CN106925251B - Aluminum-silicon-lanthanum composite oxide powder material and preparation method thereof - Google Patents
Aluminum-silicon-lanthanum composite oxide powder material and preparation method thereof Download PDFInfo
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- -1 Aluminum-silicon-lanthanum Chemical compound 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 33
- 239000000843 powder Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 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 abstract description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims description 27
- 229910052746 lanthanum Inorganic materials 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000010970 precious metal Substances 0.000 abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 3
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a new material, in particular to an aluminum-silicon-lanthanum composite oxide powder material and a preparation method thereof; the method comprises the following steps: a: firstly, hydrolyzing ethyl orthosilicate, and then adding an aluminum nitrate solution and a rare earth lanthanum nitrate solution to obtain a mixed solution; b, adding 0.5 wt% of polyethylene glycol as a dispersing agent into the mixed solution; c: stirring; d, aging; and E, drying. The preparation process is simple, the price and the cost of raw materials are low, and finally the automobile exhaust purification catalyst coating base material with high specific surface area maintained at high temperature can be prepared, and the base material with higher specific surface area can be provided for the automobile exhaust catalytic coating, so that the automobile exhaust catalytic purification efficiency is improved, and the use amount of precious metals is reduced.
Description
Technical Field
The invention relates to a new material, in particular to an aluminum-silicon-lanthanum composite oxide powder material and a preparation method thereof.
Background
The technology for decomposing harmful substances in the automobile exhaust by using the three-way catalyst is a mature technology for treating the automobile exhaust pollution at present. The technology is that the precious metal with good catalytic purification function on the automobile tail gas, such as rhodium, platinum and other salts or rhodium, platinum and other micron and nano particles are dispersed in ceramic particle slurry which is used as a catalyst coating substrate and coated on the surface of a catalyst carrier, and after high-temperature sintering, the slurry forms a coating with catalytic purification function on the automobile tail gas on the surface of the catalyst carrier. In the process of catalytic decomposition of harmful substances in automobile exhaust by using a catalyst, the specific surface area of a coating containing a noble metal catalyst such as rhodium, platinum and the like in a high-temperature working environment directly influences the catalytic purification efficiency of the catalyst on the exhaust, and the larger the specific surface area of the coating is, the higher the catalytic purification efficiency is. At present, the actually used automobile exhaust catalyst coating base material is mainly gamma-Al2O3And CeO2、ZrO2The powder material is mainly used, and the specific surface area of the powder after calcination for 4 hours at 1000 ℃ is about 100-150 m2/g。
With the stricter control of automobile exhaust emission and the decreasing price of automobiles, researchers in related fields strive to improve the exhaust purification efficiency of catalysts without increasing the amount of noble metal catalysts. For this reason, increasing the catalytic contact area of the noble metal distributed in the coating with the exhaust gas by increasing the specific surface area of the substrate material of the catalyst coating is an important way to achieve the above object. Therefore, there is a need to develop a novel catalyst coating material that can maintain a larger specific surface area at high temperatures than existing catalyst coating base materials.
Disclosure of Invention
The invention aims to provide an aluminum-silicon-lanthanum composite oxide powder material and a preparation method thereof, which solve the problem of tail gas purification efficiency of a catalyst.
The invention is realized in such a way that the aluminum-silicon-lanthanum composite oxide powder material and the preparation method thereof comprise the following steps:
a: firstly, hydrolyzing ethyl orthosilicate, and then adding an aluminum nitrate solution and a rare earth lanthanum nitrate solution to obtain a mixed solution;
b, adding 0.5 wt% of polyethylene glycol as a dispersing agent into the mixed solution;
c: stirring;
d, aging;
and E, drying.
The further technical scheme of the invention is as follows: the concentration of the aluminum nitrate solution added in the step A is 0.3 mol/L.
The further technical scheme of the invention is that the concentration of the rare earth lanthanum nitrate solution added in the step A is 0.1 mol/L.
The further technical scheme of the invention is as follows: the stirring time in the step C is 30 min; ammonia was added dropwise to the mixture while stirring until the pH of the mixture became 9.
The further technical scheme of the invention is as follows: and D, aging the mixed solution in a water bath at 70 ℃ for 1 hour to obtain a precipitate containing silicon, aluminum and lanthanum.
The further technical scheme of the invention is as follows: and E, washing and filtering the precipitate, and drying at 110 ℃ for 24 hours to obtain the aluminum-silicon-lanthanum composite oxide powder material.
The further technical scheme of the invention is as follows: and in the step E, calcining the precipitate at 500 ℃ for 2 hours to obtain the aluminum-silicon-lanthanum composite oxide powder material.
The invention has the beneficial effects that: the preparation process is simple, the price and the cost of raw materials are low, and finally the automobile exhaust purification catalyst coating base material with high specific surface area maintained at high temperature can be prepared, and the base material with higher specific surface area can be provided for the automobile exhaust catalytic coating, so that the automobile exhaust catalytic purification efficiency is improved, and the use amount of precious metals is reduced.
Detailed Description
The first embodiment is as follows: (1) mixing the hydrolyzed tetraethoxysilane with an aluminum nitrate solution, wherein the molar ratio of Al3+ to Si4+ in the mixed solution is 2.5:1, and the concentration of Al3+ in the mixed solution is controlled to be 0.3 mol/L;
(2) the amount of La (NO3)3 is determined according to the proportion that the content of La2O3 is 3 wt.% of aluminum silicon oxide, and prepared into 0.1mol/LLa (NO3)3 aqueous solution which is added into the mixed solution of tetraethoxysilane and aluminum nitrate.
(3) Adding 0.5 wt.% of PEG4000 to the mixture;
(4) under the condition of strong stirring, dropwise adding ammonia water into the mixed solution until the pH value is 9, and completely precipitating aluminum ions, silicon ions and lanthanum ions in the mixed solution;
(5) aging the mixed solution of the formed precipitate in a water bath at 70 ℃ for 1 hour, then washing, filtering, separating the precipitate, and drying the precipitate at 110 ℃ for 24 hours;
(6) calcining the precipitate at 500 ℃ for 2 hours to obtain an aluminum-silicon-lanthanum composite oxide powder material, and measuring the specific surface area of the powder to be 396.8m 2/g;
(7) the alumina-silica-lanthanum composite oxide powder material calcined at 500 ℃ is calcined at 1000 ℃ for 4 hours, and the specific surface area of the powder is measured to be 182.5m 2/g.
Example two: (1) mixing the hydrolyzed tetraethoxysilane and aluminum nitrate solution, wherein the molar ratio of Al3+ to Si4+ in the mixed solution is 3:1, and the concentration of Al3+ in the mixed solution is controlled to be 0.3 mol/L;
(2) the amount of La (NO3)3 is determined according to the proportion that the content of La2O3 is 3 wt.% of aluminum silicon oxide, and prepared into 0.1mol/LLa (NO3)3 aqueous solution which is added into the mixed solution of tetraethoxysilane and aluminum nitrate.
(3) Adding 0.5 wt.% of PEG4000 to the mixture;
(4) under the condition of strong stirring, dropwise adding ammonia water into the mixed solution until the pH value is 9, and completely precipitating aluminum ions, silicon ions and lanthanum ions in the mixed solution;
(5) aging the mixed solution of the formed precipitate in a water bath at 70 ℃ for 1 hour, then washing, filtering, separating the precipitate, and drying the precipitate at 110 ℃ for 24 hours;
(6) calcining the precipitate at 500 ℃ for 2 hours to obtain an aluminum-silicon-lanthanum composite oxide powder material, and measuring the specific surface area of the powder to be 446.7m 2/g;
(7) the alumina-silica-lanthanum composite oxide powder material calcined at 500 ℃ is calcined at 1000 ℃ for 4 hours, and the specific surface area of the powder is 233.2m 2/g.
Example three: (1) mixing the hydrolyzed tetraethoxysilane and aluminum nitrate solution, wherein the molar ratio of Al3+ to Si4+ in the mixed solution is 3.5:1, and the concentration of Al3+ in the mixed solution is controlled to be 0.3 mol/L;
(2) the amount of La (NO3)3 is determined according to the proportion that the content of La2O3 is 3 wt.% of aluminum silicon oxide, and prepared into 0.1mol/LLa (NO3)3 aqueous solution which is added into the mixed solution of tetraethoxysilane and aluminum nitrate.
(3) Adding 0.5 wt.% of PEG4000 to the mixture;
(4) under the condition of strong stirring, dropwise adding ammonia water into the mixed solution until the pH value is 9, and completely precipitating aluminum ions, silicon ions and lanthanum ions in the mixed solution;
(5) aging the mixed solution of the formed precipitate in a water bath at 70 ℃ for 1 hour, then washing, filtering, separating the precipitate, and drying the precipitate at 110 ℃ for 24 hours;
(6) calcining the precipitate at 500 ℃ for 2 hours to obtain an aluminum-silicon-lanthanum composite oxide powder material, and measuring the specific surface area of the powder to be 478.6m 2/g;
(7) the alumina-silica-lanthanum composite oxide powder material calcined at 500 ℃ is calcined at 1000 ℃ for 4 hours, and the specific surface area of the powder is 267.4m 2/g.
Example four: (1) mixing the hydrolyzed tetraethoxysilane and aluminum nitrate solution, wherein the molar ratio of Al3+ to Si4+ in the mixed solution is 3:1, and the concentration of Al3+ in the mixed solution is controlled to be 0.3 mol/L;
(2) the amount of La (NO3)3 is determined according to the proportion that the content of La2O3 is 1 wt.% of aluminum silicon oxide, and prepared into an aqueous solution with the concentration of 0.1mol/LLa (NO3)3 to be added into the mixed solution of tetraethoxysilane and aluminum nitrate.
(3) Adding 0.5 wt.% of PEG4000 to the mixture;
(4) under the condition of strong stirring, dropwise adding ammonia water into the mixed solution until the pH value is 9, and completely precipitating aluminum ions, silicon ions and lanthanum ions in the mixed solution;
(5) aging the mixed solution of the formed precipitate in a water bath at 70 ℃ for 1 hour, then washing, filtering, separating the precipitate, and drying the precipitate at 110 ℃ for 24 hours;
(6) calcining the precipitate at 500 ℃ for 2 hours to obtain an aluminum-silicon-lanthanum composite oxide powder material, and measuring the specific surface area of the powder to be 401.6m 2/g;
(7) the aluminum-silicon-lanthanum composite oxide powder material calcined at the temperature of 500 ℃ is calcined at the temperature of 1000 ℃ for 4 hours, and the specific surface area of the powder is 195.1m 2/g.
Example five: (1) mixing the hydrolyzed tetraethoxysilane and aluminum nitrate solution, wherein the molar ratio of Al3+ to Si4+ in the mixed solution is 3:1, and the concentration of Al3+ in the mixed solution is controlled to be 0.3 mol/L;
(2) the amount of La (NO3)3 is determined according to the proportion that the content of La2O3 is 5 wt.% of aluminum silicon oxide, and prepared into an aqueous solution with the concentration of 0.1mol/LLa (NO3)3 to be added into the mixed solution of tetraethoxysilane and aluminum nitrate.
(3) Adding 0.5 wt.% of PEG4000 to the mixture;
(4) under the condition of strong stirring, dropwise adding ammonia water into the mixed solution until the pH value is 9, and completely precipitating aluminum ions, silicon ions and lanthanum ions in the mixed solution;
(5) aging the mixed solution of the formed precipitate in a water bath at 70 ℃ for 1 hour, then washing, filtering, separating the precipitate, and drying the precipitate at 110 ℃ for 24 hours;
(6) calcining the precipitate at 500 ℃ for 2 hours to obtain the aluminum-silicon-lanthanum composite oxide powder material. The specific surface area of the powder is measured to be 420.5m 2/g;
(7) the alumina-silica-lanthanum composite oxide material calcined at 500 ℃ was further calcined at 1000 ℃ for 4 hours, and the specific surface area of the powder was found to be 203.6m 2/g.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (1)
1. The preparation method of the aluminum-silicon-lanthanum composite oxide powder material for purifying the automobile exhaust is characterized by comprising the following steps of:
(1) mixing the hydrolyzed ethyl orthosilicate and aluminum nitrate solution to obtain Al in the mixed solution3+With Si4+The molar ratio is 3.5:1, and Al in the mixed solution is controlled3+The concentration is 0.3 mol/L;
(2) with La2O3La (NO) was determined in a proportion of 3 wt.% of aluminum silicon oxide3)3Amount of (b) and formulated to a concentration of 0.1mol/LLa (NO)3)3Adding the aqueous solution into a mixed solution of tetraethoxysilane and aluminum nitrate;
(3) adding 0.5 wt.% of PEG4000 to the mixture;
(4) under the condition of strong stirring, dropwise adding ammonia water into the mixed solution until the pH value is 9, and completely precipitating aluminum ions, silicon ions and lanthanum ions in the mixed solution;
(5) aging the mixed solution of the formed precipitate in a water bath at 70 ℃ for 1 hour, then washing, filtering, separating the precipitate, and drying the precipitate at 110 ℃ for 24 hours;
(6) calcining the precipitate at 500 deg.C for 2 hr to obtain Al-Si-La composite oxide powder material with specific surface area of 478.6m2/g；
(7) Calcining the aluminum-silicon-lanthanum composite oxide powder material calcined at the temperature of 500 ℃ for 4 hours at the temperature of 1000 ℃ to obtain powder with the specific surface area of 267.4m2And/g, is used for the coating substrate material of the automobile exhaust purification catalyst.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978381A (en) * | 2005-12-09 | 2007-06-13 | 中国科学院兰州化学物理研究所 | Zirconium-base nano composite oxide powder and its preparing method |
| CN101239309A (en) * | 2008-02-22 | 2008-08-13 | 江苏金长江环保汽摩消声器有限公司 | High specific area cerium aluminium base composite oxides and preparation thereof |
| CN101462050A (en) * | 2007-12-19 | 2009-06-24 | 中国石油化工股份有限公司 | Mesoporous composite oxides and catalyst as well as preparation method and aromatization method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978381A (en) * | 2005-12-09 | 2007-06-13 | 中国科学院兰州化学物理研究所 | Zirconium-base nano composite oxide powder and its preparing method |
| CN101462050A (en) * | 2007-12-19 | 2009-06-24 | 中国石油化工股份有限公司 | Mesoporous composite oxides and catalyst as well as preparation method and aromatization method thereof |
| CN101239309A (en) * | 2008-02-22 | 2008-08-13 | 江苏金长江环保汽摩消声器有限公司 | High specific area cerium aluminium base composite oxides and preparation thereof |
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