CN109453769A - A kind of catalyst of the ammoxidation nitrogen oxides of perovskite oxide Supported Pt Nanoparticles - Google Patents
A kind of catalyst of the ammoxidation nitrogen oxides of perovskite oxide Supported Pt Nanoparticles Download PDFInfo
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- CN109453769A CN109453769A CN201811274010.9A CN201811274010A CN109453769A CN 109453769 A CN109453769 A CN 109453769A CN 201811274010 A CN201811274010 A CN 201811274010A CN 109453769 A CN109453769 A CN 109453769A
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- platinum
- nitrogen oxides
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 86
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010948 rhodium Substances 0.000 claims abstract description 14
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 14
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 14
- MMLSWLZTJDJYJH-UHFFFAOYSA-N calcium;propan-2-olate Chemical compound [Ca+2].CC(C)[O-].CC(C)[O-] MMLSWLZTJDJYJH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 239000011575 calcium Substances 0.000 claims abstract description 6
- QPCFYJSFLHCWBC-UHFFFAOYSA-N cerium;propan-2-ol Chemical compound [Ce].CC(C)O QPCFYJSFLHCWBC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 4
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims abstract description 4
- 239000010970 precious metal Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 19
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 14
- 239000000969 carrier Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000004448 titration Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000265 homogenisation Methods 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 35
- 229910021529 ammonia Inorganic materials 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000012552 review Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- -1 nitrotoleune Chemical compound 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PDNNQADNLPRFPG-UHFFFAOYSA-N N.[O] Chemical compound N.[O] PDNNQADNLPRFPG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- JCLOGSKIMBJQAA-UHFFFAOYSA-N [Mo].[Sn] Chemical compound [Mo].[Sn] JCLOGSKIMBJQAA-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 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 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical class [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/24—Nitric oxide (NO)
- C01B21/26—Preparation by catalytic or non-catalytic oxidation of ammonia
- C01B21/265—Preparation by catalytic or non-catalytic oxidation of ammonia characterised by the catalyst
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Abstract
The invention discloses a kind of catalyst of the ammoxidation nitrogen oxides of perovskite oxide Supported Pt Nanoparticles, with isopropanol cerium, calcium isopropoxide, isopropyl titanate, acetylacetone,2,4-pentanedione platinum, acetylacetone,2,4-pentanedione rhodium, palladium acetylacetonate is presoma, in calcium, on the basis of titanium active metal, select platinum, rhodium, at least one of palladium metal, the platinum, rhodium, the molar concentration of palladium is no more than 10%, the mass percent of the cerium is no more than 5%, perovskite supported platinum, which is prepared, by sol-gal process reviews one's lessons by oneself compound catalyst, after certain temperature calcining, ammoxidation is catalyzed nitric oxide processed under ammonia and Oxygen Condition.Gained specific surface area of catalyst is big, precious metal load capacity is small, ammoxidation is selectively good, high conversion rate, can effectively improve the conversion ratio of ammonia and reduce noble metal dosage.Alternative platinum guaze catalyst.
Description
Technical field
The present invention relates to the preparation of new material and applied technical fields, are specifically related to a kind of perovskite oxide Supported Pt Nanoparticles
Ammoxidation nitrogen oxides catalyst.
Background technique
Ammoxidation catalysis reaction is mainly used in the production of nitric acid, hydrogen cyanide, and high-temperature S removal ammonia generates nitric oxide
And HCN, platinum-rhodium alloy mesh catalyst is industrially used always.Nitric acid is important basic chemical industry product, is one of three sour two alkali, is
The extremely wide industrial chemicals of purposes.Other than chemical industry, nitric acid is also used to metallurgy, medicine, fuel, agricultural, nuclear industry etc.
Aspect.Nitric acid can be divided into two aspects of inorganic chemical industry and organic chemical industry in the application of chemical industry.Wherein, inorganic chemical industry master
To be applied to production ammonium nitrate, nitrophosphate fertilizer, nitro-compound fertilizer, all kinds of nitrate and propellant；Organic chemical industry mainly answers
It is the main former material of MDI, TDI, nylon66 fiber, engineering plastics for producing nitrobenzene, nitrotoleune, adipic acid, nitro-chlorobenzene
Material.
Have in many documents, has studied transition metal oxide and composite transition metal oxide ammoxidation reaction under high temperature
Catalysis characteristics, such as rare earth and alkaline-earth metal.It has studied ammonia and is diffused into catalyst surface, oxygenation efficiency and NO product etc..It is high
Warm ammoxidation is studied well, and under industrial condition, NO is the primary product of ammoxidation reaction, and oxide catalyst and platinum guaze are urged
The oxygenation efficiency of agent is spread both limited by the ammonia from gas phase to catalyst surface.When catalyst surface does not have ammonia, only oxygen
Or when partial oxide product, it is meant that NO selectively reaches maximum value.Critical value is loaded by comparison ammonia to evaluate oxidation
Object and platinum catalyst ammonia oxidation rate.Load refers to the ratio of volumetric gas flow rate (0 DEG C and 1atm) and catalyst section.Work as gas
Load value at the end of process is to load critical value.Linearly increasing with gas flow, diffusion layer surface thickness is reduced, and is put
When heating rate becomes smaller than heat removal rate, catalyst is cooling and extinguishes.It loads critical value and depends on surface reaction constant and catalyst
Property.According to 1atm, 10vol.% ammonia sky ratio, 0.09mm platinum filament loads critical value close to 30 000L/cm2h.Identical item
Under part, the cobalt oxide bead of 4mm is 10 000L/cm2h.The load critical value of Co3O4 catalyst depends on crystallite dimension,
F.S.Shub has studied ammonia oxygen concentration, pressure, has shown that ammonia oxidation rate formula r=K [NH3] 0.36 [O2] 0.14, K is constant,
[NH3], [O2] are the concentration close to catalyst surface respectively.Reaction activity is close to 9kcal/mol.The equation feature refers to institute
Some ammonia is completely converted into the products such as nitrogen oxides and nitrogen.Also someone equally uses similar technique study iron oxide.According to more
The higher standardization program evaluation of low reaction initiation temperature NO selectivity, effective activation energy and the order of reaction are lower, and outside is expanded
Scattered limitation is harsher.Therefore, the selectivity of NO can be used as a kind of method for measuring catalyst activity under industrial condition, actually
Activity in relation to oxide catalyst is often evaluated in this way.
Generally, it is considered that being several oxide selectivities: Co below3O4(94%), a-Fe2O3(90%), Bi2O3(90–
93%), Mn oxide (80%), compared with low selectivity: NiO (30-50%), CuO (40-50%), PbO2(50%), rare earth metal
Oxide (10-50%).Aluminium, tungsten, the oxide of molybdenum tin are inactive.High NO selectivity and yield in perovskite system, on an equal basis very
To those pure transition metal oxides are exceeded, the strong of transition-metal cation is closed by system middle-end oxygen key before being construed to well
It spends higher than single oxide.In short, perovskite or perovskite-like system be have it is highly selective in addition 700 DEG C or less they
Non- weak binding of the surface containing aerobic desorption is formed.However, the part substitution of lanthanum is cationic by other, produced within the scope of 200-600 DEG C
The raw weak oxygen combination oxygen species desorbed, are often associated with selective small size increase, perovskite are at least relied on substitution level
Property.However, it is the reasons why ammoxidation of perovskite system is at NO that this, which not can prove that weak oxygen combines,.Therefore, for La1- xSrxCoO3, with the increase of content of strontium, the strong oxygen binding species quantity of desorption increases at 800 DEG C, corresponding NO selectivity
Similarly.With the increase of cobalt surface concentration, it is meant that these oxide species are in conjunction with cobalt cation.
Although platinum guaze catalyst has its unique advantage, platinum, will be fewer and fewer as important rare strategic resource, because
This process for finding substitution platinum guaze catalyst never stops, and every country or research institution are non-in a large amount of experimental study of progress
Platinum catalyst or the considerably less carried catalyst of bullion content.
To sum up, the present invention prepares perovskite supported platinum using sol-gal process and reviews one's lessons by oneself compound catalyst, forms CeXCaTi(1-X-Y)
PtYO3Structure, for ammoxidation nitrogen oxides.
Summary of the invention
Technical problem solved by the present invention is the object of the present invention is to provide a kind of ammonia of perovskite structure carried noble metal
The preparation method of oxidation catalyst, preparation method is simple, and the catalyst of preparation has high surface area, high mechanical strength, your low gold
Belong to dosage, noble metal can effectively be adjusted according to the needs of oxidation-reduction process, and not allow that noble metal is easily caused to be formed
Oxide and be lost.Under ammoxidation reaction conditions, using the catalyst preparation nitrogen oxides, reaction temperature is reduced, production cost drop
Low, service life is long, is suitable for large-scale industrial production.
The technical scheme is that a kind of catalyst of the ammoxidation nitrogen oxides of perovskite oxide Supported Pt Nanoparticles,
Using isopropanol cerium, calcium isopropoxide, isopropyl titanate, acetylacetone,2,4-pentanedione platinum, acetylacetone,2,4-pentanedione rhodium, palladium acetylacetonate be presoma, calcium,
On the basis of titanium active metal, select platinum, rhodium, at least one of palladium metal, which is characterized in that platinum, rhodium, palladium molar concentration not
More than 10%, the mass percent of cerium is no more than 5%.
A kind of preparation method of the catalyst of the ammoxidation nitrogen oxides of above-mentioned perovskite oxide Supported Pt Nanoparticles, including with
Lower step:
S1: isopropanol cerium, calcium isopropoxide, isopropyl titanate and acetylacetone,2,4-pentanedione platinum, acetylacetone,2,4-pentanedione rhodium, acetyl are weighed respectively
Any one of acetone palladium is added PVP and is mixed, obtains mixture, said mixture is dissolved completely in by toluene, third
The in the mixed solvent of ketone, diphenyl methane composition, stirs 100-180min, obtains mixed liquor；
S2: the mixed liquor is added to by ethylene glycol, NaBH according to the ratio that mass ratio is 1:24, hydrazine composition it is mixed
It closes in reducing agent, obtains gel phase carriers presoma；
S3: being heated to 60-70 DEG C for gel phase carriers presoma, is then hydrolyzed with the ethyl alcohol of 1:1 and aqueous solution titration, from
Heart filtering, then three times with washes of absolute alcohol, dried under the conditions of 50-80 DEG C, it then calcines, calcines under the conditions of 800-1000 DEG C
Time is 1-3h, forms perovskite structure；；
S4: being passed through hydrogen and Carbon monoxide reduction for calcined product, then calcine again, and grinding screening is catalyzed
Agent.
Further, obtained mixed liquor is pre-processed: pretreatment mode are as follows:
1) at vacuum degree -0.095~-0.092MPa, under the conditions of 80~100 DEG C, with starting stirring speed
Degree is 750r/min, and by 15~20min, final speed reaches 900r/min；
2) it is cooled to room temperature after stirring, adjusting pH value is 5.6~8.0,10~20min of stewing process, is concentrated by evaporation, control
Water content is 85%, obtains pre-product；
3) pre-product will be obtained again in the case where pressure is 20~30MPa homogenization 1~2 time, at -45~-30 DEG C, vacuum degree
For 0.070-0.085MPa, the mixed gas being made of helium and argon gas according to volume ratio for 1:2, water content 2%, when being passed through
Between be that 12~18min in high voltage direct current decentralized processing after oscillation treatment makes it be uniformly dispersed.
Further, the carrier of S2 perovskite structure catalyst be containing cerium or platinum, rhodium, palldium alloy perovskite.
Further, carrier at the extrudates such as particle, spherolite, honeycomb or trilobes form.
Further, the perovskite structure catalyst that S4 is obtained includes calcium, titanium and at least two precious metal elements.
Preferably, the calcination time of step S3 is 2h.
Further, step S4 calcining manners are as follows: in microwave heating to 450~500 DEG C, preheat 15~25min, at the uniform velocity rise
For temperature to 600~650 DEG C, control pressure is 4~5Pa, and the time is 30~35min, and under magnetic fields, temperature is cooled to 220 DEG C,
15~18min of time.
Further, when high voltage direct current decentralized processing, dispersion condition are as follows: direct-current discharge electric current be 85~110A, processing 3~
10min。
Further, perovskite structure catalyst is CeXCaTi(1-X-Y)PtYO3Perovskite catalyst.
Compared with prior art, the beneficial effects of the present invention are:
1, noble metal molar concentration is lower than 10%, and noble metal utilisation greatly improves, good dispersion.
2、CeXCaTi(1-X-Y)PtYO3With the good ability stored up oxygen and put oxygen.
3, for selectivity close to 100%, specific surface area is high, up to 65m2/g。.
4, colloid load capacity made from sol-gel method is strong.
Detailed description of the invention
Fig. 1 is evaluating catalyst process and evaluating apparatus annexation figure；
Fig. 2 is the scanning electron microscope (SEM) photograph of load platinum catalyst；
Fig. 3 is the partial enlarged view of scanning electron microscope (SEM) photograph；
Fig. 4 is scanning electron microscope energy spectrum diagram；
Fig. 5 is the XRD analysis figure of perovskite supported catalyst；
Fig. 6 is that the BET of load platinum catalyst schemes；
Fig. 7 is the selectivity and conversion ratio figure of load platinum catalyst.
Wherein, 1- ammonia bottle, 2- oxygen cylinder, 3- mass flowmenter, 4- controller, 5- temperature sensor, 6- temperature controller, 7-
Reaction tube (wherein, reaction tube lateral shadow is bringing-up section, middle part black section is Catalyst packing position in reaction tube), 8- pressure
Table, 9- ball valve, 10- argon bottle, 11- gas-chromatography, 12- computer, 13- gas collection bottle one, 14- gas collection bottle two, 15- gas
Body receiving flask three, 16- airbag.
Specific embodiment
Embodiment 1
A kind of preparation method of the catalyst of the ammoxidation nitrogen oxides of above-mentioned perovskite oxide Supported Pt Nanoparticles:
S1: 1.0 grams of calcium isopropoxide are weighed respectively, 1.7 grams of isopropyl titanate, 0.12 gram of acetylacetone,2,4-pentanedione platinum, is added 0.5 gram
PVP obtains mixture, and said mixture is dissolved completely in the mixed solvent that 50ml is made of toluene, acetone, diphenyl methane
In, 100min is stirred, mixed liquor is obtained；
S2: the mixed liquor is added to by ethylene glycol, NaBH according to the ratio that mass ratio is 1:24, hydrazine composition it is mixed
It closes in reducing agent, obtains gel phase carriers presoma；
S3: being heated to 60 DEG C for gel phase carriers presoma, then with the ethyl alcohol of 1:1 and aqueous solution titration hydrolysis, centrifugation
Filtering, then three times with washes of absolute alcohol, dried under the conditions of 50 DEG C, then 1h is calcined under the conditions of 600 DEG C；
S4: being passed through hydrogen and Carbon monoxide reduction for calcined product, then calcine again, and grinding screening obtains calcium titanium
Mine structure catalyst.
Embodiment 2
A kind of preparation method of the catalyst of the ammoxidation nitrogen oxides of above-mentioned perovskite oxide Supported Pt Nanoparticles:
S1: 1.0 grams of calcium isopropoxide are weighed, 1.7 grams of isopropanol cerium, 0.12 gram of acetylacetone,2,4-pentanedione rhodium, 0.5 gram of PVP is added, obtains
To mixture, said mixture is dissolved completely in the in the mixed solvent that 50ml is made of toluene, acetone, diphenyl methane, is stirred
150min is mixed, mixed liquor is obtained；
S2: the mixed liquor is added to by ethylene glycol, NaBH according to the ratio that mass ratio is 1:24, hydrazine composition it is mixed
It closes in reducing agent, obtains gel phase carriers presoma；
S3: being heated to 65 DEG C for gel phase carriers presoma, then with the ethyl alcohol of 1:1 and aqueous solution titration hydrolysis, centrifugation
Filtering, then three times with washes of absolute alcohol, dried under the conditions of 70 DEG C, it is then calcined under the conditions of 800 DEG C, time 2h, shape
At perovskite structure；
S4: being passed through hydrogen and Carbon monoxide reduction for calcined product, then calcine again, and grinding screening obtains calcium titanium
Mine structure catalyst.
Embodiment 3
A kind of preparation method of the catalyst of the ammoxidation nitrogen oxides of above-mentioned perovskite oxide Supported Pt Nanoparticles:
S1: 1.0 grams of calcium isopropoxide are weighed, 1.7 grams of isopropyl titanate, 0.12 gram of palladium acetylacetonate, 0.5 gram of PVP is added, obtains
To mixture, said mixture is dissolved completely in the in the mixed solvent that 50ml is made of toluene, acetone, diphenyl methane, is stirred
150min is mixed, mixed liquor is obtained；
S2: the mixed liquor is added to by ethylene glycol, NaBH according to the ratio that mass ratio is 1:24, hydrazine composition it is mixed
It closes in reducing agent, obtains gel phase carriers presoma；
S3: being heated to 70 DEG C for gel phase carriers presoma, then with the ethyl alcohol of 1:1 and aqueous solution titration hydrolysis, centrifugation
Filtering, then three times with washes of absolute alcohol, dried under the conditions of 80 DEG C, it is then calcined under the conditions of 1000 DEG C, time 3h, shape
At perovskite structure；
S4: being passed through hydrogen and Carbon monoxide reduction for calcined product, then calcine again, and grinding screening obtains calcium titanium
Mine structure catalyst.
Embodiment 4
A kind of preparation method of the catalyst of the ammoxidation nitrogen oxides of above-mentioned perovskite oxide Supported Pt Nanoparticles:
S1: 1.0 grams of calcium isopropoxide are weighed, 1.7 grams of isopropyl titanate, 0.12 gram of acetylacetone,2,4-pentanedione platinum, 0.5 gram of PVP is added, obtains
To mixture, said mixture is dissolved completely in the in the mixed solvent that 50ml is made of toluene, acetone, diphenyl methane, is stirred
Mix 100min, obtain mixed liquor, mixing is pre-processed: pretreatment mode is as follows:
1) at vacuum degree -0.095MPa, under the conditions of 100 DEG C, to originate mixing speed as 750r/min,
By 20min, final speed reaches 900r/min；
2) it is cooled to room temperature after stirring, adjusting pH value is 8.0, stewing process 20min, is concentrated by evaporation, and control water content is
85%, obtain pre-product；
3) pre-product will be obtained again in the case where pressure is 30MPa homogenization 2 times, at -30 DEG C, vacuum degree 0.085MPa,
By helium and argon gas according to the mixed gas that volume ratio is that 1:2 is formed, water content 2% is passed through the time for 18min, at oscillation
In high voltage direct current decentralized processing after reason, direct-current discharge electric current is 110A, handles 10min, it is made to be uniformly dispersed；
S2: the mixed liquor is added to by ethylene glycol, NaBH according to the ratio that mass ratio is 1:24, hydrazine composition it is mixed
It closes in reducing agent, obtains gel phase carriers presoma；
S3: being heated to 65 DEG C for gel phase carriers presoma, then with the ethyl alcohol of 1:1 and aqueous solution titration hydrolysis, centrifugation
Filtering, then three times with washes of absolute alcohol, dried under the conditions of 70 DEG C, it is then calcined under the conditions of 800 DEG C, time 2h, shape
At perovskite structure；
S4: being passed through hydrogen and Carbon monoxide reduction for calcined product, and hydrogen and carbon monoxide are 2:1 according to volume ratio
Mixing, is then calcined again, and grinding screening obtains perovskite structure catalyst.
Embodiment 5
A kind of preparation method of the catalyst of the ammoxidation nitrogen oxides of above-mentioned perovskite oxide Supported Pt Nanoparticles:
S1: 1.0 grams of calcium isopropoxide are weighed, 1.7 grams of isopropyl titanate, 0.12 gram of acetylacetone,2,4-pentanedione platinum, 0.5 gram of PVP is added, obtains
To mixture, said mixture is dissolved completely in the in the mixed solvent that 50ml is made of toluene, acetone, diphenyl methane, is stirred
Mix 100min, obtain mixed liquor, mixing is pre-processed: pretreatment mode is as follows:
1) at vacuum degree -0.095MPa, under the conditions of 100 DEG C, to originate mixing speed as 750r/min,
By 20min, final speed reaches 900r/min；
2) it is cooled to room temperature after stirring, adjusting pH value is 8.0, stewing process 20min, is concentrated by evaporation, and control water content is
85%, obtain pre-product；
3) pre-product will be obtained again in the case where pressure is 30MPa homogenization 2 times, at -30 DEG C, vacuum degree 0.085MPa,
By helium and argon gas according to the mixed gas that volume ratio is that 1:2 is formed, water content 2% is passed through the time for 18min, at oscillation
In high voltage direct current decentralized processing after reason, direct-current discharge electric current is 110A, handles 10min.So that it is uniformly dispersed, keeps its dispersion equal
It is even；
S2: the mixed liquor is added to by ethylene glycol, NaBH according to the ratio that mass ratio is 1:24, hydrazine composition it is mixed
It closes in reducing agent, obtains gel phase carriers presoma；
S3: being heated to 65 DEG C for gel phase carriers presoma, then with the ethyl alcohol of 1:1 and aqueous solution titration hydrolysis, centrifugation
Filtering, then three times with washes of absolute alcohol, dried under the conditions of 70 DEG C, it is then calcined under the conditions of 800 DEG C, time 2h, shape
At perovskite structure；
S4: being passed through hydrogen and Carbon monoxide reduction for calcined product, and hydrogen and carbon monoxide are 2:1 according to volume ratio
Mixing preheats 25min, is at the uniform velocity warming up to 650 DEG C in microwave heating to 500 DEG C, and control pressure is 12Pa, time 35min,
Under magnetic fields, magnetic field strength 0.2T, temperature is cooled to 220 DEG C, time 18min, and grinding screening obtains perovskite structure
Catalyst.
Experimental example
Ammoxidation evaluation
As shown in Figure 1, be passed through after ammonia and oxygen mix in oxidation furnace evaluating apparatus, the device using temperature range 0~
1200℃；0~40 DEG C/min of heating rate, within temperature stability ± 2 DEG C, within 1 DEG C of precision of control；Burner hearth internal diameter 44mm,
Outer reactor inside diameter 34mm；Furnace superintendent 900mm, flat-temperature zone 400mm (± 2 DEG C), interior reactor diameter 14mm；Ammonia flow measures journey
100ml/min, oxygen flow meter range 500ml/min.Platinum guaze is connected by high-temperature flange, and solid powder th-1 catalyst is closed by ferrum-chromium-aluminum
Golden web is as support package, by 0.5~1.0 gram of Catalyst packing into reaction tube, heats up 10 DEG C/minute to 800 DEG C, experiment
Being passed through gas flow rate is ammonia 10ml/min, pure oxygen 200ml/min, and as experimental gas flow velocity, rear end is connected with online gas phase
Chromatography, ammonia reaction gas are totally converted, conversion ratio 100%, then the content of gas Chromatographic Determination nitrogen and nitrogen oxide determines
Nitric oxide production 98% or more selectivity, it is consistent with the nitric acid yield for being passed through 1h collection.
Predetermined purpose and technical means and efficacy achieved for the present invention is further explained pass through 5 pairs of this hairs of embodiment
Bright to be further described, by analyzing catalyst of the present invention, Fig. 2-4 show catalyst scanning electron microscope result figure,
Fig. 5 is the XRD analysis figure of perovskite supported catalyst；Fig. 6 is that the BET of load platinum catalyst schemes, and Fig. 7 is load platinum catalyst
Selectivity and conversion ratio figure.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify to technical solution documented by previous embodiment or equivalent replacement of some of the technical features；And
These are modified or replaceed, the spirit and model of technical solution of the embodiment of the present invention that it does not separate the essence of the corresponding technical solution
It encloses.
Claims (9)
1. a kind of catalyst of the ammoxidation nitrogen oxides of perovskite oxide Supported Pt Nanoparticles, using isopropanol cerium, calcium isopropoxide,
Isopropyl titanate, acetylacetone,2,4-pentanedione platinum, acetylacetone,2,4-pentanedione rhodium, palladium acetylacetonate are presoma, on the basis of calcium, titanium active metal, selection
At least one of platinum, rhodium, palladium metal, which is characterized in that the platinum, rhodium, palladium molar concentration be no more than 10%, the cerium
Mass percent is no more than 5%.
2. a kind of preparation of the catalyst of the ammoxidation nitrogen oxides of perovskite oxide Supported Pt Nanoparticles as described in claim 1
Method, which comprises the following steps:
S1: isopropanol cerium, calcium isopropoxide, isopropyl titanate and acetylacetone,2,4-pentanedione platinum, acetylacetone,2,4-pentanedione rhodium, acetylacetone,2,4-pentanedione are weighed respectively
Any one of palladium is added PVP and is mixed, obtains mixture, said mixture is dissolved completely in by toluene, acetone, two
The in the mixed solvent of phenylmethane composition, stirs 100-180min, obtains mixed liquor；
S2: the mixed liquor is added to by ethylene glycol, NaBH according to the ratio that mass ratio is 1:24, hydrazine composition mixing also
In former agent, gel phase carriers presoma is obtained；
S3: being heated to 60-70 DEG C for gel phase carriers presoma, then with the ethyl alcohol of 1:1 and aqueous solution titration hydrolysis, was centrifuged
Filter, then three times with washes of absolute alcohol, dried under the conditions of 50-80 DEG C, it is then calcined under the conditions of 600-1000 DEG C, forms calcium
Perovskite like structure；
S4: being passed through hydrogen and Carbon monoxide reduction for calcined product, then calcine again, and grinding screening obtains perovskite knot
Structure catalyst.
3. a kind of preparation of the catalyst of the ammoxidation nitrogen oxides of perovskite oxide Supported Pt Nanoparticles as claimed in claim 2
Method, which is characterized in that the mixed liquor that the step S1 is obtained will be obtained and pre-processed: pretreatment mode are as follows:
1) at vacuum degree -0.095~-0.092MPa, under the conditions of 80~100 DEG C, it is to originate mixing speed
750r/min, by 15~20min, final speed reaches 900r/min；
2) it is cooled to room temperature after stirring, adjusting pH value is 5.6~8.0,10~20min of stewing process, is concentrated by evaporation, and is controlled aqueous
Amount is 85%, obtains pre-product；
3) pre-product will be obtained again in the case where pressure is 20~30MPa homogenization 1~2 time, and at -45~-30 DEG C, vacuum degree is
0.070-0.085MPa, by helium and argon gas according to the mixed gas that volume ratio is that 1:2 is formed, water content 2% is passed through the time
For 12~18min, in high voltage direct current decentralized processing after oscillation treatment, it is made to be uniformly dispersed.
4. a kind of preparation of the catalyst of the ammoxidation nitrogen oxides of perovskite oxide Supported Pt Nanoparticles as claimed in claim 2
Method, which is characterized in that the carrier of the perovskite structure catalyst of the S4 be containing cerium or platinum, rhodium, palldium alloy perovskite.
5. a kind of preparation of the catalyst of the ammoxidation nitrogen oxides of perovskite oxide Supported Pt Nanoparticles as claimed in claim 4
Method, which is characterized in that the carrier at the extrudates such as particle, spherolite, honeycomb or trilobes form.
6. a kind of preparation of the catalyst of the ammoxidation nitrogen oxides of perovskite oxide Supported Pt Nanoparticles as claimed in claim 2
Method, which is characterized in that the perovskite structure catalyst that the S4 is obtained includes calcium, titanium and at least two precious metal elements.
7. a kind of preparation of the catalyst of the ammoxidation nitrogen oxides of perovskite oxide Supported Pt Nanoparticles as claimed in claim 2
Method, which is characterized in that the calcining manners of the step S4 are as follows: in microwave heating to 450~500 DEG C, 15~25min is preheated,
600~650 DEG C are at the uniform velocity warming up to, control pressure is 11~12Pa, and the time is 30~35min, and under magnetic fields, temperature is cooling
To 220 DEG C, 15~18min of time.
8. a kind of preparation of the catalyst of the ammoxidation nitrogen oxides of perovskite oxide Supported Pt Nanoparticles as claimed in claim 3
Method, which is characterized in that when step 3) the high voltage direct current decentralized processing, dispersion condition are as follows: direct-current discharge electric current be 85~
110A handles 3~10min.
9. a kind of preparation of the catalyst of the ammoxidation nitrogen oxides of perovskite oxide Supported Pt Nanoparticles as claimed in claim 2
Method, which is characterized in that the step 3) carries out high voltage direct current dispersion, place under the conditions of direct-current discharge electric current is 85~110A
The reason time is 3~10min.
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|---|---|---|---|---|
| CN116581314A (en) * | 2023-07-07 | 2023-08-11 | 华北电力大学 | High-entropy oxide catalyst for fuel cell and preparation method thereof |
| CN116581314B (en) * | 2023-07-07 | 2023-09-22 | 华北电力大学 | High-entropy oxide catalyst for fuel cell and preparation method thereof |
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