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Preparation and application of mixed oxide-doped nano-copper-cobalt alloy catalyst

A technology of mixed oxides and catalysts, applied in the direction of metal/metal oxide/metal hydroxide catalysts, preparation of organic compounds, preparation of hydroxyl compounds, etc., can solve the problem of long-term stability of carbon materials and the unfavorable formation of Cu-Co Alloy, reduce catalyst selectivity and other issues, to achieve the effect of low cost, improved stability, not easy to sinter

Active Publication Date: 2017-03-15
TIANJIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Increasing the content of aluminum, magnesium, zinc and other components in the hydrotalcite precursor can reduce the content of Cu-Co; but the increase of these components dilutes copper and cobalt, and the distance between copper and cobalt becomes farther, which is not conducive to interaction and Facilitate the formation of Cu-Co alloy
(2) Molding problem, the actual application of the catalyst requires molding, usually several millimeters of particles; and if the content of Cu-Co metal is high, it cannot be molded
Previously, we alleviated the formation of hot spots by doping carbon nanotubes, carbon fibers or graphite flakes (or graphene) in the catalyst [patent application numbers: 2014107794454, 2014107788415, 201410271568.7], but the problem is that these carbon species will be reduced during the calcination of the catalyst A part of copper leads to the generation of single metal copper, which reduces the selectivity of the catalyst; another problem is that there may be problems with the long-term stability of these carbon substances in the reaction process of synthesizing low-carbon alcohols. During the long-term reaction process, these carbon substances will It reacts with water in the reaction product and loses

Method used

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  • Preparation and application of mixed oxide-doped nano-copper-cobalt alloy catalyst
  • Preparation and application of mixed oxide-doped nano-copper-cobalt alloy catalyst
  • Preparation and application of mixed oxide-doped nano-copper-cobalt alloy catalyst

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Experimental program
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Effect test

Embodiment 1

[0029] Disperse the hydrotalcite-like [patent application number: 2014107794454] containing Cu, Co and Al in water, mix it with the dispersion of zirconium hydroxide in water, stir at room temperature for 12 hours, and then put the solid obtained after suction filtration at a temperature of 80°C Drying at low temperature for 12 hours, the hydrotalcite-like precursor doped with zirconium hydroxide was obtained. The catalyst precursor was added to the muffle furnace, and the temperature was raised to 500 °C for 4 h at a heating rate of 5 °C / min to obtain Al 2 o 3 and ZrO 2 Mixed oxide doped copper cobalt mixed oxide. Among them, Cu is 11.9%, Co is 22.3%, Al 2 o 3 14.2%, ZrO 2 was 51.6%.

[0030] Take the roasted product into the reactor, and feed H into the reactor 2 The mixed gas of hydrogen and argon with a volume fraction of 5% was raised to 470° at a rate of 5°C / min for reduction for 3 hours, cooled naturally to room temperature, and passed through H 2 Syngas with a ...

Embodiment 2

[0033] Disperse the hydrotalcite-like stone containing Cu, Co, Mg and Al in water, mix it with the dispersion of cerium hydroxide in water, stir at room temperature for 6 hours, then filter with suction, and dry the obtained solid at 60°C for 24 hours to obtain Hydrotalcite-like precursors doped with cerium hydroxide. The catalyst precursor was added to the muffle furnace, and the temperature was raised to 600 °C for 6 h at a heating rate of 1 °C / min to obtain Al 2 o 3 and CeO 2 Mixed oxide supported copper cobalt oxide. Among them, Cu is 5.0%, Co is 14.0%, MgO is 25.0%, Al 2 o 3 16.0%, CeO 2 was 40.0%.

[0034] Take the roasted product into the reactor, and feed H into the reactor 2 The mixed gas of hydrogen and argon with a volume fraction of 5% was raised to 500° at a rate of 10°C / min for reduction for 1 hour, and then cooled naturally to room temperature and then passed into H 2 Syngas with a molar ratio of 2:1 to CO, raise the pressure to 4MPa, and set the volumet...

Embodiment 3

[0036] Disperse the hydrotalcite-like stone containing Cu, Co, Zn and Al in water, mix it with the dispersion of silicon hydroxide in water, stir at room temperature for 20 hours, then filter with suction, and dry the obtained solid at 120°C for 8 hours to obtain Hydrotalcite-like precursors doped with silicon hydroxide. Put the catalyst precursor into the muffle furnace, heat up to 300°C at a heating rate of 5°C / min and bake for 10h to obtain Al 2 o 3 and SiO 2 Copper cobalt oxide doped with mixed oxides. Among them, Cu is 25.0%, Co is 11.7%, ZnO is 15.8%, Al 2 o 3 20.0%, SiO 2 was 27.5%.

[0037] Take the roasted product into the reactor, and feed H into the reactor 2 The mixed gas of hydrogen and argon with a volume fraction of 5% was raised to 300° at a rate of 1°C / min for reduction for 3 hours, cooled naturally to room temperature, and passed through H 2 Syngas with a molar ratio of 2:1 to CO, raise the pressure to 6MPa, and set the volumetric space velocity of th...

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Abstract

The invention relates to a preparation method and application of a mixed oxide-doped nano copper-cobalt alloy catalyst. According to the catalyst, CuCo serves as an active component and mixed oxide serves as a carrier, wherein Cu accounts for 5-25% in the catalyst in percentage by mass, Co accounts for 5-25% in the catalyst in percentage by mass, Al2O3 accounts for 13-25% in the catalyst in percentage by mass, and one of SiO2, ZrO2, CeO2 or TiO2 accounts for the balance. The mixed oxide-doped nano copper-cobalt alloy catalyst is obtained by calcinating and reducing a hydroxide-doped hydrotalcite-like precursor. Since silicon, zirconium, cerium and titanium ions cannot enter a hydrotalcite-like laminate, the dispersion of copper and cobalt on the surface is improved, the dispersion degree of active components is increased, and the formation of a hotspot in a reaction process of synthesizing low-carbon alcohol is relieved. The catalyst is relatively high in low-carbon alcohol selectivity and low-temperature activity, easy to operate, and low in cost and is applicable to industrial production.

Description

technical field [0001] The invention relates to the preparation and application of a mixed oxide-doped nano-copper-cobalt alloy catalyst, which belongs to the technical field of metal catalysts. Background technique [0002] With the increasing consumption of petroleum resources, the energy problem is intensifying, and it is imminent to develop a new energy system. Syngas (CO and H) produced from natural gas or coal or renewable biomass resources 2 Mixed gas) to prepare low-carbon alcohols (alcohols with 2-6 carbon atoms) has attracted great attention. Low-carbon alcohol can be used as a high-quality power fuel. Its combustion is more complete than gasoline and diesel, and there are fewer harmful substances in exhaust emissions. It is an environmentally friendly fuel; in addition, low-carbon alcohol can also be used as one of the means of coal liquefaction to achieve coal alkylation And solubilization and as a liquefied petroleum gas substitute. However, in the process of...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/75B01J23/83B01J23/80B01J23/889C07C31/04C07C31/08C07C31/10C07C31/12C07C31/125C07C29/156
CPCY02P20/52
Inventor 刘源曹昂刘贵龙王联防岳义智
Owner TIANJIN UNIV
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