CN109569566A - Compound hydrogen-storing material of cerium zirconium aluminium and preparation method thereof - Google Patents
Compound hydrogen-storing material of cerium zirconium aluminium and preparation method thereof Download PDFInfo
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- CN109569566A CN109569566A CN201811470341.XA CN201811470341A CN109569566A CN 109569566 A CN109569566 A CN 109569566A CN 201811470341 A CN201811470341 A CN 201811470341A CN 109569566 A CN109569566 A CN 109569566A
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- cerium
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- storing material
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- cerium zirconium
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- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 23
- 239000004411 aluminium Substances 0.000 title claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 150000001875 compounds Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 15
- 230000032683 aging Effects 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 238000003483 aging Methods 0.000 claims description 8
- 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 7
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000643 oven drying Methods 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- 150000001399 aluminium compounds Chemical class 0.000 claims description 5
- 150000001785 cerium compounds Chemical class 0.000 claims description 5
- 150000003755 zirconium compounds Chemical class 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 229910021331 inorganic silicon compound Inorganic materials 0.000 claims description 3
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- PGJHGXFYDZHMAV-UHFFFAOYSA-K azanium;cerium(3+);disulfate Chemical compound [NH4+].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PGJHGXFYDZHMAV-UHFFFAOYSA-K 0.000 claims description 2
- 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 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- 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 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 24
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 14
- 239000006104 solid solution Substances 0.000 abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 239000004115 Sodium Silicate Substances 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052911 sodium silicate Inorganic materials 0.000 abstract description 4
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 229910002637 Pr6O11 Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- -1 cerium zirconium aluminium Compound Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—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
- 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
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The present invention provides a kind of compound hydrogen-storing material of cerium zirconium aluminium, the material is using lye as precipitating reagent, liquid sodium silicate is thermostabilization auxiliary agent, it is made using coprecipitation, main component is cerium oxide, zirconium oxide, aluminium oxide and silica, and wherein cerium-oxide contents are 10-30%, zirconia content 10-50%, alumina content is 30-70%, silica content 2-8%.Each component is existed in the form of solid solution in the hydrogen-storing material, thermal stability with higher, and specific surface area is up to 80m after 1100 DEG C of high-temperature calcination 20h2/g。
Description
Technical field
The present invention relates to a kind of preparations of automotive exhaust catalysis auxiliary agent, specifically, being related to a kind of high heat stability cerium zirconium aluminium
Compound hydrogen-storing material and preparation method thereof, belongs to chemical material field.
Background technique
Carbon monoxide (CO), hydrocarbons (CH) and nitrogen oxides (NOX) be vehicle exhaust major pollutants, directly arrange
Serious pollution can be generated to environment by putting, these pollutants can be effectively removed by noble metal triple effect catalyst, but only resonable
The conversion ratio of three nearby can be just set to reach maximum by air-fuel ratio (A/F=14.6), but when automobile engine is in running order
Air-fuel ratio is not constant, but occur oxygen deprivation-it is oxygen-enriched-oxygen deprivation cyclically-varying, therefore three-way catalyst can not be same always
When eliminate these three pollutants.
Cerium is a kind of unique rare earth element, has two kinds of variable valences of trivalent and tetravalence, mutually converts in two kinds of valence states
There is storage oxygen and oxygen release ability in the process, can control the fluctuation of oxygen content, play the role of adjusting automobile engine air-fuel ratio,
To make three kinds of pollutants reach ideal conversion ratio, cerium oxide is widely used to as a kind of important catalyst aid at present
Automotive exhaust catalysis industry.
Pure CeO2Thermal stability it is poor, 800 DEG C or more easy-sinterings cause specific surface area and oxygen storage capacity sharply to decline, from
And influence the catalytic performance of noble metal catalyst.In CeO2Middle introducing ZrO2Cerium zirconium sosoloid, which is made, can be improved CeO2Storage oxygen energy
Power, storage oxygen rate and thermal stability, but due to the presence of metastable phase, temperature, which is higher than 1000 DEG C of processing, can still make ZrO2From
CeO2It is separated in crystal phase, causes the biggish variation of solid solution structure, therefore, high high-temp stability still needs to be further increased.
By cerium zirconium sosoloid and Al2O3Mixing, Al2O3It can play the role of " diffusion barrier layer ", reduce cerium zirconium sosoloid
Intergranular contact, to prevent intergranular high temperature sintering；Common Al2O3For γ-Al2O3, but γ-Al2O3In high temperature item
It is easy to happen phase transformation under part, is changed into δ-Al2O3With α-Al2O3, in γ-Al2O3In rare earth doped element (such as La, Ce, Pr, Nd
Deng) and alkaline earth element (such as Ba, Ca, Mg, Sr) its phase transition temperature can be properly increased, to improve cerium zirconium aluminum composite oxides
High-temperature stability.Al2O3It is physical mixed, under the high temperature conditions, CeO with such mode of action of cerium zirconium sosoloid2With Al2O3Meeting
It is sintered, generates CeAlO3, cause the decline of composite oxides specific surface area；In addition, the cerium zirconium aluminium prepared in this way
Composite oxides do not form solid solution structure, after being higher than 1100 DEG C of agings, γ-Al2O3It still can be to α-Al2O3Transformation, cerium zirconium are solid
Split-phase can also occur for solution, generate the species of rich cerium phase and rich zirconium phase.Therefore, a kind of cerium zirconium aluminium hydrogen-storing material resistant to high temperature is prepared
Become the hot spot of research.
Summary of the invention
It is an object of the invention to overcome the shortcomings of existing cerium-based oxygen storage material performance, a kind of compound storage oxygen of cerium zirconium aluminium is provided
Material, each component exists in the form of solid solution in the material, has higher thermal stability.
The technical solution adopted by the invention is as follows:
A kind of compound hydrogen-storing material of cerium zirconium aluminium, the material are washed by following mass percent component materials by mixing
Calcining is washed to be prepared:
The present invention also provides the preparation methods of the above-mentioned compound hydrogen-storing material of cerium zirconium aluminium, include the following steps:
1) cerium compound, zirconium compounds, aluminium compound and silicon compound are mixed, adds water and stirs dissolution, heated；
2) lye is added in step 1) mixed liquor with constant flow rate, controls pH > 8.5, stirs evenly, be aged；
3) it filters, washing；
4) dry, grinding；
5) Muffle furnace high temperature is calcined, and fresh sample is made；
6) fresh sample is placed in tube furnace high temperature aging, aged samples is made.
Cerium compound in the step 1) is cerous nitrate, cerium ammonium nitrate, cerous sulfate, ammonium sulfate cerium, appointing in cerium chloride
Meaning is one or more of, preferably cerous nitrate；Zirconium compounds is zirconium oxychloride, zirconium nitrate, any one or a few in zirconyl nitrate,
It is preferred that zirconium oxychloride；Aluminium compound is aluminum nitrate, aluminum sulfate, any one or a few in aluminium chloride, preferably aluminum nitrate；Silication
Closing object is organo-silicon compound or inorganic silicon compound.
Heating temperature is 50-80 DEG C in the step 1).
Lye in the step 2) is sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate soln
In any one or a few.
PH value range is 8.5-10.0, mixing time 1-2h, digestion time 12-24h in the step 2).
The filtered wet cake of step 3) is first washed with deionized 3-5 times, then with ethanol washing 2-3 times.
The drying mode of the step 4) is oven drying, and drying temperature is 60-80 DEG C.
The calcination temperature of Muffle furnace is 600-800 DEG C, calcination time 2-4h, heating rate 2-4 in the step 5)
℃/min。
The aging temperature of tube furnace is 1000-1100 DEG C, ageing time 8-20h in the step 6), and heating rate is
2-4℃/min。
Compared to the prior art the present invention has the following beneficial effects:
(1) thermostabilization auxiliary agent of the invention is organo-silicon compound or inorganic silicon compound, and wherein liquid sodium silicate is water-soluble
Property is good, and silicate can be effectively adsorbed on surface hydroxyl in coprecipitation process, can effectively prevent in calcination process
The sintering of intergranular, to improve the thermal stability of solid solution, furthermore liquid sodium silicate is low in cost, is suitable for heavy industrialization
Production.
(2) slurries of the invention keep little particle further growth, bulky grain further molten by 12-24h ripening
Solution, to keep product more uniform.
(3) present invention eliminates the foreign ion in sediment by washing, and 3-5 is being washed with deionized after,
It uses ethanol washing 2-3 times again, the moisture in wet cake can be replaced, the hard aggregation phenomenon being effectively prevented in drying process, thus
Improve the specific surface area of product.
(4) present invention eliminates grinding/smashing process using spray drying, this drying mode, has higher production effect
The powder-product of rate, preparation is also more uniform.
Detailed description of the invention
Fig. 1 is the XRD spectrum of the fresh state of embodiment one；
Fig. 2 is the XRD spectrum of one aging state of embodiment；
Fig. 3 is the XRD spectrum of the fresh state of embodiment two；
Fig. 4 is the XRD spectrum of two aging state of embodiment.
Specific embodiment
With reference to embodiment, the specific embodiment of the present invention is further described.Following embodiment is only used for more
Add and clearly demonstrate technical solution of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment one
Sample quality percentage composition: CeO2(10%), ZrO2(20%), Al2O3(65%), La2O3(3.5%), Pr6O11
(1.5%).
1) by 23.1g cerous nitrate (CeO2=39%), 50g zirconium oxychloride (ZrO2=36%), 4.5g lanthanum nitrate (La2O3=
37%), 3.5g praseodymium nitrate (Pr6O11=39%), 500ml deionized water is added in 1000ml round-bottomed flask, and stirring and dissolving is simultaneously
It is heated to 70 DEG C.
2) 28% ammonium hydroxide is added in above-mentioned mixed liquor with the flow velocity of 10ml/min, stop when pH value of solution=8.5 plus
Enter ammonium hydroxide, stirs 1h, 70 DEG C of ageing 12h.
3) it filters, is washed with deionized 3 times, then with ethanol washing 3 times.
4) 70 DEG C of oven dryings crush.
5) by gained powder in Muffle furnace 800 DEG C of calcining 2h, obtain fresh state cerium zirconium sosoloid sample.
6) 1.4g lanthanum nitrate is dissolved in 20g deionized water, is impregnated into 20g γ-Al2O3(SBET=130m2/ g) in, it dries
It is dry, it obtains lanthanum and stablizes aluminium oxide.
7) 6.7g cerium zirconium sosoloid is uniformly mixed with 13.3g aluminium oxide, obtains the cerium zirconium aluminium hydrogen-storing material of physical mixed state.
The method that the embodiment uses first prepares cerium zirconium sosoloid for physical mixed method, then by γ-Al2O3With rare earth member
Plain lanthanum is stablized, and then mixes the two in the proper ratio.
The specific surface area of product is as follows under each calcination temperature:
800 DEG C/2h:102m2/g；
1050 DEG C/8h:61m2/g；
1100 DEG C/20h:46m2/g；
The XRD spectrum of fresh state and aging state is shown in Figure of description 1 and attached drawing 2.Map is shown, after 1100 DEG C of aging 20h,
The stability of the material is poor, γ-Al therein2O3It undergoes phase transition, is changed into α-Al2O3, 30 ° or so of peak is cerium zirconium solid solution
The peak of body, but after high temperature ageing, this peak is split into two peaks, generates the species of rich cerium phase and rich zirconium phase, high-temperature stability
It is to be improved.
Embodiment two
Sample quality percentage composition: CeO2(10%), ZrO2(20%), Al2O3(70%).
1) by 7.7g cerous nitrate, 16.7g zirconium oxychloride, 154.4g aluminum nitrate (Al2O3=13.6%), 500ml deionized water
It is added in 1000ml round-bottomed flask, stirring and dissolving is simultaneously heated to 70 DEG C.
2) 28% ammonium hydroxide is added in above-mentioned mixed liquor with the flow velocity of 10ml/min, stop when pH value of solution=8.5 plus
Enter ammonium hydroxide, stirs 1h, 70 DEG C of ageing 12h.
3) it filters, is washed with deionized 3 times, then with ethanol washing 3 times.
4) 70 DEG C of oven dryings crush.
5) by gained powder in Muffle furnace 800 DEG C of calcining 2h, obtain fresh sample.
6) by fresh sample respectively at 1050 DEG C of calcining 8h, 1100 DEG C of calcining 20h in tube furnace.
Method used in the embodiment is coprecipitation, i.e., by cerium compound, zirconium compounds and aluminium compound co-precipitation
Form solid solution structure (being not added with any thermostabilization auxiliary agent) afterwards.
The specific surface area of product is as follows under each calcination temperature:
800 DEG C/2h:142m2/g；
1050 DEG C/8h:79m2/g；
1100 DEG C/20h:56m2/g
The XRD spectrum of fresh state and aging state is shown in Figure of description 3 and attached drawing 4.Compared with physical mixed sample, cerium zirconium aluminium
Specific surface, aging specific surface and the structural stability of solid solution all increase, and after 1100 DEG C of aging 20h, specific surface area is improved
10m2/ g, XRD spectrum show that only a small amount of aluminium oxide is separated from solid solution structure, and 30 ° or so of peak does not occur point yet
From, show solid solution thermal stability be higher than physical mixed state sample.
Embodiment three
Sample quality percentage composition: CeO2(10%), ZrO2(20%), Al2O3(65%), La2O3(3.5%), Pr6O11
(1.5%).
1) by 7.7g cerous nitrate, 16.7g zirconium oxychloride, 143.4g aluminum nitrate, 2.8g lanthanum nitrate, 1.2g praseodymium nitrate, 500ml
Deionized water is added in 1000ml round-bottomed flask, and stirring and dissolving is simultaneously heated to 70 DEG C.
2) 28% ammonium hydroxide is added in above-mentioned mixed liquor with the flow velocity of 10ml/min, stop when pH value of solution=8.5 plus
Enter ammonium hydroxide, stirs 1h, 70 DEG C of ageing 12h.
3) it filters, is washed with deionized 3 times, then with ethanol washing 3 times.
4) 70 DEG C of oven dryings crush.
5) by gained powder in Muffle furnace 800 DEG C of calcining 2h, obtain fresh sample.
6) by fresh sample respectively at 1050 DEG C of calcining 8h, 1100 DEG C of calcining 20h in tube furnace.
The specific surface area of product is as follows under each calcination temperature:
800 DEG C/2h:136m2/g；
1050 DEG C/8h:71m2/g；
1100 DEG C/20h:55m2/g；
The embodiment is added to thermostabilization auxiliary agent lanthanum and praseodymium in cerium zirconium aluminium solid solution, but specific surface and aging specific surface are all
It does not improve, there is slight reduction instead, illustrate after adding rare-earth additive in cerium zirconium aluminium solid solution structure, high-temperature thermal stability
Property cannot be effectively improved.
Example IV
Sample quality percentage composition: CeO2(10%), ZrO2(20%), Al2O3(64%), SiO2(6%).
1) 7.7g cerous nitrate, 16.7g zirconium oxychloride, 141.2g aluminum nitrate, 500ml deionized water are added to 1000ml circle
In the flask of bottom, stirring and dissolving, then 6.4g liquid sodium silicate (SiO is added dropwise2=28%) it and stirs evenly, mixed liquor is heated
To 70 DEG C.
2) 28% ammonium hydroxide is added in above-mentioned mixed liquor with the flow velocity of 10ml/min, stop when pH value of solution=8.5 plus
Enter ammonium hydroxide, stirs 1h, 70 DEG C of ageing 12h.
3) it filters, is washed with deionized 3 times, then with ethanol washing 3 times.
4) 70 DEG C of oven dryings crush.
5, by gained powder in Muffle furnace 800 DEG C of calcining 2h, obtain fresh sample.
6) by fresh sample respectively at 1050 DEG C of calcining 8h, 1100 DEG C of calcining 20h in tube furnace.
The specific surface area of product is as follows under each calcination temperature:
800 DEG C/2h:195m2/g；
1050 DEG C/8h:108m2/g；
1100 DEG C/20h:80m2/g；
The embodiment adds element silicon in cerium zirconium aluminium solid solution, and specific surface and aging specific surface, which have, significantly to be changed
It is kind.The influence on the content balance surface of element silicon is as shown in the table:
The specific surface of fresh aspect product is increased with the increase of silicone content, but after the content of silica is more than 8%, always
Change specific surface to begin to decline, therefore the content of silica is advisable with 2%-8%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of compound hydrogen-storing material of cerium zirconium aluminium, which is characterized in that the material is passed through by following mass percent component materials
Washing calcining is mixed to be prepared:
2. a kind of preparation method of the compound hydrogen-storing material of cerium zirconium aluminium according to claim 1, which is characterized in that including as follows
Step:
1) cerium compound, zirconium compounds, aluminium compound and silicon compound are mixed, adds water and stirs dissolution, heated；
2) lye is added in step 1) mixed liquor with constant flow rate, controls pH > 8.5, stirs evenly, be aged；
3) it filters, washing；
4) dry, grinding；
5) Muffle furnace high temperature is calcined, and fresh sample is made；
6) fresh sample is placed in tube furnace high temperature aging, aged samples is made.
3. the preparation method of the compound hydrogen-storing material of cerium zirconium aluminium according to claim 2, which is characterized in that in the step 1)
Cerium compound be cerous nitrate, cerium ammonium nitrate, cerous sulfate, ammonium sulfate cerium, any one or a few in cerium chloride, zirconium compounds
For any one or a few in zirconium oxychloride, zirconium nitrate, zirconyl nitrate, aluminium compound is aluminum nitrate, in aluminum sulfate, aluminium chloride
Any one or a few, silicon compound be organo-silicon compound or inorganic silicon compound.
4. the preparation method of the compound hydrogen-storing material of cerium zirconium aluminium according to claim 2, which is characterized in that in the step 1)
Heating temperature is 50-80 DEG C.
5. the preparation method of the compound hydrogen-storing material of cerium zirconium aluminium according to claim 2, which is characterized in that in the step 2)
Lye be sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, any one or a few in ammonium bicarbonate soln.
6. the preparation method of the compound hydrogen-storing material of cerium zirconium aluminium according to claim 2, which is characterized in that in the step 2)
PH value range is 8.5-10.0, mixing time 1-2h, digestion time 12-24h.
7. the preparation method of the compound hydrogen-storing material of cerium zirconium aluminium according to claim 2, which is characterized in that the step 3) is taken out
Wet cake after filter is first washed with deionized 3-5 times, then with ethanol washing 2-3 times.
8. the preparation method of the compound hydrogen-storing material of cerium zirconium aluminium according to claim 2, which is characterized in that the step 4)
Drying mode is oven drying, and drying temperature is 60-80 DEG C.
9. the preparation method of the compound hydrogen-storing material of cerium zirconium aluminium according to claim 2, which is characterized in that in the step 5)
The calcination temperature of Muffle furnace is 600-800 DEG C, calcination time 2-4h, and heating rate is 2-4 DEG C/min.
10. the preparation method of the compound hydrogen-storing material of cerium zirconium aluminium according to claim 2, which is characterized in that the step 6)
The aging temperature of middle tube furnace is 1000-1100 DEG C, ageing time 8-20h, and heating rate is 2-4 DEG C/min.
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