CN107107024B - 氧化铈颗粒及其生产方法 - Google Patents
氧化铈颗粒及其生产方法 Download PDFInfo
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- CN107107024B CN107107024B CN201580062246.4A CN201580062246A CN107107024B CN 107107024 B CN107107024 B CN 107107024B CN 201580062246 A CN201580062246 A CN 201580062246A CN 107107024 B CN107107024 B CN 107107024B
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- cerium
- cerium oxide
- oxide particles
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- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 96
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000002245 particle Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims description 38
- 230000008569 process Effects 0.000 title claims description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000005498 polishing Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims description 46
- 239000000725 suspension Substances 0.000 claims description 38
- 239000002244 precipitate Substances 0.000 claims description 35
- 229910052684 Cerium Inorganic materials 0.000 claims description 31
- 238000001354 calcination Methods 0.000 claims description 26
- -1 cerium cations Chemical class 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- 150000001450 anions Chemical class 0.000 claims description 21
- 150000000703 Cerium Chemical class 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 18
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 150000007514 bases Chemical class 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- OKJMLYFJRFYBPS-UHFFFAOYSA-J tetraazanium;cerium(4+);tetrasulfate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OKJMLYFJRFYBPS-UHFFFAOYSA-J 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims 1
- 229910052777 Praseodymium Inorganic materials 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 16
- 239000003426 co-catalyst Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000919 ceramic Substances 0.000 abstract description 4
- 239000006096 absorbing agent Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 abstract description 3
- 239000007784 solid electrolyte Substances 0.000 abstract description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 229910002651 NO3 Inorganic materials 0.000 description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical class O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000005639 Lauric acid Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical class OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 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 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
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- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
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- 239000011149 active material Substances 0.000 description 1
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- 239000001361 adipic acid Substances 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940056585 ammonium laurate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- VJCJAQSLASCYAW-UHFFFAOYSA-N azane;dodecanoic acid Chemical compound [NH4+].CCCCCCCCCCCC([O-])=O VJCJAQSLASCYAW-UHFFFAOYSA-N 0.000 description 1
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
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- KKFPIBHAPSRIPB-UHFFFAOYSA-N cerium(3+);oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Ce+3].[Ce+3] KKFPIBHAPSRIPB-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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Abstract
本发明涉及具有优异的耐热性的氧化铈颗粒,这些氧化铈颗粒对于催化剂、功能陶瓷、燃料电池用固体电解质、抛光、紫外线吸收剂等是尤其有用的,并且特别适合例如在用于净化车辆排气的催化中用作催化剂或助催化剂材料。本发明还涉及一种用于制备此类氧化铈颗粒的方法,以及一种例如用于使用这些氧化铈颗粒净化排气的催化剂。
Description
本发明涉及具有优异的耐热性的氧化铈颗粒,这些氧化铈颗粒对于催化剂、功能陶瓷、燃料电池用固体电解质、抛光、紫外线吸收剂等是尤其有用的,并且特别适合例如在用于净化车辆排气的催化中用作催化剂或助催化剂材料。本发明还涉及一种用于制备此类氧化铈颗粒的方法,以及一种例如用于使用这些氧化铈颗粒净化排气的催化剂。
现有技术
提供现有技术的以下讨论以便将本发明置于适当的技术背景下并使它的优点能够得到更充分的理解。然而,应当理解的是在整个说明书中现有技术的任何讨论不应被视为明确的或暗含的承认如此的现有技术是广泛已知的或形成本领域公知常识的一部分。
用于净化车辆排气的催化剂由诸如铂、钯、或铑的催化金属和用于增强这种金属的催化作用的助催化剂构成,两者都负载在由例如氧化铝或堇青石制成的催化剂载体上。作为这种助催化剂材料,使用具有源自于氧化铈的在氧化气氛下吸收氧气并在还原气氛下解吸氧气的特性(即氧气吸收和解吸能力)的含氧化铈的材料。具有这种氧气吸收和解吸能力,这些含氧化铈的材料以优异的效率净化排气中的有害组分,如烃类、一氧化碳、和氮氧化物。因此,使用大量的含氧化铈的材料作为助催化剂。
活化这种含氧化铈的助催化剂材料的功能最关键的是将该助催化剂保持在高温下。排气的低温(例如在发动机启动时)将导致低的净化效率。车辆制造商目前正试图通过将催化剂体系靠近发动机放置为了在从发动机将其排放到催化剂体系之后立即引入热排气来解决这个问题。还存在对于在较低的温度下活化的助催化剂材料的需要。
通常,用催化剂进行排气处理的效率与催化剂的活性相与排气之间的接触面积、以及助催化剂材料(如氧化铈)的氧气吸收和解吸能力成比例。因此,助催化剂材料需要具有足够大的比表面积和足够高的氧气吸收和解吸能力、以及在较低温度下的高活性。
为了解决这些问题,US 7,361,322 B2提出了一种用于获得具有良好的耐热性的氧化铈的方法,该氧化铈在900℃下煅烧5小时后具有高于30.0m2/g、尤其约40-50m2/g的比表面积,该方法包括以下步骤:
(a)提供铈溶液,其中不少于90mol%的铈为四价铈阳离子,所述铈溶液具有以氧化铈计的10至60g/L的铈浓度;
(b)在加热下将在步骤(a)中制备的所述铈溶液保持在60℃至220℃下;
(c)冷却所述加热的铈溶液;
(d)将沉淀剂加入到所述冷却的铈溶液中以得到沉淀物;并且
(e)煅烧所述沉淀物。
然而,似乎通过这种方法得到的这些氧化铈的比表面积的耐热性仍不足够。
此外,除了催化剂载体的比表面积的耐热性之外,还需要总孔体积的耐热性。总孔体积的高耐热性通常是指在如新鲜的和800℃的催化剂载体的两种不同老化条件的比较中孔体积的减小比率小。在以贵金属的形式将活性物质(例如活性金属)装载到催化剂载体上的情况下,贵金属以良好的可分散性装载到孔中。因此,希望即使在高温下也具有大的孔体积的氧化铈。
仍然存在提供具有较高的耐热性以及氧气吸收和解吸能力的氧化铈的需要,其可用作催化剂或适用于诸如用于净化排气的催化剂的助催化剂材料。
发明
因此,本发明的目的是提供具有优异的耐热性以及吸附和解吸能力的氧化铈(氧化铈(IV)),该氧化铈对于催化剂、功能陶瓷、燃料电池用固体电解质、抛光、紫外线吸收剂等是有用的,并且特别适合特别是在用于净化车辆排气的催化中用作催化剂或助催化剂材料。本发明的氧化铈颗粒还提供了总孔体积和比表面积的高耐热性。特别地,本发明的氧化铈颗粒能够即使在高温环境中使用时保持大的比表面积。这些氧化铈颗粒也能够在较低的温度范围内表现出高的氧气吸收和解吸能力。本发明还涉及一种用于制备这些氧化铈颗粒的方法,以及一种用于使用所述氧化铈颗粒净化排气的催化剂。
本发明的氧化铈颗粒还提供高的NOx捕获性能,然后允许从汽车的NOx排放的减少,以便遵守严格的污染物规定。然后这些氧化铈颗粒还对于NOx捕集(LNT)催化剂是有用的。
本发明然后涉及具有以下特性的氧化铈颗粒:
-在空气中在800℃下煅烧2小时后包括在80与120m2/g之间的比表面积(SBET);
-在空气中在900℃下煅烧5小时后包括在55与80m2/g之间的比表面积(SBET);
-在空气中在800℃下煅烧2小时后包括在0.9与1.6ml/g之间的总孔体积;以及
-在空气中在900℃下煅烧5小时后包括在0.85与1.5ml/g之间的总孔体积。
本发明还涉及一种用于制备氧化铈颗粒的方法,该方法至少包括以下步骤:
(a)提供包含阴离子和阳离子的铈盐溶液,其中在90与100mol%之间的铈阳离子是四价铈阳离子;
(b)在包括在60℃与220℃之间的温度下加热所述铈盐溶液,以获得包含液体介质和沉淀物的悬浮液;
(c)与在步骤(b)中的该液体介质中包含的所述阴离子相比,减少在10与90mol%之间的来自存在于该液体介质中的铈盐的阴离子的浓度;
(d)在包括在100℃与300℃之间的温度下加热在步骤(c)中获得的该悬浮液;
(e)任选地冷却在步骤(d)中获得的该悬浮液;
(f)使所述悬浮液与碱性化合物接触;
(g)任选地从该液体介质中分离出该沉淀物;
(h)向在步骤(f)中获得的该悬浮液或在步骤(g)中获得的该沉淀物中添加有机质构剂;
(i)任选地从该液体介质中分离出该沉淀物;并且
(j)煅烧在步骤(h)结束时获得的或在步骤(i)中获得的该沉淀物以获得氧化铈颗粒;本发明的所述方法至少包括所述步骤(g)和/或所述步骤(i)。
本发明还涉及易于通过该方法获得的氧化铈颗粒。
本发明的其他特征、细节和优点将在阅读下面的说明之后甚至更充分地显露。
定义
贯穿本说明,包括权利要求书,术语“包含一个/一种”应理解为是与术语“至少包含一个/一种”同义,除非另外指明,并且“在…之间”应理解为包含极限值。
应指出,为了本说明书的连续性,除非另外指明,极限值包括在给定值的范围内。
除非另外指明,含量以氧化物计给出。氧化铈是呈氧化铈(CeO2)的形式。
为了本说明书的连续性,术语“比表面积”应理解为是指根据期刊“美国化学学会杂志(The Journal of the American Chemical Society),60,309(1938)”中描述的布鲁诺-埃梅特-特勒(Brunauer-Emmett-Teller)法制定的标准ASTM D3663-78由氮气吸附确定的BET比表面积。
如在此所用的,术语“烷基”旨在是指:通过从烷烃除去氢而获得的具有式CnH2n+1的含有在1与22个之间的碳原子、有利地在1与10个之间的碳原子的饱和脂族烃基的基团。该烷基可以是直链或支链的。举例而言,这些烷基包括具有一个或多个碳原子的饱和烃,包括直链烷基,如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基;环状烷基(或“环烷基”或“脂环族的”或“碳环型的”基团),如环丙基、环戊基、环己基、环庚基、以及环辛基;支链烷基,如异丙基、叔丁基、仲丁基、以及异丁基;以及烷基取代的烷基,如烷基取代的环烷基以及环烷基取代的烷基。在复杂结构中,这些链可以是支链的或桥联的。
本发明的细节
根据本发明的方法,首先在步骤(a)中提供至少包含阴离子和阳离子的铈盐溶液,例如铈阳离子,其中在90与100mol%之间的铈阳离子中是四价的。在步骤(a)中,该铈盐溶液可优选为硝酸铈溶液、硝酸铈铵溶液、硫酸铈溶液和/或硫酸铈铵溶液。铈盐是通常由酸和碱的中和反应或用酸溶解铈化合物(如氢氧化铈)产生的离子化合物。它们由铈阳离子和阴离子构成,使得产物是电中性的。所述铈盐溶液优选为其中该液体介质为水的铈盐水溶液。
本发明的铈盐溶液可以具有包括在5与150g/L之间的以氧化铈表示的铈阳离子浓度。例如,225g/L的硝酸铈的浓度相当于100g/L的CeO2;318g/L的硝酸铈铵的浓度相当于100g/L的CeO2;193g/L的硫酸铈的浓度相当于100g/L的CeO2;270g/L的硫酸铈铵的浓度相当于100g/L的CeO2。
铈溶液的铈盐浓度可以通常用水、优选用去离子水以氧化铈计在10与120g/L之间、更优选在15与100g/L之间调节。
步骤(a)中的铈盐溶液可以具有通常在0.01与1N之间的初始酸浓度。酸,如HNO3或H2SO4,可以来自铈盐原料溶液或作为溶液的稳定剂加入。
根据本发明的方法,接着将在步骤(a)中制备的铈盐溶液在加热下保持在60℃与220℃之间,以引起步骤(b)中的铈溶液的反应,以获得包含液体介质和特别包含氢氧化铈的沉淀物的悬浮液。
任何反应容器可以在步骤(b)中使用而没有严格的限制,并且可以使用密封容器或开放容器。特别地,可以优选地使用高压釜反应器。
在步骤(b)中,温度是包括在60℃与220℃之间、优选在80℃与180℃之间、更优选在90℃与160℃之间。加热处理的持续时间通常是在10分钟与48小时之间、优选在30分钟与36小时之间、更优选在1小时与24小时之间。如果铈溶液在加热下不能充分保持,沉淀物的结晶度可能不会改进,导致目标氧化铈的不充足的耐热性。
在步骤(c)中,与步骤(b)中的液体介质中包含的阴离子相比,来自于存在于液体介质中的铈盐的阴离子的浓度在10与90mol%之间、优选在15与85mol%之间降低。如果在步骤(a)和(b)中存在相同量的阴离子,可以计算与步骤(a)或(b)中的液体介质中包含的阴离子相比步骤(c)中的液体介质中的阴离子的减少。
来自铈盐的阴离子可以是例如来自硝酸铈的硝酸根或来自硫酸铈的硫酸根。
存在于液体介质中的阴离子浓度的这种减少可以通过以下方法中的至少一种获得:
-向步骤(b)中获得的悬浮液中加入水、优选去离子水;和/或
-从步骤(b)中获得的悬浮液中除去液体介质的至少一部分,并且然后向介质中加入水、优选去离子水。所述介质根据如先前表述的液体介质的部分去除或完全去除来定义;即,在步骤中液体介质的完全去除的情况下介质可以是沉淀物,或相反地在液体介质的部分去除的情况下是沉淀物和液体介质的混合物。
液体介质与沉淀物的分离可以例如通过努彻(Nutsche)过滤法、离心、压滤或倾析进行。
根据本发明,液体介质的部分去除或完全去除应理解为是指液体介质部分地或完全地从沉淀物中除去。例如,可以在步骤(c)中去除步骤(b)中存在的按重量计在10%与100%之间、优选按重量计在10%与90%之间、更优选按重量计在15%与95%之间、尤其按重量计在20%与90%之间的液体介质。
与步骤(b)中的液体介质中包含的阴离子相比,在步骤(c)中的液体介质中存在的阴离子的浓度的降低可以在硝酸铈的情况下如下计算:
在步骤(a)开始时的材料是Ce(IV)(NO3)4和Ce(III)(NO3)3以及任选地HNO3。
1.NO3 -离子的总数(mol)的计算
NO3 -(mol)=A/172.12*[B/100*4+(100-B)/100*3]+C=D
其中:
-A是在步骤(a)中以CeO2计的铈阳离子的量(克)
-B是在步骤(b)开始时每总铈阳离子的四价铈阳离子的百分比
-C是步骤(a)中的HNO3的量(mol)(如果有的话)
2.步骤(b)中NO3 -浓度的计算
[NO3 -](mol/l)=D/E
其中E是步骤(b)中的反应介质的体积(升)。B可以是测量目录,如使用量筒或计量器。
3.步骤(c)中的NO3 -浓度的计算
[NO3 -](mol/l)=F/G
-F是NO3 -离子的量(mol)。如果液体介质未被去除,则F=D。如果液体介质被去除,则F=D*液体介质的去除率。
-G是加水后的体积(升)。
4.NO3 -浓度的降低比率
-[NO3 -]的降低比率(%)=步骤(c)中的[NO3 -]/步骤(b)中的[NO3 -]*100=(F/G)/(D/E)*100
还有可能用步骤(b)和(c)的NO3 -浓度的直接测量进行。NO3 -浓度可以通过离子色谱法或吸附测量仪(adsorptiometer)进行分析,这两种仪器通常用于分析液体介质中的NO3 -浓度。将液体介质的一部分放入分析仪中以自动测量NO3 -浓度。然后可以比较两种浓度来计算NO3 -浓度的降低比率。
在步骤(d)中,将悬浮液在包括在100℃与300℃之间、优选包括在110℃与150℃之间的温度下加热。可以使用任何反应容器而没有严格的限制,并且可以使用密封容器或开放容器。特别地,可以优选地使用高压釜反应器。加热处理的持续时间通常是在10分钟与48小时之间、优选在30分钟与36小时之间。
在步骤(d)之后,加热的悬浮液可以在任选的步骤(e)中冷却。悬浮液通常可以在搅拌下冷却。用于冷却的手段不是关键的,并且该悬浮液可以在大气中冷却或用冷却管强制冷却。在冷却后该悬浮液的温度可以是包括在20℃与90℃之间。
根据步骤(f),然后向悬浮液、或已经冷却的悬浮液中加入碱性化合物。
该碱性化合物可以是例如氢氧化钠、氢氧化钾、氨水溶液、氨气、或其混合物,其中优选氨水溶液。可以通过首先以合适的浓度制备碱性化合物的水溶液并且在搅拌下将溶液加入到步骤(e)中制备的冷却的悬浮液中来加入碱性化合物,或者当使用氨气时通过在搅拌下将氨气吹入反应容器中来加入碱性化合物。碱性化合物的量可以通过追踪溶液的pH变化来容易地确定。通常,足够量是使得溶液的pH不低于7,并且优选量是使得pH在7与9之间。
碱性化合物对于在步骤(d)或(e)结束时分散在悬浮液中的沉淀物Ce3+离子是尤其有用的,以形成Ce(OH)3沉淀物。
在步骤(g)中,液体介质与沉淀物的分离可以例如通过努彻过滤法、离心、压滤或倾析进行。该沉淀物可以任选地用水、优选用处于碱性pH的水(例如氨水溶液)洗涤。此外,沉淀物可以任选地被干燥。
可以使步骤(f)中获得的悬浮液或步骤(g)中获得的沉淀物经受在包括在90℃与220℃之间、优选在100℃与180℃之间、更优选在110℃与160℃之间的温度下的热处理步骤。加热处理的持续时间通常是在10分钟与48小时之间、优选在30分钟与36小时之间、更优选在1与24小时之间。
还有可能在该方法的步骤(c)后与步骤(h)之前的任何点添加稀土元素化合物,例如呈硝酸盐、氯化物、氧化物、氢氧化物、碳酸盐、卤化物、卤氧化物、含氧硝酸盐、和/或硫酸盐形式的稀土元素。稀土元素(REE)或稀土金属是周期表中的十七种化学元素集合(是指十五种镧系元素加上钪和钇)中的一种。优选地,稀土元素氧化物是在由以下各项组成的组中选择:氧化镧(La2O3)、氧化镨(Pr6O11)、氧化钕(Nd2O3)和氧化钇(Y2O3)。
通过本发明的方法获得的氧化铈颗粒除了氧化铈之外可以然后包含例如以按氧化物的重量计包括在1%与40%之间的比例、优选地以按氧化物的重量计包括在1%与20%之间的比例的至少一种稀土元素氧化物。氧化物在这里是指定义为氧化铈和稀土元素氧化物的整合的最终混合氧化物。
在步骤(h)中,向在前述步骤(f)中获得的悬浮液或一旦从液体介质中分离的在步骤(g)中获得的沉淀物中加入有机质构剂。
有机质构剂通常是指能够控制或改变氧化铈的介孔结构的有机化合物,如表面活性剂。“介孔结构”基本上描述了尤其包含具有包括在2与50nm之间的平均直径的孔的结构,通过术语“介孔”描述。典型地,这些结构是无定形或结晶化合物,其中这些孔通常以非常宽的孔径分布以随机方式分布。
有机质构剂可以直接或间接添加。它可以直接加入由前一步骤所产生的悬浮液或沉淀物中。也可以首先将其加入组合物中,该组合物例如包含有机质构剂的溶剂,并且然后将所述组合物加入如前面获得的悬浮液或沉淀物中。
所使用的有机质构剂的量,表示为添加剂相对于以CeO2计的铈的重量的重量百分比,通常是在5%与100%之间并且更特别地在15%与60%之间。
有机质构剂可被吸附在沉淀物的次级颗粒和初级颗粒的表面上。例如,吸附在初级颗粒上的有机质构剂将导致介孔的尺寸和沉淀物的孔体积的增加。
有机质构剂优选选自下组,该组由以下各项组成:阴离子表面活性剂、非离子表面活性剂、聚乙二醇、羧酸及其盐、以及羧甲基化的脂肪醇乙氧基化物型的表面活性剂。关于这种添加剂,可以参考申请WO-98/45212的传授内容,并且可以使用在这个文件中描述的表面活性剂。
作为阴离子类型的表面活性剂,可以提及的是乙氧基羧酸盐,乙氧基化的脂肪酸,肌胺酸盐,磷酸酯,硫酸盐如醇硫酸盐、醇醚硫酸盐和硫酸化烷醇酰胺乙氧基化物,以及磺酸盐如磺基琥珀酸盐,以及烷基苯或烷基萘磺酸盐。
作为非离子表面活性剂,可以提及的是炔属表面活性剂、醇乙氧基化物、烷醇酰胺、氧化胺、乙氧基化的烷醇酰胺、长链的乙氧基化的胺、环氧乙烷/环氧丙烷的共聚物、脱水山梨醇衍生物、乙二醇、丙二醇、甘油、聚甘油酯以及其乙氧基化的衍生物、烷基胺、烷基咪唑啉、乙氧基化的油以及烷基酚乙氧基化物。特别可以提及的是以商标和销售的产品。
关于羧酸,具体地可以使用脂肪族一元羧酸或二元羧酸,并且在这些之中,更特别地是饱和酸。也可以使用脂肪酸并且更特别地饱和脂肪酸。因此,特别可以提及的是甲酸、乙酸、丙酸、丁酸、异丁酸、戊酸、己酸、辛酸、癸酸、月桂酸、肉豆蔻酸和棕榈酸。作为二元羧酸,可以提及的是草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸和癸二酸。
还可以使用羧酸的盐,具体地铵。
举例而言,更特别地可以提及的是月桂酸和月桂酸铵。
最终,可以使用选自羧甲基化的脂肪醇乙氧基化物型的那些的表面活性剂。
表述“羧甲基化的脂肪醇乙氧基化物型的产品”旨在是指由在链的末端包含CH2-COOH基团的乙氧基化或丙氧基化的脂肪醇组成的产品。
这些产品可对应于下式:
R1-O-(CR2R3-CR4R5-O)n-CH2-COOH
其中R1表示饱和或不饱和的碳基链,其长度通常是最多22个碳原子、优选地至少12个碳原子;R2、R3、R4和R5可以是相同的并且可以表示氢或者另外R2可以表示烷基如CH3基团并且R3、R4和R5表示氢;n是可以最高达50并且更具体地在5与15之间(这些值包括在内)的非零整数。将注意的是,表面活性剂可以由具有上式的产品(其中R1可以分别是饱和或不饱和的)或者可替代地,包含–CH2-CH2-O-和–C(CH3)-CH2-O-基团二者的产品的混合物组成。
任选地,在步骤(i)中,例如通过努彻过滤法、离心、或压滤将沉淀物从液体介质中分离出来。该沉淀物可以任选地用水溶液、优选用处于碱性pH的水(例如氨水溶液)洗涤。此外,该沉淀物可以任选地被干燥至适当的程度,用于提高后续步骤的效率。
在步骤(j)中,将上述步骤中得到的沉淀物煅烧以得到作为本发明目的的氧化铈颗粒。
本发明的方法然后包括从沉淀物中分离液体介质的步骤(g)、或者从液体介质中分离出沉淀物的步骤(i)、或步骤(g)和步骤(i)两者;以便进行在步骤(h)结束时获得的或在步骤(i)中获得的沉淀物的煅烧以获得氧化铈颗粒。
在步骤(j)中,煅烧温度可以合适地选自通常在250℃与900℃之间的范围。可以如所希望的进行温度的选择,这取决于比表面积和堆密度的所要求的值。从制备其中比表面积是重要的催化剂或助催化剂材料的实际的观点看,步骤(j)中的煅烧温度可以优选是在250℃与800℃之间、更优选在250℃与700℃之间、最优选在280℃与450℃之间。煅烧的持续时间可以适当地根据温度确定,并且优选可以是在1与20小时之间。
在步骤(j)之后,通常可以将所获得的氧化铈颗粒粉碎。该粉碎可以在常用的粉碎机(如锤磨机)中充分进行,以获得具有所希望的粒度的粉末。通过本发明的方法获得的氧化铈可以通过上述粉碎产生希望的粒度。为了在用于净化排气的催化剂中用作助催化剂,例如,氧化铈的优选平均粒度是在0.5与50μm之间。
本发明的氧化铈颗粒具有以下特性:
-在空气中在800℃下煅烧2小时后包括在80与120m2/g之间的比表面积(SBET);优选包括在90与120m2/g之间。
-在空气中在900℃下煅烧5小时后包括在55与80m2/g之间的比表面积(SBET);优选包括在60与80m2/g之间。
-在空气中在800℃下煅烧2小时后包括在0.9与1.6ml/g之间的总孔体积;优选包括在1.1与1.6ml/g之间。
-在空气中在900℃下煅烧5小时后包括在0.85与1.5ml/g之间的总孔体积;优选包括在1.0与1.5ml/g之间。
总孔体积可以通过普通水银测孔仪测量。
氧化铈颗粒可以具有在800℃下煅烧2小时后获得的包括在0.5与0.7之间的S1/S2比。氧化铈颗粒可以具有在900℃下煅烧5小时后获得的包括在0.3与0.5之间的S1/S2比。
所述S1/S2比是由基线和TPR曲线在200℃至600℃的温度范围内限定的面积(S1)与由所述基线和所述TPR曲线在600℃至1000℃的温度范围内限定的面积(S2)的比率。预期氧化铈的较高的S1/S2比导致较高的氧气吸收和解吸能力以及在较低温度下较高的净化排气的活性。如在此使用的,“基线”是指从对应于200℃的TPR曲线上的点平行于表示温度的轴直到1000℃绘制的线段。
本发明的氧化铈可以优选通过根据本发明的将在以下讨论的生产方法以良好的可再现性并且以经济方式制备。
氧化铈颗粒除了氧化铈之外还可以包含例如以按氧化物的重量计包括在1%与40%之间的比例、优选地以按氧化物的重量计包括在1%与20%之间的比例的至少一种稀土元素氧化物。氧化物在这里是指定义为氧化铈和稀土元素氧化物的整合的最终混合氧化物。
如上述的或者如通过先前描述的制备方法得到的氧化铈颗粒可以呈粉末的形式,但是它们可以任选地被成形以便呈具有可变尺寸的颗粒、粒料、泡沫、珠粒、圆柱或蜂窝的形式。
本发明还涉及一种至少包含如前所定义的氧化铈颗粒的催化剂,例如用于净化排气的催化剂。
本发明的氧化铈颗粒可以原样或在组合物内施用到在催化领域中常用的任何载体上,也就是说具体地是热惰性载体。这种载体可以选自氧化铝、氧化钛、氧化铈、氧化锆、二氧化硅、尖晶石、沸石、硅酸盐、结晶硅铝磷酸盐或结晶磷酸铝。
根据本发明的用于净化排气的催化剂可以是任何类型,只要该催化剂具有包含本发明的氧化铈的助催化剂。催化剂可以例如通过通常已知的方法并且用通常已知的其他材料生产。
本发明还涉及一种至少包含如先前获得并且定义的氧化铈颗粒的组合物、优选液体组合物。更优选地,所述组合物是至少包含如先前获得并且定义的液体介质和氧化铈颗粒的悬浮液。
根据本发明的实施例,本发明还涉及如所定义和/或如在上述确定的方法中获得的氧化铈颗粒用于抛光应用的用途。例如,可以获得至少包含本发明的氧化铈颗粒的用于抛光的组合物如悬浮液。这种组合物可以,例如在晶体制造或镜子工业、平板玻璃、电视屏幕或眼镜中用于抛光玻璃,亦或用于抛光陶瓷或玻璃质类型的其他材料。这种组合物还可以最特别地用于电子工业中的CMP型抛光并且因此用于抛光构成微处理器的金属基底,以及还有用于抛光这些同样微处理器的绝缘层或夹层电介质(ILD)层,本发明的悬浮液特别适合用于抛光所述层。化学机械平坦化(CMP)是能够实现浅沟道隔离(STI)的关键过程,其在当前的集成电路制造方法中使用以实现装置隔离。这些层通常由二氧化硅(如掺杂的二氧化硅或多孔二氧化硅)制成。这种悬浮液也可以用于金属CMP,该金属CMP用于集成电路中的布线和屏障,抛光光掩模衬底(尤其由合成石英玻璃制成)。
总体上,除具有磨料特性的化合物(如这些氧化铈颗粒)之外,此类组合物包含多种添加剂如分散剂和/或氧化剂。
本发明还涉及一种用于除去衬底的一部分的方法,例如在CMP操作中,该方法包括:
-至少提供包含本发明的氧化铈颗粒的组合物,例如悬浮液,
-至少使该组合物与该有待抛光的衬底相接触,并且
-在该衬底上进行抛光。
以下实例被包括来说明本发明的实施例。不用说,本发明并不限于描述的实例。
实验部分
实例1
按量配给以CeO2计含有不小于90mol%的四价铈阳离子的50g硝酸铈溶液,并且用去离子水调节到1L的总量。将所获得的溶液加热到100℃,保持在此温度下持续30分钟,并且使其冷却到25℃,从而获得铈悬浮液。
在将母液从由此获得的铈悬浮液中除去之后,用去离子水将总体积调节到1L;与加热后液体介质中所含的阴离子相比,阴离子浓度因此降低了44%。
然后将该铈悬浮液保持在120℃下2小时,使其冷却,并且用氨水中和到pH 8.5。
向由中和产生的浆料中加入12.5g的月桂酸,并且搅拌60分钟。
通过努彻过滤器使获得的浆料经受固-液分离以获得滤饼。将该饼在空气中在300℃下煅烧10小时以获得氧化铈粉末。
在800℃下煅烧2小时并且在900℃下煅烧5小时之后通过BET方法测量所获得的复合氧化物粉末的比表面积。
实例2
以与实例1中相同的方式制备氧化铈粉末,除了与加热后在液体介质中包含的阴离子相比阴离子的浓度降低了39%之外。
以与实例1中相同的方式评估由此获得的氧化物粉末的特性。
实例3
以与实例1中相同的方式制备氧化铈粉末,除了加入12.5g的癸酸代替月桂酸之外。
以与实例1中相同的方式评估由此获得的氧化物粉末的特性。
对比实例1
根据在专利公开物US 7,361,322 B2中披露的方法制备氧化铈粉末。
按量配给以CeO2计含有不小于90mol%的四价铈离子的20g的硝酸铈溶液,并且用去离子水调节到1L的总量。将所获得的溶液加热到100℃,保持在此温度下持续24小时,并且使其冷却到室温。然后添加氨水以中和至pH 8,以获得呈浆料形式的氧化铈水合物。
然后用努彻过滤器使该浆料经受固-液分离以获得滤饼。将该饼在空气中在300℃下煅烧10小时以获得氧化铈粉末。
以与实例1中相同的方式评估由此获得的氧化物粉末的特性。
对比实例2
以与对比实例1中相同的方式制备氧化铈,除了在加入氨水后加入5.0g的月桂酸并且搅拌60分钟之外。
对比实例3
以与对比实例1中相同的方式制备氧化铈,除了在获得铈悬浮液之后除去母液之外。
对比实例4
以与实例1中相同的方式制备氧化铈,除了在获得铈悬浮液之后没有除去母液之外。
在上述定义的实例中制备的氧化铈的特性在表1中提及。
表1
分析方法的描述
BET:比表面积是按以下方式通过BET方法测量的。使用Mountech有限公司(Mountech Co.,LTD)的Macsorb分析仪使用200mg已经预先在空气中在800℃下煅烧2小时或在900℃下煅烧5小时的样品。
TPR:使用由大仓理研株式会社(Okura Riken Co.,LTD.)制造的具有含有90%氩气和10%氢气的载气的程序升温脱附分析仪以30ml/min的气体流速、以13.3℃/min的测量期间的样品加热速率并且使用已经预先在空气中在800℃下煅烧2小时或在900℃下煅烧5小时的0.5g的样品进行TPR。
S1/S2比,是由基线和TPR曲线在200℃至600℃的温度范围内限定的面积(S1)与由基线和TPR曲线在600℃至1000℃的温度范围内限定的面积(S2)的比率。
TRP曲线以Y轴的TCD(热导检测器)信号和X轴的温度表示。氧化铈的较高的S1/S2比涉及较高的氧气吸收和解吸能力以及在较低温度下较高的净化排气的活性。如在此使用的,“基线”是指从对应于200℃的TPR曲线上的点平行于表示温度的轴直到1000℃绘制的线段。
Hg孔隙率:通过压汞式孔隙率测定法按以下方式测量总孔体积。使用Micromeritics AutoPore IV 9500使用200mg已经预先在空气中在800℃下煅烧2小时或在900℃下煅烧5小时的样品。
实例2:低温NOx储存能力测试
将实例1和对比实例1的氧化铈在空气中在800℃下煅烧4h。然后按以下方式测量NOx储存能力:合成气体混合物(30L/h),代表使用组合物A的催化过程,在120℃下在90min期间通过150mg的置于固定床反应器中的氧化铈冲洗。由于Antaris IGS FTIR光谱仪,根据时间在线监测所储存的NOx的量。
组合物A
(vol%) | |
NO | 0.014 |
NO<sub>2</sub> | 0.018 |
H<sub>2</sub>O | 5 |
CO<sub>2</sub> | 5 |
O<sub>2</sub> | 10 |
N<sub>2</sub> | 余量 |
实例1和对比实例1的两种氧化铈在90min时的NOx吸附示于表2中:
表2
然后看来本发明的氧化铈具有比常规的氧化铈更高的NOx捕获性能。NSC(NOx储存能力)是评估NOx排放性能的指示。
Claims (17)
1.一种用于制备氧化铈颗粒的方法,该方法至少包括以下步骤:
(a)提供包含阴离子和阳离子的铈盐溶液,其中在90与100mol%之间的铈阳离子是四价铈阳离子;
(b)在包括在60℃与220℃之间的温度下加热所述铈盐溶液,以获得包含液体介质和沉淀物的悬浮液,加热处理的持续时间在10分钟与48小时之间;
(c)与在步骤(b)中的该液体介质中包含的所述阴离子相比,减少在10与90mol%之间的来自存在于该液体介质中的铈盐的阴离子的浓度,阴离子浓度的降低通过从步骤(b)中获得的该悬浮液中除去该液体介质的至少一部分并且然后向该介质中加入水来获得;
(d)在包括在100℃与300℃之间的温度下加热在步骤(c)中获得的该悬浮液;
(e)任选地冷却在步骤(d)中获得的该悬浮液;
(f)使所述悬浮液与碱性化合物接触;
(g)任选地从该液体介质中分离出该沉淀物;
(h)向在步骤(f)中获得的该悬浮液或在步骤(g)中获得的该沉淀物中添加有机质构剂,该有机质构剂选自下组,该组由以下各项组成:阴离子表面活性剂、非离子表面活性剂、聚乙二醇、羧酸及其盐、以及羧甲基化的脂肪醇乙氧基化物型的表面活性剂;
(i)任选地从该液体介质中分离出该沉淀物;并且
(j)煅烧在步骤(h)结束时获得的或在步骤(i)中获得的该沉淀物以获得氧化铈颗粒;本发明的所述方法至少包括所述步骤(g)和/或所述步骤(i)。
2.根据权利要求1所述的方法,其中步骤(a)中的该铈盐溶液选自下组,该组由以下各项组成:硝酸铈溶液、硝酸铈铵溶液、硫酸铈溶液和/或硫酸铈铵溶液。
3.根据权利要求1所述的方法,其中步骤(a)中的该铈盐溶液具有包括在5与150g/L之间的以氧化铈计的铈浓度。
4.根据权利要求1所述的方法,其中所述加热处理的持续时间在30分钟与36小时之间。
5.根据权利要求1所述的方法,其中所述加热处理的持续时间在1小时与24小时之间。
6.氧化铈颗粒,易于通过根据权利要求1至5中任一项所述的方法获得。
7.氧化铈颗粒,具有以下特性:
-在空气中在800℃下煅烧2小时后包括在80与120m2/g之间的比表面积(SBET);
-在空气中在900℃下煅烧5小时后包括在55与80m2/g之间的比表面积(SBET);
-在空气中在800℃下煅烧2小时后包括在0.9与1.6ml/g之间的总孔体积;以及
-在空气中在900℃下煅烧5小时后包括在0.85与1.5ml/g之间的总孔体积。
8.根据权利要求7所述的氧化铈颗粒,其中所述颗粒具有在800℃下煅烧2小时后获得的包括在0.5与0.7之间的S1/S2比。
9.根据权利要求7所述的氧化铈颗粒,其中所述颗粒具有在900℃下煅烧5小时后获得的包括在0.3与0.5之间的S1/S2比。
10.根据权利要求8所述的氧化铈颗粒,其中所述颗粒具有在900℃下煅烧5小时后获得的包括在0.3与0.5之间的S1/S2比。
11.根据权利要求7至10中任一项所述的氧化铈颗粒,其中所述氧化铈颗粒包含至少一种除氧化铈之外的稀土元素氧化物。
12.根据权利要求11所述的氧化铈颗粒,其中所述稀土元素选自由La,Pr,Nd和Y组成的组。
13.一种催化剂,至少包含通过根据权利要求1至5中任一项所述的方法获得的氧化铈颗粒或根据权利要求6至12中任一项所述的氧化铈颗粒。
14.根据权利要求13所述的催化剂,其中所述催化剂是用于净化排气的包含这些氧化铈颗粒的助催化剂。
15.一种组合物,至少包含通过根据权利要求1至5中任一项所述的方法获得的氧化铈颗粒或根据权利要求6至12中任一项所述的氧化铈颗粒。
16.根据权利要求15所述的组合物,其中所述组合物是至少包含液体介质和通过根据权利要求1至5中任一项所述的方法获得的氧化铈颗粒或根据权利要求6至12中任一项所述的氧化铈颗粒的悬浮液。
17.一种用于除去衬底的一部分的方法,该方法包括:
-至少提供包含通过根据权利要求1至5中任一项所述的方法获得的氧化铈颗粒或根据权利要求6至12中任一项所述的氧化铈颗粒的组合物
-至少使该组合物与该有待抛光的衬底相接触,并且
-在该衬底上进行抛光。
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