CN112717919A - Catalyst for producing isobutene by dehydrogenating isobutane - Google Patents
Catalyst for producing isobutene by dehydrogenating isobutane Download PDFInfo
- Publication number
- CN112717919A CN112717919A CN201910970939.3A CN201910970939A CN112717919A CN 112717919 A CN112717919 A CN 112717919A CN 201910970939 A CN201910970939 A CN 201910970939A CN 112717919 A CN112717919 A CN 112717919A
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- Prior art keywords
- catalyst
- sample
- isobutane
- carrier
- hours
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 215
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 200
- 239000001282 iso-butane Substances 0.000 title claims abstract description 100
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000011148 porous material Substances 0.000 claims abstract description 57
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 40
- 230000000737 periodic effect Effects 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical group [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 170
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 94
- 238000001035 drying Methods 0.000 claims description 80
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 74
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 74
- 238000006243 chemical reaction Methods 0.000 claims description 74
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 68
- 239000000203 mixture Substances 0.000 claims description 52
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 43
- 150000002500 ions Chemical class 0.000 claims description 43
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 42
- 238000001914 filtration Methods 0.000 claims description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 32
- 239000011651 chromium Substances 0.000 claims description 20
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 14
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- RSYUFYQTACJFML-DZGCQCFKSA-N afzelechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C=C1 RSYUFYQTACJFML-DZGCQCFKSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910001570 bauxite Inorganic materials 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 2
- 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 claims 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- -1 alpha-titanic acid Chemical compound 0.000 claims 1
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 claims 1
- 235000015217 chromium(III) sulphate Nutrition 0.000 claims 1
- 239000011696 chromium(III) sulphate Substances 0.000 claims 1
- YECBRSTWAYLPIM-UHFFFAOYSA-N chromium;hydrochloride Chemical compound Cl.[Cr] YECBRSTWAYLPIM-UHFFFAOYSA-N 0.000 claims 1
- OSYUGTCJVMTNTO-UHFFFAOYSA-D oxalate;tantalum(5+) Chemical compound [Ta+5].[Ta+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OSYUGTCJVMTNTO-UHFFFAOYSA-D 0.000 claims 1
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 claims 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims 1
- 238000002336 sorption--desorption measurement Methods 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 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 claims 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 122
- 239000008367 deionised water Substances 0.000 description 84
- 229910021641 deionized water Inorganic materials 0.000 description 84
- 235000013847 iso-butane Nutrition 0.000 description 81
- 239000000243 solution Substances 0.000 description 80
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 50
- 238000001354 calcination Methods 0.000 description 42
- 239000000706 filtrate Substances 0.000 description 40
- 238000002791 soaking Methods 0.000 description 34
- 238000005303 weighing Methods 0.000 description 31
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 30
- 229910052708 sodium Inorganic materials 0.000 description 16
- 239000011734 sodium Substances 0.000 description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 15
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000010438 heat treatment 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
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- DRHABPMHZRIRAH-UHFFFAOYSA-N 2,4,4,6,6-pentamethylhept-2-ene Chemical group CC(C)=CC(C)(C)CC(C)(C)C DRHABPMHZRIRAH-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- PXXRROSTRSLPET-UHFFFAOYSA-J C(C)(=O)[O-].[W+4].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].[W+4].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] PXXRROSTRSLPET-UHFFFAOYSA-J 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910002847 PtSn Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- UBFMILMLANTYEU-UHFFFAOYSA-H chromium(3+);oxalate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UBFMILMLANTYEU-UHFFFAOYSA-H 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical group [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
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Abstract
The invention relates to a catalyst for producing isobutene by dehydrogenating isobutane, which takes VIB group elements in a periodic table of elements as a main active component, at least one element in IIA group in the periodic table of elements as an alkaline auxiliary agent, and at least one element in IVB and VB groups in the periodic table of elementsThe element is other auxiliary agents, and the carrier is silicon-aluminum oxide. Wherein the carrier is treated by a hot solution containing elements in the IIA group of the periodic table of elements, and then other components are loaded to obtain the carrier with the specific surface area of 100-300 m2A dehydrogenation catalyst with an average pore diameter of 2-20 nm. The catalyst obtained by the method can improve the problem of low activity and selectivity of the isobutane dehydrogenation catalyst prepared by the prior art, and can be used for industrial application of isobutane dehydrogenation.
Description
Technical Field
The invention relates to a catalyst for producing isobutene by dehydrogenating isobutane.
Background
The butylene is an important petrochemical basic raw material next to ethylene and propylene, and the isobutylene is an intermediate product of important chemicals and can be used for producing deep-processed products such as butyl rubber, polyisobutylene, diisobutylene, triisobutylene, methyl methacrylate, tert-butyl alcohol, methacrylic acid, methacrylonitrile, isoprene and the like. The isobutene is obtained from C4 fraction raffinate of a catalytic cracking unit (FCC) and an ethylene cracking unit of an oil refinery worldwide, almost all isobutene resources of China come from the FCC unit and a steam cracking unit of the refinery, and due to the limitation of processes and the like, C of China is a major source of isobutene4The hydrocarbon utilization rate is always low, only about 40%, and reaches 80% in European and American countries. With the deep improvement of crude oil processing in an oil refinery and the development of shale gas exploitation technology, the yield of C4 alkane is rapidly increased, the corresponding isobutene is produced by isobutane catalytic dehydrogenation technology, the additional value of isobutane can be effectively improved, the technology is low in investment, high in product yield and huge in market development potential.
The catalytic dehydrogenation technology of isobutane is a reaction with strong heat absorption, reversibility and increased molecular number, and one molecule of isobutene is obtained after dehydrogenation of one molecule of isobutane. Commercially available processes for dehydrogenating alkanes worldwide include the Oleflex process from UOP, the Catofin process from rumus, the STAR process from philips oil, and the Snamprogetti fluidized bed dehydrogenation process developed by russian labe research institute in conjunction with the amamprogetti engineering corporation, among others. The Oleflex process adopts a moving bed continuous regeneration type reaction system; the Catofin and STAR process adopts a fixed bed intermittent regeneration reaction system; and the Snamprogetti process adopts a fluidized bed reaction regeneration system. In addition, there are alkane dehydrogenation technologies developed in conjunction with Linde and BASF. Catalysts currently used for this reactionThere are two main types of systems: one is a platinum-based noble metal catalyst, mainly a PtSn catalyst; another class is the chromium-based catalytic systems, mainly Cr2O3/Al2O3A catalyst. The Pt dehydrogenation catalyst is used for isobutane dehydrogenation, has the advantages of environmental friendliness, high activity and the like, but has high price, complex preparation and high requirement on the purity of reaction raw materials. The Cr series catalyst has low price, relatively high activity, low requirement on the purity of raw materials, certain influence on the environment, frequent regeneration in the reaction process, harsh dehydrogenation conditions and the like.
Patent CN104289218 discloses a catalyst for preparing isobutene by dehydrogenating isobutane, wherein a metal salt solution is added into slurry containing an inorganic carrier, a solution of a reducing agent is added into the slurry under the protection of inert gas, and the catalyst containing Pt, Sn and K is obtained by solid-liquid separation, wherein the highest conversion rate of the catalyst to isobutane is 51%, and the selectivity of isobutene reaches 91%. Patent CN101862669 discloses a catalyst for preparing isobutene by isobutane dehydrogenation and a preparation method thereof, wherein the catalyst takes alumina with a tin-containing framework as a carrier and alkali metal as a modifier for co-soaking H2PtCl6And SnCl4The mixed aqueous solution of (1) is used for preparing a catalyst with 0.01-10% of active metal Pt, 0.01-10% of Sn and 0.01-5% of alkaline auxiliary agent, wherein the conversion rate of the iso-butane is 36% and the selectivity of the isobutene is 95% under the conditions of high temperature and low pressure. Patent CN 101940922A discloses a low-carbon alkane dehydrogenation catalyst and a preparation method thereof, wherein the patent takes Cr as an active metal component, the content of chromium oxide is 10.0-45.0%, and the promoter component is one or more of K, Na and Li. When the prepared catalyst reacts for 10 minutes, the conversion rate of isobutane is about 57%, and the selectivity of isobutene is about 91%. US20050075243a1 discloses a dehydrogenation catalyst for fixed bed or fluidized bed, using Cr as active component, preferably Zr, Mg promoter for alkane dehydrogenation, the results show that the catalyst has higher selectivity than single chromium oxide-alumina catalyst, the conversion rate of fresh catalyst to isobutane is about 75%, the selectivity of isobutene is about 85%, and the results show that the selectivity of isobutene is obviously lower.
Although the direct isobutane dehydrogenation catalyst has made great progress, the existing dehydrogenation catalyst still has the problems of low activity and low selectivity, and the defects greatly affect the commercial application of preparing corresponding high-value-added isobutene by using isobutane as a raw material. W has more applications in the petrochemical industry, and the synergistic effect of W and Cr can make the catalyst have better catalytic selectivity and activity. The invention uses Cr and/or W as the active component of the catalyst, and elements of the IIA and VB groups in the periodic table of elements are added in the preparation, thereby better solving the problems and having good application prospect.
Disclosure of Invention
The invention aims to solve the technical problem that the activity and selectivity of an isobutane dehydrogenation catalyst in the prior art are low, and provides a catalyst for producing isobutene by isobutane dehydrogenation. The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst corresponding to the first technical problem. The invention aims to solve the third technical problem and provides a catalyst corresponding to the first technical problem for producing the butylene by dehydrogenating the isobutane.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the catalyst for producing isobutene through isobutane dehydrogenation uses VIB group elements in the periodic table as main active components, at least one element in IIA group in the periodic table as an alkaline assistant, at least one element in IVB and VB groups in the periodic table as other assistants, and a carrier is silicon-aluminum oxide. Wherein the carrier is treated by a hot solution containing elements in the IIA group of the periodic table of elements, and then other components are loaded to obtain 100-300 m2A dehydrogenation catalyst with an average pore diameter of 2-20 nm.
The specific surface area and pore structure analysis instrument adopts a physical adsorption instrument TriStar3000 of American Mike instruments company, and the analysis steps are as follows: accurately weighing the sample, putting the sample and the sample tube into an adsorption instrument, selecting the whole process of measuring speed (generally medium speed), specific surface area and pore structure according to the requirement, starting clicking, and automatically testing. The test result processing generally selects multipoint BET specific surface area, adsorption and desorption curve and corresponding pore structure parameters.
The catalyst comprises, by weight, 1-30 parts of VIB group elements, and 0-5 parts, 0-6 parts and 0-10 parts of IIA group elements, IVB group elements and VB group elements.
In the technical scheme, the specific surface area of the prepared dehydrogenation catalyst is 100-250 m as known by a physical-chemical adsorption and desorption instrument2(ii)/g, the average pore diameter is 3-18 nm.
In the technical scheme, the more preferable range of the specific surface area of the prepared dehydrogenation catalyst is 120-240 m2(ii)/g, the average pore diameter is 5-15 nm.
In the technical scheme, the parts of Cr and/or W elements or oxides thereof are 5-25 parts by weight of the isobutane catalyst.
In the technical scheme, the parts of Cr and/or W elements or oxides thereof are 10-20 parts by weight of the isobutane catalyst.
In the above technical solution, it is more preferable that the alloy simultaneously includes Cr and W elements or oxides thereof, wherein the weight ratio of Cr to W element is: (0.1-9): 1. in the above technical solution, preferably, the alloy simultaneously includes Cr and W elements or oxides thereof, wherein the weight ratio of Cr to W elements is: (0.25-4): 1.
in the technical scheme, the part of the element selected from the IIA group of the periodic table or the oxide thereof is 0.01-3 parts by weight of the isobutane catalyst, wherein the element selected from the IIA group is at least one of Mg, Ca and Ba.
In the technical scheme, the part of the element selected from IVB group of the periodic table or the oxide thereof is 0.01-5 parts by weight of the isobutane catalyst, wherein the element of IVB group is selected from at least one of Ti and Zr.
In the above technical solution, more preferably, the range of group ivb element or oxide thereof in the periodic table of elements is 0.3 to 3 parts, and the group ivb element or oxide thereof is selected from Ti and Zr, Ti: the weight ratio of Zr is (0.25-3): 1.
In the technical scheme, the part of the element selected from the VB group in the periodic table or the oxide thereof is 0.01-5 parts by weight of the isobutane catalyst, wherein the element selected from the VB group is at least one of V, Nb and Ta.
In the above technical solution, it is more preferable that the group vb element of the periodic table or the oxide thereof is a mixture of V and Nb.
In the above technical solution, it is more preferable that the group vb element of the periodic table or an oxide thereof is a mixture of V and Ta.
In the technical scheme, the preferable range of the part of the element selected from the VB group in the periodic table or the oxide thereof is 0.2-3 parts by weight of the isobutane catalyst.
In the above embodiments, the group vb element or its oxide is a mixture of V, Nb and Ta, which is the most preferable embodiment. In the technical scheme, the adopted silicon-aluminum oxide carrier can be silicon oxide, aluminum oxide or a mixture of the silicon oxide and the aluminum oxide.
To solve the second technical problem, the invention adopts the following technical scheme: a catalyst carrier for producing isobutene by isobutane dehydrogenation is characterized in that the carrier is modified and prepared by a hydrothermal method, and the catalyst carrier comprises the following steps:
a) weighing a certain amount of soluble bauxite and a soluble salt of group IIA of the periodic Table of elements to contact;
b) adding a proper amount of alkali, and adjusting the pH value to 8-10 to enable the salt to form a colloid; transferring the obtained sample into a high-pressure kettle, and carrying out hydrothermal reaction for 10-72 hours at the temperature of 110-200 ℃;
c) and cooling, washing and filtering the sample obtained by the hydrothermal process to obtain a solid sample, and drying and roasting the solid sample to obtain the catalyst carrier.
In the above-mentioned embodiment, the a) aluminum source may be one or more of boehmite, aluminum hydroxide, aluminum nitrate, aluminum chloride, aluminum sulfate, etc., and the soluble salt of group iia of the periodic table of elements is preferably magnesium nitrate, calcium nitrate, barium nitrate, or their corresponding chlorides, sulfates, etc.
B) The base is preferably ammonia.
C) Cooling the sample to room temperature after hydrothermal treatment, and washing with deionized water for 3-5 timesNext, until Cl therein-、SO4 -The ion content is less than 50 ppm; drying at 60-150 ℃ for 2-24 hours; the roasting temperature is 400-800 ℃ and the roasting time is 2-24 h.
In the technical scheme adopted by the invention, the catalyst for isobutane dehydrogenation and the preparation method thereof comprise the following steps:
a) tabletting and screening a catalyst carrier to obtain a pretreated carrier I;
b) mixing a carrier I with a required amount of soluble salt (including but not limited to chromium nitrate, chromium chloride, alkali chromium sulfate, chromium potassium sulfate, potassium tungstate, sodium tungstate and the like) containing Cr and/or W and soluble salt (including but not limited to chloroplatinic acid, potassium tetrachloroplatinate and the like, and/or chlorate of Pd, Ru and Rh, an organic complex and the like) in IVB group and VB group of the periodic table of elements to obtain a mixture I, and adjusting the pH value of the mixture I to be 1-4 by using inorganic ammonia or an inorganic ammonium salt solution at the temperature of 10-80 ℃ to obtain a mixture II;
d) and (3) soaking the mixture II for 0.5-8 hours at the temperature of 10-100 ℃, filtering, drying, and roasting at 300-800 ℃ for 0.5-12 hours to obtain the required isobutane dehydrogenation catalyst.
The soluble salt of Cr can be selected from one of nitrate, acetate or oxalate; the W soluble salt is selected from tungstate, metatungstate or acetate. Ti and Zr are selected from one of nitrate, acetate and other soluble salts; v, Nb and Ta are selected from one of their nitrate, acetate and other soluble salts.
In the technical scheme, the preferable scheme of the inorganic ammonia or inorganic ammonium salt is selected from ammonia water, ammonium carbonate or ammonium bicarbonate, and the preferable range of the pH value of the solution is 1-7, and the more preferable range is 1-3; the preferred range of the dipping temperature is 50-80 ℃, the preferred range of the dipping time is 1-3 hours, the preferred range of the roasting temperature of the catalyst is 400-600 ℃, and the preferred range of the roasting time is 4-8 hours.
The third technical problem to be solved by the invention is that the technical scheme adopted by the invention is as follows: the reaction raw material is isobutane, and the reaction conditions are as follows: the reaction pressure is 0-1 MPa,The temperature is 520-650 ℃, and the mass space velocity is 0.1-10 h-1(ii) a The reaction raw material and the catalyst are contacted and reacted to obtain isobutene. The catalyst prepared by the method is subjected to activity evaluation in an isothermal fixed bed reactor, and the process for preparing isobutene by dehydrogenating isobutane is as follows:
the flow of isobutane is regulated through a mass flow meter, the isobutane enters a preheating zone to be preheated, and then enters a reaction zone, a heating zone and a reaction zone of a reactor are heated by adopting electric heating wires to reach a preset temperature, and the reactor is a reaction tube with the inner diameter of phi 9 mm-phi 6mm and the length of 400-580 mm. The reacted gas passes through a condensing tank and enters a gas phase chromatography for analyzing the composition of the gas.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: loading about 0.5 g of catalyst into isothermal reactor with internal diameter of phi 9 mm-phi 6mm, reaction pressure being normal pressure and gas mass space velocity of 1.0 hr-1And the reaction temperature was 540 ℃. The conversion rate of the isobutane is obtained by multiplying the sum of the isobutane content in all gas-phase products after reaction by 100%; selectivity of isobutene as the percentage of isobutene content in other gaseous components except isobutane after reaction, i.e. isobutene content divided by C1、C2、C3And the percentage of the sum of the isobutene contents.
The Cr catalyst used in the direct dehydrogenation of isobutane has low activity due to the strong acidity of the surface and easy carbon deposition. The element W of the VIB group has various variable valence states, Cr and/or W are combined, and the alkaline earth metal element IIA is added to effectively change the acid-base distribution and the like on the surface of the catalyst, so that the catalyst has higher selectivity, and elements such as Ti, Zr and the like in the IVA can disperse active components and can also improve the strength of a carrier; and the catalyst is cooperated with V, Nb, Ta and other elements in VB to further improve the catalytic activity site. The catalyst obtained by adopting the conditions is used for isobutane dehydrogenation reaction, the isobutane conversion rate is 57%, the isobutene selectivity is 95%, and a good technical effect is achieved.
Drawings
FIG. 1 is a graph showing the adsorption and desorption curves of the dehydrogenation catalyst obtained in the present invention
FIG. 2 is a graph showing the pore size distribution of the dehydrogenation catalyst obtained in the present invention.
In the figure, catalyst 1 is the adsorption and desorption curve and the pore size distribution diagram of the sample obtained in example 1 of the present invention, catalyst 2 is the adsorption and desorption curve and the pore size distribution diagram of the sample obtained in example 2 of the present invention, and catalyst 3 is the adsorption and desorption curve and the pore size distribution diagram of the sample obtained in comparative example 1 of the present invention.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 220 ml of water are weighed, 3.70 g of magnesium nitrate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then moved into an autoclave and kept for 24 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 650 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 79 g of chromium nitrate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate, adding the chromium nitrate, the sodium titanate and the ammonium vanadate into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst is 180m2G, average pore diameter 7nm, as in catalyst 1 in FIG. 1.
The flow of isobutane gas is regulated through a mass flow meter, the isobutane gas enters a preheating zone to be preheated, and then enters a reaction zone, a heating zone and a reaction zone of a reactor are heated by adopting electric heating wires to reach a preset temperature, and the inner diameter of the reactor is a quartz tube with the phi 6mm, and the length of the quartz tube is about 400 mm. The reacted gas was passed through a condensing pot and then analyzed for composition by gas chromatography.
Catalyst evaluation conditions in isothermal fixed bed reactorThe following were used: 0.5 g of the catalyst is loaded into the isothermal fixed bed reactor, the reaction pressure is normal pressure, and the gas mass space velocity is 1.0 hour-1And the reaction temperature was 540 ℃. The results are shown in Table 1.
[ example 2 ]
Weighing 500 g of silica sol with the solid content of 20%, adding 100 ml of water, simultaneously adding 3.70 g of magnesium nitrate, stirring for 30 minutes, dropwise adding ammonia water to form sol, standing the sol overnight, then transferring the sol into a high-pressure kettle, keeping the sol in the high-pressure kettle for 24 hours at the temperature of 150 ℃, then cooling the sample, and washing the sample for 3 times by using deionized water; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 650 deg.C for 4 hr to obtain silica carrier. 100 g of silica was pressed into tablets, sieved and designated as carrier I. Weighing 79 g of chromium nitrate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate, adding the chromium nitrate, the sodium titanate and the ammonium vanadate into 100 ml of deionized water, then adding 82 g of silicon oxide carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, then soaking the solution in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to roast the sample at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 218m2G, average pore diameter 9nm, as catalyst 2 in FIG. 1. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 3 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then is moved into an autoclave and kept for 48 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 650 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. 79 g of chromium nitrate, 1.26 g of sodium titanate and 12.14 g of niobium oxalate are weighed and added into 100 ml of deionized water, 82 g of alumina carrier I is added, and the pH value of the solution is adjusted to 3.5 by using 2.5 percent ammonia water, thenThen soaking in water bath at 80 ℃ for 1 hour, taking out the sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 172m2G, average pore diameter of 12 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 4 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.01 g of magnesium sulfate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.3, the sol is placed overnight and then is moved into an autoclave and kept for 60 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 650 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 79 g of chromium nitrate, 1.26 g of sodium titanate and 3.42 g of sodium tantalate, adding the chromium nitrate, the sodium titanate and the sodium tantalate into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst is 199m2G, average pore diameter 10 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 5 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.3, the sol is placed overnight and then is moved into an autoclave and kept for 60 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain oxygenAn alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 16.4 g of ammonium tungstate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate, adding the weighed materials into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 126m2G, average pore diameter of 13 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 6 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then is moved into an autoclave and kept for 60 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 10 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 16.4 g of ammonium tungstate, 1.26 g of sodium titanate and 12.14 g of niobium oxalate, adding the materials into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 175m2G, average pore diameter 10 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 7 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water were weighed, 2.38 g of magnesium chloride was added simultaneously, the mixture was stirred for 30 minutes, ammonia was added dropwise to maintain the pH at 9.5, the sol was left to stand overnight and then transferredPlacing the mixture into an autoclave, keeping the mixture at 150 ℃ for 60 hours, cooling the sample, washing the sample with deionized water for 3 times until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 16.4 g of ammonium tungstate, 1.26 g of sodium titanate and 3.42 g of sodium tantalate, adding the materials into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 220m2G, average pore diameter 8 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 8 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 0.24 g of magnesium chloride is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then is moved into an autoclave and kept for 24 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 79 g of chromium nitrate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate, adding the chromium nitrate, the sodium titanate and the ammonium vanadate into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst is 241m2G, average pore diameter 6 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 9 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 4.76 g of magnesium chloride is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then moved into an autoclave and kept for 72 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 79 g of chromium nitrate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate, adding the chromium nitrate, the sodium titanate and the ammonium vanadate into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 163m2G, average pore diameter of 12 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 10 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 2.93 g of calcium nitrate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then moved into an autoclave and kept for 24 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 79 g of chromium nitrate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate, adding the chromium nitrate, the sodium titanate and the ammonium vanadate into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and putting the sample into a muffle furnaceCalcining at 550 deg.C for 4 hr to obtain the desired catalyst. The specific surface area of the catalyst is 146m2G, average pore diameter of 13 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 11 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 1.70 g of barium nitrate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then is moved into an autoclave and kept for 24 hours at the temperature of 150 ℃, then the sample is cooled and washed for 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 79 g of chromium nitrate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate, adding the chromium nitrate, the sodium titanate and the ammonium vanadate into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst is 212m2G, average pore diameter 7 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 12 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added simultaneously, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 10, the sol is placed overnight and then is moved into an autoclave and kept for 24 hours at 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. 79 g of chromium nitrate, 3.70 g of magnesium nitrate and 1.26 g of titanic acid were weighedSodium, 3.45 g of ammonium vanadate and 6.08 g of niobium oxalate are added into 100 ml of deionized water, 82 g of alumina carrier I is added, the pH value of the solution is adjusted to 3.5 by using 2.5% ammonia water, the solution is immersed in a water bath at 80 ℃ for 1 hour, then a sample is taken out and filtered, the sample is dried in an oven at 120 ℃ for 8 hours, and then the sample is placed into a muffle furnace to be roasted at 550 ℃ for 4 hours, so that the required catalyst is obtained. The specific surface area of the catalyst is 130m2G, average pore diameter 14 nm. The isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 13 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 8.5, the sol is placed overnight and then is moved into an autoclave and kept for 60 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 79 g of chromium nitrate, 1.26 g of sodium titanate, 3.45 g of ammonium vanadate and 1.71 g of sodium tantalate, adding into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 169m2G, average pore diameter 10 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 14 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water were weighed, 3.70 g of magnesium nitrate was added simultaneously, the mixture was stirred for 30 minutes, ammonia was added dropwise to maintain the pH at 9.5, the sol was left overnight and then transferred to an autoclave and maintained at 150 ℃ for 24 hours, and then the sample was cooledHowever, deionized water was washed 3 times until the filtrate was Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 650 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. 16.4 g of ammonium tungstate, 1.26 g of sodium titanate, 3.45 g of ammonium vanadate and 6.08 g of niobium oxalate were weighed and added to 100 ml of deionized water, and 82 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier I with the pore diameter of 15nm to 7 by using 2.5% ammonia water, soaking in a water bath at the temperature of 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at the temperature of 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at the temperature of 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 188m2G, average pore diameter 9 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 15 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then is moved into an autoclave and kept for 60 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 16.4 g of ammonium tungstate, 1.26 g of sodium titanate, 3.45 g of ammonium vanadate and 1.71 g of sodium tantalate, adding into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 1 by using 2.5% ammonia water, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 156m2G, average pore diameter of 12 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 16 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added simultaneously, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then transferred into an autoclave and kept at 180 ℃ for 24 hours, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 47.2 g of chromium oxalate, 1.26 g of sodium titanate, 2.3 g of ammonium vanadate, 4.05 g of niobium oxalate and 1.14 g of sodium tantalate, adding into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 5 by using 2.5% ammonia water, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 183m2G, average pore diameter 11 nm. The isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 17 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.01 g of magnesium sulfate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then transferred into an autoclave and kept for 24 hours at 180 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 16.4 g of ammonium tungstate, 1.26 g of sodium titanate, 2.3 g of ammonium vanadate, 4.05 g of niobium oxalate and 1.14 g of sodium tantalate, adding into 100 ml of deionized water, adding 82 g of specific surface area alumina carrier I, adjusting the pH value of the solution to 3 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour,and taking out the sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 151m2G, average pore diameter of 13 nm. The reaction of the raw material of iso-butane with the above catalyst was carried out under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 18 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.01 g of magnesium sulfate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.0, the sol is placed overnight and then transferred into an autoclave and kept for 48 hours at 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. 39.5 g of chromium nitrate, 3.89 g of tungsten acetate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate are weighed and added into 100 ml of deionized water, 82 g of alumina carrier I is added, the pH value of the solution is adjusted to 3.5 by using 2.5% ammonia water, then the solution is immersed in a water bath at 50 ℃ for 1 hour, a sample is taken out and filtered, the sample is dried in an oven at 120 ℃ for 8 hours, and then the sample is put into a muffle furnace and roasted at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 139m2G, average pore diameter of 15 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 19 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 2.38 g of magnesium chloride is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then is moved into an autoclave and kept for 60 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. Get100 grams of alumina was tableted, sieved and designated as Carrier I. Weighing 13.17 g of chromium nitrate, 2.73 g of ammonium tungstate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate, adding into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 199m2G, average pore diameter 8 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 20 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added simultaneously, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then transferred into an autoclave and kept for 60 hours at 180 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 650 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. 65.83 g of chromium nitrate, 13.63 g of ammonium tungstate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate are weighed and added into 100 ml of deionized water, 82 g of alumina carrier I is added, the pH value of the solution is adjusted to 3.5 by using 2.5% ammonia water, then the solution is immersed in a water bath at 50 ℃ for 1 hour, a sample is taken out and filtered, the sample is dried in an oven at 120 ℃ for 8 hours, and then the sample is put into a muffle furnace and roasted at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst is 215m2G, average pore diameter 6 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 21 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water were weighed, 3.70 g of magnesium nitrate was added simultaneously, the mixture was stirred for 30 minutes, ammonia was added dropwise to maintain the pH at 9.5, and the sol was placedStanding overnight, transferring into autoclave, maintaining at 150 deg.C for 60 hr, cooling sample, washing with deionized water for 3 times until filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 650 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. 26.33 g of chromium nitrate, 5.46 g of ammonium tungstate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate are weighed and added into 100 ml of deionized water, 82 g of alumina carrier I is added, the pH value of the solution is adjusted to 3.5 by using 2.5% ammonia water, then the solution is immersed in a water bath at 50 ℃ for 1 hour, a sample is taken out and filtered, the sample is dried in an oven at 120 ℃ for 8 hours, and then the sample is put into a muffle furnace and roasted at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 207m2G, average pore diameter 7 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 22 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then is moved into an autoclave and kept for 72 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 650 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 52.66 g of chromium nitrate, 10.93 g of ammonium tungstate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate, adding the mixture into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 211m2G, average pore diameter 8 nm. The isobutane raw material and the catalyst are reacted under the same reaction conditionThe reaction was carried out under the same conditions as in example 1, and the results are shown in Table 1.
[ example 23 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then is moved into an autoclave and kept for 24 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 650 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 39.5 g of chromium nitrate, 8.2 g of ammonium tungstate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate, adding into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 165m2G, average pore diameter 11 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 24 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then is moved into an autoclave and kept for 60 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. 39.5 g of chromium nitrate, 8.2 g of ammonium tungstate, 1.26 g of sodium titanate and 12.15 g of niobium oxalate are weighed, added into 100 ml of deionized water, 82 g of silicon oxide carrier I is added, the pH value of the solution is adjusted to 3.5 by using 2.5% ammonia water, and then the solution is put into a water bath at 50 DEG CAfter 1 hour of immersion, the sample was taken out and filtered, dried in an oven at 120 ℃ for 8 hours, and then calcined in a muffle furnace at 550 ℃ for 4 hours to obtain the desired catalyst. The specific surface area of the catalyst was 183m2G, average pore diameter of 13 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 25 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added simultaneously, the mixture is stirred for 30 minutes, ammonia is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then transferred into an autoclave and kept at 180 ℃ for 48 hours, then the sample is cooled and washed 3 times with deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 700 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. 39.5 g of chromium nitrate, 8.2 g of ammonium tungstate, 1.26 g of sodium titanate and 3.42 g of sodium tantalate are weighed and added into 100 ml of deionized water, 82 g of alumina carrier I is added, the pH value of the solution is adjusted to 3.5 by using 2.5% ammonia water, then the solution is immersed in a water bath at 50 ℃ for 1 hour, a sample is taken out and filtered, the sample is dried in an oven at 120 ℃ for 8 hours, and then the sample is put into a muffle furnace and roasted at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst is 232m2G, average pore diameter 6 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 26 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added simultaneously, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 10, the sol is placed overnight and then is moved into an autoclave and kept for 48 hours at 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 700 deg.C for 4 hr to obtain oxygenAn alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. 39.5 g of chromium nitrate, 8.2 g of ammonium tungstate, 1.26 g of sodium titanate, 3.45 g of ammonium vanadate and 6.08 g of niobium oxalate are weighed and added into 100 ml of deionized water, 82 g of alumina carrier I is added, the pH value of the solution is adjusted to 3.5 by using 2.5% ammonia water, then the solution is immersed in a water bath at the temperature of 50 ℃ for 1 hour, a sample is taken out and filtered, the sample is dried in an oven at the temperature of 120 ℃ for 8 hours, and then the sample is put into a muffle furnace and roasted at the temperature of 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 181m2G, average pore diameter 10 nm. The isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 27 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added simultaneously, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 10, the sol is placed overnight and then transferred into an autoclave and kept for 24 hours at 180 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 15.8 g of chromium nitrate, 13.12 g of ammonium tungstate, 1.26 g of sodium titanate, 3.45 g of ammonium vanadate and 6.08 g of niobium oxalate, adding the materials into 100 ml of deionized water, adding 82 g of aluminum oxide carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and baking the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 161m2G, average pore diameter of 12 nm. The isobutane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 28 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added simultaneously, and the mixture is stirred for 30After minutes, ammonia was added dropwise to maintain the pH at 9.5, the sol was allowed to stand overnight, then transferred to an autoclave and maintained at 150 ℃ for 72 hours, then the sample was cooled and washed 3 times with deionized water until the filtrate contained Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 700 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 63.2 g of chromium nitrate, 3.28 g of ammonium tungstate, 1.26 g of sodium titanate, 3.45 g of ammonium vanadate and 6.08 g of niobium oxalate, adding the materials into 100 ml of deionized water, adding 82 g of aluminum oxide carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and baking the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst is 197m2G, average pore diameter 10 nm. The isobutane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 29 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.0, the sol is placed overnight and then moved into an autoclave and kept for 48 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 700 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. 39.5 g of chromium nitrate, 8.2 g of ammonium tungstate, 1.26 g of sodium titanate, 3.45 g of ammonium vanadate and 1.71 g of sodium tantalate are weighed, added into 100 ml of deionized water, 82 g of alumina carrier I is added, the pH value of the solution is adjusted to 3.5 by using 2.5% ammonia water, then the solution is immersed in a water bath at 50 ℃ for 1 hour, a sample is taken out and filtered, the sample is dried in an oven at 120 ℃ for 8 hours, and then the sample is put into a muffle furnace and roasted at 550 ℃ for 4 hours to obtain the required catalyst. The catalyst has a specific surface area of182m2G, average pore diameter 11 nm. The isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 30 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added at the same time, the mixture is stirred for 1 hour, ammonia water is added dropwise to keep the pH value at 9.0, the sol is placed overnight and then moved into an autoclave and kept for 60 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 700 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 15.8 g of chromium nitrate, 13.12 g of ammonium tungstate, 1.26 g of sodium titanate, 3.45 g of ammonium vanadate and 1.71 g of sodium tantalate, adding the chromium nitrate, the ammonium tungstate, the sodium titanate, the ammonium vanadate and the sodium tantalate into 100 ml of deionized water, adding 82 g of an aluminum oxide carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and baking the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 179m2G, average pore diameter of 12 nm. The isobutane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 31 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then is moved into an autoclave and kept for 48 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 700 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. 63.2 g of chromium nitrate, 3.28 g of ammonium tungstate, 1.26 g of sodium titanate, 3.45 g of ammonium vanadate and 1.71 g of sodium tantalate are weighed and addedAdding 82 g of alumina carrier I into 100 ml of deionized water, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and baking the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 189m2G, average pore diameter 10 nm. The isobutane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 32 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added simultaneously, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 10, the sol is placed overnight and then moved into an autoclave and kept for 72 hours at 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 700 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. 39.5 g of chromium nitrate, 8.2 g of ammonium tungstate, 1.26 g of sodium titanate, 2.3 g of ammonium vanadate, 4.05 g of niobium oxalate and 1.14 g of sodium tantalate are weighed and added into 100 ml of deionized water, 82 g of alumina carrier I is added, the pH value of the solution is adjusted to 3.5 by using 2.5% ammonia water, then the solution is immersed in a water bath at 50 ℃ for 1 hour, a sample is taken out and filtered, the sample is dried in an oven at 120 ℃ for 8 hours, and then the sample is put into a muffle furnace and roasted at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst is 125m2G, average pore diameter of 15 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 33 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water were weighed, 3.70 g of magnesium nitrate was added simultaneously, the mixture was stirred for 2 hours, ammonia was added dropwise to maintain the pH at 9.5, the sol was left overnight and then transferred to an autoclave and maintained at 150 ℃ for 60 hours, and then the sample was cooled and deionizedWashing with water 3 times until Cl is in the filtrate-、SO4 -An ion content of less than 50 ppm; drying at 120 deg.C for 6 hr, transferring into muffle furnace, and calcining at 650 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 15.8 g of chromium nitrate, 13.12 g of ammonium tungstate, 1.26 g of sodium titanate, 2.3 g of ammonium vanadate, 4.05 g of niobium oxalate and 1.14 g of sodium tantalate, adding into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 187m2G, average pore diameter 11 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
[ example 34 ]
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added simultaneously, the mixture is stirred for 30 minutes, ammonia is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then transferred into an autoclave and kept at 180 ℃ for 48 hours, then the sample is cooled and washed 3 times with deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 120 deg.C for 4 hr, transferring into muffle furnace, and calcining at 650 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 63.2 g of chromium nitrate, 3.28 g of ammonium tungstate, 1.26 g of sodium titanate, 2.3 g of ammonium vanadate, 4.05 g of niobium oxalate and 1.14 g of sodium tantalate, adding into 100 ml of deionized water, adding 84 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 176m2G, average pore diameter 11 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1The results are shown in Table 1.
Comparative example 1
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, stirred for 30 minutes, ammonia is added dropwise to maintain the pH value at 9.0, the sol is placed overnight and then transferred into an autoclave and maintained at 150 ℃ for 48 hours, then the sample is cooled and washed 3 times with deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was tableted and sieved and designated as carrier I. 63.2 g of chromium nitrate, 3.28 g of ammonium tungstate and 1.26 g of sodium titanate are weighed, added into 100 ml of deionized water, then 82 g of alumina carrier I is added, the pH value of the solution is adjusted to 3.5 by using 2.5% ammonia water, then the solution is immersed in a water bath at 50 ℃ for 1 hour, a sample is taken out and filtered, the sample is dried in an oven at 120 ℃ for 8 hours, and then the sample is placed into a muffle furnace to be roasted at 550 ℃ for 4 hours, so that the required catalyst is obtained. The specific surface area of the catalyst was 171m2G, average pore diameter 3.5nm, as catalyst 3 in FIG. 1. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
Comparative example 2
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, stirred for 30 minutes, ammonia is added dropwise to maintain the pH value at 9.5, the sol is placed overnight and then moved into an autoclave and maintained at 180 ℃ for 24 hours, then the sample is cooled and washed 3 times with deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 700 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was tableted and sieved and designated as carrier I. Weighing 16.4 g of ammonium tungstate and 1.26 g of sodium titanate, adding the ammonium tungstate and the sodium titanate into 100 ml of deionized water, adding 85 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in water bath at 50 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, putting the sample into a muffle furnace, and baking the sample at 550 DEG CThe desired catalyst was obtained by firing for 4 hours. The specific surface area of the catalyst was 136m2G, average pore diameter 17 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
Comparative example 3
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, 3.70 g of magnesium nitrate is added at the same time, the mixture is stirred for 30 minutes, ammonia water is added dropwise to keep the pH value at 9.5, the sol is placed overnight and then is moved into an autoclave and kept for 60 hours at the temperature of 150 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 16.4 g of ammonium tungstate and 3.70 g of magnesium nitrate, adding the ammonium tungstate and the magnesium nitrate into 100 ml of deionized water, adding 84 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to roast the sample at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 85m2G, average pore diameter of 22 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
Comparative example 4
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, stirred for 30 minutes, ammonia is added dropwise to maintain the pH value at 10, the sol is placed overnight, then the sol is transferred into an autoclave and maintained at 180 ℃ for 24 hours, then the sample is cooled and washed 3 times with deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 700 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was tableted and sieved and designated as carrier I. 79 g of chromium nitrate, 0.68 g of sodium carbonate and 3.03 g of ferric nitrate are weighed, added into 100 ml of deionized water, and 82 g of alumina carrier is addedI, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, then soaking the solution in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in a 120 ℃ oven for 8 hours, and then roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst is 98m2G, average pore diameter 21 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
Comparative example 5
1372.4 g of aluminum nitrate, 5.94 g of PVA and 300 ml of water are weighed, stirred for 30 minutes, ammonia is added dropwise to maintain the pH value at 9.5, the sol is placed overnight and then transferred into an autoclave and maintained at 150 ℃ for 60 hours, then the sample is cooled and washed 3 times with deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 700 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was tableted and sieved and designated as carrier I. Weighing 15.8 g of chromium nitrate and 13.12 g of ammonium tungstate, adding the chromium nitrate and the ammonium tungstate into 100 ml of deionized water, adding 85 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst was 89m2G, average pore diameter 21 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
Comparative example 6
1372.4 g of aluminum nitrate, 5.94 g of PVA and 220 ml of water are weighed, 3.70 g of magnesium nitrate is added simultaneously, ammonia water is added dropwise while stirring directly to keep the pH value at 14, the sol is placed overnight and then is moved into an autoclave and kept for 24 hours at the temperature of 100 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 650 deg.C for 4 hr to obtainAn alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 79 g of chromium nitrate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate, adding the chromium nitrate, the sodium titanate and the ammonium vanadate into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 6.5 by using 2.5% ammonia water, soaking the solution in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst is 350m2G, average pore diameter of 1.4 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
Comparative example 7
1372.4 g of aluminum nitrate, 5.94 g of PVA and 220 ml of water are weighed, 3.70 g of magnesium nitrate is added simultaneously, stirring is carried out for 30 minutes, ammonia water is added dropwise to keep the pH value at 12, the sol is placed overnight and then is moved into an autoclave and kept for 36 hours at 80 ℃, then the sample is cooled and washed 3 times by deionized water until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 150 deg.C for 6 hr, transferring into muffle furnace, and calcining at 750 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 79 g of chromium nitrate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate, adding the chromium nitrate, the sodium titanate and the ammonium vanadate into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 750 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst is 60m2G, average pore diameter of 27 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
Comparative example 8
1372.4 g of aluminum nitrate, 5.94 g of PVA and 220 ml of water were weighed, 3.70 g of magnesium nitrate was added simultaneously, the mixture was stirred for 30 minutes, ammonia was added dropwise to maintain the pH at 12, the sol was left to stand overnight and then transferred to a high temperatureKeeping the temperature in a pressure kettle at 210 ℃ for 24 hours, then cooling the sample, washing the sample with deionized water for 3 times until the filtrate contains Cl-、SO4 -An ion content of less than 50 ppm; drying at 100 deg.C for 6 hr, transferring into muffle furnace, and calcining at 750 deg.C for 4 hr to obtain alumina carrier. 100 g of alumina was pressed into tablets, sieved and designated as carrier I. Weighing 79 g of chromium nitrate, 1.26 g of sodium titanate and 6.9 g of ammonium vanadate, adding the chromium nitrate, the sodium titanate and the ammonium vanadate into 100 ml of deionized water, adding 82 g of alumina carrier I, adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water, soaking the solution in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The specific surface area of the catalyst is 45m2G, average pore diameter 33 nm. Isobutane feed was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in table 1.
TABLE 1
Claims (10)
1. A catalyst for producing isobutene by dehydrogenating isobutane comprises a main active component of an element in the VIB group of the periodic table of elements, an alkaline auxiliary agent of at least one element in the IIA group of the periodic table of elements, other auxiliary agents of at least one element in the IVB group and the VB group of the periodic table of elements, and a silicon-aluminum oxide serving as a carrier; the specific surface area of the dehydrogenation catalyst is 100-300 m2(ii)/g, the average pore diameter is 2-20 nm.
2. The catalyst for producing isobutene through isobutane dehydrogenation according to claim 1, characterized in that the specific surface area of the dehydrogenation catalyst is 100-250 m as characterized by sample adsorption-desorption2A specific surface area of 120 to 240m is preferred, wherein the average pore diameter is 3 to 18nm2(iv)/g, average pore diameter is 5-15 nm.
3. The catalyst for producing isobutene through isobutane dehydrogenation according to claim 1, wherein the component taking an element in group VIB of the periodic table of elements as a main active component is 5-25 parts by weight of Cr and/or W element or an oxide thereof based on the parts by weight of the isobutane catalyst.
4. The catalyst for dehydrogenating isobutane to produce isobutene as claimed in claim 3, characterized by the fact that the elements Cr and W are selected from the group VIB elements in the weight ratio: (0.1-9): 1.
5. the catalyst for producing isobutene through isobutane dehydrogenation according to claim 1, wherein the component of the group IIA of the periodic table of elements is used as an auxiliary agent, and the part of the component is 0.01-5 parts by weight based on the part by weight of the isobutane catalyst, wherein the element of the group IIA is selected from at least one of Mg, Ca and Ba;
and the IVB group component is an auxiliary agent, and the parts are 0.01-5 parts by weight of the isobutane catalyst, wherein the IVB group element is selected from at least one of Ti and Zr.
Preferably, the range of the IVB group element or the oxide thereof is 0.3-3 parts, and the IVB group element or the oxide thereof is selected from Ti and Zr, wherein the ratio of Ti: the weight ratio of Zr is (0.25-3): 1.
6. The catalyst for producing isobutene through isobutane dehydrogenation according to claim 1, wherein the component of group vb of the periodic table of elements is used as an auxiliary agent, and the part of the component is 0.01-5 parts by weight based on the part by weight of the isobutane catalyst, wherein the element of group vb is selected from at least one of V, Nb and Ta; preferably V and Nb, or preferably V and Ta; or V, Nb and Ta are preferred.
7. A catalyst carrier for producing isobutene by isobutane dehydrogenation is characterized in that the carrier is modified and prepared by a hydrothermal method and comprises the following steps:
a) contacting soluble bauxite with a soluble salt of group IIA of the periodic Table of elements;
b) adding a proper amount of alkali, and adjusting the pH value to 8-10 to enable the salt to form a colloid; transferring the obtained colloidal sample into a high-pressure kettle, and carrying out hydrothermal reaction for 10-72 hours at the temperature of 110-200 ℃;
c) and further comprising the steps of cooling, washing and filtering the sample obtained by the hydrothermal process to obtain a solid sample, and drying and roasting the solid sample to obtain the catalyst carrier.
8. The catalyst support for the dehydrogenation of isobutane to produce isobutene according to claim 7, characterized in that the support preparation comprises:
A) the aluminum source is selected from one or more of boehmite, aluminum hydroxide, aluminum nitrate, aluminum chloride and aluminum sulfate, and the soluble salt of the IIA group in the periodic table of elements is preferably magnesium nitrate, calcium nitrate and barium nitrate or the corresponding chloride and sulfate thereof;
B) the alkali is preferably ammonia water;
C) cooling the hydrothermal sample, washing with water for 3-5 times, and adding Cl in the washed solution-、SO4 -The ion content is less than 50 ppm; drying at 60-150 ℃ for 2-24 hours; the roasting temperature is 400-800 ℃, and the roasting time is 2-24 h.
9. A preparation method of a catalyst for producing isobutene by isobutane dehydrogenation is characterized by comprising the following steps:
a) tabletting and screening a catalyst carrier to obtain a pretreated carrier I;
b) mixing a carrier I with a required amount of soluble salt (including but not limited to chromium nitrate, chromium chloride, basic chromium sulfate, chromium potassium sulfate, potassium tungstate, sodium tungstate and the like) containing Cr and/or W and soluble salt (including but not limited to titanium nitrate, alpha-titanic acid, zirconium nitrate, zirconium chloride, ammonium vanadate, sodium vanadate, potassium vanadate, niobium or tantalum oxalate, niobium or tantalum nitrate, tantalum and the like) in IVB group and VB group to obtain a mixture I, and adjusting the pH value of the mixture I to be within a range of 1-4 by using inorganic ammonia or an inorganic ammonium salt solution to obtain a mixture II;
c) and filtering and drying the mixture II to obtain the required isobutane dehydrogenation catalyst.
10. A method for dehydrogenating isobutane by using the catalyst of any one of claims 1 to 15 under the following reaction conditions: the reaction pressure is 0-1 MPa, the temperature is 520-650 ℃, and the mass space velocity is 0.1-10 h-1(ii) a The reaction raw material is directly contacted with the catalyst for reaction to obtain the isobutene.
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| CN115779885A (en) * | 2021-09-10 | 2023-03-14 | 中国石油化工股份有限公司 | Light hydrocarbon dehydrogenation catalyst and preparation method and application thereof |
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