CN105727930A - 一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用 - Google Patents
一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用 Download PDFInfo
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- CN105727930A CN105727930A CN201610156988.XA CN201610156988A CN105727930A CN 105727930 A CN105727930 A CN 105727930A CN 201610156988 A CN201610156988 A CN 201610156988A CN 105727930 A CN105727930 A CN 105727930A
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- Prior art keywords
- catalyst
- oxide
- chromium
- zirconium
- alumina
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000001294 propane Substances 0.000 title claims abstract description 35
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 23
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 46
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 21
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical group [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- VCRLKNZXFXIDSC-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[Al+3].[Zr+4] VCRLKNZXFXIDSC-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 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 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- HVXCTUSYKCFNMG-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O-2].[Zr+4].[Al+3] HVXCTUSYKCFNMG-UHFFFAOYSA-N 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 2
- 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 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 claims description 2
- 238000012661 block copolymerization Methods 0.000 claims 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 238000011068 loading method Methods 0.000 abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 3
- 230000008021 deposition Effects 0.000 abstract 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 10
- 239000004317 sodium nitrate Substances 0.000 description 5
- 235000010344 sodium nitrate Nutrition 0.000 description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 229910001948 sodium oxide Inorganic materials 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- ODPUKHWKHYKMRK-UHFFFAOYSA-N cerium;nitric acid Chemical compound [Ce].O[N+]([O-])=O ODPUKHWKHYKMRK-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- NTWUDWUVKKRQRK-UHFFFAOYSA-N aluminum;cerium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Ce+3] NTWUDWUVKKRQRK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- -1 boron Hydrocarbon Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- FTWGTNVTSDGLFG-UHFFFAOYSA-N nitric acid zirconium Chemical compound [Zr].O[N+]([O-])=O FTWGTNVTSDGLFG-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/26—Chromium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
本发明提供了一种用于丙烷直接脱氢制丙烯的催化剂及其制备方法与应用。该催化剂是以规整介孔氧化铝?氧化锆或氧化铝?氧化铈复合氧化物为载体,以氧化铬为活性组分,以碱金属氧化物为助剂,以所述氧化铝的重量计,所述氧化锆或氧化铈的含量为2~10%,所述氧化铬的负载量为5~15%,所述碱金属氧化物的负载量0.05~0.5%。本发明还提供了上述催化剂的制备方法及其在丙烷脱氢制丙烯领域的应用。本发明的丙烷脱氢制丙烯催化剂,具有较高的丙烷转化率和较高的丙烯选择性,并可抑制积碳的生成,具有良好的高温稳定性。
Description
技术领域
本发明涉及一种用于丙烷直接脱氢制丙烯的催化剂及其制备方法,确切的说涉及一种以规整介孔氧化铝-氧化锆或氧化铝-氧化铈复合物为载体负载氧化铬的负载型催化剂及其制备方法,属于石油化工领域,特别是催化脱氢技术领域。
背景技术
丙烯作为重要的化工原料,需求量逐年增加。丙烯主要来源于蒸汽裂解和催化裂化副产,其供应很大程度上受乙烯和汽、柴油的制约,难以通过单纯的蒸汽裂解扩能来满足要求,因此,采用丙烷脱氢反应是生产丙烯的重要补充途径。
丙烷脱氢制丙烯包括丙烷直接脱氢和丙烷氧化脱氢。丙烷氧化脱氢是在氧气或二氧化碳存在下进行脱氢反应,可以在较低温度下达到较高的丙烷转化率,但由于丙烯容易深度氧化,降低了丙烯的选择性。丙烷直接脱氢是目前丙烷脱氢制丙烯的工业生产方式。
目前已经工业化的丙烷直接脱氢制丙烯催化剂主要有铂基催化剂和氧化铬基催化剂。
在丙烷脱氢催化剂中,氧化铬催化剂具有活性高、价格低、对原料杂质要求低等优点,但催化剂容易积碳失活而需要频繁的再生,大大降低了设备的生产能力。
专利CN101940922公开了一种低碳烃脱氢催化剂及其制备方法,首先采用混捏法制备含铬氧化铝载体,然后采用浸渍法负载铬和碱金属,提高了氧化铬的含量,提高了催化剂活性,催化剂稳定性有所提高。
专利CN104148070和CN104209123分别公开了含有骨架银和骨架硼的低碳烃脱氢催化剂及其制备方法,采用含有银或硼的氧化铝作为载体,氧化铬为活性组分,钠、钾、钙、镁、铜、锆、铈、银为助剂,骨架银或硼的引入提高了催化剂的稳定性和抗积碳能力。
专利CN 104128175公开了一种水热稳定性好的低碳烃脱氢催化剂及其制备方法,向氧化铝中添加镁、锌,制成尖晶石结构的复合载体后负载氧化铬、碱金属或碱土金属氧化物作为助剂,镁和锌的引入增加了催化剂的水热稳定性,防止催化剂在再生期间发生粉化。
专利CN103769156公开了一种脱氢催化剂及其制备方法,采用氨处理氧化铝为载体,铬为活性组分,以钾和锰、钴、铁、镍、铜、锌为助剂,具有氧化铬含量低、活性高、丙烯选择性好等优点。
丙烷脱氢催化剂的积碳主要是催化剂中酸性过强造成的,采用碱金属或碱土金属氧化物可有效降低酸性强度,但存在分布不均匀的缺点,因此,对氧化铝骨架的酸性进行调控可有效降低催化剂的酸性,增加抗积碳能力。
发明内容
本发明的目的是针对丙烷脱氢制备丙烯的反应过程,提供一种高催化活性、高烯烃选择性、抗积碳性能好的催化剂,提高烯烃产率、降低催化剂再生频率。
本发明的目的还在于提供上述催化剂的制备方法。
为达到上述目的,本发明提供了一种丙烷脱氢制丙烯用催化剂,该催化剂以规整介孔氧化铝-氧化锆或氧化铝-氧化铈复合氧化物作为载体,以氧化铬为活性组分,以碱金属氧化物为助剂;以所述氧化铝的重量计,所述氧化锆或氧化铈的含量为2~10%,所述氧化铬的负载量为5~15%,所述碱金属氧化物的负载量0.05~0.5%。
根据本发明所述的催化剂,碱金属为钠、钾、锂中的一种或几种组合,优选为钠。
根据本发明所述的催化剂,氧化铝-氧化锆或氧化铝-氧化铈复合氧化物载体采用模板法制备得到。
模板法包含以下步骤:
按照模板剂:氧化铝的摩尔比为1:10-1:50的比例,将模板剂溶解在无水乙醇中,制得溶液1;按照氧化锆:氧化铝的重量比例为1:10-1:50的比例将氧化锆前驱物和氧化铝前驱物溶解在68-70%的硝酸水溶液中,制得溶液2;将溶液2加入到溶液1中,搅拌0.5-4h后,30-70℃下加热24-72h蒸去溶剂,残余物在500-900℃下煅烧3-8h,得到复合氧化物。
所述氧化铝-氧化铈复合氧化物的制备方法与所述氧化铝-氧化铈复合氧化物的制备方法相同。
根据本发明所述催化剂,氧化铝前驱物为异丙醇铝、硝酸铝、铝酸钠,优选为异丙醇铝。
根据本发明所述催化剂,氧化锆前驱物为硝酸锆、碱式碳酸锆,优选为硝酸锆。
根据本发明所述催化剂,氧化铈前驱物为硝酸铈、碱式碳酸铈,优选为硝酸铈。
根据本发明所述催化剂,模板剂为嵌段共聚物P123、嵌段共聚物F127、十二烷基三甲基溴化胺、十四烷基三甲基溴化胺、十六烷基三甲基溴化胺,优选为嵌段共聚物P123。
本发明还提供了上述丙烷脱氢制丙烯用催化剂的制备方法,该方法包括以下步骤:
将氧化铬前驱物和碱金属前驱物溶解到水中制成均匀的溶液,加入到上述氧化铝-氧化锆或氧化铝-氧化铈复合氧化物载体中,搅拌均匀,成型后室温干燥12~24h,100℃干燥2~18h,500-900℃下煅烧2~8h,得到丙烷脱氢用催化剂。
根据本发明所述催化剂,氧化铬前驱物为硝酸铬、铬酸、三氧化铬、乙酰丙酮铬、乙酸铬、草酸铬,优选为铬酸和乙酸铬,更优选为乙酸铬。
根据本发明所述催化剂,氧化钠前驱物为硝酸钠、乙酸钠、氢氧化钠,优选为硝酸钠。
本发明所述催化剂成型的机器为压片机、辊式制粒机、制丸机、挤条机等,成型后的形状为球形、片状、圆柱体、星形、三叶形。
本发明所述催化剂在丙烷脱氢制丙烯时,反应温度为550-650℃,反应压力为0.01-1MPa,丙烷空速为150-1000h-1,丙烷转化率大于50%,丙烯选择性高于90%,催化剂再生间隔时间为30min。
本发明的优点:
1、本发明采用规整介孔氧化铝-氧化锆或氧化铝-氧化铈复合氧化物载体,可充分利用载体本身均匀的孔道结构,提高了氧化铬在载体上的分散度,同时降低了丙烷和丙烯的传质阻力,从而提高了催化效率。
2、本发明采用氧化锆或氧化铈来调整氧化铝的酸结构,抑制了积碳的生成,具有良好的高温稳定性。
具体实施方式
实施例1:
复合载体制备:
称取58g P123溶解在1000ml的无水乙醇中,制得溶液1;称取硝酸锆3.3g,异丙醇铝81.6g溶解在500ml 70%的硝酸水溶液中,制得溶液2;将溶液2在30min内滴加到溶液1中,搅拌4h至完全混合。将溶液缓慢加热到60℃,保持温度下加热48h,蒸去溶剂后得到白色粉末,650℃下煅烧4h,得到复合氧化物载体21.6g。
催化剂负载:
将乙酸铬6.2g和硝酸钠0.16g溶解在10ml水中,加入上述氧化铝-氧化锆复合氧化物21.6g,搅拌30min后,室温干燥18h,100℃干燥12h,750℃煅烧6h,采用压片机压制成片状,制得丙烷脱氢催化剂A。该催化剂中氧化锆的含量为5.9%、氧化铬的负载量为10%、氧化钠的负载量0.3%,以上均以氧化铝的重量计。
实施例2:
复合载体制备:
称取58g P123溶解在1000ml的无水乙醇中,制得溶液1;称取硝酸铈4.6g,异丙醇铝81.6g溶解在500ml 70%的硝酸水溶液中,制得溶液2;将溶液2在30min内滴加到溶液1中,搅拌4h至完全混合。将溶液缓慢加热到60℃,保持温度下加热42h,蒸去溶剂后得到白色粉末,650℃下煅烧4h,得到氧化铝-氧化铈复合氧化物载体。
催化剂负载:
将乙酸铬7.4g和硝酸钠0.16g溶解在10ml水中,加入上述氧化铝-氧化铈复合氧化物22.4g,搅拌30min后,室温干燥24h,100℃干燥12h,750℃煅烧6h,采用压片机压制成片状,制得丙烷脱氢催化剂B。该催化剂中氧化铈的含量为9.8%、氧化铬的负载量为12%、氧化钠的负载量0.3%,以上均以氧化铝的重量计。
实施例3:
复合载体制备与实施例1相同。
催化剂负载:
将乙酸铬6.2g和硝酸钠0.16g溶解在8.2ml水中,加入上述氧化铝-氧化锆复合氧化物21.6g,搅拌30min后,挤条成型,室温干燥24h,100℃干燥12h,750℃煅烧6h,制得丙烷脱氢催化剂C。该催化剂中氧化锆的含量为5.9%、氧化铬的负载量为10%、氧化钠的负载量0.3%,以上均以氧化铝的重量计。
上述实施例得到的催化剂的物理性质如表1。
表1各实施例得到催化剂的物理性质
催化剂A | 催化剂B | 催化剂C | |
Cr2O3/Al2O3重量比 | 0.1 | 0.12 | 0.1 |
Na2O/Al2O3重量比 | 0.003 | 0.003 | 0.003 |
比表面积,m2/g | 123.2 | 118.2 | 120.3 |
孔容,cm3/g | 0.45 | 0.38 | 0.42 |
孔径,nm | 4.3 | 4.3 | 4.3 |
堆密度,g/cm3 | 1.213 | 1.208 | 1.023 |
实施例4:
采用实施例1~3中所述催化剂A、催化剂B和催化剂C在常压微反装置中进行丙烷脱氢反应,采用固定床反应器,反应器内径20mm,催化剂装填量为10g,反应温度为590℃,反应压力为0.05MPa,丙烷气体空速为300h-1,丙烷转化率和丙烯选择性见表2。
表2实施例中催化剂催化丙烷脱氢的反应性能
从表2的结果可知,在实验进行30min后,本发明催化剂的活性、选择性均没有明显降低,说明催化剂的稳定性较好,催化剂使用寿命长。
Claims (10)
1.一种用于丙烷脱氢制丙烯的催化剂,其特征在于:该催化剂是以规整介孔氧化铝-氧化锆或氧化铝-氧化铈复合氧化物作为载体,以氧化铬为活性组分,以碱金属氧化物为助剂;以所述氧化铝的重量计,所述氧化锆或氧化铈的含量为2~10%、所述氧化铬的负载量为5~15%、所述碱金属氧化物的负载量0.05~0.5%。
2.根据权利要求1所述催化剂,其特征在于:所述氧化铝-氧化锆或氧化铝-氧化铈复合氧化物载体采用模板法制备得到,该模板法包含以下步骤:
⑴按照模板剂:氧化铝的摩尔比为1:10-1:50的比例,将模板剂溶解在无水乙醇中,制得溶液①;
⑵按照氧化锆或氧化铈:氧化铝的重量比例为1:10-1:50的比例将氧化锆或氧化铈前驱物和氧化铝前驱物溶解在68-70%的硝酸水溶液中,制得溶液②;
⑶将溶液②加入到溶液①中,搅拌0.5-4h后,30-70℃下加热24-72h蒸去溶剂,残余物在500-900℃下煅烧3-8h,得到复合氧化物。
3.根据权利要求2所述催化剂,其特征在于:所述氧化铝前驱物为异丙醇铝、硝酸铝、铝酸钠。
4.根据权利要求2所述催化剂,其特征在于:所述氧化锆前驱物为硝酸锆、碱式碳酸锆。
5.根据权利要求2所述催化剂,其特征在于:所述氧化铈前驱物为硝酸铈、碱式碳酸铈。
6.根据权利要求2所述催化剂,其特征在于:所述模板剂为嵌段共聚物P123、嵌段共聚物F127、十二烷基三甲基溴化胺、十四烷基三甲基溴化胺、十六烷基三甲基溴化胺。
7.根据权利要求1所述催化剂,其特征在于:所述碱金属为钠、钾、锂中的一种或几种组合。
8.根据权利要求1所述催化剂,其特征在于:所述氧化铬,其前驱物为硝酸铬、铬酸、三氧化铬、乙酰丙酮铬、乙酸铬、草酸铬。
9.一种权利要求1所述催化剂的制备方法,其特征在于:步骤如下:
将氧化铬前驱物和碱金属前驱物溶解到水中制成均匀的溶液,将该溶液加入到上述氧化铝-氧化锆或氧化铝-氧化铈复合氧化物载体中,搅拌均匀,成型后室温干燥12~24h,100℃干燥2~18h,500-900℃下煅烧2~8h,得到丙烷脱氢用催化剂。
10.一种权利要求1所述催化剂在丙烷脱氢制丙烯中的应用,其特征在于:脱氢反应操作条件如下:反应温度为550-650℃,反应压力为0.01-1MPa,丙烷空速为150-1000h-1。
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