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Catalyst for hydrogenation of carbon dioxide to generate methanol and preparation method thereof

A carbon dioxide and methanol production technology, which is applied in the direction of metal/metal oxide/metal hydroxide catalyst, organic compound preparation, physical/chemical process catalyst, etc., can solve the problem of low yield of methanol from hydrogenation

Inactive Publication Date: 2010-07-28
XIAMEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, from a practical point of view, existing CuO-based catalysts catalyze CO 2 The yield of hydrogenation to methanol is low

Method used

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  • Catalyst for hydrogenation of carbon dioxide to generate methanol and preparation method thereof
  • Catalyst for hydrogenation of carbon dioxide to generate methanol and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] 0.311g of cobalt acetate (Co(CH 3 COO) 2 4H 2 (2, the purity is AR grade) and put into a beaker filled with 50mL ethylene glycol (the purity is AR grade), stir until the cobalt acetate is completely dissolved, add an appropriate amount of KOH aqueous solution (concentration is 4mol / L), to adjust and maintain the concentration of the feed liquid When the pH value is in the range of 9.3 to 9.4, stir for 30 minutes, then add 1.228g of CNT, the feed liquid is ultrasonically treated for 30 minutes, and then placed in a microwave oven (2450MHz, 640W), heated by microwave radiation for 100s, stopped heating for 20s, and then heated for 10s , repeat the operation of "stop heating for 20s and reheat for 10s" once, and then take out the feed liquid and place it in a cold water bath to let it cool rapidly. After filtering, the filter cake is washed with acetone and deionized water successively until the filtrate is neutral. After drying at 110°C, metal Co-modified CNTs were obta...

Embodiment 2

[0032] 7.00g of Cu(NO 3 ) 2 ·3H 2 O, 2.16g Zn(NO 3 ) 2 ·6H 2 O and 4.84g ZrO(NO 3 ) 2 2H 2 O (purity are all AR grade) three mixed, add 100mL deionized water to make solution A; another 5.77g of Na 2 CO 3 (Purity is AR grade) dissolved in 100mL deionized water to make solution B; at 70°C, add solutions A and B at a constant velocity and dropwise into a beaker pre-installed with 0.570g CNT and 200mL deionized water , carry out the co-precipitation reaction at a constant temperature of 70°C, stirring continuously and keeping the pH value of the liquid material layer at about 7.5. , washed with deionized water until the filtrate was neutral, the filter cake was dried at 110°C for 6 hours, pure N 2 Calcined at 350°C for 2 hours in the atmosphere, the stoichiometric formula is Cu 8 Zn 2 Zr 5 - Catalyst (oxidation state) of 12.5% ​​CNT.

[0033]Catalyst to CO 2 The catalytic activity evaluation experiment of methanol hydrogenation is the same as that in Example 1. Th...

Embodiment 3

[0035] 7.00g of Cu(NO 3 ) 2 ·3H 2 O, 0.54g Zn(NO 3 ) 2 ·6H 2 O and 4.84g ZrO(NO 3 ) 2 2H 2 O (purity are all AR grade) three mixed, add 100mL deionized water to make solution A; another 5.19g of Na 2 CO 3 (Purity is AR grade) was dissolved in 100mL of deionized water to make solution B; at 70°C, solutions A and B were added dropwise at a constant rate to 0.520g of 4.5% Co / CNT and 200mL of deionized water In the beaker of ionized water, carry out co-precipitation reaction under the condition of constant temperature of 70°C, constant stirring and keeping the pH value of the liquid material layer at about 7.5. The precipitate was filtered by centrifugation, washed with deionized water until the filtrate was neutral, and the filter cake was dried at 110°C for 6 hours, pure N 2 Calcined at 350°C for 2 hours in the atmosphere, the stoichiometric formula is Cu 8 Zn 0.5 Zr 5 - 12.5% ​​(4.5% Co / CNT) catalyst (oxidation state).

[0036] Catalyst to CO 2 The catalytic acti...

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Abstract

The invention relates to a catalyst, in particular to the catalyst for hydrogenation of carbon dioxide to generate methanol and a preparation method thereof. A carbon nanotube-based material is adopted as an accelerating agent. When being used for the catalytic hydrogenation of the carbon dioxide to generate the methanol, the catalyst can effectively increase the hydrogenation converting rate of the carbon dioxide and the one-path yield rate of the methanol. The catalyst comprises main metal components and the accelerating agent of the carbon nanotube-based material. The main metal components include Cu, Zn and Or. The accelerating agent of the carbon nanotube-based material means CNT or y% Co / CNT, and the chemical formula is CuiZnjZrk-x% (CNT or y% Co / CNT). The mass percent of each component is as follows: Zn: 5 to 20%; Zr: 25 to 50%; the accelerating agent of the carbon nanotube-based material: 1 to 18%; and the rest is Cu. The catalyst is prepared through coprecipitation. A multi-wall carbon nanotube modified by metal cobalt is prepared by utilizing liquid-phase microwaves of polyalcohol to assist in chemical reduction and deposition.

Description

technical field [0001] The invention relates to a catalyst, in particular to a copper-zinc-zirconium catalyst promoted by carbon nanotube-based nanomaterials and a preparation method thereof. Background technique [0002] CO 2 Hydrogenation is considered to be the current method for fixing large CO emissions in a short period of time. 2 One of the most economical and effective methods. In order to improve climate conditions and solve the carbon resource problem, it is necessary to develop 2 Technologies that transform into valuable materials. Among the options considered, the CO 2 The research on conversion to methanol by hydrogenation has attracted much attention. In the past 20 years, the CO 2 There have been many reports on the research or development of catalysts for hydrogenation of methanol; the earliest and most widely studied are CuO-based catalysts. Amenomiya et al. ([1] Amenomiya Y., et al., Proc9 th Intern.Congr.Catal.(Chem.Inst.of Canada, Calgary), 1988,...

Claims

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Application Information

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IPC IPC(8): B01J23/80B01J21/18C07C31/04C07C29/154C07C29/156
CPCY02P20/52
Inventor 张鸿斌刘志铭林国栋
Owner XIAMEN UNIV
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