CN104853827A - 中空微球催化剂载体及其制作方法 - Google Patents
中空微球催化剂载体及其制作方法 Download PDFInfo
- Publication number
- CN104853827A CN104853827A CN201380066413.3A CN201380066413A CN104853827A CN 104853827 A CN104853827 A CN 104853827A CN 201380066413 A CN201380066413 A CN 201380066413A CN 104853827 A CN104853827 A CN 104853827A
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- Prior art keywords
- catalyst
- metal oxide
- hollow
- microballoon
- composition according
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 149
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000004005 microsphere Substances 0.000 title abstract description 84
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 49
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 49
- 238000002485 combustion reaction Methods 0.000 claims abstract description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 40
- 239000002002 slurry Substances 0.000 claims description 30
- 239000003381 stabilizer Substances 0.000 claims description 29
- 230000003197 catalytic effect Effects 0.000 claims description 28
- 239000002105 nanoparticle Substances 0.000 claims description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 238000001694 spray drying Methods 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 10
- 239000002912 waste gas Substances 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 239000012702 metal oxide precursor Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000000629 steam reforming Methods 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 140
- 239000010410 layer Substances 0.000 description 37
- 239000002245 particle Substances 0.000 description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 28
- 238000002360 preparation method Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- 239000011805 ball Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 229910052763 palladium Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 239000010948 rhodium Substances 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 229910052703 rhodium Inorganic materials 0.000 description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 238000001802 infusion Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- -1 NOx compound Chemical class 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000003870 refractory metal Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 241000907788 Cordia gerascanthus Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- ZBAFFZBKCMWUHM-UHFFFAOYSA-N propiram Chemical compound C=1C=CC=NC=1N(C(=O)CC)C(C)CN1CCCCC1 ZBAFFZBKCMWUHM-UHFFFAOYSA-N 0.000 description 2
- 229950003779 propiram Drugs 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 229910025794 LaB6 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- VCRLKNZXFXIDSC-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[Al+3].[Zr+4] VCRLKNZXFXIDSC-UHFFFAOYSA-N 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011214 refractory ceramic Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 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
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明提供了中空多孔金属氧化物微球。所述微球可用作催化剂,特别是用于内燃机的废气处理催化剂的载体。本发明还提供了制备所述微球的方法、使用所述微球作为催化剂载体的方法和使用包含所述微球的催化剂制品处理废气的方法。
Description
技术领域
本发明涉及用于处理摩托车和汽车发动机废气的催化剂和催化剂载体的领域。
背景
内燃机的废气含有污染空气的诸如烃、一氧化碳和氮氧化物(NOx)的污染物。各国政府已设置了对于未燃烧的烃、一氧化碳和氮氧化物污染物的排放标准,旧的车辆和新的车辆必须满足这些排放标准。为了满足这样的标准,可以在内燃机的废气管线中安置含有三效催化剂(TWC)的催化转换器(catalytic converter)。使用废气催化剂有助于显著改善空气质量。TWC是最常用的催化剂,它提供氧化CO、氧化未燃烧的烃(HC’s)及将NOx还原成N2的三种功能。TWC通常使用一种或多种铂族金属(PGM)来同时氧化CO和HC并还原NOx化合物。TWC最常见的催化组分是铂(Pt)、铑(Rh)和钯(Pd)。
TWC催化剂中的铂族金属(PGM)(例如,铂、钯、铑、钌和铱)通常被分散于高表面积、耐熔金属氧化物载体(例如,高表面积氧化铝涂层)上或氧存储组分(OSC)上,或它们的混合物上。载体承载于合适的载物(carrier)或基底上(例如包含耐熔陶瓷或金属蜂窝结构的整体基底)或耐熔颗粒(例如合适的耐熔材料的圆球或短的挤出部分)。TWC催化剂基底也可以是丝网,通常是金属丝网,它在小型发动机中特别有用。
耐熔金属氧化物(例如氧化铝、稀土金属氧化物、氧化锆、二氧化钛及它们的组合)及其它材料通常被用作催化剂制品的催化组分的催化剂和作为氧存储材料(OSC)。现在,几乎所有的氧化铝催化剂载体和OSC都是具有范围为约5-100微米的粒度的固体粉末颗粒的形式或大于100微米尺寸的大挤出物。氧化铝载体材料通常表现出高于60平方米每克(“m2/g”)的BET表面积,经常高达约200m2/g或更高。
在内燃机中,这些催化剂载体材料也需要具有高的微观和宏观孔隙率来增强气相扩散,这使得催化剂在高空间速度下更有效地获得高的氮氧化物(NOx)和烃(HC)转化。在这方面,多孔微球(包括中空微球)已被用来作为催化剂载体用于提高催化基面涂层(基面涂层)的孔隙率的目的。文献报道了这样的微球的多种制备方法。然而,在通常情况下,在较低温度下形成的中空氧化铝微球是薄壁蛋壳结构,其太脆弱无法抵抗催化剂制备过程中的机械研磨和发动机中的水热陈化。厚壁中空氧化铝球对机械和热陈化更稳健,并且是可商购获得的(例如,作为绝缘材料),但这些材料或者具有大的粒度或已经被在过高的温度下烧结用于催化剂应用。使用离子萃取勃姆石溶胶,接着在1200℃下烧制成的中空氧化铝微球已被证明具有厚壁;但是,这些微球为致密的α晶相。
对于通过简单制备方法制成的适合用作催化剂载体的并且具有厚壁及小球直径的中空多孔微球仍有需求。这样的微球的可用性也带来了原材料(例如贵金属、氧化铝和OSC)使用的显著降低,因此,由于消除了传统固体颗粒的中央中的死空间(dead space)所以成本大幅降低。
发明概述
在一方面,本发明涉及一种包含中空多孔金属氧化物微球的组合物。在一具体实施方案中,所述微球包含具有约1-5μm、通常约1-3μm或约2μm厚度的围绕中空中央的壁,并且所述中空多孔金属氧化物微球的直径范围为约5-15μm、通常约8-12μm或约9-11μm。希望的是,平均直径(D90)为约10μm。所述微球还可以包含催化剂,例如用于处理发动机废气的催化剂。
在所述中空多孔金属氧化物微球的一个实施方案中,催化剂被并入所述中空多孔金属氧化物微球的壁内。在另一个实施方案中,催化剂以较高的浓度存在于所述微球的外表面上或附近。
前述实施方案的任一个的特定变型中,所述微球还包含稳定剂。合适的稳定剂的实例包括但不限于镧系元素、硅、碱土金属、过渡金属或它们的组合。镧系元素例如镧是用于本发明的特定稳定剂。
在另一方面,本发明涉及一种用于内燃机中的催化剂制品,所述催化剂制品包含形成于基底上的催化层,并且所述催化层包含前述中空金属氧化物微球组合物中的任一种。
在前述催化剂制品的某些实施方案中,所述基底是整体基底或金属基底。
在某些实施方案中,通过在基底上沉积浆料来形成催化层或多层而制成催化剂制品,所述浆料包含含有催化剂的前述中空多孔金属氧化物微球组合物中的任一种。
在另一方面,本发明涉及用于处理包含烃、一氧化碳和/或氮氧化物的发动机废气的方法,所述方法包括在适于氧化一氧化碳、氧化烃和/或还原氮氧化物的条件下使所述废气与上述中空多孔金属氧化物微球或催化剂制品接触。
在另一方面,本发明涉及一种用于处理发动机废气的排放物处理系统,所述排放物处理系统包括与发动机废气流进行排放物流动连通的根据任意前述实施方案的催化剂制品。在某些实施方案中,所述排放物处理系统还包含柴油氧化催化剂、柴油颗粒过滤器、催化部分氧化催化剂、氨氧化催化剂、还原剂喷射器、空气喷射器、烃喷射器和选择性催化还原催化剂中的至少一种。
在另一方面,本发明涉及用于制备中空多孔金属氧化物微球的方法,其包括将可热降解的聚合物模板溶解于水性介质中以形成聚合物模板的胶束;用所述溶解的聚合物模板浆化金属氧化物前体的纳米颗粒;对所述浆料进行喷雾干燥;并且煅烧所述喷雾干燥的浆料来热降解所述聚合物模板,从而形成中空金属氧化物微球。在某些实施方案中,所述聚合物模板为软质聚合物模板。在其它实施方案中,在喷雾干燥之前将催化剂并入所述浆料中。在另一个实施方案中,在喷雾干燥之后将催化剂浸渍于所述微球之中。
在中空多孔金属氧化物微球的组合物或包含催化剂的催化制品的任一实施方案中,所述催化剂可以为铂族金属。合适的铂族金属包括任意的铂、钯、铑和它们的组合。
附图简述
图1A是通过喷雾干燥制成的固体ZrO2/Al2O3颗粒的SEM横截面。图1B根据本发明通过喷雾干燥制成的ZrO2/Al2O3中空微球的SEM横截面。
图2A、2B和2C是图示出具有不同结构组分的基面涂层(底washcoat)的宏观孔隙率的SEM横截面。图2A是由固体颗粒组成的传统基面涂层。图2B是由中空微球和固体颗粒的混合物组成的基面涂层。图2C是完全由中空微球组成的基面涂层。
图3A和图3B图示出了实施例1的结果,示出了根据本发明的典型的中空微球氧化铝的SEM形态(图1A)和横截面(图1B)。
图4图示出实施例1的结果,示出了假勃姆石前体和中空微球氧化铝的粒度分布。
图5图示出实施例1的结果,示出了固体颗粒、实心球和中空微球氧化铝的夯实密度。
图6图示出实施例5的结果,示出了催化剂载体对单层、Pd催化剂芯样品的起燃温度的影响。
图7图示出实施例6的结果,比较了中空氧化铝微球/铂/钯/铑催化剂和固体氧化铝颗粒/铂/钯/铑催化剂在摩托车应用中的CO、烃和一氧化氮的转化率。
发明详述
在描述本发明的几个示例性实施方案之前,应当理解,本发明不限于在下面的描述中所阐述构造或工艺步骤的细节。本发明能够是其它实施方案并能够被实施或以多种方式进行。
本说明书通篇所提到的“一个实施方案”、“某些实施方案”、“一个或多个实施方案”或“实施方案”表示结合所述实施方案所描述的特定的特征、结构、材料或特性并入本发明的至少一个实施方案中。因此,本说明书通篇多处出现的诸如“在一个或多个实施方案中”、“在某些实施方案中”、“在一个实施方案中”或“在实施方案中”的短语不一定是指本发明的相同的实施方案。另外,在一个或多个实施方案中,这些特定的特征、结构、材料或特性可以任何合适的方式进行组合。
如本文中所使用,术语“纳米颗粒”或“纳米尺寸的颗粒”是指具有纳米范围(约1-999nm)内的直径的颗粒。术语“微粒”是指具有微米范围(约1-999μm)内的直径的颗粒。类似地,术语“微球”通常是指具有微米范围内的直径的较小颗粒的球形结块。
如本文中所使用,关于催化剂载体的术语“结块”、“结块的”等是指一种或多种组分的个体较小颗粒围绕中央颗粒模板聚集成为较大、大体上球形的颗粒或团块。在移除模板之后,结块的颗粒保持为具有由围绕中空中央的结块的颗粒组成的壁的中空微球。
本发明的某些方面提供了适合用作催化剂载体的中空多孔微球,所述微球包含金属氧化物的结块的纳米颗粒,例如高表面积金属氧化物。所述催化剂载体对于承载一种或多种催化剂或催化剂组分在中空微球的表面上或壁内是有用的。在一个或多个实施方案中,所述金属氧化物包含选自由下列组成的组的活化的化合物:氧化铝、勃姆石、假勃姆石、氧化铈、氧化锆、氧化铈-氧化锆、氧化铝-氧化锆、氧化铝-氧化铈-氧化锆、氧化镧-氧化铝、氧化镧-氧化锆-氧化铝、氧化钡-氧化铝、氧化钡-氧化镧-氧化铝、氧化钡-氧化镧-氧化钕氧化铝和氧化铝-氧化铈。在一个或多个具体实施方案中,所述纳米颗粒为氧化铝或勃姆石纳米颗粒。在其它具体实施方案中,所述纳米颗粒为CeO2纳米颗粒。
在某些实施方案中,所述金属氧化物纳米颗粒的平均直径为约50-500nm。在具体实施方案中,所述金属氧化物纳米颗粒的平均直径为约100nm。如果起始材料的颗粒较大,则它们可以在形成催化剂载体之前被研磨至所需尺寸。在喷雾干燥之后,所述中空多孔微球的平均直径(以D90测量)为约5-20μm、通常为约8-12μm或约9-11μm。理想地,D90直径范围为约10μm。微球的壁厚为约1-5μm、通常为约1-3μm、并且更通常为约2μm。如果需要取得所需直径范围,则可以研磨所述中空多孔微球可以研磨来减低所述平均直径范围。
在另一个实施方案中,根据任意前述实施方案的中空多孔微球还可以包含稳定剂,例如镧系元素、碱土金属、硅、过渡金属或它们的组合。合适的稳定剂包括钡氧化物、镧氧化物、锆的氧化物及它们的组合。稳定剂的含量在1-20重量%之间的范围内。所述稳定剂可以被并入作为氧化物形式或作为前体(例如硝酸盐形式)随后被氧化的中空多孔微球之中。在其中所述中空多孔微球包含稳定剂的本发明的任一实施方案中,所述稳定可以被并入所述微球的壁中或在其表面。所述稳定剂在喷雾干燥前可以被添加至具有金属氧化物纳米颗粒的浆料。此过程得到具有金属氧化物和微球的壁中的稳定剂的结块的金属氧化物颗粒。或者,稳定剂可以在喷雾干燥并移除模板之后被浸渍到微球的壁中。所述稳定剂和金属氧化物纳米颗粒可以作为壁内的混合物存在;然而,在某些实施方案中,可以发现所述稳定剂在高浓度淀积在微球的外表面上,因此,以层的形式展现。中空多孔金属氧化物/稳定剂微球的具体实例包括ZrO2/CeO2和ZrO2/Al2O3。
在具体实施方案中,所述微球包含在它的外表面上或附近的氧化锆。已经观察到,在喷雾干燥之前被添加到具有氧化铝纳米颗粒的浆料中的氧化锆在喷雾干燥过程中以较高浓度积聚在所述微球的外表面或外表面上,这使得氧化锆的外层在SEM上是可见的。这种层状构造作为屏障将微球中的铑催化剂从氧化铝分离是非常有用的。多层结构示于图1B中,其中,氧化锆的外层在SEM上被看作中空微球的氧化铝壁上较浅的层。图1A示出了类似的氧化锆层当它们被喷雾干燥且无软质聚合物模板时也形成于固体氧化铝纳米颗粒的外表面上,并且不形成中空微球。
在另一个实施方案中,中空多孔微球的任意前述实施方案还可以包含一种或多种催化剂或催化剂组分,其一旦煅烧或使用会分解或以其它方式转换为催化剂的催化活性形式(通常是金属或金属氧化物)。在具体实施例中,所述中空多孔微球可以保护金属氧化剂纳米颗粒、稳定剂和一种或多种催化剂和/或一种或多种催化剂组分。如果存在,所述催化剂或催化剂组分在所述浆料的水性液体中应是水溶的或水分散性的。作为一个实施例,合适的催化剂包括一种或多种PGM催化剂或PGM催化剂组分。在某些实施方案中,所述催化剂或催化剂组分被并入微球的壁中,这可以通过将它在制备过程中并入具有金属氧化物纳米颗粒的浆料中来完成或通过将它在制备之后浸渍在所述壁中来完成。
在另一个实施方案中,根据任意前述实施方案的中空多孔微球还可以包含附加组分,例如促进剂。这些促进剂可以是锌、镍和铋的金属氧化物。这样的附加组分也可以通过将它们在制备过程中并入具有金属氧化物纳米颗粒的浆料中来并入所述微球的壁中或通过将它们在制备之后浸渍在所述壁中来并入所述微球的壁中。
已经发现本文所述中空多孔微球比相应的固体粉末金属氧化物密度低,当它们被用作用于发动机废气处理应用的催化剂载体和被并入用于发动机废气处理应用的催化剂制品中时,这提供了重量优势。在某些实施例中,微球的密度与相应的固体粉末相比降低了约37%。中空多孔微球在陈化(例如750℃/10%H2O/空气/20小时)后保持它们的完整性。在陈化后,良好的催化剂分布也保持在中空多孔微球上,并且所述中空结构减少了死空间和制备中所需的材料的量。
应指出的是,中空多孔微球的微观孔隙率与相应的固体颗粒金属氧化物类似,如下面的中空心多孔氧化铝微球的实施例中所示出的那样。这是因为中空球结构的形成增加了材料的宏观孔隙率,而不是它们的微球结构。图2A、2B和2C是示出不同Al2O3/OSC基面涂层的宏观孔隙率不同的SEM。图2A示出了由氧化铝固体颗粒(深色)和OSC(浅色)组成的传统基面涂层。可以看出传统基面涂层具有低宏观孔隙率,这得到气体扩散穿过所述基面涂层的限制。图2B示出由根据本发明的中空微球氧化铝和固体OSC颗粒的混合物组成的基面涂层。该调配物产生了具有与传统基面涂层相比提高的宏观孔隙率的基面涂层,并且它表现出改善的催化剂活性。图2C示出了完全由根据本发明的中空微球氧化铝和OSC组成的基面涂层。该基面涂层具有最高的宏观孔隙率,因此具有通过基面涂层的最高的气体扩散率和最完善的催化剂活性。
本发明的另一方面提供了一种催化剂制品,其包含基底上的催化剂层,所述催化剂层包含根据任一前述实施方案的中空多孔微球作为催化剂载体。所述中空多孔微球包含结块的金属氧化物纳米球、承载于所述催化剂载体上的催化剂及任选的稳定剂。所述催化剂载体可以是在基底上的基面涂层的形式。在具体实施方案中,所述催化剂可以是一种或多种PGM催化剂,例如钯、铂、铑或它们的组合。
根据所述催化剂制品的一个或多个实施方案,被施加所述催化剂载体的基底可以是通常用于制备TWC催化剂制品的任意材料并且通常会包含金属或陶瓷结构。可以使用任意合适的基底,例如下列类型的整体基底:具有多个从所述基底的入口或出口面延伸贯穿所述基底的细小、平行气流通道,从而使得通道对于贯穿流过所述基底的流体是开放的。所述通道从它们的流体入口到它们的流体出口基本上是直的路径,所述通道通过壁来限定,在所述壁上通过基面涂层涂覆所述催化材料,从而使得流过通道的气体接触所述催化材料。整体基底的流通道是薄壁通道,其可以是任意合适的横截面形状和尺寸,例如梯形、矩形、正方形、正弦形、六边形、椭圆形、圆形等。这样的结构可以含有约60至约600或更多的气体入口开口(即“小室(cell)”)/平方英寸的横截面。可以通过任意本领域已知的涂覆方法(例如手动浸渍或气雾喷刷(airbrushing))完成涂覆,接着干燥和煅烧,通常是在490-550℃下进行1-2小时。
陶瓷基底可以由任意合适的耐熔材料制成、例如堇青石、堇青石-α氧化铝、氮化硅、锆莫来石、锂辉石、氧化铝-二氧化硅氧化镁、硅酸锆、硅线石、镁硅酸盐、锆石、透锂长石、α氧化铝、硅铝酸盐等。对于本发明的催化剂载体有用的基底也可以由一种或多种金属或金属合金组成。所述金属基底可以以丝网或整体形式的多种形状(例如波纹片、金属板)使用。
本发明的再另一个方面提供了制备所述中空多孔微球的方法。在一个实施方案中,可以通过喷雾干燥方法来制备本发明的中空多孔微球,其得到所述金属的纳米颗粒结块于大体上球形的聚合物胶束模板上。煅烧所述结块的纳米颗粒烧掉中央的胶束模板来制备本发明的厚壁的中空金属氧化物微球。任意合适的可热降解的聚合物可用作本发明的方法中的模板。实例包括烷芳基聚醚醇或乙烯氧化物和丙烯氧化物的合成共聚物。在中空球氧化铝合成中有用的三种软质聚合物模板的实例为两种来自BASF的普鲁兰尼克聚合物(pluronic polymers)和及来自Union Carbide的非离子表面活性剂普鲁兰尼克聚合物是由下面的化学结构表示的乙烯氧化物和丙烯氧化物的合成共聚物:
HO(C2H4O)a(C3H6O)b(C2H4O)aH (1)
而所述类型的非离子表面活性剂通常被描述为烷芳基聚醚醇并且具有下面的结构式:
在前述方法的一个或多个实施方案中,所述聚合物模板材料被溶解于水性液体中(例如水)来形成大体上球形的模板材料的胶束,其中亲水性基团指向胶束的表面。所述纳米尺寸的金属氧化物颗粒被添加至次水性混合物来形成浆料。在某些实施方案中,约1-5重量%的所述模板被溶于所述水性液体中。基于所述金属氧化物纳米颗粒的干重计算聚合物重量百分数。所述浆料随后被喷雾干燥以使所述水性液体挥发并造成所述纳米尺寸的金属氧化物颗粒结块于大体上球形的模板的亲水表面。所述模板随后通过煅烧被从所述喷雾干燥的结块的中央烧掉以形成厚壁的金属氧化物的中空微球。任意合适的金属氧化物的纳米颗粒可以被用于制备上述中空多孔微球的方法中;然而,在一具体实施方案中,所述金属氧化物为勃姆石或假勃姆石,其具有如下优势:用于制备所述中空微球氧化铝的比活化的氧化铝(例如γ-氧化铝)小很多的粒度。
在具体实施方案中,如上所述的稳定剂被并入所述浆料中,从而当所述浆料被喷雾干燥并煅烧时,所得到的中空微球还包含分散于所述壁内或作为沉积在外表面上或外表面中的层存在的稳定剂。任意合适的稳定剂可以被用于如上所述的本发明的方法中;但是,在一具体实施方案中,所述稳定剂可以是镧。在包括稳定剂的任一前述实施方案中,所述稳定剂可以作为氧化物形式或作为前体(例如硝酸盐形式,其随后被氧化)的形式被并入浆料中。
在某些实施方案中,催化剂或催化剂组分(例如一种或多种PGM)在喷雾干燥之前被并入所述浆料中,在此情况下所述催化剂在单个步骤中被并入到微球催化剂载体的壁。或者,可以将催化剂在喷雾干燥之后使用传统浸渍技术浸渍到所述微球催化剂载体的壁中或表面上。例如,可以通过初湿浸渍(incipient wetness)法将催化剂或催化剂成分(例如铂族金属)的溶液置于所述催化剂载体的孔中,其中稀释的铂族金属的体积约等于所述催化剂载体的孔体积。初湿浸渍法通常带来贯穿所述壁的孔体系或所述中空微球催化剂载体的表面上的催化剂富集层的前体溶液的基本上均匀的分布。
可以在本文所述制备方法中使用适于使所述浆料的水性液体组分挥发并制成所述中空多孔微球的任意喷雾干燥工艺。如上所讨论,在多个实施方案中,所述浆料可以包含1)所述金属氧化物纳米颗粒;2)所述金属氧化物纳米颗粒和所述稳定剂二者;3)所述金属氧化物纳米颗粒、所述稳定剂和所述催化剂或催化剂组分;或4)所述金属氧化物纳米颗粒、所述稳定剂和所述催化剂或催化剂组分,及至少一种附加组分例如促进剂。如果诸如所述稳定剂和/或所述催化剂的组分在喷雾干燥前不被并入所述浆料中,则它们可以在喷雾干燥后被浸渍于所述中空多孔微球中。虽然金属氧化物的纳米颗粒是用于制备所述中空微球氧化物的优选前体,但是也可以在用于喷雾干燥的浆料中使用水溶性盐,例如金属氧化物的硝酸盐和乙酸盐。在一个实施方案中,所述喷雾干燥工艺包括(1)将假勃姆石纳米颗粒分散于水中,(2)将软质聚合物分别溶解于水中,(3)添加所述聚合物水性溶液至所述假勃姆石水性浆料中同时搅拌,(4)喷雾干燥混合的浆料,及(5)在约400-600℃(例如550℃)下,空气中,煅烧所述喷雾干燥的粉末。所述喷雾干燥工艺允许所述金属氧化物纳米颗粒在聚合物-模板上形成层。一旦煅烧,则所述聚合物模板芯被移除来产生中空结构。通过此方法制成的中空微球的粒度通常也适合涂覆在基底上的三效催化剂无需显著地研磨。然而,如果需要或想要取得特别的尺寸范围,则可以再煅烧之后研磨所述中空微球。使用喷雾干燥工艺来制备所述中空多孔微球也提供了从所述工艺基本上100%收率的优势,并且,由于多组分产品可以在单一喷雾干燥工艺中生产,所以提供了成本节约。
一般地,制备本发明的中空多孔微球的方法通常得到具有大约10μm的平均直径的微球。直径的D90范围通常为约5-20μm。在具体实施方案中,微球的平均直径范围为8-12μm或9-11μm(D90测量)。
在另一方面,本发明提供了用于处理来自内燃机的包含一氧化碳、烃和/或氮氧化物的废气的方法,如上文所述,在适于氧化CO、氧化HC和/或还原NOx的条件下,所述方法包括使所述发动机的废气流中的气体与中空多孔微球承载的催化剂接触。所述中空多孔微球催化剂可以作为载体上的层形成用作如上文所述的催化剂制品。具体地,废气流中的CO和NOx可以通过与本发明的催化剂和催化剂制品接触来减少。
在另一方面,包含所述中空多孔微球承载的催化剂的催化剂制品可以被并入用于处理内燃机废气的排放物处理系统中。所述处理系统包括与发动机废气流进行排放物流动连通的催化剂制品。在某些实施方案中,所述排放物处理系统还包括一种或多种柴油氧化催化剂(DOC)、柴油颗粒过滤器(DPF)、催化部分氧化催化剂(CPO)、氨氧化催化剂(AMOX)、还原剂喷射器、空气喷射器、烃喷射器、选择性催化还原催化剂(SCR)、水气变换催化剂和蒸汽重整催化剂。处理废气流的方法的某些实施方案包括使所述废气流通过本文所述催化剂制品或使所述废气流与本文所述催化剂制品接触。
实施例
实施例1:中空微球氧化铝的制备和物理性能
中空微球氧化铝的制备包括(1)将1330克假勃姆石在7500克去离子水中浆化;以形成浆料A,(2)将35克软质聚合物溶解于250克水中以形成溶液B;(3)添加溶液B至浆料A,同时搅拌;从而形成浆料C,(4)在310℃的入口温度、110℃和120℃之间的出口温度、30,000RPM(转/每分钟)的雾化轮转速和50cc/分钟的浆料进料速率下使用喷雾干燥器对浆料C进行喷雾干燥,及(5)将喷雾干燥的粉末在流动空气中以1℃/min的加热速率加热至550℃并保持在550℃下2小时。
在具有Bruker Ge EDS系统的JEOL JEM2011 200KeV LaB6源显微镜上使用Spirit软件手机SEM数据。用底部安装的Gatan 2K CCD照相机和Digital Micrograph收集软件捕获电子图像。制备并分析作为200网眼花边碳涂覆的Cu网上的干分散物所有横截面样品。横截面的样品被安装在Buehler Epothin环氧树脂/固化剂(含有S和Cl)中并使用DentonDV-502A Vacuum Coater涂覆30nm碳层。图3示出了通过此方法制成的中空微球氧化铝的横截面形态的SEM(扫描电子显微镜)图像。虽然大部分颗粒是中空球的形式,但是还有一些破碎的球和实心球。还有被封在较大的中空结构中的小的中空球。多种形状的中空球和实心球的分散取决于所述合成中所使用的氧化铝前体和聚合物模板的类型和量。
在Horiba LA-950粒度分析仪上测量平均粒度。对于典型测量,将0.1g的吸附剂在水中浆化。所述粒度(直径)被分别表示为少于总颗粒的50%和90%(D50和D90)的值。中空微球氧化铝的D90为约10μm,如图3中所示,与起始的假勃姆石的约100nm(0.1μm)相比。在550℃下煅烧之后,中空球结构对研磨或水热处理相当稳健。例如,所述中空结构在950℃/10%H2O/空气/4小时水热陈化或物理球研磨约30分钟后仍保持相对完整。细假勃姆石粒子在煅烧后变为γ-氧化铝并形成强键合的中空微球结构。
夯实密度测量涉及填充吸附剂样品至100ml刻度的塑料圆筒中的60ml的水平,在RoTAP R-30050(WS Tayler,Inc)上自动夯实所述圆筒3000次,随后测量样品的最终体积和质量。夯实密度被定义为治理除以最终的体积。测量的相对误差为约±5%。因为中空微球的内部空隙,夯实密度低于固体颗粒或实心球,如图5中所示。一般情况下,中空微球比用与中空微球相同的方法除未用聚合物模板外制成的固体颗粒轻约30%,比用与中空微球相同的方法除未用聚合物模板外制成的固体微球轻20%。
在Micromeritics TriStar 3000孔隙率分析器上得到N2孔隙率_数据。首先在300℃下将0.3-0.5克样品脱气6小时,然后在液氮中平衡。基于BET方法计算总表面积。使用单一点总孔体积计算之间的半径的孔的孔体积(PV)。通过BET使用4V/A的方法计算平均孔直径(PD)。表1示出了中空微球Al2O3和ZrO2/Al2O3与通过煅烧假勃姆石无喷雾干燥而得到的固体氧化铝颗粒相比的N2孔隙率数据。在550℃下,在空气中煅烧新样品2小时。陈化的样品在750℃下用10%H2O于空气中蒸汽陈化20小时。
表1:中空微球氧化铝对固体氧化铝颗粒的N2孔隙率
实施例2:含有镧或钡稳定剂的中空微球氧化铝的制备。
通过初湿浸渍法用镧或钡水溶液浸渍根据实施例1制备的中空微球氧化铝。干燥糊状物,粉碎,并在550℃下在空气中煅烧2小时。在最终煅烧的粉末中的镧或钡的干增益为4%。La-稳定的或Ba-稳定的中空微球氧化铝分别被认定为HMA-La4和HMA-Ba4。为比较,用固体氧化铝颗粒(未喷雾干燥的)或实心球形氧化铝颗粒替代中空微球氧化铝(未使用聚合物模板而喷雾干燥的)。
实施例3:含有承载于中空微球氧化铝上的钯的单层芯催化剂的制备。
通过将中空微球氧化铝或La-稳定的或Ba-稳定的中空微球氧化铝用硝酸钯水溶液浸渍来制备含有中空球氧化铝的粉末催化剂。在110℃下干燥浸渍的糊状物过夜,粉碎,并在550℃下在空气中煅烧2小时。氧化铝上钯的干增益(DG)为2%。
通过混合2%Pd/氧化铝粉末与氧化铝粘合剂和去离子水来制成涂覆浆料。所述浆料被球研磨,得到D90粒度约10μm。所述浆料被涂覆在陶瓷整体蜂窝芯(1英寸直径×1英寸高度)上。干燥涂覆的芯,随后在550℃下在空气中煅烧2小时。芯上粉末的DG为0.60克/芯,同时得到25克/ft3的贵金属负载。为比较,用参比La-稳定的氧化铝颗粒或La-稳定的实心球氧化铝替代中空微球氧化铝,同时保持其它催化剂组合物不变。
实施例4:完全调配的催化剂部分的制备
(1)底部催化层的配制。将20%水性溶液形式的钯组分和13%水性溶液形式的铂组分与La-稳定的中空微球氧化铝和水混合以形成通过初湿浸渍法得到的湿粉末。分别的,将20%水性溶液形式的钯组分与OSC材料和水混合以形成通过初湿浸渍法得到的湿粉末。混合两种湿粉末,并研磨至D90粒度为约20μm。添加氧化铈-氧化锆、辛醇、乙酸、氧化铝粘合剂和乙酸锆,并在行星式混合器(P-混合器)中与Pd/载体混合物合并。用本领域已知的用于沉积催化剂于金属基底上的沉积法将浆料涂覆在金属载体载物上。在涂覆后,干燥具有底部催化层的载物,然后在550℃下在空气中煅烧2小时。最终底部涂覆催化剂组合物含有下列组分:La-稳定的中空微球氧化铝54.7%的干增益(DG)、OSC 41.0%的DG、氧化钡2.7%的DG、钯1.6%的DG及铂0.01%的DG。
(2)顶部涂覆催化层的调配。使用所述底部涂覆基本相似的过程将由承载于OSC材料上的铑和铂组成的第二催化层涂覆于所述第一催化层(底部涂覆)。最终顶部涂覆催化剂层组合物含有下列组分:OSC 69.6%的DG、Zr-稳定的氧化铝27.8%的DG、ZrO2 2.3%的DG、铑0.19%的DG及铂0.08%的DG。为了比较,在底涂覆中用参比的La-稳定的氧化铝颗粒替代中空微球氧化铝,同时保持其它催化剂组合物不变。
实施例5:使用实验室反应器在单层芯催化剂上评估催化剂活性
在流通式反应器中,40,000hr-1的空间速度用如下气体组合物评估实施例3中制备的单层Pd/氧化铝催化剂芯的催化性能:CO约0.5-5.6%;CO210%,HC 1350ppm(C3H6/C3H8=2);NO 400ppm;H2O约6-7%。λ随CO/O2变化来匹配富(λ约0.93)和贫(λ约1.04)条件。在900℃下,10%H2O于空气中进行蒸汽陈化4小时。催化剂性能表示起燃温度T50,其被定义为污染物的转化率达到其初始值的50%时的温度。结果示于图6中。含有La-稳定的或Ba-稳定的中空微球氧化铝的催化剂表现出对于CO、HC和NO比含有传统固体La-稳定的氧化铝颗粒的参比催化剂显著低的T50值(或高的催化剂活性)。
实施例6:完全调配的催化剂的摩托车评估
在摩托车应用中,在发动机运作条件下测试根据实施例4的含有中空多孔微球氧化铝的完全调配的催化剂部分。常规的固体颗粒氧化铝催化剂(40g/ft3Pt/Pd/Rh=1/20/2)与承载相同催化剂的中空多孔微球相比。在900℃下于空气和氮气中通过蒸汽陈化共8小时后评估CO、HC和NO转化率。结果示于图7中。使用中空微球催化剂的CO转化率比参比催化剂优20%,HC转化率比参比催化剂优1%,并且NO转化率比参比催化剂优41%。
虽然已经参照具体实施方案描述了本发明,但应理解,这些实施方案仅仅是本发明的原理和应用的说明。对本领域技术人员来说,可以对本发明的方法和装置进行各种修改和变化而不偏离本发明的精神和范围,这是显而易见的。因此,意图是本发明包括所附权利要求及其等效方案的范围之内的修改和变化。
Claims (15)
1.一种包含中空金属氧化物微球的组合物,所述微球包含具有约1-5微米厚度的围绕中空中央的壁,其中所述中空金属氧化物微球的D90直径为约5-15微米。
2.根据权利要求1所述的组合物,其还包含催化剂。
3.根据权利要求2所述的组合物,其中所述催化剂被并入所述中空金属氧化物微球的壁中。
4.根据权利要求2或3所述的组合物,其还包含选自由下列组成的组的稳定剂:镧系元素、碱土金属、硅、过渡金属或它们的组合。
5.根据权利要求4所述的组合物,其中所述稳定剂为4%La。
6.根据权利要求2-5中任一项所述的组合物,其中所述催化剂为铂族金属催化剂。
7.一种用于内燃机中的催化剂制品,其包含形成于基底上的催化层,所述催化层包含权利要求2-6中任一项所述的组合物。
8.根据权利要求7所述的催化剂制品,其中所述基底为整体基底。
9.根据权利要求7或8所述的催化剂制品,其中所述基底为金属基底。
10.一种处理包含烃、一氧化碳和/或氮氧化物的发动机废气的方法,所述方法包括在适于氧化一氧化碳、氧化烃和/或还原氮氧化物的条件下使所述废气与权利要求7-9中任一项所述的催化剂制品接触。
11.一种排放物处理系统,其包括与发动机废气流进行排放物流动连通的催化剂制品,其中所述催化剂制品包含形成于基底上的催化层,所述催化层包含权利要求2-6中任一项所述的组合物。
12.根据权利要求11所述的排放物处理系统,其还包括柴油氧化催化剂、柴油颗粒过滤器、催化部分氧化催化剂、氨氧化催化剂、水气变换催化剂、蒸汽重整催化剂、还原剂喷射器、空气喷射器、烃喷射器和选择性催化还原催化剂中的至少一种。
13.一种制备中空金属氧化物微球的方法,其包括:
a)将可热降解的软质聚合物溶解于水性介质中以形成所述聚合物的胶束模板;
b)用所述溶解的聚合物模板浆化一种或多种金属氧化物前体的纳米颗粒或水溶性盐;
c)对所述浆料进行喷雾干燥;并且
d)煅烧所述喷雾干燥的浆料来热降解所述聚合物模板,从而形成中空金属氧化物微球。
14.根据权利要求13所述的方法,其还包括将催化剂在喷雾干燥之并入所述浆料之中。
15.根据权利要求13所述的方法,其还包括将催化剂在喷雾干燥之后浸渍于所述微球之中。
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- 2013-12-19 CA CA2895843A patent/CA2895843A1/en not_active Abandoned
- 2013-12-19 CN CN201380066413.3A patent/CN104853827B/zh not_active Expired - Fee Related
- 2013-12-19 KR KR1020157019086A patent/KR102194005B1/ko active IP Right Grant
- 2013-12-19 EP EP13818925.3A patent/EP2934721A1/en not_active Withdrawn
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CN107500246A (zh) * | 2017-08-30 | 2017-12-22 | 北京三聚环保新材料股份有限公司 | 一种催化剂微球成型部件及其应用 |
CN107500246B (zh) * | 2017-08-30 | 2019-06-04 | 北京三聚环保新材料股份有限公司 | 一种催化剂微球成型部件及其应用 |
CN111601691A (zh) * | 2017-09-11 | 2020-08-28 | 哈佛大学 | 包含多分散聚合物纳米球的微球和多孔金属氧化物微球 |
CN113597416A (zh) * | 2019-03-12 | 2021-11-02 | 巴斯夫欧洲公司 | 成型人造聚合物制品 |
WO2021083267A1 (zh) * | 2019-10-31 | 2021-05-06 | 中国石油化工股份有限公司 | 载体、ft合成催化剂及其制备方法和应用 |
CN112588288A (zh) * | 2020-11-20 | 2021-04-02 | 湖南省吉安特技术有限公司 | 一种铑-铝复合氧化物纳米空心粉体的制备方法 |
CN112588288B (zh) * | 2020-11-20 | 2022-06-14 | 湖南省吉安特技术有限公司 | 一种铑-铝复合氧化物纳米空心粉体的制备方法 |
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CN115254132B (zh) * | 2021-04-30 | 2024-03-12 | 中国石油化工股份有限公司 | 一种焦炉气加氢脱硫催化剂及其应用 |
CN114735763A (zh) * | 2022-04-01 | 2022-07-12 | 青岛爱尔家佳新材料股份有限公司 | 一种中空多壳层金属氧化物及其制备方法和用于方舱的防爆聚脲 |
CN114735763B (zh) * | 2022-04-01 | 2023-11-21 | 青岛爱尔家佳新材料股份有限公司 | 一种中空多壳层金属氧化物及其制备方法和用于方舱的防爆聚脲 |
Also Published As
Publication number | Publication date |
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RU2015129342A (ru) | 2017-01-26 |
BR112015014404A2 (pt) | 2017-08-22 |
CN104853827B (zh) | 2019-02-19 |
CA2895843A1 (en) | 2014-06-26 |
US9358533B2 (en) | 2016-06-07 |
US20140178262A1 (en) | 2014-06-26 |
JP6396922B2 (ja) | 2018-09-26 |
KR20150096733A (ko) | 2015-08-25 |
KR102194005B1 (ko) | 2020-12-22 |
MX2015008006A (es) | 2015-10-22 |
JP2016502929A (ja) | 2016-02-01 |
EP2934721A1 (en) | 2015-10-28 |
WO2014100387A1 (en) | 2014-06-26 |
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