CN110124710A - A kind of NEW TYPE OF COMPOSITE metal oxide catalyst and preparation method thereof - Google Patents
A kind of NEW TYPE OF COMPOSITE metal oxide catalyst and preparation method thereof Download PDFInfo
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- CN110124710A CN110124710A CN201910543206.1A CN201910543206A CN110124710A CN 110124710 A CN110124710 A CN 110124710A CN 201910543206 A CN201910543206 A CN 201910543206A CN 110124710 A CN110124710 A CN 110124710A
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- Prior art keywords
- catalyst
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- metal oxide
- new type
- composite metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 37
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 22
- JFCSMCOOWAPNFY-UHFFFAOYSA-N C=C.C(CC(O)(C(=O)O)CC(=O)O)(=O)O Chemical group C=C.C(CC(O)(C(=O)O)CC(=O)O)(=O)O JFCSMCOOWAPNFY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- ZLBAASVJXVQLFZ-UHFFFAOYSA-M azanium sodium 2-hydroxypropane-1,2,3-tricarboxylic acid carbonate Chemical compound C([O-])([O-])=O.[Na+].C(CC(O)(C(=O)O)CC(=O)O)(=O)O.[NH4+] ZLBAASVJXVQLFZ-UHFFFAOYSA-M 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 238000009841 combustion method Methods 0.000 claims description 7
- 239000002816 fuel additive Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 244000248349 Citrus limon Species 0.000 claims description 3
- 235000005979 Citrus limon Nutrition 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 3
- OQUFOZNPBIIJTN-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;sodium Chemical compound [Na].OC(=O)CC(O)(C(O)=O)CC(O)=O OQUFOZNPBIIJTN-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- XABNKAQYYIZELW-UHFFFAOYSA-K trisodium 3-carboxy-3,5-dihydroxy-5-oxopentanoate carbonate Chemical compound C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].OC(=O)O.[Na+].[Na+] XABNKAQYYIZELW-UHFFFAOYSA-K 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 14
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 4
- 239000012855 volatile organic compound Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910002226 La2O2 Inorganic materials 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- -1 polyparaphenylene Polymers 0.000 description 7
- 229910002254 LaCoO3 Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229920000265 Polyparaphenylene Polymers 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910018279 LaSrMnO Inorganic materials 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- WWPVPDAZUAHBHK-WCCKRBBISA-N (2s)-2-amino-5-(diaminomethylideneamino)pentanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.OC(=O)[C@@H](N)CCCNC(N)=N WWPVPDAZUAHBHK-WCCKRBBISA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 description 1
- 229930064664 L-arginine Natural products 0.000 description 1
- 235000014852 L-arginine Nutrition 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- TYXNQDAIWMHZAY-UHFFFAOYSA-N [C].NC(N)=O Chemical compound [C].NC(N)=O TYXNQDAIWMHZAY-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- NLNLFIQELFXBSN-UHFFFAOYSA-M azanium;sodium;3-carboxy-3-hydroxypentanedioate Chemical compound [NH4+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O NLNLFIQELFXBSN-UHFFFAOYSA-M 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- 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
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
- B01D2257/7025—Methane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of NEW TYPE OF COMPOSITE metal oxide catalyst and preparation method thereof, the general formula of the active component of the catalyst is ABO3‑BOn‑A2O2CO3, wherein A is selected from one or both of alkali earth metal or rare earth element, and B is selected from transition metal element, and the value range of n is 1-2.NEW TYPE OF COMPOSITE metal oxide catalyst provided by the invention, passes through ABO3、BOn、A2O2CO3Synergistic effect between three kinds of oxides, significantly improve the catalytic activity of catalyst, the catalyzed conversion of methane can be realized under cryogenic without adding noble metal, with excellent low-temperature catalytic activity and service life, it can be applied to the fields such as processing, CO catalysis oxidation and the VOCs processing of low-concentration methane tail gas.
Description
Technical field
The present invention relates to catalysis material preparation technical field more particularly to a kind of NEW TYPE OF COMPOSITE metal oxide catalyst and
Preparation method.
Background technique
As getting worse for environmental pollution and energy shortage problem subtracts there is an urgent need to more effectively utilize the existing energy
The generation of of low pollution object.In recent years, a series of environment of bring and health problem cause in natural gas extraction and application process
Extensive concern.There are lean combustion methane gas (CH in the exhaust gas such as coalmine ventilation gas, industrial combustion4< 1%Vol), concentration is extremely low
Can not directly be burnt utilization, and methane is a kind of potent greenhouse gases, and direct emission will cause air pollution.Therefore, it realizes poor
It is very necessary that combustion methane gas, which effectively purifies,.
Methane catalytic combustion technology can realize effective conversion of lean combustion methane gas under lower temperature.But it can be produced in reacting
Raw a large amount of vapor, while containing a small amount of sulphur in natural gas, this requires catalyst that must have higher low temperature active and water
Thermal stability, and certain anti-poisoning capability.Currently, the common catalyst in the field can be divided into noble metal by its active component
Catalyst and non-noble metal oxide type catalyst two major classes.It is studied in noble metal catalyst more for Pd, Pt, Au or it is more
First catalyst, activity mostly come from noble metal outer space d track and capture the reactivity keto species (O/O that oxygen is formed2-), greatly
The catalysis ignition of methane mostly can be realized at 400 DEG C or less.Non-noble metal oxide type catalyst can be divided into single metal oxidation
Object type catalyst and mixed-metal oxides.Such catalyst has ideal controllable metal state, and lattice oxygen evolution can produce
Raw Lacking oxygen or migration form adsorption activity oxygen species.In practical applications, although noble metal catalyst low temperature active is excellent,
The poisoning of its easy-sintering, or fall off from carrier, lead to catalyst inactivation, to limit its development.In contrast, base metal oxygen
Compound has certain low-temperature catalytic activity, and resourceful, and low in cost, stability is good, and there is more wide research to answer
Use prospect.Rare earth element can effectively improve the stability and activity of catalyst, but its catalytic activity is urged apart from noble metal
Also there is a big difference for agent.How on the basis of keeping the stability of rare earth O composite metallic oxide catalyst, reaction is improved
Activity is the important research direction of its further industrial applications.
Summary of the invention
Aiming at the problem that it still needs further improvement for the activity of composite metal oxide catalyst in the prior art, the present invention is provided
A kind of NEW TYPE OF COMPOSITE metal oxide catalyst and preparation method thereof.
In order to solve the above technical problems, present invention provide the technical scheme that
A kind of NEW TYPE OF COMPOSITE metal oxide catalyst, the general formula of the active component of the catalyst are xABO3-yBOn-
zA2O2CO3, wherein A is selected from one or both of alkali earth metal or rare earth element, and B is selected from transition metal element, n's
Value range is 1-2.
Compared with the existing technology, in NEW TYPE OF COMPOSITE metal oxide catalyst provided by the invention, there are Ca-Ti ore type oxygen
Compound ABO3, transition metal oxide BOnWith metal carbon oxide A2O2CO3Mixture, make perofskite type oxide, transition gold
Belong to oxide and metal carbon oxide to mix in molecular level, ABO3、BOn、A2O2CO3It acts synergistically, shows between three kinds of oxides
The catalytic activity that work improves catalyst can realize 50% first without adding noble metal under 360 DEG C or so of cryogenic conditions
The catalyzed conversion of alkane, the catalyzed conversion of 450 DEG C or so 90% methane of realization, has excellent low-temperature catalytic activity, can be applied to
The fields such as processing, CO catalysis oxidation and the VOCs processing of low-concentration methane tail gas.
N be with the matched oxygen atomicity of B element valence state, even if the oxygen of the chemical valence of oxygen element and B element equivalence
Atomicity.The value range of n is preferably 1-2.If the metal state of oxide contained in composite oxides is the value of+3, n
It is 3/2；If the value that the metal state of the oxide is+2, n is 1；If the metal state of the oxide is that the value of+4, n is
2.If B is Co or Fe, when n 4/3, B are Mn, when n 2, B are Ni or Cu, n 1.
It, can representated by two kinds of elements if A is two kinds of elements in alkali earth metal or rare earth element in the present invention
It can be mixed between soluble metal salts with any molar ratio.
Preferably, the alkaline earth element is Mg, Ca, Sr or Ba and/or the thulium is La, Ce or Sm；
And/or the transition metal element is Co, Mn, Cu, Ni or Fe.
Preferred element species can make catalyst have good low-temperature catalytic activity and higher catalyst to use the longevity
Life.
X, y, z is respectively ABO3、BOn、A2O2CO3The molal quantity of three kinds of oxides, it is preferred that x:y:z=0.6-1:0.8-
1:2-2.5。
The content of each oxide can make to cooperate between the oxide of three kinds of forms in catalyst and reach in preferred catalyst
Optimal catalytic activity makes catalyst have both the advantages of thermostabilization is good, catalytic activity is high and long service life.
The present invention also provides a kind of preparation methods of NEW TYPE OF COMPOSITE metal oxide catalyst, include at least following step
It is rapid:
Step a prepares perovskite type catalyst ABO3；
Step b, by the perovskite type catalyst ABO3It is added in hydrothermal reaction kettle, deionized water, lemon is then added
Acid-ethylenediamine water solubility carbon dots modifying agent and/or sodium citrate-ammonium hydrogen carbonate water solubility carbon dots modifying agent, are uniformly dispersed, in
200-240 DEG C of reaction 2-8h is filtered, and is washed, and grinding, gained powder roasts 1- under conditions of temperature programming is to 480-520 DEG C
1.5h obtains the NEW TYPE OF COMPOSITE metal oxide catalyst.
The preparation method of NEW TYPE OF COMPOSITE metal oxide catalyst provided by the invention is prepared first with conventional method
Obtain perovskite type catalyst ABO3, secondary treatment then is carried out to it using hydro-thermal method, so that perovskite originally easy to reunite
Type catalyst is partly dissolved recrystallization under conditions of hydro-thermal method high temperature and pressure, improves the specific surface area of catalyst；And in the mistake
Citrate-ethylene diamine water solubility carbon dots modifying agent and/or sodium citrate-ammonium hydrogen carbonate water solubility carbon dots modifying agent are added in journey,
Enter carbon dots organic molecule inside perovskite structure, the overall performance of modified catalyst, rather than adsorb only on perovskite
The physical and chemical performance on its surface of the surface modification of structure obtains the ABO of novel porous structure finally by roasting3-B3O4-A2O2CO3
Catalyst.
The ABO that the present invention is prepared3-B3O4-A2O2CO3Three objects are not mutually simple physical mixeds in catalyst, three
Special C-O key is formd between kind molecule, there are chemical interaction, three's synergistic effect plays rush to whole catalysis reaction
Into effect, energy effective activation methane gas molecule realizes the catalysis oxidation under cryogenic conditions to low-concentration methane.
Preferably, the preparation method of the Citrate-ethylene diamine water solubility carbon dots modifying agent includes the following steps: second two
Amine and citric acid are added in deionized water, are uniformly mixed, and in 170-190 DEG C of reaction 8-10h, obtain Citrate-ethylene diamine water solubility
Carbon dots modifying agent.
The sodium citrate-ammonium hydrogen carbonate water solubility carbon dots modifying agent preparation method includes the following steps: ethylenediamine
And citric acid or sodium citrate and ammonium hydrogen carbonate, it is added in deionized water, is uniformly mixed, in 170-190 DEG C of reaction 8-10h, obtains
Sodium citrate-ammonium hydrogen carbonate water solubility carbon dots modifying agent.
Citrate-ethylene diamine modifying agent provided by the invention and sodium citrate-ammonium bicarbonate modifiers are to ABO3-B3O4-
A2O2CO3Catalyst affinity with higher, can be during perovskite type catalyst secondary crystallization well into Ca-Ti ore type
In the internal structure of catalyst, so that the catalyst of preparation has, specific surface area of catalyst is big, pore quantity is more, active site
Advantage more, catalytic activity is high.
Preferably, the molar ratio of the citric acid and ethylenediamine is 80-100:1.
Preferably, the molar ratio of the sodium citrate and ammonium hydrogen carbonate is 1:20-50.
Preferably, the additional amount of the deionized water is the citric acid and ethylenediamine quality sum or the citric acid
30-40 times of sodium and ammonium hydrogen carbonate quality sum.
Temperature, the control of time in the ratio and preparation process of preferred each substance, can make the water-soluble carbon dots of preparation
For relatively uniform spheric granules, the partial size of carbon dots is in nearly normal distribution, average grain diameter 6-8nm.
Preferably, in step b, the additional amount of the deionized water is that 10-15mL is added in every gram of perovskite type catalyst.
Preferably, the additional amount of the modifying agent is that 2-5mL is added in every gram of perovskite type catalyst.
The ratio of preferred each substance is conducive to the Kong Rong, specific surface area and the catalytic activity that improve catalyst.
Preferably, in step a, perovskite type catalyst ABO is prepared using sol-gal process3, have that steps are as follows:
The soluble metallic salt of element representated by A, B is weighed according to the molar ratio of 1:0.8-1.5, and deionized water is added
In, it is uniformly mixed, obtains the mixed solution of 0.8-2.0mol/L；
The amount that substance is added is 1.2-1.5 times of molal quantity summation of the citric acid addition mixing for the element that A and B is represented
It in solution, is uniformly mixed, forms wet colloidal sol in 75-85 DEG C of stirring, in 90-100 DEG C of standing 1-1.5h, be cooled to 20-30 DEG C always
Change 8-10h, dry, grinding, 450-500 DEG C of progress first time roasting, 750-800 DEG C carries out second and roast, and obtains Ca-Ti ore type
Catalyst ABO3。
Perovskite type catalyst ABO is prepared by above-mentioned sol-gal process3, it is horizontal to can be realized metal salt precursor molecule
On dispersion, avoid the agglomeration between catalyst granules as far as possible so that preparation catalyst specific surface area with higher.
Preferably, in step a, perovskite type catalyst ABO is prepared using solution combustion method3, have that steps are as follows:
The soluble metallic salt of element representated by A, B is weighed according to the molar ratio of 1:0.8-1.5, and deionized water is added
In, it is uniformly mixed, obtains the mixed solution of 0.5-1.5mol/L；
Fuel and fuel additive are added in the mixed solution, is uniformly mixed, in 600-800 DEG C of roasting 4-6h, obtains
Perovskite type catalyst ABO3；
Wherein, the molar ratio of the molal quantity summation for the element that the fuel, fuel additive and A and B are represented is 2-5:1:
1。
Heretofore described fuel can be one of urea, glycine, sucrose or citric acid, and the fuel additive can
For one of ammonium acetate, starch or polyethylene glycol.
Perovskite type catalyst ABO is prepared by above-mentioned solution combustion method3, it is swift in response, saves the reaction time, and obtain
Specific surface area of catalyst it is larger, and preparation process is simple, saves preparation cost.
Preferably, in step b, the rate of temperature programming is 0.8-1.2 DEG C/min.
Preferred heating rate can reduce the agglomeration in calcination process between catalyst granules to the greatest extent, and be conducive to press down
The increase of catalyst granules processed makes the more active sites of catalyst exposure, further increases the activity of catalyst.
The soluble metallic salt of element representated by A, B is nitrate in the present invention.
Detailed description of the invention
Fig. 1 is (XRD) map of O composite metallic oxide catalyst prepared by embodiment 1；
Fig. 2 is the catalytic activity curve graph of O composite metallic oxide catalyst catalysis oxidation methane prepared by embodiment 1；
Fig. 3 is O composite metallic oxide catalyst and La prepared by embodiment 12O2CO3、Co3O4And LaCoO3Three kinds pure
The C1s of the x-ray photoelectron spectroscopy (XPS) of substance analyzes map；(a) embodiment 1, (b) La2O2CO3, (c) CoO3, (d)
LaCoO3；
Fig. 4 is (XRD) map of O composite metallic oxide catalyst prepared by embodiment 2；
Fig. 5 is the catalytic activity curve graph of O composite metallic oxide catalyst catalysis oxidation methane prepared by embodiment 2；
Fig. 6 is (XRD) map of O composite metallic oxide catalyst prepared by embodiment 3；
Fig. 7 is the catalytic activity curve graph of O composite metallic oxide catalyst catalysis oxidation methane prepared by embodiment 3.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment 1
The embodiment of the present invention provides a kind of NEW TYPE OF COMPOSITE metal oxide catalyst, and preparation method includes the following steps:
1. preparing LaCoO using sol-gal process3:
La:Co=1:1.2 weighs lanthanum nitrate and cobalt nitrate in molar ratio, and the amount of additive is the sum of La and Co mole
1.4 times of citric acid dissolves in deionized water, obtains the precursor solution of metal molar concentration 1.0mol/L；Solution is placed in
80 DEG C in heating water bath pot, mechanical stirring is to wet colloidal sol is formed, and 90 DEG C of standing 1h, aging 8h obtains gel under room temperature later；It will
Gel is placed in 90 DEG C of baking oven and is dried to obtain xerogel；Xerogel grinding, 500 DEG C of pre-burnings of electric furnace move to horse to black powder later
Not 800 DEG C of roasting 5h of furnace obtain the LaCoO of sol-gal process preparation after natural cooling3。
2. preparing Citrate-ethylene diamine water solubility carbon dots modifying agent:
1:80-100 weighs ethylenediamine and citric acid in molar ratio, is put into reaction kettle, and deionized water is added to reaction kettle
Compactedness obtains Citrate-ethylene diamine water solubility carbon dots modifying agent to 60%-80%, 170 DEG C of hydro-thermal 10h.
3. by the LaCoO of preparation3Carry out hydrothermal modification treatment:
Using polyparaphenylene reaction kettle liner, deionized water, LaCoO are sequentially added3With Citrate-ethylene diamine water-soluble carbon
Point modifying agent, 200 DEG C of hydrothermal temperature, hydro-thermal duration 4h.Product filtering and washing is taken out, 80 DEG C of baking ovens place 4h, and natural cooling is ground
Mill, 500 DEG C of roasting 1h (1 DEG C/min heating rate) of Muffle furnace, sample natural cooling aoxidize to get to new and effective composition metal
Object type catalyst, main object phase composition are 16%LaCoO3- 20%Co3O4- 64%La2O2CO3。
The additional amount of deionized water is that 10-15mL is added in every gram of perovskite type catalyst；Citrate-ethylene diamine is water-soluble
The additional amount of carbon dots modifying agent is that 2-5mL is added in every gram of perovskite type catalyst.
0.8LaCoO3-0.9Co3O4-2.2La2O2CO3The XRD spectrum of catalyst is as shown in Figure 1.
The metal composite oxide 0.8LaCoO prepared in the present embodiment 1 is evaluated using catalyst test apparatus3-
0.9Co3O4-2.2La2O2CO3, the 200mg catalyst, catalyst particle size 40-60 mesh are taken, reaction gas forms (volume fraction):
1%CH4, 99% mixing air, gas velocity 99mL/min, the air inlet of methane and tail gas concentration are divided online using gas-chromatography
Analysis.The catalyst activity test curve of the present embodiment 1 is as shown in Figure 2.Mixed-metal oxides in the present embodiment 1
0.8LaCoO3-0.9Co3O4-2.2La2O2CO3T50%It is 369 DEG C, T90%It is 431 DEG C, complete conversion temperature is 466 DEG C, is kept
Temperature follow-on test 72h, methane conversion is still 95%, and it is excellent methyl hydride catalyzed to illustrate that catalyst prepared by the present invention has
Activity and service life.
Reaction condition in this present embodiment in step a, step c replaces with other reaction conditions that the present invention limits, system
Standby obtained LaCoO3-Co3O4-La2O2CO3Catalyst can obtain and the comparable performance of above-mentioned catalyst.
In order to study the interaction in catalyst prepared by the present invention between three kinds of oxides, inventor is prepared for
La2O2CO3、Co3O4And LaCoO3The pure material of three kinds of object phases, and to mixing gold prepared by these three pure materials and embodiment 1
Belong to oxide and carried out XPS analysis, the C1s fitting map of four kinds of substances is as shown in Figure 3.
In La2O2CO3、Co3O4And LaCoO3Middle C1s can be fitted to two main peaks, oxygen-free C-C in aromatic rings
(284.8eV) and CO3 2-(288.9eV).And the C1s map of 1 sample catalyst of embodiment can be fitted to three main peaks, i.e., it is fragrant
Oxygen-free C-C (284.73eV), C-O (285.7eV) and CO in fragrant ring3 2-(289.51eV), C-O key therein other three
It is not observed in kind pure material.Therefore C-O component is formd in embodiment 1 sample, three kinds of object phase interfaces, existed between oxide
Chemical interaction.This demonstrate that not being simply mixed between three kinds of object phases in the present invention, it is special to form between three kinds of object phases
C-O key.
The XPS swarming data of the C1s of above-mentioned four kinds of substances are as shown in table 1.
Table 1
| C-C | C-O | CO3 2- | |
| LaCoO3 | 284.82 | - | 288.97 |
| Co3O4 | 284.34 | - | 288.21 |
| La2O2CO3 | 284.76 | - | 289.17 |
| Embodiment 1 | 284.73 | 285.70 | 289.51 |
The pure material of above-mentioned three kinds of object phases the preparation method is as follows:
(1) LaCoO is prepared using solution combustion method3:
Stoichiometrically La:Co=1:1 weighs lanthanum nitrate and cobalt nitrate, and urea and ethylenediamine are successively dissolved in deionization
In water, the precursor solution of the metal molar concentration of 1.5mol/L is obtained, 30min is stirred at room temperature, and roast 5h at 700 DEG C,
Obtain the LaCoO of solution combustion method preparation3。
The molar ratio of the lanthanum nitrate and cobalt nitrate total mole number, urea and ethylenediamine is 1:4:1.
(2) Co is prepared using hydro-thermal method3O4:
Stoichiometrically 1:3 weighs cobalt nitrate and sodium hydroxide solution (1mol/L), is dissolved in deionized water, obtains
The precursor solution of the metal molar concentration of 1.5mol/L, is stirred at room temperature 20min, and acquired solution is placed in polyparaphenylene reaction kettle
230 DEG C of hydro-thermal 12h, taking-up roast 200min at 300 DEG C, obtain the Co of hydro-thermal method preparation3O4。
(3) La is prepared using hydro-thermal method2O2CO3:
Stoichiometrically 1:1.2 weighs lanthanum nitrate and sodium hydroxide solution (4mol/L), is dissolved in deionized water, obtains
To the precursor solution of the metal molar concentration of 0.8mol/L, 20min is stirred at room temperature, acquired solution is placed in polyparaphenylene reaction kettle
In 180 DEG C of hydro-thermals for 24 hours, taking-up roast 180min at 500 DEG C, obtain hydro-thermal method preparation La2O2CO3。
Embodiment 2
The embodiment of the present invention provides a kind of NEW TYPE OF COMPOSITE metal oxide catalyst, and preparation method includes the following steps:
1. preparing LaCoO using solution combustion method3:
La:Mn=1:1 weighs lanthanum nitrate and manganese nitrate in molar ratio, and citric acid and polyethylene glycol are dissolved in deionized water,
30min is stirred at room temperature, obtains the precursor solution that total concentration of metal ions is 1.5mol/L, precursor solution is roasted in 700 DEG C
5h is burnt, the LaMnO of solution combustion method preparation is obtained3。
Wherein, the molar ratio of the total mole number of lanthanum nitrate and manganese nitrate, citric acid and polyethylene glycol is 1:4:1.
2. preparing sodium citrate-ammonium hydrogen carbonate water solubility carbon dots modifying agent:
1:20-50 weighs sodium citrate and ammonium hydrogen carbonate in molar ratio, is put into reaction kettle, and deionized water is added to reaction
For kettle compactedness to 60%-80%, 180 DEG C of hydro-thermals to 9h obtain Citrate-ethylene diamine water solubility carbon dots modifying agent.
3. by the LaCoO of preparation3Carry out hydrothermal modification treatment:
Using polyparaphenylene reaction kettle liner, deionized water, LaMnO are sequentially added3It is water-soluble with sodium citrate-ammonium hydrogen carbonate
Property carbon dots modifying agent, 220 DEG C of hydrothermal temperature, hydro-thermal duration 6h.Product filtering and washing is taken out, 80 DEG C of baking ovens place 4h, naturally cold
But grind, 500 DEG C of roasting 1h (0.8 DEG C/min heating rate) of Muffle furnace, sample natural cooling to get arrive new and effective compound gold
Belong to oxide type catalyst, main object phase composition is 18%LaMnO3- 24%MnO2- 64%La2O2CO3。
The additional amount of deionized water is that 10-15mL is added in every gram of perovskite type catalyst；Sodium citrate-ammonium hydrogen carbonate water
The additional amount of dissolubility carbon dots modifying agent is that 2-5mL is added in every gram of perovskite type catalyst.
0.9LaMnO3-1.0MnO2-2.1La2O2CO3The XRD spectrum of catalyst is as shown in Figure 4.
The metal composite oxide 0.9LaMnO prepared in the present embodiment 1 is evaluated using catalyst test apparatus3-
1.0MnO2-2.1La2O2CO3, the 200mg catalyst, catalyst particle size 40-60 mesh are taken, reaction gas forms (volume fraction):
1%CH4, 99% mixing air, gas velocity 99mL/min, the air inlet of methane and tail gas concentration are divided online using gas-chromatography
Analysis.The catalyst activity test curve of the present embodiment 1 is as shown in Figure 5.Mixed-metal oxides in the present embodiment 2
0.9LaMnO3-1.0MnO2-2.1La2O2CO3T50%It is 376 DEG C, T90%It is 452 DEG C, complete conversion temperature is 500 DEG C, is kept
Temperature follow-on test 72h, methane conversion is still 95%, and it is excellent methyl hydride catalyzed to illustrate that catalyst prepared by the present invention has
Activity and service life.
Reaction condition in the present embodiment in step a, step c is replaced with into other reaction conditions that the present invention limits, system
Standby obtained LaMnO3-MnO2-La2O2CO3Catalyst can obtain and the comparable performance of above-mentioned catalyst.
Embodiment 3
The embodiment of the present invention provides a kind of NEW TYPE OF COMPOSITE metal oxide catalyst, and preparation method includes the following steps:
1. preparing LaSrMnO using sol-gal process3:
(La+Sr): Co=1:1 weighs lanthanum nitrate, strontium nitrate and cobalt nitrate in molar ratio, and the amount of additive is La and Co
The citric acid that 1.5 times of the sum of mole dissolves in deionized water, obtains the precursor solution of metal molar concentration 1.2mol/L；
Solution is placed in heating water bath pot 80 DEG C, mechanical stirring is to wet colloidal sol is formed, and 90 DEG C of standing 1h, aging 8h is obtained under room temperature later
To gel；Gel is placed in 90 DEG C of baking oven and is dried to obtain xerogel；Xerogel grinding, 500 DEG C of pre-burnings of electric furnace to black powder, it
It moves back to 750 DEG C of roasting 5h of Muffle furnace, the LaSrMnO of sol-gal process preparation is obtained after natural cooling3。
The molar ratio of lanthanum nitrate and strontium nitrate is 1:1.
4. preparing Citrate-ethylene diamine water solubility carbon dots modifying agent:
1:80-100 weighs ethylenediamine and citric acid in molar ratio, is put into reaction kettle, and deionized water is added to reaction kettle
To 60%-80%, 190 DEG C of hydro-thermals to 8h bring it about redox reaction and obtain Citrate-ethylene diamine water-soluble carbon compactedness
Point modifying agent.
5. by the LaSrMnO of preparation3Carry out hydrothermal modification treatment:
Using polyparaphenylene reaction kettle liner, deionized water, LaSrMnO are sequentially added3With Citrate-ethylene diamine water solubility
Carbon dots modifying agent, 200 DEG C of hydrothermal temperature, hydro-thermal duration 5h.Product filtering and washing is taken out, 80 DEG C of baking ovens place 4h, natural cooling
Grinding, 500 DEG C of roasting 1h (1.2 DEG C/min heating rate) of Muffle furnace, sample natural cooling is to get to new and effective composition metal
Oxide type catalyst, main object phase composition are 0.8LaSrMnO3-0.9Co3O4-2.3La2O2CO3。
The additional amount of deionized water is that 10-15mL is added in every gram of perovskite type catalyst；Citrate-ethylene diamine is water-soluble
The additional amount of carbon dots modifying agent is that 2-5mL is added in every gram of perovskite type catalyst.
0.8LaSrMnO3-0.9Co3O4-2.3La2O2CO3The XRD spectrum of catalyst is as shown in Figure 6.
The metal composite oxide 0.8LaSrMnO prepared in the present embodiment 1 is evaluated using catalyst test apparatus3-
0.9Co3O4-2.3La2O2CO3, the 200mg catalyst, catalyst particle size 40-60 mesh are taken, reaction gas forms (volume fraction):
1%CH4, 99% mixing air, gas velocity 99mL/min, the air inlet of methane and tail gas concentration are divided online using gas-chromatography
Analysis.The catalyst activity test curve of the present embodiment 1 is as shown in Figure 7.Mixed-metal oxides in the present embodiment 3
0.8LaSrMnO3-0.9Co3O4-2.3La2O2CO3T50%It is 351 DEG C, T90%It is 440 DEG C, complete conversion temperature is 480 DEG C, is protected
Temperature follow-on test 72h is held, methane conversion is still 95%, illustrates that there is catalyst prepared by the present invention excellent methane to urge
Change activity and service life.
Embodiment 1-3 preparation O composite metallic oxide catalyst and BET test result as shown in table 2
Table 2
| Specific surface area (m2g-1) | Aperture (nm) | Kong Rong (cc/g) | |
| Embodiment 1 | 29.328 | 3.953 | 0.092 |
| Embodiment 2 | 27.969 | 3.943 | 0.098 |
| Embodiment 3 | 32.154 | 3.954 | 0.108 |
Embodiment 4-7
The preparation method of embodiment 4-7 is same as Example 1, and specific reaction condition is referring to table 3.
Table 3
The molar ratio of La, Ca are 0.5:1 in embodiment 6, and the molar ratio of La, Mg are 1:3 in embodiment 7.
ABO in the catalyst obtained by above-mentioned preparation method3Catalyst content in 15%-25%, BOnContent
In 20%-30%, A2O2CO3Content in the range of 50%-65%.
Comparative example 1
This comparative example provides a kind of NEW TYPE OF COMPOSITE metal oxide catalyst, and preparation method is same as Example 1, different
Be using L-arginine-glycerine-urea carbon dots modifying agent replace embodiment 1 in Citrate-ethylene diamine carbon dots modifying agent,
Specific preparation process is as follows for urea carbon dots modifying agent for L-arginine-glycerine-:
L-arginine, glycerine, urea are weighed for 1:5:5 in molar ratio, is put into reaction kettle, and deionized water is added to anti-
It answers kettle compactedness to 60%-80%, baking oven hydro-thermal is put in 200 DEG C to 4h, obtains L-arginine-glycerine-urea carbon dots modifying agent.
Prepare LaCoO3With the LaCoO that will be prepared3The step of carrying out hydrothermal modification treatment is same as Example 1, herein no longer
It repeats.
It is evaluated according to the catalyst that comparative example 1 is prepared in the method in embodiment 1, what this comparative example obtained urges
The T of agent50%It is 412 DEG C, T90%It is 478 DEG C.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of NEW TYPE OF COMPOSITE metal oxide catalyst, which is characterized in that the general formula of the active component of the catalyst is
xABO3-yBOn-zA2O2CO3, wherein A is selected from one or both of alkali earth metal or rare earth element, and B is selected from transition gold
Belong to one of element, the value range of n is 1-2.
2. NEW TYPE OF COMPOSITE metal oxide catalyst as described in claim 1, which is characterized in that the alkaline earth element be Mg,
Ca, Sr or Ba and/or the thulium are La, Ce or Sm；And/or the transition metal element is Co, Mn, Cu, Ni
Or Fe.
3. NEW TYPE OF COMPOSITE metal oxide catalyst as described in claim 1, which is characterized in that x:y:z=0.6-1:0.8-
1:2-2.5。
4. a kind of preparation method of the described in any item NEW TYPE OF COMPOSITE metal oxide catalysts of claim 1-3, feature exist
In including at least following steps:
Step a prepares perovskite type catalyst ABO3；
Step b, by the perovskite type catalyst ABO3It is added in hydrothermal reaction kettle, deionized water and modifying agent is then added, point
It dissipates uniformly, in 200-240 DEG C of reaction 2-8h, filters, wash, grinding, condition of the gained powder in temperature programming to 480-520 DEG C
Lower roasting 1-1.5h obtains the NEW TYPE OF COMPOSITE metal oxide catalyst；
Wherein, the modifying agent is Citrate-ethylene diamine water solubility carbon dots modifying agent or sodium citrate-ammonium hydrogen carbonate water-soluble carbon
One or both of point modifying agent.
5. the preparation method of NEW TYPE OF COMPOSITE metal oxide catalyst as claimed in claim 4, which is characterized in that the lemon
Acid-ethylenediamine water solubility carbon dots modifying agent preparation method include the following steps: by raw material ethylenediamine and citric acid addition go from
In sub- water, it is uniformly mixed, in 170-190 DEG C of reaction 8-10h, obtains the Citrate-ethylene diamine water solubility carbon dots modifying agent；
The sodium citrate-ammonium hydrogen carbonate water solubility carbon dots modifying agent preparation method includes the following steps: raw material citric acid
Sodium and ammonium hydrogen carbonate are added in deionized water, are uniformly mixed, in 170-190 DEG C of reaction 8-10h, obtain the sodium citrate-carbonic acid
Hydrogen ammonium water solubility carbon dots modifying agent.
6. the preparation method of NEW TYPE OF COMPOSITE metal oxide catalyst as claimed in claim 5, which is characterized in that the lemon
The molar ratio of acid and ethylenediamine is 80-100:1；The molar ratio of the sodium citrate and ammonium hydrogen carbonate is 1:20-50；It is described go from
The additional amount of sub- water is 30-40 times of corresponding total mass of raw material.
7. the preparation method of NEW TYPE OF COMPOSITE metal oxide catalyst as claimed in claim 4, which is characterized in that in step b,
The additional amount of the deionized water is that 10-15mL is added in every gram of perovskite type catalyst；And/or the additional amount of the modifying agent
For 2-5mL is added in every gram of perovskite type catalyst.
8. the preparation method of NEW TYPE OF COMPOSITE metal oxide catalyst as claimed in claim 4, which is characterized in that in step a,
Perovskite type catalyst ABO is prepared using sol-gal process3, preparation step is as follows:
The soluble metallic salt of element A and B element is weighed according to the molar ratio of 1:0.8-1.5, is added in deionized water, and mixing is equal
It is even, obtain the mixed solution of 0.8-2.0mol/L；
Citric acid is added in the mixed solution, is uniformly mixed, forms wet colloidal sol in 75-85 DEG C of stirring, it is quiet in 90-100 DEG C
Set 1-1.5h, be cooled to 20-30 DEG C of aging 8-10h, dry, grinding, 450-500 DEG C of progress first time roasting, 750-800 DEG C into
Second of roasting of row, obtains perovskite type catalyst ABO3；
Wherein, the additional amount of the citric acid is 1.2-1.5 times of the sum of molal quantity of element A and B element.
9. the preparation method of NEW TYPE OF COMPOSITE metal oxide catalyst as claimed in claim 4, which is characterized in that in step a,
Perovskite type catalyst ABO is prepared using solution combustion method3, have that steps are as follows:
The soluble metallic salt of element A and B element is weighed according to the molar ratio of 1:0.8-1.5, is added in deionized water, and mixing is equal
It is even, obtain the mixed solution of 0.5-1.5mol/L；
Fuel and fuel additive are added in the mixed solution, is uniformly mixed, in 600-800 DEG C of roasting 4-6h, obtains calcium titanium
Mine type catalyst ABO3；
Wherein, the molar ratio of the molal quantity summation of the fuel, fuel additive and element A and B element is 2-5:1:1.
10. the preparation method of NEW TYPE OF COMPOSITE metal oxide catalyst as claimed in claim 4, which is characterized in that step b
In, the rate of temperature programming is 0.8-1.2 DEG C/min.
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| CN112742366A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Nano carbon-based material and preparation method thereof and catalytic oxidation method of cycloparaffin |
| CN114577782A (en) * | 2020-12-01 | 2022-06-03 | 四川大学 | Method for detecting organic amine through ratio-type catalytic luminescence |
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