CN106040271B - 一种丙烷脱氢制丙烯用催化剂及其制备方法 - Google Patents
一种丙烷脱氢制丙烯用催化剂及其制备方法 Download PDFInfo
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- CN106040271B CN106040271B CN201610371582.3A CN201610371582A CN106040271B CN 106040271 B CN106040271 B CN 106040271B CN 201610371582 A CN201610371582 A CN 201610371582A CN 106040271 B CN106040271 B CN 106040271B
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- Prior art keywords
- catalyst
- oxide
- predecessor
- phosphate
- chromium
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 239000001294 propane Substances 0.000 title claims abstract description 29
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 18
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010452 phosphate Substances 0.000 claims abstract description 18
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 15
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 4
- 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 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 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 6
- 238000001035 drying Methods 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 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 description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 3
- 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 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical group [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 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
- 230000008859 change Effects 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
- 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 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- -1 phosphate radical Chemical class 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- 239000012695 Ce precursor Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 5
- 235000021317 phosphate Nutrition 0.000 description 11
- 230000000694 effects Effects 0.000 description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- BNQYBOIDDNFHHC-UHFFFAOYSA-N chromium;oxalic acid Chemical compound [Cr].OC(=O)C(O)=O BNQYBOIDDNFHHC-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
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical class [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical class [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019785 monomagnesium phosphate Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 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
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2527/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
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Abstract
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。该催化剂是以磷酸盐处理氧化铝为载体，以氧化铬为活性组分，以碱金属和/或碱土金属和/或过渡金属氧化物为助剂，以所述氧化铝的重量计，所述磷酸盐重量为0.1～10％，所述氧化铬的负载量为5～15％，所述碱金属或碱土金属或过渡金属氧化物的负载量为0.05～1％。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
本发明属于催化脱氢技术领域，涉及丙烷脱氢制丙烯用催化剂，尤其是一种丙烷脱氢制丙烯用催化剂及其制备方法。
背景技术
丙烷脱氢制丙烯过程因日益增加的丙烯需求而受到广泛关注并得到工业应用。在丙烷脱氢催化剂中，氧化铬催化剂具有活性高、价格低、对原料纯度要求低等优点，但催化剂容易积碳而需要频繁的再生过程，影响了其催化能力的充分发挥，大大降低了设备的生产能力，因此对催化剂的酸性进行调节是降低积碳的有效方法。
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。
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。
催化剂载体所具有的酸性可以提高催化剂的活性，但过强的酸性又会导致催化剂容易发生积碳，采用碱金属或碱土金属氧化物可有效降低酸性强度，但又会对催化剂的活性造成不利影响，因此，对催化剂的酸性进行适度调节是保证催化剂具有较高活性和较低积碳量的有效方法。
发明内容
本发明的目的在于克服现有技术的不足之处，提供一种高催化活性、高烯烃选择性、抗积碳性能好的丙烷脱氢制丙烯用催化剂及其制备方法，该催化剂提高了烯烃收率、降低了催化剂再生频率。
本发明解决技术问题所采用的技术方案是：
一种丙烷脱氢制丙烯用催化剂，该催化剂以磷酸盐处理氧化铝作为载体，以氧化铬为活性组分，以碱金属和/或碱土金属和/或过渡金属氧化物为助剂。
而且，所述磷酸盐质量百分含量为0.1～10％，以所述氧化铝的重量计。
而且，所述氧化铬的负载量为5～15％，所述助剂的负载量为0.05～1％，均以所述氧化铝的重量计。
而且，磷酸盐的阴离子为磷酸根、磷酸氢根、磷酸二氢根，优选为磷酸二氢根；磷酸盐的阳离子为锂、钠、钾、钙、镁、锌、锡，优选为钠。
而且，碱金属为钠、钾、锂中的一种或几种组合，优选为钠。
碱土金属为镁、钙、锶、钡中的一种或几种组合，优选为钙。
过渡金属为钛、锆、镧、铈中的一种或几种组合，优选为锆。
一种丙烷脱氢制丙烯用催化剂的制备方法，步骤如下：
⑴磷酸盐处理氧化铝载体采用等体积浸渍或过量浸渍法制备，将磷酸盐溶解在水中制成均匀的溶液，加入到氧化铝载体中，搅拌均匀，室温干燥2～24h，100℃干燥1～18h，500-800℃下煅烧2～6h，制得磷酸盐处理氧化铝载体；
⑵以磷酸盐处理的氧化铝为载体负载氧化铬催化剂采用等体积浸渍或过量浸渍法或喷涂法制备，将氧化铬前驱物和碱金属和/或碱土金属和/或过渡金属前驱物溶解到水中制成均匀的溶液，加入到上述磷酸盐处理的氧化铝载体中，搅拌均匀，成型后室温干燥2～24h，100℃干燥2～18h，500-900℃下煅烧2～8h，得到丙烷脱氢制丙烯用催化剂。
而且，所述的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。
而且，所述的碱金属前驱物或碱土金属前驱物为硝酸盐、乙酸盐、氢氧化物，优选为硝酸盐；所述的过渡金属前驱物为氧化锆前驱物、氧化镧前驱物、氧化铈前驱物、氧化钛前驱物。
而且，所述的氧化锆前驱物为硝酸锆、碱式碳酸锆，优选为硝酸锆。；所述的氧化镧前驱物为硝酸镧、碱式碳酸镧，优选为硝酸镧；所述的氧化铈前驱物为硝酸铈、碱式碳酸铈，优选为硝酸铈；所述的氧化钛前驱物为乙醇钛、异丙醇钛、硝酸钛，优选为乙醇钛。
本发明所述催化剂成型的机器包括压片机、辊式制粒机、制丸机、挤条机等，成型后的形状包括球形、片状、圆柱体、星形、三叶形。
而且，丙烷脱氢制丙烯反应条件为：反应温度为580-630℃，反应压力为0.01-1MPa，丙烷空速为150-1000h-1。
本发明的优点和积极效果是：
本发明采用碱式磷酸盐处理氧化铝作为载体，采用磷酸根来增加催化剂的中强酸强度，增加催化剂的活性；同时阳离子碱可减弱氧化铝中强酸的强度，抑制了积碳的生成，在保证高催化活性的同时，具有良好的高温稳定性。
附图说明
图1为本发明催化剂的XRD图。
具体实施方式
下面通过具体实施例对本发明作进一步详述，以下实施例只是描述性的，不是限定性的，不能以此限定本发明的保护范围。
实施例1：
称取0.1g磷酸氢二钠溶解在10ml的水中，加入20gγ-氧化铝，搅拌30min，室温干燥12h，100℃干燥4h，600℃下煅烧4h，得到磷酸盐处理氧化铝载体20.1g，其中氧化钠/氧化铝重量比为0.11％，五氧化二磷/氧化铝重量比为0.25％。
将乙酸铬6.02g、硝酸钠0.10g和硝酸锆0.17g溶解在10ml水中，加入上述磷酸盐处理氧化铝载体20.1g，搅拌30min后，室温干燥18h，采用压片机压制成片状，100℃干燥12h，750℃煅烧6h，制得丙烷脱氢催化剂A，其中氧化铬/氧化铝重量比为10％，氧化锆/氧化铝重量比为0.5％，氧化钠/氧化铝重量比为0.3％，五氧化二磷/氧化铝重量比为0.25％。
实施例2：
称取0.077g磷酸二氢镁溶解在10ml的水中，加入20gγ-氧化铝，搅拌30min，室温干燥12h，100℃干燥4h，600℃下煅烧6h，得到磷酸盐处理氧化铝载体20.1g，其中氧化镁/氧化铝重量比为0.07％，五氧化二磷/氧化铝重量比为0.25％。
将乙酸铬6.02g、硝酸钠0.27g和硝酸锆0.17g溶解在10ml水中，加入上述磷酸盐处理氧化铝载体20.1g，搅拌30min后，室温干燥18h，采用压片机压制成片状，100℃干燥12h，750℃煅烧6h，制得丙烷脱氢催化剂B，其中氧化铬/氧化铝重量比为10％，氧化锆/氧化铝重量比为0.5％，氧化钠/氧化铝重量比为0.3％，氧化镁/氧化铝重量比为0.07％，五氧化二磷/氧化铝重量比为0.25％。
上述实施例1得到的催化剂A及实施例2得到的催化剂B的物理性质如表1所示。
表1各实施例得到催化剂的物理性质
实施例3：
采用实施例1～2中所述催化剂A和催化剂B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，催化剂粉碎后筛取20～50目催化剂10g装到固定床反应器中，反应温度为590℃，反应压力为0.05MPa，丙烷空速为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40min后，本发明催化剂的活性均高于55％，丙烯选择性没有明显降低，说明催化剂的活性高、稳定性较好。
以上所述的仅是本发明的优选实施方式，应当指出，对于本领域的普通技术人员来说，在不脱离发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。
Claims (8)
1.一种丙烷脱氢制丙烯用催化剂，其特征在于：该催化剂以磷酸盐处理氧化铝作为载体，以氧化铬为活性组分，以碱金属和/或碱土金属和/或过渡金属氧化物为助剂，磷酸盐的阴离子为磷酸根、磷酸氢根、磷酸二氢根，磷酸盐的阳离子为锂、钠、钾、钙、镁，所述磷酸盐质量百分含量为0.1～10％，以所述氧化铝的重量计。
2.根据权利要求1所述的催化剂，其特征在于：所述氧化铬的负载量为5～15％，所述助剂的负载量为0.05～1％，均以所述氧化铝的重量计。
3.根据权利要求1所述的丙烷脱氢制丙烯用催化剂，其特征在于：碱金属为钠、钾、锂中的一种或几种组合，碱土金属为镁、钙、锶、钡中的一种或几种组合，过渡金属为钛、锆、镧、铈中的一种或几种组合。
4.一种权利要求1所述的丙烷脱氢制丙烯用催化剂的制备方法，步骤如下：
⑴将磷酸盐溶解在水中制成均匀的溶液，加入到氧化铝载体中，搅拌均匀，室温干燥2～24h，100℃干燥1～18h，500-800℃下煅烧2～6h，制得磷酸盐处理氧化铝载体；
⑵将氧化铬前驱物和碱金属和/或碱土金属和/或过渡金属前驱物溶解到水中制成均匀的溶液，加入到上述磷酸盐处理的氧化铝载体中，搅拌均匀，成型后室温干燥2～24h，100℃干燥2～18h，500-900℃下煅烧2～8h，得到丙烷脱氢制丙烯用催化剂。
5.根据权利要求4所述的制备方法，其特征在于：所述的氧化铬前驱物为硝酸铬、铬酸、乙酰丙酮铬、乙酸铬、草酸铬。
6.根据权利要求4所述的制备方法，其特征在于：所述的碱金属前驱物或碱土金属前驱物为硝酸盐、乙酸盐、氢氧化物；所述的过渡金属前驱物为氧化锆前驱物、氧化镧前驱物、氧化铈前驱物、氧化钛前驱物。
7.根据权利要求6所述的制备方法，其特征在于：所述的氧化锆前驱物为硝酸锆、碱式碳酸锆；所述的氧化镧前驱物为硝酸镧、碱式碳酸镧；所述的氧化铈前驱物为硝酸铈、碱式碳酸铈；所述的氧化钛前驱物为乙醇钛、异丙醇钛、硝酸钛。
8.根据权利要求1所述的丙烷脱氢制丙烯用催化剂，其特征在于：丙烷脱氢制丙烯反应条件为：反应温度为580-630℃，反应压力为0.01-1MPa，丙烷空速为150-1000h-1。
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| CN107715862B (zh) * | 2017-09-30 | 2020-09-25 | 大连理工大学 | 一种抗积碳铬基丙烷脱氢制丙烯催化剂、制备方法及应用 |
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| CN109289831A (zh) * | 2018-10-09 | 2019-02-01 | 天津科技大学 | 具有高抗积碳性的丙烷脱氢制丙烯的催化剂及其制备方法 |
| CN109331811A (zh) * | 2018-11-06 | 2019-02-15 | 中国科学院兰州化学物理研究所苏州研究院 | 介孔铬铝复合氧化物催化剂及其制备方法与应用 |
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| CN113145102A (zh) * | 2020-01-22 | 2021-07-23 | 中国石油天然气股份有限公司 | 一种负载型催化剂及其制备与应用 |
| CN113058586A (zh) * | 2021-03-31 | 2021-07-02 | 四川大学 | 用于二氧化碳氧化低碳烷烃制烯烃的催化剂及其制备方法 |
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