CN114870835B - Supported palladium-based catalyst and preparation method and application thereof - Google Patents
Supported palladium-based catalyst and preparation method and application thereof Download PDFInfo
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- CN114870835B CN114870835B CN202210423024.2A CN202210423024A CN114870835B CN 114870835 B CN114870835 B CN 114870835B CN 202210423024 A CN202210423024 A CN 202210423024A CN 114870835 B CN114870835 B CN 114870835B
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 85
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 77
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 51
- 239000011029 spinel Substances 0.000 claims abstract description 51
- 239000002131 composite material Substances 0.000 claims abstract description 40
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 39
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 19
- 239000011701 zinc Substances 0.000 claims abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 18
- 239000010941 cobalt Substances 0.000 claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 17
- 239000011777 magnesium Substances 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 14
- 238000000151 deposition Methods 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- -1 palladium ions Chemical class 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 239000012696 Pd precursors Substances 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 239000011268 mixed slurry Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 238000007254 oxidation reaction Methods 0.000 abstract description 18
- 230000003647 oxidation Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 230000010718 Oxidation Activity Effects 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910000943 NiAl Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 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
- B01J23/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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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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Abstract
The invention provides a supported palladium-based catalyst and a preparation method and application thereof, wherein the supported palladium-based catalyst comprises a spinel/alumina composite carrier and active component palladium supported on the surface of the composite carrier, the spinel/alumina composite carrier is prepared by co-depositing or independently impregnating one of nickel, cobalt, magnesium and zinc with aluminum to modify the surface of alumina, and the alumina comprises gamma-crystal type alumina 2 O 3 As carrier, nickel, cobalt, magnesium and zinc as auxiliary agentThe palladium-based catalyst has better low-temperature activity in the catalytic complete oxidation reaction of methane under the condition of high space velocity.
Description
Technical Field
The invention belongs to the technical field of catalysts, and relates to a supported palladium-based catalyst, and a preparation method and application thereof.
Background
With the rapid development of economy, energy demand is increasing. The sulfur and nitrogen contents in the natural gas are far lower than those of other fossil resources, the hydrocarbon ratio of methane is low, the natural gas has the advantages of high heat value, lower carbon emission and the like, and the natural gas is used as an energy chemical raw material and has obvious rising trend in application. However, a large amount of escaped methane exists in the oil gas and coal exploitation process, and a large amount of low-concentration (0.1-1%) methane also exists in combustion tail gases such as transportation fuel gas, city life fuel gas and power plant fuel gas. The greenhouse effect of methane is CO 2 21 times of the total amount of the second greenhouse gas, which is second to carbon dioxide, there is a need to develop a high-efficiency catalytic complete oxidation technology to realize the reduction of low-concentration methane in the energy exploitation and application process.
The noble metal catalyst has more excellent low-temperature activity and poisoning resistance than the non-noble metal catalyst, wherein the catalytic activity sequence of the noble metal is Pd & gtPt & gtRh & gtAu. The Pd catalyst has higher catalytic activity for the complete oxidation reaction of methane, has the best oxidation catalytic performance and is most applied as a supported methane low-temperature oxidation catalyst. The catalytic activity of the oxide supported Pd-based catalyst is obviously related to the carrier and is reduced in the following order: sn (Sn)>Zr>Al>Ga>In>Ti>Si>Y>Nb, etc., wherein is due to gamma-Al 2 O 3 Has excellent specific surface area and pore structure property, is low in cost, and is the carrier which is most widely used.
CN103203233A discloses a nail containing metallic palladium as an active componentThe catalyst is prepared from mesoporous alumina prepared from pseudo-boehmite serving as an aluminum source. The carrier is prepared by roasting, and the palladium loading mode is equal volume impregnation. Wherein the specific surface area of the mesoporous alumina is 200-400 m 2 Per gram, the pore volume is 0.2-0.8 cm 3 And/g, wherein the aperture is 3-10 nm; the content of the active component palladium is 0.1% -1% of the total weight of the catalyst, the complete conversion rate of methane can be realized at a lower space velocity, but the catalyst activity is poor at a higher space velocity.
CN107262093a discloses a lanthanum oxide modified alumina supported noble metal-based methane catalytic combustion catalyst, wherein the outside of the active component is coated with a metal oxide layer as a coating layer for providing oxygen vacancies, and the catalyst further comprises a catalyst promoter cerium zirconium solid solution, and the preparation process is complex.
CN108993560a discloses a water-resistant high-temperature-resistant methane oxidation catalyst and a preparation method thereof. The catalyst consists of 0.5 to 5 weight percent of PdO, 1 to 10 weight percent of BaCO and 85 to 98.5 weight percent of AlO, wherein the mol ratio of AlO to BaCO is 16.5 to 190.7; the mol ratio of BaCO/AlO to PdO is 7.8-81.4; the molar ratio of BaCO to PdO was 1.25. The preparation method comprises the following steps: (1) Dipping a Ba precursor on an AlO material, and roasting the Ba precursor in air to form a BaCO/AlO carrier; (2) And (3) impregnating the Pd precursor on the carrier prepared in the step (2), and drying and roasting the Pd precursor in air to prepare the PdO/BaCO/AlO water-resistant high-temperature-resistant methane oxidation catalyst.
Methane as a greenhouse gas can be purified by catalytic full oxidation (MOC), i.e. by catalytic action of CH 4 Complete oxidation to H 2 O and CO 2 The key of the technology is the development of the catalyst. Noble metal catalysts are highly approved, and palladium-based catalysts have received much attention. However, it is still difficult to achieve low temperature catalytic full oxidation of methane at high space velocity and high water vapor content.
Disclosure of Invention
The invention aims to provide a supported palladium-based catalyst, a preparation method and application thereof, and the supported palladium-based catalyst uses gamma crystal form Al 2 O 3 Palladium-based catalyst as carrier and nickel as auxiliary agent for methane catalysis under high space velocity conditionThe catalyst has better low-temperature activity in the complete oxidation reaction.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a supported palladium-based catalyst comprising a spinel/alumina composite support and an active component palladium supported on the surface of the spinel/alumina composite support, the composite support being prepared by co-depositing or separately impregnating a modified alumina surface with any one or a combination of at least two of nickel, cobalt, magnesium or zinc, the alumina comprising gamma-alumina.
Gamma crystal form Al in the supported palladium-based catalyst 2 O 3 Al relative to other crystal forms 2 O 3 Has the largest specific surface area, has stronger interaction with the loaded active substance PdO, and is characterized in that 2 O 3 Ni, co, mg or Zn is introduced on the surface to form an aluminum-based spinel structure, so that the dispersion and structural stability of the PdO of the active substance loaded by the aluminum-based spinel structure are promoted, the active substance is not easy to decompose when heated and is easy to reoxidize after being decomposed, and therefore, the gamma-crystal Al is deposited by Ni or impregnated and modified 2 O 3 The palladium-based catalyst as a carrier has better low-temperature activity in the catalytic oxidation reaction of methane.
Preferably, in the spinel/alumina composite support, spinel AAl 2 O 4 And A of (2) is any one or a combination of at least two of nickel, cobalt, magnesium or zinc.
Preferably, the mass of A is 0.2 to 10wt% of alumina, for example: 0.2wt%, 0.5wt%, 1wt%, 5wt% or 10wt%, etc., preferably 0.5 to 5wt%.
Preferably, in the supported palladium-based catalyst, the palladium loading is 0.1 to 5wt.%, for example: 0.1wt.%, 1wt.%, 2wt.%, 3wt.%, 4wt.%, or 5wt.%, etc.
In a second aspect, the present invention provides a method for preparing the supported palladium-based catalyst according to the first aspect, the method comprising the steps of:
(1) Mixing the gamma-crystal alumina dispersion liquid with a salt solution of any one or a combination of at least two of a nickel source, a cobalt source, a magnesium source and a zinc source, and evaporating to dryness, or mixing the gamma-crystal alumina dispersion liquid with a nitrate solution and an aluminum salt solution of any one or a combination of at least two of the nickel source, the cobalt source, the magnesium source and the zinc source, adding a precipitant, and performing one-step roasting treatment to obtain the spinel/alumina composite carrier;
(2) Mixing the spinel/alumina composite carrier obtained in the step (1), a solvent and a palladium precursor to obtain mixed slurry, drying, and performing two-step roasting treatment to obtain the supported palladium-based catalyst.
The invention uses common nickel, cobalt, magnesium or zinc to deposit, deposit or dip and modify gamma crystal form alumina, so that the alumina surface forms an aluminum-based spinel structure, the addition of nickel, cobalt, magnesium and zinc improves the oxidation-reduction property of active substances while maintaining the original large specific surface area, overcomes the inherent defect of weak interaction between gamma crystal form alumina carrier and active components, and is more beneficial to realizing the catalytic oxidation process of methane at low temperature at high airspeed.
Preferably, the gamma-alumina of step (1) is prepared by sintering pseudo-boehmite.
Preferably, the sintering temperature is 500 to 800 ℃, for example: 500 ℃, 550 ℃, 600 ℃, 700 ℃, 800 ℃, etc.
Preferably, the sintering time is 1 to 4 hours, for example: 1h, 1.5h, 2h, 3h or 4h, etc.
The nickel source of step (1) comprises nickel nitrate and/or nickel chloride.
Preferably, the cobalt source comprises cobalt nitrate and/or cobalt chloride.
Preferably, the magnesium source comprises magnesium nitrate and/or magnesium chloride.
Preferably, the zinc source comprises zinc nitrate and/or zinc chloride.
Preferably, the precipitant comprises any one or a combination of at least two of ammonia, ammonium carbonate, ammonium bicarbonate or urea with cetyltrimethylammonium bromide (CTAB).
Preferably, the molar ratio of cetyltrimethylammonium bromide to metal ions in the nickel, cobalt, magnesium or zinc source in the precipitant is (0.01-0.3): 1, for example: 0.01:1, 0.05:1, 0.1:1, 0.2:1, or 0.3:1, etc.
Preferably, the end point of the precipitation reaction is ph=5 to 10, for example: 5. 6, 7, 8, 9 or 10, etc.
Preferably, the step (1) is preceded by a baking treatment.
Preferably, the temperature of the drying is 80 to 120 ℃, for example: 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃ and the like.
Preferably, the temperature of the one-step firing treatment is 500 to 1000 ℃, for example: 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃ or 1000 ℃ and the like.
Preferably, the one-step firing treatment is performed for 0.5 to 6 hours, for example: 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, etc.
Preferably, the palladium precursor of step (2) comprises any one or a combination of at least two of palladium nitrate, palladium chloride, palladium acetate or tetra-ammine palladium nitrate.
Preferably, the mass concentration of palladium ions in the mixed slurry is 0.1 to 5wt.%, for example: 0.1wt.%, 1wt.%, 2wt.%, 3wt.%, 4wt.%, or 5wt.%, etc.
Preferably, the drying mode in the step (2) comprises rotary evaporation.
Preferably, the temperature of the rotary evaporation to dryness is 50-90 ℃, for example: 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃ and the like.
Preferably, the temperature of the two-step firing is 500 to 700 ℃, for example: 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, etc.
Preferably, the two-step firing time is 0.5 to 3 hours, for example: 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, etc.
In a third aspect, the present invention provides the use of a supported palladium-based catalyst according to the first aspect for the catalytic oxidation of methane.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention uses common nickel, cobalt, magnesium or zinc and aluminum codeposition precipitation or independent impregnation modification gamma crystal form alumina carrier to lead the surface of the alumina to form spinel structure, and the addition of nickel, cobalt, magnesium and zinc improves the oxidation-reduction property of active substances while maintaining the original large specific surface area, makes up the inherent defect of weak interaction between the gamma crystal form alumina carrier and active components, and is more beneficial to the low-temperature complete oxidation process of methane.
(2) According to the invention, spinel is directly deposited on the surface of alumina, the corresponding A-site modified element is immersed, and then the spinel/alumina composite structure carrier is obtained through roasting, and palladium active components are loaded, so that the activity of the catalyst on methane oxidation is obviously improved, and the ignition stability and burnout temperature are both shifted to low temperature.
Drawings
FIG. 1 is a graph showing the change in conversion rate of catalytically oxidized methane with respect to temperature for the catalysts of examples 1-6 and comparative examples 1-2 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a supported palladium-based catalyst, which is prepared by the following steps:
(1) Roasting pseudo-boehmite for 4 hours at 600 ℃ to obtain gamma-crystal alumina, mixing the alumina with water for 0.1 hour to prepare alumina dispersion liquid, mixing nickel nitrate with an alumina nitrate mixed solution (Ni: al=1:2), adding an alumina dispersion liquid, mixing, adding a combined precipitator of ammonia water-CTAB (CTAB: ni=0.15:1), adjusting pH to 10, evaporating at 60 ℃ to obtain a solid, drying, and roasting at 700 ℃ for 4 hours to obtain a nickel-aluminum spinel/alumina structure composite carrier, wherein the mass of nickel in the nickel-aluminum spinel/alumina structure composite carrier is 0.25% of the mass of alumina;
(2) Mixing the nickel-aluminum spinel/aluminum oxide structure composite carrier obtained in the step (1) with water for 0.1h to obtain nickel-aluminum spinel/aluminum oxide structure composite carrier dispersion, adding palladium nitrate, rotationally evaporating at 60 ℃, and sintering at 600 ℃ for 2h to obtain the supported palladium-based catalyst, wherein the load of palladium element in the supported palladium-based catalyst is 1wt.%.
Example 2
The embodiment provides a supported palladium-based catalyst, which is prepared by the following steps:
(1) Roasting pseudo-boehmite for 4.2 hours at 620 ℃ to obtain gamma-crystal alumina, mixing the alumina with water for 0.1 hour to prepare alumina dispersion liquid, mixing nickel nitrate with the alumina dispersion liquid, stirring for 1 hour, evaporating at 60 ℃ to obtain a solid, and roasting at 650 ℃ for 4 hours to obtain a nickel-aluminum composite carrier, wherein the mass of nickel in the nickel-aluminum spinel/alumina composite carrier is 1% of that of the alumina;
(2) Mixing the nickel-aluminum spinel/aluminum oxide structure composite carrier obtained in the step (1) with water for 0.1h to obtain nickel-aluminum spinel/aluminum oxide structure composite carrier dispersion, adding palladium nitrate, rotationally evaporating at 65 ℃, and sintering at 620 ℃ for 2h to obtain the supported palladium-based catalyst, wherein the load of palladium element in the supported palladium-based catalyst is 1wt.%.
Example 3
This example differs from example 1 only in that the nickel content in the nickel aluminate spinel/alumina structured composite support is 0.5% of the alumina content, and other conditions and parameters are identical to those of example 1.
Example 4
This example differs from example 1 only in that the nickel content in the nickel aluminate spinel/alumina structured composite support is 1.5% of the alumina content, and other conditions and parameters are identical to those of example 1.
Example 5
This example differs from example 1 only in that the nickel content in the nickel aluminate spinel/alumina structured composite support is 3% of the alumina content, and other conditions and parameters are exactly the same as in example 1.
Example 6
This example differs from example 1 only in that the nickel content in the nickel aluminate spinel/alumina structured composite support is 8% of the alumina content, and other conditions and parameters are exactly the same as in example 1.
Example 7
This example differs from example 2 only in that the nickel content in the nickel aluminate spinel/alumina structured composite support is 0.5% of the alumina content, and other conditions and parameters are exactly the same as in example 2.
Example 8
This example differs from example 2 only in that the nickel content in the nickel aluminate spinel/alumina structured composite support is 3% of the alumina content, and other conditions and parameters are exactly the same as in example 2.
Example 9
This example differs from example 2 only in that the nickel content in the nickel aluminate spinel/alumina structured composite support is 8% of the alumina content, and other conditions and parameters are exactly the same as in example 2.
Example 10
The difference between this example and example 1 is that in the cobalt aluminate spinel/alumina structured composite support, instead, cobalt nitrate was used, the cobalt content was 1% of the alumina content, and other conditions and parameters were identical to those of example 1.
Example 11
The difference between this example and example 1 is that in the cobalt aluminate spinel/alumina structured composite support, instead of using magnesium nitrate, the nickel nitrate content is 1% of the alumina content, and other conditions and parameters are identical to those in example 1.
Example 12
The difference between this example and example 1 is that in the cobalt aluminate spinel/alumina structured composite support, zinc nitrate is used instead, the zinc content is 1% of the alumina content, and other conditions and parameters are identical to those of example 1.
Comparative example 1
This comparative example differs from example 1 only in that no modifying element is added in step (1), and other conditions and parameters are exactly the same as in example 1.
Comparative example 2
The comparative example differs from comparative example 1 only in that the temperature of the calcined pseudo-boehmite is 700 c, and other conditions and parameters are exactly the same as those of comparative example 1.
Comparative example 3
This comparative example differs from example 1 only in that step (1) was directly mixed with a source of beta alumina and nickel, with the other conditions and parameters being exactly the same as in example 1.
Performance test:
0.1g of the catalyst obtained in examples 1-12 and comparative examples 1-2 was charged into a fixed bed reactor to form a catalyst bed, and a methane-containing mixed gas was passed through the catalyst bed at a flow rate of 500mL/min (the mixed gas comprising methane, oxygen, carbon dioxide, and water vapor and nitrogen, wherein the concentration of methane was 1000ppm, the volume fraction of oxygen was 3.5vol.%, the volume fraction of carbon dioxide was 6vol.%, the volume fraction of water vapor was 10%), and the space velocity in the fixed bed reactor was 300000h -1 The temperature of the reaction system is increased from 200 ℃ to 600 ℃ at a heating rate of 5 ℃/min, and the temperature is kept for 10min at 25 ℃ when the temperature is increased. Methane is subjected to catalytic oxidation to obtain carbon dioxide and water, the methane concentration in the outlet gas of the fixed bed reactor is measured by GC2060 gas chromatography, and the methane conversion rate at each temperature is calculated by the inlet methane concentration and the outlet methane concentration, and the test results are shown in FIG. 1 and Table 1:
TABLE 1
As can be seen from Table 1, according to examples 1 to 12, the spinel/alumina composite structure carrier is obtained by directly depositing spinel on the surface of alumina and impregnating corresponding A-site modified elements and then roasting, palladium active components are loaded, the activity of the catalyst on methane oxidation is obviously improved, and the light-off stability and the burnout temperature are both shifted to low temperature.
The graphs of the conversion rate of methane catalyzed by the catalysts of examples 1, 3-6 and comparative examples 1-2 versus temperature are shown in FIG. 1. As can be seen from FIG. 1, the low temperature methane oxidation activity of the catalysts supported on spinel/alumina composite oxide catalysts having Ni deposition levels of 0.25wt%, 0.5wt%, 1wt%, 3 wt%, 8 wt%, respectively, are higher than that of pure gamma-Al under the same reaction conditions 2 O 3 Catalytic activity of the catalyst being a support. Direct co-deposition of NiAl on pure alumina surfaces 2 O 4 The spinel/alumina structure is obviously beneficial to the improvement of the low-temperature activity of the catalyst, and the Ni deposition amount can obviously influence the catalytic performance of the obtained catalyst.
As can be seen from Table 1, the low-temperature methane oxidation activities of the catalysts supported on spinel/alumina composite structure oxides of examples 2, 7 to 9 and comparative examples 1 to 2 were also higher than those of pure gamma-Al under the same reaction conditions with Ni impregnation amounts of 1wt%, 0.5wt%, 3 wt% and 8 wt%, respectively 2 O 3 The catalytic activity of the supported catalyst is illustrated by the direct separate impregnation of nickel on the pure alumina surface followed by calcination to form NiAl 2 O 4 Spinel/alumina is also effective in promoting the increase in low temperature activity of the catalyst and Ni impregnation loading can affect the catalytic performance of the resulting catalyst.
As can be seen from Table 1, the supported palladium-based catalyst of the present invention has better low-temperature complete oxidation activity than the catalyst prepared by immersing nickel alone to obtain nickel-aluminum spinel/alumina composite oxide as the supported palladium active component under the same reaction conditions and under the same Ni addition amount conditions, as compared with the catalyst prepared by immersing nickel alone in the same reaction conditions in the same manner as in examples 1, 3-6 and examples 2 and 7-9.
As can be seen from table 1, comparison between examples 1, 10-12 and comparative examples 1 and 2 shows that, in the supported palladium-based catalyst of the present invention, under the same reaction conditions and the same modification element addition amount conditions, the introduction of Co, ni, mg, zn in a co-deposition precipitation manner is a modification manner, so that the promotion of the catalyst activity is significantly improved, the promotion degree is close, and the reason of the promotion of the activity is further explained by the optimized regulation and control of the spinel/alumina structure on the dispersion of the active component.
The content of the modified element (Co, ni, mg, zn) in the carrier can influence the catalytic performance, the quality of the spinel A-site element (Co, ni, mg, zn) and the quality of the alumina in the spinel/alumina composite oxide carrier are controlled to be (0.001-0.06): 1, the catalytic performance of the prepared catalyst is better, if the content of the A-site element in the spinel is too large, the formed spinel is too thick, the pore diameter and the specific surface of the composite oxide carrier are reduced, so that the dispersity of the active component is reduced, the corresponding active site is reduced, the performance of the catalyst is reduced, and if the content of the A-site element in the spinel is too large, the formed spinel/active component interface is insufficient, and part of unmodified alumina/active component interface is remained, so that the activity improvement is not obvious.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (20)
1. The application of a supported palladium-based catalyst with low-temperature activity is characterized in that the supported palladium-based catalyst is used for catalyzing and oxidizing methane;
the supported palladium-based catalyst comprises a spinel/alumina composite carrier and active component palladium supported on the surface of the spinel/alumina composite carrier, wherein in the spinel/alumina composite carrier, spinel AAl 2 O 4 Wherein A is any one or the combination of at least two of nickel, cobalt, magnesium or zinc, the mass of A is 0.25-0.5wt% of alumina, and the composite carrier is prepared by co-depositing any one or the combination of at least two of nickel, cobalt, magnesium or zinc and aluminum to modify the surface of aluminaThe alumina comprises gamma-crystalline alumina;
the preparation method of the supported palladium-based catalyst comprises the following steps:
(1) Mixing gamma-crystal alumina dispersion liquid with nitrate solution and aluminum salt solution of any one of nickel source, cobalt source, magnesium source or zinc source, adding precipitant, and roasting to obtain spinel/alumina composite carrier;
(2) Mixing the spinel/alumina composite carrier obtained in the step (1), a solvent and a palladium precursor to obtain mixed slurry, drying, and performing two-step roasting treatment to obtain the supported palladium-based catalyst;
the precipitant comprises any one or a combination of at least two of ammonia water, ammonium carbonate, ammonium bicarbonate or urea and hexadecyl trimethyl ammonium bromide, and the mole ratio of the hexadecyl trimethyl ammonium bromide to metal ions in a nickel source, a cobalt source, a magnesium source or a zinc source in the precipitant is (0.01-0.3): 1.
2. The use according to claim 1, wherein the supported palladium-based catalyst has a palladium loading of 0.1 to 5wt.%.
3. The use according to claim 1, wherein the gamma crystalline form of alumina of step (1) is produced by sintering pseudo-boehmite.
4. The use according to claim 3, wherein the sintering temperature is 500-800 ℃.
5. The use according to claim 3, wherein the sintering time is 1 to 4 hours.
6. Use according to claim 1, wherein the nickel source of step (1) comprises nickel nitrate and/or nickel chloride.
7. Use according to claim 1, wherein the cobalt source comprises cobalt nitrate and/or cobalt chloride.
8. Use according to claim 1, wherein the magnesium source comprises magnesium nitrate and/or magnesium chloride.
9. Use according to claim 1, wherein the zinc source comprises zinc nitrate and/or zinc chloride.
10. The use according to claim 1, wherein the precipitation reaction is terminated at a ph=5 to 10.
11. The use according to claim 1, wherein the one-step firing process of step (1) is preceded by a drying process.
12. The use according to claim 11, wherein the temperature of the drying is 80-120 ℃.
13. The use according to claim 1, wherein the one-step firing treatment is carried out at a temperature of 500-1000 ℃.
14. The use according to claim 1, wherein the one-step calcination treatment is carried out for a period of 0.5 to 6 hours.
15. The use of claim 1, wherein the palladium precursor of step (2) comprises any one or a combination of at least two of palladium nitrate, palladium chloride, palladium acetate, or tetra-ammine palladium nitrate.
16. The use according to claim 1, wherein the mass concentration of palladium ions in the mixed slurry is 0.1-5 wt.%.
17. The use according to claim 1, wherein the drying in step (2) comprises rotary evaporation.
18. The use according to claim 17, wherein the rotary evaporation to dryness is at a temperature of 50-90 ℃.
19. The use according to claim 1, wherein the two-step firing is at a temperature of 500-700 ℃.
20. The use of claim 1, wherein the two-step firing time is 0.5 to 3 hours.
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