CN111644169B - Metal composite modified nano zirconium oxide catalyst and preparation method and application thereof - Google Patents
Metal composite modified nano zirconium oxide catalyst and preparation method and application thereof Download PDFInfo
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- CN111644169B CN111644169B CN202010554036.XA CN202010554036A CN111644169B CN 111644169 B CN111644169 B CN 111644169B CN 202010554036 A CN202010554036 A CN 202010554036A CN 111644169 B CN111644169 B CN 111644169B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000002905 metal composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims description 66
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims description 66
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000011858 nanopowder Substances 0.000 claims abstract description 33
- 238000000227 grinding Methods 0.000 claims abstract description 32
- 150000003754 zirconium Chemical class 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 claims description 11
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- ZFQCFWRSIBGRFL-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;zirconium(4+) Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZFQCFWRSIBGRFL-UHFFFAOYSA-B 0.000 claims description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 26
- 229910002091 carbon monoxide Inorganic materials 0.000 description 26
- 238000000034 method Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 239000003245 coal Substances 0.000 description 7
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- -1 ethylene, propylene Chemical group 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910001341 Crude steel Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
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- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a metal composite modified nano-zirconia catalyst and a preparation method and application thereof, belonging to the technical field of synthesis gas chemical industry and catalyst preparation. The preparation method of the catalyst comprises the following steps: putting a mixed solution consisting of a soluble zirconium salt solution, an alkali solution, a surfactant and hydrogen peroxide into a hydrothermal reaction at the temperature of between 150 and 200 ℃ for 10 to 30 hours to obtain a zirconium salt precursor; then calcining and grinding to obtain ZrO 2 A nanopowder; then ZrO is reacted 2 Nanopowder and metal oxide M x O y Mixing with dispersant, and grinding. The metal composite modified nano zirconia catalyst prepared by the invention can increase oxygen vacancy and improve the conversion rate of CO, and the prepared low-carbon olefin has high selectivity and good stability. In addition, the catalyst has simple preparation process and lower raw material cost, and is suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of synthesis gas chemical industry and catalyst preparation, and particularly relates to a metal composite modified nano-zirconia catalyst and a preparation method and application thereof.
Background
The low-carbon olefin refers to ethylene, propylene and butylene, is a key intermediate for synthesizing plastics, fibers and various chemical materials, is a very important basic organic chemical raw material, and is a base stone in the field of modern chemical industry. In recent years, with the rapid increase of national economy, the demand of petroleum and petrochemical products is rapidly increased, and the contradiction between supply and demand of low-carbon olefins is gradually highlighted due to insufficient petroleum resources, so that the healthy and stable development of the petrochemical industry and the petrochemical products in China is severely restricted.
The coal, the crude steel, the cement and the synthetic ammonia are rich in coal, oil and gas, the coal reserves are rich, the requirements of 74% of electricity, 8 hundred million tons of crude steel, 24 hundred million tons of cement and 0.7 hundred million tons of synthetic ammonia in China can be met, and chemical raw materials such as oil, olefin, methanol, ethylene glycol and the like can be produced through the coal. Syngas is composed mainly of carbon monoxide (CO) and hydrogen (H) 2 ) The raw material gas is a chemically synthesized raw material gas which can be converted from carbon-containing resources such as coal, petroleum, natural gas, coke oven gas, biomass and the like. However, with the increasing price of petroleum, scientists have proposed the concept of C1 chemistry, and since then the utilization of syngas has attracted considerable attention from researchers in various countries. Therefore, a novel coal chemical technology is developed, and a low-carbon olefin preparation technology taking synthesis gas as a main hub is a feasible route for preparing low-carbon olefin from non-petroleum resources.
The synthesis gas preparation of lower olefins is mainly concerned by the following 2 routes: (1) Directly converting the synthesis gas into low-carbon olefin through a Fischer-Tropsch synthesis process (FTS); (2) The low-carbon olefin is prepared by using an oxide-molecular sieve bifunctional catalyst (XO-ZEO). For example, in Fischer-Tropsch synthesis, although the conversion rate of CO is very high, the product distribution is limited by ASF distribution, the selectivity of low-carbon olefin can only reach 60% at most, the catalyst is seriously influenced by reverse water-gas reaction, and CO is 2 High selectivity, low utilization rate of catalyst carbon and easy loss of active components of the catalyst. The bifunctional catalytic route to lower olefins also requires attention to several areas: the pore channel structure of the molecular sieve is optimized and adjusted, so that the thermal stability of the molecular sieve is improved, and the occurrence of carbon deposition is inhibited; the two active components have thermal coupling effect and product conversion coupling effect to make the two active components have two activitiesThe components are properly matched, so that the product distribution is effectively regulated and controlled; a micro-area environment with good mass transfer and heat transfer performances is constructed, so that the intermediate and the product are quickly and effectively transferred, and the secondary hydrogenation reaction of the low-carbon olefin is prevented.
ZrO 2 The surface of the semiconductor has multiple chemical and physical properties, and the semiconductor is acidic, alkaline, oxidizing and reducing, is a p-type semiconductor and is easy to generate oxygen holes. ZrO (zirconium oxide) 2 As an active component of a catalyst, a catalyst carrier or an auxiliary agent, and is widely applied to a catalytic system. The concept of isomerism synthesis was first proposed by Pichler and it was found that zirconia can directly convert syngas to isobutene and isobutane (Pichler H, ziesecke KH. Isosynthesis by reduced oxide catalysts J]Brennst Chem,1949, 30. Xuya (application No: CN 92109866.9) discloses a preparation method of a ferro-manganese catalyst for preparing low-carbon olefin by CO hydrogenation, wherein the conversion rate of CO is 83.4 percent and the selectivity of the low-carbon olefin is 62.1 percent when MgO is loaded, and although the conversion rate of CO is high, the selectivity of the low-carbon olefin is lower.
Disclosure of Invention
Aiming at the problems or defects of the prior art, the invention aims to provide a metal composite modified nano-zirconia catalyst, and a preparation method and application thereof.
In order to achieve one of the above objects of the present invention, the present invention adopts the following technical solutions:
a preparation method of a metal composite modified nano zirconia catalyst specifically comprises the following steps:
(1) Mixing the soluble zirconium salt solution, the alkali solution and the surfactant according to the proportion, and uniformly stirring to obtain a mixed solution 1; adding hydrogen peroxide into the mixed solution 1, and continuously stirring uniformly to obtain a mixed solution 2; transferring the mixed solution 2 into a hydrothermal reaction kettle, sealing, heating the reaction kettle to 150-200 ℃, carrying out constant-temperature hydrothermal reaction for 10-30 h, cooling to room temperature after the reaction is finished, centrifuging, washing and drying the obtained product to obtain ZrO 2 A precursor;
(2) Subjecting the ZrO obtained in the step (1) 2 The precursor is placed in a muffle furnace and heatedHeating to 300-700 ℃ in air atmosphere, calcining for 3-8 h at constant temperature, and obtaining white ZrO after calcining 2 A powder;
(3) Subjecting the white ZrO obtained in the step (2) 2 Mixing the powder with a proper amount of grinding aid, and grinding for 10-40 min to obtain ZrO 2 A nanopowder;
(4) Proportionally mixing the ZrO prepared in the step (3) 2 Nanopowder and metal oxide M x O y Mixing, and grinding the obtained mixture for 10-40 min to obtain the metal composite modified nano zirconia catalyst.
Further, in the above technical solution, in the soluble zirconium salt solution in step (1), the solute is soluble zirconium salt, and the solvent is any one of deionized water, ethanol, acetone, and the like; wherein: the soluble zirconium salt is zirconium nitrate pentahydrate (Zr (NO) 3 ) 4 ·5H 2 O), zirconyl nitrate, zirconium chloride, zirconium acetate, zirconium citrate, zirconium n-propoxide, and the like.
Preferably, in the above technical solution, the soluble zirconium salt in step (1) is zirconium nitrate pentahydrate.
Further, in the above technical solution, in the soluble zirconium salt solution in the step (1), the dosage ratio of the soluble zirconium salt to the solvent is (15-30) g: (50-120) mL.
Preferably, in the above technical solution, in the soluble zirconium salt solution in the step (1), the dosage ratio of the soluble zirconium salt to the solvent is (15-30) g: (70-90) mL.
Further, in the above technical solution, the alkali solution in the step (1) may be any one or more of a urea solution, an ammonia solution, or a hydrazine hydrate solution. The alkaline solution used in the invention is used as a precipitant.
Preferably, in the above technical solution, the concentration of the alkali solution in the step (1) is 1 to 10mol/L, and more preferably 5 to 8mol/L.
Further, in the above technical solution, the surfactant in the step (1) is preferably polyethylene glycol 600. The surfactant molecules adopted by the invention contain hydrophilic groups and hydrophobic groups, and are commonly used for reducing the surface energy of ultrafine particles and preventing the agglomeration of new particles. Therefore, the use of surfactants is often advantageous for obtaining ultrafine powders.
Further, in the above technical solution, the mass ratio of the soluble zirconium salt in the soluble zirconium salt solution in the step (1), the alkali in the alkali solution, and the surfactant is (15-30): (20 to 60): (1-10).
Further, in the technical scheme, the dosage ratio of the surfactant to the hydrogen peroxide in the step (1) is (1-10) by mass: (3-10) parts by volume, wherein: the mass portion and the volume portion are as follows: mL as a reference.
Further, in the above technical scheme, the time for stirring twice in step (1) is not limited, as long as the raw materials can be uniformly mixed, and for example, the time for stirring twice can be 10 to 50min.
Further, in the above technical scheme, the hydrothermal reaction kettle in the step (1) has a polytetrafluoroethylene lining, and the volume of the hydrothermal reaction kettle is 100-500 mL.
Further, in the above technical solution, the filling degree of the mixed solution 2 in the step (1) is preferably controlled to be 50% to 80% of the volume of the reaction vessel.
Further, in the above technical scheme, the temperature of the hydrothermal reaction in the step (1) is preferably 170 to 190 ℃, and the reaction time is preferably 15 to 25 hours.
Further, in the above technical scheme, the solvent used for washing in step (1) is deionized water.
Further, in the above-mentioned technical means, the number of times of the centrifugation and washing in the step (1) is not limited, and may be 1 time, 2 times or more, and more preferably 1 to 3 times.
Further, in the technical scheme, the drying process in the step (1) is to place the solid product obtained by centrifugation and washing in a drying oven, control the drying temperature of the drying oven to be 40-150 ℃ and control the drying time to be 8-24 h.
Preferably, in the technical scheme, the drying temperature in the step (1) is 50-70 ℃, and the drying time is 10-14 h.
Further, the technical scheme and the steps(1) The hydrogen peroxide adopted in the method has the functions as follows: inhibiting zirconium ion (Zr) in zirconium salt 4+ ) Reduction of (2).
Furthermore, in the above technical scheme, the calcination temperature in the step (2) is preferably 450 to 600 ℃, and the calcination time is preferably 4 to 6 hours. The calcination of the present invention is intended to convert the precursor hydroxide of zirconium to zirconium oxide.
Further, in the above technical solution, the grinding aid in step (3) is an alcohol organic solvent having a branched structure, for example, the alcohol organic solvent may be isopropanol or 2-butanol, and isopropanol is more preferable. The invention adopts the alcohol organic solvent with a branched chain structure, has more reaction active points, can obviously inhibit powder agglomeration in the grinding process, and is beneficial to obtaining products with smaller grain diameter.
Further, the above technical solution, step (3) is the ZrO 2 The grain diameter of the nano powder is 30-80 nm.
Further, in the above technical solution, the grinding aid and the white ZrO in the step (3) 2 The mass ratio of the powder is 20-40: 100.
further, in the above technical solution, the metal oxide M in the step (4) x O y In the formula, M is any one of Zn, ce, Y and In, x is 1 or 2, and Y is 1 or 2 or 3. For example, the metal oxide M x O y May be ZnO or CeO 2 、Y 2 O 3 、I 2 O 3 Any one of them.
Further, in the above technical solution, the metal oxide M in the step (4) x O y And ZrO 2 The mass ratio of the nano powder is 0.5-2: 100.
further, in the above technical solution, the mixture in step (4) further includes a dispersant, the dispersant is preferably a polycarboxylic acid, and the polycarboxylic acid is selected from any one or more of oxalic acid, malonic acid, tricarballylic acid, succinic acid, adipic acid, and the like.
Preferably, in the above technical solution, the dispersant in step (4) is tricarballylic acid.
Further, the technical scheme isThe amount of the dispersant added in the step (4) is not more than ZrO 2 5% of the mass of the nanopowder.
Further, the purpose of the grinding in the step (4) is to modify ZrO by metal 2 And (4) nano powder.
The second purpose of the invention is to provide the metal composite modified nano-zirconia catalyst prepared by the method.
The third purpose of the invention is to provide the application of the metal composite modified nano-zirconia catalyst prepared by the method in catalyzing CO hydrogenation.
The mechanism that the metal composite modified nano-zirconia catalyst can simultaneously improve the CO hydrogenation conversion rate and the low-carbon olefin selectivity is as follows:
ZrO 2 surface oxygen vacancies can activate CO to form formic acid species in H 2 Under the atmosphere, methoxy species are generated by hydrogenation. However, zrO 2 H of (A) 2 The dissociation capability is weaker and the CO conversion is lower. The metal composite modified nano-zirconia catalyst of the invention can promote the reaction in H 2 The dissociation and adsorption of the catalyst can form hydrogen species which can participate in hydrogenation reaction, thereby improving the CO conversion rate and the selectivity of the low-carbon olefin.
Compared with the prior art, the invention has the following beneficial effects:
(1) The metal composite modified nano-zirconia catalyst prepared by the invention can increase oxygen vacancy, improve the CO hydrogenation conversion rate, and has high selectivity and good stability of low-carbon olefin.
(2) The catalyst has simple preparation process and low cost of raw materials, and is suitable for industrial large-scale production.
(3) In the process of preparing the metal composite modified nano zirconia catalyst, the surfactant polyethylene glycol 600 is added, so that the particle size of the prepared zirconia catalyst is reduced, and the zirconia superfine powder is obtained.
(4) According to the invention, the grinding aid is added after roasting, so that the agglomeration of the zirconia superfine powder is inhibited, the dispersibility of the prepared catalyst is improved, and the selectivity of methane is reduced in the CO hydrogenation process.
(5) The invention is in the metal oxide M x O y And ZrO 2 In the middle grinding process, the dispersing agent is added, so that the CO is effectively inhibited 2 The selectivity and the alkene ratio of the low-carbon olefin are improved.
(6) In the CO hydrogenation reaction process, the surfactant, the grinding aid and the dispersing agent have the synergistic effect, so that the product distribution of the catalyst is improved, the carbon deposition of the catalyst is effectively inhibited, and the stability of the catalyst is improved.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, without limiting the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
In the following examples, all the starting components, unless otherwise specified, are commercially available products well known to those skilled in the art.
Example 1
The preparation method of the metal composite modified nano-zirconia catalyst of the embodiment comprises the following steps:
(1) Preparation of ZrO 2 Precursor body
(a) Preparing a soluble zirconium salt solution: 17.1g of zirconium nitrate pentahydrate (Zr (NO) was weighed 3 ) 4 ·5H 2 O), dissolving the weighed zirconium nitrate pentahydrate into 80mL of deionized water, and mechanically stirring for 3min under the condition of the rotating speed of 300rad/min to obtain a soluble zirconium salt solution;
(b) Preparing a urea solution: 38.3g of urea ((NH) were weighed out 2 ) 2 CO) particles, dissolving weighed urea in 80mL deionized water, and mechanically stirring for 5min under the condition of the rotating speed of 300rad/min to obtain a urea solution;
(c) Mixing the soluble zirconium salt solution obtained in the step (a), the urea solution obtained in the step (b) and 1g of polyethylene glycol 600, and mechanically stirring for 10min at the rotation speed of 500rad/min to obtain a uniform mixed solution 1; then 5mL of hydrogen peroxide is added into the mixed solution 1, and the mixture is continuously mechanically stirred for 30min under the condition of 500rad/min of rotation speed to be completely dissolved, so that a uniform mixed solution 2 is obtained; transferring the mixed solution 2 into a stainless steel reaction kettle with a polytetrafluoroethylene lining with the volume of 300mL, sealing, heating the reaction kettle to 180 ℃, carrying out constant-temperature hydrothermal reaction for 20 hours, cooling to room temperature after the reaction is finished, alternately centrifuging and washing the obtained product for 1 time respectively, placing the obtained solid product into a drying oven for drying at the drying temperature of 60 ℃ for 12 hours to obtain ZrO 2 A precursor;
(2) Subjecting the ZrO obtained in the step (1) 2 Placing the precursor in a muffle furnace, heating to 500 ℃ in the air atmosphere, calcining at constant temperature for 4h, and obtaining white ZrO after calcining 2 Powder;
(3) Subjecting the white ZrO obtained in the step (2) 2 Mixing the powder with isopropanol as grinding aid, and grinding for 20min to obtain ZrO 2 Nano-powder of said ZrO 2 The grain diameter of the nano powder is 30-80 nm; wherein: the grinding aid and white ZrO 2 The mass ratio of the powder is 30:100.
(4) Subjecting the ZrO obtained in the step (3) 2 Mixing the nanopowder, znO and dispersant, and grinding the resulting mixture for 20min to obtain the metal composite modified nano-zirconia catalyst, labeled 0.5% 2 (ii) a Wherein: the dispersant is tricarballylic acid; the addition amount of the dispersing agent is ZrO 2 3% of the mass of the nanopowder; the ZnO and ZrO 2 The mass ratio of the nano powder is 0.5:100.
example 2
The preparation method of a metal composite modified nano-zirconia catalyst of this example is substantially the same as that of example 1, except that: in step (4) of this embodiment, the ZnO and ZrO 2 The mass ratio of the nano powder is 1:100. accordingly, the metal composite modified nano-zirconia catalyst prepared in this example was labeled as 1% Zn-ZrO 2 。
Example 3
The preparation method of a metal composite modified nano-zirconia catalyst of this example is substantially the same as that of example 1, except that: in step (4) of this example, the ZnO and ZrO 2 The mass ratio of the nano powder is 2:100. accordingly, the metal composite modified nano-zirconia catalyst prepared in this example was labeled as 2% Zn-ZrO 2 。
Example 4
The preparation method of the metal composite modified nano-zirconia catalyst of the embodiment comprises the following steps:
(1) Preparation of ZrO 2 Precursor body
(a) Preparing a soluble zirconium salt solution: 17.1g of zirconium nitrate pentahydrate (Zr (NO) was weighed 3 ) 4 ·5H 2 O), dissolving weighed zirconium nitrate pentahydrate into 50mL of deionized water, and mechanically stirring for 10min under the condition of the rotating speed of 300rad/min to obtain a soluble zirconium salt solution;
(b) Preparing a urea solution: 38.3g of urine are weighedHormone ((NH) 2 ) 2 CO) particles, dissolving weighed urea in 100mL deionized water, and mechanically stirring for 5min under the condition of the rotating speed of 300rad/min to obtain a urea solution;
(c) Mixing the soluble zirconium salt solution obtained in the step (a), the urea solution obtained in the step (b) and 3g of polyethylene glycol 600, and mechanically stirring for 20min at the rotation speed of 500rad/min to obtain a uniform mixed solution 1; then adding 3mL of hydrogen peroxide into the mixed solution 1, and continuously mechanically stirring for 20min at the rotating speed of 500rad/min to completely dissolve the hydrogen peroxide to obtain a uniform mixed solution 2; transferring the mixed solution 2 into a stainless steel reaction kettle with a polytetrafluoroethylene lining with the volume of 300mL, sealing, heating the reaction kettle to 150 ℃, carrying out constant-temperature hydrothermal reaction for 30 hours, cooling to room temperature after the reaction is finished, alternately centrifuging and washing the obtained product for 2 times, placing the obtained solid product into a drying oven for drying at the drying temperature of 40 ℃ for 24 hours to obtain ZrO 2 A precursor;
(2) Subjecting the ZrO obtained in the step (1) 2 Placing the precursor in a muffle furnace, heating to 300 ℃ in the air atmosphere, calcining at constant temperature for 8h, and obtaining white ZrO after calcining 2 A powder;
(3) Subjecting the white ZrO obtained in the step (2) 2 Mixing the powder with isopropanol as grinding aid, and grinding for 10min to obtain ZrO 2 Nano-powder of said ZrO 2 The grain diameter of the nano powder is 30-80 nm; wherein: the grinding aid and white ZrO 2 The mass ratio of the powder is 25:100.
(4) Subjecting the ZrO obtained in the step (3) 2 Nanopowder, ceO 2 Mixing with dispersant, grinding the mixture for 30min to obtain the metal composite modified nano zirconia catalyst, marking as 1% 2 (ii) a Wherein: the dispersing agent is succinic acid; the addition amount of the dispersing agent is ZrO 2 1% of the mass of the nanopowder; the CeO 2 And ZrO 2 The mass ratio of the nano powder is 1:100.
example 5
The preparation method of the metal composite modified nano-zirconia catalyst of the embodiment comprises the following steps:
(1) Preparation of ZrO 2 Precursor body
(a) Preparing a soluble zirconium salt solution: 30g of zirconium nitrate pentahydrate (Zr (NO) was weighed 3 ) 4 ·5H 2 O), dissolving the weighed zirconium nitrate pentahydrate into 120mL of deionized water, and mechanically stirring for 3min under the condition of the rotating speed of 300rad/min to obtain a soluble zirconium salt solution;
(b) Mixing the soluble zirconium salt solution obtained in the step (a), 150mL of ammonia water solution with the concentration of 6mol/L and 10g of polyethylene glycol 600, and mechanically stirring for 50min under the condition of the rotation speed of 500rad/min to obtain a uniform mixed solution 1; then adding 10mL of hydrogen peroxide into the mixed solution 1, and continuously mechanically stirring for 50min at the rotating speed of 500rad/min to completely dissolve the hydrogen peroxide to obtain a uniform mixed solution 2; transferring the mixed solution 2 into a stainless steel reaction kettle with a polytetrafluoroethylene lining with the volume of 300mL, sealing, heating the reaction kettle to 200 ℃ for constant-temperature hydrothermal reaction for 10 hours, cooling to room temperature after the reaction is finished, alternately centrifuging and washing the obtained product for 1 time respectively, placing the obtained solid product into a drying oven for drying at the drying temperature of 150 ℃ for 8 hours to obtain ZrO 2 A precursor;
(2) Subjecting the ZrO obtained in the step (1) 2 Placing the precursor in a muffle furnace, heating to 700 ℃ in the air atmosphere, calcining for 3h at constant temperature, and obtaining white ZrO after calcining 2 Powder;
(3) Subjecting the white ZrO obtained in the step (2) 2 Mixing the powder with grinding aid 2-butanol, and grinding for 10min to obtain ZrO 2 Nano-powder of said ZrO 2 The grain diameter of the nano powder is 30-80 nm; wherein: the grinding aid and white ZrO 2 The mass ratio of the powder is 40:100.
(4) Subjecting the ZrO obtained in the step (3) 2 Nano powder, in 2 O 3 Mixing with dispersant, and grinding the mixture for 40min to obtain the metal composite modified nano-zirconia catalyst, wherein the mark is 1% in-ZrO 2 (ii) a Wherein: the dispersing agent is malonic acid; the addition amount of the dispersing agent is ZrO 2 2% by mass of the nanopowder; said In 2 O 3 And ZrO 2 The mass ratio of the nano powder is 1:100.
example 6
The preparation method of the metal composite modified nano-zirconia catalyst of the embodiment comprises the following steps:
(1) Preparation of ZrO 2 Precursor body
(a) Preparing a soluble zirconium salt solution: weighing 15g of zirconium nitrate pentahydrate (Zr (NO) 3 ) 4 ·5H 2 O), dissolving weighed zirconium nitrate pentahydrate into 90mL of deionized water, and mechanically stirring for 10min under the condition of the rotating speed of 300rad/min to obtain a soluble zirconium salt solution;
(b) Mixing the soluble zirconium salt solution obtained in the step (a), 90mL of hydrazine hydrate solution with the concentration of 5moL/L and 2g of polyethylene glycol 600, and mechanically stirring for 30min at the rotation speed of 500rad/min to obtain a uniform mixed solution 1; then adding 5mL of hydrogen peroxide into the mixed solution 1, and continuously mechanically stirring for 30min at the rotating speed of 500rad/min to completely dissolve the hydrogen peroxide to obtain a uniform mixed solution 2; transferring the mixed solution 2 into a stainless steel reaction kettle with a polytetrafluoroethylene lining with the volume of 300mL, sealing, heating the reaction kettle to 170 ℃, carrying out constant-temperature hydrothermal reaction for 25 hours, cooling to room temperature after the reaction is finished, alternately centrifuging and washing the obtained product for 2 times, placing the obtained solid product into a drying oven for drying at the drying temperature of 80 ℃ for 10 hours to obtain ZrO 2 A precursor;
(2) Subjecting the ZrO obtained in the step (1) 2 Placing the precursor in a muffle furnace, heating to 450 ℃ in the air atmosphere, calcining at constant temperature for 5h, and obtaining white ZrO after the calcining is finished 2 A powder;
(3) Subjecting the white ZrO obtained in the step (2) 2 Mixing the powder with isopropanol as grinding aid, and grinding for 10min to obtain ZrO 2 Nano-powder of the ZrO 2 The grain diameter of the nano powder is 30-80 nm; wherein: the grinding aid and white ZrO 2 The mass ratio of the powder is 20:100.
(4) Subjecting the ZrO obtained in the step (3) 2 Nanopowder, Y 2 O 3 Mixing with dispersant, grinding the mixture for 20min to obtain the metal composite modified nanoZirconium oxide rice catalyst, marked 1% Y-ZrO 2 (ii) a Wherein: the dispersant is tricarballylic acid; the addition amount of the dispersing agent is ZrO 2 1% of the mass of the nanopowder; said Y is 2 O 3 And ZrO 2 The mass ratio of the nano powder is 1:100.
and (3) testing and characterizing the performance of the catalyst:
the catalysts prepared in the above examples 1 to 6 of the present invention were prepared into catalyst particles of 20 to 40 mesh, respectively, in order to allow the catalysts to react better without clogging the reaction tube.
The method adopts a miniature fixed bed reactor to evaluate the catalyst, and the process conditions are that 0.5-5 mL of 20-40 mesh catalyst, the reaction temperature is 300-600 ℃, the reaction pressure is 0.5-8 MPa, and the feed gas H 2 the/CO =1 or 2, and the space velocity is 500-5000. H -1 。
For example, the performance of the catalyst prepared in example 1 was evaluated in a mini-fixed bed reactor, with the following specific operating steps: weighing 1mL of the metal composite modified nano-zirconia catalyst prepared in example 1, and filling the metal composite modified nano-zirconia catalyst into a constant temperature area in the middle of a reaction tube, wherein the volume of a feed gas H 2 /CO =2, temperature 400 ℃, pressure 3MPa, space velocity (GHSV) 2000h -1 And after the steady state is reached, sampling and analyzing, and sampling once at an interval of 3 h. The gas chromatography is used for carrying out quantitative and qualitative analysis on the raw material gas and the product. H in coal-based Fischer-Tropsch synthesis tail gas 2 、N 2 、CO、CO 2 And C 1 ～C 8 Hydrocarbon determination and gas chromatography methane correlation method, and calculating the CO conversion rate and the selectivity of each component substance.
Table 1 is a comparison table of the hydrogenation catalytic process parameters and performance test results of the metal composite modified nano zirconia catalysts prepared in the above examples 1 to 5. As can be seen from Table 1, the nano-zirconia catalyst compositely modified by Zn metal has improved CO conversion rate and CO distribution 2 The selectivity change is not obvious, the selectivity is maintained to be about 50 percent, and the hydrocarbon product change is obvious. 1% of Zn-ZrO-prepared in example 2 in the Metal composite modified Nano zirconia catalyst prepared in Each example of the present invention 2 The catalyst has the best performance of catalyzing CO hydrogenation and can be used for preparing low-carbon olefinHydrocarbon selectivity as high as 75.1%, and C 4 The ratio of isobutylene in the olefin was 96.7%, and the ratio of alkylene (O/P) was 8.8.
TABLE 1 comparison of the Process parameters and Performance test results for the hydrogenation catalytic reaction of the Metal composite modified Nano-zirconia catalysts prepared in examples 1-5
Claims (4)
1. The application of the metal composite modified nano zirconia catalyst in preparing low-carbon olefin by catalyzing CO hydrogenation is characterized in that: the preparation method of the catalyst specifically comprises the following steps:
(1) Mixing the soluble zirconium salt solution, the alkali solution and the surfactant according to the proportion, and uniformly stirring to obtain a mixed solution 1; adding hydrogen peroxide into the mixed solution 1, and continuously stirring uniformly to obtain a mixed solution 2; transferring the mixed solution 2 into a hydrothermal reaction kettle, sealing, heating the reaction kettle to 150-200 ℃, carrying out constant-temperature hydrothermal reaction for 10-30 h, cooling to room temperature after the reaction is finished, centrifuging, washing and drying the obtained product to obtain ZrO 2 A precursor; wherein: the mass ratio of the soluble zirconium salt in the soluble zirconium salt solution to the alkali in the alkali solution to the surfactant is (15-30): (20 to 60): (1-10); the surfactant is polyethylene glycol 600;
(2) Subjecting the ZrO prepared in the step (1) 2 Placing the precursor in a muffle furnace, heating to 300-700 ℃ in the air atmosphere, calcining for 3-8 h at constant temperature, and obtaining white ZrO after calcining 2 A powder;
(3) Subjecting the white ZrO obtained in the step (2) 2 Mixing the powder with a proper amount of grinding aid, and grinding for 10-40 min to obtain ZrO 2 A nano-powder;
(4) Proportionally mixing the ZrO prepared in the step (3) 2 Nanopowder and metal oxide M x O y Mixing, grinding the obtained mixture for 10-40 min to obtain the metal composite modified nano zirconium oxide catalyst; wherein: the metal oxideM x O y Is ZnO or CeO 2 、Y 2 O 3 、In 2 O 3 Any one of the above; the metal oxide M x O y And ZrO 2 The mass ratio of the nano powder is 0.5-2: 100, respectively; the mixture also comprises a dispersant which is polycarboxylic acid, and the polycarboxylic acid is selected from any one or more of oxalic acid, malonic acid, tricarballylic acid, succinic acid and adipic acid.
2. Use according to claim 1, characterized in that: in the soluble zirconium salt solution in the step (1), a solute is soluble zirconium salt, and a solvent is any one of deionized water, ethanol and acetone; wherein: the soluble zirconium salt is any one of pentahydrate zirconium nitrate, zirconyl nitrate, zirconium chloride, zirconium acetate, zirconium citrate and zirconium n-propoxide.
3. Use according to claim 1, characterized in that: the alkali solution in the step (1) is any one or more of a urea solution, an ammonia water solution or a hydrazine hydrate solution.
4. Use according to claim 1, characterized in that: the grinding aid and white ZrO in the step (3) 2 The mass ratio of the powder is 20-40: 100.
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