CN108325536A - A kind of catalyst and its preparation method and application of the rare earth doped element of manganese-copper-base composite oxidate of catalysis VOCs - Google Patents
A kind of catalyst and its preparation method and application of the rare earth doped element of manganese-copper-base composite oxidate of catalysis VOCs Download PDFInfo
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- CN108325536A CN108325536A CN201810137600.0A CN201810137600A CN108325536A CN 108325536 A CN108325536 A CN 108325536A CN 201810137600 A CN201810137600 A CN 201810137600A CN 108325536 A CN108325536 A CN 108325536A
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- manganese
- catalyst
- copper
- metal oxides
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 35
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 150000002910 rare earth metals Chemical class 0.000 title claims description 22
- 239000000919 ceramic Substances 0.000 claims abstract description 72
- 239000011248 coating agent Substances 0.000 claims abstract description 63
- 238000000576 coating method Methods 0.000 claims abstract description 63
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 46
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 45
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 241000264877 Hippospongia communis Species 0.000 claims description 73
- 239000002002 slurry Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 30
- 239000004202 carbamide Substances 0.000 claims description 30
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 27
- 239000011159 matrix material Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 13
- NXKAMHRHVYEHER-UHFFFAOYSA-J hafnium(4+);disulfate Chemical compound [Hf+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NXKAMHRHVYEHER-UHFFFAOYSA-J 0.000 claims description 11
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 11
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 229910001593 boehmite Inorganic materials 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- LBHDWLPRRAROQZ-UHFFFAOYSA-N [Ce].[La].[Hf] Chemical compound [Ce].[La].[Hf] LBHDWLPRRAROQZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 5
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- 238000001935 peptisation Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 2
- 239000003517 fume Substances 0.000 claims 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 21
- 229910000510 noble metal Inorganic materials 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 239000010953 base metal Substances 0.000 abstract description 4
- -1 hafnium lanthanum cerium oxide Chemical compound 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 230000035939 shock Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 22
- 238000007598 dipping method Methods 0.000 description 11
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000007084 catalytic combustion reaction Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011224 oxide ceramic Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 208000005374 Poisoning Diseases 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000001147 anti-toxic effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 210000002700 urine Anatomy 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000133 brain stem Anatomy 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
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- 239000000686 essence Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
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- 210000003734 kidney Anatomy 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
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- 210000004185 liver Anatomy 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 238000005504 petroleum refining Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 210000002345 respiratory system Anatomy 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
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- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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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
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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
- 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
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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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Abstract
A kind of catalyst and its preparation method and application of the basis composite oxides doped rare earth element of copper-manganese of catalysis VOCs.Catalyst disclosed by the invention coats the first coating of metal oxides, the second coating of metal oxides and third layer coating of metal oxides successively from inside to outside using the cordierite honeycomb ceramics material of Gao Kongrong as carrier；First coating of metal oxides is active alundum (Al2O3), and second coating of metal oxides is hafnium lanthanum cerium oxide, and the third coating of metal oxides is copper-manganese base oxide.Catalyst provided by the invention replaces noble metal using base metal；Catalyst coat provided by the invention is uniformly dispersed, active component is strong with basal body binding force, not easily to fall off or cracking, it remains to keep greater activity under high-speed flow and thermal shock, reuse activity stabilized, strong to VOCs gas catalysis activity, preparation process is simple, it is of low cost, it is suitble to large-scale production.
Description
Technical field
The present invention relates to a kind of catalyst of rare earth doped element of manganese-copper-base composite oxidate of catalysis VOCs and its preparations
Methods and applications belong to environmental protection catalysis material and technical field of atmospheric pollution control.
Background technology
Volatile organic compounds abbreviation VOCs refers to that saturated vapor pressure is more than boiling point under 133.32 Pa, normal pressure under room temperature
In 50-260 DEG C of organic compound below, or the organic solid that can be volatilized any at normal temperatures and pressures or liquid.It is main to generate
In petroleum refining industry and electronics, printing, coating, medicine, spray painting, printing, artificial leather, pesticide, rubber, electronic component
The industries such as degreasing and vehicle exhaust.VOCs can constitute ecological environment and human health and greatly threaten.In positive light and heat
The lower nitrogen oxide that participates in of effect reacts to form ozone, leads to air quality variation and is summer photochemical fog, city gray haze
Main component；And form fine particle（PM2.5）With the important precursor of ozone, proportions of the VOCs in PM2.5 in air
20%-40% or so is accounted for, also part PM2.5 is transformed by VOCs；VOCs is mostly the rooms Warm effect gas, can cause greenhouse effect
A series of ecocatas-trophes should be waited.Most of chemical compositions have toxicity, VOCs be more than a certain concentration when, can stimulate people eyes and
Respiratory tract, make skin allergy, pharyngalgia with it is weak；VOCs injures the liver, kidney, brain and nervous system of people, causes acute and chronic
Poisoning or even carcinogenic and mutation.With the improvement of people's living standards, the requirement to living environment is also higher and higher, such gas
The extensive concern for causing people is effectively treated in body.
Improvement to organic exhaust gas, people already have research, and have developed some fruitful control technologies,
As it is widely used and study it is more have absorption method, condensation method, absorption process, biological treatment, membrane separation technique, photocatalysis,
Direct combustion method, Production by Catalytic Combustion Process and plasma technology etc..Wherein Production by Catalytic Combustion Process is multiple in the big component of processing, low concentration, ingredient
When miscellaneous VOCs, in lower temperature（200-500℃）It is lower, it can be achieved that VOCs complete oxidation, have equipment is simple, low energy consumption,
Purification efficiency is high and does not generate the advantages that secondary pollution.Therefore it has become and administers one of most promising method, the technology
Core is catalyst, is known as integral catalyzer using the catalyst of block carrier as skeleton matrix.Integral catalyzer has
The hollow duct of a large amount of macroscopic views has great advantage compared with fine catalyst in heat transfer, mass transfer and pressure drop performance.Commonly
Carrier is cordierite honeycomb ceramic, and the specific surface of itself is less than 1g/m2, it is necessary to so that the active component of load is dispersed in host material
Surface.Common active component is mostly noble metal platinum, palladium, rhodium, silver, ruthenium etc., wherein especially with platinum, rhodium using most commonly seen.From urging
For agent activity, according to the electronic structure of noble metal, it is thus understood that d electron orbits are unfilled, the easy adsorption reaction object of particle surface,
And moderate strength, intermediate " reactive compound " is advantageously formed, there is higher catalytic activity；From catalyst choice and stabilization
Property for, noble metal catalyst has high temperature resistant, characteristics, the treatment effect such as anti-oxidant, corrosion-resistant more satisfactory, and application is more wide
It is general.But VOCs as contain chlorine or sulfur organic, by the species generated after catalysis oxidation can be adsorbed on by force noble metal catalyst surface or
With active component chemical combination, lead to loss of active component, catalyst poisoning inactivation, while generating other organic matters and causing secondary dirt
Dye.And noble metal catalyst is of high cost, limits its application.
For the above technical bottleneck, the strong oxidative degradation catalyst of research and development low cost, high activity, antitoxin performance is
Epochmaking project in the field of environmental catalysis investigation of materials at present, is widely paid close attention to.
Invention content
The purpose of the present invention is in view of the deficienciess of the prior art, providing a kind of copper-based composite oxygen of manganese-of catalysis VOCs
The catalyst and its preparation method and application of the rare earth doped element of compound.Catalyst disclosed by the invention is with the cordierite of Gao Kongrong
Ceramic honeycomb material be carrier, coat successively from inside to outside the first coating of metal oxides, the second coating of metal oxides and
Third layer coating of metal oxides；First coating of metal oxides is active alundum (Al2O3), the second metal oxidation
Object coating is hafnium-lanthanum-cerium oxide, and the third coating of metal oxides is that the copper-based oxide of manganese-is to solve technical problem.
The technical scheme is that：
A kind of catalyst for VOCs catalysis burnings, which is using cordierite honeycomb ceramic matrix as skeleton, to account for bee
The activated alumina of nest ceramic matrix quality 5-15% be coating, the Mn oxide to account for ceramic honey comb substrate quality 1-5% and/or
The rare earth oxide of Cu oxide and 0.5-2% are as active component.
In first coating of metal oxides, active alundum (Al2O3) weightening ratio is 5%-15%, preferably 10%-
15%；
In second coating of metal oxides, lanthanum-oxides, hafnium oxide and cerium oxide weightening ratio are respectively 0.5%-
2%, preferably 1%-2%；
In the third coating of metal oxides, Mn oxide and Cu oxide weightening ratio are respectively 1%-5%, preferably
2.5%-5%。
The mixed oxide is manganese, copper, rare earth mixed oxide, and wherein rare earth metal can have multivalent state, 30-
60wt% MnO2、15-29wt% CuO、18-33wt% HfO2、18-33wt%La203And 18-33wt%CeO2.Optimum proportioning is 43-
49wt% MnO2, 23-28wt%CuO, 28-33wt% HfO2、28-33wt%La203And 28-33wt%CeO2。
Content of the hafnium oxide relative to lanthanum-oxides and cerium oxide in mixture, weight are less than 50%.Due to above-mentioned
For element each other there are specific distribution relation, the mixed oxide for forming catalyst activity component has the characteristics that p-type half
Conductor (in these semiconductors, conductivity exponentially increases with temperature).In these oxides, it is adsorbed on material surface
Gaseous oxygen participates in oxidation reaction together with Lattice Oxygen, and the activity of coating stability and catalyst can be improved.
In order to preferably be combined with coating, stable, efficient integral catalyzer, the preferably described violet of the present invention are formed
Pretreatment of the green stone honeycomb ceramic carrier through including the following steps：Cordierite honeycomb ceramic matrix is put into dilute pin acid（It is preferred that dense
Spend 5%-10%）Middle immersion 4-12 hours is taken out 1-6 hours dry at 80 DEG C -150 DEG C.
The second coating and/or the load capacity of third coating are one of the cores that catalyst is capable of efficient catalytic.This hair
The percentage that the gross mass of bright preferably described two coating of metal oxides accounts for the carrier quality is 1.5%-8%, preferably 5%-
7%。
Invention also provides the preparation methods of the catalyst for catalytic combustion, include the following steps：
（1）Cordierite honeycomb ceramic carrier is put into the dilute pin acid of a concentration of 5%-10% and is impregnated 4-12 hours, after taking-up 80 DEG C-
It is 1-6 hours dry at 150 DEG C；
（2）By step（1）Treated ceramic honey comb matrix immerses in Aluminum sol, dry after taking-up, under nitrogen protection 400
DEG C -900 DEG C roast 1-6 hour, the first coating of metal oxides of formation；
（3）By step（2）In obtained cordierite honeycomb ceramic be impregnated in a kind of hafnium-lanthanum-cerium solution, it is dry after taking-up,
It roasts 1-6 hours for 400 DEG C -600 DEG C under nitrogen protection, forms the second coating of metal oxides；
（4）By step（3）In obtained cordierite honeycomb ceramic be impregnated in a kind of manganese-copper salt solution, it is dry after taking-up, in nitrogen
Lower 400 DEG C -550 DEG C of gas shielded roasts 1-6 hours, forms third coating of metal oxides.The preparation method of the Aluminum sol is：
Boehmite powder mixes in proportion with deionized water, adds urea, is sufficiently stirred at room temperature, and concentrated nitric acid is added dropwise and adjusts slurries pH
=2-5, peptization react 60-240min to get stable Aluminum sol, wherein boehmite powder：Deionized water：The quality of urea
Than for：（3-5）:（25-30）：（1.5-2.5）.
In order to ensure coating load amount reaches desired value, the present invention preferably formed the second coating of metal oxides and/or
During forming third coating of metal oxides, the immersion and the operation of drying and roasting are repeated, until coating load amount reaches
It is roasted after to desired value.
It is dry 1-6 hours dry preferably at 80 DEG C -150 DEG C in the preparation process；Roasting preferably 400 DEG C-
900 DEG C roast 1-6 hours.In order to which gained catalyst combines, closer, stability is more preferable, the second layer that the present invention is preferably formed as
The calcination temperature of coating of metal oxides is 400 DEG C -600 DEG C, and the calcination temperature for forming third coating of metal oxides is 400
℃-550℃.To ensure the activity of third layer coating of metal oxides, when roasting, it is preferable to use nitrogen to be protected.
The step（3）The preparation method of middle hafnium-lanthanum-cerium solution is：By hafnium sulfate, lanthanum sulfate and six nitric hydrate ceriums
It is soluble in water, add urea, constant temperature（20-50℃）Lower stirring is to get hafnium-lanthanum-cerium solution.Wherein hafnium sulfate：Lanthanum sulfate：
Six nitric hydrate ceriums：Urea：Water quality ratio is（0.01-0.5）：（0.01-0.5）：（0.01-0.5）：1：1.
The step（4）The preparation method of middle manganese-copper salt solution is：Manganese nitrate and copper nitrate are added to the water, then added
Add urea, is stirred to get manganese-copper salt solution under constant temperature.Wherein, manganese nitrate：Copper nitrate：Urea：Water quality ratio is（0.01-
0.5）：（0.01-0.5）：1：1.
The present invention further protects application of the catalyst for catalytic combustion in the industrial volatile organic compounds of processing.
The application is specially：Industrial volatile organic compounds are made into institute by the catalyst under burning condition
State exhaust gas conversion or degradation.It as a preferred embodiment, can be with air speed 18000-22000 h-1It is 1500-2200 by total hydrocarbon concentration
mg/m3Organic exhaust gas by the catalyst, reactor inlet temperature is 100-300 DEG C, preferably 225 DEG C -300 DEG C, more
Preferably 250 DEG C -300 DEG C, it can be achieved that exhaust gas efficient degradation.
Industry volatile organic compounds of the present invention are preferably benzene,toluene,xylene, acetone, cyclohexanone, positive fourth
Alcohol, styrene, ethyl acetate etc., when being catalyzed above-mentioned exhaust gas, catalyst provided by the invention can embody best burning and urge
Change effect.
The beneficial effects of the present invention are：
1. catalyst provided by the invention replaces noble metal using base metal, catalyst activity component is on the one hand formed
Mixed oxide has the characteristics that p-type semiconductor (in these semiconductors, conductivity exponentially increases with temperature) such as Fig. 1 institutes
Show.The gaseous oxygen for being adsorbed on material surface participates in oxidation reaction together with Lattice Oxygen, and coating stability and catalyst can be improved
It is expensive to solve noble metal for activity.Special perovskite structure solves the shortcomings of traditional catalyst antitoxin poor performance,
On the other hand, base metal raw material is easy to get, simple process；The addition of wherein Ce can not only improve the redox of catalysis catalyst
Performance, moreover it is possible to promote being uniformly distributed for other active components.So catalyst coat provided by the invention is uniformly dispersed, activity
Component is combined closely with carrier, and thermal stability is high, catalytic activity is strong, and service life is long, and is easy to large-scale industrial production.
2. the present invention replaces noble metal using the composite oxides of base metal lanthanum, hafnium, cerium, manganese and copper, on the one hand solve
Conventional precious metal catalyst easy-sintering, easily poisoning and it is expensive the problems such as, on the other hand, above-mentioned raw metal is easy to get, work
Skill is easy, and catalytic performance is efficient, is easy to large-scale industrial production.
3. oxide coating is dexterously divided into three layers by the present invention, the first coating of metal oxides is in direct contact with carrier,
The coating mainly increases the specific surface area of material, outer to coat the second metal oxygen containing hafnium oxide, lanthana and cerium oxide again
Compound coating, the rare earth ions such as lanthanum which includes mainly are the metal oxides for having special band structure so that catalysis
Agent has light outstanding, electricity, magnetic property, further enhances catalytic activity；It is outer coat again containing manganese oxide and copper oxide the
Three coating of metal oxides are dispersed in the whole of active oxidation aluminium surface to form hafnium, lanthanum, cerium, manganese, copper isoreactivity component
Body catalyst.Present invention process ensures that there are stronger phases between active component hafnium, lanthanum, cerium, manganese, copper and activated alumina component
Interaction avoids the formation of catalytic removal of nox as shown in Fig. 2, catalytic activity higher, thermal stability is stronger, to the organic gas of VOCs
Very strong facilitation is played in the catalysis burning of body.
Description of the drawings
Fig. 1 is the pictorial diagram of catalyst.
Fig. 2 is the electron-microscope scanning figure of catalyst.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, technical scheme of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
The every other embodiment that those of ordinary skill in the art are obtained under the premise of not making the creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
A kind of rare earth doped element catalyst of manganese-copper-base composite oxidate is present embodiments provided, is prepared by the following method：
（1）Cordierite honeycomb ceramic matrix is put into a concentration of 5% dilute pin acid and impregnates 4h pretreatments, after taking-up at 90 DEG C
Dry 6h, it is spare.
（2）By step（1）Treated, and cordierite honeycomb ceramic matrix immerses in Aluminum sol, and raffinate is blown away in taking-up, 90
Dry 6h at DEG C, 250 DEG C of roasting 2h, obtains the ceramic honey comb coated with aluminum oxide coating layer, the preparation method of the Aluminum sol is：It is quasi-
Boehmite powder mixes in proportion with deionized water, adds urea, is sufficiently stirred at room temperature, and dropwise addition concentrated nitric acid adjusting slurries pH=
2, peptization reacts 60min to get stable Aluminum sol, wherein boehmite powder：Deionized water：The mass ratio of urea is：3:
25：1.5.
（3）40g hafnium sulfates, six nitric hydrate ceriums of 46g lanthanum sulfates 90g are dissolved in 2000g water, 2000g urea is added,
1h is stirred at 25 DEG C, is made into slurry A.Slurry A is coated on cordierite honeycomb ceramic, after the completion of coating, by cordierite honeycomb
Ceramics stand 6h at room temperature, the operation of then weigh, repeat after 100 DEG C of dry 4h coating and drying, until reaching negative
The 1.5% of total weight is carried, 450 DEG C of roasting 1h, acquisition under nitrogen protection is loaded with HfO2、CeO2And La2O3Rare-earth oxide
Ceramic honey comb.
（4）200g manganese nitrates and 250g cupric sulfate pentahydrates are dissolved in 2000g water, 2000g urea is added, is stirred at 35 DEG C
1h is mixed, slurry B is made into.By step（3）In obtained cordierite honeycomb ceramic be impregnated in slurry B, stand 3h at room temperature,
It weighs after 100 DEG C of dryings, repeats the operation of dipping and drying, until reaching the 3% of load total weight, by carrier in N2Atmosphere
In in 600 DEG C roast 6h, finally obtain MnO2-CuO-HfO2-CeO2-La2O3The ceramic honeycomb catalyst of metal oxide is such as schemed
Shown in 1, electron microscope is as shown in Figure 2.
Embodiment 2
A kind of rare earth doped element catalyst of manganese-copper-base composite oxidate is present embodiments provided, is prepared by the following method：
（1）Cordierite honeycomb ceramic matrix is put into a concentration of 10% dilute pin acid and impregnates 12h pretreatments, at 150 DEG C after taking-up
Lower dry 1h, it is spare.
（2）By step（1）Treated, and cordierite honeycomb ceramic matrix immerses in Aluminum sol, and raffinate is blown away in taking-up, 90
Dry 6h at DEG C, 250 DEG C of roasting 2h, obtains the ceramic honey comb coated with aluminum oxide coating layer, the preparation method of the Aluminum sol is：It is quasi-
Boehmite powder mixes in proportion with deionized water, adds urea, is sufficiently stirred at room temperature, and dropwise addition concentrated nitric acid adjusting slurries pH=
5, peptization reacts 240min to get stable Aluminum sol, wherein boehmite powder：Deionized water：The mass ratio of urea is：
5: 30：2.5.
（3）45g hafnium sulfates, six nitric hydrate ceriums of 46g lanthanum sulfates 100g are dissolved in 2000g water, 2000g urea is added,
1h is stirred at 25 DEG C, is made into slurry A.Slurry A is coated on cordierite honeycomb ceramic, after the completion of coating, by cordierite bee
Nest ceramics stand 6h at room temperature, the operation of then weigh, repeat after 100 DEG C of dry 4h coating and drying, until reaching
The 1.5% of total weight, 400 DEG C of roasting 6h are loaded, acquisition is loaded with HfO2、CeO2And La2O3The ceramic honey comb of rare-earth oxide.
（4）200g manganese nitrates and 250g cupric sulfate pentahydrates are dissolved in 2000g water, 2000g urea is added, is stirred at 35 DEG C
1h is mixed, slurry B is made into.By step（3）In obtained cordierite honeycomb ceramic be impregnated in slurry B, stand 3h at room temperature,
It weighs after 100 DEG C of dryings, repeats the operation of dipping and drying, until reaching the 3% of load total weight, by carrier in N2Atmosphere
In in 550 DEG C roast 2h, finally obtain MnO2-CuO-HfO2-CeO2-La2O3The ceramic honeycomb catalyst of metal oxide.
Embodiment 3
A kind of rare earth doped element catalyst of manganese-copper-base composite oxidate is present embodiments provided, is prepared by the following method：
（1）Cordierite honeycomb ceramic matrix is put into a concentration of 8% dilute pin acid and impregnates 8h pretreatments, after taking-up at 90 DEG C
Dry 3h, it is spare.
（2）By step（1）Treated, and cordierite honeycomb ceramic matrix immerses in Aluminum sol, and raffinate is blown away in taking-up, 90
Dry 6h at DEG C, 250 DEG C of roasting 2h, obtains the ceramic honey comb coated with aluminum oxide coating layer, the preparation method of the Aluminum sol is：It is quasi-
Boehmite powder mixes in proportion with deionized water, adds urea, is sufficiently stirred at room temperature, and dropwise addition concentrated nitric acid adjusting slurries pH=
3, peptization reacts 150min to get stable Aluminum sol, wherein boehmite powder：Deionized water：The mass ratio of urea is：4:
28：2.
（3）20.5g hafnium sulfates, six nitric hydrate ceriums of 28.3g lanthanum sulfates 43.4g are dissolved in 2000g water, 2000g is added
Urea stirs 1h at 25 DEG C, is made into slurry A.Slurry A is coated on cordierite honeycomb ceramic, after the completion of coating, by violet blueness
Stone ceramic honey comb stands 6h at room temperature, the operation of then weigh, repeat after 100 DEG C of dry 4h coating and drying, until
Reach the 1.5% of load total weight, 450 DEG C of roasting 2h, acquisition is loaded with HfO2、CeO2And La2O3The honeycomb of rare-earth oxide
Ceramics.
（4）278g manganese nitrates and 250g cupric sulfate pentahydrates are dissolved in 2000g water, 2000g urea is added, is stirred at 35 DEG C
1h is mixed, slurry B is made into.By step（3）In obtained cordierite honeycomb ceramic be impregnated in slurry B, stand 3h at room temperature,
It weighs after 100 DEG C of dryings, repeats the operation of dipping and drying, until reaching the 3% of load total weight, by carrier in N2Atmosphere
In in 550 DEG C roast 2h, finally obtain MnO2-CuO-HfO2-CeO2-La2O3The ceramic honeycomb catalyst of metal oxide.
Embodiment 4
A kind of rare earth doped element catalyst of manganese-copper-base composite oxidate is present embodiments provided, is prepared by the following method：
（1）Cordierite honeycomb ceramic matrix is put into dipping pretreatment in diluted acid, takes out the dry 6h at 90 DEG C, it is spare.
（2）By step（1）Treated, and cordierite honeycomb ceramic matrix immerses in alumina sol, and raffinate is blown away in taking-up,
The dry 6h at 90 DEG C, 250 DEG C of roasting 2h, obtains the ceramic honey comb coated with aluminum oxide coating layer.
（3）25g hafnium sulfates, six nitric hydrate ceriums of 1000g lanthanum sulfates 43.4g are dissolved in 2000g water, 2000g urine is added
Element stirs 1h at 25 DEG C, is made into slurry A.Slurry A is coated on cordierite honeycomb ceramic, after the completion of coating, by cordierite
Ceramic honey comb stands 6h at room temperature, the operation of then weigh, repeat after 100 °C of dry 4h coating and drying, until reaching
To the 1.5% of load total weight, 450 °C of roasting 2h, acquisition is loaded with HfO2、CeO2And La2O3The honeycomb of rare-earth oxide is made pottery
Porcelain.
（4）1000g manganese nitrates and 20g cupric sulfate pentahydrates are dissolved in 2000g water, 2000g urea is added, is stirred at 35 DEG C
1h is mixed, slurry B is made into.By step（3）In obtained cordierite honeycomb ceramic be impregnated in slurry B, stand 3h at room temperature,
It weighs after 100 DEG C of dryings, repeats the operation of dipping and drying, until reaching the 3% of load total weight, by carrier in N2 atmosphere
In in 550 DEG C roast 2h, finally obtain MnO2-CuO-HfO2-CeO2-La2O3The ceramic honeycomb catalyst of metal oxide.
Embodiment 5
A kind of rare earth doped element catalyst of manganese-copper-base composite oxidate is present embodiments provided, is prepared by the following method：
（1）Cordierite honeycomb ceramic matrix is put into dipping pretreatment in diluted acid, takes out the dry 6h at 90 DEG C, it is spare.
（2）Step (1) treated cordierite honeycomb ceramic matrix to be immersed in alumina sol, raffinate is blown away in taking-up,
The dry 6h at 90 DEG C, 250 DEG C of roasting 2h, obtains the ceramic honey comb coated with aluminum oxide coating layer.
（3）43.4 gram of six 20.5g hafnium sulfates, 28.3g lanthanum sulfates nitric hydrate cerium are dissolved in 2000g water, 2000g is added
Urea stirs 1h at 25 DEG C, is made into slurry A.Slurry A is coated on cordierite honeycomb ceramic, after the completion of coating, by violet blueness
Stone ceramic honey comb stands 6h at room temperature, the operation of then weigh, repeat after 100 °C of dry 4h coating and drying, until
Reach the 1.5% of load total weight, 450 °C of roasting 2h, acquisition is loaded with HfO2、CeO2And La2O3The honeycomb of rare-earth oxide
Ceramics.
（4）300g manganese nitrates and 350g cupric sulfate pentahydrates are dissolved in 2000g water, 2000g urea is added, is stirred at 35 DEG C
1h is mixed, slurry B is made into.By step（3）In obtained cordierite honeycomb ceramic be impregnated in slurry B, stand 3h at room temperature,
It weighs after 100 DEG C of dryings, repeats the operation of dipping and drying, until reaching the 3% of load total weight, by carrier in N2Atmosphere
In in 550 DEG C roast 2h, finally obtain MnO2-CuO-HfO2-CeO2-La2O3The ceramic honeycomb catalyst of metal oxide.
Embodiment 6
A kind of rare earth doped element catalyst of manganese-copper-base composite oxidate is present embodiments provided, is prepared by the following method：
（1）Cordierite honeycomb ceramic matrix is put into dipping pretreatment in diluted acid, takes out the dry 3h at 110 DEG C, it is spare.
（2）Step (1) treated cordierite honeycomb ceramic matrix to be immersed in alumina sol, raffinate is blown away in taking-up,
The dry 2h at 120 DEG C, 250 DEG C of roasting 2h, obtains the ceramic honey comb coated with aluminum oxide coating layer.
（3）150g hafnium sulfates, six nitric hydrate ceriums of 350g lanthanum sulfates 1000g are dissolved in 2000g water, 2000g urine is added
Element stirs 1h at 40 DEG C, is made into slurry A.Slurry A is coated on cordierite honeycomb ceramic, after the completion of coating, by cordierite
Ceramic honey comb stands 4h at room temperature, the operation of then weigh, repeat after 120 °C of dry 3h coating and drying, until reaching
To the 2% of load total weight, 450 °C of roasting 1h, acquisition is loaded with HfO2、CeO2And La2O3The ceramic honey comb of rare-earth oxide.
（4）300g manganese nitrates and 350g cupric sulfate pentahydrates are dissolved in 2000g water, 2000g urea is added, is stirred at 40 DEG C
1h is mixed, slurry B is made into.By step（3）In obtained cordierite honeycomb ceramic be impregnated in slurry B, stand 2h at room temperature,
It weighs after 120 DEG C of dryings, repeats the operation of dipping and drying, until reaching the 4% of load total weight, by carrier in N2 atmosphere
In in 550 DEG C roast 2h, finally obtain MnO2-CuO-HfO2-CeO2-La2O3The ceramic honeycomb catalyst of metal oxide.
Embodiment 7
（1）Cordierite honeycomb ceramic matrix is put into dipping pretreatment in diluted acid, takes out the dry 3h at 110 DEG C, it is spare.
（2）By step（1）Treated, and cordierite honeycomb ceramic matrix immerses in alumina sol, and raffinate is blown away in taking-up,
The dry 2h at 120 DEG C, 250 DEG C of roasting 2h, obtains the ceramic honey comb coated with aluminum oxide coating layer.
（3）20g hafnium sulfates, six nitric hydrate ceriums of 1000g lanthanum sulfates 25g are dissolved in 2000g water, 60g urea is added,
1h is stirred at 40 DEG C, is made into slurry A.Slurry A is coated on cordierite honeycomb ceramic, after the completion of coating, by cordierite honeycomb
Ceramics stand 4h at room temperature, the operation of then weigh, repeat after 120 °C of dry 3h coating and drying, until reaching negative
The 2% of total weight, 400 °C of roasting 1h are carried, acquisition is loaded with HfO2、CeO2And La2O3The ceramic honey comb of rare-earth oxide.
（4）200g manganese nitrates and 300g cupric sulfate pentahydrates are dissolved in 2000g water, 2000g urea is added, is stirred at 40 DEG C
1h is mixed, slurry B is made into.By step（3）In obtained cordierite honeycomb ceramic be impregnated in slurry B, stand 2h at room temperature,
It weighs after 120 DEG C of dryings, repeats the operation of dipping and drying, until reaching the 4% of load total weight, by carrier in N2 atmosphere
In in 550 DEG C roast 1h, finally obtain MnO2-CuO-HfO2-CeO2-La2O3The ceramic honeycomb catalyst of metal oxide.
Application examples
In order to evaluate treatment effect of the catalyst to organic exhaust gas, catalyst for catalytic combustion that the present invention provides each embodiment into
Row activity rating and estimation of stability.Evaluation condition is：Air speed is 20000 h-1, toluene concentration is 1500 mg/m3, reactor
Inlet temperature is 100-300 DEG C, and evaluation results are shown in Table 1 after continuously running 480 hours.
As can be seen that the catalyst that each embodiment provides can reach 90% at 225 DEG C -300 DEG C to the catalytic efficiency of toluene
More than, wherein 250 DEG C of -300 DEG C of temperature sections can reach 98% or more, and catalyst activity keeps stablizing, and illustrates offer of the present invention
Catalyst activity have higher stability, be suitble to industrial organic exhaust gas processing.
Table 1 is the experimental result for the catalyst toluene that each embodiment provides（Toluene is continuous to transport at a temperature of 250 DEG C
Conversion ratio after turning 480 hours）.
Table 1：Catalyst activity evaluation result
As can be seen from Table 1, catalyst for catalytic combustion organic removal rate provided by the invention is high, after continuously running 480 hours,
Higher removal rate is still remain, illustrates that the catalyst has good antitoxinization performance and stability.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (10)
1. a kind of catalyst of the rare earth doped element of manganese-copper-base composite oxidate of catalysis VOCs, it is characterised in that：The catalysis
Agent coats the first coating of metal oxides, the second metal oxide applies successively from inside to outside using cordierite honeycomb ceramic as carrier
Layer and third layer coating of metal oxides；The first coating of metal oxides main component is active alundum (Al2O3), described
Second coating of metal oxides main component is lanthanum-oxides, hafnium oxide and cerium oxide, the third metal oxide
Coating main component is Mn oxide and Cu oxide.
2. the catalyst of the rare earth doped element of manganese-copper-base composite oxidate of catalysis VOCs as described in claim 1, feature
It is：The carrier cordierite honeycomb ceramic hexagon, circle or it is rectangular in any one, cordierite-base ceramic honey comb be it is rectangular
When, a length of 5-15cm, width 5-15cm, a height of 5-15cm, the density in hole is 100-500 mesh on cordierite-base ceramic honey comb.
3. the catalyst of the rare earth doped element of manganese-copper-base composite oxidate of catalysis VOCs as described in claim 1, feature
It is：In first coating of metal oxides, active alundum (Al2O3) weightening ratio is 5%-15%, preferably 10%-15%；Institute
It states in the second coating of metal oxides, lanthanum-oxides, hafnium oxide and cerium oxide weightening ratio are respectively 0.5%-2%, preferably
For 1%-2%；In the third coating of metal oxides, Mn oxide and Cu oxide weightening ratio are respectively 1%-5%, preferably
2.5%-5%。
4. the catalyst of the rare earth doped element of manganese-copper-base composite oxidate of catalysis VOCs as described in claim 1, feature
It is：It is MnO that the oxide component containing lower valency, which accounts for each painting stratum proportion, in the oxide2 30-60wt%、CuO15-29wt%、
HfO218-33 wt%、La20318-33 wt%、CeO2 18-33 wt%。
5. the rare earth doped element of manganese-copper-base composite oxidate of the catalysis VOCs as described in claim 1-4 any one is urged
The preparation method of agent, it is characterised in that steps are as follows：
（1）Cordierite honeycomb ceramic carrier is put into the dilute pin acid of a concentration of 5%-10% and is impregnated 4-12 hours, after taking-up 80 DEG C-
It is 1-6 hours dry at 150 DEG C；
（2）By step（1）Treated ceramic honey comb matrix immerses in Aluminum sol, dry after taking-up, under nitrogen protection 400
DEG C -900 DEG C roast 1-6 hour, the first coating of metal oxides of formation；
（3）By step（2）In obtained cordierite honeycomb ceramic be impregnated in a kind of hafnium-lanthanum-cerium solution, it is dry after taking-up,
It roasts 1-6 hours for 400 DEG C -600 DEG C under nitrogen protection, forms the second coating of metal oxides；
（4）By step（3）In obtained cordierite honeycomb ceramic be impregnated in a kind of manganese-copper salt solution, it is dry after taking-up, in nitrogen
Lower 400 DEG C -550 DEG C of gas shielded roasts 1-6 hours, forms third coating of metal oxides.
6. the preparation of the catalyst of the rare earth doped element of manganese-copper-base composite oxidate of catalysis VOCs as claimed in claim 5
Method, it is characterised in that：The step（2）The preparation method of middle Aluminum sol is：Boehmite powder and deionized water are in proportion
Mixing, add urea, be sufficiently stirred at room temperature, be added dropwise concentrated nitric acid adjust slurries pH=2-5, peptization react 60-240min to get
Stable Aluminum sol, wherein boehmite powder：Deionized water：The mass ratio of urea is：（3-5）:（25-30）：（1.5-
2.5）.
7. the preparation of the catalyst of the rare earth doped element of manganese-copper-base composite oxidate of catalysis VOCs as claimed in claim 5
Method, which is characterized in that the step（3）The preparation method of middle hafnium-lanthanum-cerium solution is：By hafnium sulfate, lanthanum sulfate and six water
It is soluble in water to close cerous nitrate, adds urea, stirring is to get hafnium-lanthanum-cerium solution under constant temperature；Wherein, hafnium sulfate：Lanthanum sulfate：
Six nitric hydrate ceriums：Urea：Water quality ratio is（0.01-0.5）：（0.01-0.5）：（0.01-0.5）：1：1.
8. the preparation of the catalyst of the rare earth doped element of manganese-copper-base composite oxidate of catalysis VOCs as claimed in claim 5
Method, which is characterized in that the step（4）The preparation method of middle manganese-copper salt solution is：Manganese nitrate and copper nitrate are added to water
In, then urea is added, stirring is to get manganese-copper salt solution under constant temperature；Wherein, manganese nitrate：Copper nitrate：Urea：Water quality ratio is
（0.01-0.5）：（0.01-0.5）： 1：1.
9. being catalyzed the rare earth doped element of manganese-copper-base composite oxidate of VOCs such as claim 1-4,6-8 any one of them
Application of the catalyst in the degradation of VOCs exhaust fume catalytic oxidation processes.
10. the catalyst of the rare earth doped element of manganese-copper-base composite oxidate of catalysis VOCs is in VOCs as claimed in claim 9
Application in the degradation of exhaust fume catalytic oxidation processes, it is characterised in that：The VOCs exhaust gas is benzene,toluene,xylene, acetone, ring
Hexanone, n-butanol, styrene and/or ethyl acetate.
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