CN117753402A - Preparation method of high-specific-surface-area anti-aging CeZr precursor - Google Patents
Preparation method of high-specific-surface-area anti-aging CeZr precursor Download PDFInfo
- Publication number
- CN117753402A CN117753402A CN202311724701.5A CN202311724701A CN117753402A CN 117753402 A CN117753402 A CN 117753402A CN 202311724701 A CN202311724701 A CN 202311724701A CN 117753402 A CN117753402 A CN 117753402A
- Authority
- CN
- China
- Prior art keywords
- cezr
- aging
- specific surface
- surface area
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 34
- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000012065 filter cake Substances 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 25
- 238000001354 calcination Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 abstract description 8
- 238000005054 agglomeration Methods 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000002270 dispersing agent Substances 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of an anti-aging CeZr precursor with high specific surface area, which comprises the following steps: (1) Adding ammonia water to Ce (NH) 4 ) 2 (NO 3 ) 6 、ZrO(NO 3 ) 2 、La(NO 3 ) 3 、Y(NO 3 ) 3 In the mixed oxide, water washing and centrifugal dehydration are carried out to obtain CeZrLaY paste; (2) Adding deionized water into the paste and stirring the mixture to obtain dispersed slurry; (3) Adding the dispersed slurry into an autoclave, and adding polyvinylpyrrolidone and ethylene glycol under inert gas for reaction; (4) carrying out vacuum suction filtration on the reactant to obtain a filter cake; (5) And adding ethylene glycol butyl ether into the filter cake to calcine to obtain the CeZr precursor. The preparation method of the high specific surface area anti-aging CeZr precursor adopts high-pressure reaction, and adds the compound dispersing agent in the reaction, thereby reducing agglomeration, improving the sintering resistance and the aging resistance of pores, and further reducing by adding SFA in calcinationLittle agglomeration.
Description
Technical Field
The invention belongs to the technical field of tail gas purifying catalyst materials, and particularly relates to a preparation method of an anti-aging CeZr precursor with high specific surface area.
Background
The Cezr catalyst is a composite catalyst composed of cerium and zirconium, and has high activity and selectivity in catalytic reaction. The method generally selects a metal compound with higher catalytic activity and stability as a starting material, and obtains a precursor of the Cezr catalyst through a specific synthesis method, and the precursor can obtain the Cezr catalyst after proper activation treatment.
Cezr catalyst precursors are an important step in the preparation of Cezr catalysts. At present, the methods for preparing the Cezr catalyst precursor at home and abroad mainly comprise a high-energy ball milling method, a coprecipitation method, a sol-gel method and a hydrothermal method, wherein the coprecipitation method and the hydrothermal method are main methods for industrial production of the Cezr catalyst precursor. However, the cerium-zirconium composite oxide prepared by the coprecipitation method has larger crystal grains, low specific surface area, smaller crystal grain aggregation of the cerium-zirconium composite oxide prepared by the hydrothermal method, slightly improved specific surface area compared with the oxide obtained by the coprecipitation method, weaker ageing resistance and performance which cannot meet the increasingly strict requirements of emission regulations.
Therefore, a need exists for a method of preparing an anti-aging CeZr precursor with a high specific surface area.
Disclosure of Invention
The invention aims to provide a preparation method of an anti-aging CeZr precursor with high specific surface area, and the prepared CeZr precursor has high specific surface area and strong anti-aging capability.
The invention solves the problems by adopting the following technical scheme: the preparation method of the high specific surface area anti-aging CeZr precursor comprises the following steps:
(1) Preparation of CeZrLaY paste
Adding ammonia water to Ce (NH) 4 ) 2 (NO 3 ) 6 、ZrO(NO 3 ) 2 、La (NO 3 ) 3 、Y (NO 3 ) 3 Controlling the pH value of the mixed oxide to be more than 10, and obtaining CeZrLaY paste after washing and centrifugal dehydration;
(2) Dispersed CeZrLaY paste
Adding deionized water into the CeZrLaY paste, and stirring to obtain slurry, wherein no large particles are ensured to be present;
(3) Autoclave reaction
Adding the dispersed slurry into an autoclave, and adding polyvinylpyrrolidone and ethylene glycol under the inert gas environment for reaction;
(4) After the reaction, carrying out vacuum suction filtration on the reactant to obtain a filter cake;
(5) Filter cake calcination
And (3) adding ethylene glycol butyl ether into the filter cake in the step (4), and calcining to obtain the CeZr precursor.
Preferably, the Ce (NH) in step (1) 4 ) 2 (NO 3 ) 6 、ZrO(NO 3 ) 2 、La (NO 3 ) 3 、Y (NO 3 ) 3 The mass ratio of (2) is 45:40:10:5.
Preferably, the water used for the washing in step (1) has a conductivity of < 2. Mu.s/cm.
Preferably, the slurry concentration after dispersion in step (2) is 100g/L and the pH is > 8.5.
Preferably, in the step (3), the reaction temperature is 150-180 ℃, the reaction time is 2-3 h, and the reaction pressure is 70-90 bars.
Preferably, in the step (3), the mass ratio of polyvinylpyrrolidone, ethylene glycol and mixed oxide is 1:1:1.
Preferably, in the step (5), the mass ratio of the ethylene glycol butyl ether to the mixed oxide is 1.5:1.
Preferably, the calcination temperature in step (5) is 750 ℃ and the calcination time is 5 hours.
Compared with the prior art, the invention has the advantages that:
the preparation method of the CeZr precursor adopts high-pressure reaction, the reaction temperature is high, the reaction pressure is high, and a compound dispersing agent (polyvinylpyrrolidone and ethylene glycol) is added in the high-pressure reaction, so that agglomeration is reduced, the pore sintering resistance is improved, and the ageing resistance is improved; in addition, ethylene glycol butyl ether is added in the calcination process, so that agglomeration is further reduced.
Description of the embodiments
The present invention is described in further detail below with reference to examples.
Example 1
The preparation method of the high specific surface area anti-aging CeZr precursor comprises the following steps:
(1) Preparation of CeZrLaY paste
Adding ammonia water to Ce (NH) 4 ) 2 (NO 3 ) 6 、ZrO(NO 3 ) 2 、La (NO 3 ) 3 、Y (NO 3 ) 3 Controlling the pH value of the mixed oxide to be more than 10, washing with water (the conductivity of water used for washing=1.5 mu s/cm), and centrifugally dehydrating to obtain CeZrLaY paste; the Ce (NH) 4 ) 2 (NO 3 ) 6 、ZrO(NO 3 ) 2 、La (NO 3 ) 3 、Y (NO 3 ) 3 The mass ratio of (2) is 45:40:10:5.
(2) Dispersed CeZrLaY paste
And adding deionized water into the CeZrLaY paste, stirring to obtain slurry, wherein the concentration of the slurry is 100g/L, and the pH=9, and ensuring that no large particles exist.
(3) Autoclave reaction
Adding the dispersed slurry into an autoclave, adding polyvinylpyrrolidone and ethanol under the inert gas environment, and reacting for 2.5 hours under the condition that the reaction temperature is 170 ℃ and the reaction pressure is 85 bars; the mass ratio of the polyvinylpyrrolidone to the glycol to the mixed oxide is 1:1:1.
(4) After the reaction, carrying out vacuum suction filtration on the reactant to obtain a filter cake;
(5) Filter cake calcination
Adding ethylene glycol butyl ether into the filter cake in the step (4), and calcining for 5 hours at the temperature of 750 ℃ to obtain a CeZr precursor; the mass ratio of the ethylene glycol butyl ether to the mixed oxide is 1.5:1.
Example 2
The preparation method of the high specific surface area anti-aging CeZr precursor comprises the following steps:
(1) Preparation of CeZrLaY paste
Adding ammonia water to Ce (NH) 4 ) 2 (NO 3 ) 6 、ZrO(NO 3 ) 2 、La (NO 3 ) 3 、Y (NO 3 ) 3 Controlling the pH value of the mixed oxide to be more than 10, washing with water (the conductivity of water used for washing=1.5 mu s/cm), and centrifugally dehydrating to obtain CeZrLaY paste; the Ce (NH) 4 ) 2 (NO 3 ) 6 、ZrO(NO 3 ) 2 、La (NO 3 ) 3 、Y (NO 3 ) 3 The mass ratio of (2) is 45:40:10:5.
(2) Dispersed CeZrLaY paste
Adding deionized water into the CeZrLaY paste, and stirring to obtain slurry, wherein no large particles are ensured to be present; the slurry concentration after dispersion was 100g/L, pH=9.
(3) Autoclave reaction
Adding the dispersed slurry into an autoclave, adding polyvinylpyrrolidone and ethanol under the inert gas environment, and reacting for 2 hours under the conditions of the reaction temperature of 180 ℃ and the reaction pressure of 90 bars; the mass ratio of the polyvinylpyrrolidone to the glycol to the mixed oxide is 1:1:1.
(4) After the reaction, carrying out vacuum suction filtration on the reactant to obtain a filter cake;
(5) Filter cake calcination
Adding ethylene glycol butyl ether SFA into the filter cake in the step (4), and calcining for 5 hours at the temperature of 750 ℃ to obtain a CeZr precursor; the mass ratio of the ethylene glycol butyl ether to the mixed oxide is 1.5:1.
Example 3
The preparation method of the high specific surface area anti-aging CeZr precursor comprises the following steps:
(1) Preparation of CeZrLaY paste
Adding ammonia water to Ce (NH) 4 ) 2 (NO 3 ) 6 、ZrO(NO 3 ) 2 、La (NO 3 ) 3 、Y (NO 3 ) 3 Controlling the pH value of the mixed oxide to be more than 10, washing with water (the conductivity of water used for washing=1.5 mu s/cm), and centrifugally dehydrating to obtain CeZrLaY paste; the Ce (NH) 4 ) 2 (NO 3 ) 6 、ZrO(NO 3 ) 2 、La (NO 3 ) 3 、Y (NO 3 ) 3 The mass ratio of (2) is 45:40:10:5.
(2) Dispersed CeZrLaY paste
Adding deionized water into the CeZrLaY paste, and stirring to obtain slurry, wherein no large particles are ensured to be present; the slurry concentration after dispersion was 100g/L, pH=9.
(3) Autoclave reaction
Adding the dispersed slurry into an autoclave, adding polyvinylpyrrolidone and ethanol under the inert gas environment, and reacting for 3 hours under the conditions of the reaction temperature of 175 ℃ and the reaction pressure of 88 bars; the mass ratio of the polyvinylpyrrolidone to the glycol to the mixed oxide is 1:1:1.
(4) After the reaction, carrying out vacuum suction filtration on the reactant to obtain a filter cake;
(5) Filter cake calcination
Adding ethylene glycol butyl ether into the filter cake in the step (4), and calcining for 5 hours at the temperature of 750 ℃ to obtain a CeZr precursor; the mass ratio of the ethylene glycol butyl ether to the mixed oxide is 1.5:1.
Comparative example 1
The only difference from example 1 is that: and (3) reacting at normal pressure.
Comparative example 2
The only difference from example 1 is that: only ethylene glycol was added.
Comparative example 3
The only difference from example 1 is that: only polyvinylpyrrolidone was added.
Comparative example 4
The only difference from example 1 is that: no ethylene glycol butyl ether was added.
The CeZr precursors prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to specific surface area tests, and the test results are shown in table 1.
The specific surface area testing method comprises the following steps: the detection was performed using a NOVA fully automated specific surface area and void analyzer at 77K using nitrogen as the adsorption gas. The sample needs to be degassed for 1-2 hours at 250 ℃ before nitrogen adsorption and desorption test to remove moisture and air in the pore canal of the material, and then detection is carried out. The specific surface area is calculated by the multipoint BET method.
TABLE 1 specific surface area test results for CeZr precursors prepared in examples 1-3 and comparative examples 1-4
From the test results of the specific surface areas of the example 1 and the comparative example 1 in the table, the agglomeration can be reduced by adopting high pressure in the preparation method of the CeZr precursor, so that the prepared CeZr precursor has high specific surface area, the pore sintering resistance and the ageing resistance are improved; from the test results of specific surface areas of the embodiment 1 and the comparative examples 2-3, the addition of the compound dispersing agent consisting of polyvinylpyrrolidone and ethylene glycol in the high-pressure reaction can reduce agglomeration, so that the prepared CeZr precursor has high specific surface area and ageing resistance; from the results of the specific surface area test of example 1 and comparative example 4, it is understood that the addition of butyl cellosolve can reduce agglomeration, so that the finished product has a high specific surface area.
In addition to the above embodiments, the present invention also includes other embodiments, and all technical solutions that are formed by equivalent transformation or equivalent substitution should fall within the protection scope of the claims of the present invention.
Claims (8)
1. A preparation method of an anti-aging CeZr precursor with high specific surface area is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparation of CeZrLaY paste
Adding ammonia water to Ce (NH) 4 ) 2 (NO 3 ) 6 、ZrO(NO 3 ) 2 、La (NO 3 ) 3 、Y (NO 3 ) 3 In mixed oxide, controlMaking pH > 10, and then washing with water and centrifugally dewatering to obtain CeZrLaY paste;
(2) Dispersed CeZrLaY paste
Adding deionized water into the CeZrLaY paste, and stirring to obtain slurry, wherein no large particles are ensured to be present;
(3) Autoclave reaction
Adding the dispersed slurry into an autoclave, and adding polyvinylpyrrolidone and ethylene glycol under the inert gas environment for reaction;
(4) After the reaction, carrying out vacuum suction filtration on the reactant to obtain a filter cake;
(5) Filter cake calcination
And (3) adding ethylene glycol butyl ether into the filter cake in the step (4), and calcining to obtain the CeZr precursor.
2. The method for preparing the high specific surface area anti-aging CeZr precursor according to claim 1, wherein the method comprises the steps of: the Ce (NH) in step (1) 4 ) 2 (NO 3 ) 6 、ZrO(NO 3 ) 2 、La (NO 3 ) 3 、Y (NO 3 ) 3 The mass ratio of (2) is 45:40:10:5.
3. The method for preparing the high specific surface area anti-aging CeZr precursor according to claim 1, wherein the method comprises the steps of: the conductivity of the water used for washing in the step (1) is less than 2 mu s/cm.
4. The method for preparing the high specific surface area anti-aging CeZr precursor according to claim 1, wherein the method comprises the steps of: the concentration of the dispersed slurry in the step (2) is 100g/L, and the pH value is more than 8.5.
5. The method for preparing the high specific surface area anti-aging CeZr precursor according to claim 1, wherein the method comprises the steps of: in the step (3), the reaction temperature is 150-180 ℃, the reaction time is 2-3 h, and the reaction pressure is 70-90 bars.
6. The method for preparing the high specific surface area anti-aging CeZr precursor according to claim 1, wherein the method comprises the steps of: and (3) the mass ratio of polyvinylpyrrolidone, ethylene glycol and mixed oxide in the step (3) is 1:1:1.
7. The method for preparing the high specific surface area anti-aging CeZr precursor according to claim 1, wherein the method comprises the steps of: and (3) the mass ratio of the ethylene glycol butyl ether to the mixed oxide in the step (5) is 1.5:1.
8. The method for preparing the high specific surface area anti-aging CeZr precursor according to claim 1, wherein the method comprises the steps of: in the step (5), the calcination temperature is 750 ℃ and the calcination time is 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311724701.5A CN117753402A (en) | 2023-12-15 | 2023-12-15 | Preparation method of high-specific-surface-area anti-aging CeZr precursor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311724701.5A CN117753402A (en) | 2023-12-15 | 2023-12-15 | Preparation method of high-specific-surface-area anti-aging CeZr precursor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117753402A true CN117753402A (en) | 2024-03-26 |
Family
ID=90313801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311724701.5A Pending CN117753402A (en) | 2023-12-15 | 2023-12-15 | Preparation method of high-specific-surface-area anti-aging CeZr precursor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117753402A (en) |
-
2023
- 2023-12-15 CN CN202311724701.5A patent/CN117753402A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6471240B2 (en) | Cerium-zirconium composite oxide, production method thereof and use of catalyst | |
| EP1894620B1 (en) | Porous zirconia powder and production method of same | |
| CN110227560B (en) | Preparation method of honeycomb-shaped copper chloride/SCR (Selective catalytic reduction) demercuration catalyst | |
| CN108722408B (en) | Catalyst for synthesizing ethylene glycol by dimethyl oxalate gas phase hydrogenation and preparation method thereof | |
| CN102658114A (en) | Method for preparing aluminum oxide for catalyst | |
| US20230339773A1 (en) | Alpha-phase nickel hydroxide and preparation method and use thereof | |
| CN113200567A (en) | High-sintering-activity zirconium oxide powder and preparation method thereof | |
| CN103357441B (en) | Silver catalyst carrier, its preparation method, the catalyst be made up of it and application | |
| CN109772288B (en) | Surface cerium-rich nano cerium-zirconium composite oxide and preparation and application thereof | |
| KR20070045186A (en) | Catalyst for cycloolefin production and process for production | |
| CN111774055B (en) | Perovskite type monolithic catalyst and preparation method and application thereof | |
| CN117753402A (en) | Preparation method of high-specific-surface-area anti-aging CeZr precursor | |
| CN115318298B (en) | Copper-based three-way catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method and application thereof | |
| CN112573569B (en) | Rare earth composite oxide with high heat resistance and preparation method thereof | |
| CN106964385A (en) | Carrier-free copper bismuth catalyst for preparing 1,4 butynediols and preparation method thereof | |
| CN104495906A (en) | Method for preparing gamma-alumina doped rare earth oxide | |
| US11964255B2 (en) | Mixed oxide with improved reducibility | |
| Zhao et al. | The in situ growth of Mg–Al hydrotalcite on spherical alumina and its application as a support of a Pt-based catalyst for isobutane dehydrogenation | |
| CN110694622A (en) | Precious metal-loaded cerium-zirconium composite oxide and preparation method and application thereof | |
| CN106732706B (en) | Furfuraldehyde hydrogenation catalyst and preparation method thereof containing rare earth element | |
| CN111135815B (en) | Preparation method of high-purity nano cerium-zirconium solid solution material | |
| US20230149906A1 (en) | Compositions containing zirconium and cerium and methods for preparing same using oxalic acid and an alcohol | |
| CN114870847B (en) | Preparation method of copper-zinc-aluminum gas-phase hydrogenation catalyst, prepared catalyst and application | |
| CN116493040B (en) | Preparation method of high-performance Cu-based small-pore molecular sieve catalyst, obtained product and application | |
| CN111346495B (en) | Preparation method of metakaolin-based flue gas denitration agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |