CN112237926A - 金属负载催化剂及其制备方法 - Google Patents
金属负载催化剂及其制备方法 Download PDFInfo
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- CN112237926A CN112237926A CN201910648815.3A CN201910648815A CN112237926A CN 112237926 A CN112237926 A CN 112237926A CN 201910648815 A CN201910648815 A CN 201910648815A CN 112237926 A CN112237926 A CN 112237926A
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- catalyst
- oxide
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- nitrate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 10
- 239000002184 metal Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 21
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002407 reforming Methods 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 9
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 9
- 239000010948 rhodium Substances 0.000 claims abstract description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 43
- 239000001569 carbon dioxide Substances 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 31
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- PCCNIENXBRUYFK-UHFFFAOYSA-O azanium;cerium(4+);pentanitrate Chemical compound [NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PCCNIENXBRUYFK-UHFFFAOYSA-O 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- -1 carbon alkane Chemical class 0.000 claims description 2
- LQCIDLXXSFUYSA-UHFFFAOYSA-N cerium(4+);tetranitrate Chemical compound [Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LQCIDLXXSFUYSA-UHFFFAOYSA-N 0.000 claims description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 2
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract description 49
- 230000008021 deposition Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 43
- 239000002994 raw material Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 24
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 20
- 238000001035 drying Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 13
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 8
- WLLURKMCNUGIRG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[Ce] WLLURKMCNUGIRG-UHFFFAOYSA-N 0.000 description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 7
- HGTPFADPABTGKP-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Ce+6].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Ce+6].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] HGTPFADPABTGKP-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229940044658 gallium nitrate Drugs 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- RBZGEUJLKTVORU-UHFFFAOYSA-N 12014-84-5 Chemical compound [Ce]#[Si] RBZGEUJLKTVORU-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- UFNRFBFHJJPDNF-UHFFFAOYSA-N [Zn].[Ce] Chemical compound [Zn].[Ce] UFNRFBFHJJPDNF-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- RRTQFNGJENAXJJ-UHFFFAOYSA-N cerium magnesium Chemical compound [Mg].[Ce] RRTQFNGJENAXJJ-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/8906—Iron and noble 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
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Abstract
本发明涉及一种金属负载型催化剂,其特征在于,以催化剂重量份数计,所述催化剂包括80‑99.9份载体和0.1‑20份活性组分;所述活性组分包括铁元素和选自钴、镍、钌、铑、钯、铱、铂元素中的至少一种,所述载体包括铈氧化物和主族元素氧化物。本发明催化剂在较低的反应温度下具有高乙烷干重整催化活性和选择性,同时具有良好的抗积碳能力。本发明催化剂制备方法简单,对环境影响小。
Description
技术领域
本发明属于催化剂技术领域,具体涉及一种金属负载催化剂及其制备方法和应用。
背景技术
合成气以一氧化碳和氢气为主要组分,是一种重要的化工原料气,一般可用于生产羰基合成醇、甲醇或作为费-托合成的原料,此外合成气也是用于合成氨反应中氢气的主要来源。目前,工业上合成气主要由天然气、液化气和石脑油等原料的蒸汽重整过程制得,还可以由重油经部分氧化法生产。但这些现有过程还存在一些缺陷。例如,蒸汽重整是强吸热过程,反应温度较高并伴随着大量积碳生成;重油氧化则需要氧气或富氧空气,在高温高压条件下进行,对反应装置的要求非常严格。
页岩气中通常含有相当程度的乙烷,近年来,由于页岩油气的持续开发,页岩气产地乙烷的供应过剩日益凸显,每年有近1/3的乙烷被当作燃料消耗,未进行高附加值的利用,除用于乙烷脱氢制乙烯外,发展乙烷干重整制合成气同样可以作为具有应用前景的方案。同甲烷干重整相比,使用乙烷作原料,可以有效降低反应温度和能耗,抑制反应中的积碳生成,提升经济效益。
目前,关于乙烷和二氧化碳氧化脱氢催化剂的报道较少,文献中比较有代表性的体系包括三金属钙钛矿(ACS Symposium Series 2003,852,69-82;J.Catal.2018,358,168-178)和负载镍的复盐材料(ACS Sustainable Chem.Eng.2018,6,13551-13561),沙特基础公司的专利CN107406349A中报道了K-Ce-Mn-Cr/SiO2催化剂,这些催化剂在高温下表现出较好的乙烷干重整活性,但需要的反应温度均在650℃以上,高能耗和积碳制约了进一步的工业化。
发明内容:
本发明的目的在于提供一种低碳烷烃和二氧化碳干重整制合成气的金属负载催化剂及其制备方法。
一种金属负载型催化剂,以催化剂重量份数计,所述催化剂包括80-99.9份载体和0.1-20份活性组分;所述活性组分包括铁元素和选自钴、镍、钌、铑、钯、铱、铂元素中的至少一种。
上述技术方案中,所述载体包括铈氧化物和主族元素氧化物。优选0.1-20份活性组分,15-85份铈氧化物,10-80份主族元素氧化物。优选以铈氧化物铈原子的摩尔百分数计,所述载体中三价铈的摩尔质量百分比为13-55%。本发明一实施例中30.6%。
上述技术方案中,所述活性组分包括铁元素和选自钴、镍、钌、铑、钯、铱、铂中至少一种元素的摩尔比为1:9-5:1。
上述技术方案中,所述铈氧化物包括二氧化铈、三氧化二铈以及组成介于二者之间的铈氧化物。
上述技术方案中,所述主族元素氧化物包括氧化镁、氧化铝、氧化硅、氧化钙、氧化镓或氧化锡。
本发明还提供一种负载型催化剂的制备方法,包括如下步骤,合成含铈氧化物和主族元素氧化物的载体,将包括铁元素和选自钴、镍、钌、铑、钯、铱、铂元素中的至少一种元素的活性组分负载在所述载体上。
上述技术方案中,采用溶胶凝胶法合成含铈氧化物和主族元素氧化物的载体,优选地,具体步骤如下:将表面活性剂、溶剂、可溶性铈盐、另一种主族元素的可溶性盐混合,加热,煅烧。
上述技术方案中,所述可溶性铈盐包括硝酸铈(III)、硝酸铈(IV)、硝酸铈铵(IV)中的一种或几种;优选所述表面活性剂包括聚氧乙烯-聚氧丙烯-聚氧乙烯三嵌段聚合物、聚乙二醇、聚丙二醇;优选溶剂包括甲醇、乙醇、水。
上述技术方案中,所述加热温度为30~120℃,优选30~60℃和100~120℃;加热时间12~72小时,优选12-36h;所述在空气中煅烧的温度为400~800℃,优选600~800℃,煅烧时间4~8小时。
上述技术方案中,将活性组分负载在所述载体上,具体为,将包括铁元素和选自钴、镍、钌、铑、钯、铱、铂元素中的至少一种元素的可溶性盐、溶剂、载体混合。
上述技术方案中,所述溶剂包括乙醇、水、乙醇水溶液,优选体积分数为20~80%乙醇水溶液,较优选体积分数为60-80%。
上述技术方案中,所述负载还包括干燥、成型、过筛步骤。
上述技术方案中,所述的干燥温度为40~120℃,优选为60~100℃,干燥时间4~24h,优选为8~15h。
本发明还提供一种低碳烷烃和二氧化碳干重整制合成气反应,采用上述催化剂,或者采用上述方法制得的催化剂。
上述技术方案中,所述反应具体步骤为:
(1)催化剂在氢气气氛下还原,还原温度300~600℃,优选为400~500℃,还原时间0.5~4h,优选为1~2h;
(2)反应在常压固定床反应器中进行,反应温度500~650℃,原料气为低碳烷烃、二氧化碳和氩气混合气,总流量10~100mL·min-1,其中乙烷的摩尔分数为10~40%,二氧化碳的摩尔分数为20%~50%,其余为氩气平衡气。
其中,所述低碳烷烃包括乙烷、丙烷、丁烷。
本发明提供的催化剂采用包括铁元素和选自钴、镍、钌、铑、钯、铱、铂元素中的至少一种元素为金属活性组分,金属活性组分负载在铈氧化物和一种主族元素氧化物组成的载体上,活性组分与载体的作用力增强,在较低的反应温度下具有高乙烷干重整催化活性和选择性,同时具有良好的抗积碳能力。本发明催化剂制备方法简单,对环境影响小。
附图说明:
下面结合附图说明本发明:
图1为铈铝复合氧化物和氧化铈负载铁镍催化剂的氢气程序升温还原图。由图中样品的还原峰位置可以得到活性组分与载体的相互作用情况,主族金属的引入使催化剂活性组分的还原温度上升,增强了活性组分与载体的相互作用,提高了催化剂的干重整反应性能。
具体实施方式:
下面通过实施例对本发明作进一步阐述,但本发明的应用不受这些实施例的限制。
实施例1
将2.0gP123溶解于40mL乙醇中,加入10mmol硝酸铈(VI)和10mmol硝酸铝并搅拌至完全溶解,继续搅拌形成溶胶,在40℃下挥发溶剂48小时得到凝胶,再在100℃下干燥24小时,所得干凝胶在空气气氛下600℃煅烧4小时,得到铈铝摩尔比为1:1的氧化物载体。将0.24mmol硝酸铁与0.08mmol氯铂酸溶解在5mL 80%乙醇水溶液中,加入0.981g载体搅拌4小时,60℃下蒸发溶剂过夜,再在120℃下干燥1小时,得到催化剂A。
在固定床常压微反应器中测试催化剂A的乙烷和二氧化碳干重整活性,催化剂用量0.1g,反应前在400℃下,40mL·min-1的H2气氛下还原1小时,再通入原料气,气体流速40mL·min-1,原料气组成为C2H6:CO2:Ar=1:4:3,反应在常压下进行,反应温度600℃。催化剂A的乙烷转化率为32.4%,二氧化碳转化率为20.1%,合成气选择性为95.8%。
实施例2
将2.0gP123溶解于40mL乙醇中,加入10mmol硝酸铈(III)和10mmol硝酸铝并搅拌至完全溶解,继续搅拌形成溶胶,在40℃下挥发溶剂48小时得到凝胶,再在100℃下干燥24小时,所得干凝胶在空气气氛下600℃煅烧4小时,得到铈铝摩尔比为1:1的氧化物载体。将0.24mmol硝酸铁与0.08mmol硝酸镍溶解在10mL 80%乙醇水溶液中,加入0.981g载体搅拌4小时,60℃下蒸发溶剂过夜,再在120℃下干燥1小时,得到催化剂B。通过X射线光电子能谱测定载体铈氧化物中三价铈摩尔百分比为30.6%。
在固定床常压微反应器中测试催化剂B的乙烷和二氧化碳干重整活性,催化剂用量0.1g,反应前在400℃下,40mL·min-1的H2气氛下还原1小时,再通入原料气,气体流速40mL·min-1,原料气组成为C2H6:CO2:Ar=1:4:3,反应在常压下进行,反应温度600℃。催化剂B的乙烷转化率为41.9%,二氧化碳转化率为31.7%,合成气选择性为96.0%。
实施例3
将2.0gP123溶解于40mL乙醇中,加入10mmol硝酸铈(III)和10mmol四甲氧基硅烷并搅拌至完全溶解,继续搅拌形成溶胶,在30℃下挥发溶剂48小时得到凝胶,再在100℃下干燥24小时,所得干凝胶在空气气氛下600℃煅烧4小时,得到铈硅摩尔比为1:1的氧化物载体。将0.24mmol硝酸铁与0.08mmol硝酸镍溶解在10mL 80%乙醇水溶液中,加入0.981g载体搅拌4小时,60℃下蒸发溶剂过夜,再在120℃下干燥1小时,得到催化剂C。
在固定床常压微反应器中测试催化剂C的乙烷和二氧化碳干重整活性,催化剂用量0.1g,反应前在500℃下,40mL·min-1的H2气氛下还原1小时,再通入原料气,气体流速40mL·min-1,原料气组成为C2H6:CO2:Ar=1:4:3,反应在常压下进行,反应温度600℃。催化剂C的乙烷转化率为29.0%,二氧化碳转化率为23.1%,合成气选择性为97.3%。
实施例4
将2.0gP123溶解于40mL乙醇中,加入12mmol硝酸铈(VI)和8mmol硝酸镁并搅拌至完全溶解,继续搅拌形成溶胶,在30℃下挥发溶剂48小时得到凝胶,再在100℃下干燥24小时,所得干凝胶在空气气氛下600℃煅烧4小时,得到铈镁摩尔比为3:2的氧化物载体。将0.24mmol硝酸铁与0.08mmol氯铂酸溶解在5mL 80%乙醇水溶液中,加入0.981g载体搅拌4小时,60℃下蒸发溶剂过夜,再在120℃下干燥1小时,得到催化剂D。
在固定床常压微反应器中测试催化剂D的乙烷和二氧化碳干重整活性,催化剂用量0.1g,反应前在400℃下,40mL·min-1的H2气氛下还原1小时,再通入原料气,气体流速40mL·min-1,原料气组成为C2H6:CO2:Ar=1:4:3,反应在常压下进行,反应温度600℃。催化剂D的乙烷转化率为27.5%,二氧化碳转化率为29.6%,合成气选择性为97.6%。
实施例5
将2.0gP123溶解于40mL乙醇中,加入12mmol硝酸铈(III)和8mmol硝酸镓并搅拌至完全溶解,继续搅拌形成溶胶,在40℃下挥发溶剂48小时得到凝胶,再在100℃下干燥24小时,所得干凝胶在空气气氛下600℃煅烧4小时,得到铈镓摩尔比为3:2的氧化物载体。将0.24mmol硝酸铁与0.08mmol硝酸镍溶解在5mL 80%乙醇水溶液中,加入0.981g载体搅拌4小时,60℃下蒸发溶剂过夜,再在120℃下干燥1小时,得到催化剂E。
在固定床常压微反应器中测试催化剂E的乙烷和二氧化碳干重整活性,催化剂用量0.1g,反应前在400℃下,40mL·min-1的H2气氛下还原1小时,再通入原料气,气体流速40mL·min-1,原料气组成为C2H6:CO2:Ar=1:4:3,反应在常压下进行,反应温度600℃。催化剂E的乙烷转化率为17.9%,二氧化碳转化率为17.8%,合成气选择性为94.3%。
实施例6
将2.0gP123溶解于40mL乙醇中,加入16mmol硝酸铈(VI)和4mmol硝酸铝并搅拌至完全溶解,继续搅拌形成溶胶,在30℃下挥发溶剂48小时得到凝胶,再在100℃下干燥24小时,所得干凝胶在空气气氛下600℃煅烧4小时,得到铈铝摩尔比为4:1的氧化物载体。将0.24mmol硝酸铁、0.08mmol硝酸镍和0.08mmol氯铂酸溶解在10mL 80%乙醇水溶液中,加入0.981g载体搅拌4小时,60℃下蒸发溶剂过夜,再在120℃下干燥1小时,得到催化剂F。
在固定床常压微反应器中测试催化剂F的乙烷和二氧化碳干重整活性,催化剂用量0.1g,反应前在400℃下,40mL·min-1的H2气氛下还原1小时,再通入原料气,气体流速40mL·min-1,原料气组成为C2H6:CO2:Ar=1:4:3,反应在常压下进行,反应温度600℃。催化剂F的乙烷转化率为51.6%,二氧化碳转化率为44.7%,合成气选择性为82.7%。
实施例7
将2.0gP123溶解于40mL乙醇中,加入10mmol硝酸铈(III)和10mmol硝酸镓并搅拌至完全溶解,继续搅拌形成溶胶,在40℃下挥发溶剂48小时得到凝胶,再在100℃下干燥24小时,所得干凝胶在空气气氛下600℃煅烧4小时,得到铈镓摩尔比为1:1的氧化物载体。将0.24mmol硝酸铁与0.08mmol氯化铱溶解在5mL 80%乙醇水溶液中,加入0.981g载体搅拌4小时,60℃下蒸发溶剂过夜,再在120℃下干燥1小时,得到催化剂G。
在固定床常压微反应器中测试催化剂G的乙烷和二氧化碳干重整活性,催化剂用量0.1g,反应前在400℃下,40mL·min-1的H2气氛下还原1小时,再通入原料气,气体流速40mL·min-1,原料气组成为C2H6:CO2:Ar=1:4:3,反应在常压下进行,反应温度600℃。催化剂G的乙烷转化率为21.2%,二氧化碳转化率为18.2%,合成气选择性为90.1%。
实施例8
将2.0gP123溶解于40mL乙醇中,加入10mmol硝酸铈(III)和10mmol硝酸铝并搅拌至完全溶解,继续搅拌形成溶胶,在30℃下挥发溶剂48小时得到凝胶,再在100℃下干燥24小时,所得干凝胶在空气气氛下600℃煅烧4小时,得到铈铝摩尔比为1:1的氧化物载体。将0.24mmol硝酸铁与0.08mmol氯铂酸溶解在10mL 80%乙醇水溶液中,加入0.981g载体搅拌4小时,60℃下蒸发溶剂过夜,再在120℃下干燥1小时,得到催化剂H。
在固定床常压微反应器中测试催化剂H的乙烷和二氧化碳干重整活性,催化剂用量0.1g,反应前在500℃下,40mL·min-1的H2气氛下还原1小时,再通入原料气,气体流速40mL·min-1,原料气组成为C2H6:CO2:Ar=1:4:3,反应在常压下进行,反应温度600℃。催化剂H的乙烷转化率为39.5%,二氧化碳转化率为30.6%,合成气选择性为91.0%。
对比例1
将2.0gP123溶解于40mL乙醇中,加入20mmol硝酸铈(III)搅拌至完全溶解,继续搅拌形成溶胶,在40℃下挥发溶剂48小时得到凝胶,再在100℃下干燥24小时,所得干凝胶在空气气氛下600℃煅烧4小时,得到铈氧化物载体。将0.24mmol硝酸铁与0.08mmol硝酸镍溶解在10mL 80%乙醇水溶液中,加入0.981g载体搅拌4小时,60℃下蒸发溶剂过夜,再在120℃下干燥1小时,得到催化剂I。
在固定床常压微反应器中测试催化剂I的乙烷和二氧化碳干重整活性,催化剂用量0.1g,反应前在400℃下,40mL·min-1的H2气氛下还原1小时,再通入原料气,气体流速40mL·min-1,原料气组成为C2H6:CO2:Ar=1:4:3,反应在常压下进行,反应温度600℃。催化剂I的乙烷转化率为9.1%,二氧化碳转化率为7.3%,合成气选择性为76.5%。
对比例2
将2.0g P123溶解于40mL乙醇中,加入10mmol硝酸铈(III)和10mmol硝酸锌并搅拌至完全溶解,继续搅拌形成溶胶,在40℃下挥发溶剂48小时得到凝胶,再在100℃下干燥24小时,所得干凝胶在空气气氛下600℃煅烧4小时,得到铈锌摩尔比为1:1的氧化物载体。将0.24mmol硝酸铁与0.08mmol硝酸镍溶解在10mL 80%乙醇水溶液中,加入0.981g载体搅拌4小时,60℃下蒸发溶剂过夜,再在120℃下干燥1小时,得到催化剂J。
在固定床常压微反应器中测试催化剂J的乙烷和二氧化碳干重整活性,催化剂用量0.1g,反应前在400℃下,40mL·min-1的H2气氛下还原1小时,再通入原料气,原料气气体流速40mL·min-1,组成为C2H6:CO2:Ar=1:4:3,反应在常压下进行,反应温度600℃。催化剂J的乙烷转化率为9.5%,二氧化碳转化率为10.2%,合成气选择性为87.6%。
对比例3
将2.0g P123溶解于40mL乙醇中,加入10mmol硝酸铈(III)和10mmol硝酸铝并搅拌至完全溶解,继续搅拌形成溶胶,在40℃下挥发溶剂48小时得到凝胶,再在100℃下干燥24小时,所得干凝胶在空气气氛下600℃煅烧4小时,得到铈铝摩尔比为1:1的氧化物载体。将0.24mmol硝酸铁溶解在10mL 80%乙醇水溶液中,加入0.981g载体搅拌4小时,60℃下蒸发溶剂过夜,再在120℃下干燥1小时,得到催化剂K。
在固定床常压微反应器中测试催化剂K的乙烷和二氧化碳干重整活性,催化剂用量0.1g,反应前在400℃下,40mL·min-1的H2气氛下还原1小时,再通入原料气,原料气气体流速40mL·min-1,组成为C2H6:CO2:Ar=1:4:3,反应在常压下进行,反应温度600℃。催化剂K的乙烷转化率为4.5%,二氧化碳转化率为3.7%,合成气选择性为74.8%。
对比例4
将2.0g P123溶解于40mL乙醇中,加入10mmol硝酸铈(III)和10mmol硝酸铝并搅拌至完全溶解,继续搅拌形成溶胶,在40℃下挥发溶剂48小时得到凝胶,再在100℃下干燥24小时,所得干凝胶在空气气氛下600℃煅烧4小时,得到铈铝摩尔比为1:1的氧化物载体。将0.24mmol硝酸镍溶解在10mL 80%乙醇水溶液中,加入0.981g载体搅拌4小时,60℃下蒸发溶剂过夜,再在120℃下干燥1小时,得到催化剂L。
在固定床常压微反应器中测试催化剂L的乙烷和二氧化碳干重整活性,催化剂用量0.1g,反应前在400℃下,40mL·min-1的H2气氛下还原1小时,再通入原料气,原料气气体流速40mL·min-1,组成为C2H6:CO2:Ar=1:4:3,反应在常压下进行,反应温度600℃。催化剂L的乙烷转化率为19.5%,二氧化碳转化率为11.4%,合成气选择性为94.2%。
具体催化测试结果如表1所示。
表1
催化剂 | 乙烷转化率(%) | 二氧化碳转化率(%) | 选择性(%) |
A | 32.4 | 20.1 | 95.8 |
B | 41.9 | 31.7 | 96.0 |
C | 29.0 | 23.1 | 97.3 |
D | 27.5 | 29.6 | 97.6 |
E | 17.9 | 17.8 | 94.3 |
F | 51.6 | 44.7 | 82.7 |
G | 21.2 | 18.2 | 90.1 |
H | 39.5 | 30.6 | 91.0 |
I | 9.1 | 7.3 | 76.5 |
J | 9.5 | 10.2 | 87.6 |
K | 4.5 | 3.7 | 78.4 |
L | 19.5 | 11.4 | 94.2 |
Claims (10)
1.一种金属负载型催化剂,其特征在于,以催化剂重量份数计,所述催化剂包括80-99.9份载体和0.1-20份活性组分;所述活性组分包括铁元素和选自钴、镍、钌、铑、钯、铱、铂中的至少一种元素,所述载体包括铈氧化物和主族元素氧化物。
2.如权利要求1所述催化剂,其特征在于,所述活性组分包括铁元素和选自钴、镍、钌、铑、钯、铱、铂中的至少一种元素的摩尔比为1:9-5:1。
3.如权利要求1所述催化剂,其特征在于,所述主族元素氧化物包括氧化镁、氧化铝、氧化硅、氧化钙、氧化镓或氧化锡。
4.如权利要求1所述催化剂,其特征在于,以催化剂重量份数计,所述催化剂包括0.1-20份活性组分,15-85份铈氧化物,10-80份主族元素氧化物;优选以铈氧化物中铈原子的摩尔百分数计,所述载体铈氧化物中三价铈摩尔百分比为13-55%。
5.一种负载型催化剂的制备方法,包括如下步骤,合成含铈氧化物和主族元素氧化物的载体,将包括铁元素和选自钴、镍、钌、铑、钯、铱、铂中的至少一种元素的活性组分负载在所述载体上。
6.根据权利要求5所述的催化剂的制备方法,其特征在于,采用溶胶凝胶法合成含铈氧化物和主族元素氧化物的载体,优选地,具体步骤如下:
将表面活性剂、溶剂、可溶性铈盐、另一种主族元素的可溶性盐混合,加热,煅烧。
7.根据权利要求6所述的催化剂的制备方法,其特征在于,所述可溶性铈盐包括硝酸铈(III)、硝酸铈(IV)、硝酸铈铵(IV)中的一种或几种;优选所述表面活性剂包括聚氧乙烯-聚氧丙烯-聚氧乙烯三嵌段聚合物、聚乙二醇、聚丙二醇;优选溶剂包括甲醇、乙醇、水。
8.根据权利要求6中所述的催化剂的制备方法,其特征在于,所述加热温度为30~120℃,加热时间12~72小时;所述在空气中煅烧的温度为400~800℃,煅烧时间4~8小时。
9.根据权利要求5所述的催化剂的制备方法,其特征在于,将包括活性组分负载在所述载体上,具体为,将活性组分的可溶性盐、溶剂、载体混合。
10.低碳烷烃和二氧化碳干重整制合成气反应,采用权利要求1-4所述催化剂,或者采用权利要求5-9所述方法制得的催化剂。
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