CN1582258A - 二氧化铈及其制备法和废气净化用催化剂 - Google Patents
二氧化铈及其制备法和废气净化用催化剂 Download PDFInfo
- Publication number
- CN1582258A CN1582258A CNA028221060A CN02822106A CN1582258A CN 1582258 A CN1582258 A CN 1582258A CN A028221060 A CNA028221060 A CN A028221060A CN 02822106 A CN02822106 A CN 02822106A CN 1582258 A CN1582258 A CN 1582258A
- Authority
- CN
- China
- Prior art keywords
- cerium
- hours
- cerium dioxide
- calcinings
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 17
- 229940044927 ceric oxide Drugs 0.000 title abstract 6
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000005352 clarification Methods 0.000 title 1
- 238000001354 calcination Methods 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052684 Cerium Inorganic materials 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 22
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000000746 purification Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007669 thermal treatment Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 239000003426 co-catalyst Substances 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 25
- 229910000420 cerium oxide Inorganic materials 0.000 description 15
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 15
- 239000012065 filter cake Substances 0.000 description 10
- 239000004570 mortar (masonry) Substances 0.000 description 10
- 238000010298 pulverizing process Methods 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000004438 BET method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- -1 cerium ion Chemical class 0.000 description 5
- 235000014347 soups Nutrition 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QIICBUVIQUVXPN-UHFFFAOYSA-N cerium(4+);oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[Ce+4] QIICBUVIQUVXPN-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0207—Compounds of Sc, Y or Lanthanides
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- 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
- B01J35/31—Density
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
- C01P2006/13—Surface area thermal stability thereof at high temperatures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
实质上仅由二氧化铈构成,在900℃煅烧5小时后的比表面积为30.0m2/g以上的二氧化铈、其制备方法以及使用该二氧化铈的废气净化用催化剂,其中所述二氧化铈作为适于废气净化用催化剂的助催化剂,具有优良的耐热性和吸收放出氧的能力,即使在高温环境下使用也能维持高比表面积,在高温下使用时仍能维持在低温域的吸收放出氧的能力。
Description
技术领域
本发明涉及具有优良耐热性的二氧化铈及其制备法和使用了该二氧化铈的废气净化用催化剂,所述二氧化铈可用于催化剂、功能陶瓷、燃料电池用的固体电解质等,特别可优选用作汽车的废气净化用催化剂中的助催化剂材料。
背景技术
汽车等的废气净化用催化剂由在氧化铝、堇青石等催化剂载体上附载催化金属铂、钯或铑以及用于提高这些金属的催化作用的助催化剂构成。作为该助催化剂材料的二氧化铈系材料因为能通过在氧化气氛下吸收氧气,在还原气氛下放出氧气这一二氧化铈的特性,即通过吸收放出氧气的能力高效地净化废气中的有害成分烃、一氧化碳及氧化氮而被大量使用。
使这类助催化剂材料发挥功效最重要的条件是维持高温,而象发动机启动时那样废气温度低的情况,则净化率差。近年汽车制造商,用缩短引擎与催化剂装置的距离,把排气后的高温气体直接导入催化剂装置的方式来解决这个问题。此外,期待能在低温度下更具有活性的助催化剂材料。
催化剂对废气处理的效率一般与催化剂的活性相和废气的接触面积成比例,此外因为与助催化剂材料二氧化铈所具有的吸收放出氧气的能力成比例,因此所使用的助催化剂材料必须充分增大它的比表面积和吸收放出氧气的能力,而且提高更低温下的活性。
因此作为具有优良耐热性的二氧化铈的制备法,在日本专利特公平7-61863号公报中有提案,即把在pH6~约10的反应媒介中沉淀得到的二氧化铈用压热器在100~350℃处理后,在300~1000℃煅烧得到二氧化铈的制备法。但通过该方法得到的二氧化铈在900℃煅烧后的比表面积是15m2/g,不能说具有充分的耐热性。
此外,日本专利特开2001-89143号公报、特开2000-281343号公报、特许第2789313号说明书、特开2000-128537号公报中,也提到了改善了OSC能的铈系氧化物。但是这些都是在二氧化铈中固溶了至少一种以上元素的复合氧化物,与高纯度的二氧化铈不同。
而且日本专利特公平3-24478号公报、特公平3-24411号公报、特许2537662号说明书中,记载了将硝酸高铈水溶液回流、过滤加水分解的产物、洗净、干燥、煅烧的二氧化铈制备方法。但是这个方法得到的二氧化铈,耐热性低、在900℃煅烧5小时后的比表面积不过10m2/g以下。
发明内容
本发明的目的是提供二氧化铈及其制备法以及使用该二氧化铈的废气净化用催化剂,该二氧化铈特别是作为适用于废气净化催化剂的助催化剂,具有优良的耐热性和吸收放出氧气的能力,即使在高温环境下使用仍能维持较高的比表面积,而且即使在更高温环境下使用时,也能维持低温域的吸收放出氧气的能力。
本发明者们为解决上述课题进行了深入的探讨,首先关于通过以前的技术得到的二氧化铈即使在持有大比表面积的情况下,如果高温加热,比表面积仍会急剧下降的原因,对二氧化铈的前体二氧化铈水化物的结晶性对上述情况的影响进行了详细的研究。其结果是确认:通过以前已知的得到具有良好耐热性的二氧化铈的方法,即将铈溶胶、铈盐水溶液或它们的混合液干燥后得到的二氧化铈前体的结晶性,可能因为微结晶而对热能极敏感,在高温域烧结及结晶生长明显,不能维持高比表面积。因此在尝试提高前体阶段的结晶度的反复试验后,开发出了在高温、氧化气氛下提高前体结晶度的反应法,从而完成了本发明。
本发明提供二氧化铈,其为实质上仅由二氧化铈构成的氧化物,在900℃煅烧5小时后得到的比表面积是30.0m2/g以上。
本发明提供上述二氧化铈的制备方法,该方法包括下述步骤:准备90mol%以上的铈离子为4价的铈溶液的步骤(a),将步骤(a)准备的铈溶液加热保持在60~220℃的步骤(b),将加热保持的铈溶液冷却的步骤(c),通过向冷却后的铈溶液中添加沉淀剂而得到沉淀物的步骤(d)和沉淀物煅烧步骤(e)。
本发明还提供具备含上述二氧化铈的助催化剂的废气净化用催化剂。
附图简述:
图1是实施例1和9以及比较例1和2中测定得到的TPR曲线的图表。
发明的优选实施方式
以下对本发明进行更详细的说明。
本发明的二氧化铈是实质上仅由二氧化铈构成的氧化物,在900℃煅烧5小时后的比表面积在30.0m2/g以上,优选40.0m2/g以上,更优选50.0m2/g以上。在900℃煅烧5小时后的比表面积没有特定的上限限定,但通常是100m2/g左右。
本发明的二氧化铈具有较高的比表面积,通常,如果在250℃煅烧5小时,比表面积在180m2/g以上;如果在300℃煅烧5小时,比表面积在160m2/g以上;如果在800℃煅烧5小时,比表面积在40.0m2/g以上;如果在900℃煅烧5小时,比表面积在30.0m2/g以上;如果在1000℃煅烧5小时,比表面积在20.0m2/g以上。在这样的煅烧温度下具有高水平比表面积的二氧化铈是以前不知道的。一般在加热氧化物粉末时,在依据组成及该粉末的制造过程而定的特定温度域之上,烧结及结晶生长明显,会产生急剧的比表面积下降。对于二氧化铈,已知在大约800℃以上,此减少明显,废气净化用催化剂装置通常也要考虑这些原料的耐热性进行设计。
如上所述,本发明的二氧化铈因为在900℃煅烧5小时后仍有较高的比表面积,因此今后可作为需要在900℃左右的高温下使用的助催化剂材料。
本发明中的比表面积是指按照作为粉末比表面积测定法的最标准的通过氮气吸附进行的BET法测定的值。
本发明的二氧化铈在1000℃煅烧5小时后,200~600℃温度域的TPR曲线和基线所围面积(S1)与600~1000℃的温度域的TPR曲线和基线所围面积(S2)之比S1/S2通常在0.120以上,优选0.150以上,更优选0.190以上。所谓S1/S2在0.120以上,是指在1000℃高温下煅烧后,在600℃以下的低温域表现出良好的还原性。S1/S2越高,二氧化铈的吸收放出氧气的能力及低温下的废气净化活性可望越高。这里基线是指在200℃的TPR曲线上的点平行于温度轴引到1000℃止的线的部分。
前述TPR是使用(株)大仓理研制的自动升温脱离分析装置(装置名TP-5000),在载气:90%氩气-10%氢,气体流量:30ml/分钟,测定中样品升温速度:13.3℃/分钟,样品重量0.5g条件下测定的值。
本发明的二氧化铈,在900℃煅烧5小时后,在400℃的评价中,OSC在0.60mlO2/g/s以上为宜。OSC的上限没有特别的限定,通常为2.0mlO2/g/s。具有这样高水平OSC能的二氧化铈以前是不知道的。汽车废气净化用催化剂中,很重视以二氧化铈为代表的助催化剂材料的OSC能及其活性温度。汽车废气净化用催化剂通常在没有升温到一定温度时不起作用,结果废气中的有害成分未经净化就排出了。因此如何在低温下表现良好的OSC能,为大家所关注。本发明的二氧化铈因为显示出上述优良的OSC性能,作为汽车废气净化用催化剂极为有用。
本发明中上述的OSC是将30mg在大气中于900℃保持5小时后冷却至常温的样品升温到400℃,使2种载气(95%He-5%CO,及97.5%He-2.5%O2)以1秒间隔、流量200ml/分钟交替流动,通过质量分析仪,测定样品通过后的CO和O2的量,根据下式求的值:
OSC(mg/g/s)=(ΔCO×rCO)/2×WT
式中,ΔCO表示单位时间的CO减少量,rCO表示CO气体的流量,WT表示样品的重量。
本发明的二氧化铈在300℃煅烧10小时后的堆积密度通常是1.3g/ml以下,特别优选1.2g/ml以下。堆积密度的下限没有特别限定,但通常为0.80g/ml左右。该堆积密度可通过将10g在300℃煅烧10小时后的二氧化铈装入20ml的气缸中,以堆积高度2cm,堆积次数200次测定。
本发明的二氧化铈在300℃煅烧10小时后的微孔体积通常是0.50ml/g以上,特别优选0.60ml/g以上。微孔体积的上限没有特别限定,但通常为1.5ml/g。该微孔体积通常可用水银压入法测定。
为了具有良好再现性且经济地配制,优选通过如下所示本发明的制备法进行本发明的二氧化铈的制备。
在本发明的制备法中,首先进行步骤(a),即,准备90mol%以上铈离子为4价的铈溶液。
在步骤(a)中,90mol%以上铈离子为4价的铈溶液可优选使用硝酸高铈溶液。该硝酸高铈溶液的初期物理性质,用二氧化铈换算浓度,每1升有250g份,其初期的酸浓度通常是0.1~1N。该初期酸浓度与反应的酸浓度相关,如果酸浓度过低,则后述的沉淀物结晶性不会提高,最终得到的二氧化铈的耐热性可能会低下。而如果酸浓度过高,则在形成铈沉淀的中和反应中需要过剩的碱,这对工业生产不利。
因此上述铈溶液的酸浓度,用二氧化铈换算浓度,通常是5~150g/L,优选10~120g/L,更优选15~100g/L。铈溶液的配制通常可用水,特别优选用去离子水。
在本发明的制备法中,接着进行步骤(b),将步骤(a)准备的铈溶液加热保持在60~220℃,使铈溶液反应,步骤(b)所使用的反应器并不重要,密闭型的容器、开放型的容器都可以,优选压热反应器。
步骤(b)中加热保持的温度是60~220℃,优选80~180℃,更优选90~160℃。加热保持时间通常是10分钟~48小时,优选30分钟~36小时,更优选1小时~24小时。如果加热保持不充分,则后述的沉淀结晶性不会提高,有可能最后得到的二氧化铈的耐热性不足。如果保持加热时间过长,虽然对耐热性影响很小,但对工业生产不利。
在本发明的制备法中,步骤(b)后,通常进行将加热保持后的铈溶液冷却的步骤(c)。
步骤(c)中的冷却通常可以在搅拌下进行,冷却的手段没有临界限定,可以自然慢慢冷却,也可以用冷凝管强制冷却。冷却温度通常在60℃以下,优选室温以下。通过该步骤(c)的冷却,得到前体液体。
在本发明的制备法中,接着进行通过向上述冷却后的溶液中添加沉淀剂,得到沉淀物的步骤(d)。
作为步骤(d)所用的沉淀剂有:NaOH、氢氧化钾、氨水、氨气,或它们的混合物的碱。特别优选氨水。
上述沉淀剂的添加可通过例如:把沉淀剂配成适当浓度的水溶液,边搅拌边加入到步骤(c)得到的前体溶液中的方式,或氨气的场合,可以通过边搅拌边向反应器中吹入的方法实施。沉淀剂的添加量,可以通过追踪溶液的PH变化很容易地进行控制。通常溶液的PH在7以上时,添加量就充分,优选PH7~8的添加量。
通过步骤(d)的沉淀反应,可以使结晶生长的产物形成沉淀。该产物就是本发明的得到二氧化铈的合适前体。该前体可以通过例如Nutsche法、离心分离法或压滤法进行分离。此外也可以附加进行必要程度的沉淀物水洗。进而,为提高下一个步骤(e)的效率,也可以附加对沉淀物进行适度干燥的步骤。
此外,为了进一步提高最终得到的二氧化铈的耐热性,也可以在步骤(e)之前,进行步骤(d-1),即把步骤(d)得到的沉淀物用水等溶剂进行分散,通常在60~220℃,优选在80~180℃,更优选在90~160℃热处理后,再度得到沉淀。上述的热处理时间,通常是10分钟~48小时,优选30分钟~36小时,更优选1小时~24小时。
在本发明的制备法中,接着通过煅烧得到沉淀物的步骤(e),可以得到所希望的二氧化铈。
步骤(e)中的煅烧温度通常可以在250~900℃间任意选择。虽然可由要求或保证的比表面积及堆密度的值任意选择该煅烧温度,但是作为重视比表面积的助催化剂材料,从实用的观点出发,优选250~800℃,更优选250~700℃,进一步优选280~450℃。煅烧时间可以结合温度进行适当的设置,优选1~10小时。
步骤(e)后通常可以将得到的二氧化铈粉碎,所述粉碎可以用一般的粉碎机如锤磨机进行,能得到具有所需粒度的粉末。
通过本发明的制备法得到的二氧化铈的粒径虽然可以通过上述粉碎得到所需粒径,但在例如作为废气净化用催化剂的助催化剂使用时,优选平均粒径1~50μm。
本发明的废气净化用催化剂,除了具备含本发明二氧化铈的助催化剂之外,没有特别的限制,其制备方法、其他材料等都可以使用公知的东西。
本发明的二氧化铈具有高比表面积,特别是在900℃煅烧5小时后可保持至少30.0m2/g的比表面积,因而可以替代以前的二氧化铈,特别是作为废气用催化剂的助催化剂等使用。因此,可用于效率高于以前的废气净化用催化剂领域。
通过本发明的制备法可以再现性好且经济地得到上述二氧化铈。
实施例
以下通过实施例和比较例更详细地说明本发明,但本发明并不限于此。
实施例1
取用二氧化铈换算为20g份的含有90mol%以上4价铈离子的硝酸高铈溶液后,用纯水调整总量到1升。此时的二氧化铈换算浓度是20g/L,接着将得到的溶液导入压热反应器,升温到100℃,保持24小时后,自然冷却至室温。
接着加氨水中和至PH8,得到二氧化铈水合物的浆状物。将该浆状物真空吸滤过滤进行固液分离,分离母液后得到滤饼。将该滤饼放在箱型电炉内空气氛围中,在300℃煅烧10小时得到二氧化铈,接着用研钵粉碎得到二氧化铈粉末(以下称为粉末(A))。用BET法测定得到的粉末(A)的比表面积。此外分别用BET法测定粉末(A)在800℃煅烧2小时后的比表面积,粉末(A)在900℃煅烧5小时后的比表面积,粉末(A)在1000℃煅烧5小时后的比表面积。进而测定粉末(A)的堆积密度和微孔体积。此外测定粉末(A)在900℃煅烧5小时后得到的二氧化铈粉末在400℃的OSC能。这些结果如表1所示。
进一步进行粉末(A)在1000℃煅烧5小时后的TPR测定。结果如图1所示。接着测定粉末(A)在1000℃煅烧5小时后,200~600℃的温度域的TPR曲线和基线所围的面积(S1)与600~1000℃的温度域的TPR曲线和基线所围的面积(S2)之比(S1/S2)。结果如表1所示。
实施例2
除了配制的硝酸高铈溶液的加热保持温度、保持时间变成表1记载的条件外,其余步骤与实施例1一样,配制二氧化铈粉末。
实施例3
通过与实施例1一样的方法得到滤饼。将得到的滤饼投入压热反应器,用水分散使其再度浆化,并升温至100℃,保持一小时后,冷却至室温。将得到的浆状物真空吸滤过滤进行固液分离,再度得到滤饼。将这样得到的滤饼放在箱型电炉内空气氛围中,在300℃煅烧10小时,接着用研钵粉碎得到二氧化铈粉末。将得到的粉末进行与实施例1一样的各种测定,结果如表1所示。
实施例4~11
除了配制的硝酸高铈溶液的浓度、加热保持温度、保持时间变成表1记载的条件外,其余步骤与实施例3一样,制备二氧化铈粉末。将得到的粉末进行与实施例1一样的各种测定,结果如表1所示。此外对于实施例9,将在300℃煅烧10小时后研钵粉碎得到的二氧化铈粉末再在500℃煅烧5小时或在700℃煅烧5小时后,分别测定其堆积密度和微孔体积,结果也如表1所示。另外对于实施例9,与实施例1一样,将在300℃煅烧10小时后研钵粉碎得到的二氧化铈粉末再在1000℃煅烧5小时后,测定其TPR,结果如图1所示。
比较例1
以特公平7-61863号公报的例9的内容为基础,进行以下实验。
在室温下,向有效容积是2升的压热反应器中导入922ml含有150g/L CeO2的硝酸亚铈溶液和将38ml过氧化氢水溶液稀释至200ml而得到的溶液。接着在保持内容物温度是80℃条件下,添加用150ml3N的氨水,使内容物的PH达到9.5,然后在8℃条件下保持1小时得到沉淀物。之后真空吸滤并进行水洗分离沉淀物。
使所有的该沉淀物悬浮于150ml 1N氨水中,导入压热反应器。接着在160℃在进行4小时的压热釜处理。该热处理结束后,真空吸滤分离。将得到的二氧化铈粉末进行与实施例1一样的各种测定,结果如表2所示。此外与实施例9一样,测定500℃、5小时和700℃、5小时煅烧后的堆积密度和微孔体积,这些结果如表2所示。另外与实施例1一样,将在300℃煅烧10小时后乳钵粉碎得到的二氧化铈粉末在1000℃煅烧5小时后,测定其TPR,结果如图1所示。
比较例2
取二氧化铈换算为20g份的含有90mol%以上4价铈离子的硝酸高铈溶液后,用纯水调整总量到1升。此时的二氧化铈换算浓度是20g/L。接着通过压热反应器,不升温而直接用氨水中和至PH8,得到二氧化铈水合物的浆状物。将该浆状物真空吸滤进行固液分离,分离母液后得到滤饼。将该滤饼放在箱型电炉内空气氛围下,在300℃煅烧10小时,接着用研钵粉碎得到二氧化铈粉末。将得到的粉末进行与实施例1一样的各种测定,结果如表2所示。另外与实施例1一样,将在300℃煅烧10小时后研钵粉碎得到的二氧化铈粉末在1000℃煅烧5小时后,测定其TPR,结果如图1所示。
比较例3
与比较例2一样得到滤饼。将得到的滤饼用与实施例3同样的方法,进行热处理与煅烧,得到二氧化铈粉末。将得到的粉末进行与实施例1一样的各种测定,结果如表2所示。
此外,表1与表2中,REO浓度表示硝酸高铈溶液中铈的二氧化铈换算浓度。此外,BET(1)表示在300℃煅烧10小时后乳钵粉碎得到的二氧化铈粉末的通过BET法测定的比表面积值;BET(2)表示将BET(1)用过的粉末再在800℃煅烧2小时后的通过BET法测定的比表面积值;BET(3)表示将BET(1)用过的粉末再在900℃煅烧5小时后的通过BET法测定的比表面积值;BET(4)表示将BET(1)用过的粉末再在1000℃煅烧5小时后的通过BET法测定的比表面积值。此时,比表面积值的单位是m2/g。此外、堆积密度(1)表示在300℃煅烧10小时后乳钵粉碎得到的二氧化铈粉末的堆积密度;堆积密度(2)表示将堆积密度(1)用过的粉末进一步在500℃煅烧5小时后的堆积密度;堆积密度(3)表示将堆积密度(1)用过的粉末进一步在700℃煅烧5小时后的堆积密度。此时的堆积密度值的单位是g/ml。另外微孔体积(1)表示在300℃煅烧10小时后乳钵粉碎得到的二氧化铈粉末的微孔体积;微孔体积(2)表示将微孔体积(1)用过的粉末进一步在500℃煅烧5小时后的微孔体积;微孔体积(3)表示将微孔体积(1)用过的粉末进一步在700℃煅烧5小时后的微孔体积。此时的微孔体积值的单位是ml/g。
表1
实施例 | |||||||||||
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | |
REO浓度(g/L) | 20 | 20 | 20 | 15 | 25 | 40 | 60 | 20 | 20 | 10 | 30 |
温度(℃) | 100 | 130 | 100 | 100 | 100 | 100 | 100 | 100 | 120 | 120 | 120 |
时间(h) | 24 | 1 | 24 | 24 | 24 | 24 | 24 | 6 | 6 | 6 | 6 |
BET(1) | 175.4 | 155.1 | 197.4 | 236.6 | 213.4 | 166.0 | 172.0 | 241.4 | 217.1 | 215.3 | 220.0 |
BET(2) | 73.3 | 75.5 | 85.6 | 80.0 | 80.1 | 68.3 | 72.5 | 78.6 | 88.6 | 81.6 | 84.4 |
BET(3) | 33.6 | 36.6 | 47.7 | 44.6 | 42.3 | 31.1 | 30.8 | 40.7 | 48.0 | 53.2 | 50.3 |
BET(4) | 21.6 | 22.4 | 23.7 | 22.2 | 21.6 | 21.1 | 22.3 | 21.0 | 24.2 | 23.7 | 23.0 |
堆积密度(1) | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 | 1.2 | 1.2 | 1.1 | 1.1 | 1.1 | 1.1 |
堆积密度(2) | - | - | - | - | - | - | - | - | 1.1 | - | - |
堆积密度(3) | - | - | - | - | - | - | - | - | 1.1 | - | - |
微孔体积(1) | 0.65 | 0.63 | 0.71 | 0.68 | 0.65 | 0.66 | 0.66 | 0.63 | 0.74 | 0.72 | 0.75 |
微孔体积(2) | - | - | - | - | - | - | - | - | 0.76 | - | - |
微孔体积(3) | - | - | - | - | - | - | - | - | 0.83 | - | - |
OSC(ml2/g/s) | 0 63 | 0 65 | 1.05 | 1.01 | 0.98 | 0.61 | 0.61 | 0.94 | 1.08 | 1.27 | 1.20 |
S1/S2比 | 0.189 | 0.191 | 0.211 | 0.208 | 0.202 | 0.188 | 0.185 | 0.195 | 0.214 | 0.225 | 0.217 |
表2
比较例 | |||
1 | 2 | 3 | |
BET(1) | 140.8 | 100.5 | 105.6 |
BET(2) | 21.0 | 15.6 | 16.0 |
BET(3) | 16.0 | 9.40 | 9.20 |
BET(4) | 7.40 | 3.20 | 3.40 |
堆积密度(1) | 1.8 | 1.9 | 1.8 |
堆积密度(2) | 1.7 | - | - |
堆积密度(3) | 1.8 | - | - |
微孔体积(1) | 0.35 | 0.33 | 0.34 |
微孔体积(2) | 0.38 | - | - |
微孔体积(3) | 0.49 | - | - |
OSC(ml2/g/s) | 0.40 | 0.29 | 0.30 |
S1/S2比 | 0.108 | 0.077 | 0.071 |
Claims (9)
1、二氧化铈,其为实质上仅由二氧化铈构成的氧化物,在900℃煅烧5小时后的比表面积为30.0m2/g以上。
2、权利要求1的二氧化铈,其在1000℃煅烧5小时后,在200~600℃温度域的TPR曲线和基线所围的面积(S1)与在600~1000℃温度域的TPR曲线和基线所围的面积(S2)之比S1/S2为0.120以上。
3、权利要求1的二氧化铈,其在900℃煅烧5小时后,在400℃具有0.60mlO2/g/s以上的OSC。
4、权利要求1的二氧化铈,其在300℃煅烧10小时后的堆积密度在1.3g/ml以下。
5、权利要求1的二氧化铈,其在300℃煅烧10小时后的微孔体积在0.50ml/g以上。
6、权利要求1的二氧化铈的制备方法,该方法包括下述步骤:准备其中90mol%以上的铈离子为4价的铈溶液的步骤(a),将步骤(a)准备的铈溶液加热保持在60~220℃的步骤(b),冷却加热保持后的铈溶液的步骤(c),通过向冷却后的铈溶液中添加沉淀剂得到沉淀物的步骤(d)以及锻烧沉淀物的步骤(e)。
7、权利要求6的制备方法,其中步骤(a)的铈溶液中的铈浓度换算为二氧化铈浓度是5~150g/L,且步骤(e)的煅烧温度是250~900℃。
8、权利要求6的制备方法,该方法还包括在步骤(d)之后、步骤(e)之前,将步骤(d)所得的沉淀物在溶剂中于60~220℃热处理得到沉淀物的步骤(d1)。
9、废气净化用催化剂,该催化剂具备含权利要求1的二氧化铈的助催化剂。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP272054/2001 | 2001-09-07 | ||
JP2001272054 | 2001-09-07 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1582258A true CN1582258A (zh) | 2005-02-16 |
CN1290770C CN1290770C (zh) | 2006-12-20 |
Family
ID=19097479
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB028221060A Expired - Lifetime CN1290770C (zh) | 2001-09-07 | 2002-09-05 | 二氧化铈、其制备法和用于净化废气的催化剂 |
Country Status (8)
Country | Link |
---|---|
US (2) | US20040234438A1 (zh) |
EP (1) | EP1435338B1 (zh) |
JP (1) | JP4382482B2 (zh) |
KR (1) | KR100890773B1 (zh) |
CN (1) | CN1290770C (zh) |
CA (1) | CA2459496C (zh) |
DE (1) | DE60239212C5 (zh) |
WO (1) | WO2003022740A1 (zh) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103833569A (zh) * | 2012-11-23 | 2014-06-04 | 益海(连云港)精细化学工业有限公司 | 脂肪族羧酸酰胺的制备方法 |
CN109476495A (zh) * | 2016-05-18 | 2019-03-15 | 罗地亚经营管理公司 | 氧化铈颗粒及其生产方法 |
CN106040241B (zh) * | 2016-06-03 | 2019-04-26 | 浙江科技学院 | 一种废弃物沼渣制备非均相Fenton催化剂的方法和应用 |
CN111089763A (zh) * | 2019-11-28 | 2020-05-01 | 中国汽车技术研究中心有限公司 | 一种用于obd验证试验的临界汽车尾气催化剂制备方法 |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11181403A (ja) * | 1997-12-18 | 1999-07-06 | Hitachi Chem Co Ltd | 酸化セリウム研磨剤及び基板の研磨法 |
JP4602165B2 (ja) * | 2004-06-02 | 2010-12-22 | 財団法人電力中央研究所 | 揮発性有機化合物の分解除去法と分解除去用触媒 |
KR100640583B1 (ko) * | 2004-08-16 | 2006-10-31 | 삼성전자주식회사 | 산화세륨 연마 입자 및 그 제조 방법과 cmp용 슬러리조성물 및 그 제조 방법과 이들을 이용한 기판 연마 방법 |
TWI323741B (en) * | 2004-12-16 | 2010-04-21 | K C Tech Co Ltd | Abrasive particles, polishing slurry, and producing method thereof |
KR100641348B1 (ko) * | 2005-06-03 | 2006-11-03 | 주식회사 케이씨텍 | Cmp용 슬러리와 이의 제조 방법 및 기판의 연마 방법 |
JP4982692B2 (ja) * | 2006-03-17 | 2012-07-25 | Dowaエレクトロニクス株式会社 | 触媒用酸化セリウム粉体およびdpf |
FR2917646B1 (fr) | 2007-06-20 | 2011-06-03 | Anan Kasei Co Ltd | Oxyde mixte a haute surface specifique de cerium et d'autre terre rare, procede de preparation et utilisation en catalyse |
RU2560376C2 (ru) | 2009-12-25 | 2015-08-20 | Анан Касеи Ко., Лтд. | Сложный оксид, способ его получения и катализатор для очистки выхлопных газов |
JP5831946B2 (ja) * | 2011-01-14 | 2015-12-09 | 株式会社三徳 | 触媒の製造法 |
WO2014202149A1 (en) | 2013-06-21 | 2014-12-24 | Rhodia Operations | Composite oxide based on cerium oxide, silicon oxide and titanium oxide |
JP2015120844A (ja) * | 2013-12-24 | 2015-07-02 | 旭硝子株式会社 | 研磨剤の製造方法、研磨方法および半導体集積回路装置の製造方法 |
EP3020689A1 (en) * | 2014-11-12 | 2016-05-18 | Rhodia Operations | Cerium oxide particles and method for production thereof |
US11306052B2 (en) | 2014-12-22 | 2022-04-19 | Performance Polyamides, Sas | Cycloalkane oxidation catalysts and method to produce alcohols and ketones |
EP3070074A1 (en) | 2015-03-20 | 2016-09-21 | Rhodia Operations | Dehydration of alcohols |
WO2018040058A1 (en) * | 2016-09-02 | 2018-03-08 | Rhodia Operations | Dehydration of diols |
WO2019042911A1 (en) | 2017-08-29 | 2019-03-07 | Rhodia Operations | USE OF A MIXED OXIDE TO ABSORB NOX |
WO2019042910A1 (en) | 2017-08-29 | 2019-03-07 | Rhodia Operations | MIXED OXIDE WITH ENHANCED REDOX PROPERTIES |
FR3077566A1 (fr) | 2018-02-02 | 2019-08-09 | Rhodia Operations | Procede de preparation d'un oxyde a base de cerium et/ou de zirconium |
FR3077567A1 (fr) | 2018-02-02 | 2019-08-09 | Rhodia Operations | Procede de preparation d'un oxyde a base de cerium et/ou de zirconium |
EP3841063A4 (en) | 2018-08-24 | 2022-06-01 | Rhodia Operations | ALUMINOTITANOSILICATE MICROPOROUS CRYSTALLINE ZEOLITE, METHOD FOR PREPARATION AND APPLICATIONS |
EP3902771A1 (en) | 2018-12-28 | 2021-11-03 | Rhodia Operations | Cerium oxide particles and method for production thereof |
US11548791B2 (en) | 2020-11-24 | 2023-01-10 | Lynas Rare Earths Limited | Materials, methods and techniques for generating doped cerium oxide |
EP4347116A1 (en) | 2021-05-28 | 2024-04-10 | Rhodia Operations | Composition of aluminium oxide and cerium oxide with a particular porosity profile |
KR20240041366A (ko) | 2021-07-30 | 2024-03-29 | 로디아 오퍼레이션스 | 산화알루미늄과 산화세륨의 조성물 |
CN114368774B (zh) * | 2021-12-20 | 2024-02-13 | 兰州大学 | 一种多孔氧化铈的制备方法及处理氮氧化物的方法 |
WO2023242394A1 (en) | 2022-06-17 | 2023-12-21 | Rhodia Operations | Suspension of cerium oxide particles |
WO2024133613A1 (de) | 2022-12-22 | 2024-06-27 | Umicore Ag & Co. Kg | Reformierungskatalysator, herstellung desselben, verwendung desselben zur erzeugung von wasserstoff sowie vorrichtung zur stromerzeugung |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2559755A1 (fr) * | 1984-02-20 | 1985-08-23 | Rhone Poulenc Spec Chim | Oxyde cerique a nouvelles caracteristiques morphologiques et son procede d'obtention |
FR2559754A1 (fr) * | 1984-02-20 | 1985-08-23 | Rhone Poulenc Spec Chim | Oxyde cerique a nouvelles caracteristiques morphologiques et son procede d'obtention |
FR2617153B1 (fr) * | 1987-06-26 | 1991-04-05 | Rhone Poulenc Chimie | Procede d'obtention d'un oxyde cerique et oxyde cerique a nouvelles caracteristiques morphologiques |
EP0300853B1 (fr) * | 1987-06-29 | 1991-09-18 | Rhone-Poulenc Chimie | Procédé d'obtention d'un oxyde cérique |
US5174984A (en) * | 1987-06-29 | 1992-12-29 | Rhone-Poulenc Chimie | Ceric oxide with new morphological characteristics and method for obtaining same |
FR2617154B1 (fr) * | 1987-06-29 | 1990-11-30 | Rhone Poulenc Chimie | Procede d'obtention d'oxyde cerique et oxyde cerique a nouvelles caracteristiques morphologiques |
US5279789A (en) * | 1988-12-23 | 1994-01-18 | Rhone-Poulenc Chimie | Ceric oxide particulates having improved morphology |
FR2640954B1 (zh) * | 1988-12-23 | 1991-03-29 | Rhone Poulenc Chimie | |
FR2640953B1 (zh) * | 1988-12-23 | 1991-02-08 | Rhone Poulenc Chimie | |
JP2641108B2 (ja) * | 1990-06-21 | 1997-08-13 | 大日精化工業株式会社 | 酸化セリウム微粉体の製造方法 |
JP2794645B2 (ja) * | 1991-10-15 | 1998-09-10 | 三徳金属工業株式会社 | 酸素吸収・放出能を有する酸化セリウム及びその製造法 |
AU1670597A (en) * | 1996-02-07 | 1997-08-28 | Hitachi Chemical Company, Ltd. | Cerium oxide abrasive, semiconductor chip, semiconductor device, process for the production of them, and method for the polishing of substrates |
JPH11330015A (ja) * | 1996-03-29 | 1999-11-30 | Hitachi Chem Co Ltd | 酸化セリウム研磨剤及び基板の製造法 |
JP4053623B2 (ja) * | 1996-12-27 | 2008-02-27 | 阿南化成株式会社 | ジルコニウム−セリウム系複合酸化物及びその製造方法 |
DE19714707A1 (de) * | 1997-04-09 | 1998-10-15 | Degussa | Sauerstoff speicherndes Material mit hoher Temperaturstabilität sowie Verfahren zu seiner Herstellung |
US6200143B1 (en) * | 1998-01-09 | 2001-03-13 | Tessera, Inc. | Low insertion force connector for microelectronic elements |
US6887566B1 (en) * | 1999-11-17 | 2005-05-03 | Cabot Corporation | Ceria composition and process for preparing same |
WO2002090260A1 (en) * | 2001-05-07 | 2002-11-14 | The Trustees Of Columbia University In The City Of New York | Apparatus and method for preparing cerium oxide nanoparticles |
US7025943B2 (en) * | 2002-05-15 | 2006-04-11 | The Curators Of The University Of Missouri | Method for preparation of nanometer cerium-based oxide particles |
US20050113249A1 (en) * | 2003-11-24 | 2005-05-26 | Robin Ziebarth | Catalyst for a diesel particulate filter |
-
2002
- 2002-09-05 CA CA2459496A patent/CA2459496C/en not_active Expired - Lifetime
- 2002-09-05 CN CNB028221060A patent/CN1290770C/zh not_active Expired - Lifetime
- 2002-09-05 US US10/488,826 patent/US20040234438A1/en active Pending
- 2002-09-05 JP JP2003526823A patent/JP4382482B2/ja not_active Expired - Lifetime
- 2002-09-05 KR KR1020047003356A patent/KR100890773B1/ko active IP Right Grant
- 2002-09-05 EP EP02767896A patent/EP1435338B1/en not_active Expired - Lifetime
- 2002-09-05 DE DE60239212.8T patent/DE60239212C5/de not_active Expired - Lifetime
- 2002-09-05 WO PCT/JP2002/009025 patent/WO2003022740A1/ja active Application Filing
-
2007
- 2007-02-09 US US11/673,352 patent/US7361322B2/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103833569A (zh) * | 2012-11-23 | 2014-06-04 | 益海(连云港)精细化学工业有限公司 | 脂肪族羧酸酰胺的制备方法 |
CN103833569B (zh) * | 2012-11-23 | 2016-12-21 | 丰益高分子材料(连云港)有限公司 | 脂肪族羧酸酰胺的制备方法 |
CN109476495A (zh) * | 2016-05-18 | 2019-03-15 | 罗地亚经营管理公司 | 氧化铈颗粒及其生产方法 |
CN106040241B (zh) * | 2016-06-03 | 2019-04-26 | 浙江科技学院 | 一种废弃物沼渣制备非均相Fenton催化剂的方法和应用 |
CN111089763A (zh) * | 2019-11-28 | 2020-05-01 | 中国汽车技术研究中心有限公司 | 一种用于obd验证试验的临界汽车尾气催化剂制备方法 |
Also Published As
Publication number | Publication date |
---|---|
DE60239212C5 (de) | 2021-09-23 |
US20070128097A1 (en) | 2007-06-07 |
EP1435338B1 (en) | 2011-02-16 |
KR100890773B1 (ko) | 2009-03-31 |
EP1435338A1 (en) | 2004-07-07 |
CA2459496C (en) | 2011-11-22 |
JPWO2003022740A1 (ja) | 2004-12-24 |
JP4382482B2 (ja) | 2009-12-16 |
KR20040039332A (ko) | 2004-05-10 |
WO2003022740A1 (fr) | 2003-03-20 |
US20040234438A1 (en) | 2004-11-25 |
CA2459496A1 (en) | 2003-03-20 |
EP1435338A4 (en) | 2006-01-25 |
US7361322B2 (en) | 2008-04-22 |
DE60239212D1 (de) | 2011-03-31 |
CN1290770C (zh) | 2006-12-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1290770C (zh) | 二氧化铈、其制备法和用于净化废气的催化剂 | |
KR102580600B1 (ko) | 세륨- 및 지르코늄-기재 혼합 산화물 | |
RU2727187C2 (ru) | Композиции на основе оксида циркония, используемые в качестве тройных катализаторов | |
EP2505262B1 (en) | Complex oxide, method for producing same and exhaust gas purifying catalyst | |
CN1269566C (zh) | 用于分解一氧化二氮的催化剂和分解含n2o气体中n2o的工艺的实施方法 | |
RU2509725C2 (ru) | Композиция на основе оксида церия и оксида циркония с особой пористостью, способ получения и применение в катализе | |
CN1098811C (zh) | 锆-铈系复合氧化物及其制造方法以及废气净化用助催化剂 | |
EP3188829A1 (en) | High porosity cerium and zirconium containing oxide | |
CN1724147A (zh) | 钙钛矿型复合氧化物和催化剂 | |
CN1398196A (zh) | 用于分解n2o的催化剂,其用途及其制备工艺 | |
CN101053833A (zh) | 一种用于高温甲醇水蒸汽重整制氢贵金属催化剂 | |
JPWO2011065417A1 (ja) | 複合酸化物、その製造法及び排ガス浄化用触媒 | |
CN100444955C (zh) | 氧化铈/氧化锆复合介孔三效催化材料及其制备方法 | |
CN1548227A (zh) | 用于制备碳纳米管的催化剂及其制备方法 | |
CN111974439B (zh) | 负载型催化剂及其制备方法和应用 | |
CN102658137B (zh) | 一种铈锆钯纳米粉体催化剂及其制备和应用 | |
JPH06100319A (ja) | ペロブスカイト型構造複合酸化物およびその製造方法 | |
CN1032644C (zh) | 将甲烷转化为高级烃产物的方法和催化剂 | |
JP4972868B2 (ja) | 表面修飾されたセリア・ジルコニア系水和酸化物、その酸化物及びそれらの製造方法並びに用途 | |
EP2954950B1 (en) | Catalyst for purifying nox occlusion reduction-type exhaust gas and exhaust gas purification method using said catalyst | |
CN1680020A (zh) | 过渡金属取代型六铝酸盐天然气燃烧催化剂的制备工艺 | |
CN114177902B (zh) | 一种具有微米级大孔的铈锆固溶体及其制备方法和应用 | |
JP2008150264A (ja) | セリア−ジルコニア系複合酸化物及びその製造方法 | |
CN1206029C (zh) | 一种以M/Mn/A1水滑石为前驱体制备的催化剂及其制备方法 | |
JP2022179935A (ja) | セリア-ジルコニア系微結晶粉末、それを用いた酸素吸放出材料、及びその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C56 | Change in the name or address of the patentee | ||
CP03 | Change of name, title or address |
Address after: Tokushima County Patentee after: The special chemical Japan Co.,Ltd. Address before: Kobe City, Hyogo Prefecture, Japan Patentee before: ANAN KASEI Co.,Ltd. |
|
CX01 | Expiry of patent term |
Granted publication date: 20061220 |
|
CX01 | Expiry of patent term |