CN111804293A - Preparation method of porous alumina-supported transition metal and application of porous alumina-supported transition metal in removing COS - Google Patents
Preparation method of porous alumina-supported transition metal and application of porous alumina-supported transition metal in removing COS Download PDFInfo
- Publication number
- CN111804293A CN111804293A CN202010458183.7A CN202010458183A CN111804293A CN 111804293 A CN111804293 A CN 111804293A CN 202010458183 A CN202010458183 A CN 202010458183A CN 111804293 A CN111804293 A CN 111804293A
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- Prior art keywords
- transition metal
- porous alumina
- aluminum
- preparation
- acid
- Prior art date
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Links
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 59
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 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 51
- 238000001723 curing Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 17
- -1 transition metal salt Chemical class 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 21
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 229920002873 Polyethylenimine Polymers 0.000 claims description 9
- 235000015165 citric acid Nutrition 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000011641 cupric citrate Substances 0.000 claims description 2
- 235000019855 cupric citrate Nutrition 0.000 claims description 2
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- DAOVYDBYKGXFOB-UHFFFAOYSA-N tris(2-methylpropoxy)alumane Chemical compound [Al+3].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] DAOVYDBYKGXFOB-UHFFFAOYSA-N 0.000 claims description 2
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 claims description 2
- 239000011746 zinc citrate Substances 0.000 claims description 2
- 235000006076 zinc citrate Nutrition 0.000 claims description 2
- 229940068475 zinc citrate Drugs 0.000 claims description 2
- STDMRMREKPZQFJ-UHFFFAOYSA-H tricopper;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O STDMRMREKPZQFJ-UHFFFAOYSA-H 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 40
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 239000011148 porous material Substances 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 2
- 230000036619 pore blockages Effects 0.000 abstract description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 64
- 239000007789 gas Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- UNRNJMFGIMDYKL-UHFFFAOYSA-N aluminum copper oxygen(2-) Chemical compound [O-2].[Al+3].[Cu+2] UNRNJMFGIMDYKL-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
- B01J23/06—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
- 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
- B01D53/8603—Removing sulfur compounds
-
- 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
- B01J23/72—Copper
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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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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
- 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
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/308—Carbonoxysulfide COS
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- Organic Chemistry (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention provides a preparation method of porous alumina supported transition metal and application thereof in removing COS, wherein the preparation method of the porous alumina supported transition metal comprises the following steps: grinding the precursor compound of the aluminum, the transition metal salt and the soft template, dripping acid, curing, washing, drying and roasting to obtain the aluminum-based composite material. The preparation method adopts a grinding mode, does not need to add an organic solvent, and does not cause harm to the environment; the washing step after curing can improve the pore structure and the specific surface area of the catalyst; a drying step before calcination, which can prevent pore blockage and increase the specific surface area of the catalyst; the soft template can be converted into carbon dioxide and water to be removed through a roasting step, and a precursor compound of aluminum is converted into aluminum oxide and loaded with transition metal, so that the catalytic performance of the aluminum oxide is improved; and the preparation method is simple, and the prepared porous alumina loaded transition metal has good stability and high COS conversion rate.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method of porous alumina-supported transition metal and application of the porous alumina-supported transition metal in removing COS.
Background
Carbonyl sulfide (COS) widely exists in chemical raw material gas produced by taking coal, coke, residual oil, natural gas and the like as raw materials, and sulfide not only corrodes pipeline equipment, but also poisons sulfur to a catalyst on a downstream process flow to lose activity of the catalyst. The removal of carbonyl sulfide is of great significance.
The COS removal method can be mainly divided into a dry method and a wet method, wherein the wet method comprises an organic amine absorption method, a potassium hydroxide absorption method and the like, and the wet method has the advantages of large gas flow for treatment and low organic sulfur removal rate and poor gas selectivity; compared with the wet method, the dry method has the advantages of high desulfurization precision, simple operation and the like, and mainly comprises a hydrolysis conversion method, an oxidation conversion method and a hydrogenation conversion method. Most of the water vapor required by the hydrolysis conversion method in the hydrolysis process is already in the raw material gas, and no additional addition is needed; and the reaction does not need a hydrogen source; compared with the oxidation conversion method and the hydrogenation conversion method, the method has the advantages of energy consumption saving, low temperature, no raw material consumption, less side reaction and the like. Therefore, the hydrolytic conversion process is most widely used.
The most used hydrolysis catalyst at present is Al2O3As a carrier, other active components or auxiliary agents are loaded, the catalytic activity is improved, and the hydrolysis conversion rate of COS is improved. In Al2O3The active components loaded on the catalyst comprise alkali metal, alkaline earth metal and transition metal oxide. For example, chinese patent document CN106861665A discloses a method for preparing an alumina carbonyl sulfide catalyst, which comprises the following steps of (1) providing soluble aluminum salt, polystyrene microspheres, mesoporous template agent P123, potassium oxalate, oxalic acid, ethylene glycol, methanol, absolute ethanol, fatty alcohol-polyoxyethylene ether, and distilled water; (2) preparing a solution of an alumina precursor, a solution of a mesoporous template, a polystyrene microsphere macroporous template and a potassium oxalate coordination solution of an active component precursor; (3) mixing the solution of the alumina precursor and the solution of the mesoporous template to obtain a mixed solution; (4) immersing the polystyrene microsphere macroporous template into the mixed solution and filling the mixed solution into the polystyrene microsphere macroporous template to obtain a primary composite; (5) spraying the active component precursor potassium oxalate coordination solution into the primary composite and allowing the active component precursor potassium oxalate coordination solution to permeate into the primary composite to obtain a secondary composite; (6) and roasting the secondary complex by a two-stage temperature programming roasting method to obtain the alumina carbonyl sulfide hydrolysis catalyst with the step holes.
Although the alumina carbonyl sulfide catalyst prepared by the method has good desulfurization effect, the preparation method is not only complicated in preparation process, but also uses a large amount of organic solvent, and pollutes the environment.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the preparation method of the alumina carbonyl sulfide catalyst in the prior art is complicated and a large amount of organic solvent is used in the preparation process, thereby providing a preparation method of porous alumina supported transition metal and application thereof in removing COS.
Therefore, the invention provides the following technical scheme:
a preparation method of porous alumina supported transition metal comprises the following steps:
grinding the precursor compound of the aluminum, the transition metal salt and the soft template, dripping acid, curing, washing, drying and roasting to obtain the aluminum-based composite material.
Further, the grinding time is 3-10 min.
Further, the molar ratio of the precursor compound of aluminum to the transition metal salt is (8-12) to (0.02-0.04);
the mass ratio of the precursor compound of the aluminum to the soft template is (1.8-2.2) to (0.125-1);
the mass-to-volume ratio of the precursor compound of aluminum to the acid is (1.8-2.2) g: (0.01-0.1) ml.
Furthermore, the curing temperature is 60-180 ℃ and the time is 1-24 h.
Further, the solvent used for washing is ethanol;
the drying temperature is 60-80 deg.C, and the drying time is 6-10 h.
Further, the roasting temperature is 400-550 ℃, the time is 1-24h, and the heating rate is 2-5 ℃/min.
Further, the precursor compound of Al is at least one of aluminum isopropoxide, aluminum isobutoxide, aluminum sec-butoxide and aluminum ethoxide;
the transition metal salt is acetate and/or citrate of transition metal;
the soft template is Cetyl Trimethyl Ammonium Bromide (CTAB) and/or Polyethyleneimine (PEI);
the acid is at least one of acetic acid, phosphoric acid, sulfuric acid, formic acid, hydrochloric acid, oxalic acid and citric acid.
Further, the acetate is at least one of iron acetate, cobalt acetate, nickel acetate, copper acetate and zinc acetate;
the citrate is at least one of ferric citrate, cobalt citrate, nickel citrate, cupric citrate and zinc citrate.
The invention also provides the porous alumina supported transition metal prepared by the preparation method of the porous alumina supported transition metal.
The invention also provides application of the porous alumina supported transition metal prepared by the preparation method of the porous alumina supported transition metal in removing COS.
The technical scheme of the invention has the following advantages:
1. the preparation method of the porous alumina supported transition metal provided by the invention comprises the following steps: grinding the precursor compound of the aluminum, the transition metal salt and the soft template, dripping acid, curing, washing, drying and roasting to obtain the aluminum-based composite material. The preparation method adopts a grinding mode, does not need to add an organic solvent, does not cause harm to the environment, does not generate pressure in the reaction process, and is beneficial to large-scale production; in the washing step after curing, unreacted precursor compounds of aluminum and the soft template can be washed away, so that the pore structure and the specific surface area of the catalyst are improved; a drying step before calcination, which can prevent pore blockage and increase the specific surface area of the catalyst; the soft template can be converted into carbon dioxide and water to be removed through a roasting step, and a precursor compound of aluminum is converted into aluminum oxide and loaded with transition metal, so that the catalytic performance of the aluminum oxide is improved; and the preparation method is simple, and the prepared porous alumina-supported transition metal has high conversion rate of carbonyl sulfide (COS) and good stability.
2. According to the preparation method of the porous alumina supported transition metal, provided by the invention, the grinding time is limited, so that the catalytic performance and stability of the prepared porous alumina supported transition metal can be further improved; poor pore structure distribution caused by too short grinding time is prevented; the grinding time is too long, resulting in slight clogging of the pore size.
3. According to the preparation method of the porous alumina supported transition metal, provided by the invention, the pore structure, the formability, the specific surface area and the catalytic performance of the prepared porous alumina supported transition metal can be further improved by limiting the dosage of the precursor compound of aluminum, the transition metal salt, the soft template and the acid.
4. According to the preparation method of the porous alumina supported transition metal, provided by the invention, the pore size distribution, the specific surface area and the catalytic performance of the prepared porous alumina supported transition metal can be further improved by limiting the curing temperature and time.
5. According to the preparation method of the porous alumina supported transition metal, provided by the invention, the pore size distribution and the pore structure of the prepared porous alumina supported transition metal can be further improved by limiting ethanol as a washing solvent, and the washed waste liquid can be recycled without causing pollution.
6. According to the preparation method of the porous alumina supported transition metal, provided by the invention, the specific surface area, the catalytic performance and the stability of the prepared porous alumina supported transition metal can be further improved by limiting the roasting temperature, time and heating rate.
7. According to the preparation method of the porous alumina-supported transition metal, provided by the invention, the pore size distribution, the pore structure, the specific surface area and the catalytic performance of the prepared porous alumina-supported transition metal can be further improved by limiting the precursor compound, the transition metal salt, the soft template and the acid.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an XRD pattern of porous alumina supported transition metals prepared in examples 1-3 of the present invention;
FIG. 2 shows transition metal-supported N on porous alumina prepared in examples 1 to 3 of the present invention2Adsorption and desorption curves;
FIG. 3 is a graph of the specific surface area-pore size distribution of porous alumina supporting transition metals prepared in examples 1-3 of the present invention;
FIG. 4 is a selective adsorption curve of carbonyl sulfide (COS), nitrogen and hydrogen of the transition metal supported on the porous alumina prepared in example 1 of the present invention.
Reference numerals:
the numerical designations in the various drawings each represent a corresponding embodiment.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a catalyst with zinc loaded on porous alumina, and the preparation method comprises the following steps:
mixing and grinding aluminum isopropoxide, zinc acetate and CTAB for 5min, transferring to a reaction kettle with a polytetrafluoroethylene lining, dropwise adding acetic acid, uniformly stirring, transferring to a drying oven at 100 ℃ for curing for 24h, washing unreacted aluminum isopropoxide and CTAB with ethanol after curing, drying at 70 ℃ for 6h, heating to 550 ℃ at the speed of 2 ℃/min in the air atmosphere, and roasting for 20h to obtain the aluminum oxide zinc-loaded catalyst.
Wherein the molar ratio of aluminum isopropoxide to zinc acetate is 10: 0.03;
the mass ratio of aluminum isopropoxide to CTAB is 2.0: 0.5;
the mass-volume ratio of aluminum isopropoxide to acetic acid is 2.0 g: 0.1 ml.
Example 2
This example provides a porous alumina supported iron catalyst, which is prepared as follows:
mixing and grinding aluminum isopropoxide, iron acetate and CTAB for 3min, transferring to a reaction kettle with a polytetrafluoroethylene lining, dropwise adding formic acid, uniformly stirring, transferring to a drying oven at 60 ℃ for curing for 18h, washing unreacted aluminum isopropoxide and CTAB with ethanol after curing, drying at 80 ℃ for 10h, heating to 500 ℃ at the speed of 5 ℃/min in an air atmosphere, and roasting for 24h to obtain the aluminum oxide supported iron catalyst.
Wherein the molar ratio of aluminum isopropoxide to iron acetate is 8: 0.02;
the mass ratio of aluminum isopropoxide to CTAB is 1.8: 1;
the mass-volume ratio of aluminum isopropoxide to acetic acid is 1.8 g: 0.01 ml.
Example 3
The embodiment provides a porous alumina copper-loaded catalyst, and the preparation method comprises the following steps:
mixing and grinding aluminum isopropoxide, copper acetate and CTAB for 10min, transferring to a reaction kettle with a polytetrafluoroethylene lining, dropwise adding hydrochloric acid, uniformly stirring, transferring to a drying oven at 180 ℃ for curing for 3h, washing unreacted aluminum isopropoxide and CTAB with ethanol after curing, drying at 60 ℃ for 7h, heating to 450 ℃ at the speed of 3 ℃/min in the air atmosphere, and roasting for 1h to obtain the aluminum oxide copper-loaded catalyst.
Wherein the molar ratio of the aluminum isobutyl alkoxide to the copper acetate is 8: 0.04;
the mass ratio of the aluminum iso-butoxide to the CTAB is 1.8: 0.125;
the mass-volume ratio of the aluminum iso-butoxide to the acetic acid is 1.8 g: 0.1 ml.
Example 4
The embodiment provides a catalyst of porous alumina supported cobalt and copper, and the preparation method comprises the following steps:
mixing and grinding aluminum sec-butoxide, cobalt citrate, copper citrate and CTAB for 4min, transferring into a reaction kettle with a polytetrafluoroethylene lining, dropwise adding citric acid, uniformly stirring, transferring into a drying box at 80 ℃ for curing for 20h, washing away unreacted aluminum isopropoxide and CTAB by using ethanol after curing, drying at 70 ℃ for 8h, heating to 400 ℃ at the speed of 4 ℃/min in an air atmosphere, and roasting for 15h to obtain the catalyst of the aluminum oxide loaded with cobalt and copper.
Wherein the molar ratio of the aluminum sec-butoxide to the cobalt citrate to the copper citrate is 12:0.01: 0.01;
the mass ratio of the aluminum sec-butoxide to the CTAB is 2.2: 0.125;
the mass-volume ratio of the aluminum sec-butoxide to the citric acid is 2.2 g: 0.01 ml.
Example 5
The embodiment provides a catalyst with porous alumina supported nickel, which is prepared by the following steps:
mixing and grinding aluminum ethoxide, nickel acetate, CTAB and PEI for 8min, transferring into a reaction kettle with a polytetrafluoroethylene lining, dropwise adding acetic acid and citric acid, uniformly stirring, transferring into a drying oven at 120 ℃ for curing for 6h, washing unreacted aluminum isopropoxide, CTAB and PEI with ethanol after curing, drying at 70 ℃ for 9h, heating to 530 ℃ at the speed of 5 ℃/min in the air atmosphere, and roasting for 5h to obtain the aluminum oxide supported nickel catalyst.
Wherein the molar ratio of aluminum ethoxide to nickel acetate is 12: 0.04;
the mass ratio of aluminum ethoxide to PEI to CTAB is 2.2:0.5: 0.5;
the mass-volume ratio of the aluminum ethoxide, the acetic acid and the citric acid is 2.2 g: 0.05 ml: 0.05 ml.
Example 6
This example provides a catalyst with copper and iron supported on porous alumina, and its preparation method is as follows:
mixing and grinding aluminum isopropoxide, aluminum ethoxide, copper citrate, iron acetate and PEI for 6min, transferring to a reaction kettle with a polytetrafluoroethylene lining, dropwise adding citric acid, uniformly stirring, transferring to a drying box at 150 ℃ for curing for 1h, washing unreacted aluminum isopropoxide, aluminum ethoxide and PEI with ethanol after curing, drying at 70 ℃ for 6h, heating to 420 ℃ at the speed of 2 ℃/min in the air atmosphere, and roasting for 12h to obtain the aluminum oxide supported copper and iron catalyst.
Wherein the molar ratio of aluminum isopropoxide to aluminum ethoxide to copper citrate to iron acetate is 5:5:0.01: 0.01;
the mass ratio of the mixture of aluminum isopropoxide and aluminum ethoxide to PEI is 2.0: 0.8;
the mass-to-volume ratio of the mixture of aluminum isopropoxide and aluminum ethoxide to citric acid is 2.0 g: 0.05 ml.
Comparative example 1
The comparative example provides a porous alumina zinc-loaded catalyst, the preparation method of which is as follows:
dissolving aluminum isopropoxide, zinc acetate and CTAB in ethanol, uniformly mixing, dropwise adding acetic acid, uniformly stirring, transferring to a drying oven at 100 ℃ for curing for 24h, washing unreacted aluminum isopropoxide and CTAB with ethanol after curing, drying at 70 ℃ for 6h, heating to 550 ℃ at the speed of 2 ℃/min in the air atmosphere, and roasting for 20h to obtain the aluminum oxide zinc-loaded catalyst.
Wherein the molar ratio of aluminum isopropoxide to zinc acetate is 10: 0.03;
the mass ratio of aluminum isopropoxide to CTAB is 2.0: 0.5;
the mass-volume ratio of aluminum isopropoxide to acetic acid is 2.0 g: 0.1 ml.
Experimental example 1
The porous alumina supported transition metal catalysts prepared in examples 1 to 3 were subjected to XRD, pore size distribution and adsorption performance tests, respectively, wherein XRD was tested by using an X-ray diffractometer manufactured by PANalytical, the model of which is X' pertro, in the netherlands, and the specific test method was:
the X-ray source is a Cu target, the incident wavelength of K alpha is 0.15418nm, the graphite monochromator has the working voltage of 40kV, the working current of 40mA, the scanning speed of 0.20s/step, the step length of 0.013 degree/step and the scanning range of 20-80 degrees.
The analysis of physical structure parameters such as specific surface area and pore size of the micropores was carried out using an ASAP 2020M physical adsorption apparatus from Micrometric corporation, USA. The specific test method comprises the following steps: weighing 0.1g of the sieved catalyst sample of 40-60 meshes respectively, degassing at 160 ℃ under high vacuum for 12h, and treating with high-purity N2As adsorbates, in liquidsThe low temperature N is obtained by testing at the nitrogen temperature (-196 ℃)2Absorbing and desorbing the isotherm, and obtaining the specific surface area and the pore size distribution of the catalyst.
COS and N of the catalyst were carried out using a TriStar II physical adsorption apparatus manufactured by Micrometric corporation, USA2And H2Selective adsorption performance test. The specific test method comprises the following steps: weighing 100mg of the sieved catalyst sample of 40-60 meshes, degassing at 160 deg.C under high vacuum for 12h, and respectively treating with high-purity COS and N2、H2For adsorbate gas, the test temperature was 0 ℃.
As can be seen from FIG. 1, the catalysts obtained in examples 1-3 all showed two relatively weak diffraction peaks at 40-50 ° and 60-70 °, indicating that the catalyst structure using alumina as a carrier has been synthesized, and no diffraction peak of the transition metal is observed, indicating that the transition metal is uniformly dispersed on the alumina carrier.
As can be seen from FIGS. 2 and 3, the catalysts obtained in examples 1 to 3 all exhibited typical type IV isotherms, N2The adsorption capacity is 0.6<P/P0<The sharp increase within the range of 0.9 indicates that mesopores exist, and the mesoporous material has larger specific surface area, relatively larger pore diameter and regular pore channel structure and can well adsorb sulfide.
As can be seen from FIG. 4, in COS and N2And H2The catalyst prepared in example 1 has excellent selective adsorption performance on COS in the ternary gas.
Experimental example 2
The catalysts prepared in the examples and the comparative examples are respectively subjected to catalytic performance tests, the test results are shown in table 1, and the specific test method comprises the following steps: the loading of the catalyst is 0.2g, the reaction temperature is 30-170 ℃, and the concentration of COS in the feed gas is 110mg/m3，N2The inner diameter of the reaction tube is 5mm for equilibrium gas, the flow rate of the raw material gas is 20ml/min, and the temperature of the water vapor in the reactant is 40 ℃.
The stability test is carried out on the same device, and the test conditions are as follows: the loading of the catalyst was 0.2g, the reaction temperature was 110 ℃ and the concentration of COS in the feed gas was 110mg/m3，N2The inner diameter of the reaction tube is 5mm for balance gas, and the flow rate of the raw material gas20ml/min, the temperature of water vapor in reactants is 40 ℃, and the long-acting stability test time is 40 h.
The activity and stability results of the catalysts prepared in each example and comparative example were expressed in terms of COS conversion, and the COS concentrations in the feed gas and the effluent gas were signal-traced by FL-GC9720 gas chromatograph.
The calculation formula of the COS conversion rate is as follows:
the conversion (%) of COS was (mass of COS in the feed gas-mass of COS in the effluent gas)/mass of COS in the feed gas × 100%.
TABLE 1 test results
As can be seen from the data in the table above, the porous alumina catalyst loaded with transition metals provided by the invention has good carbonyl sulfide (COS) conversion efficiency and good stability; the preparation method is simple, and no organic solvent is required to be added in the preparation process.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A preparation method of porous alumina supported transition metal is characterized by comprising the following steps: grinding the precursor compound of the aluminum, the transition metal salt and the soft template, dripping acid, curing, washing, drying and roasting to obtain the aluminum-based composite material.
2. The method for preparing transition metal supported on porous alumina according to claim 1, wherein the grinding time is 3 to 10 min.
3. The method for preparing a transition metal supported on porous alumina according to claim 1 or 2, wherein the molar ratio of the precursor compound of aluminum to the transition metal salt is (8-12): 0.02-0.04);
the mass ratio of the precursor compound of the aluminum to the soft template is (1.8-2.2) to (0.125-1);
the mass-volume ratio of the precursor compound of aluminum to the acid is (1.8-2.2): (0.01-0.1).
4. The method for preparing a transition metal supported on porous alumina according to any of claims 1 to 3, wherein the curing temperature is 60 to 180 ℃ and the curing time is 1 to 24 hours.
5. The method for preparing a transition metal supported on porous alumina according to any one of claims 1 to 4, wherein the solvent used for washing is ethanol;
the drying temperature is 60-80 deg.C, and the drying time is 6-10 h.
6. The method for preparing the porous alumina-supported transition metal according to any one of claims 1 to 5, wherein the calcination temperature is 400-550 ℃, the time is 1-24h, and the temperature rise rate is 2-5 ℃/min.
7. The method of any one of claims 1-6, wherein the precursor compound of Al is at least one of aluminum isopropoxide, aluminum isobutoxide, aluminum sec-butoxide, and aluminum ethoxide;
the transition metal salt is acetate and/or citrate of transition metal;
the soft template is cetyl trimethyl ammonium bromide and/or polyethyleneimine;
the acid is at least one of acetic acid, phosphoric acid, sulfuric acid, formic acid, hydrochloric acid, oxalic acid and citric acid.
8. The method for preparing the transition metal supported on the porous alumina according to claim 7, wherein the acetate is at least one of iron acetate, cobalt acetate, nickel acetate, copper acetate or zinc acetate;
the citrate is at least one of ferric citrate, cobalt citrate, nickel citrate, cupric citrate and zinc citrate.
9. A porous alumina supported transition metal produced by the method of any one of claims 1 to 8.
10. Use of a porous alumina supported transition metal prepared by the process for its preparation according to any one of claims 1 to 8 for the removal of COS.
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