CN102614863A - Hydrothermal synthesis preparation method of La and Zr doped gamma-Al2O3 - Google Patents
Hydrothermal synthesis preparation method of La and Zr doped gamma-Al2O3 Download PDFInfo
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- CN102614863A CN102614863A CN201210047310XA CN201210047310A CN102614863A CN 102614863 A CN102614863 A CN 102614863A CN 201210047310X A CN201210047310X A CN 201210047310XA CN 201210047310 A CN201210047310 A CN 201210047310A CN 102614863 A CN102614863 A CN 102614863A
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- hydro
- doped gamma
- isopropoxide
- washing
- propoxide
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Abstract
The invention discloses a hydrothermal synthesis preparation method of La and Zr doped gamma-Al2O3. The hydrothermal synthesis preparation method comprises three steps of mixing and stirring raw materials; performing hydrothermal synthesis; and separating, washing, drying and sintering the product. By the hydrothermal synthesis preparation method, the composite has thin crystal grains of nanosize; the whole synthesis process has no pollutant and is environment-friendly and safe; the crystal orientation transformation temperature of the synthesized composite can reach above 1100 DEG C; the temperature resistance of the gamma-Al2O3 material is obviously improved; and reliable guarantee is provided for high temperature resistance of catalyst.
Description
Technical field
The present invention relates to that the motorcycle three-element catalytic is high temperature resistant, the catalyst coat material preparation method of high-specific surface area, is a kind of La, Zr doped gamma-Al specifically
2O
3Hydro-thermal synthetic preparation method.
Background technology
Along with the raising day by day of motorcycle recoverable amount, administering motorcycle tail gas pollution becomes crucial at present and in the future problem.
At present, the catalytic effect of general fresh attitude catalyst all can satisfy laws and regulations requirement, like γ-Al
2O
3Material, it is applied to the automobile catalyst coating has had the history in a lot of years, not ccontaining doubtful γ-Al
2O
3It is the important prerequisite that guarantees catalyst quality that porous and heat endurance are only, because γ-Al
2O
3It is tightly packed that oxonium ion is approximately cube center of area in the structure, Al
3+Be distributed among the octahedron and tetrahedron space that surrounds by oxonium ion porous characteristic highly significant brokenly.
And in the reality, the operating mode of motorcycle is more abominable than automobile, and especially the rotating speed of motorcycle and temperature are higher, and thermic load and catalysis load significantly increases concerning catalyst converter, for γ-Al
2O
3Material, it can change α-Al into when high temperature
2O
3, α-Al
2O
3Oxonium ion is that six sides are tightly packed, Al
3+Be distributed in the octahedral coordination center that oxonium ion surrounds symmetrically, γ-Al
2O
3Change α-Al into
2O
3Cause crystal grain to reunite, specific area reduces same very remarkable.
For overcoming above problem, general method is at γ-Al
2O
3Middle auxiliary agent La, the Zr of adding comes obviously to improve γ-Al with this
2O
3Heat endurance and crystal orientation transition temperature.
At present similar research and application about this respect is also many; Invention disclosed has: the patent CN1668534 of Rhodia Electronics And Catalys's application; Based on the composition of the oxide of zirconia and cerium, lanthanum and another kind of rare earth element, its preparation method and its purposes as catalyst; The patent CN1752012 of Zhejiang University's application, the preparation method of cerium lanthanium complex oxide; The above preparation method is mechanical mixing, the precipitation method, sol method mostly, and is the conversion of nitrate mostly, and the compound crystal grain that obtains is thicker; In building-up process, pollute the environment; This deviates from the environmental protection theory of advocating at present mutually, in addition, and γ-Al in the compound of acquisition
2O
3Generally at 900 ℃-1000 ℃, this crystal orientation transition temperature is on the low side relatively for material crystal orientation transition temperature, is difficult to satisfy the needs of the actual use of motorcycle.
Summary of the invention
To the problems referred to above, the present invention has designed a kind of La, Zr doped gamma-Al
2O
3Hydro-thermal synthetic preparation method, make the compound crystal grain that obtains thinner, be nanoscale, and the entire synthesis process contamination-free produces, Environmental Safety, the crystal orientation transition temperature of the compound that crucial is synthesizes can reach more than 1100 ℃, has obviously improved γ-Al
2O
3The heat resistance of material is for catalyst provides reliable assurance in high temperature durability.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
A kind of La, Zr doped gamma-Al
2O
3Hydro-thermal synthetic preparation method, comprise following step:
A, raw-material mixing and stirring
According to mol ratio aluminium isopropoxide, lanthanum isopropoxide, zirconium iso-propoxide are mixed, and add ionized water, stir about 1 hour, add the pH value conditioning agent afterwards again to make solution obtain suitable substance P H value, and then stirred 30 minutes according to 30% solid solution ratio;
B, hydro-thermal are synthesized
The above-mentioned material that stirs is joined in the agitated reactor; Heating makes temperature remain on 180 ~ 200 ℃, and pressure remains on 35-40MPa, will notice in heating process checking that seals at can not reveal; After the successive reaction 600 minutes; Stop heating, equitemperature drops to below 70 ℃ opens agitated reactor, takes out product;
The separation of c, product, washing and drying and sintering
Product is collected, and the speed centrifugation of putting into supercentrifuge 10000RPM was removed supernatant liquid after 15 minutes; The sediment of lower floor is taken out adding adequate amount of ethanol dissolving washing; And the removal of the supernatant liquid after will washing, add the operation of ethanol repeated washing more again twice or thrice, the ethanol volatilization that obtains in the product is complete; Then will precipitate to take out places 120 ℃ of oven dryings after about 4 hours; Be placed in the sintering furnace 700 ℃ of insulations 4 hours, can obtain the La of clean, dry, Zr doped gamma-Al
2O
3
Further, the mol ratio of above-mentioned aluminium isopropoxide, lanthanum isopropoxide, zirconium iso-propoxide is aluminium isopropoxide 100, lanthanum isopropoxide 1 ~ 10, zirconium iso-propoxide 1 ~ 5.
Further, the purity of above-mentioned aluminium isopropoxide, lanthanum isopropoxide, zirconium iso-propoxide all will reach more than 99%.
Further, above-mentioned pH value conditioning agent is a red fuming nitric acid (RFNA).
Further, the addition of above-mentioned pH value conditioning agent finally should guarantee PH=3 ~ 4 of solution.
The present invention is a kind of La, Zr doped gamma-Al
2O
3Hydro-thermal synthetic preparation method; It is in the preparation process; With aluminium isopropoxide, lanthanum isopropoxide, zirconium iso-propoxide mixed in molar ratio and stir according to the rules, and generate composite oxides through the synthetic reaction of HTHP and certain hour, and after the repeatedly washing of ethanol; And obtain pure La, Zr doped gamma-Al after the final drying
2O
3Material.
The compound crystal grain that obtains through preparation method of the present invention is thinner, is nanoscale, and the generation of entire synthesis process contamination-free, Environmental Safety, and the most important point is, through the γ-Al of above preparation method's acquisition
2O
3Structural stability improves greatly, and the fresh attitude of specific area can reach 180-230 m
2/ g, 1100 ℃ of aging specific areas after 4 hours can reach 120-150 m
2/ g makes γ-Al
2O
3The crystal orientation transition temperature is brought up to more than 1000 ℃ by 800 ℃ ~ 900 ℃, and the ageing resistace of catalyst has been played conclusive effect.
The specific embodiment
A kind of La, Zr doped gamma-Al
2O
3Hydro-thermal synthetic preparation method, comprise following step:
The first step: take by weighing aluminium isopropoxide: lanthanum isopropoxide: zirconium iso-propoxide=2042.4 grams: 65.9 grams: 56.9 grams mix, and add 5052.1 gram deionized waters, stir after 1 hour; Add an amount of red fuming nitric acid (RFNA) again; Test PH=3.9 stirred 30 minutes again, stopped to stir.
Second step: said mixture is placed agitated reactor back heated sealed to 190 ℃, and adjustment pressure is heat-insulation pressure keeping behind the 38.0MPa, stops heating and pressurization after 600 minutes, and when waiting temperature of reaction kettle to reduce by 70 ℃, removal pressure is opened agitated reactor, takes out product.
The 3rd step: the speed centrifugation of product being collected and being positioned over supercentrifuge 10000RPM stopped centrifuge after 15 minutes.
The 4th step: the supernatant liquid of removing product; The absolute ethyl alcohol that adds 800ML afterwards washs, and the removal of the supernatant liquid after will washing, and adds the absolute ethyl alcohol continuous washing again 2 times; The products that obtain at last etc. are put into 120 ℃ of insulations of baking oven 4H after wherein ethanol all volatilized about 2 hours again; Be placed in the sintering furnace 700 ℃ of insulations 4 hours again, promptly obtained dry pure La, Zr doped gamma-Al
2O
3
γ-Al through above preparation method's acquisition
2O
3Structural stability improves greatly, and the fresh attitude of specific area can reach 192 m
2/ g, 1100 ℃ of aging specific areas after 4 hours can reach 120 m
2/ g makes γ-Al
2O
3The crystal orientation transition temperature is brought up to more than 1000 ℃ by 800 ℃ ~ 900 ℃, and the ageing resistace of catalyst has been played conclusive effect.
The La that preparation method of the present invention obtains, Zr doped gamma-Al
2O
3It is to have passed through the emission test of durable 200H on the 150CC motorcycle that material is applied in discharge capacity, can reach 94%, 92%, 89% respectively to the conversion ratio of CO, HC, NOX.
Claims (5)
1. a La, Zr doped gamma-Al
2O
3Hydro-thermal synthetic preparation method, it is characterized in that: comprise following step,
A, raw-material mixing and stirring
According to mol ratio aluminium isopropoxide, lanthanum isopropoxide, zirconium iso-propoxide are mixed, and add ionized water, stir about 1 hour, add the pH value conditioning agent afterwards again to make solution obtain suitable substance P H value, and then stirred 30 minutes according to 30% solid solution ratio;
B, hydro-thermal are synthesized
The above-mentioned material that stirs is joined in the agitated reactor; Heating makes temperature remain on 180 ~ 200 ℃, and pressure remains on 35-40MPa, will notice in heating process checking that seals at can not reveal; After the successive reaction 600 minutes; Stop heating, equitemperature drops to below 70 ℃ opens agitated reactor, takes out product;
The separation of c, product, washing and drying and sintering
Product is collected, and the speed centrifugation of putting into supercentrifuge 10000RPM was removed supernatant liquid after 15 minutes; The sediment of lower floor is taken out adding adequate amount of ethanol dissolving washing; And the removal of the supernatant liquid after will washing, add the operation of ethanol repeated washing more again twice or thrice, fully with the volatilization of the ethanol in the product that obtains; Then will precipitate to take out places 120 ℃ of oven dryings after about 4 hours; Be placed in the sintering furnace 700 ℃ of insulations 4 hours again, can obtain the La of clean, dry, Zr doped gamma-Al
2O
3
2. a kind of La as claimed in claim 1, Zr doped gamma-Al
2O
3Hydro-thermal synthetic preparation method, it is characterized in that: the mol ratio of said aluminium isopropoxide, lanthanum isopropoxide, zirconium iso-propoxide is aluminium isopropoxide 100, lanthanum isopropoxide 1 ~ 10, zirconium iso-propoxide 1 ~ 5.
3. according to claim 1 or claim 2 a kind of La, Zr doped gamma-Al
2O
3Hydro-thermal synthetic preparation method, it is characterized in that: the purity of said aluminium isopropoxide, lanthanum isopropoxide, zirconium iso-propoxide all will reach more than 99%.
4. a kind of La as claimed in claim 1, Zr doped gamma-Al
2O
3Hydro-thermal synthetic preparation method, it is characterized in that: said pH value conditioning agent is a red fuming nitric acid (RFNA).
5. like claim 1 or 4 described a kind of La, Zr doped gamma-Al
2O
3Hydro-thermal synthetic preparation method, it is characterized in that: the addition of said pH value conditioning agent finally should guarantee PH=3 ~ 4 of solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210047310XA CN102614863A (en) | 2012-02-28 | 2012-02-28 | Hydrothermal synthesis preparation method of La and Zr doped gamma-Al2O3 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210047310XA CN102614863A (en) | 2012-02-28 | 2012-02-28 | Hydrothermal synthesis preparation method of La and Zr doped gamma-Al2O3 |
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| CN102614863A true CN102614863A (en) | 2012-08-01 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108788173A (en) * | 2018-06-25 | 2018-11-13 | 天津大学 | A kind of hydrothermal preparing process of ultrafine yttria doping tungsten composite powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1668534A (en) * | 2002-06-26 | 2005-09-14 | 罗狄亚电子与催化公司 | Composition based on zirconium oxide and oxides of cerium, lanthanum and of another rare earth, a method for preparing same and use thereof as catalyst |
| CN1752012A (en) * | 2005-07-14 | 2006-03-29 | 浙江大学 | Preparation method of cerium lanthanium complex oxide |
-
2012
- 2012-02-28 CN CN201210047310XA patent/CN102614863A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1668534A (en) * | 2002-06-26 | 2005-09-14 | 罗狄亚电子与催化公司 | Composition based on zirconium oxide and oxides of cerium, lanthanum and of another rare earth, a method for preparing same and use thereof as catalyst |
| CN1752012A (en) * | 2005-07-14 | 2006-03-29 | 浙江大学 | Preparation method of cerium lanthanium complex oxide |
Non-Patent Citations (1)
| Title |
|---|
| 朱洪伟等: "氧化铝-氧化锆复合材料的水热合成及其性能研究", 《第六届全国环境催化与环境材料学术会议论文集》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108788173A (en) * | 2018-06-25 | 2018-11-13 | 天津大学 | A kind of hydrothermal preparing process of ultrafine yttria doping tungsten composite powder |
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Application publication date: 20120801 |