-based catalyst provided by the invention has the advantages that the activation time is 1-48 hours; preferably, the activation time is 2-36 hours; more preferably, the activation time is 4-24 hours; and, most preferably, the activation time is 6 to 15 hours.
In one embodiment, the activation time is 12 hours.
On the other hand, the invention adopts the following technical scheme: a preparation method of a high-activity molybdenum-based catalyst comprises the following steps:
(1) according to the mass percentage composition of molybdenum element and cocatalyst, dissolving soluble salt of molybdenum and soluble salt of cocatalyst in water, then dropwise adding a precipitator to enable the precipitation to be complete, adjusting the pH value to 7.0-9.0, aging for a certain time, filtering, drying, then crushing, and performing compression molding to obtain a catalyst precursor;
(2) roasting the catalyst precursor obtained in the step (1) at 300-500 ℃ in an inert gas atmosphere; then, at the temperature of 200-400 ℃, the mass ratio of the substances is 1: 2, activating in mixed gas consisting of hydrogen fluoride and inert gas to prepare the high-activity molybdenum-based catalyst.
The preparation method comprises the following steps of (1) preparing a soluble salt of molybdenum, wherein the soluble salt of molybdenum comprises at least one or more of molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride and molybdenum hexachloride; preferably, the soluble salt of molybdenum is selected from at least one or more of molybdenum trichloride, molybdenum pentachloride and molybdenum hexachloride; more preferably, the soluble salt of molybdenum is selected from at least one or more of molybdenum trichloride and molybdenum pentachloride; and, most preferably, the soluble salt of molybdenum is selected from molybdenum trichloride.
According to the preparation method, the molybdenum element and the cocatalyst are 65-100% and 0-35% in percentage by mass respectively; preferably, the mass percentage compositions of the molybdenum element and the cocatalyst are respectively 70-100% and 0-30%; more preferably, the mass percentage compositions of the molybdenum element and the cocatalyst are respectively 75-95% and 5-25%; and, most preferably, the mass percentage composition of the molybdenum element and the cocatalyst is 80-95% and 5-20%, respectively.
In one embodiment, the molybdenum element and the promoter are 90% and 10% by weight, respectively. In another embodiment, the molybdenum element and the promoter are 80% and 20% by weight, respectively.
The preparation method of the invention is characterized in that the soluble salt of the promoter comprises but is not limited to at least one or more of nitrate, chloride or acetate of the promoter; preferably, the soluble salt of the promoter is selected from at least one or several of nitrate or acetate salts of the promoter; and, most preferably, the soluble salt of the promoter is selected from the nitrate salts of cocatalysts.
The preparation method comprises the step of selecting at least one or more of Al, Mg, Ni, Co, Ti, Zr, V, Fe, Zn, In, Cu, Ag, Cd, Hg, Ga, Sn, Pb, Mn, Ba, Re, Sc, Sr, Ru, Nb, Ta, Ca, Ce, Sb, Tl and Hf as the cocatalyst. Preferably, the cocatalyst is selected from at least one or more of Al, Mg, Ni, Co, Ti, Fe, Zn, Cu, Cd, Mn, Ba, Re, Sc, Sr, Nb and Ca; more preferably, the cocatalyst is selected from at least one or more of Ni, Co, Fe, Zn, Cu, Mn, Re, Sc and Nb; and, most preferably, the promoter is selected from Ni and/or Co.
In one embodiment, the promoter is selected from Ni; that is, the soluble salt of the catalyst is selected from nickel nitrate. In another embodiment, the promoter is selected from Co; that is, the soluble salt of the promoter is selected from cobalt nitrate.
The preparation method of the invention, wherein the precipitant comprises at least one or more of ammonia water, sodium hydroxide, potassium hydroxide, cesium hydroxide and rubidium hydroxide; preferably, the precipitant is selected from at least one or more of ammonia water, sodium hydroxide and potassium hydroxide; more preferably, the precipitant is selected from at least one or more of ammonia water and sodium hydroxide; and, most preferably, the precipitating agent is selected from aqueous ammonia.
The preparation method provided by the invention is characterized in that the aging time is 1-96 hours; preferably, the aging time is 3-72 hours; more preferably, the aging time is 6-48 hours; and, most preferably, the aging time is 9 to 36 hours.
In one embodiment, the aging time is 12 hours.
The production method according to the present invention, wherein the inert gas is selected from nitrogen, helium, neon, argon, krypton, and xenon; preferably, the inert gas is selected from nitrogen, helium, neon and argon; more preferably, the inert gas is selected from nitrogen and helium; and, most preferably, the inert gas is selected from nitrogen.
The preparation method provided by the invention is characterized in that the drying condition is drying for 6-96 hours at 60-100 ℃; preferably, the drying condition is drying at 70-90 ℃ for 12-72 hours; more preferably, the drying condition is drying at 75-85 ℃ for 18-60 hours; and, most preferably, the drying condition is drying at 80 ℃ for 24-48 hours.
In one embodiment, the drying conditions are drying at 80 ℃ for 36 hours.
The preparation method provided by the invention is characterized in that the roasting time is 1-48 hours; preferably, the roasting time is 2-36 hours; more preferably, the roasting time is 4-24 hours; and, most preferably, the calcination time is 6 to 15 hours.
In one embodiment, the firing time is 8 hours.
The preparation method provided by the invention is characterized in that the activation time is 1-48 hours; preferably, the activation time is 2-36 hours; more preferably, the activation time is 4-24 hours; and, most preferably, the activation time is 6 to 15 hours.
In one embodiment, the activation time is 12 hours.
In another aspect, the invention adopts the following technical scheme: the high-activity molybdenum-based catalyst is used for preparing fluorine-containing olefin by carrying out gas-phase catalysis on halogenated olefin to generate fluorine-chlorine exchange reaction under the high-temperature condition.
The use according to the present invention, wherein the fluorine-chlorine exchange reaction includes, but is not limited to, the following reactions of formulae (1) to (5):
wherein cat represents the high-activity molybdenum-based catalyst of the present invention.
The use according to the invention, wherein the halogenated olefin may or may not contain a fluorine atom, but must contain one or more halogen atoms other than a fluorine atom, such as a chlorine atom or a bromine atom or an iodine atom. In the formula (1), the halogenated olefin is cyclo-CF2CF2CF2CCl is CCl, and the fluorine-containing olefin is cyclo-CF2CF2CF2CF ═ CCl; cyclo denotes the attachment CF2Cyclic covalent bond to terminal CCl group. In the formula (2), the halogenated olefin is 2-chloro-3, 3, 3-trifluoropropene (abbreviated as HCFO-1233xf) and the fluorine-containing olefin is 2,3,3, 3-tetrafluoropropene (abbreviated as HFO-1234 yf). In the formula (3), the halogenated olefin is E/Z-1-chloro-2, 3,3, 3-tetrafluoropropene (abbreviated as E/Z-HCFO-1224yd), and the fluorine-containing olefin is E/Z-1,2,3,3, 3-pentafluoropropene (abbreviated as E/Z-HFO-1225 ye). In formula (4), the halogenated olefin is E-1-chloro-3, 3, 3-trifluoropropene, and the fluoroolefin is E/Z-1,3,3, 3-tetrafluoropropene (abbreviated as E/Z-HFO-1234 ze). In formula (5), the halogenated olefin is Z-1-chloro-3, 3, 3-trifluoropropene (abbreviated as Z-HCFO-1233zd) and the fluorine-containing olefin is E/Z-1,3,3, 3-tetrafluoropropene (abbreviated as E/Z-HFO-1234 ze).
The use according to the invention, wherein the high temperature conditions (or fluorine-chlorine exchange reaction temperature) are from about 100 ℃ to about 700 ℃, preferably from about 150 ℃ to about 600 ℃, more preferably from about 200 ℃ to about 550 ℃, and, most preferably, from about 250 ℃ to about 500 ℃. Further, the high temperature conditions may be a more preferred temperature range for different types of fluorine-chlorine exchange reactions. When the fluorine-chlorine exchange reaction is a reaction of formula (1), the high temperature condition may be further preferably about 270 ℃ to about 420 ℃, and most preferably about 300 ℃ to about 390 ℃. When the fluorine-chlorine exchange reaction is the reaction of formula (2), the high temperature condition may be further preferably about 300 ℃ to about 400 ℃, and most preferably about 330 ℃ to about 360 ℃. When the fluorine-chlorine exchange reaction is a reaction of formula (3), the high temperature condition may be further preferably about 270 ℃ to about 350 ℃, and most preferably about 300 ℃ to about 320 ℃. When the fluorine-chlorine exchange reaction is a reaction of formulae (4) and (5), the high temperature condition may be further preferably about 350 ℃ to about 480 ℃, and most preferably about 400 ℃ to about 450 ℃.
The use according to the invention, wherein the fluorine-chlorine exchange reaction is carried out in a common fluorination reactor. Such reactors typically have a lining material that is resistant to corrosion by hydrogen fluoride. The reactor pressure is not critical during the reaction and can be vacuum, atmospheric pressure or elevated pressure. During the reaction, the halogenated olefin is reacted with HF in the gas phase in contact with a fluorination catalyst.
The use according to the invention, wherein the molar ratio of HF to haloolefin is greater than or equal to about 1: 1. Preferably, the molar ratio of HF to haloolefin is from about 1:1 to about 50: 1; more preferably, the molar ratio of HF to haloolefin is from about 1:1 to about 30: 1; most preferably, the molar ratio of HF to haloolefin is from about 2:1 to about 15: 1. The water in the HF reacts with and deactivates the catalyst. Thus substantially anhydrous HF is preferred. By "substantially anhydrous" is meant that the HF contains less than about 0.03 wt% water, preferably less than about 0.01 wt% water.
The use according to the invention, wherein the fluorine-chlorine exchange reaction can be carried out in batch or continuous mode. In a continuous process, the haloolefin and HF are typically fed simultaneously to the reactor after the reactor has reached the desired temperature. The temperature and pressure of the fluorine-chlorine exchange reaction remain substantially the same in both batch and continuous modes of operation. The contact time or residence time is from about 1 second to about 1 hour, preferably from about 2 seconds to about 30 minutes, more preferably from about 3 seconds to about 5 minutes, and most preferably from about 5 seconds to about 2 minutes. In the reactor, sufficient catalyst must be present to effect the fluorine-chlorine exchange during the residence time described above. For the purposes of the present invention, "contact time" is the time required for the gaseous reactants to flow through the catalyst bed, assuming that the catalyst bed is 100% void (void).
The invention firstly adopts a coprecipitation method to prepare a catalyst precursor, wherein the catalyst precursor mainly comprises a hydroxide of molybdenum and a hydroxide of a promoter. When the catalyst precursor is calcined at a high temperature, the hydroxide of the promoter is pyrolyzed to obtain the oxide of the promoter, and the hydroxide of molybdenum is pyrolyzed to obtain the oxide of molybdenum. Subsequently, the catalyst precursor enters an activation stage of hydrogen fluoride, thus promoting the catalystThe oxide of the catalyst is fluorinated to give a fluoride of the promoter, while the oxide of molybdenum is partially fluorinated to give fluorinated molybdic acid and molybdic oxyfluoride acid. Depending on the valence of the molybdenum ion, fluorinated molybdic acid may be represented as HxWyFmIn the form of (1), molybdic oxyfluoride may be represented by HxWyOzFmIn the form of (1). In one embodiment, the fluorinated molybdic acid may be H2[MoF8]The molybdic acid fluoride may be H2[WO2F4]。
Without wishing to be bound by any theory, during the above-mentioned activation phase of hydrogen fluoride, the molybdenum element is mainly present in the form of molybdenum oxides in different valence states from divalent to hexavalent, molybdic fluoride and molybdic oxyfluoride acid. The molybdenum-based catalyst has strong catalytic activity due to the strong Lewis acidity of molybdenum oxide, particularly molybdic acid fluoride and molybdic acid fluoroxide, and other metal elements are used as promoters, so that the stability of the molybdenum-based catalyst is further enhanced. The molybdenum-based catalyst prepared by the method has the advantages of high use temperature, high catalytic activity and long service life.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) for human beings, molybdenum is the only known element essential to human beings in the second and third transition elements, and compared with the transition elements of the same type, the molybdenum has extremely low toxicity and can be considered as basically nontoxic. Researches show that the incidence rate of cancer is low in areas with high molybdenum content in soil. Therefore, compared with the chromium-based catalyst, the molybdenum-based catalyst has the characteristics of safety, environmental protection and harmlessness.
(2) When the molybdenum-based catalyst is activated by mixed gas consisting of hydrogen fluoride and inert gas, part of molybdenum oxide can react with HF to obtain strongly acidic molybdic acid fluoride and molybdic acid fluoroxide, so that the molybdenum-based catalyst has stronger catalytic activity, and the molybdenum-based catalyst is modified by metal elements, thereby greatly improving the stability of the molybdenum-based catalyst.
(3) The molybdenum-based catalyst is suitable for gas-phase catalysis of halogenated olefin at high temperature to generate fluorine-chlorine exchange reaction to prepare fluorine-containing olefin, and the using temperature is higher than 400 ℃, even can reach 450 ℃, and is obviously higher than 330 ℃ in the prior art.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these embodiments are merely illustrative of the present invention and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents also fall within the scope of the claims of the present application.
In the following examples, the conversion of halogenated olefin and selectivity of fluorine-containing olefin were measured using the following conditions.
An analytical instrument: shimadzu GC-2010, DB-VRX caliper column (i.d. 0.32mm; length 30 m; J & Mo Scientific Inc.).
GC analysis method: and washing, alkali washing and drying the reaction product, and then taking a gas sample for GC analysis. The temperature of the detector is 250 ℃, the temperature of the vaporization chamber is 250 ℃, the initial temperature of the column is 40 ℃, the temperature is kept for 10 minutes, the temperature is increased to 230 ℃ at the speed of 15 ℃/min, and the temperature is kept for 8 minutes.
Example 1
According to the percentage composition of molybdenum element and nickel element being 90% and 10%, molybdenum trichloride and nickel nitrate are dissolved in water, concentrated ammonia water is added dropwise for precipitation, the pH value is adjusted to 7.5, then the solution is aged for 12 hours, washed by water and filtered, dried in an oven at 80 ℃ for 36 hours, the obtained solid is crushed and tableted for forming to obtain a catalyst precursor, 10mL of the catalyst precursor is put into a Monel tubular reactor with the inner diameter of 1/2 inches and the length of 30cm, nitrogen is introduced to roast for 8 hours at 450 ℃, and the space velocity of nitrogen is 200 hours-1Then, the temperature is reduced to 300 ℃, and simultaneously the mass ratio of the introduced substances is 1: 2, the total space velocity of the gas is 220h-1And activating for 12 hours, and stopping the mixed gas to prepare the molybdenum-based catalyst.
Example 2
The catalyst was prepared by substantially the same procedure as in example 1, except that the percentage compositions of the molybdenum element and the nickel element were 100% and 0.
Example 3
The catalyst was prepared by substantially the same procedure as in example 1, except that the percentage composition of the molybdenum element and the nickel element was 80% and 20%.
Example 4
The catalyst was prepared by substantially the same procedure as in example 1, except that the percentage composition of the molybdenum element and the nickel element was 70% and 30%.
Example 5
The catalyst was prepared by substantially the same procedure as in example 1, except that the percentage composition of molybdenum and nickel elements was 60% and 40%.
Example 6
The catalyst was prepared by substantially the same procedure as in example 1, except that nickel nitrate was changed to aluminum nitrate, and the percentage composition of molybdenum and aluminum elements was 90% and 10%.
Example 7
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to magnesium nitrate, and the percentage composition of molybdenum and magnesium elements was 90% and 10%.
Example 8
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to manganese nitrate, and the percentage composition of molybdenum and manganese elements was 90% and 10%.
Example 9
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to cobalt nitrate, and the percentage composition of molybdenum and cobalt elements was 90% and 10%.
Example 10
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to titanium nitrate, and the percentage composition of molybdenum and titanium elements was 90% and 10%.
Example 11
The catalyst was prepared by a process substantially the same as in example 1, except that nickel nitrate was changed to zirconium nitrate, and the percentage composition of molybdenum and zirconium elements was 90% and 10%.
Example 12
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to vanadyl nitrate, and the percentage composition of molybdenum and vanadium was 90% and 10%.
Example 13
The catalyst was prepared by a process substantially the same as in example 1, except that nickel nitrate was changed to ferric nitrate, and the percentage composition of molybdenum and iron elements was 90% and 10%.
Example 14
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to zinc nitrate, and the percentage composition of molybdenum and zinc elements was 90% and 10%.
Example 15
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to indium nitrate, and the percentage composition of molybdenum and indium was 90% and 10%.
Example 16
The catalyst was prepared by a process substantially the same as in example 1, except that nickel nitrate was changed to copper nitrate, and the percentage composition of molybdenum and copper elements was 90% and 10%.
Example 17
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to silver nitrate, and the percentage composition of molybdenum and silver elements was 90% and 10%.
Example 18
The preparation process of the catalyst is basically the same as that of the catalyst in the embodiment 1, except that nickel nitrate is changed into cadmium nitrate, and the percentage composition of molybdenum element and cadmium element is 90% and 10%.
Example 19
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to mercury nitrate, and the percentage composition of molybdenum and mercury elements was 90% and 10%.
Example 20
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to gallium nitrate, and the percentage composition of molybdenum and gallium elements was 90% and 10%.
Example 21
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to tin nitrate, and the percentage composition of molybdenum and tin elements was 90% and 10%.
Example 22
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to lead nitrate, and the percentage composition of molybdenum and lead elements was 90% and 10%.
Example 23
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to strontium nitrate, and the percentage composition of molybdenum and strontium elements was 90% and 10%.
Example 24
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to barium nitrate, and the percentage composition of molybdenum and barium was 90% and 10%.
Example 25
The catalyst was prepared by essentially the same procedure as in example 1, except that nickel nitrate was changed to rhenium nitrate, and the percentage composition of the molybdenum element and the rhenium element was 90% and 10%.
Example 26
The catalyst was prepared by a process substantially the same as in example 1, except that nickel nitrate was changed to scandium nitrate, and the percentage composition of molybdenum and scandium was 90% and 10%.
Example 27
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to ruthenium nitrate, and the percentage composition of molybdenum element and ruthenium element was 90% and 10%.
Example 28
The catalyst was prepared by a process substantially the same as in example 1, except that nickel nitrate was changed to niobium nitrate, and the percentage composition of molybdenum and niobium elements was 90% and 10%.
Example 29
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to tantalum nitrate, and the percentage composition of molybdenum and tantalum was 90% and 10%.
Example 30
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to calcium nitrate, and the percentage composition of molybdenum and calcium elements was 90% and 10%.
Example 31
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to cerium nitrate, and the percentage composition of molybdenum and cerium was 90% and 10%.
Example 32
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to antimony nitrate, and the percentage composition of molybdenum and antimony elements was 90% and 10%.
Example 33
The catalyst was prepared by a process substantially the same as in example 1, except that nickel nitrate was changed to thallium nitrate, and the percentage composition of the molybdenum element and the thallium element was 90% and 10%.
Example 34
The catalyst was prepared by a process substantially the same as in example 1, except that nickel nitrate was changed to hafnium nitrate, and the percentage composition of the molybdenum element and the hafnium element was 90% and 10%.
Example 35
The preparation process of the catalyst was substantially the same as in example 1, except that nickel nitrate was changed to nickel chloride, and the percentage composition of molybdenum and nickel elements was 90% and 10%.
Example 36
The catalyst was prepared by a process substantially the same as in example 1, except that nickel nitrate was changed to nickel acetate, and the percentage composition of molybdenum and nickel elements was 90% and 10%.
Example 37
The catalyst was prepared by a procedure substantially the same as in example 1, except that molybdenum trichloride was replaced with molybdenum dichloride.
Example 38
The catalyst was prepared by a procedure substantially the same as in example 1, except that molybdenum trichloride was replaced with molybdenum tetrachloride.
Example 39
The preparation process of the catalyst is basically the same as that of example 1, except that molybdenum trichloride is replaced by molybdenum pentachloride.
Example 40
The catalyst was prepared by a procedure substantially the same as in example 1, except that molybdenum trichloride was replaced with molybdenum hexachloride.
EXAMPLE 41
The catalyst was prepared by essentially the same procedure as in example 1, except that the activation stage was free of hydrogen fluoride.
Application example 1
The fluoro-chloro exchange catalyst prepared in example 1 was used in the following reaction to synthesize a series of fluorine-containing olefins:
after 20 hours of reaction, the reaction product was washed with water and then washed with alkali to remove HF, and the organic composition was analyzed by GC, and the results are shown in Table 1. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 1
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 2
The catalyst prepared in example 2 was used in the reaction for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 2. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 2
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 3
The catalyst prepared in example 3 was used in the reaction for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 3. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 3
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 4
The catalyst prepared in example 4 was used in the reaction for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 4. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 4
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 5
The catalyst prepared in example 5 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 5. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 5
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 6
The catalyst prepared in example 6 was used in the reaction for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 6. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 6
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 7
The catalyst prepared in example 7 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 7. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 7
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 8
The catalyst prepared in example 8 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 8. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 8
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 9
The catalyst prepared in example 9 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 9. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 9
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 10
The catalyst prepared in example 10 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 10. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 10
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 11
The catalyst prepared in example 11 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 11. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 11
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 12
The catalyst prepared in example 12 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 12. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 12
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 13
The catalyst prepared in example 13 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 13. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 13
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 14
The catalyst prepared in example 14 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 14. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 14
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 15
The catalyst prepared in example 15 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 15. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 15
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 16
The catalyst prepared in example 16 was used in the reaction for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 16. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 16
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 17
The catalyst prepared in example 17 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 17. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 17
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 18
The catalyst prepared in example 18 was used in a reaction for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 18. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 18
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 19
The catalyst prepared in example 19 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 19. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 19
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 20
The catalyst prepared in example 20 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 20. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 20
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 21
The catalyst prepared in example 21 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 21. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 21
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 22
The catalyst prepared in example 22 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 22. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 22
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 23
The catalyst prepared in example 23 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 23. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 23
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 24
The catalyst prepared in example 24 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 24. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 24
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 25
The catalyst prepared in example 25 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 25. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
TABLE 25
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 26
The catalyst prepared in example 26 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 26. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 26
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 27
The catalyst prepared in example 27 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 27. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 27
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 28
The catalyst prepared in example 28 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 28. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 28
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 29
The catalyst prepared in example 29 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 29. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 29
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 30
The catalyst prepared in example 30 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 30. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 30
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 31
The catalyst prepared in example 31 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 31. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 31
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 32
The catalyst prepared in example 32 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 32. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 32
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 33
The catalyst prepared in example 33 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 33. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 33
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 34
The catalyst prepared in example 34 was used in a reaction for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 34. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 34
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 35
The catalyst prepared in example 35 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 35. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 35
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 36
The catalyst prepared in example 36 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 36. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 36
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 37
The catalyst prepared in example 37 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 37. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 37
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 38
The catalyst prepared in example 38 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 38. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 38
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 39
The catalyst prepared in example 39 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 39. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 39
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 40
The catalyst prepared in example 40 was used in reactions for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 40. The catalyst is continuously operated for 1000 hours, and the catalytic activity of the catalyst is basically unchanged.
Watch 40
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
Application example 41
The catalyst prepared in example 41 was used in the reaction for synthesizing a series of fluorine-containing olefins under substantially the same conditions as in application example 1, and the results are shown in table 41. After the catalyst is continuously operated for 1000 hours, the catalytic activity of the catalyst is remarkably reduced.
Table 41
The fluoroolefin selectivity refers to the ratio of the target products, and refers to the sum of the selectivities to E-HFO-1225ye and Z-HFO-1225ye for reaction (3), and to the sum of the selectivities to E-HFO-1234ze and Z-HFO-1234ze for reactions (4) and (5), and the selectivities to the single target product for the other reactions are all the same.
The results show that the high-activity molybdenum-based catalyst can provide higher olefin conversion rate and higher fluorine-containing olefin selectivity; at the same time, the catalyst has high stability and a service life of more than 1000 hours. In addition, the reaction of the formulas (4) and (5) can still maintain higher catalytic activity at the use temperature of over 400 ℃.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (13)
1. A high-activity molybdenum-based catalyst, the active metal of the catalyst consists of molybdenum element and a cocatalyst; the catalyst is characterized in that the mass percentages of the molybdenum element and the cocatalyst are respectively 80-90% and 10-20%; the cocatalyst is selected from one of metal elements of Al, Mg, Co, Ti, Zr, V, Fe, Zn, In, Cu, Ag, Cd, Hg, Ga, Sn, Pb, Mn, Ba, Re, Sc, Sr, Ru, Nb, Ta, Ca, Ce, Sb, Tl and Hf, and the molybdenum-based catalyst is prepared by a preparation method comprising the following steps,
(1) according to the mass percentage composition of molybdenum element and cocatalyst, dissolving soluble salt of molybdenum and soluble salt of cocatalyst in water, then dropwise adding a precipitator to enable the precipitation to be complete, adjusting the pH value to 7.0-9.0, aging for a certain time, filtering, drying, then crushing, and performing compression molding to obtain a catalyst precursor;
(2) roasting the catalyst precursor obtained in the step (1) at 300-500 ℃ in an inert gas atmosphere; then, at the temperature of 200-400 ℃, the mass ratio of the substances is 1: 2, activating in mixed gas consisting of hydrogen fluoride and inert gas to prepare the high-activity molybdenum-based catalyst.
2. The high activity molybdenum-based catalyst according to claim 1, wherein the soluble salt of molybdenum is selected from at least one or several of molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum hexachloride.
3. The high activity molybdenum-based catalyst according to claim 1, wherein the soluble salt of the promoter is selected from at least one or several of nitrate, chloride or acetate salts of cocatalysts.
4. The high activity molybdenum-based catalyst of claim 3, wherein the soluble salt of the promoter is selected from cobalt nitrate.
5. The high activity molybdenum-based catalyst of claim 1, wherein the precipitating agent is selected from at least one or more of ammonia, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide.
6. The high activity molybdenum-based catalyst according to claim 1, wherein the aging time is 1 to 96 hours; the drying condition is drying for 6-96 hours at 60-100 ℃; the roasting time is 1-48 hours; the activation time is 1-48 hours.
7. A process for preparing the high activity molybdenum-based catalyst of any one of claims 1 to 6, comprising the steps of:
(1) according to the mass percentage composition of molybdenum element and cocatalyst, dissolving soluble salt of molybdenum and soluble salt of cocatalyst in water, then dropwise adding a precipitator to enable the precipitation to be complete, adjusting the pH value to 7.0-9.0, aging for a certain time, filtering, drying, then crushing, and performing compression molding to obtain a catalyst precursor;
(2) roasting the catalyst precursor obtained in the step (1) at 300-500 ℃ in an inert gas atmosphere; then, at the temperature of 200-400 ℃, the mass ratio of the substances is 1: 2, activating in mixed gas consisting of hydrogen fluoride and inert gas to prepare the high-activity molybdenum-based catalyst.
8. Use of the high activity molybdenum-based catalyst of any one of claims 1 to 6 for the gas-phase catalysis of fluoroolefins by fluorine-chlorine exchange at elevated temperature to produce fluoroolefins.
9. Use according to claim 8, wherein the fluorine-chlorine exchange reaction is selected from the reactions of the following formulae (1) to (5):
(1)
(2)
(3)
(4)
(5)
wherein cat represents the high-activity molybdenum-based catalyst of any one of claims 1 to 7.
10. Use according to claim 8, wherein the high temperature conditions are from 100 ℃ to 700 ℃.
11. Use according to claim 8, wherein the high temperature conditions are from 150 ℃ to 600 ℃.
12. Use according to claim 8, wherein the high temperature conditions are from 200 ℃ to 550 ℃.
13. Use according to claim 8, wherein the high temperature conditions are from 250 ℃ to 500 ℃.
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| CN107213889B (en) * | 2017-04-18 | 2020-07-03 | 北京宇极科技发展有限公司 | Preparation of molybdenum-base and tungsten-base fluorine-chlorine exchange catalyst by blending method |
| CN109999788B (en) * | 2019-04-28 | 2022-01-11 | 泉州宇极新材料科技有限公司 | High-valence metal fluorination catalyst, preparation method and application |
| CN115624966B (en) * | 2022-10-13 | 2024-07-05 | 中国科学院深圳先进技术研究院 | Metal oxide composite material and preparation method and application thereof |
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