CN114405515B - 一种梯级孔复合金属氧化物催化剂和制备方法及其应用 - Google Patents
一种梯级孔复合金属氧化物催化剂和制备方法及其应用 Download PDFInfo
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- CN114405515B CN114405515B CN202210118869.0A CN202210118869A CN114405515B CN 114405515 B CN114405515 B CN 114405515B CN 202210118869 A CN202210118869 A CN 202210118869A CN 114405515 B CN114405515 B CN 114405515B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 39
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 31
- 239000011148 porous material Substances 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 8
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 239000011651 chromium Substances 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 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 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 239000011591 potassium Substances 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 239000010937 tungsten Substances 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
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- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 230000032683 aging Effects 0.000 claims description 23
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 22
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- 150000001875 compounds Chemical class 0.000 claims description 21
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 13
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 8
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 8
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- -1 benzoic aldehydes Chemical class 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000011863 silicon-based powder Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 4
- 244000275012 Sesbania cannabina Species 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
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- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
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- 239000008117 stearic acid Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 239000010703 silicon Substances 0.000 abstract description 4
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- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
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- 239000002994 raw material Substances 0.000 abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
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- 238000004438 BET method Methods 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
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- 238000013329 compounding Methods 0.000 description 2
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
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- 235000012239 silicon dioxide Nutrition 0.000 description 2
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- 239000011787 zinc oxide Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910002519 Co-Fe 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
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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Classifications
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/651—50-500 nm
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Abstract
本发明涉及一种梯级孔复合金属氧化物催化剂和制备方法及其应用。所述梯级孔复合金属氧化物催化剂,其特征在于,具有介孔和大孔,化学式表示为Mo12BiaCobFecXdYeZfOg,其中X为钒或钨元素的一种或二种;Y为银、铜、铁、锰、钴、铬、镍、铈、锌、钾、铯或锑元素的化合物中的一种或两种以上;Z为铝、硅、锌、钛元素的一种或二种以上;a=0.5~2,b=3~10,c=1.5~6,d=0~0.5,e=0.1~6,f=0.5~4,g是满足其他元素的氧化状态的数值。本发明采用超声辅助制备复合金属氧化物催化剂,在制备过程中通过超声辅助、分步加入纳米分散剂和高分子造孔剂,制备出具有介孔‑大孔梯级孔径分布的复合金属氧化物催化剂,使其在选择氧化反应中表现出优异原料转化率和产物选择性。
Description
技术领域
本发明涉及一种超声辅助梯级孔复合金属氧化物催化剂、其制备方法及应用,属催化剂技术领域。
背景技术
低级烯烃催化氧化生产α,β-不饱和醛酮反应已被广泛工业化应用,例如丙烯选择氧化为丙烯醛,异丁烯选择氧化制甲基丙烯醛等。以异丁烯选择氧化制甲基丙烯醛为例,目前该反应催化剂的研究多是以Mo-Bi-Co-Fe为基础的复合氧化物体系,反应过程中易生成较多副产物:丙酮、异丁醛、乙酸、甲基丙烯酸等。由于该催化剂制备的传统方法多采用共沉淀法,存在颗粒团聚、活性组分分散不均匀等问题,比表面积较小(3m2/g左右),且反应为强放热反应,反应热若不能及时移走,催化剂表面会形成“局部过热点”,导致深度氧化加剧,产品收率降低;更可能导致催化剂高温烧结,破坏活性结构,严重降低催化剂使用寿命,使生产成本加大、生产能力受限。因此,提高催化剂活性和选择性的关键在于改善催化剂的孔结构。
许多专利和文献也针对复合氧化物催化剂进行了相关孔性质的研究,通过改变孔径分布来提高催化剂的性能:CN 112675866A,公开了一种针对烯丙基氧化反应的复合金属氧化物催化剂,通过在制备催化剂过程中引入微波和扩孔剂,极大的缩短了制备时间、改善了孔道结构,异丁烯转化率高达99.9%,甲基丙烯醛选择性达到96.2%。CN 101066528A,公开了一种含Mo、Bi、卤素、硅的烯烃氧化用催化剂,其比表面积在5~25m2/g,细孔容积在0.2~0.7cc/g,孔容积在0.2~0.7cc/g,0.03以下的细孔约占总细孔容积的10%以下,0.03~0.1μm的细孔约占总细孔容积的30%以上、0.1~1μm的细孔约占总细孔容积内的20%以上,该专利公布的催化剂形成梯级孔道结构,丙烯转化率高达99%、丙烯醛选择性大于95%。
基于已有的研究结果,针对现有催化剂的缺点和不足,本发明提出了一种采用超声辅助制备具有梯级孔结构的复合金属氧化物催化剂的方法及应用。
发明内容
本发明的目的在于一种梯级孔复合金属氧化物催化剂、其制备方法及应用,在催化剂制备过程中采用超声辅助,通过加入纳米分散剂增加催化剂介孔结构;在催化剂成型过程中通过加入高分子造孔剂增加催化剂大孔结构;最终实现制备出具有介孔-大孔梯级孔径分布的复合金属氧化物催化剂目的。介孔结构可以大幅度地增加催化剂比表面积,增多催化剂所暴露的活性位,有效提升催化剂的使用效率;大孔结构有利于增加催化剂的通透性,能及时移走反应产物,减小生成COx的过度氧化反应,提高催化剂的催化性能,具有广泛的工业应用前景。
为实现上述目的,本发明提供的技术方案为:
一种梯级孔复合金属氧化物催化剂,具有介孔-大孔,化学式表示为Mo12BiaCobFecXdYeZfOg,其中X为钒或钨元素的一种或二种;Y为银、铜、铁、锰、钴、铬、镍、铈、锌、钾、铯或锑元素的化合物中的一种或两种以上;Z为铝、硅、锌、钛元素的一种或二种以上;a=0.5~2,b=3~10,c=1.5~6,d=0~0.5,e=0.1~6,f=0.5~4,g是满足其他元素的氧化状态的数值。
所述催化剂在20nm以下(比如2~15nm)和50~900nm(优选50~500nm)处出现梯级的介孔-大孔复合结构,比表面积2~30m2/g,孔容0.1~0.6cm3/g,平均孔径50~700nm,堆密度0.8~1.5g/mL。
进一步地,催化剂在大孔级(50-900nm,优选50-500nm)所占比例在60%以上,优选在70%以上,更优选在80%以上。
本发明还公开了该催化剂的制备方法,包括如下步骤:
(1)将含钼,以及含钒或钨元素的化合物搅拌加入水中,得到均匀的溶液A;
(2)将含铋元素的化合物搅拌加入硝酸溶液中,得到均匀的溶液B;
(3)将含银、铜、铁、锰、钴、铬、镍、铈、锌、钾、铯或锑元素的化合物中的一种或两种以上搅拌加入水中,得到均匀的溶液C;
溶液A、B、C的配制在超声波辅助下进行,并且在其中一种或多种溶液中加入纳米分散剂;
(4)在超声波辅助下,将溶液B和溶液C同时滴加至搅拌的溶液A中,继续超声并搅拌,得到均匀的混合溶液;
(5)在超声波辅助下将步骤(4)的混合溶液搅拌老化,老化温度为20~100℃,老化时间为1~24h;
(6)将步骤(5)所得混合溶液经干燥得到复合金属氧化物催化剂粉末;
(7)将步骤(6)所得复合金属氧化物催化剂粉末与高分子造孔剂按照质量比100:1~5进行掺混,混合均匀后成型、焙烧,得到复合金属氧化物催化剂颗粒。
在上述技术方案的基础上,本发明还可以对上述的技术方案作出如下的改进:
进一步,所述含钼元素的化合物为三氧化钼、硝酸钼或钼酸铵;所述含钒元素的化合物为五氧化二钒或偏钒酸铵,优选偏钒酸铵;所述含钨元素的化合物为三氧化钨、钨酸铵;所述含铋元素的化合物为硝酸铋或乙酸铋;所述含银、铜、铁、锰、钴、铬、镍、铈、锌、钾、铯或锑元素的化合物为相应元素的硝酸盐或乙酸盐。在配制溶液A、B、C时,各物质的添加量满足最终所得复合金属氧化物的上述化学式Mo12BiaCobFecXdYeZfOg,其中X为钒或钨元素的一种或二种;Y为银、铜、铁、锰、钴、铬、镍、铈、锌、钾、铯或锑元素的化合物中的一种或两种以上;Z为铝、硅、锌、钛元素的一种或二种以上;a=0.5~2,b=3~10,c=1.5~6,d=0~0.5,e=0.1~6,f=0.5~4。
进一步,溶液A、B、C的配置都需用频率20~100kHz,功率100~500W的超声波辅助,超声时间10~50min,优选超声处理条件为频率20~60kHz,特别是40kHz;功率200~400W,超声时间15~40min,特别是15~30min;
更进一步,纳米分散剂加入溶液A、B、C中的一种或多种溶液中,优选加入溶液A中;纳米分散剂选择氧化铝、铝溶胶、二氧化硅、硅溶胶、钛白粉、氧化锌、硅粉等分散介质的一种或多种,优选钛白粉和硅粉按照质量比1-2:1-2的复配;分散剂的平均粒径为5~25nm;纳米分散剂与A、B、C混合液中金属离子摩尔比为1:10~50,优选1:15~30。
进一步,步骤(4)的溶液混合过程中,温度50-90℃,优选60-80℃,超声处理条件为频率20~100kHz,功率300~1000W,优选频率20~50kHz,功率500~800W;滴加完成后继续超声并搅拌10min~2h,优选20~60min。
进一步,步骤(5)的溶液老化过程中,超声处理条件为频率20~100kHz,功率500~1200W,时间为1~24h,优选20~50kHz功率600~1000W,时间为2~6h。
进一步,步骤(6)的干燥为高温蒸干或喷雾干燥。
进一步,步骤(7)中,高分子造孔剂选自羧甲基纤维素、聚丙烯酰胺、淀粉、聚乙烯醇、聚乙二醇、田菁粉、阿拉伯胶、硬脂酸的一种或多种;优选为聚乙二醇和羧甲基纤维素按照质量比3-5:1的复配。催化剂粉末与高分子造孔剂的质量比100:1~5,优选100:1.5~3。
发明人预料不到地发现,在溶液A、B、C的配制中使用钛白粉和硅粉复配的纳米分散剂,在步骤(7)高分子造孔剂采用聚乙二醇和羧甲基纤维素的复配,最终得到的复合金属氧化物催化剂具有稳定且丰富的介孔-大孔的结构,并且大孔占比较大。此孔径分布对快速放热类反应非常重要,介孔-大孔复合孔结构可明显提高该类反应速控步骤-传质过程的速率,特别是目的产物外扩散过程的速率,这可以大幅度提高目的产物的收率,防止催化剂结焦失活。
所述催化剂制备方法中催化剂成型形状为球形、三叶草条形、圆柱条形、拉西环。
所述催化剂制备方法中催化剂焙烧条件为焙烧温度350~800℃,焙烧时间2~10h,优选焙烧温度450~650℃,焙烧时间3~8h。
本发明制备得到的复合金属氧化物催化剂可以用于甲苯及其衍生物选择氧化生产苯醛类反应;或者用于丙烯、异丁烯、环己烯选择性氧化生产α,β-不饱和醛酮类反应中的应用。
本发明的特点和有益效果在于:
与现有的多相复合金属氧化物催化剂相比,本发明所制备的催化剂介孔孔道丰富、大孔结构明显增多,形成具有介孔-大孔特殊梯级孔结构的复合氧化物催化剂,该催化剂能够有效移走反应热、减轻深度氧化、提高产物收率;有效减少催化剂活性组分结构破坏与流失,延长催化剂使用寿命。与现有的工业催化剂体系相比,本发明提供的催化剂在这类反应过程中绿色友好,活性组分得到最大限度的利用,节约了成本,有望在工业上得到应用。
附图说明
图1为本发明实施例5和对比例所制催化剂的扫描电镜(SEM)照片;
图2为本发明实施例4、5与对比例所制催化剂孔径分布图。
具体实施方式
以下结合实例对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。
实施例1
一种超声辅助梯级孔复合金属氧化物催化剂的制备方法,步骤如下:
(1)取118.6g钼酸铵和6g二氧化硅(平均粒径15nm)加入110mL去离子水中,用超声仪在50kHz、300W条件下超声15min后得到均匀的溶液A1;
(2)取20g硝酸铋入30mL硝酸溶液中,用超声仪在50kHz、300W条件下超声15min后得到均匀的溶液B1;
(3)取55.3g硝酸钴、48.8g硝酸铁、18.1g硝酸锰、18.5g硝酸镍加入95mL去离子水中,用超声仪在50kHz、300W条件下超声15min后得到均匀的溶液C1;
(4)在60℃、30kHz、600W的超声条件下搅拌溶液A1,并将溶液B1和溶液C1一起滴加至溶液A1中,继续超声并搅拌30min后,得到均匀的混合溶液;
(5)将步骤(4)的混合溶液在30kHz、600W的超声条件下搅拌老化,老化温度为60℃,老化时间为3h;
(6)老化后,再经过180℃高温蒸干,得到复合金属氧化物粉末;
(7)将步骤(6)所得复合金属氧化物催化剂粉末与羧甲基纤维素按照质量比100:2进行掺混,混合均匀后成型,在540℃条件下焙烧6h,得到复合金属氧化物催化剂Mo12Bi1Co6Fe4Mn2Ni2Si2Ox。
实施例2
一种超声辅助梯级孔复合金属氧化物催化剂的制备方法,步骤如下:
(1)取118.6g钼酸铵、1.7g偏钒酸铵和8.2g的氧化锌(平均粒径10nm)加入120mL去离子水中,用超声仪在20kHz、300W条件下超声20min后得到均匀的溶液A2;
(2)取25g硝酸铋加入30mL硝酸溶液中,用超声仪在20kHz、300W条件下超声20min后得到均匀的溶液B2;
(3)取55.3g硝酸钴、48.8g硝酸铁、18.1g硝酸锰、43.8g硝酸铈加入95mL去离子水中,用超声仪在20kHz、300W条件下超声20min后得到均匀的溶液C2;
(4)在70℃、40kHz、800W的超声条件下搅拌溶液A2,并将溶液B2和溶液C2一起滴加至溶液A2中,继续超声并搅拌40min后,得到均匀的混合溶液;
(5)将步骤(4)的混合溶液在40kHz、800W的超声条件下搅拌老化,老化温度为80℃,老化时间为4h;
(6)老化后,再经过180℃喷雾干燥,得到复合金属氧化物粉末;
(7)将步骤(6)所得复合金属氧化物催化剂粉末与田菁粉按照质量比100:2进行掺混,混合均匀后成型,在550℃条件下焙烧6h,得到复合金属氧化物催化剂Mo12Bi1.25Co6Fe4V0.3Mn2Ce2Zn2Ox。
实施例3
其他条件和实施例1相同,区别在于步骤(1)中纳米分散剂为2.9g硅粉(平均粒径15nm)、4g钛白粉(平均粒径20nm)。
实施例4
其他条件和实施例1相同,区别在于步骤(7)中造孔剂为聚乙烯醇和羧甲基纤维素按照质量比5:1的复配。
实施例5
其他条件和实施例1相同,区别在于步骤(1)中纳米分散剂为2.9g硅粉(平均粒径15nm)、4g钛白粉(平均粒径20nm);以及步骤(7)中造孔剂为聚乙烯醇和羧甲基纤维素按照质量比5:1的复配。
对比例
(1)取118.6g钼酸铵和1.7g偏钒酸铵溶于110mL去离子水中,得到溶液A';
(2)取20g硝酸铋溶于30mL硝酸溶液,得到溶液B';
(3)取55.3g硝酸钴、38g硝酸铜、18.1g硝酸锰溶于95mL去离子水中,得到溶液C';
(4)在80℃条件下,搅拌溶液A',并将溶液B'和溶液C'一起滴加至溶液A'中,继续搅拌30min后,得混合溶液;
(5)将步骤(4)的混合溶液搅拌老化,老化温度为85℃,老化时间为4h;
(6)老化后,再经过200℃喷雾干燥,得到复合金属氧化物粉末;
(7)将步骤(6)的粉末在530℃条件下焙烧4h,得复合金属氧化物催化剂Mo12Bi1Co6Fe4V0.3Mn2Cu4Ox。
性能测试对比
1.扫描电镜(SEM)
见图1,实施例5和对比例所制催化剂,通过扫描电镜观察催化剂的微观结构;
由SEM图可以看出,实施例5制得的催化剂与对比例制得的催化剂相比,实施例5表现出丰富且均匀的孔道分布结构,这将极大地提高反应物吸附与反应产物的扩散速率,有利于改善催化剂的催化活性。
2.孔径分布图
见图2,取实施例5制得的催化剂,通过BET法和压汞法测定其孔径分布。由图2可知,实施例5制得的催化剂具有更适宜的介孔-大孔梯级孔径分布,既保留了2nm左右的孔,同时在7nm处显现出较多的介孔结构,在227nm处的大孔数量增多。其中7nm处的介孔增大催化剂比表面积,可以为丙烯、异丁烯、甲苯等的选择氧化反应提供更多的活性位点,有利于原料催化反应;227nm处的大孔能增强催化剂的传质效率,既能保证产物烯醛(烯酮)快速扩散到催化剂表面,防止发生深度氧化反应;又能防止氧化过程中产生的副产物乙酸、丙烯酸等进一步聚合引起催化剂结焦,从而提高了催化剂使用寿命。
取实施例1-5制得的催化剂及对比例制得的催化剂,其比表面积、孔容、孔径分布采用BET法和压汞法测定,测试结果示于表1:
表1各催化剂性能结果
由表1数据可知,实施例1-5所制得的催化剂及对比例均出现介孔-大孔梯级孔径分布,但实施例1-5所制得的催化剂其比表面积、孔容均优于对比例制得的催化剂,且大孔含量更高,更有利于原料转化及产物扩散,为其催化性能优异提供可能。
3.催化剂的活性测试
对实施例1-5和对比例所制得的催化剂的催化性能进行测试,在不锈钢管式反应器(内径30mm,长度550mm)中,使用10g具有梯级孔径分布的复合金属氧化物催化剂(6-20目),并在0.1MPa下测试催化剂性能。取丙烯/异丁烯/甲苯作为反应物,O2:N2=3:12(体积比),设置空速为1100h-1,采用本发明的催化剂进行催化反应,反应温度为260-450℃,反应时间不少于50min。对冷却吸收剂吸收的产物取样进行色谱分析。
3-1、丙烯选择氧化反应中的转化率和选择性
取实施例1-5制得的催化剂及对比例制得的催化剂,测试其在丙烯选择氧化反应中的丙烯转化率、丙烯醛选择性和CO2选择性,见表2:
表2各催化剂在丙烯选择氧化反应中的结果
样品 | 温度(℃) | 丙烯转化率(%) | 丙烯醛选择性(%) | CO2选择性(%) |
实施例1 | 340 | 96.7 | 86.7 | 3.9 |
实施例2 | 340 | 97.2 | 88.9 | 3.2 |
实施例3 | 340 | 98.7 | 88.0 | 2.7 |
实施例4 | 340 | 99.3 | 87.2 | 4.6 |
实施例5 | 340 | 99.7 | 91.3 | 3.5 |
对比例 | 340 | 95.1 | 82.4 | 8.2 |
由表2数据可知,在340℃时,在本发明催化剂的催化作用下,丙烯基本全部参与反应,同时对目标产物的选择性保持在85%以上左右,优选实施例5可以达到90%以上;CO2的选择性保持在较低水平,说明该催化剂体系没有造成目标产物深度氧化。尤其是实施例3的催化剂,在丙烯的转化率和丙烯醛的选择性都保持在较高水平的情况下,CO2的选择性只有2.7%。本发明形成的复合金属氧化物催化剂,的确可以提高催化剂的性能。
3-2、异丁烯选择氧化反应中的转化率和选择性
取实施例1-5制得的催化剂及对比例制得的催化剂,测试其在异丁烯选择氧化反应中的异丁烯转化率、甲基丙烯醛选择性和CO2选择性,见表3:
表3各催化剂在异丁烯选择氧化反应中的结果
样品 | 温度(℃) | 异丁烯转化率(%) | 甲基丙烯醛选择性(%) | CO2选择性(%) |
实施例1 | 360 | 97.3 | 87.8 | 3.4 |
实施例2 | 360 | 97.2 | 87.2 | 4.7 |
实施例3 | 360 | 98.7 | 88.7 | 3.6 |
实施例4 | 360 | 98.5 | 88.3 | 3.1 |
实施例5 | 360 | 99.8 | 92.4 | 2.5 |
对比例 | 360 | 96.1 | 82.6 | 7.9 |
由表3数据可知,在360℃时,在本发明催化剂的催化作用下,异丁烯转化率及目标产物的选择性均保持在较高水平;CO2的选择性均较低,说明该催化剂体系没有造成目标产物深度氧化。从结果上来看,实施例1-5所制得的催化剂性能均优于对比例所制得的催化剂,尤其是实施例5的催化剂。本发明形成的复合金属氧化物催化剂,的确可以提高催化剂的性能。
3-3、甲苯选择氧化反应中的转化率和选择性
取实施例1-5制得的催化剂及对比例制得的催化剂,测试其在甲苯选择氧化反应中的甲苯转化率、苯甲醛选择性和CO2选择性,见表4:
表4含不同造孔剂的催化剂在甲苯选择氧化反应中的结果
样品 | 温度(℃) | 甲苯转化率(%) | 苯甲醛选择性(%) | CO2选择性(%) |
实施例1 | 400 | 18.1 | 87.2 | 2.9 |
实施例2 | 400 | 21.9 | 86.5 | 2.2 |
实施例3 | 400 | 22.6 | 87.9 | 2.5 |
实施例4 | 400 | 24.3 | 85.8 | 3.6 |
实施例5 | 400 | 31.7 | 89.6 | 1.3 |
对比例 | 400 | 9.4 | 84.5 | 4.2 |
由表4数据可知,在400℃时,在本发明催化剂的催化作用下,甲苯转化率和苯甲醛的选择性均优于对比例所制得的催化剂;尤其是实施例5所制得的催化剂,甲苯转化率达30%以上,远高于现有文献报道。本发明形成的复合金属氧化物催化剂,的确可以提高催化性能。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (16)
1.一种梯级孔复合金属氧化物催化剂的制备方法,其特征在于,包括如下步骤:
(1) 将含钼,以及含钒或钨元素的化合物搅拌加入水中,得到均匀的溶液A;
(2)将含铋元素的化合物搅拌加入硝酸溶液中,得到均匀的溶液B;
(3) 将含钴的化合物、含铁的化合物,与含银、铜、锰、铬、镍、铈、锌、钾、铯或锑元素的化合物中的一种或两种以上搅拌加入水中,得到均匀的溶液C;
其中溶液A、B、C的配制在超声波辅助下进行,纳米分散剂加入溶液A中;纳米分散剂为钛白粉和硅粉按照质量比1-2:1-2的复配;纳米分散剂的平均粒径为5~25 nm;纳米分散剂与A、B、C混合液中金属离子摩尔比为1:10~50;
(4)在超声波辅助下,将溶液B和溶液C同时滴加至搅拌的溶液A中,继续超声并搅拌,得到均匀的混合溶液;
(5) 在超声波辅助下将步骤(4)的混合溶液搅拌老化,老化温度为20~100 oC,老化时间为1~24 h;
(6) 将步骤(5)所得混合溶液经干燥得到复合金属氧化物催化剂粉末;
(7) 将步骤(6)所得复合金属氧化物催化剂粉末与高分子造孔剂按照质量比100:1~5进行掺混,混合均匀后成型、焙烧,得到复合金属氧化物催化剂颗粒;
所述催化剂具有介孔和大孔,化学式表示为Mo12BiaCobFecXdYeZfOg,其中X为钒或钨元素的一种或二种;Y为银、铜、锰、铬、镍、铈、锌、钾、铯或锑元素的化合物中的一种或两种以上;Z为硅和钛;a=0.5~2,b=3~10,c=1.5~6,d=0~0.5,e=0.1~6,f=0.5~4,g是满足其他元素的氧化状态的数值。
2.根据权利要求1所述的制备方法,其特征在于,所述催化剂在20nm以下和50~900 nm处出现梯级的介孔-大孔复合结构。
3.根据权利要求1所述的制备方法,其特征在于,所述催化剂在2~15 nm和50~500nm处出现梯级的介孔-大孔复合结构。
4.根据权利要求1所述的制备方法,其特征在于,所述催化剂的比表面积2~30 m2/g,孔容0.1~0.6 cm3/g,平均孔径50~700 nm,堆密度0.8~1.5 g/mL。
5.根据权利要求1所述的制备方法,其特征在于,所述催化剂在大孔级所占比例在60%以上,所述大孔级为50-900nm。
6.根据权利要求5所述的制备方法,其特征在于,所述催化剂在大孔级所占比例在70%以上。
7.根据权利要求5所述的制备方法,其特征在于,所述催化剂在大孔级所占比例在80%以上。
8.根据权利要求1所述的制备方法,其特征在于,所述含钼元素的化合物为三氧化钼、硝酸钼或钼酸铵;所述含钒元素的化合物为五氧化二钒或偏钒酸铵;所述含钨元素的化合物为三氧化钨、钨酸铵;所述含铋元素的化合物为硝酸铋或乙酸铋;所述含银、铜、铁、锰、钴、铬、镍、铈、锌、钾、铯或锑元素的化合物为相应元素的硝酸盐或乙酸盐。
9.根据权利要求1所述的制备方法,其特征在于,步骤(1)至步骤(3)中,超声波辅助是在频率20~100 kHz,功率100~500 W,超声时间10~50 min;步骤(4)中,超声波辅助是在频率20~100 kHz,功率300~1000 W条件下进行,滴加完成后继续超声并搅拌10 min~2 h;步骤(5)的溶液老化过程中,超声波辅助是频率20~100 kHz,功率500~1200 W,老化时间为1~24h。
10.根据权利要求9所述的制备方法,其特征在于,步骤(1)至步骤(3)中,超声波辅助的频率为20~60 kHz,功率200~400 W,超声时间15~40 min;步骤(4)中,超声波辅助的频率为20~50 kHz,功率为500~800 W;滴加完成后继续超声并搅拌20~60 min;步骤(5)的溶液老化过程中,超声波辅助是频率20~50 kHz功率600~1000 W,老化时间为2~6 h。
11.根据权利要求1所述的制备方法,其特征在于,纳米分散剂与A、B、C混合液中金属离子摩尔比为1:15~30。
12.根据权利要求1所述的制备方法,其特征在于,步骤(7)中,高分子造孔剂选自羧甲基纤维素、聚丙烯酰胺、淀粉、聚乙烯醇、聚乙二醇、田菁粉、阿拉伯胶、硬脂酸的一种或多种;催化剂粉末与高分子造孔剂的质量比100:1~5。
13.根据权利要求12所述的制备方法,其特征在于,步骤(7)中,高分子造孔剂为聚乙二醇和羧甲基纤维素按照质量比3-5:1的复配。
14.根据权利要求12所述的制备方法,其特征在于,催化剂粉末与高分子造孔剂的质量比为100:1.5~3。
15.权利要求1-14任一项所述制备方法制得的梯级孔复合金属氧化物催化剂在氧化反应中作为催化剂的应用。
16.根据权利要求15所述的应用,其特征在于,所述氧化反应是甲苯及其衍生物选择氧化生产苯醛类反应中的应用;或者丙烯、异丁烯、环己烯选择性氧化生产α,β-不饱和醛酮类反应。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1585673A (zh) * | 2001-11-08 | 2005-02-23 | 三菱化学株式会社 | 复合氧化物催化剂及其制备方法 |
CN102365128A (zh) * | 2009-01-27 | 2012-02-29 | 科学设计公司 | 具有双峰孔径分布的催化剂及其应用 |
CN104801312A (zh) * | 2015-03-17 | 2015-07-29 | 烟台大学 | 一种复合氧化物催化剂及制备方法 |
CN106660019A (zh) * | 2014-06-13 | 2017-05-10 | Ifp 新能源公司 | 通过共研获得的具有活性相的介孔与大孔催化剂 、其制备方法及其用于渣油的加氢处理的用途 |
CN108940363A (zh) * | 2017-05-19 | 2018-12-07 | 宁波大学 | 一种大孔/介孔复合型光催化剂及其制备方法 |
CN111185186A (zh) * | 2020-02-19 | 2020-05-22 | 烟台大学 | 一种单相复合金属氧化物催化剂、其制备方法及应用 |
CN112675866A (zh) * | 2020-12-24 | 2021-04-20 | 烟台大学 | 一种复合金属氧化物催化剂、其制备方法及应用 |
-
2022
- 2022-02-08 CN CN202210118869.0A patent/CN114405515B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1585673A (zh) * | 2001-11-08 | 2005-02-23 | 三菱化学株式会社 | 复合氧化物催化剂及其制备方法 |
CN102365128A (zh) * | 2009-01-27 | 2012-02-29 | 科学设计公司 | 具有双峰孔径分布的催化剂及其应用 |
CN106660019A (zh) * | 2014-06-13 | 2017-05-10 | Ifp 新能源公司 | 通过共研获得的具有活性相的介孔与大孔催化剂 、其制备方法及其用于渣油的加氢处理的用途 |
CN104801312A (zh) * | 2015-03-17 | 2015-07-29 | 烟台大学 | 一种复合氧化物催化剂及制备方法 |
CN108940363A (zh) * | 2017-05-19 | 2018-12-07 | 宁波大学 | 一种大孔/介孔复合型光催化剂及其制备方法 |
CN111185186A (zh) * | 2020-02-19 | 2020-05-22 | 烟台大学 | 一种单相复合金属氧化物催化剂、其制备方法及应用 |
CN112675866A (zh) * | 2020-12-24 | 2021-04-20 | 烟台大学 | 一种复合金属氧化物催化剂、其制备方法及应用 |
Non-Patent Citations (1)
Title |
---|
Novel urea-assisted hydrothermal synthesis of tetrametallic Co6Fe4Mo12Bi1.5Ox phase for the selective oxidation of tert-butyl alcohol to methacrolein;Lei Wang等;《Catalysis Communications》;第 105762(1-5)页 * |
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