CN112657501A - CO oxidation catalyst and preparation method and application thereof - Google Patents
CO oxidation catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a CO oxidation catalyst, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) dissolving the copper salt by using deionized water, and adding inorganic acid to adjust the pH value of the copper salt solution to be less than or equal to 2; (2) adding a cerium dioxide carrier into the copper salt solution, and stirring the mixture until the mixture is uniform; (3) drying, roasting and grinding the obtained product in sequence to obtain the CO oxidation catalyst which is CuO/CeO2Type catalyst in which the molar fraction of Cu [ Cu/(Cu + Ce)]5-30%, the catalyst is used for CO oxidation reaction. Compared with the prior art, the invention has the advantages of low cost, easy preparation and convenient useHas the advantages of higher CO oxidation activity and the like.
Description
Technical Field
The invention relates to the field of catalysts, and particularly relates to a CO oxidation catalyst, and a preparation method and application thereof.
Background
The supported catalyst plays an important role in the fields of petrochemical industry and environmental catalysis, wherein CuO/CeO2Catalysts of the type widely used in carbon monoxide oxidation and selective oxidation reactions, due to CeO2The excellent oxygen storage performance and the strong interaction between Cu and Ce ensure that the copper-cerium catalyst has CO oxidation and selective oxidation activities superior to those of a noble metal catalyst, and simultaneously, the CuO has rich sources and low price, so that the catalyst becomes an important class in the current CO oxidation and selective oxidation catalysts. Currently, CuO/CeO is prepared2The catalyst may be prepared by impregnation, coprecipitation, or the like.
Among all the preparation methods, the dipping method is a more common preparation method. Gurbani et al prepared CuO/CeO by impregnation2The research shows that the catalyst prepared by the equal-volume impregnation method can completely convert CO at 110-120 ℃. The method has the advantages of simple operation and low cost, and has the defect that copper species are easy to migrate along with water in the drying process of the copper-based catalyst, thereby causing uneven distribution of active components. The patent CN 1554480A discloses a Cu-Ce composite oxide catalyst, which is prepared by preparing a cerium dioxide carrier by a sol-gel method and preparing CuO/CeO by an impregnation method2The catalyst prepared by the method has the temperature for completely converting CO above 140 ℃, and obviously, the preparation process of the method is more complicated and the activity is lower. The principle of operation of the co-precipitation method is to precipitate multiple salt solutions simultaneously. Jung adopts a coprecipitation method to prepare a copper-cerium catalyst, researches show that the catalyst prepared by the method forms a Cu-Ce-O solid solution, and CO is completely converted at 170 ℃.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a CO oxidation catalyst which is low in cost, easy to prepare and higher in CO oxidation activity, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a method of preparing a CO oxidation catalyst, the method comprising the steps of:
(1) dissolving the copper salt by using deionized water, and adding inorganic acid to adjust the pH value of the copper salt solution to be less than or equal to 2;
(2) adding a cerium dioxide carrier into the copper salt solution, and stirring the mixture until the mixture is uniform;
(3) and drying, roasting and grinding the obtained product in sequence to obtain the CO oxidation catalyst.
Further, the copper salt is copper nitrate. Further, the inorganic acid is nitric acid.
Further, the concentration of the nitric acid is 1-15 mol/L.
Further, the drying temperature is 20-120 ℃, and the drying time is 10-15 h.
Further, the roasting temperature is 400-500 ℃, and the time is 4-6 h.
A CO oxidation catalyst prepared as described above, the catalyst being CuO/CeO2Type catalyst in which the molar fraction of Cu [ Cu/(Cu + Ce)]Is 5-30%.
Use of a CO oxidation catalyst as described above for a CO oxidation reaction, the reaction comprising in particular the steps of:
(1) fixing a quartz tube filled with a CO oxidation catalyst in a reactor, and introducing high-purity nitrogen for pretreatment;
(2) cooling to room temperature, introducing CO and O2、N2The mixed gas of (3) is subjected to CO oxidation reaction.
Further, the temperature of the pretreatment is 200 ℃ and 250 ℃, and the time is 1-2 h.
Further, the CO and O2And N2The concentration of (C) is CO (1-4 vol.%), O2(2.5-10vol.％)，N2(balance), the temperature of the oxidation reaction is 50-150 ℃, and the space velocity of the mixed gas is 18000 and 30000 mL/(g.h).
Compared with the prior art, the catalyst is prepared by regulating the pH value of the copper salt impregnation liquid, and the acidity of the copper salt solution is regulated by using the inorganic acid nitric acid, so that the dispersion of the active components can be effectively promoted, the condition that the active components are unevenly distributed due to the migration of copper species along with water is improved, and other impurity ions cannot be introduced. The method is simple to operate, and simultaneously improves the activity of CO oxidation reaction.
Drawings
FIG. 1 is a graph comparing CO oxidation activities of catalysts prepared in examples 1 to 3 and comparative example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
CuO/CeO2A catalyst of the type wherein the molar fraction of Cu (Cu/(Cu + Ce)) is between 5 and 30%, the process for the preparation of the catalyst comprising the steps of:
(1) dissolving copper nitrate by using a certain amount of deionized water, and adding 1-15mol/L nitric acid to adjust the pH value of the copper salt solution to 0.1-2.0;
(2) adding a certain amount of cerium dioxide carrier into the solution obtained in the step (1) and stirring the mixture until the mixture is uniform;
(3) drying the product obtained in the step (2) at 20-120 ℃ for 10-15h, roasting at 400-500 ℃ for 4-6h, and grinding uniformly to obtain CuO/CeO2A catalyst of the type (I) is provided.
The resulting CuO/CeO2Catalysts of type (iii) may be used in CO oxidation reactions where the process conditions for the reaction include:
(1) fixing a quartz tube filled with a catalyst in a reactor, introducing high-purity nitrogen, and pretreating at the temperature of 200-250 ℃ for 1-2 h.
(2) Cooling to room temperature, introducing CO and O2、N2The mixed gas of (1), wherein the concentration of each gas is: CO (1-4 vol.%), O2(2.5-10vol.％)，N2(balance), and performing CO oxidation reaction at 50-150 ℃. Wherein the space velocity of the mixed gas is 18000 and 30000 mL/(g.h).
The following examples are given in detail to illustrate the embodiments and specific procedures of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
CuO/CeO for CO oxidation2A catalyst of the type (I) and a process for its preparation comprising the steps of:
(1) dissolving 0.249g of copper nitrate in 1.1mL of deionized water, and adding nitric acid to adjust the pH of the copper salt solution to 0.1;
(2) adding 1g of cerium dioxide carrier into the copper salt solution in the step (1), and stirring uniformly;
(3) aging the product obtained in the step (2) at room temperature for 3h, drying in an oven at 110 ℃ for 12h, grinding the dried sample, placing the ground sample in a muffle furnace, roasting at 400 ℃ for 4h, taking out the sample, and grinding to obtain CuO/CeO2Catalyst, noted as 0.1-15 CC.
Example 2
The difference from example 1 is that CuO/CeO was prepared by adjusting the pH of the copper salt solution to 1.02Catalyst 1.0-15 CC.
Example 3
The difference from example 1 is that CuO/CeO was prepared by adjusting the pH of the copper salt solution to 2.02Catalyst 2.0-15 CC.
Comparative example 1
The difference from example 1 is that CuO/CeO was prepared by adjusting the pH of the copper salt solution to 2.82Catalyst 2.8-15 CC.
The catalysts prepared in examples 1 to 3, comparative example 1 were evaluated for their catalytic activity for CO oxidation reaction, which comprises: the quartz tube (inner diameter 5mm, length 400mm) containing the catalyst was fixed in the reactor at 200 ℃ with N at a flow rate of 30mL/min2Purging for 1h, then cooling to room temperature, and then converting the gas into CO, O2、N2The mixed gas of (1), wherein the concentration of each gas is: CO (1 vol.%), O2(2.5vol.％)，N2(balance), and performing CO oxidation reaction at 50-150 ℃. Wherein the space velocity of the mixed gas is 18000 mL/(g.h). The activity results are shown in figure 1 and table 1.
TABLE 1 reactivity of the catalysts
As can be seen from fig. 1 and table 1, when the pH of the copper salt impregnation solution was adjusted to 0.1 to 2.0 with nitric acid, the temperature at which the CO conversion rate reached 99% or more was 95 to 102 ℃; compared with the common impregnation method, the activity is obviously improved at 115 ℃ when no acid is added for regulation and control (2.8-15 CC). The pH value of the copper salt impregnation liquid is regulated and controlled by acid, so that the acidity of the copper salt impregnation liquid is enhanced, and the activity of CO oxidation reaction can be effectively improved. And the catalyst is simple to prepare and operate, short in preparation period and low in cost.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method of preparing a CO oxidation catalyst, the method comprising the steps of:
(1) dissolving the copper salt by using deionized water, and adding inorganic acid to adjust the pH value of the copper salt solution to be less than or equal to 2;
(2) adding a cerium dioxide carrier into the copper salt solution, and stirring the mixture until the mixture is uniform;
(3) and drying, roasting and grinding the obtained product in sequence to obtain the CO oxidation catalyst.
2. The method of claim 1, wherein the copper salt is copper nitrate.
3. The method of claim 1 or 2, wherein the inorganic acid is nitric acid.
4. The method of claim 3, wherein the nitric acid concentration is 1 to 15 mol/L.
5. The method of claim 1, wherein the drying is performed at a temperature of 20-120 ℃ for a time of 10-15 hours.
6. The method as claimed in claim 1, wherein the calcination temperature is 400-500 ℃ and the calcination time is 4-6 h.
7. A CO oxidation catalyst prepared according to the process of any one of claims 1 to 6, wherein the catalyst is CuO/CeO2Type catalyst in which the molar fraction of Cu [ Cu/(Cu + Ce)]Is 5-30%.
8. Use of a CO oxidation catalyst according to claim 7 in a CO oxidation reaction, the reaction comprising in particular the steps of:
(1) fixing a quartz tube filled with a CO oxidation catalyst in a reactor, and introducing high-purity nitrogen for pretreatment;
(2) cooling to room temperature, introducing CO and O2、N2The mixed gas of (3) is subjected to CO oxidation reaction.
9. The use of a CO oxidation catalyst as claimed in claim 8, wherein the temperature of the pretreatment is 200 ℃ and 250 ℃ for 1-2 h.
10. Use of a CO oxidation catalyst according to claim 8 wherein the CO, O2And N2The concentration of (C) is CO (1-4 vol.%), O2(2.5-10vol.％)，N2(balance), the temperature of the oxidation reaction is 50-150 ℃, and the space velocity of the mixed gas is 18000 and 30000 mL/(g.h).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385976A (en) * | 2008-10-30 | 2009-03-18 | 上海应用技术学院 | Preparation method of cuprum cerium composite oxides catalyst |
| CN101549296A (en) * | 2009-05-06 | 2009-10-07 | 中国科学院山西煤炭化学研究所 | Method for preparing water-resistant carbon-dioxide-resistant CO low-temperature oxidation catalyst |
| CN103055875A (en) * | 2012-11-05 | 2013-04-24 | 昆明理工大学 | Preparation method of catalytic material mixed by copper and cerium oxide |
| CN107597130A (en) * | 2017-09-29 | 2018-01-19 | 济南大学 | Different scale high-specific surface area cerium oxide cupric oxide composite mesopore ball and preparation method |
-
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- 2020-12-23 CN CN202011532631.XA patent/CN112657501A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385976A (en) * | 2008-10-30 | 2009-03-18 | 上海应用技术学院 | Preparation method of cuprum cerium composite oxides catalyst |
| CN101549296A (en) * | 2009-05-06 | 2009-10-07 | 中国科学院山西煤炭化学研究所 | Method for preparing water-resistant carbon-dioxide-resistant CO low-temperature oxidation catalyst |
| CN103055875A (en) * | 2012-11-05 | 2013-04-24 | 昆明理工大学 | Preparation method of catalytic material mixed by copper and cerium oxide |
| CN107597130A (en) * | 2017-09-29 | 2018-01-19 | 济南大学 | Different scale high-specific surface area cerium oxide cupric oxide composite mesopore ball and preparation method |
Non-Patent Citations (3)
| Title |
|---|
| JINGFANG SUN: ""Comparative study on the catalytic CO oxidation properties of CuO/CeO2 catalysts prepared by solid state and wet impregnation"", 《CHINESE JOURNAL OF CATALYSIS》 * |
| 曹建亮: "《一氧化碳低温催化氧化用氧化铜基纳米催化材料》", 31 August 2017, 中国矿业大学出版社 * |
| 赵建宏: "《催化剂的结构与分子设计》", 30 November 1998, 中国工人出版社 * |
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