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Copper fluoride based hydrotalcite-like catalyst, method for preparing same and application of copper fluoride based hydrotalcite-like catalyst

A technology of hydrotalcite and copper fluoride, which is applied in the direction of physical/chemical process catalysts, chemical instruments and methods, and the preparation of hydroxyl compounds. It can solve the problems of difficult control of the amount of fluoride ion introduced, agglomeration, and time-consuming, etc., to improve methanol selection. The effect of high stability, stable performance, and a large number of strong alkaline sites

Active Publication Date: 2016-06-01
SHANGHAI ADVANCED RES INST CHINESE ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, this method is cumbersome and time-consuming, and it is easy to cause the growth and agglomeration of the hydrotalcite-like laminates in the secondary treatment process, and the introduction of fluoride ions is not easy to control

Method used

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  • Copper fluoride based hydrotalcite-like catalyst, method for preparing same and application of copper fluoride based hydrotalcite-like catalyst

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Effect test

Embodiment 1

[0033] According to Cu / Zn=2, (Cu+Zn) / Al=2, Na 3 AlF 6 / Al(NO 3 ) 3 =0.05 ratio (molar ratio), copper nitrate, zinc nitrate, aluminum nitrate and Na 3 AlF 6 Dissolve in deionized water to form a mixed aqueous solution, add dropwise to 1.0mol / L sodium hydroxide solution at 20°C, fully stir during the dropping process, and keep the final pH value at 8. After the precipitation reaction is completed, the obtained The product was aged at 70° C. for 24 h under stirring, and then the obtained precipitate was washed several times with deionized water, and then vacuum-dried at 70° C. overnight to obtain a fluorinated hydrotalcite-like material. The obtained material was heat-treated at 270° C. for 12 h under a pure hydrogen atmosphere to obtain a copper fluoride-based hydrotalcite-like catalyst. The carbon dioxide hydrogenation to methanol reaction is carried out in a stainless steel reactor with an inner diameter of 6mm, and the reaction conditions are as follows: P=5.0MPa, T=230°...

Embodiment 2

[0035] According to Cu / Zn=2, (Cu+Zn) / Al=2, Na 3 AlF 6 / Al(NO 3 ) 3 =0.15 ratio (molar ratio), copper nitrate, zinc nitrate, aluminum nitrate and Na 3 AlF 6 Dissolve in deionized water to form a mixed aqueous solution, add dropwise to 1.0mol / L sodium hydroxide solution at 20°C, fully stir during the dropping process, and keep the final pH value at 9. After the precipitation reaction is completed, the obtained The product was aged at 70° C. for 24 h under stirring, and then the obtained precipitate was washed several times with deionized water, and then vacuum-dried at 80° C. overnight to obtain a fluorinated hydrotalcite-like material. The obtained material was heat-treated at 290° C. for 8 h under a pure hydrogen atmosphere to obtain a copper fluoride-based hydrotalcite-like catalyst. The carbon dioxide hydrogenation to methanol reaction is carried out in a stainless steel reactor with an inner diameter of 6mm, and the reaction conditions are as follows: P=5.0MPa, T=250°C...

Embodiment 3

[0037] According to Cu / Zn=2, (Cu+Zn) / Al=2, Na 3 AlF 6 / Al(NO 3 ) 3 =0.25 ratio (molar ratio), copper nitrate, zinc nitrate, aluminum nitrate and Na 3 AlF 6 Dissolve in deionized water to make a mixed aqueous solution, add dropwise to 1.0mol / L sodium hydroxide solution at 25°C, fully stir during the dropping process, and keep the final pH value at 9. After the precipitation reaction, the obtained The product was aged at 80° C. for 12 h under stirring, and then the obtained precipitate was washed several times with deionized water, and then vacuum-dried at 90° C. overnight to obtain a fluorinated hydrotalcite-like material. The obtained material was heat-treated at 300° C. for 8 h in a pure hydrogen atmosphere to obtain a copper fluoride-based hydrotalcite-like catalyst. Carbon dioxide hydrogenation to methanol reaction is carried out in a stainless steel reactor with an inner diameter of 6mm, and the reaction conditions are as follows: P=4.0MPa, T=270°C, GHSV=5000h -1 , n...

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Abstract

The invention discloses a copper fluoride based hydrotalcite-like catalyst, a method for preparing the same and application of the copper fluoride based hydrotalcite-like catalyst. The copper fluoride based hydrotalcite-like catalyst comprises Cu, ZnO, Al2O3 and fluoride. A molar ratio of Cu elements to Zn elements is 2, a ratio of a total molar number of the Cu elements and the Zn elements to a molar number of Al elements is 0.5-4, and a molar ratio of F elements to the Al elements is 0.29-2.57. The copper fluoride based hydrotalcite-like catalyst, the method and the application have the advantages that the copper fluoride based hydrotalcite-like catalyst is high in metal element dispersion degree and strongly alkaline site quantity and favorable for dissociating and adsorbing H2 and stably adsorbing CO2, and is stable in performance during CO2 hydrogenation reaction operation, and the methanol selectivity can be obviously enhanced while a high CO2 conversion rate is guaranteed; the method is simple and is easy to implement, and industrial up-scale can be facilitated.

Description

technical field [0001] The invention relates to the field of catalysts, in particular to a copper fluoride-based hydrotalcite-like catalyst and a preparation method and application thereof. Background technique [0002] Atmospheric CO 2 The greenhouse effect caused by the increase in concentration and the increasing depletion of fossil fuels are of great concern. will CO 2 Conversion to methanol is an effective way to solve the two major problems of greenhouse gas emissions and fossil fuel substitution, because methanol is not only an important organic chemical raw material, but also a non-petroleum-based clean synthetic fuel. Compared with industrial synthesis gas to methanol, CO 2 hydrogenation reaction higher CO 2 and H 2 concentration promotes the reverse water gas shift reaction Instead, CO is produced, resulting in methanol selectivity much lower than the syngas route. Therefore, how to suppress the formation of by-product CO and improve methanol selectivit...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/12C07C31/04C07C29/154
CPCY02P20/52B01J27/12C07C29/154C07C31/04
Inventor 王慧杨海艳高鹏孙予罕魏伟夏林张辰肖硕
Owner SHANGHAI ADVANCED RES INST CHINESE ACADEMY OF SCI
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