WO2014067186A1 - Noble metal-integrated catalyst and preparation method therefor - Google Patents
Noble metal-integrated catalyst and preparation method therefor Download PDFInfo
- Publication number
- WO2014067186A1 WO2014067186A1 PCT/CN2012/084944 CN2012084944W WO2014067186A1 WO 2014067186 A1 WO2014067186 A1 WO 2014067186A1 CN 2012084944 W CN2012084944 W CN 2012084944W WO 2014067186 A1 WO2014067186 A1 WO 2014067186A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxide
- active component
- noble metal
- polyoxyethylene ether
- precious metal
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 66
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 57
- 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 group [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 56
- 239000000919 ceramic Substances 0.000 claims abstract description 49
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 17
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims description 61
- 239000010970 precious metal Substances 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 52
- 239000007762 w/o emulsion Substances 0.000 claims description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- 238000002485 combustion reaction Methods 0.000 claims description 27
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 26
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 10
- -1 diesel Substances 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 7
- 238000000889 atomisation Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 claims description 5
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000009841 combustion method Methods 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000001593 sorbitan monooleate Substances 0.000 claims description 5
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 5
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 5
- 238000001089 thermophoresis Methods 0.000 claims description 5
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 claims description 4
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 claims description 4
- 239000004147 Sorbitan trioleate Substances 0.000 claims description 4
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 4
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000001570 sorbitan monopalmitate Substances 0.000 claims description 4
- 235000011071 sorbitan monopalmitate Nutrition 0.000 claims description 4
- 229940031953 sorbitan monopalmitate Drugs 0.000 claims description 4
- 235000019337 sorbitan trioleate Nutrition 0.000 claims description 4
- 229960000391 sorbitan trioleate Drugs 0.000 claims description 4
- 239000001589 sorbitan tristearate Substances 0.000 claims description 4
- 235000011078 sorbitan tristearate Nutrition 0.000 claims description 4
- 229960004129 sorbitan tristearate Drugs 0.000 claims description 4
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 3
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 claims description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 3
- 239000003502 gasoline Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 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 description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229940035044 sorbitan monolaurate Drugs 0.000 claims description 3
- 239000001587 sorbitan monostearate Substances 0.000 claims description 3
- 235000011076 sorbitan monostearate Nutrition 0.000 claims description 3
- 229940035048 sorbitan monostearate Drugs 0.000 claims description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 2
- CYMRPDYINXWJFU-UHFFFAOYSA-N 2-carbamoylbenzoic acid Chemical compound NC(=O)C1=CC=CC=C1C(O)=O CYMRPDYINXWJFU-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 229940031728 cocamidopropylamine oxide Drugs 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- HOVAGTYPODGVJG-UHFFFAOYSA-N methyl beta-galactoside Natural products COC1OC(CO)C(O)C(O)C1O HOVAGTYPODGVJG-UHFFFAOYSA-N 0.000 claims description 2
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims description 2
- 239000003760 tallow Substances 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 2
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 claims 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 claims 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 1
- 239000000600 sorbitol Substances 0.000 claims 1
- 229940114926 stearate Drugs 0.000 claims 1
- 238000005137 deposition process Methods 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 24
- 229910052760 oxygen Inorganic materials 0.000 description 24
- 239000001301 oxygen Substances 0.000 description 24
- 238000000151 deposition Methods 0.000 description 18
- 239000008346 aqueous phase Substances 0.000 description 17
- 239000011572 manganese Substances 0.000 description 17
- 235000019198 oils Nutrition 0.000 description 16
- 239000012071 phase Substances 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 12
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 12
- 239000007921 spray Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000012855 volatile organic compound Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012702 metal oxide precursor Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- JYCQQPHGFMYQCF-UHFFFAOYSA-N 4-tert-Octylphenol monoethoxylate Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCO)C=C1 JYCQQPHGFMYQCF-UHFFFAOYSA-N 0.000 description 1
- SBRHIQVQSGMQGZ-UHFFFAOYSA-N CCCCCCCCCCCCCCC1=C(C(C)(C)Cl)C=CC=C1.N Chemical compound CCCCCCCCCCCCCCC1=C(C(C)(C)Cl)C=CC=C1.N SBRHIQVQSGMQGZ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 229940098691 coco monoethanolamide Drugs 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229940075529 glyceryl stearate Drugs 0.000 description 1
- 229940116364 hard fat Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WRARMYFEJSUSRJ-UHFFFAOYSA-N manganese(2+);oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[O-2].[Mn+2].[Zr+4] WRARMYFEJSUSRJ-UHFFFAOYSA-N 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N mono-n-propyl amine Natural products CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012694 precious metal precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940100515 sorbitan Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QAPWOTLZCRSPJZ-UHFFFAOYSA-M trimethyl(sulfanyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)S QAPWOTLZCRSPJZ-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
-
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B01J35/56—
-
- 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
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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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
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
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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
- B01J37/0248—Coatings comprising impregnated particles
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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
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
- F23C13/08—Apparatus in which combustion takes place in the presence of catalytic material characterised by the catalytic material
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Definitions
- the invention belongs to the technical field of preparation of catalysts, and relates to a method for efficiently preparing a monolithic catalyst.
- the active component is directly deposited on a cordierite honeycomb ceramic carrier by an emulsion flame combustion method to form a noble metal monolith catalyst. method.
- Precious metal monolith catalysts are an important class of catalysts involved in the catalytic reaction industry. They are widely used in automotive exhaust gas purification, industrial flue gas denitrification and desulfurization, and the elimination of volatile organic compounds.
- Precious Metal Monolithic catalysts typically consist of a precious metal active component, a support and a coating.
- the precious metal active component is a catalytically active host in the catalyst, and its distribution state and bulk properties determine parameters such as activity, selectivity and lifetime of the catalyst; the carrier functions as a catalytic reaction while carrying the coating and the active component. Provide a suitable fluid passage.
- the carrier has a small specific surface area, and the precious metal active component is difficult to adhere to the carrier, and therefore a metal oxide is generally used as a coating bonding carrier and an active component.
- a metal oxide is generally used as a coating bonding carrier and an active component.
- some of the coatings use catalytically active metal oxides, so that the coating has a certain catalytic effect, which improves the activity, selectivity or lifetime of the catalyst as a whole.
- the monolith catalyst was prepared by solution impregnation.
- the ceramic-based or metal (mesh)-based carrier is repeatedly impregnated, dried, and calcined in a coating precursor solution, and a coating is applied to the carrier to form a composite carrier.
- the composite carrier is repeatedly impregnated, dried, and calcined in a precious metal precursor solution, and the active component is supported on the composite carrier.
- a nickel-palladium monolith catalyst for the purification of volatile organic compounds is prepared, as disclosed in the patent CN200510030697.8, by impregnating the coating and supporting the active component.
- the catalyst comprises cordierite as a carrier, a cerium-zirconium solid solution, a rare earth oxide and an alumina as a coating, and nickel palladium as an active component.
- Patent CN201010169260.3 discloses a monolithic catalyst preparation method for purifying organic waste gas. Through two The first coating zirconium manganese oxide and the second coating precious metal palladium active component are respectively deposited on the carrier by a process of sub-dipping, drying, baking, and the like.
- the problem of the use of such a catalyst is that the bond strength between the carrier-coating-active component is weak, especially in a long-term harsh environment, the catalyst has low mechanical and thermal shock resistance, and the powder dropping phenomenon is serious, resulting in long-term catalyst.
- the activity is unstable.
- the pores of the carrier cause capillary phenomenon under the action of the interfacial tension of the solution, resulting in uneven dispersion of the coating and active components in the pores, and clogging in the field pores in severe cases, affecting the catalysis. Mass transfer, heat transfer and momentum transfer in the process ultimately result in reduced activity.
- One object of the present invention is to provide a noble metal monolith catalyst having a high binding strength to a carrier of an active metal monolith catalyst and stable activity.
- a noble metal monolith catalyst characterized in that the noble metal monolith catalyst comprises a carrier and a noble metal active component, the carrier is a cordierite honeycomb ceramic, and the active component is supported on a rare earth metal oxide and a transition metal A precious metal on the oxide.
- the precious metal active component has a mass of 0.01 to 10% of the total mass of the noble metal monolith catalyst, for example, 0.08 ⁇ / ⁇ , 0.12%, 0.78%, 1.5%, 3.2% 4.2% 5.3%, 6.4% 7.5%, 8.6 %, 9.4%, preferably 0.05 to 9%, further preferably 0.1 to 8%.
- the cordierite honeycomb ceramic is preferably a high pore density cordierite honeycomb ceramic, and the "pore density" in the high pore density cordierite honeycomb ceramic support refers to the number of pores per square inch of the cross section.
- the high pore density means that the number of pores per square inch of the cross section is greater than or equal to 100 CPSI
- the cordierite honeycomb ceramic preferably has a pore density of 100 600 CPSI
- the cordierite honeycomb ceramic has a pore density of preferably 400 CPSI.
- the noble metal is selected from any one of Ag, Pt, Ru, Pd or Rh or a mixture of at least two.
- the mixture such as a mixture of Pt and Pd, a mixture of Pt and Rh, a mixture of Pd and Rh, a mixture of Pt, Pd and Rh, a mixture of Ag and Pt, a mixture of Ru, Ag and Pt, Pd, Ag, Pt and A mixture of Rh.
- the transition metal oxide is selected from any one or a mixture of at least two of Cu oxide, Cr oxide, Fe oxide, Co oxide, Ni oxide or Mn oxide.
- the mixture is, for example, a mixture of Mn oxide and Ni oxide, a mixture of Co oxide and Fe oxide, a mixture of Mn oxide, Ni oxide and Co oxide, Cu oxide, Co oxide and Fe oxide. mixture.
- the Fe oxide has Fe 2 O 3
- the Co oxide has Co 2 0 3
- the Ni oxide has NiO
- the Mn oxide has Mn 3 0 4
- the Cu oxide has CuO
- the Cr oxide has Cr 2 0 3 .
- the rare earth metal oxide is an oxide of La or/and an oxide of Ce.
- the oxide of La such as La 2 O 3
- the oxide of Ce has Ce0 2 .
- Exemplary precious metal monolithic catalysts are:
- the carrier is a cordierite honeycomb ceramic and the noble metal active component is a noble metal monolith catalyst composed of Rh supported on Ce0 2 and MO; the carrier is cordierite honeycomb ceramic and the precious metal active component is supported on L3 ⁇ 40 3 and Fe 2 0 3 a noble metal monolith catalyst composed of Pt; the support is a cordierite honeycomb ceramic and the noble metal active component is a noble metal monolith catalyst composed of Ag and Pt supported on Ce0 2 and Mn 3 0 4 ; the support is cordierite honeycomb ceramic and precious metal
- the active component is a noble metal monolithic catalyst composed of Ru supported on L3 ⁇ 40 3 and Co 2 0 3 ; the support is a cordierite honeycomb ceramic and the noble metal active component is a noble metal monolith catalyst composed of Pd supported on L3 ⁇ 40 3 and CuO
- the carrier is cordierite honeycomb ceramic and the precious metal active component is a noble metal monolith catalyst composed of Pt and Pd supported on L3 ⁇ 40 3 and Fe 2 0 3 ; the carrier
- a second object of the present invention is to provide a method for preparing a noble metal monolith catalyst as described above, which is an emulsion flame combustion deposition method, wherein a precious metal active component is deposited under the action of thermophoresis at the moment of formation. On the carrier, the bond strength between the carrier-active components is remarkably improved.
- a method for preparing a noble metal monolith catalyst is an emulsion flame combustion method, the method comprising the following steps:
- the noble metal active component is deposited by a thermophoretic force on a cordierite honeycomb ceramic support placed above the atomizing nozzle of the flame combustion apparatus to obtain a noble metal monolith catalyst.
- FIG. 1 is a schematic view showing the preparation of a noble metal monolith catalyst in the present invention.
- the emulsion is atomized by atomization of oxygen into a spray droplet, and the atomizing nozzle outlet surrounds a combustion-supporting flame composed of combustion-supporting oxygen and combustion-supporting formazan, the spray liquid
- the oil phase and the aqueous phase in the drop burn to form a precious metal active component.
- a large amount of combustion heat causes the aqueous phase solvent coated in the spray droplets
- the volatile, transition metal oxide precursor and rare earth metal oxide precursor are pyrolyzed into corresponding metal oxides, and the noble metal precursor is burned to form noble metal particles.
- the noble metal particles are supported on the transition metal oxide and the rare earth metal oxide by homogeneous nucleation or heterogeneous nucleation to obtain a noble metal active component.
- the noble metal active component is directly deposited on the cordierite honeycomb ceramic support above the flame under the action of thermophoresis to obtain a noble metal monolith catalyst.
- the precursor of the transition metal oxide is selected from the group consisting of Fe(N0 3 ) 3 , Cr 2 (S0 4 ) 3 Cr(N0 3 ) 3 , Cu(C 3 ⁇ 4COO) 2 , Cu(N0 3 ) 2 , Mn(N0 3 ) 2. Any one or a mixture of at least two of Mn(C3 ⁇ 4COO) 2 , Co(N0 3 ) 2 , Co(C3 ⁇ 4COO) 2 , Ni NO ⁇ or Ni C3 ⁇ 4COO;) 2 .
- the mixture is, for example, a mixture of Ni(C3 ⁇ 4COO) 2 and Cr(N0 3 ) 3 , a mixture of Co(CH 3 COO) 2 and Mn(N0 3 ) 2 , a mixture of Mn(C 3 ⁇ 4COO) 2 and Cu(N0 3 ) 2 , a mixture of Fe(N0 3 ) 3 , Ni(C 3 ⁇ 4COO) 2 and Cu(N0 3 ) 2 , Co(CH 3 COO) 2 , Cr(N0 3 ) 2 , Mn(C 3 ⁇ 4COO) 2 and Fe(N0 3 ) 3 mixture.
- the precursor of the rare earth metal oxide is selected from La(N0 3 ) 3 , La(CH 3 COO) 3 , Ce(CH 3 COO) 3 or Ce (N0 3 ; > 3 or at least two a mixture of La(CH 3 COO) 3 and Ce(CH 3 COO) 3 , a mixture of La(N0 3 ) 3 and Ce(N0 3 ) 3 , La(N0 3 ) 3 and Ce ( a mixture of C3 ⁇ 4COO) 3, a mixture of La(N0 3 ) 3 , La(C3 ⁇ 4COO) 3 and Ce(C3 ⁇ 4COO) 3 .
- the precursor of the noble metal is selected from any one of Ag(acac), Pd(acac) 2 , Pt(acac) 2 , Rh(acac) 3 or Ru(acac) 3 or a mixture of at least two.
- the mixture is, for example, a mixture of Pd acac ⁇ and Pt(acac) 2, a mixture of Rh(acac) 3 and Ag(acac), a mixture of Pd(acac) 2 , Pt(acac) 2 and Rh(acac) 3 , Ag A mixture of (acac), Rh(acac) 3 or Ru(acac) 3 .
- the volume ratio of the oil phase to the aqueous phase is 10:1 to 3:1, for example 8:1, 7:1, 6:1, 5:1, 5.5:1, 6.5:1, 8.5:1, 9.5: 1, preferably 9:1 ⁇ 4:1.
- the organic solvent is hexanyl, ruthenium, octyl, cyclopentanyl, cyclohexanthene, benzene, toluene, xylene, a mixture of gasoline, diesel, kerosene or a mixture of at least two, such as a mixture of hexanthene and hydrazine, a mixture of octyl and cyclopentanyl, a mixture of cyclohexane and benzene, toluene and xylene Mixture, a mixture of gasoline and diesel, a mixture of diesel and kerosene.
- the surfactant is selected from the group consisting of mercaptotrimethylammonium chloride, dodecyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride, tetradecyldimethylbenzyl chloride Ammonium, octadecyl dimethyl benzyl ammonium chloride, dodecyl dimethyl amine oxide, lauryl propyl propyl amine oxide, cocamidopropyl amine oxide, coco monoethanolamide, coconut oil Acid diethanolamide, di(hydrogenated tallow) phthalic acid amide, fatty alcohol polyoxyethylene ether, methyl glucoside polyoxyethylene ether, castor oil polyoxyethylene ether, ethylene glycol mono (double:) hard fat Acid ester, mono (double:) glyceryl stearate, nonylphenol ethoxylate, octylphenol ethoxylate, dodecyl polyoxyethylene ether, dinony
- the water supply temperature of the water-in-oil emulsion precursor is 1 to 20 ml/mm, for example, 1.5 ml/min, 4 ml/min, 7 ml/min, 10 ml/min, 12 ml/min, 14 ml/min, and 16 ml/min. 17 ml/min, 19 ml/min, preferably 2 to 18 ml/min, further preferably 3 to 15 ml/min.
- the flow rate is low, the reaction efficiency is low, the efficiency is too low, the flow rate is too high, and the emulsion is not completely atomized to enter the flame region, so that the reaction in the flame region is incomplete and affects the activity of the finally obtained catalyst.
- the precious metal active component is deposited on the cordierite honeycomb ceramic carrier under the action of thermophoresis.
- the deposition of precious metal active components is deposited in the high temperature flame region, i.e., in the flame region of 400 to 1200 °C.
- the deposition time is 180-900 s, for example, 240s, 360s, 480s, 540s, 600s, 720s, 840s.
- spray droplets continuously enter the flame region, react, generate precious metal active components, and deposit in On the carrier.
- the carrier placed above the nozzle of the flame burner can be removed and the precious metal monolith catalyst can be collected.
- the cordierite honeycomb ceramic carrier is placed 10 to 20 cm above the atomizing nozzle of the flame burning apparatus, preferably 15 cm above the atomizing nozzle of the flame burning apparatus.
- a third object of the present invention is to provide the use of a noble metal monolith catalyst as described above for the catalytic combustion of volatile organic compounds (VOCs).
- VOCs volatile organic compounds
- SPIMS-1000 The VOCs mass spectrometry (SPIMS-1000) analysis of the reactants and products, under the experimental conditions, the catalyst module volume is lcm X lcm X 5cm, the gas flow rate is 100ml / min, the test temperature range is 100 ⁇ 300 ° C, VOCs The concentration is 100 ⁇ 1000ppm. Most or all of the VOCs in the system can be converted to carbon dioxide and water using the noble metal monolith catalyst of the present invention.
- the flame combustion apparatus of the present invention is of the prior art, and those skilled in the art are fully capable of obtaining the flame combustion apparatus of the present invention in accordance with the flame combustion apparatus disclosed in Fig. 1 and in the prior art.
- the flame spray combustion system of the present invention is also referred to as a flame combustion apparatus.
- the flame combustion method for emulsion as a precursor directly deposits the active component formed in the high temperature flame on the cordierite honeycomb ceramic carrier, and has the following advantages compared with the prior art:
- the invention discards the traditional liquid phase method for coating and preparing the catalyst coating and the active component, and directly deposits the active component on the carrier by means of flame combustion deposition, thereby realizing the preparation of the active component and the deposition process, which is greatly completed.
- the present invention adopts a method of flame combustion deposition, so that the active component is deposited on the carrier under the action of thermophoresis at the moment of formation, and the bonding strength between the carrier-active component is greatly improved, and the prepared precious metal as a whole is prepared.
- Catalyst has good reactivity and stability, and the precious metal monolith catalyst
- the composition of the components is uniform, the load is controllable, and the binding strength of the cordierite honeycomb ceramic carrier and the active component is low, the powder of the monolithic catalyst prepared by the solution impregnation method and the cordierite honeycomb ceramic carrier channel are blocked by the active component.
- the problem is conducive to mass transfer heat transfer and momentum transfer.
- FIG. 1 is a schematic flow chart of preparing a noble metal monolith catalyst in the present invention
- the cordierite carrier is a cordierite honeycomb ceramic carrier, and the deposited layer is a noble metal active component;
- Fig. 3 is a graph showing the relationship between the temperature and the conversion rate of the catalytic combustion of the noble metal monolith catalyst prepared by the different water-in-oil emulsion precursor flow rates in the present invention
- Figure 4 is a graph showing the relationship between temperature and conversion rate of benzene catalytic combustion of monolithic catalyst prepared at different deposition times in the present invention
- 1-water-in-oil emulsion precursor 2-atomized oxygen; 3-combustible formazan; 4-combustible oxygen; 5-combustion flame; 6-flame region; 7- cordierite honeycomb ceramic carrier.
- the precursor of the noble metal is dissolved in xylene, and the precursor of the rare earth metal oxide and the transition metal oxide is dissolved in water, and the two are mixed in a certain ratio in the presence of a surfactant to form a water-in-oil emulsion precursor.
- the emulsion precursor supply flow rate was 1.875 ml/min
- the atomized oxygen flow rate was 4.0 L/min
- the combustion-supporting formazan and combustion-supporting oxygen flow rates were 2.4 L/mm and 4.0 L/mm, respectively.
- the cordierite honeycomb ceramic was placed 15 cm above the nozzle and the deposition time was 360 s.
- the cordierite monolithic catalyst was obtained and the benzene catalytic combustion test was carried out. The results are shown in Fig. 3.
- the water-in-oil emulsion precursor prepared in Example 1 was supplied to a flame spray combustion system, wherein the water-in-oil emulsion precursor supply flow rate was 5.535 ml/min, the atomized oxygen flow rate was 4.0 L/min, combustion-supporting formazan and combustion-supporting The oxygen flow rates were 2.4 L/mm and 4.0 L/mm, respectively.
- the cordierite honeycomb ceramic was placed 15 cm above the nozzle and the deposition time was 360 s.
- the cordierite monolithic catalyst was obtained and the benzene catalytic combustion test was carried out. The results are shown in Fig. 3.
- the water-in-oil emulsion precursor prepared in Example 1 was supplied to a flame spray combustion system, wherein the water-in-oil emulsion precursor supply flow rate was 9.225 ml/min, the atomized oxygen flow rate was 4.0 L/min, combustion-supporting formazan and combustion-supporting The oxygen flow rates were 2.4 L/mm and 4.0 L/mm, respectively.
- the cordierite honeycomb ceramic was placed 15 cm above the nozzle and the deposition time was 360 s.
- the cordierite monolithic catalyst was obtained and the benzene catalytic combustion test was carried out. The results are shown in Fig. 3.
- the water-in-oil emulsion precursor prepared in Example 1 was supplied to a flame spray combustion system, wherein the water-in-oil emulsion precursor supply flow rate was 5.535 ml/min, the atomized oxygen flow rate was 4.0 L/min, combustion-supporting formazan and combustion-supporting The oxygen flow rates were 2.4 L/mm and 4.0 L/mm, respectively.
- the cordierite honeycomb ceramic was placed 15 cm above the nozzle and the deposition time was 180 s.
- the cordierite monolithic catalyst was obtained and the benzene catalytic combustion test was carried out. The results are shown in Fig. 4.
- Example 5 The water-in-oil emulsion precursor prepared in Example 1 was supplied to a flame spray combustion system, wherein the water-in-oil emulsion precursor supply flow rate was 5.535 ml/min, the atomized oxygen flow rate was 4.0 L/min, combustion-supporting formazan and combustion-supporting The oxygen flow rates were 2.4 L/mm and 4.0 L/mm, respectively.
- the cordierite honeycomb ceramic was placed 15 cm above the nozzle and the deposition time was 600 s.
- the cordierite monolithic catalyst was obtained and the benzene catalytic combustion test was carried out. The results are shown in Fig. 4.
- the water-in-oil emulsion precursor prepared in Example 1 was supplied to a flame spray combustion system, wherein the water-in-oil emulsion precursor supply flow rate was 5.535 ml/min, the atomized oxygen flow rate was 4.0 L/min, combustion-supporting formazan and combustion-supporting The oxygen flow rates were 2.4 L/mm and 4.0 L/mm, respectively.
- the cordierite honeycomb ceramic was placed 15 cm above the nozzle and the deposition time was 900 s.
- the cordierite monolithic catalyst was obtained and the benzene catalytic combustion test was carried out. The results are shown in Fig. 4.
- the water-in-oil emulsion precursor is supplied to the flame burning device, after ignition, atomization, combustion, and then cooled and agglomerated to obtain a precious metal active component, wherein the water-in-oil emulsion precursor is supplied at a flow rate of 1 ml. /min, the flow rate of atomized oxygen is 4.0L/min, the flow rate of combustion-supporting formazan and combustion-supporting oxygen is 2.4L/min and 4.0L/min respectively ;
- the precious metal active component is deposited by the thermophoretic force on a 10 cm cordierite honeycomb ceramic carrier placed above the atomizing nozzle of the flame burning device, deposition time For 180 s, a precious metal monolith catalyst was obtained.
- the noble metal catalyst is a monolithic cordierite honeycomb carrier and a noble metal active component composition
- the active component is a noble metal: Fe 2 0 Pd supported on 3 and L3 ⁇ 40 3.
- the precious metal active component comprises 0.1% of the total mass of the precious metal monolith catalyst.
- aqueous phase is added dropwise to the oil phase, and a surfactant fatty alcohol polyoxyethylene ether is added to form a water-in-oil emulsion precursor, wherein the volume ratio of the oil phase to the aqueous phase is 7:1.
- the water-in-oil emulsion precursor is supplied to the flame burning device, after ignition, atomization, combustion, and then cooled and agglomerated to obtain a precious metal active component, wherein the water-in-oil emulsion precursor is supplied at a flow rate of 15 ml. /min, the flow rate of atomized oxygen is 4.0L/min, the flow rate of combustion-supporting formazan and combustion-supporting oxygen is 2.4L/min and 4.0L/min respectively ;
- the precious metal active component is deposited by a thermophoretic force on a 15 cm cordierite honeycomb ceramic carrier placed above the atomizing nozzle of the flame burning device, and the deposition time is 500 s.
- a noble metal monolith catalyst is obtained.
- the noble metal monolith catalyst comprises a cordierite honeycomb ceramic support and a noble metal active component, and the noble metal active component is: Rh composition supported on Mn 3 0 4 and Ce0 2 .
- the precious metal active component comprises 5% of the total mass of the precious metal monolith catalyst.
- aqueous phase is added dropwise to the oil phase, and the surfactant sorbitan monooleate is added to form a water-in-oil emulsion precursor, wherein the volume ratio of the oil phase to the aqueous phase is 10:1.
- the water-in-oil emulsion precursor is supplied to the flame burning device, after ignition, atomization, combustion, and then cooled and agglomerated to obtain a precious metal active component, wherein the water-in-oil emulsion precursor is supplied at a flow rate of 20 ml. /min, the flow rate of atomized oxygen is 4.0L/min, the flow rate of combustion-supporting formazan and combustion-supporting oxygen is 2.4L/min and 4.0L/min respectively ;
- the precious metal active component is deposited by a thermophoretic force on a 20 cm cordierite honeycomb ceramic carrier placed above the mist nozzle of the flame burning device, and the deposition time is 900 s.
- Precious metal monolithic catalyst is deposited by a thermophoretic force on a 20 cm cordierite honeycomb ceramic carrier placed above the mist nozzle of the flame burning device, and the deposition time is 900 s.
- Precious metal monolithic catalyst is deposited by a thermophoretic force on a 20 cm cordierite honeycomb ceramic carrier placed above the mist nozzle of the flame burning device.
- the noble metal monolith catalyst consists of a cordierite honeycomb ceramic support and a noble metal active component, and the noble metal active component is: Pt supported on Co 2 0 3 , ⁇ and Ce0 2 .
- the precious metal active component comprises 10% of the total mass of the precious metal monolith catalyst.
- aqueous phase is added dropwise to the oil phase, and a surfactant fatty alcohol polyoxyethylene ether is added to form a water-in-oil emulsion precursor, wherein the volume ratio of the oil phase to the aqueous phase is 3:1.
- the water-in-oil emulsion precursor is supplied to the flame burning device, after ignition, atomization, combustion, and then cooled and agglomerated to obtain a precious metal active component, wherein the water-in-oil emulsion precursor is supplied at a flow rate of 15 ml.
- the flow rate of atomized oxygen is 4.0L/min
- the flow rate of combustion-supporting formazan and combustion-supporting oxygen is 2.4L/min and 4.0L/min respectively ;
- the precious metal active component is deposited by a thermophoretic force on a 15 cm cordierite honeycomb ceramic carrier placed above the atomizing nozzle of the flame burning device, and the deposition time is 500 s.
- a noble metal monolith catalyst is obtained.
- the noble metal monolith catalyst comprises a cordierite honeycomb ceramic support and a noble metal active component, and the noble metal active component is: Rh composition supported on Mn 3 0 4 and Ce0 2 .
- the precious metal active component comprises 0.01% of the total mass of the precious metal monolith catalyst.
Abstract
Disclosed are a noble metal-integrated catalyst and a preparation method therefor. The noble metal-integrated catalyst comprises a carrier and a noble metal as an active component, wherein the carrier is a cordierite honeycomb ceramic with high cell density, and the active component is a noble metal supported on rare earth metal oxide and transition metal oxide. The noble metal-integrated catalyst has good reactivity and stability, and the active component is uniformly distributed with the load controllable. The present invention solves the problems of low bonding strength between the cordierite honeycomb ceramic carrier and the active component and blockage of carrier channels by the active component, enables preparation of the active component and the deposition process to be completed in one step, and significantly simplifies the preparation process of the noble metal-integrated catalyst.
Description
一种贵金属整体式催化剂及其制备方法 技术领域 Precious metal monolith catalyst and preparation method thereof
本发明属于催化剂的制备技术领域， 涉及一种高效制备整体式催化剂的方 法， 具体地， 是采用乳液火焰燃烧法将生成的活性组分直接沉积在堇青石蜂窝 陶瓷载体上形成贵金属整体式催化剂的方法。 The invention belongs to the technical field of preparation of catalysts, and relates to a method for efficiently preparing a monolithic catalyst. Specifically, the active component is directly deposited on a cordierite honeycomb ceramic carrier by an emulsion flame combustion method to form a noble metal monolith catalyst. method.
背景技术 Background technique
贵金属整体式催化剂是涉及到催化反应工业中一类重要的催化剂， 广泛应 用于汽车尾气净化， 工业烟气脱硝脱硫及挥发性有机物的消除等领域。 贵金属 整体式催化剂通常由贵金属活性组分、 载体和涂层组成。 其中贵金属活性组分 是催化剂中起催化活性的主体， 其分布状态及本体性质决定着催化剂的活性、 选择性及寿命等参数； 载体的作用是承载涂层和活性组分的同时， 为催化反应 提供合适的流体通道。 载体具有较小的比表面积， 贵金属活性组分很难附着在 载体上， 因此一般采用金属氧化物作为涂层黏结载体和活性组分。 此外部分涂 层采用具有催化活性的金属氧化物， 从而使涂层具有一定的助催化效应， 提高 了催化剂整体的活性、 选择性或者寿命。 Precious metal monolith catalysts are an important class of catalysts involved in the catalytic reaction industry. They are widely used in automotive exhaust gas purification, industrial flue gas denitrification and desulfurization, and the elimination of volatile organic compounds. Precious Metal Monolithic catalysts typically consist of a precious metal active component, a support and a coating. The precious metal active component is a catalytically active host in the catalyst, and its distribution state and bulk properties determine parameters such as activity, selectivity and lifetime of the catalyst; the carrier functions as a catalytic reaction while carrying the coating and the active component. Provide a suitable fluid passage. The carrier has a small specific surface area, and the precious metal active component is difficult to adhere to the carrier, and therefore a metal oxide is generally used as a coating bonding carrier and an active component. In addition, some of the coatings use catalytically active metal oxides, so that the coating has a certain catalytic effect, which improves the activity, selectivity or lifetime of the catalyst as a whole.
整体式催化剂采用溶液浸渍法制备。 陶瓷基或者金属 （网） 基载体置于涂 层前驱体溶液中反复浸渍、 干燥、 焙烧， 在载体上涂覆涂层， 形成复合载体。 复合载体置于贵金属前驱体溶液中反复浸渍、 干燥、 焙烧， 在复合载体上负载 活性组分。如专利 CN200510030697.8公布了浸渍涂覆涂层和负载活性组分的方 式， 制备了挥发性有机物染污净化用的镍 -钯整体式催化剂。 该催化剂以堇青石 为载体， 铈锆固溶体、 稀土氧化物、 氧化铝为涂层， 以镍钯为活性组分。 专利 CN201010169260.3公布了一种净化有机废气的整体式催化剂制备方法。 通过两
次浸渍、 干燥、 焙烧等过程， 分别在载体上沉积了第一涂层锆锰氧化物和第二 涂层贵金属钯活性组分。 The monolith catalyst was prepared by solution impregnation. The ceramic-based or metal (mesh)-based carrier is repeatedly impregnated, dried, and calcined in a coating precursor solution, and a coating is applied to the carrier to form a composite carrier. The composite carrier is repeatedly impregnated, dried, and calcined in a precious metal precursor solution, and the active component is supported on the composite carrier. A nickel-palladium monolith catalyst for the purification of volatile organic compounds is prepared, as disclosed in the patent CN200510030697.8, by impregnating the coating and supporting the active component. The catalyst comprises cordierite as a carrier, a cerium-zirconium solid solution, a rare earth oxide and an alumina as a coating, and nickel palladium as an active component. Patent CN201010169260.3 discloses a monolithic catalyst preparation method for purifying organic waste gas. Through two The first coating zirconium manganese oxide and the second coating precious metal palladium active component are respectively deposited on the carrier by a process of sub-dipping, drying, baking, and the like.
通常此类催化剂在使用中存在的问题是载体-涂层-活性组分之间的结合强 度弱， 尤其是长期严酷环境中， 催化剂抗机械及热震动性能低， 掉粉现象严重， 导致催化剂长期活性不稳定。 另一方面， 催化剂制备过程中， 载体的孔道在溶 液的界面张力的作用下引起毛细现象， 造成涂层和活性组分在提在孔道中分散 不均匀， 严重时在场孔道堵塞等现象， 影响催化过程中的传质、 传热及动量传 递， 最终造成活性降低。 Generally, the problem of the use of such a catalyst is that the bond strength between the carrier-coating-active component is weak, especially in a long-term harsh environment, the catalyst has low mechanical and thermal shock resistance, and the powder dropping phenomenon is serious, resulting in long-term catalyst. The activity is unstable. On the other hand, during the preparation of the catalyst, the pores of the carrier cause capillary phenomenon under the action of the interfacial tension of the solution, resulting in uneven dispersion of the coating and active components in the pores, and clogging in the field pores in severe cases, affecting the catalysis. Mass transfer, heat transfer and momentum transfer in the process ultimately result in reduced activity.
发明内容 Summary of the invention
本发明的目的之一在于提供一种贵金属整体式催化剂， 所述贵金属整体式 催化剂的载体与活性组分的结合强度高， 活性稳定。 SUMMARY OF THE INVENTION One object of the present invention is to provide a noble metal monolith catalyst having a high binding strength to a carrier of an active metal monolith catalyst and stable activity.
为了达到上述目的， 本发明采用了如下技术方案： In order to achieve the above object, the present invention adopts the following technical solutions:
一种贵金属整体式催化剂， 其特征在于， 所述贵金属整体式催化剂由载体 和贵金属活性组分组成， 所述载体为堇青石蜂窝陶瓷， 所述活性组分为负载在 稀土金属氧化物和过渡金属氧化物上的贵金属。 A noble metal monolith catalyst characterized in that the noble metal monolith catalyst comprises a carrier and a noble metal active component, the carrier is a cordierite honeycomb ceramic, and the active component is supported on a rare earth metal oxide and a transition metal A precious metal on the oxide.
所述贵金属活性组分的质量占贵金属整体式催化剂总质量的 0.01~10%， 例 Π 0.08ο/ο、 0.12%、 0.78%, 1.5%, 3.2% 4.2% 5.3%, 6.4% 7.5%, 8.6%, 9.4%, 优选 0.05~9%， 进一歩优选 0.1~8%。 The precious metal active component has a mass of 0.01 to 10% of the total mass of the noble metal monolith catalyst, for example, 0.08 ο / ο , 0.12%, 0.78%, 1.5%, 3.2% 4.2% 5.3%, 6.4% 7.5%, 8.6 %, 9.4%, preferably 0.05 to 9%, further preferably 0.1 to 8%.
所述堇青石蜂窝陶瓷优选高孔密度的堇青石蜂窝陶瓷， 所述高孔密度的堇 青石蜂窝陶瓷载体中的 "孔密度"是指每平方英寸横截面上的孔道数。 高孔密 度是指每平方英寸横截面上的孔道数大于等于 100 CPSI, 所述堇青石蜂窝陶瓷 的孔密度优选为 100 600 CPSI，所述堇青石蜂窝陶瓷的孔密度进一歩优选为 400 CPSI。
所述贵金属选自 Ag、 Pt、 Ru、 Pd或 Rh中的任意一种或者至少两种的混合 物。所述混合物例如 Pt和 Pd的混合物， Pt和 Rh的混合物， Pd和 Rh的混合物， Pt、 Pd和 Rh的混合物， Ag和 Pt的混合物， Ru、 Ag和 Pt的混合物， Pd、 Ag、 Pt和 Rh的混合物。 The cordierite honeycomb ceramic is preferably a high pore density cordierite honeycomb ceramic, and the "pore density" in the high pore density cordierite honeycomb ceramic support refers to the number of pores per square inch of the cross section. The high pore density means that the number of pores per square inch of the cross section is greater than or equal to 100 CPSI, the cordierite honeycomb ceramic preferably has a pore density of 100 600 CPSI, and the cordierite honeycomb ceramic has a pore density of preferably 400 CPSI. The noble metal is selected from any one of Ag, Pt, Ru, Pd or Rh or a mixture of at least two. The mixture such as a mixture of Pt and Pd, a mixture of Pt and Rh, a mixture of Pd and Rh, a mixture of Pt, Pd and Rh, a mixture of Ag and Pt, a mixture of Ru, Ag and Pt, Pd, Ag, Pt and A mixture of Rh.
所述过渡金属氧化物选自 Cu氧化物、 Cr氧化物、 Fe氧化物、 Co氧化物、 Ni氧化物或 Mn氧化物中的任意一种或者至少两种的混合物。 所述混合物例如 Mn氧化物和 Ni氧化物的混合物， Co氧化物和 Fe氧化物的混合物， Mn氧化物、 Ni氧化物和 Co氧化物的混合物， Cu氧化物、 Co氧化物和 Fe氧化物的混合物。 所述 Fe氧化物有 Fe203， Co氧化物有 Co203， Ni氧化物有 NiO， Mn的氧化物 有 Mn304、 Cu氧化物有 CuO、 Cr氧化物有 Cr203。 The transition metal oxide is selected from any one or a mixture of at least two of Cu oxide, Cr oxide, Fe oxide, Co oxide, Ni oxide or Mn oxide. The mixture is, for example, a mixture of Mn oxide and Ni oxide, a mixture of Co oxide and Fe oxide, a mixture of Mn oxide, Ni oxide and Co oxide, Cu oxide, Co oxide and Fe oxide. mixture. The Fe oxide has Fe 2 O 3 , the Co oxide has Co 2 0 3 , the Ni oxide has NiO, the Mn oxide has Mn 3 0 4 , the Cu oxide has CuO, and the Cr oxide has Cr 2 0 3 .
所述稀土金属氧化物为 La的氧化物或 /和 Ce的氧化物。 La的氧化物例如 La203， Ce的氧化物有 Ce02。 The rare earth metal oxide is an oxide of La or/and an oxide of Ce. The oxide of La such as La 2 O 3 , the oxide of Ce has Ce0 2 .
示例性的贵金属整体式催化剂有： Exemplary precious metal monolithic catalysts are:
载体为堇青石蜂窝陶瓷和贵金属活性组分为负载在 Ce02和 MO上的 Rh组 成的贵金属整体式催化剂； 载体为堇青石蜂窝陶瓷和贵金属活性组分为负载在 L¾03和 Fe203上的 Pt组成的贵金属整体式催化剂；载体为堇青石蜂窝陶瓷和贵 金属活性组分为负载在 Ce02和 Mn304上的 Ag和 Pt组成的贵金属整体式催化剂； 载体为堇青石蜂窝陶瓷和贵金属活性组分为负载在 L¾03和 Co203上的 Ru组成 的贵金属整体式催化剂； 载体为堇青石蜂窝陶瓷和贵金属活性组分为负载在 L¾03和 CuO上的 Pd组成的贵金属整体式催化剂； 载体为堇青石蜂窝陶瓷和贵 金属活性组分为负载在 L¾03和 Fe203上的 Pt和 Pd组成的贵金属整体式催化剂； 载体为堇青石蜂窝陶瓷和贵金属活性组分为负载在 Ce02和 Cr203上的 Pd和 Ag 组成的贵金属整体式催化剂； 载体为堇青石蜂窝陶瓷和贵金属活性组分为负载
在 Ce02和 Mn304上的 Pd组成的贵金属整体式催化剂； 载体为堇青石蜂窝陶瓷 和贵金属活性组分为负载在 La203和 Mn304上的 Pt、 Pd和 Ag组成的贵金属整 体式催化剂。 The carrier is a cordierite honeycomb ceramic and the noble metal active component is a noble metal monolith catalyst composed of Rh supported on Ce0 2 and MO; the carrier is cordierite honeycomb ceramic and the precious metal active component is supported on L3⁄40 3 and Fe 2 0 3 a noble metal monolith catalyst composed of Pt; the support is a cordierite honeycomb ceramic and the noble metal active component is a noble metal monolith catalyst composed of Ag and Pt supported on Ce0 2 and Mn 3 0 4 ; the support is cordierite honeycomb ceramic and precious metal The active component is a noble metal monolithic catalyst composed of Ru supported on L3⁄40 3 and Co 2 0 3 ; the support is a cordierite honeycomb ceramic and the noble metal active component is a noble metal monolith catalyst composed of Pd supported on L3⁄40 3 and CuO The carrier is cordierite honeycomb ceramic and the precious metal active component is a noble metal monolith catalyst composed of Pt and Pd supported on L3⁄40 3 and Fe 2 0 3 ; the carrier is cordierite honeycomb ceramic and the precious metal active component is supported on Ce0 2 And a noble metal monolithic catalyst composed of Pd and Ag on Cr 2 O 3 ; the support is a cordierite honeycomb ceramic and a noble metal active component is a load a noble metal monolith catalyst composed of Pd on Ce0 2 and Mn 3 0 4 ; the support is a cordierite honeycomb ceramic and the noble metal active component is composed of Pt, Pd and Ag supported on La 2 0 3 and Mn 3 0 4 Precious metal monolithic catalyst.
本发明的目的之二在于提供一种如上所述的贵金属整体式催化剂的制备方 法， 所述方法为乳液火焰燃烧沉积方法， 使得贵金属活性组分在生成的瞬间， 在热泳力的作用下沉积在载体上， 显著提高了载体-活性组分之间的结合强度。 A second object of the present invention is to provide a method for preparing a noble metal monolith catalyst as described above, which is an emulsion flame combustion deposition method, wherein a precious metal active component is deposited under the action of thermophoresis at the moment of formation. On the carrier, the bond strength between the carrier-active components is remarkably improved.
为了达到上述目的， 本发明采用了如下技术方案： In order to achieve the above object, the present invention adopts the following technical solutions:
一种贵金属整体式催化剂的制备方法， 为乳液火焰燃烧法， 所述方法包括 如下歩骤： A method for preparing a noble metal monolith catalyst is an emulsion flame combustion method, the method comprising the following steps:
( 1 ) 将过渡金属氧化物的前驱体和稀土金属氧化物的前驱体分散于水中， 形成水相； (1) dispersing a precursor of a transition metal oxide and a precursor of a rare earth metal oxide in water to form an aqueous phase;
(2) 将贵金属的前驱体分散于有机溶剂中， 形成油相； (2) dispersing a precursor of a noble metal in an organic solvent to form an oil phase;
(3 ) 将所述水相逐滴加入所述油相中， 同时加入表面活性剂， 形成油包水 乳液前驱体； (3) adding the aqueous phase dropwise to the oil phase while adding a surfactant to form a water-in-oil emulsion precursor;
(4) 将所述油包水乳液前驱体供给到火焰燃烧装置中， 经点火， 雾化后， 燃烧， 然后冷却， 凝聚， 得到贵金属活性组分； (4) supplying the water-in-oil emulsion precursor to a flame burning device, igniting, atomizing, burning, then cooling, and agglomerating to obtain a precious metal active component;
(5) 在火焰燃烧装置中的火焰区域， 贵金属活性组分在热泳力的作用下， 沉积到置于火焰燃烧装置的雾化喷嘴上方的堇青石蜂窝陶瓷载体上， 得到贵金 属整体式催化剂。 (5) In the flame region of the flame combustion apparatus, the noble metal active component is deposited by a thermophoretic force on a cordierite honeycomb ceramic support placed above the atomizing nozzle of the flame combustion apparatus to obtain a noble metal monolith catalyst.
图 1 为本发明中制备贵金属整体式催化剂的示意图。 将油包水乳液前驱体 通过泵供给到火焰燃烧装置中后， 点火， 乳液被雾化氧气雾化成喷雾液滴， 雾 化喷嘴出口处环绕由助燃氧气和助燃甲垸构成的助燃火焰， 喷雾液滴中的油相 和水相燃烧生成贵金属活性组分。 大量燃烧热使喷雾液滴中所包覆的水相溶剂
挥发， 过渡金属氧化物前驱体和稀土金属氧化物前驱体热解为相应金属氧化物， 贵金属前驱体燃烧生成贵金属颗粒。 在高温火焰区域， 贵金属颗粒通过均相成 核或者异相成核作用负载在过渡金属氧化物和稀土金属氧化物上， 得到贵金属 活性成分。 贵金属活性成分在热泳力的作用下， 直接沉积在火焰上方的堇青石 蜂窝陶瓷载体上， 得到贵金属整体式催化剂。 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view showing the preparation of a noble metal monolith catalyst in the present invention. After the water-in-oil emulsion precursor is supplied to the flame combustion device through a pump, the emulsion is atomized by atomization of oxygen into a spray droplet, and the atomizing nozzle outlet surrounds a combustion-supporting flame composed of combustion-supporting oxygen and combustion-supporting formazan, the spray liquid The oil phase and the aqueous phase in the drop burn to form a precious metal active component. A large amount of combustion heat causes the aqueous phase solvent coated in the spray droplets The volatile, transition metal oxide precursor and rare earth metal oxide precursor are pyrolyzed into corresponding metal oxides, and the noble metal precursor is burned to form noble metal particles. In the high temperature flame region, the noble metal particles are supported on the transition metal oxide and the rare earth metal oxide by homogeneous nucleation or heterogeneous nucleation to obtain a noble metal active component. The noble metal active component is directly deposited on the cordierite honeycomb ceramic support above the flame under the action of thermophoresis to obtain a noble metal monolith catalyst.
所述过渡金属氧化物的前驱体选自 Fe(N03)3、 Cr2(S04)3 Cr(N03)3 , Cu(C¾COO)2、 Cu(N03)2、 Mn(N03)2、 Mn(C¾COO)2、 Co(N03)2、 Co(C¾COO)2、 Ni NO^或 Ni C¾COO;)2中的任意一种或者至少两种的混合物。 所述混合物例 如 Ni(C¾COO)2和 Cr(N03)3的混合物， Co(CH3COO)2和 Mn(N03)2的混合物， Mn(C¾COO)2和 Cu(N03)2的混合物， Fe(N03)3、 Ni(C¾COO)2和 Cu(N03)2的混 合物， Co(CH3COO)2、 Cr(N03)2、 Mn(C¾COO)2和 Fe(N03)3的混合物。 The precursor of the transition metal oxide is selected from the group consisting of Fe(N0 3 ) 3 , Cr 2 (S0 4 ) 3 Cr(N0 3 ) 3 , Cu(C 3⁄4COO) 2 , Cu(N0 3 ) 2 , Mn(N0 3 ) 2. Any one or a mixture of at least two of Mn(C3⁄4COO) 2 , Co(N0 3 ) 2 , Co(C3⁄4COO) 2 , Ni NO^ or Ni C3⁄4COO;) 2 . The mixture is, for example, a mixture of Ni(C3⁄4COO) 2 and Cr(N0 3 ) 3 , a mixture of Co(CH 3 COO) 2 and Mn(N0 3 ) 2 , a mixture of Mn(C 3⁄4COO) 2 and Cu(N0 3 ) 2 , a mixture of Fe(N0 3 ) 3 , Ni(C 3⁄4COO) 2 and Cu(N0 3 ) 2 , Co(CH 3 COO) 2 , Cr(N0 3 ) 2 , Mn(C 3⁄4COO) 2 and Fe(N0 3 ) 3 mixture.
所述稀土金属氧化物的前驱体选自 La(N03)3、 La(CH3COO)3, Ce(CH3COO)3 或 Ce(N03;>3 中的任意一种或者至少两种的混合物。 所述混合物例如 La(CH3COO)3和 Ce(CH3COO)3的混合物， La(N03)3和 Ce(N03)3的混合物， La(N03)3和 Ce(C¾COO)3的混合物， La(N03)3、 La(C¾COO)3和 Ce(C¾COO)3 的混合物。 The precursor of the rare earth metal oxide is selected from La(N0 3 ) 3 , La(CH 3 COO) 3 , Ce(CH 3 COO) 3 or Ce (N0 3 ; > 3 or at least two a mixture of La(CH 3 COO) 3 and Ce(CH 3 COO) 3 , a mixture of La(N0 3 ) 3 and Ce(N0 3 ) 3 , La(N0 3 ) 3 and Ce ( a mixture of C3⁄4COO) 3, a mixture of La(N0 3 ) 3 , La(C3⁄4COO) 3 and Ce(C3⁄4COO) 3 .
所述贵金属的前驱体选自 Ag(acac)、 Pd(acac)2、 Pt(acac)2、 Rh(acac)3或 Ru(acac)3中的任意一种或者至少两种的混合物。 所述混合物例如 Pd acac^和 Pt(acac)2的混合物， Rh(acac)3和 Ag(acac)的混合物， Pd(acac)2、 Pt(acac)2和 Rh(acac)3的混合物， Ag(acac)、 Rh(acac)3或 Ru(acac)3的混合物。 The precursor of the noble metal is selected from any one of Ag(acac), Pd(acac) 2 , Pt(acac) 2 , Rh(acac) 3 or Ru(acac) 3 or a mixture of at least two. The mixture is, for example, a mixture of Pd acac^ and Pt(acac) 2, a mixture of Rh(acac) 3 and Ag(acac), a mixture of Pd(acac) 2 , Pt(acac) 2 and Rh(acac) 3 , Ag A mixture of (acac), Rh(acac) 3 or Ru(acac) 3 .
所述油相和水相的体积比为 10:1~3:1，例如 8:1、 7:1、 6:1、 5:1、 5.5:1、 6.5:1、 8.5:1、 9.5:1， 优选 9:1~4:1。 The volume ratio of the oil phase to the aqueous phase is 10:1 to 3:1, for example 8:1, 7:1, 6:1, 5:1, 5.5:1, 6.5:1, 8.5:1, 9.5: 1, preferably 9:1~4:1.
所述有机溶剂为己垸、 庚垸、 辛垸、 环戊垸、 环己垸、 苯、 甲苯、 二甲苯、
汽油、 柴油、 煤油中的一种或者至少两种的混合物， 所述混合物例如己垸和庚 垸的混合物， 辛垸和环戊垸的混合物， 环己垸和苯的混合物， 甲苯和二甲苯的 混合物， 汽油和柴油的混合物， 柴油和煤油的混合物。 The organic solvent is hexanyl, ruthenium, octyl, cyclopentanyl, cyclohexanthene, benzene, toluene, xylene, a mixture of gasoline, diesel, kerosene or a mixture of at least two, such as a mixture of hexanthene and hydrazine, a mixture of octyl and cyclopentanyl, a mixture of cyclohexane and benzene, toluene and xylene Mixture, a mixture of gasoline and diesel, a mixture of diesel and kerosene.
所述表面活性剂选自垸基三甲基氯化铵、 十二垸基三甲基氯化铵、 十二垸 基二甲基苄基氯化铵、 十四垸基二甲基苄基氯化铵、 十八垸基二甲基苄基氯化 铵、 十二垸基二甲基氧化胺、 月桂酰胺丙基氧化胺、 椰油酰胺丙基氧化胺、 椰 油酸单乙醇酰胺、 椰油酸二乙醇酰胺、 二 (氢化牛脂基)邻苯二甲酸酰胺、 脂肪醇 聚氧乙烯醚、 甲基葡萄糖苷聚氧乙烯醚、 蓖麻油聚氧乙烯醚、 乙二醇单 (双：)硬脂 酸酯、 单 (双：)硬脂酸甘油酯、 壬基酚聚氧乙烯醚、 辛基酚聚氧乙烯醚、 十二垸基 聚氧乙烯醚、 二壬基酚聚氧乙烯醚、 聚氧乙烯 -8-辛基苯基醚、 失水山梨醇单月 桂酸酯聚氧乙烯醚、 失水山梨醇单棕榈酸酯聚氧乙烯醚、 失水山梨醇单硬脂酸 酯聚氧乙烯醚、 失水山梨醇三硬脂酸酯聚氧乙烯醚、 失水山梨醇单油酸酯聚氧 乙烯醚、 失水山梨醇三油酸酯聚氧乙烯醚、 失水山梨醇单月桂酸酸酯、 失水山 梨醇单棕榈酸酯、 失水山梨醇单硬脂酸酯、 失水山梨醇三硬脂酸酯、 失水山梨 醇单油酸酯、 失水山梨醇三油酸酯中的任意一种或者至少两种的混合物。 The surfactant is selected from the group consisting of mercaptotrimethylammonium chloride, dodecyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride, tetradecyldimethylbenzyl chloride Ammonium, octadecyl dimethyl benzyl ammonium chloride, dodecyl dimethyl amine oxide, lauryl propyl propyl amine oxide, cocamidopropyl amine oxide, coco monoethanolamide, coconut oil Acid diethanolamide, di(hydrogenated tallow) phthalic acid amide, fatty alcohol polyoxyethylene ether, methyl glucoside polyoxyethylene ether, castor oil polyoxyethylene ether, ethylene glycol mono (double:) hard fat Acid ester, mono (double:) glyceryl stearate, nonylphenol ethoxylate, octylphenol ethoxylate, dodecyl polyoxyethylene ether, dinonyl phenolic polyoxyethylene ether, polyoxygen Ethylene-8-octylphenyl ether, sorbitan monolaurate polyoxyethylene ether, sorbitan monopalmitate polyoxyethylene ether, sorbitan monostearate polyoxyethylene ether, Sorbitan tristearate polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, sorbitan trioleate Polyoxyethylene ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monohydrate Any one or a mixture of at least two of an acid ester, sorbitan trioleate.
火焰燃烧装置中， 油包水乳液前驱体的供给流速为 l~20ml/mm， 例如 1.5ml/min、4ml/min、7ml/min、 10ml/min、 12ml/min、 14ml/min、 16ml/min、 17ml/min、 19ml/min， 优选 2~18ml/min， 进一歩优选 3~15ml/min。 流速低， 反应效率低， 导致效率太低， 流速太高， 乳液来不及被完全雾化就进入火焰区域， 使在火焰 区域的反应不能完全， 影响最终得到的催化剂的活性。 In the flame combustion apparatus, the water supply temperature of the water-in-oil emulsion precursor is 1 to 20 ml/mm, for example, 1.5 ml/min, 4 ml/min, 7 ml/min, 10 ml/min, 12 ml/min, 14 ml/min, and 16 ml/min. 17 ml/min, 19 ml/min, preferably 2 to 18 ml/min, further preferably 3 to 15 ml/min. The flow rate is low, the reaction efficiency is low, the efficiency is too low, the flow rate is too high, and the emulsion is not completely atomized to enter the flame region, so that the reaction in the flame region is incomplete and affects the activity of the finally obtained catalyst.
在 400~1200°C的火焰区域内， 贵金属活性组分在热泳力的作用下， 沉积到 堇青石蜂窝陶瓷载体上。 在火焰区域中， 存在不同温度的区域， 贵金属活性组 分的沉积在高温火焰区域内， 即 400~1200°C的火焰区域内沉积。
所述沉积时间为 180~900s，例如 240s、 360s、 480s、 540s、 600s、 720s、 840s 在反应过程中， 不断地有喷雾液滴进入火焰区域， 发生反应， 生成贵金属活性 组分， 并沉积在载体上。 超过上述沉积时间， 即可拿掉置于火焰燃烧装置喷嘴 上方的载体， 收集得到贵金属整体式催化剂。 In the flame region of 400 to 1200 ° C, the precious metal active component is deposited on the cordierite honeycomb ceramic carrier under the action of thermophoresis. In the flame region, there are regions of different temperatures, and the deposition of precious metal active components is deposited in the high temperature flame region, i.e., in the flame region of 400 to 1200 °C. The deposition time is 180-900 s, for example, 240s, 360s, 480s, 540s, 600s, 720s, 840s. During the reaction, spray droplets continuously enter the flame region, react, generate precious metal active components, and deposit in On the carrier. Above the deposition time, the carrier placed above the nozzle of the flame burner can be removed and the precious metal monolith catalyst can be collected.
所述堇青石蜂窝陶瓷载体置于火焰燃烧装置的雾化喷嘴上方的 10~20cm 处， 优选置于火焰燃烧装置的雾化喷嘴上方的 15cm处。 The cordierite honeycomb ceramic carrier is placed 10 to 20 cm above the atomizing nozzle of the flame burning apparatus, preferably 15 cm above the atomizing nozzle of the flame burning apparatus.
本发明的目的之三在于提供一种如上所述的贵金属整体式催化剂的用途， 所述贵金属整体式催化剂用于挥发性有机物气体 （VOCs) 的催化燃烧过程。 通 过 VOCs质谱完成 （SPIMS-1000) 对反应物与产物的分析， 在实验条件下， 催 化剂模块体积为 lcm X lcm X 5cm， 气体流速为 100ml/min， 测试温度范围为 100~300°C , VOCs浓度为 100~1000ppm。采用本发明所述贵金属整体式催化剂， 可以将体系中大部分或者全部 VOCs转化为二氧化碳和水。 A third object of the present invention is to provide the use of a noble metal monolith catalyst as described above for the catalytic combustion of volatile organic compounds (VOCs). The VOCs mass spectrometry (SPIMS-1000) analysis of the reactants and products, under the experimental conditions, the catalyst module volume is lcm X lcm X 5cm, the gas flow rate is 100ml / min, the test temperature range is 100 ~ 300 ° C, VOCs The concentration is 100~1000ppm. Most or all of the VOCs in the system can be converted to carbon dioxide and water using the noble metal monolith catalyst of the present invention.
本发明所述火焰燃烧装置为已有的技术， 所属领域的技术人员根据图 1 以 及现有技术中所公开的火焰燃烧装置， 完全有能力得到本发明所述火焰燃烧装 置。 本发明中火焰喷雾燃烧系统， 也称火焰燃烧装置。 The flame combustion apparatus of the present invention is of the prior art, and those skilled in the art are fully capable of obtaining the flame combustion apparatus of the present invention in accordance with the flame combustion apparatus disclosed in Fig. 1 and in the prior art. The flame spray combustion system of the present invention is also referred to as a flame combustion apparatus.
本发明用以乳液为前驱体的火焰燃烧法直接将高温火焰中生成的活性组分 沉积在堇青石蜂窝陶瓷载体上， 与现有技术相比， 具有以下优点： The flame combustion method for emulsion as a precursor directly deposits the active component formed in the high temperature flame on the cordierite honeycomb ceramic carrier, and has the following advantages compared with the prior art:
( 1 ) 本发明摒弃传统液相方法涂覆制备催化剂涂层及活性组分， 直接将活 性组分采用火焰燃烧沉积的方式沉积在载体上， 实现活性组分制备、 沉积过程 单歩完成， 大大简化了催化剂制备工艺与周期； (1) The invention discards the traditional liquid phase method for coating and preparing the catalyst coating and the active component, and directly deposits the active component on the carrier by means of flame combustion deposition, thereby realizing the preparation of the active component and the deposition process, which is greatly completed. Simplified catalyst preparation process and cycle;
(2) 本发明采用火焰燃烧沉积的方法， 使得活性组分在生成的瞬间， 在热 泳力的作用下沉积在载体上， 载体-活性组分之间的结合强度大大提升， 所制备 的贵金属整体式催化剂具有良好的反应性及稳定性， 贵金属整体式催化剂的活
性组分分布均匀， 负载量可控， 并且克服了堇青石蜂窝陶瓷载体与活性组分结 合强度低、 溶液浸渍法制备整体式催化剂存在的掉粉及堇青石蜂窝陶瓷载体通 道被活性组分阻塞的问题， 有利于传质传热以及动量传递。 (2) The present invention adopts a method of flame combustion deposition, so that the active component is deposited on the carrier under the action of thermophoresis at the moment of formation, and the bonding strength between the carrier-active component is greatly improved, and the prepared precious metal as a whole is prepared. Catalyst has good reactivity and stability, and the precious metal monolith catalyst The composition of the components is uniform, the load is controllable, and the binding strength of the cordierite honeycomb ceramic carrier and the active component is low, the powder of the monolithic catalyst prepared by the solution impregnation method and the cordierite honeycomb ceramic carrier channel are blocked by the active component. The problem is conducive to mass transfer heat transfer and momentum transfer.
附图说明 DRAWINGS
下面结合附图并通过具体实施方式来进一歩说明本发明的技术方案。 The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments.
图 1为本发明中制备贵金属整体式催化剂的流程示意图； 1 is a schematic flow chart of preparing a noble metal monolith catalyst in the present invention;
图 2 为本发明中采用火焰燃烧法所制备得到的贵金属整体式催化剂中载体 与沉积层界面微结构， 所述堇青石载体即堇青石蜂窝陶瓷载体， 所述沉积层即 贵金属活性组分； 2 is a microstructure of a carrier and a deposition layer in a noble metal monolith catalyst prepared by a flame combustion method according to the present invention, wherein the cordierite carrier is a cordierite honeycomb ceramic carrier, and the deposited layer is a noble metal active component;
图 3 为本发明中不同油包水乳液前驱体供给流速下制备的贵金属整体式催 化剂对苯催化燃烧的温度与转化率关系图； Fig. 3 is a graph showing the relationship between the temperature and the conversion rate of the catalytic combustion of the noble metal monolith catalyst prepared by the different water-in-oil emulsion precursor flow rates in the present invention;
图 4 为本发明中不同沉积时间下制备的整体式催化剂对苯催化燃烧的温度 与转化率关系图； Figure 4 is a graph showing the relationship between temperature and conversion rate of benzene catalytic combustion of monolithic catalyst prepared at different deposition times in the present invention;
说明书附图中的附图标记如下所述： The reference numerals in the drawings of the specification are as follows:
1-油包水乳液前驱体； 2-雾化氧气； 3-助燃甲垸； 4-助燃氧气； 5-助燃火焰； 6-火焰区域； 7-堇青石蜂窝陶瓷载体。 1-water-in-oil emulsion precursor; 2-atomized oxygen; 3-combustible formazan; 4-combustible oxygen; 5-combustion flame; 6-flame region; 7- cordierite honeycomb ceramic carrier.
具体实施方式 detailed description
为更好地说明本发明， 便于理解本发明的技术方案， 本发明的典型但非限 制性的实施例如下： In order to better explain the present invention, it is convenient to understand the technical solution of the present invention, and a typical but non-limiting embodiment of the present invention is as follows:
实施例 1 Example 1
将贵金属的前驱体溶于二甲苯， 稀土金属氧化物和过渡金属氧化物的前驱 体溶于水， 两者在表面活性剂的存在下按一定比例混合形成油包水乳液前驱体。
乳液前驱体供给流速为 1.875ml/min， 雾化氧气流量为 4.0L/min， 助燃甲垸及助 燃氧气流量分别为 2.4L/mm及 4.0L/mm。堇青石蜂窝陶瓷置于喷嘴上方 15cm处， 沉积时间为 360s， 得到堇青石整体式催化剂， 进行苯催化燃烧测试， 结果如图 3 所示。 The precursor of the noble metal is dissolved in xylene, and the precursor of the rare earth metal oxide and the transition metal oxide is dissolved in water, and the two are mixed in a certain ratio in the presence of a surfactant to form a water-in-oil emulsion precursor. The emulsion precursor supply flow rate was 1.875 ml/min, the atomized oxygen flow rate was 4.0 L/min, and the combustion-supporting formazan and combustion-supporting oxygen flow rates were 2.4 L/mm and 4.0 L/mm, respectively. The cordierite honeycomb ceramic was placed 15 cm above the nozzle and the deposition time was 360 s. The cordierite monolithic catalyst was obtained and the benzene catalytic combustion test was carried out. The results are shown in Fig. 3.
实施例 2 Example 2
将实施例 1 中制备的油包水乳液前驱体供给到火焰喷雾燃烧系统， 其中油 包水乳液前驱体供给流速为 5.535ml/min， 雾化氧气流量为 4.0L/min， 助燃甲垸 及助燃氧气流量分别为 2.4L/mm及 4.0L/mm。 堇青石蜂窝陶瓷置于喷嘴上方 15cm处， 沉积时间为 360s， 得到堇青石整体式催化剂， 进行苯催化燃烧测试， 结果如图 3所示。 The water-in-oil emulsion precursor prepared in Example 1 was supplied to a flame spray combustion system, wherein the water-in-oil emulsion precursor supply flow rate was 5.535 ml/min, the atomized oxygen flow rate was 4.0 L/min, combustion-supporting formazan and combustion-supporting The oxygen flow rates were 2.4 L/mm and 4.0 L/mm, respectively. The cordierite honeycomb ceramic was placed 15 cm above the nozzle and the deposition time was 360 s. The cordierite monolithic catalyst was obtained and the benzene catalytic combustion test was carried out. The results are shown in Fig. 3.
实施例 3 Example 3
将实施例 1 中制备的油包水乳液前驱体供给到火焰喷雾燃烧系统， 其中油 包水乳液前驱体供给流速为 9.225ml/min， 雾化氧气流量为 4.0L/min， 助燃甲垸 及助燃氧气流量分别为 2.4L/mm及 4.0L/mm。 堇青石蜂窝陶瓷置于喷嘴上方 15cm处， 沉积时间为 360s， 得到堇青石整体式催化剂， 进行苯催化燃烧测试， 结果如图 3所示。 The water-in-oil emulsion precursor prepared in Example 1 was supplied to a flame spray combustion system, wherein the water-in-oil emulsion precursor supply flow rate was 9.225 ml/min, the atomized oxygen flow rate was 4.0 L/min, combustion-supporting formazan and combustion-supporting The oxygen flow rates were 2.4 L/mm and 4.0 L/mm, respectively. The cordierite honeycomb ceramic was placed 15 cm above the nozzle and the deposition time was 360 s. The cordierite monolithic catalyst was obtained and the benzene catalytic combustion test was carried out. The results are shown in Fig. 3.
实施例 4 Example 4
将实施例 1 中制备的油包水乳液前驱体供给到火焰喷雾燃烧系统， 其中油 包水乳液前驱体供给流速为 5.535ml/min， 雾化氧气流量为 4.0L/min， 助燃甲垸 及助燃氧气流量分别为 2.4L/mm及 4.0L/mm。 堇青石蜂窝陶瓷置于喷嘴上方 15cm处， 沉积时间为 180s， 得到堇青石整体式催化剂， 进行苯催化燃烧测试， 结果如图 4所示。 The water-in-oil emulsion precursor prepared in Example 1 was supplied to a flame spray combustion system, wherein the water-in-oil emulsion precursor supply flow rate was 5.535 ml/min, the atomized oxygen flow rate was 4.0 L/min, combustion-supporting formazan and combustion-supporting The oxygen flow rates were 2.4 L/mm and 4.0 L/mm, respectively. The cordierite honeycomb ceramic was placed 15 cm above the nozzle and the deposition time was 180 s. The cordierite monolithic catalyst was obtained and the benzene catalytic combustion test was carried out. The results are shown in Fig. 4.
实施例 5
将实施例 1 中制备的油包水乳液前驱体供给到火焰喷雾燃烧系统， 其中油 包水乳液前驱体供给流速为 5.535ml/min， 雾化氧气流量为 4.0L/min， 助燃甲垸 及助燃氧气流量分别为 2.4L/mm及 4.0L/mm。 堇青石蜂窝陶瓷置于喷嘴上方 15cm处， 沉积时间为 600s， 得到堇青石整体式催化剂， 进行苯催化燃烧测试， 结果如图 4所示。 Example 5 The water-in-oil emulsion precursor prepared in Example 1 was supplied to a flame spray combustion system, wherein the water-in-oil emulsion precursor supply flow rate was 5.535 ml/min, the atomized oxygen flow rate was 4.0 L/min, combustion-supporting formazan and combustion-supporting The oxygen flow rates were 2.4 L/mm and 4.0 L/mm, respectively. The cordierite honeycomb ceramic was placed 15 cm above the nozzle and the deposition time was 600 s. The cordierite monolithic catalyst was obtained and the benzene catalytic combustion test was carried out. The results are shown in Fig. 4.
实施例 6 Example 6
将实施例 1 中制备的油包水乳液前驱体供给到火焰喷雾燃烧系统， 其中油 包水乳液前驱体供给流速为 5.535ml/min， 雾化氧气流量为 4.0L/min， 助燃甲垸 及助燃氧气流量分别为 2.4L/mm及 4.0L/mm。 堇青石蜂窝陶瓷置于喷嘴上方 15cm处， 沉积时间为 900s， 得到堇青石整体式催化剂， 进行苯催化燃烧测试， 结果如图 4所示。 The water-in-oil emulsion precursor prepared in Example 1 was supplied to a flame spray combustion system, wherein the water-in-oil emulsion precursor supply flow rate was 5.535 ml/min, the atomized oxygen flow rate was 4.0 L/min, combustion-supporting formazan and combustion-supporting The oxygen flow rates were 2.4 L/mm and 4.0 L/mm, respectively. The cordierite honeycomb ceramic was placed 15 cm above the nozzle and the deposition time was 900 s. The cordierite monolithic catalyst was obtained and the benzene catalytic combustion test was carried out. The results are shown in Fig. 4.
实施例 7 Example 7
( 1 ) 将过渡金属氧化物的前驱体 Fe(N03;)3和稀土金属氧化物的前驱体 La(N03)3分散于水中， 形成水相； (1) dispersing a precursor of the transition metal oxide, Fe(N0 3 ;) 3 and a precursor of the rare earth metal oxide, La(N0 3 ) 3 , in water to form an aqueous phase;
(2) 将贵金属的前驱体 Pd acac^分散于二甲苯中， 形成油相； (2) dispersing the precursor of the noble metal Pd acac^ in xylene to form an oil phase;
(3 )将水相逐滴加入油相中， 并加入表面活性剂十二垸基二甲基苄基氯化 铵， 形成油包水乳液前驱体， 其中， 油相与水相的体积比为 5:1。 (3) adding the aqueous phase dropwise to the oil phase, and adding the surfactant, dodecyldimethylbenzylammonium chloride, to form a water-in-oil emulsion precursor, wherein the volume ratio of the oil phase to the aqueous phase is 5:1.
(4)将油包水乳液前驱体供给到火焰燃烧装置中， 经点火， 雾化后， 燃烧， 然后冷却， 凝聚， 得到贵金属活性组分， 其中， 油包水乳液前驱体的供给流速 为 lml/min， 雾化氧气的流量为 4.0L/min， 助燃甲垸和助燃氧气流量分别为 2.4L/min禾口 4.0L/min; (4) The water-in-oil emulsion precursor is supplied to the flame burning device, after ignition, atomization, combustion, and then cooled and agglomerated to obtain a precious metal active component, wherein the water-in-oil emulsion precursor is supplied at a flow rate of 1 ml. /min, the flow rate of atomized oxygen is 4.0L/min, the flow rate of combustion-supporting formazan and combustion-supporting oxygen is 2.4L/min and 4.0L/min respectively ;
( 5 )在 400~1200°C的火焰区域， 贵金属活性组分在热泳力的作用下， 沉积 到置于火焰燃烧装置的雾化喷嘴上方 10cm的堇青石蜂窝陶瓷载体上，沉积时间
为 180s， 得到贵金属整体式催化剂。 (5) In the flame region of 400~1200 °C, the precious metal active component is deposited by the thermophoretic force on a 10 cm cordierite honeycomb ceramic carrier placed above the atomizing nozzle of the flame burning device, deposition time For 180 s, a precious metal monolith catalyst was obtained.
所述贵金属整体式催化剂由堇青石蜂窝陶瓷载体和贵金属活性组分组成， 贵金属活性组分为：负载在 Fe203和 L¾03上的 Pd。所述贵金属活性组分占贵金 属整体式催化剂总质量的 0.1%。 The noble metal catalyst is a monolithic cordierite honeycomb carrier and a noble metal active component composition, the active component is a noble metal: Fe 2 0 Pd supported on 3 and L¾0 3. The precious metal active component comprises 0.1% of the total mass of the precious metal monolith catalyst.
实施例 8 Example 8
( 1 ) 将过渡金属氧化物的前驱体 Mn NO^和稀土金属氧化物的前驱体 Ce(CH3COO)3分散于水中， 形成水相； (1) dispersing a precursor of a transition metal oxide, Mn NO^, and a precursor of a rare earth metal oxide, Ce(CH 3 COO) 3 , in water to form an aqueous phase;
(2) 将贵金属的前驱体 Rh acac 分散于二甲苯中， 形成油相； (2) dispersing a precursor of the noble metal Rh acac in xylene to form an oil phase;
(3 ) 将水相逐滴加入油相中， 并加入表面活性剂脂肪醇聚氧乙烯醚， 形成 油包水乳液前驱体， 其中， 油相与水相的体积比为 7:1。 (3) The aqueous phase is added dropwise to the oil phase, and a surfactant fatty alcohol polyoxyethylene ether is added to form a water-in-oil emulsion precursor, wherein the volume ratio of the oil phase to the aqueous phase is 7:1.
(4)将油包水乳液前驱体供给到火焰燃烧装置中， 经点火， 雾化后， 燃烧， 然后冷却， 凝聚， 得到贵金属活性组分， 其中， 油包水乳液前驱体的供给流速 为 15ml/min， 雾化氧气的流量为 4.0L/min， 助燃甲垸和助燃氧气流量分别为 2.4L/min禾口 4.0L/min; (4) The water-in-oil emulsion precursor is supplied to the flame burning device, after ignition, atomization, combustion, and then cooled and agglomerated to obtain a precious metal active component, wherein the water-in-oil emulsion precursor is supplied at a flow rate of 15 ml. /min, the flow rate of atomized oxygen is 4.0L/min, the flow rate of combustion-supporting formazan and combustion-supporting oxygen is 2.4L/min and 4.0L/min respectively ;
(5)在 400~1200°C的火焰区域， 贵金属活性组分在热泳力的作用下， 沉积 到置于火焰燃烧装置的雾化喷嘴上方 15cm的堇青石蜂窝陶瓷载体上，沉积时间 为 500s， 得到贵金属整体式催化剂。 (5) In the flame region of 400~1200 °C, the precious metal active component is deposited by a thermophoretic force on a 15 cm cordierite honeycomb ceramic carrier placed above the atomizing nozzle of the flame burning device, and the deposition time is 500 s. A noble metal monolith catalyst is obtained.
所述贵金属整体式催化剂由堇青石蜂窝陶瓷载体和贵金属活性组分组成， 贵金属活性组分为： 负载在 Mn304和 Ce02上的 Rh组成。 所述贵金属活性组分 占贵金属整体式催化剂总质量的 5%。 The noble metal monolith catalyst comprises a cordierite honeycomb ceramic support and a noble metal active component, and the noble metal active component is: Rh composition supported on Mn 3 0 4 and Ce0 2 . The precious metal active component comprises 5% of the total mass of the precious metal monolith catalyst.
实施例 9 Example 9
( 1 )将过渡金属氧化物的前驱体 Co(N03;>2、 Ni NO^和稀土金属氧化物的 前驱体 Ce(C¾COO)3分散于水中， 形成水相；
(2) 将贵金属的前驱体 Pt acac 分散于二甲苯中， 形成油相； (1) dispersing a precursor of a transition metal oxide, Co(N0 3 ;> 2 , Ni NO^, and a precursor of a rare earth metal oxide, Ce(C3⁄4COO) 3, in water to form an aqueous phase; (2) dispersing the precursor of the noble metal Pt acac in xylene to form an oil phase;
(3 ) 将水相逐滴加入油相中， 并加入表面活性剂失水山梨醇单油酸酯， 形 成油包水乳液前驱体， 其中， 油相与水相的体积比为 10:1。 (3) The aqueous phase is added dropwise to the oil phase, and the surfactant sorbitan monooleate is added to form a water-in-oil emulsion precursor, wherein the volume ratio of the oil phase to the aqueous phase is 10:1.
(4)将油包水乳液前驱体供给到火焰燃烧装置中， 经点火， 雾化后， 燃烧， 然后冷却， 凝聚， 得到贵金属活性组分， 其中， 油包水乳液前驱体的供给流速 为 20ml/min， 雾化氧气的流量为 4.0L/min， 助燃甲垸和助燃氧气流量分别为 2.4L/min禾口 4.0L/min; (4) The water-in-oil emulsion precursor is supplied to the flame burning device, after ignition, atomization, combustion, and then cooled and agglomerated to obtain a precious metal active component, wherein the water-in-oil emulsion precursor is supplied at a flow rate of 20 ml. /min, the flow rate of atomized oxygen is 4.0L/min, the flow rate of combustion-supporting formazan and combustion-supporting oxygen is 2.4L/min and 4.0L/min respectively ;
( 5 )在 400~1200°C的火焰区域， 贵金属活性组分在热泳力的作用下， 沉积 到置于火焰燃烧装置的雾喷嘴上方 20cm的堇青石蜂窝陶瓷载体上，沉积时间为 900s, 得到贵金属整体式催化剂。 (5) In the flame region of 400~1200 °C, the precious metal active component is deposited by a thermophoretic force on a 20 cm cordierite honeycomb ceramic carrier placed above the mist nozzle of the flame burning device, and the deposition time is 900 s. Precious metal monolithic catalyst.
所述贵金属整体式催化剂由堇青石蜂窝陶瓷载体和贵金属活性组分组成， 贵金属活性组分为： 负载在 Co203、 ΝιΟ和 Ce02上的 Pt。 所述贵金属活性组分 占贵金属整体式催化剂总质量的 10%。 The noble metal monolith catalyst consists of a cordierite honeycomb ceramic support and a noble metal active component, and the noble metal active component is: Pt supported on Co 2 0 3 , ΝιΟ and Ce0 2 . The precious metal active component comprises 10% of the total mass of the precious metal monolith catalyst.
实施例 10 Example 10
( 1 ) 将过渡金属氧化物的前驱体 Mn NO^和稀土金属氧化物的前驱体 Ce(CH3COO)3分散于水中， 形成水相； (1) dispersing a precursor of a transition metal oxide, Mn NO^, and a precursor of a rare earth metal oxide, Ce(CH 3 COO) 3 , in water to form an aqueous phase;
(2) 将贵金属的前驱体 Rh acac 分散于二甲苯中， 形成油相； (2) dispersing a precursor of the noble metal Rh acac in xylene to form an oil phase;
(3 ) 将水相逐滴加入油相中， 并加入表面活性剂脂肪醇聚氧乙烯醚， 形成 油包水乳液前驱体， 其中， 油相与水相的体积比为 3: 1。 (3) The aqueous phase is added dropwise to the oil phase, and a surfactant fatty alcohol polyoxyethylene ether is added to form a water-in-oil emulsion precursor, wherein the volume ratio of the oil phase to the aqueous phase is 3:1.
(4)将油包水乳液前驱体供给到火焰燃烧装置中， 经点火， 雾化后， 燃烧， 然后冷却， 凝聚， 得到贵金属活性组分， 其中， 油包水乳液前驱体的供给流速 为 15ml/min， 雾化氧气的流量为 4.0L/min， 助燃甲垸和助燃氧气流量分别为 2.4L/min禾口 4.0L/min;
( 5 )在 400~1200°C的火焰区域， 贵金属活性组分在热泳力的作用下， 沉积 到置于火焰燃烧装置的雾化喷嘴上方 15cm的堇青石蜂窝陶瓷载体上，沉积时间 为 500s， 得到贵金属整体式催化剂。 (4) The water-in-oil emulsion precursor is supplied to the flame burning device, after ignition, atomization, combustion, and then cooled and agglomerated to obtain a precious metal active component, wherein the water-in-oil emulsion precursor is supplied at a flow rate of 15 ml. /min, the flow rate of atomized oxygen is 4.0L/min, the flow rate of combustion-supporting formazan and combustion-supporting oxygen is 2.4L/min and 4.0L/min respectively ; (5) In the flame region of 400~1200 °C, the precious metal active component is deposited by a thermophoretic force on a 15 cm cordierite honeycomb ceramic carrier placed above the atomizing nozzle of the flame burning device, and the deposition time is 500 s. A noble metal monolith catalyst is obtained.
所述贵金属整体式催化剂由堇青石蜂窝陶瓷载体和贵金属活性组分组成， 贵金属活性组分为： 负载在 Mn304和 Ce02上的 Rh组成。 所述贵金属活性组分 占贵金属整体式催化剂总质量的 0.01%。 The noble metal monolith catalyst comprises a cordierite honeycomb ceramic support and a noble metal active component, and the noble metal active component is: Rh composition supported on Mn 3 0 4 and Ce0 2 . The precious metal active component comprises 0.01% of the total mass of the precious metal monolith catalyst.
申请人声明， 本发明通过上述实施例来说明本发明的详细方法， 但本发明 并不局限于上述详细方法， 即不意味着本发明必须依赖上述详细方法才能实施。 所属技术领域的技术人员应该明了， 对本发明的任何改进， 对本发明产品各原 料的等效替换及辅助成分的添加、 具体方式的选择等， 均落在本发明的保护范 围和公开范围之内。
The Applicant claims that the present invention is described by the above-described embodiments, but the present invention is not limited to the above detailed methods, that is, it does not mean that the present invention must be implemented by the above detailed methods. It will be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the product of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.
Claims
1、 一种贵金属整体式催化剂， 其特征在于， 所述贵金属整体式催化剂由载 体和贵金属活性组分组成， 所述载体为堇青石蜂窝陶瓷， 所述活性组分为负载 在稀土金属氧化物和过渡金属氧化物上的贵金属。 1. A precious metal monolithic catalyst, characterized in that, the precious metal monolithic catalyst is composed of a carrier and a precious metal active component, the carrier is cordierite honeycomb ceramic, the active component is supported on rare earth metal oxides and Noble metals on transition metal oxides.
2、 如权利要求 1所述的贵金属整体式催化剂， 其特征在于， 所述贵金属活 性组分的质量占贵金属整体式催化剂总质量的 0.01~10%， 优选 0.05~9%， 进一 歩优选 0.1~8%； 2. The precious metal monolithic catalyst according to claim 1, characterized in that the mass of the precious metal active component accounts for 0.01~10% of the total mass of the precious metal monolithic catalyst, preferably 0.05~9%, and further preferably 0.1~ 8%;
优选地， 所述贵金属选自 Ag、 Pt、 Ru、 Pd或 Rh中的任意一种或者至少两 种的混合物； Preferably, the noble metal is selected from any one or a mixture of at least two of Ag, Pt, Ru, Pd or Rh;
优选地， 所述堇青石蜂窝陶瓷为高孔密度的堇青石蜂窝陶瓷， 堇青石蜂窝 陶瓷的孔密度优选为 100 600 CPSI, 所述堇青石蜂窝陶瓷的孔密度进一歩优选 为 400 CPSI。 Preferably, the cordierite honeycomb ceramic is a cordierite honeycomb ceramic with high pore density. The pore density of the cordierite honeycomb ceramic is preferably 100-600 CPSI, and the pore density of the cordierite honeycomb ceramic is further preferably 400 CPSI.
3、 如权利要求 1或 2所述的贵金属整体式催化剂， 其特征在于， 所述过渡 金属氧化物选自 Fe氧化物、 Cr氧化物、 Cu氧化物、 Co氧化物、 Ni氧化物或 Mn氧化物中的任意一种或者至少两种的混合物； 3. The precious metal monolithic catalyst according to claim 1 or 2, characterized in that the transition metal oxide is selected from the group consisting of Fe oxide, Cr oxide, Cu oxide, Co oxide, Ni oxide or Mn oxide. Any one or a mixture of at least two of them;
优选地， 所述稀土金属氧化物为 La的氧化物或 /和 Ce的氧化物。 Preferably, the rare earth metal oxide is an oxide of La or/and an oxide of Ce.
4、 一种如权利要求 1-3之一所述的贵金属整体式催化剂的制备方法， 其特 征在于， 所述制备方法为乳液火焰燃烧法， 包括如下歩骤： 4. A method for preparing a precious metal monolithic catalyst according to any one of claims 1 to 3, characterized in that the preparation method is an emulsion flame combustion method, which includes the following steps:
( 1 ) 将过渡金属氧化物的前驱体和稀土金属氧化物的前驱体分散于水中， 形成水相； (1) Dispersing the precursors of transition metal oxides and rare earth metal oxides in water to form a water phase;
(2) 将贵金属的前驱体分散于有机溶剂中， 形成油相； (2) Disperse the precursor of the precious metal in an organic solvent to form an oil phase;
(3 ) 将所述水相逐滴加入所述油相中， 同时加入表面活性剂， 形成油包水 乳液前驱体； (3) Add the water phase dropwise to the oil phase, and add surfactant at the same time to form a water-in-oil emulsion precursor;
(4) 将所述油包水乳液前驱体供给到火焰燃烧装置中， 经点火， 雾化后，
燃烧， 然后冷却， 凝聚， 得到贵金属活性组分； (4) Supply the water-in-oil emulsion precursor to a flame combustion device, and after ignition and atomization, Burn, then cool and condense to obtain precious metal active components;
(5) 在火焰燃烧装置中的火焰区域， 贵金属活性组分在热泳力的作用下， 沉积到置于火焰燃烧装置的雾化喷嘴上方的堇青石蜂窝陶瓷载体上， 得到贵金 属整体式催化剂。 (5) In the flame area of the flame combustion device, the precious metal active components are deposited on the cordierite honeycomb ceramic carrier placed above the atomization nozzle of the flame combustion device under the action of thermophoresis force to obtain a precious metal monolithic catalyst.
5、 如权利要求 4所述的方法， 其特征在于， 所述过渡金属氧化物的前驱体 选自 Fe(N03)3、 Cr2(S04)3、 Cr(N03)3、 Cu(C¾COO)2、 Cu(N03)2、 Mn(N03)2、 Mn(CH3COO)2、 Co(N03)2、 Co(CH3COO)2、 Ni(N03)2或 Ni(C¾COO)2中的任意 一种或者至少两种的混合物； 5. The method of claim 4, wherein the precursor of the transition metal oxide is selected from the group consisting of Fe(N0 3 ) 3 , Cr 2 (S0 4 ) 3 , Cr(N0 3 ) 3 , Cu( C¾COO) 2 , Cu(N0 3 ) 2 , Mn(N0 3 ) 2 , Mn(CH 3 COO) 2 , Co(N0 3 ) 2 , Co(CH 3 COO) 2 , Ni(N0 3 ) 2 or Ni( C¾COO) 2 any one or a mixture of at least two;
优选地， 所述稀土金属氧化物的前驱体选自 La N03;>3、 La(CH3COO)3 , Ce(CH3COC 3或 Ce(N03;>3中的任意一种或者至少两种的混合物。 Preferably, the precursor of the rare earth metal oxide is selected from any one of LaNO 3 ;> 3 , La(CH 3 COO) 3 , Ce(CH 3 COC 3 or Ce(N0 3 ;> 3) or at least A mixture of both.
6、 如权利要求 4或 5所述的方法， 其特征在于， 所述贵金属的前驱体选自 Ag(acac)、 Pd(acac)2、 Pt(acac)2、 Rh(acac)3或 Ru(acac)3中的任意一种或者至少两 种的混合物。 6. The method of claim 4 or 5, wherein the noble metal precursor is selected from the group consisting of Ag(acac), Pd(acac) 2 , Pt(acac) 2 , Rh(acac) 3 or Ru( acac) 3 any one or a mixture of at least two.
7、 如权利要求 4-6之一所述的方法， 其特征在于， 所述油相和水相的体积 比为 10:1-3:1 , 优选 9:1~4:1； 7. The method according to any one of claims 4 to 6, characterized in that the volume ratio of the oil phase and the water phase is 10:1-3:1, preferably 9:1~4:1;
优选地， 所述有机溶剂为己垸、 庚垸、 辛垸、 环戊垸、 环己垸、 苯、 甲苯、 二甲苯、 汽油、 柴油、 煤油中的一种或者至少两种的混合物。 Preferably, the organic solvent is one or a mixture of at least two of hexane, heptane, octane, cyclopentane, cyclohexane, benzene, toluene, xylene, gasoline, diesel, and kerosene.
8、 如权利要求 4-7之一所述的方法， 其特征在于， 所述表面活性剂选自垸 基三甲基氯化铵、 十二垸基三甲基氯化铵、 十二垸基二甲基苄基氯化铵、 十四 垸基二甲基苄基氯化铵、 十八垸基二甲基苄基氯化铵、 十二垸基二甲基氧化胺、 月桂酰胺丙基氧化胺、 椰油酰胺丙基氧化胺、 椰油酸单乙醇酰胺、 椰油酸二乙 醇酰胺、 二 (氢化牛脂基)邻苯二甲酸酰胺、 脂肪醇聚氧乙烯醚、 甲基葡萄糖苷聚 氧乙烯醚、 蓖麻油聚氧乙烯醚、 乙二醇单 (双：)硬脂酸酯、 单 (双：)硬脂酸甘油酯、
壬基酚聚氧乙烯醚、 辛基酚聚氧乙烯醚、 十二垸基聚氧乙烯醚、 二壬基酚聚氧 乙烯醚、 聚氧乙烯 -8-辛基苯基醚、 失水山梨醇单月桂酸酯聚氧乙烯醚、 失水山 梨醇单棕榈酸酯聚氧乙烯醚、 失水山梨醇单硬脂酸酯聚氧乙烯醚、 失水山梨醇 三硬脂酸酯聚氧乙烯醚、 失水山梨醇单油酸酯聚氧乙烯醚、 失水山梨醇三油酸 酯聚氧乙烯醚、 失水山梨醇单月桂酸酸酯、 失水山梨醇单棕榈酸酯、 失水山梨 醇单硬脂酸酯、 失水山梨醇三硬脂酸酯、 失水山梨醇单油酸酯、 失水山梨醇三 油酸酯中的任意一种或者至少两种的混合物； 8. The method according to any one of claims 4 to 7, characterized in that the surfactant is selected from the group consisting of alkyltrimethylammonium chloride, dodecyltrimethylammonium chloride, and dodecyltrimonium chloride. Dimethylbenzylammonium chloride, Tetradecyldimethylbenzylammonium chloride, Octadecyldimethylbenzylammonium chloride, Dodecyldimethylamine oxide, Laurylamide propyl oxide Amine, cocamidopropyl amine oxide, coco acid monoethanolamide, coco acid diethanolamide, bis(hydrogenated tallow) phthalic acid amide, fatty alcohol polyoxyethylene ether, methyl glucoside polyoxyethylene Ether, castor oil polyoxyethylene ether, ethylene glycol mono(bis:) stearate, mono(bis:) stearic acid glyceryl ester, Nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, dodecyl polyoxyethylene ether, dinonylphenol polyoxyethylene ether, polyoxyethylene-8-octylphenyl ether, sorbitol Monolaurate polyoxyethylene ether, sorbitan monopalmitate polyoxyethylene ether, sorbitan monostearate polyoxyethylene ether, sorbitan tristearate polyoxyethylene ether, Sorbitan monooleate polyoxyethylene ether, sorbitan trioleate polyoxyethylene ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monooleate Any one of stearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate or a mixture of at least two of them;
优选地， 火焰燃烧装置中， 油包水乳液前驱体的供给流速为 l~20ml/mm， 优选 2~18ml/min， 进一歩优选 3~15ml/min。 Preferably, in the flame combustion device, the supply flow rate of the water-in-oil emulsion precursor is 1~20ml/mm, preferably 2~18ml/min, and further preferably 3~15ml/min.
9、 如权利要求 4-8之一所述的方法， 其特征在于， 在 400 1200 °C的火焰区 域内， 贵金属活性组分在热泳力的作用下， 沉积到堇青石蜂窝陶瓷载体上； 所 述沉积时间为 180~900s; 9. The method according to any one of claims 4 to 8, characterized in that, in the flame region of 400-1200°C, the noble metal active component is deposited on the cordierite honeycomb ceramic carrier under the action of thermophoretic force; The above deposition time is 180~900s;
优选地， 所述堇青石蜂窝陶瓷载体置于火焰燃烧装置的雾化喷嘴上方的 10~20cm处， 优选置于火焰燃烧装置的雾化喷嘴上方的 15cm处。 Preferably, the cordierite honeycomb ceramic carrier is placed 10 to 20 cm above the atomizing nozzle of the flame burning device, preferably 15 cm above the atomizing nozzle of the flame burning device.
10、一种如权利要求 1-3之一所述的贵金属整体式催化剂的用途，其特征在 于，所述贵金属整体式催化剂用于挥发性有机物气体（VOCs)的催化燃烧过程。
10. The use of a noble metal monolithic catalyst as claimed in one of claims 1 to 3, characterized in that the noble metal monolithic catalyst is used in the catalytic combustion process of volatile organic gases (VOCs).
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| Publication number | Publication date |
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| CN103785487A (en) | 2014-05-14 |
| CN103785487B (en) | 2016-01-27 |
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