CN1695798A - Ce-Zr-Al based oxygen stored material and preparation method - Google Patents
Ce-Zr-Al based oxygen stored material and preparation method Download PDFInfo
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- CN1695798A CN1695798A CN 200510020615 CN200510020615A CN1695798A CN 1695798 A CN1695798 A CN 1695798A CN 200510020615 CN200510020615 CN 200510020615 CN 200510020615 A CN200510020615 A CN 200510020615A CN 1695798 A CN1695798 A CN 1695798A
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- 239000000463 material Substances 0.000 title claims abstract description 89
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000001301 oxygen Substances 0.000 title claims abstract description 68
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 24
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003381 stabilizer Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 229910002651 NO3 Inorganic materials 0.000 claims description 18
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000006104 solid solution Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- RGRFMLCXNGPERX-UHFFFAOYSA-L oxozirconium(2+) carbonate Chemical compound [Zr+2]=O.[O-]C([O-])=O RGRFMLCXNGPERX-UHFFFAOYSA-L 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- 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 5
- 239000007790 solid phase Substances 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 4
- 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 4
- 239000000047 product Substances 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 17
- 239000007789 gas Substances 0.000 abstract description 12
- 238000004140 cleaning Methods 0.000 abstract description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 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 abstract 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 abstract 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- 238000003860 storage Methods 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052684 Cerium Inorganic materials 0.000 description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 8
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 229910004116 SrO 2 Inorganic materials 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 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
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 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 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ROLJWXCAVGNMAK-UHFFFAOYSA-N [Ce]=O Chemical compound [Ce]=O ROLJWXCAVGNMAK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- -1 carbon amine Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
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Abstract
A Ce-Zr-Al based oxygen bearing material used as the catalyst for cleaning the tail gas of car contains cerium oxide, zirconium oxide, aluminium oxide and the stabilizer chosen from lanthanum oxide, yttrium oxide and alkali-earth metal oxide. Its preparing process is also disclosed.
Description
One, technical field
The present invention relates to the hydrogen-storing material technical field, more particularly, relate to a kind of hydrogen-storing material technical field that is used for cleaning catalyst for tail gases of automobiles.
Two, technical background
Vehicle exhaust is the one of the main reasons that causes atmosphere pollution, has caused the great attention of countries in the world, drops into substantial contribution, technology and manpower and administers.Cleaning catalyst for tail gases of automobiles is just obtaining increasingly extensive application as environmental protection with catalyst.As everyone knows, because CeO
2The storage oxygen and the oxygen release performance of its uniqueness are arranged, and become the key component of three-effect catalyst for purifying tail gas of car.
In the purifying vehicle exhaust process, in order better to transform carbon monoxide (CO), imperfect combustion hydrocarbon (HC) and nitrogen oxide (NO
x) wait and mainly contain harmful substances, adopted and in catalyst, added oxygen storage components such as cerium oxide.The mechanism of the storage oxygen of cerium oxide is, when having excess of oxygen in tail gas, by making the Ce in the cerium oxide
3+Become Ce
4+Come in conjunction with oxygen, when in tail gas, lacking oxygen, by making the Ce in the cerium oxide
4+Be reduced into Ce
3+Discharge oxygen once more.Promptly pass through CeO
2Middle Ce
4+/ Ce
3+Redox cycle makes that the ratio of Oxidizing and Reducing Agents maintains certain stoichiometric proportion in the tail gas, thereby makes pollutant reach best conversion ratio.
CeO
2A major defect is arranged, promptly about 850 ℃ sintering takes place, particle is grown up, and specific area reduces, thereby reduces even lose Ce
4+/ Ce
3+Redox performance causes catalysqt deactivation.And the motor vehicle exhaust emission temperature is generally 500-600 ℃, in some cases can be up to 1000 ℃.Therefore, as the hydrogen-storing material of cleaning catalyst for tail gases of automobiles, need under 1000 ℃ high temperature, also can normally bring into play its purifying and catalyzing effect.Cleaning catalyst for tail gases of automobiles is operate as normal under high like this temperature environment, needs at high temperature can keep Ce
4+/ Ce
3+Redox property guarantees that cleaning catalyst has good heat endurance.Therefore, improve CeO
2Heat endurance be very important.In order to improve CeO
2Performance at high temperature, people have carried out relevant therewith a large amount of research work, find CeO
2Mixing ZrO
2Oxidation-reduction quality and heat endurance behind the generation cerium zirconium sosoloid have obtained significant raising.The storage oxygen performance of cerium zirconium sosoloid and the heat endurance of structure are much larger than ceria.
The cerium zirconium hydrogen-storing material of US20020132732 patent preparation through 1000 ℃ of roastings after 4 hours oxygen storage capacity still can reach more than the 300umol/g, but specific area is less than 10m
2/ g is even less than 5 or 3m
2/ g.
Cerium zirconium sosoloid at high temperature can keep good storage oxygen performance, but the heat endurance of texture is relatively poor, shows that specific area is low; The heat endurance of structure is also relatively poor, shows in the cerium zirconium sosoloid, and having of zirconium ion may dissociate cubic phase zirconium dioxide under higher temperature, makes single cube to be transformed into heterogeneous coexistence mutually.Good storage oxygen performance, texture property and the structural behaviour of cerium zirconium sosoloid not only can improve the catalytic efficiency of cleaning catalyst for tail gases of automobiles and prolong life of catalyst, and can also reduce the consumption of noble metal in the catalyst.For the performance that makes the gained catalyst reaches best, the texture of cerium zirconium sosoloid and the heat endurance of structure remain further to be improved.
U.S. Pat 20020090512,20020160912 and 20020049137 discloses the cerium Al based oxygen stored material of three kinds of technical schemes, but the cerium Al based oxygen stored material of these three kinds of technical schemes does not all form solid solution, and the X-ray diffraction diagram shows aluminium oxide and cerium zirconium sosoloid peak.The cerium Al based oxygen stored material of US20020090512 preparation through 600 ℃ of roastings after 5 hours pore volume be about 0.07ml/g, through 800 ℃ the calcining 5 hours after pore volume reduce to about 0.04ml/g, and the reaction mass of preparation is the ageing of pressurizeing under 100～200 ℃ temperature, production equipment is a pressure vessel, production equipment is huge, has increased the cost input in the production process; The cerium Al based oxygen stored material of US20020160912 preparation through 900 ℃ of roastings after 5 hours pore volume be not less than 2ml/g, but specific area has only 20m
2About/g, specific area is less than normal, and the preparation ambient condition be water-oil mixture, need in the preparation process to consume a large amount of organic solvents, increased the cost input in the production process; The cerium Al based oxygen stored material of US20020049137 preparation through 800 ℃ of roastings after 5 hours specific area have only 40m
2About/g, specific area is also less than normal.
Publication number is that the Chinese patent application of CN1200954A discloses a kind of method of taking the immersion process for preparing cerium-based oxygen storage material, promptly by the infuse mode with cerium oxide and ceria stabilized agent infuse on the aluminium oxide of high surface area, calcining made in 10 hours under 900 ℃ condition.The best specific area of prepared cerium-based oxygen storage material is 30m
2About/g.The X-ray diffraction diagram of thing phase presents CeO
2And Al
2O
3Diffraction maximum, the storage oxygen performance of briefing material not.
Three, technology contents
At the deficiency that the prior art hydrogen-storing material exists, purpose of the present invention aims to provide and a kind ofly can solve Ce-Zr-Al based oxygen stored material of following technical problem and preparation method thereof:
1, by in material, mixing metal suboxide such as Al
3+, Y
3+And La
3+Deng the structural stability that improves material;
2, further improve the heat endurance of material texture and the stability of oxygen storage capacity;
3, adopt non-pressure equipment to prepare material, reduce the investment in production equipment expense;
Have Ce-Zr-Al based oxygen stored material of following technical scheme and preparation method thereof, can realize foregoing invention purpose of the present invention.
The composition component of Ce-Zr-Al based oxygen stored material mainly contains aluminium oxide, cerium oxide, zirconia and stabilizing agent, and aluminium oxide, zirconia and stabilizing agent exist with the solid solution form of cerium oxide, and the material crystals structure is the homogeneous solid solution structure.
In such scheme, aluminium oxide, cerium oxide and zirconia are the basic composition components of hydrogen-storing material compound, but they can combine with other additional elements, as yttrium, rare earth element and alkaline-earth metal.Additional elements is mainly used to stablize cerium oxide, also can be used for stablizing aluminium oxide.Therefore preferably also contain the stabilizing agent that is useful on Stable Oxygen cerium and aluminium oxide in the hydrogen-storing material, make material have better heat endurance.Therefore stabilizing agent can be selected from least a in the oxide of yttrium, rare earth element or alkali earth metal, promptly can be in these metallic element oxides a kind of, two or more.And the metallic element in the stabilizing agent also is that the solid solution form with cerium exists.Stabilizing agent preferentially is selected from least a in the oxide of yttrium, lanthanum, strontium and barium.
The composition component and the constituent content of Ce-Zr-Al based oxygen stored material constitute, by weight percentage:
Zirconia 10～45%
Stabilizing agent 5～15%.
In the said components of material constituted, the ratio of the weight content of component aluminium oxide in Ce-Zr-Al based oxygen stored material compound of the present invention accounted for 10% of entire compound weight at least.Also can only account for 75% of entire compound weight at the most, preferable range is 25～70%.
In the said components of material constituted, the weight ratio scope that cerium oxide and zirconic weight content preferably are controlled at two kinds of components was at 1.0-5.0: between the 1.0-5.0, preferably than being 1: 1 (oxide weight compares).
The above Ce-Zr-Al based oxygen stored material can be by following process preparation, and described process specifically comprises following processing step:
(1), constitutes the weight content that the constituent content of determining aluminium oxide, cerium oxide, zirconia and stabilizing agent converses cerous nitrate, zirconyl carbonate/zirconyl nitrate, aluminum nitrate and stabilizing agent nitrate according to material component earlier, and then the nitrate mixed solution that forms by cerous nitrate, zirconyl carbonate/zirconyl nitrate, aluminum nitrate and stabilizing agent nitrate of preparation, i.e. first mixed solution, and precipitant solution, said precipitant solution is an alkaline solution.
(2), adopt cocurrent process to import reaction vessel above-mentioned two kinds of solution that prepare and carry out precipitation reaction, two kinds of solution and conductance are gone into the precipitation reaction mixed liquor that reaction vessel forms and are kept being alkalescence, be that the pH value is not less than 7, after precipitation reaction finished, ageing was no less than 2 hours under the condition of 90～100 ℃ of temperature;
(3), the reaction feed liquid after abundant ageing is carried out Separation of Solid and Liquid, the solid phase of separating is washed earlier, and then is mixed with slurries with surfactant and water;
(4), the above-mentioned slurries that make are carried out Separation of Solid and Liquid by the mode of evaporation drying, the gained solid phase is no less than 5 hours at 600-1000 ℃ roasting temperature after drying, promptly makes Ce-Zr-Al based oxygen stored material.
The preparation nitrate mixed solution, when the presoma of zirconium is zirconyl carbonate, add entry again after by the adding red fuming nitric acid (RFNA) zirconyl carbonate being dissolved earlier and prepare nitrate mixed solution, when the presoma of zirconium is zirconyl nitrate, can prepare nitrate mixed solution by directly adding entry.The oxide weight concentration of nitrate mixed solution is found in the research, and its scope can be very wide, we can say that its concentration is unrestricted, but from exercisable angle, generally should not be lower than 5%.
In above-mentioned preparation technology's method, said precipitant solution is an alkaline solution.Alkaline solution is a kind of aqueous solution that contains alkali.Usually used alkaline solution is the mixed solution that is mixed with by ammoniacal liquor and ammonium carbonate.But here of particular note, the mixed solution of ammoniacal liquor-carbon amine is preferred.Because they have improved the heat endurance of material significantly in the process of preparation hydrogen-storing material.Be equipped with ammoniacal liquor-ammonium carbonate mixed solution, ammonia can be in the scope of 1.0-5.0: 1.0-5.0 with the ratio of the amount of ammonium carbonate, and solution concentration should not be lower than 3mol/l in ammonia.
The ratio of nitrate mixed solution and precipitant solution addition, because the alkalescence of the acidity of nitrate mixed solution and precipitant solution is different, the ratio of addition changes, therefore should not directly control the ratio of their additions by the addition of control nitrate mixed solution and precipitant solution, preferred mode is to control the ratio of their additions by the pH value of control precipitation reaction mixed liquor.The pH value of precipitation mixed reaction solution should not be less than 7, and the preferential scope of selecting is 9.0-11.Desired pH value is by regulating mixed nitrate solution, and promptly the flow velocity of nitrate mixed solution and precipitant solution reaches.
In above-mentioned preparation technology's method, slurries weight of precipitate concentration is in 5～40% scopes, and the surfactant in the slurries, its weight consumption are controlled at and are not less than 20% of oxide weight.Said surfactant can be polyethylene glycol, polyvinyl alcohol or both mixtures.Slurries carry out Separation of Solid and Liquid by the evaporation drying mode, preferably take spray-dired mode to carry out Separation of Solid and Liquid.
The Ce-Zr-Al based oxygen stored material of the present invention preparation, the auxiliary agent of useful as catalysts or carrier are in particular for the auxiliary agent or the carrier of the cleaning catalyst of handling exhaust emissions from internal combustion engines.
The inventor tests with X-line diffraction Ce-Zr-Al based oxygen stored material disclosed by the invention, test result X-ray diffraction diagram only shows the diffraction maximum of cube phase of cerium oxide, do not detect the diffraction maximum of other oxide, this explanation is in Ce-Zr-Al based oxygen stored material disclosed by the invention, the metallic element of its contained zirconia, aluminium oxide and stabilizer oxide has entered the lattice of cerium oxide, cerium oxide, zirconia, aluminium oxide and formed the solid solution of homogeneous as the oxide of stabilizing agent.This is one of main difference of the present invention and prior art Ce-Zr-Al based oxygen stored material.In containing in the aluminium hydrogen-storing material of prior art, the metallic element of other oxide does not enter the lattice of cerium oxide, and the main composition component of hydrogen-storing material does not form the solid solution of homogeneous.Main contribution of the present invention has provided a kind of hydrogen-storing material of new crystal structure, i.e. the Ce-Zr-Al based oxygen stored material of solid solution structure.It is not main inventive point of the present invention that the concrete component of hydrogen-storing material constitutes.
Ce-Zr-Al based oxygen stored material disclosed by the invention is carried out oxygen storage capacity to the inventor and texture property is measured.The result shows that the Ce-Zr-Al based oxygen stored material that the present invention prepares has good storage oxygen performance and texture property.This can be confirmed from the following examples.The Ce-Zr-Al based oxygen stored material of the present invention's preparation after 5 hours, confirms still have very good structural behaviour, texture property and storage oxygen performance through XRD, oxygen storage capacity and texture test in 1000 ℃ of calcinings of atmospheric environment condition.Illustrate that Ce-Zr-Al based oxygen stored material of the present invention has very high heat endurance, i.e. the heat endurance of structure, texture and oxygen storage capacity.Its good structural stability show through 1000 ℃ of calcinings after 5 hours hydrogen-storing material still keep cube crystalline phase of cerium oxide, do not have other thing and occur mutually.Texture stability shows that the specific surface of hydrogen-storing material is still reaching as high as 110m through 1000 ℃ of calcinings after 5 hours
2More than/the g, can reach 38m at least
2/ g.Pore volume rate and average pore size are also bigger.The stability of storage oxygen performance show through 1000 ℃ of calcinings after 5 hours oxygen storage capacity still higher, fall is little.This can obtain proof from the following examples.This is for particularly the auxiliary agent or the carrier of catalyst for purifying internal combustion engine tail gas are very important as catalyst.
The preparation of Ce-Zr-Al based oxygen stored material of the present invention, production equipment do not relate to pressure vessel, and production technology is simple, and the investment of production equipment expense is low.
Specification is specifically implemented part and is described having in of the present invention more specifically, can understand other characteristics of the present invention, details and advantage by this part of reading specification more full and accurately.
Four, description of drawings
Fig. 1 is the X-ray diffractogram of the present invention at 600 ℃ of calcinings Powdered hydrogen-storing material sample of preparation after 5 hours.
Fig. 2 is that the Powdered hydrogen-storing material that the present invention prepares is calcined 5 hours sample X-ray diffractograms after the burin-in process through 1000 ℃.
In accompanying drawing 1 and accompanying drawing 2, abscissa is the angle of diffraction, and ordinate is a diffraction peak intensity.A in the accompanying drawing, b, c, d, the e curve is represented different embodiment respectively, wherein.A: embodiment 1; B: embodiment 8; C: embodiment 9; D: embodiment 10; E: embodiment 11.
Five, the specific embodiment
Provide the specific embodiment of the present invention below by embodiment.Except as otherwise noted, ratio that provides among the embodiment below and percentage are meant part by weight and percetage by weight.
(1), the embodiment of the Ce-Zr-Al based oxygen stored material specific embodiment
The composition component of each embodiment and constituent content (weight content) constitute:
1、Al
2O
3?10％；CeO
2?45％；ZrO
2?35％；La
2O
3?5％；Y
2O
3?5％。
2、Al
2O
3?10％；CeO
2?45％；ZrO
2?35％；Y
2O
3?10％。
3、Al
2O
3?10％；CeO
2?45％；ZrO
2?35％；La
2O
3?10％
4、Al
2O
3?10％；CeO
2?45％；ZrO
2?35％；La
2O
3?5％；SrO
2?5％
5、Al
2O
3?10％；CeO
2?45％；ZrO
2?35％；BaO
2?5％；?Y
2O
3?5％
6、Al
2O
3?10％；CeO
2?60％；ZrO
2?15％；La
2O
3?5％；Y
2O
3?5％；SrO
25％。
7、Al
2O
3?10％；CeO
2?60％；ZrO
2?15％；La
2O
3?5％；Y
2O
3?5％；BaO
25％。
8、Al
2O
3?1O％；CeO
2?60％；ZrO
2?15％；La
2O
3?5％；Y
2O
3?5％；SrO
23％；BaO
2?2％。
9、Al
2O
3?25％；CeO
2?45％；ZrO
2?15％；La
2O
3?5％；Y
2O
3?5％；SrO
2?3％；BaO
2?2％。
10、Al
2O
3?35％；CeO
2?35％；ZrO
2?15％；La
2O
3?5％；Y
2O
3?5％；SrO
23％；BaO
2?2％。
11、Al
2O
3?60％；CeO
2?10％；ZrO
2?15％；La
2O
3?5％；Y
2O
3?5％；SrO
23％；BaO
2?2％。
The Ce-Zr-Al based oxygen stored material of the various embodiments described above preparation shows that through X-ray diffraction analysis zirconia, aluminium oxide and stabilizer oxide exist with the solid solution form of cerium oxide, and the Ce-Zr-Al based oxygen stored material crystal structure is the solid solution of homogeneous.
(2), the embodiment of the Ce-Zr-Al based oxygen stored material preparation method specific embodiment
Embodiment 1
Form component Al according to Ce-Zr-Al based oxygen stored material specific embodiment part embodiment 1
2O
3, CeO
2, ZrO
2, La
2O
3, Y
2O
3In metal element content, calculate the weight requirements amount of each oxide precursor cerous nitrate, zirconyl carbonate, aluminum nitrate, yttrium nitrate and lanthanum nitrate.Take by weighing cerous nitrate, zirconyl carbonate, aluminum nitrate, yttrium nitrate and the lanthanum nitrate of the amount of determining in proportion, above-mentioned oxide precursor is inserted in the container, the concentration that adds zirconyl carbonate total amount about 80% is that 60% red fuming nitric acid (RFNA) is with the dissolving zirconyl carbonate, and then in container the distilled water of oxygenates total amount about 90% and the polyvinyl alcohol of oxide aggregate 20%, preparation nitrate solution (first mixed solution) is stand-by.
In another container, with distilled water diluting ammonium hydroxide (25%NH
3) and ammonium carbonate, preparation ammonia concentration is the mixed aqueous solution of ammoniacal liquor-ammonium carbonate of 10%, and is stand-by as precipitant solution.
The nitrate solution of above-mentioned preparation and ammonia spirit employing and stream mode import carries out precipitation reaction in the container.Solution stirs while importing in the process that imports container.The ratio of nitrate solution and ammonia spirit addition should keep the pH value of precipitation reaction mixed liquor to be about 9.Product is the purplish red sediment.Wait to precipitate and fully separate out post precipitation, ageing is 10 hours under about 90 ℃ of condition of normal pressure, carry out Separation of Solid and Liquid in the mode of filtering then, the solid phase of gained is inserted in the container after washing, adding is equipped to solvent by polyethylene glycol and distilled water, stir while adding, evenly disperse, be prepared into slurries until sediment.In slurries, sedimentary weight concentration is 10%, and the content of polyethylene glycol is 20% of oxide in the solvent.Adopt the mode of spray-drying evaporation to carry out drying in slurries, obtain granular material.
Dried granular material 600 ℃ of following roastings 5 hours, is the Ce-Zr-Al based oxygen stored material finished product that will prepare.In order to measure the storage oxygen performance of hydrogen-storing material under 1000 ℃ of environment, the finished product of producing was calcined 5 hours at 1000 ℃, must get the aged samples of Ce-Zr-Al based oxygen stored material.
Embodiment 2
The preparation hydrogen-storing material is implemented the hydrogen-storing material of part embodiment 2, and concrete preparation method is basic identical with the method for this part embodiment 1, different places be that the pH value of maintenance reaction medium is 8.
Embodiment 3
The preparation hydrogen-storing material is implemented the hydrogen-storing material of part embodiment 3, and the method for concrete prepare side and this part embodiment 1 is basic identical, different places be that the pH value of maintenance reaction medium is 10.
Embodiment 4
The preparation hydrogen-storing material is implemented the hydrogen-storing material of part embodiment 4, and concrete preparation method is basic identical with the method for this part embodiment 1, different places be that one to be to use ammoniacal liquor be alkaline precipitating agent, the 2nd, the pH value of maintenance reaction medium is 10.
Embodiment 5
The preparation hydrogen-storing material is implemented the hydrogen-storing material of part embodiment 5, and the method for concrete preparation method and this part embodiment 1 is basic identical, different places be, use carbon amine to be alkaline precipitating agent.
The preparation method of embodiment 6-11 hydrogen-storing material is substantially the same manner as Example 1.
The hydrogen-storing material of preparation adopts BET method measurement the specific area, pore volume and average pore size with the automatic adsorption/desorption instrument of ZXF-5 type of Xibei Chemical Inst's design, adopts O
2Gas pulse determining adsorption oxygen storage capacity, test result is listed following table in.The XRD test of the hydrogen-storing material that embodiment 1 and embodiment 12～15 are prepared is to carry out on Japan's motor D of science/max-rA type X hot line diffractometer, and the result of test invests Fig. 1 and Fig. 2.
Claims (10)
1, a kind of Ce-Zr-Al based oxygen stored material, material is formed component and is mainly contained aluminium oxide, cerium oxide, zirconia and stabilizing agent, it is characterized in that described material crystals structure is the homogeneous solid solution structure, and aluminium oxide, zirconia and stabilizing agent exist with the solid solution form of cerium oxide.
2, Ce-Zr-Al based oxygen stored material as claimed in claim 1 is characterized in that said stabilizing agent is to be selected from least a in the oxide of rare earth element or alkali earth metal, and stabilizer oxide exists with the solid solution form of cerium oxide.
3, Ce-Zr-Al based oxygen stored material as claimed in claim 2 is characterized in that described stabilizing agent is to be selected from least a in the oxide of yttrium, lanthanum, strontium and barium.
4, as claim 1 or 2 or 3 described Ce-Zr-Al based oxygen stored materials, it is characterized in that constituting of material composition component, by weight percentage:
Aluminium oxide 10～75%
Cerium oxide 10～70%
Zirconia 10～45%
Stabilizing agent 5～15%.
5, Ce-Zr-Al based oxygen stored material as claimed in claim 4 is characterized in that it is 25～70% that material is formed the weight content of component aluminium oxide.
6, Ce-Zr-Al based oxygen stored material as claimed in claim 4 is characterized in that cerium oxide and zirconic weight ratio that material is formed in the component are 1.0-5.0: 1.0-5.0.
7, the method for the described Ce-Zr-Al based oxygen stored material of each claim in the preparation claim 1 to 6 is characterized in that comprising following processing step:
(1), to form the component preparation by given material be the nitrate mixed solution of solute with the contained oxide precursor cerous nitrate of material, zirconyl carbonate or zirconyl nitrate, aluminum nitrate and stabilizing agent nitrate, and precipitant solution, precipitant solution is an alkaline solution;
(2), adopt cocurrent process to import reaction vessels above-mentioned two kinds of solution that prepare to carry out precipitation reaction, it is alkaline that the pH value of precipitation reaction liquid keeps being, after product was fully separated out, ageing was no less than 2 hours under 90～100 ℃ of conditions again;
(3), the reaction feed liquid after the ageing carries out Separation of Solid and Liquid, the solid phase precipitation thing of separating washs earlier, and then is mixed with slurries with surfactant and water;
(4), the above-mentioned slurries that make carry out Separation of Solid and Liquid by the mode of evaporation drying, the gained solid phase is no less than 2 hours at 500～1000 ℃ roasting temperatures after drying, promptly makes Ce-Zr-Al based oxygen stored material.
8, the method for preparing Ce-Zr-Al based oxygen stored material as claimed in claim 7, it is characterized in that said nitrate mixed solution is not less than 5% by oxide weight concentration, precipitant solution is that the pH value is not less than 9 alkaline solution, the said weight of precipitate concentration that is mixed with slurries by sediment and surfactant and water is 5～40%, and the weight consumption of surfactant is not less than 20% of oxide weight.
9, as claim 7 or the 8 described methods that prepare Ce-Zr-Al based oxygen stored material, it is characterized in that said alkaline solution is the mixed aqueous solution of ammoniacal liquor and ammonium carbonate, ammonia is 1.0-5.0: 1.0-5.0 with the ratio of the amount of ammonium carbonate, and solution concentration is not less than 3mol/l in ammonia.
10,, it is characterized in that the pH value of precipitation reaction liquid is 9.0-11 as claim 7 or the 8 described methods that prepare Ce-Zr-Al based oxygen stored material.
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