CN113634263A - Perfluoroolefin epoxidation catalyst and application thereof - Google Patents
Perfluoroolefin epoxidation catalyst and application thereof Download PDFInfo
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Abstract
The invention discloses a perfluoroolefin epoxidation catalyst and application thereof, wherein the catalyst consists of a catalyst carrier and an active component loaded on the catalyst carrier, the catalyst carrier comprises an energy-variable oxide AOx which is easy to generate oxygen vacancies, the active component is Pd-M alloy, M is a metal element which is easier to oxidize than Pd, the load content of Pd on the catalyst is 0.001-0.5 wt%, and the load content of M on the catalyst is 3-10 wt%. The catalyst can activate molecular oxygen to enable fluorine-containing olefin to generate epoxidation reaction, and an epoxidation product is obtained. Compared with other existing processes, the catalyst has the advantages of high catalytic selectivity, no generation of solid wastes and the like.
Description
Technical Field
The invention relates to a perfluoroolefin epoxidation catalyst and application thereof.
Background
Perfluoro-2-methyl-3-pentanone (perfluoroketone) is a novel efficient, low-toxicity and clean fire extinguishing agent, has an ozone consumption value of 0 and a low greenhouse effect, and therefore has great application potential. Perfluoro-2-methyl-3-pentanone is then formed by double bond oxidation of hexafluoropropylene dimer with sodium hypochlorite (and alkaline, NaOH) to form an epoxidation product, which is then catalyzed. Sodium hypochlorite and hexafluoropropylene dimer that its epoxidation reaction process used form a large amount of solid waste material (NaCl) after the reaction, contain trace sodium fluoride in its solid useless moreover, difficult separation, it is very difficult to its recycle, so become the biggest link of solid useless production in the whole technological process, cause the pollution to the environment, be the problem that the enterprise is waited to solve urgently. The reaction process is as follows:
although the process is also industrially used for preparing and producing the epoxy compound by a peracid oxidation method with simple process and high efficiency, the peroxy acid has high price and potential safety hazard, the epoxy compound is easy to open and decompose in an acidic environment, the yield of the product is low, and the method is gradually replaced by other safer and more economical methods at present. The use of hydrogen peroxide is also an efficient epoxidation process, but the selectivity in the perfluoroolefin epoxidation reaction is poor, the selectivity of a target product is generally not higher than 80%, and the requirement of industrial production cannot be met.
Therefore, the development of a green high-efficiency catalytic system with mild conditions for the perfluoroolefin epoxidation reaction is of great significance.
Disclosure of Invention
In view of the above technical problems in the prior art, the present invention aims to provide a perfluoroolefin epoxidation catalyst and an application thereof.
The perfluoroolefin epoxidation catalyst is characterized by comprising a catalyst carrier and an active component loaded on the catalyst carrier, wherein the catalyst carrier comprises an energy valence-variable oxide AOx which is easy to generate oxygen vacancies, the active component is a Pd-M alloy, and M is a metal element which is easier to oxidize than Pd, such as Cu, Zn or Ag; the load content of Pd on the catalyst is 0.001-0.5 wt%, preferably 0.1-0.5 wt%, and the load content of M on the catalyst is 3-10 wt%.
The perfluoroolefin epoxidation catalyst is characterized in that the load content of Pd on the catalyst is 0.1-0.2 wt%, and the load content of M on the catalyst is 3-5 wt%.
The perfluoroolefin epoxidation catalyst is characterized in that in an oxide AOx, A represents Ti, Ce, Mn, Co, Fe or Mo.
The perfluoroolefin epoxidation catalyst is characterized in that other elements G are doped in the catalyst carrier, the catalyst carrier represents a composite oxide of A and G, and the other elements G represent Y, La, Pr, Nd, Eu, Tm or Yb elements; the molar ratio of A to G in the catalyst carrier is 1: 0.1-2, preferably 1: 0.3-0.8.
The perfluoroolefin epoxidation catalyst is characterized in that the preparation method comprises the following steps:
1) adding citric acid into a salt A aqueous solution, wherein the molar ratio of the citric acid to the salt A is 0.5-2: 1, evaporating excessive water from the obtained mixed solution at the temperature of 75-85 ℃ to obtain a dark yellow viscous liquid sample, drying at the temperature of 100-160 ℃, grinding, and dispersing the obtained powder in deionized water for later use, wherein the obtained powder is marked as AOx dispersion liquid;
2) preheating a mixed aqueous solution of Pd salt and M salt to 35-45 ℃, then dropwise and slowly adding the mixed aqueous solution into the AOx dispersion liquid obtained in the step 1), and after completely mixing, adjusting the pH to 9-10 by using 0.05-0.15mol/L ammonia water solution;
3) and after completely standing and precipitating, drying the precipitate, roasting for 0.5-5 h at 150-250 ℃ in an inert atmosphere, switching the atmosphere to be air-introduced for 0.5-5 h while keeping the roasting temperature unchanged, and heating to 300-800 ℃ under the condition of keeping the air-introduced for roasting for 2-8 h, thus completing the preparation of the catalyst.
The perfluoroolefin epoxidation catalyst is characterized in that anions of the salt A, the salt Pd and the salt M are respectively and independently selected from nitrate ions, oxalate ions, chloride ions or citrate ions.
The application of the catalyst in catalyzing perfluoroolefin epoxidation reaction is characterized in that reaction raw materials of perfluoroolefin, solvent and the catalyst are placed in a reaction kettle, then the reaction kettle is sealed, heated to the reaction temperature, then oxygen is introduced into the reaction kettle until the reaction pressure is reached, and the epoxidation reaction of the perfluoroolefin is catalyzed under stirring.
The catalyst is applied to catalyzing the epoxidation reaction of perfluoroolefin, and is characterized in that the perfluoroolefin raw material is R1R2C＝CR3R4Wherein R is1～R4Each independently selected from F or a linear or branched perfluoroalkyl group having 1 to 3 carbon atoms; the volume ratio of the perfluoroolefin raw material to the solvent is 1: 5-20, the solvent has high oxygen dissolving performance, the oxygen capacity of the solvent is more than 8mmol/L, and the solvent is selected from ionic liquid or hydrofluoroether of which the anion is organic fluorine ion.
The catalyst is applied to catalyzing the epoxidation reaction of perfluoroolefin, and is characterized in that the reaction temperature is 100-300 ℃, the pressure is 0.1-5 Mpa, and the reaction time is 4-24 hours.
The beneficial effects obtained by the invention are as follows:
the catalyst can activate molecular oxygen to enable fluorine-containing olefin to generate epoxidation reaction, and an epoxidation product is obtained. Compared with other existing processes, the catalyst has the advantages of high catalytic selectivity, no generation of solid wastes and the like.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
12.2g of citric acid was slowly added to 58mL of 1mol/L Ce (NO)3)3The combined solution was then placed in a water bath at 80 ℃ and stirred while evaporating excess water to give a dark yellow viscous liquid sample, which was then transferred to an oven and dried at 120 ℃ to give a solid product. After grinding, the powder is dispersed in deionized water and marked as CeO2And (3) dispersing the mixture.
0.25g of PdCl is taken2Solution (PdCl)2Pd in solution2+Concentration of 0.04g/g) and 16mL of Cu (NO) with concentration of 0.5mol/L3)2Mixing the solutions, preheating the obtained mixed solution at 40 ℃, and dropwise and slowly adding the prepared CeO2In the dispersion, after the two solutions are completely mixed, adjusting the pH of the reaction solution to about 9-10 by using 0.1mol/L ammonia water solution; standing for precipitation, drying the precipitate at 80 deg.C, calcining at 180 deg.C under inert atmosphere (nitrogen, the same below) for 3 hr, switching to air introduction for 1 hr while maintaining the calcining temperature, heating to 500 deg.C while maintaining the air introduction, and calcining for 6 hr to obtain the catalyst labeled as 0.1Pd-5Cu/CeO2A catalyst.
Example 2:
12.2g of citric acid was slowly added to 58mL of 1mol/L Ce (NO)3)3The combined solution was then placed in a water bath at 80 ℃ and stirred while evaporating excess water to give a dark yellow viscous liquid sample, which was then transferred to an oven and dried at 120 ℃ to give a solid product. After grinding, the powder is dispersed in deionized water and marked as CeO2And (3) dispersing the mixture.
0.5g of PdCl is taken2Solution (PdCl)2Pd in solution2+Concentration of 0.04g/g) and 16mL of Cu (NO) with concentration of 0.5mol/L3)2Mixing the solutions, preheating the obtained mixed solution at 40 ℃, and dropwise and slowly adding the prepared CeO2In the dispersion, after the two solutions are completely mixed, adjusting the pH of the reaction solution to about 9-10 by using 0.1mol/L ammonia water solution; standing for precipitation, drying the precipitate at 80 deg.C, calcining at 180 deg.C under inert atmosphere for 3h, switching to air introduction for 1h while keeping the calcining temperature unchanged, heating to 500 deg.C while keeping the air introduction, and calcining for 6h to obtain the catalyst labeled as 0.2Pd-5Cu/CeO2A catalyst.
Example 3:
26.3g of citric acid were slowly added to 125mL of 1mol/L TiCl4Adding the mixed solution into water bath at 80 deg.C, stirring to evaporate excessive water to obtain dark yellow viscous liquid sample, transferring into ovenDrying at 120 ℃ gives the solid product. After grinding, the powder was dispersed in deionized water and recorded as TiO2And (3) dispersing the mixture.
0.5g of PdCl is taken2Solution (PdCl)2Pd in solution2+Concentration of 0.04g/g) and 16mL of Cu (NO) with concentration of 0.5mol/L3)2Mixing the solutions, preheating the obtained mixed solution, and dropwise and slowly adding the prepared TiO2In the dispersion, after the two solutions are completely mixed, adjusting the pH of the reaction solution to about 9-10 by using 0.1mol/L ammonia water solution; standing for precipitation, drying the precipitate at 80 deg.C, calcining at 180 deg.C under inert atmosphere for 3h, switching to air introduction for 1h while keeping the calcining temperature unchanged, heating to 500 deg.C while keeping the air introduction, and calcining for 6h to obtain the final product, wherein the catalyst is labeled as 0.2Pd-5Cu/TiO2A catalyst.
Example 4:
12.2g of citric acid were slowly added to 58mL of 1mol/L Ce (SO)4)2The combined solution was then placed in a water bath at 80 ℃ and stirred while evaporating excess water to give a dark yellow viscous liquid sample, which was then transferred to an oven and dried at 120 ℃ to give a solid product. After grinding, the powder is dispersed in deionized water and marked as CeO2And (3) dispersing the mixture.
0.25g of PdCl is taken2Solution (PdCl)2Pd in solution2+Concentration of 0.04g/g) and 15.3mL of ZnSO with concentration of 0.5mol/L4Mixing the solutions, preheating the obtained mixed solution, and dropwise and slowly adding the prepared CeO2In the dispersion, after the two solutions are completely mixed, adjusting the pH of the reaction solution to about 9-10 by using 0.1mol/L ammonia water solution; standing for precipitation, drying the precipitate at 80 deg.C, calcining at 180 deg.C under inert atmosphere for 3h, switching to air introduction for 1h while keeping the calcining temperature unchanged, heating to 500 deg.C while keeping the air introduction, and calcining for 6h to obtain the catalyst labeled as 0.1Pd-5Zn/CeO2A catalyst.
Example 5:
24.2g of citric acid were slowly added to 115mL of 1mol/L MnSO4The combined solution was then placed in a water bath at 80 ℃ and stirred while evaporating excess water to give a dark yellow viscous liquid sample, which was then transferred to an oven and dried at 120 ℃ to give a solid product. After grinding, the particles are dispersed in deionized water for later use and marked as MnO2And (3) dispersing the mixture.
0.25g of PdCl is taken2Solution (PdCl)2Pd in solution2+Concentration of 0.04g/g) and 9.18mL of ZnSO with concentration of 0.5mol/L4Mixing the solutions, preheating the obtained mixed solution, and dropwise and slowly adding the prepared CeO2In the dispersion, after the two solutions are completely mixed, adjusting the pH of the reaction solution to about 9-10 by using 0.1mol/L ammonia water solution; standing for precipitation, drying the precipitate at 80 deg.C, calcining at 180 deg.C under inert atmosphere for 3h, switching to air introduction for 1h while keeping the calcining temperature unchanged, heating to 500 deg.C while keeping the air introduction, and calcining for 6h to obtain the catalyst labeled as 0.1Pd-3Zn/MnO2A catalyst.
Example 6:
4.2g of citric acid and 3.62g of La were mixed2O3Slowly add 20mL of 1mol/L Ce (NO)3)3The combined solution was then placed in a water bath at 80 ℃ and stirred while evaporating excess water to give a dark yellow viscous liquid sample, which was then transferred to an oven and dried at 120 ℃ to give a solid product. After grinding, the dispersion was in deionized water and marked La2Ce2O7And (3) dispersing the mixture.
0.25g of PdCl is taken2Solution (PdCl)2Pd in solution2+Concentration of 0.04g/g) and 16mL of Cu (NO) with concentration of 0.5mol/L3)2Mixing the solution, preheating the obtained mixed solution, and dropwise and slowly adding the prepared La dropwise2Ce2O7In the dispersion, after the two solutions are completely mixed, adjusting the pH of the reaction solution to about 9-10 by using 0.1mol/L ammonia water solution; standing for precipitation, and heating the precipitate to 80 deg.CDrying at the temperature, roasting at 180 ℃ for 3h in an inert atmosphere, switching the atmosphere to air introduction for 1h while keeping the roasting temperature unchanged, heating to 500 ℃ while keeping the air introduction, and roasting for 6h to finish the preparation of the catalyst, wherein the mark of the catalyst is 0.1Pd-5Cu/La2Ce2O7A catalyst.
Example 7:
24.2g of citric acid were slowly added to 115mL of 1mol/L MnSO4The combined solution was then placed in a water bath at 80 ℃ and stirred while evaporating excess water to give a dark yellow viscous liquid sample, which was then transferred to an oven and dried at 120 ℃ to give a solid product. After grinding, the particles are dispersed in deionized water for later use and marked as MnO2And (3) dispersing the mixture.
0.5g of PdCl is taken2Solution (PdCl)2Pd in solution2+Concentration of 0.04g/g) and 5.6mL of AgNO with concentration of 0.5mol/L3Mixing the solutions, preheating the obtained mixed solution, and dropwise and slowly adding the prepared CeO2In the dispersion, after the two solutions are completely mixed, adjusting the pH of the reaction solution to about 9-10 by using 0.1mol/L ammonia water solution; standing for precipitation, drying the precipitate at 80 deg.C, calcining at 180 deg.C under inert atmosphere for 3h, switching to air introduction for 1h while keeping the calcining temperature unchanged, heating to 500 deg.C while keeping the air introduction, and calcining for 6h to obtain the final product, wherein the catalyst is labeled as 0.2Pd-3Ag/MnO2A catalyst.
Example 8:
4.2g of citric acid and 3.62g of La were mixed2O3Slowly add 20mL of 1mol/L Ce (NO)3)3The combined solution was then placed in a water bath at 80 ℃ and stirred while evaporating excess water to give a dark yellow viscous liquid sample, which was then transferred to an oven and dried at 120 ℃ to give a solid product. After grinding, the dispersion was in deionized water and marked La2Ce2O7And (3) dispersing the mixture.
0.25g of PdCl is taken2Solution (PdCl)2Pd in solution2+Concentration of 0.04g/g) and 9.3mL of AgNO with concentration of 0.5mol/L3Mixing the solution, preheating the obtained mixed solution, and dropwise and slowly adding the prepared La dropwise2Ce2O7In the dispersion, after the two solutions are completely mixed, adjusting the pH of the reaction solution to about 9-10 by using 0.1mol/L ammonia water solution; standing for precipitation, drying the precipitate at 80 deg.C, calcining at 180 deg.C under inert atmosphere for 3h, switching to air introduction for 1h while keeping the calcining temperature unchanged, heating to 500 deg.C while keeping the air introduction, and calcining for 6h to obtain the final product, wherein the catalyst is labeled as 0.1Pd-5Ag/La2Ce2O7A catalyst.
Example 9:
to a 500mL reactor was added 20mL perfluoroolefin, 200mL solvent, and 2g of 0.2Pd-5Cu/CeO prepared in example 22As a catalyst. The reaction kettle is sealed, and the temperature is raised to 373 +/-5K. Oxygen was introduced at a rate of 50mL/min to make the internal pressure of the reaction vessel 1.5bar, and the introduction was stopped. The reaction stirring speed is 600r/min, the reaction is stopped after 6h, the reacted substances are taken out after the temperature of the system is reduced to room temperature, a filter head is used for separating products and catalysts, the solution is layered, the lower-layer products are taken out, the epoxide is obtained after rectification, and the conversion rate and the selectivity are calculated. When different types of perfluoroolefin reactants and solvents were used as the catalytic reaction conditions, the results are summarized in Table 1.
TABLE 10.2 Pd-5Cu/CeO2Catalytic performance of catalysts in different systems
Wherein in Table 1, when the reactant is perfluoro-2-methyl-2-pentene, perfluoro-3-isopropyl-2-methyl-2-pentene, perfluoro-2, 4-dimethyl-3-ethyl-2-pentene, the corresponding reaction products (i.e., epoxides) are perfluoro-2-methyl-2, 3-epoxypentane, perfluoro-3-isopropyl-2-methyl-2, 3-epoxypentane, and perfluoro-2, 4-dimethyl-3-ethyl-2, 3-epoxypentane, respectively.
Example 10:
to a 500mL reactor was added 20mL perfluoroolefin, 200mL solvent, and 2g of 0.1Pd-5Zn/CeO prepared in example 42As a catalyst. The reaction kettle is sealed, and the temperature is raised to 373 +/-5K. Oxygen was introduced at a rate of 50mL/min to make the internal pressure of the reaction vessel 1.5bar, and the introduction was stopped. The reaction stirring speed is 600r/min, the reaction is stopped after 6h, the reacted substances are taken out after the temperature of the system is reduced to room temperature, a filter head is used for separating products and catalysts, the solution is layered, the lower-layer products are taken out, the epoxide is obtained after rectification, and the conversion rate and the selectivity are calculated. When different types of perfluoroolefin reactants and solvents were used as the catalytic reaction conditions, the results are summarized in Table 2.
TABLE 20.1 Pd-5Zn/CeO2Catalytic performance of catalysts in different systems
Example 11:
to a 500mL reaction vessel were added 20mL of perfluoro-2-methyl-2-pentene, 200mL of 1-butyl-1-methylpyridine bistrifluoromethanesulfonimide as a reaction solvent, and 2g of a catalyst was added. The reaction kettle is sealed, and the temperature is raised to 373 +/-5K. Oxygen was introduced at a rate of 50mL/min to make the internal pressure of the reaction vessel 1.5bar, and the introduction was stopped. The reaction stirring speed is 600r/min, the reaction is stopped after 6h, the reacted substances are taken out after the temperature of the system is reduced to room temperature, a filter head is used for separating products and the catalyst, the solution is layered, the lower-layer products are taken out, the perfluoro-2-methyl-2, 3-epoxypentane is obtained after rectification, and the conversion rate and the selectivity of the catalyst are calculated. When the catalysts for the above catalytic reactions were the catalysts prepared in examples 1 to 8, respectively, the results of the catalytic reactions are summarized in Table 3.
TABLE 3 epoxidation of perfluoro-2-methyl-2-pentene with different catalysts
Comparative example 1:
preparation method of catalyst in comparative example 1 the catalyst in example 2 was repeated except for the difference from example 2 in that "Cu (NO) was not added during the preparation3)2Solution ", the remaining steps were repeated as in example 2. That is, in the preparation of the catalyst of comparative example 1, only PdCl was added2The solution is dripped into the prepared CeO2In the dispersion, after the dispersion is completely mixed, adjusting the pH of the reaction solution to be about 9-10 by using 0.1mol/L ammonia water solution; precipitating, drying, and calcining in inert atmosphere and air to obtain 0.2Pd/CeO2A catalyst.
To a 500mL reaction vessel were added 20mL of perfluoro-2-methyl-2-pentene, 200mL of 1-butyl-1-methylpyridine bistrifluoromethanesulfonimide salt as a reaction solvent, and 2g of 0.2Pd/CeO prepared in comparative example 12As a catalyst. The reaction kettle is sealed, and the temperature is raised to 373 +/-5K. Oxygen was introduced at a rate of 50mL/min to make the internal pressure of the reaction vessel 1.5bar, and the introduction was stopped. The reaction stirring speed is 600r/min, after 6 hours of reaction, the temperature is reduced to room temperature, a filter head is used for separating products and a catalyst, the solution is layered, the lower-layer products are taken out, rectification is carried out, the perfluoro-2-methyl-2, 3-epoxypentane is obtained, the reaction conversion rate is 34.3 percent, and the selectivity is 55.2 percent.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (9)
1. A perfluoroolefin epoxidation catalyst is characterized by comprising a catalyst carrier and an active component loaded on the catalyst carrier, wherein the catalyst carrier comprises a variable valence oxide AOx which is easy to generate oxygen vacancy, the active component is Pd-M alloy, M is a metal element which is easier to oxidize than Pd, and M is selected from Cu, Zn or Ag; the load content of Pd on the catalyst is 0.001-0.5 wt%, preferably 0.1-0.5 wt%, and the load content of M on the catalyst is 3-10 wt%.
2. The catalyst for epoxidizing perfluoroolefin according to claim 1, wherein the supported amount of Pd on the catalyst is 0.1 to 0.2wt%, and the supported amount of M on the catalyst is 3 to 5 wt%.
3. The catalyst for epoxidizing perfluoroolefin according to claim 1, wherein A in the oxide AOx represents Ti, Ce, Mn, Co, Fe or Mo.
4. The catalyst for epoxidizing perfluoroolefin according to claim 1, wherein the catalyst carrier is further doped with another element G, the catalyst carrier represents a composite oxide of a and G, and the other element G represents Y, La, Pr, Nd, Eu, Tm or Yb; the molar ratio of A to G in the catalyst carrier is 1: 0.1-2, preferably 1: 0.3-0.8.
5. The catalyst according to claim 1, which is prepared by a process comprising the steps of:
1) adding citric acid into an aqueous solution of A salt, wherein the molar ratio of the citric acid to the A salt is 0.5-2: 1, evaporating excessive water from the obtained mixed solution at the temperature of 75-85 ℃ to obtain a dark yellow viscous liquid sample, drying at the temperature of 100-160 ℃, grinding, and dispersing the obtained powder in deionized water for later use, wherein the obtained powder is marked as AOx dispersion liquid;
2) the mixed aqueous solution of Pd salt and M salt is brought to 35-45 ℃, then the mixed aqueous solution is gradually added into the AOx dispersion liquid obtained in the step 1) drop by drop, and after the mixture is completely mixed, the pH value is adjusted to 9-10 by 0.05-0.15mol/L ammonia aqueous solution;
3) and after completely standing and precipitating, drying the precipitate, roasting for 0.5-5 h at 150-250 ℃ in an inert atmosphere, switching the atmosphere to be air-introduced for 0.5-5 h while keeping the roasting temperature unchanged, and heating to 300-800 ℃ under the condition of keeping the air-introduced for roasting for 2-8 h, thus completing the preparation of the catalyst.
6. The perfluoroolefin epoxidation catalyst of claim 5, wherein the anions of the salt A, Pd and M are each independently selected from the group consisting of nitrate, oxalate, chloride and citrate.
7. The use of the catalyst according to claim 1 in the catalysis of the epoxidation of perfluoroolefin, wherein the perfluoroolefin, the solvent and the catalyst are placed in a reaction vessel, the reaction vessel is then sealed, heated to a reaction temperature, oxygen is introduced into the reaction vessel until a reaction pressure is reached, and the epoxidation of perfluoroolefin is catalyzed while stirring.
8. The use of claim 7 wherein the perfluoroolefin feedstock is R1R2C=CR3R4Wherein R is1~ R4Each independently selected from F or a linear or branched perfluoroalkyl group having 1 to 3 carbon atoms; the volume ratio of the perfluoroolefin raw material to the solvent is 1: 5-20, the solvent has high oxygen dissolving performance, the oxygen capacity of the solvent is more than 8mmol/L, and the solvent is selected from ionic liquid or hydrofluoroether of which the anion is organic fluorine ion.
9. The method of claim 7, wherein the reaction temperature is 100-300 ℃, the pressure is 0.1-5 MPa, and the reaction time is 4-24 hours.
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Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1019788A (en) * | 1964-10-28 | 1966-02-09 | Du Pont | Process for the production of fluorinated carbonyl compounds |
| CN1364855A (en) * | 2000-12-29 | 2002-08-21 | 中国石油化工股份有限公司 | Selective hydrogenization catalyst and its preparing method and use |
| CN1486305A (en) * | 2001-01-19 | 2004-03-31 | ���ƻ�ѧ������˾ | Epoxidation catalyst and process |
| JP2010089032A (en) * | 2008-10-09 | 2010-04-22 | Jgc Catalysts & Chemicals Ltd | Metal-particle supporting catalyst, and method of producing the same |
| US20120192550A1 (en) * | 2009-10-02 | 2012-08-02 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purification catalyst for removing co or hc, and method for manufacturing same |
| CN102728351A (en) * | 2011-04-11 | 2012-10-17 | 中国石油化工股份有限公司 | Pd-Ag/Al2O3-TiO2 catalyst for selective hydrogenation of cracked gasoline or its fractions, and preparation method thereof |
| CN102784642A (en) * | 2012-07-19 | 2012-11-21 | 上海师范大学 | Supported bimetal alloy catalyst, its preparation method and its use |
| WO2014123307A1 (en) * | 2013-02-05 | 2014-08-14 | 고려대학교 산학협력단 | Palladium-copper catalyst for reducing nitrate nitrogen in water, supported on titania support, and preparation method therefor |
| CN104588006A (en) * | 2013-10-31 | 2015-05-06 | 中国科学院大连化学物理研究所 | Alloy single atom catalyst for selective hydrogenation of alkyne |
| CN105198719A (en) * | 2015-09-06 | 2015-12-30 | 浙江工业大学 | Preparation method of perfluoro-2-methyl-3-pentanone |
| CN105327702A (en) * | 2015-11-24 | 2016-02-17 | 扬州大学 | Propylene epoxidation catalyst and preparation method thereof |
| CN105597744A (en) * | 2014-11-03 | 2016-05-25 | 中国石油化工股份有限公司 | Supported bimetal catalyst, preparation method and applications thereof |
| CN105727945A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Pd/Ag-series supported hydrogenation catalyst |
| CN108554406A (en) * | 2018-01-04 | 2018-09-21 | 厦门大学 | A kind of load alloy-type soot oxidation catalyst and preparation method thereof |
| CN108927156A (en) * | 2018-07-18 | 2018-12-04 | 北京化工大学 | A kind of alkynes selective hydrogenation support type alloy catalyst and preparation method thereof |
| CN109701552A (en) * | 2019-01-07 | 2019-05-03 | 北京理工大学 | A kind of palladium-copper system support type sub-nanometer catalyst and preparation method thereof |
-
2021
- 2021-06-16 CN CN202110666806.4A patent/CN113634263B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1019788A (en) * | 1964-10-28 | 1966-02-09 | Du Pont | Process for the production of fluorinated carbonyl compounds |
| CN1364855A (en) * | 2000-12-29 | 2002-08-21 | 中国石油化工股份有限公司 | Selective hydrogenization catalyst and its preparing method and use |
| CN1486305A (en) * | 2001-01-19 | 2004-03-31 | ���ƻ�ѧ������˾ | Epoxidation catalyst and process |
| JP2010089032A (en) * | 2008-10-09 | 2010-04-22 | Jgc Catalysts & Chemicals Ltd | Metal-particle supporting catalyst, and method of producing the same |
| US20120192550A1 (en) * | 2009-10-02 | 2012-08-02 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purification catalyst for removing co or hc, and method for manufacturing same |
| CN102728351A (en) * | 2011-04-11 | 2012-10-17 | 中国石油化工股份有限公司 | Pd-Ag/Al2O3-TiO2 catalyst for selective hydrogenation of cracked gasoline or its fractions, and preparation method thereof |
| CN102784642A (en) * | 2012-07-19 | 2012-11-21 | 上海师范大学 | Supported bimetal alloy catalyst, its preparation method and its use |
| WO2014123307A1 (en) * | 2013-02-05 | 2014-08-14 | 고려대학교 산학협력단 | Palladium-copper catalyst for reducing nitrate nitrogen in water, supported on titania support, and preparation method therefor |
| CN104588006A (en) * | 2013-10-31 | 2015-05-06 | 中国科学院大连化学物理研究所 | Alloy single atom catalyst for selective hydrogenation of alkyne |
| CN105597744A (en) * | 2014-11-03 | 2016-05-25 | 中国石油化工股份有限公司 | Supported bimetal catalyst, preparation method and applications thereof |
| CN105727945A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Pd/Ag-series supported hydrogenation catalyst |
| CN105198719A (en) * | 2015-09-06 | 2015-12-30 | 浙江工业大学 | Preparation method of perfluoro-2-methyl-3-pentanone |
| CN105327702A (en) * | 2015-11-24 | 2016-02-17 | 扬州大学 | Propylene epoxidation catalyst and preparation method thereof |
| CN108554406A (en) * | 2018-01-04 | 2018-09-21 | 厦门大学 | A kind of load alloy-type soot oxidation catalyst and preparation method thereof |
| CN108927156A (en) * | 2018-07-18 | 2018-12-04 | 北京化工大学 | A kind of alkynes selective hydrogenation support type alloy catalyst and preparation method thereof |
| CN109701552A (en) * | 2019-01-07 | 2019-05-03 | 北京理工大学 | A kind of palladium-copper system support type sub-nanometer catalyst and preparation method thereof |
Non-Patent Citations (8)
| Title |
|---|
| HAODONG TANG ET AL: "The in situ redispersion of a PdCu/AC alloy catalyst under a CFCl2CF2Cl/H2 atmosphere: a combination of experimental and DFT study" * |
| HONG-KUI WANG ET AL: "Ag-Cu Bimetallic Nanoparticles Prepared by Microemulsion Method as Catalyst for Epoxidation of Styrene" * |
| J.C. DELLAMORTE ET AL: "Palladium-silver bimetallic catalysts with improved activity and selectivity for ethylene epoxidation" * |
| OPEYEMI A. OJELADE ET AL: "Optimizing Pd:Zn molar ratio in PdZn/CeO2 for CO2 hydrogenation to methanol" * |
| 冯树波等: "H2-O2气氛中丙烯环氧化反应研究进展" * |
| 曾伟等: "Pd-Au/1cTiO2/SiO2催化剂的制备及其烯烃的环氧化性能" * |
| 王瑛等: "光沉积法制备Pd-Cu/TiO2催化还原硝酸盐的研究" * |
| 郭志伟: "钯铜合金纳米材料的制备、表征及其电催化甲酸和甲醇氧化性能的研究" * |
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