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Copper-doped ZnO-ZrO2 sosoloid catalyst and preparing method and application thereof

A catalyst and solid solution technology, which is applied in the field of catalysts for hydrogenation of carbon dioxide to methanol and their preparation, can solve the problems of low carbon dioxide conversion rate and poor methanol selectivity, and achieve the effects of excellent catalyst performance, high methanol selectivity and improved dispersion.

Inactive Publication Date: 2019-04-16
YANCHENG INST OF TECH
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Problems solved by technology

[0005] The object of the present invention is to provide a copper-doped ZnO-ZrO 2 Solid solution catalyst and its preparation method and application to solve the problems of low carbon dioxide conversion rate and poor methanol selectivity in the hydrogenation of carbon dioxide to methanol in the prior art

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  • Copper-doped ZnO-ZrO2 sosoloid catalyst and preparing method and application thereof

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preparation example Construction

[0023] Copper-doped ZnO-ZrO of the present invention 2 The solid solution catalyst is prepared by the following method:

[0024] (1) Adding Cu(NO 3 ) 2 ·3H 2 O, Zn(NO 3 ) 2 ·6H 2 O and Zr(NO 3 ) 4 ·5H 2 O was dissolved in deionized water to prepare a mixed solution of metal nitrate, and make it completely dissolved and mixed; wherein, the raw material Cu(NO 3 ) 2 ·3H 2 O, Zn(NO 3 ) 2 ·6H 2 O and Zr(NO 3 ) 4 ·5H 2 In O, the molar percentage of Cu is 0%~10%, but does not include 0; The molar ratio of Zn and Zr is Zn:Zr=1:4;

[0025] (2) Under the reaction temperature of 50~90 DEG C, the metal nitrate mixed solution that step (1) obtains and the Na that concentration is 0.5~1mol / L 2 CO 3 The solution is added dropwise into the reaction vessel by means of co-current addition, and magnetic stirring is used to promote the formation of precipitates, and the pH of the titration end point is kept at 7-8; Aging at reaction temperature for 3 to 5 hours;

[0026] (3) ...

Embodiment 1

[0055] (1) Weigh Zn(NO 3 ) 2 ·6H 2 O 1.49g and Zr(NO 3 ) 4 ·5H 2 O 8.59g, weigh Cu(NO 3 ) 2 ·3H 2 O 0.03g was dissolved in deionized water to prepare Na with a concentration of 0.5mol / L 2 CO 3 solution;

[0056] (2) At a reaction temperature of 70°C, slowly drop the above solution in parallel in a three-necked flask, and at the same time perform magnetic stirring to control the pH value of the solution at the end point of the titration to be about 7.5. After the titration is completed, continue stirring for 1 hour and then stop stirring. Stand still at the reaction temperature for 3 hours, centrifugally filter the solution at a rotating speed of 10000r / min, add deionized water to wash 3 times, and obtain a solid precipitate;

[0057] (3) drying in a vacuum oven at 105° C. for 12 hours to obtain a copper-doped zinc-zirconium solid solution catalyst precursor.

[0058] (4) The catalyst precursor obtained after drying was calcined in a tube furnace at 500°C for 3 hours...

Embodiment 2

[0060] (1) Weigh Zn(NO 3 ) 2 ·6H 2 O 1.49g and Zr(NO 3 ) 4 ·5H 2 O 8.59g, weigh Cu(NO 3 ) 2 ·3H 2 O 0.06g was dissolved in deionized water to prepare Na with a concentration of 0.5mol / L 2 CO 3 solution;

[0061] (2) At a reaction temperature of 70°C, slowly drop the above solution in parallel in a three-necked flask, and at the same time perform magnetic stirring to control the pH value of the solution at the end point of the titration to be about 7.5. After the titration is completed, continue stirring for 1 hour and then stop stirring. Stand still at the reaction temperature for 3 hours, centrifugally filter the solution at a rotating speed of 10000r / min, add deionized water to wash 3 times, and obtain a solid precipitate;

[0062] (3) drying in a vacuum oven at 105° C. for 12 hours to obtain a copper-doped zinc-zirconium solid solution catalyst precursor.

[0063] (4) The catalyst precursor obtained after drying was calcined in a tube furnace at 500°C for 3 hours...

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Abstract

The invention discloses a copper-doped ZnO-ZrO2 sosoloid catalyst and a preparing method and application thereof. The preparing method of the catalyst comprises the steps of preparing a metal and nitrate mixed solution through Cu(NO3)2.3H2O, Zn(NO3)2.6H2O and Zr(NO3)4.5H2O; at the reaction temperature of 50-90 DEG C, dropwise adding the metal and nitrate mixed solution and a Na2CO3 solution into areaction container, maintaining the reaction temperature, conducting stirring, and conducting ageing at the reaction temperature; conducting centrifuging to obtain a solid precipitate after a productis cooled; then utilizing deionized water for washing the solid precipitate; then drying the precipitate to obtain a catalyst precursor; putting the catalyst precursor into a tube furnace for calcination to obtain a catalyst parent. By means of the copper-doped ZnO-ZrO2 sosoloid catalyst and the preparing method and application thereof, the dispersity of active components in the catalyst is improved, the sintering and aggregation phenomena of the catalyst are effectively inhibited, and the carbon dioxide conversion rate and methyl alcohol selectivity are high.

Description

technical field [0001] The invention belongs to the technical field of chemical catalysis, and in particular relates to a catalyst for hydrogenation of carbon dioxide to methanol and a preparation method thereof. Background technique [0002] Carbon dioxide is the most important greenhouse gas. Since the industrial revolution, the use of fossil energy has caused the emission of carbon dioxide to increase year by year. Therefore, the reduction of carbon dioxide emission has become a common goal of all countries in the world. There are many conversion and utilization methods of carbon dioxide, among which the hydrogenation conversion of carbon dioxide is more valuable for research. Through hydroconversion, carbon dioxide is converted into valuable chemicals such as methane, methanol, formic acid, etc. Because these products are bulk chemicals and are closely related to energy supply, they have high energy utilization value. [0003] Among the possible products of carbon diox...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/80B01J35/10C07C29/157C07C31/04
CPCC07C29/154B01J23/80B01J35/394B01J35/61C07C31/04Y02P20/52
Inventor 宋夫交程文强许琦曹燕高佳
Owner YANCHENG INST OF TECH
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