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Nano-copper-cobalt bimetallic catalyst as well as preparation method and application thereof

A bimetallic catalyst and nano-copper technology, applied in the direction of metal/metal oxide/metal hydroxide catalyst, hydroxyl compound preparation, organic compound preparation, etc., can solve the problem of low carrier content, low specific surface area, easy sintering of catalyst, etc. problem, to achieve the effect of high dispersion, good stability and high selectivity

Active Publication Date: 2014-04-16
TIANJIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] However, the above-mentioned catalysts all have low carrier content and too low specific surface area; this is because the active component and the carrier are obtained by reducing the perovskite composite oxide, and the ratio adjustment of the carrier and the active component is limited.
On such a catalyst, the conversion rate of carbon monoxide is low, the selectivity of alcohols is not high, and the catalyst is easy to sinter when it is used for a long time, so it has no application value

Method used

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  • Nano-copper-cobalt bimetallic catalyst as well as preparation method and application thereof
  • Nano-copper-cobalt bimetallic catalyst as well as preparation method and application thereof
  • Nano-copper-cobalt bimetallic catalyst as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] 0.3574 g lanthanum nitrate, 0.1665 g cobalt nitrate, 0.0589 g copper nitrate, 0.4088 g citric acid and 0.0242 g ethylene glycol were dissolved in 2.1 ml deionized water. An equal volume of the above solution was impregnated in 2.1 g of ZrO 2 on the carrier. Stand for aging for 24 hours, then dry at 120°C for 24 hours, heat up at 2°C / min to 300°C for 2 hours, and repeat the above impregnation and drying process once. Finally, heat up to 300°C at 2°C / min and bake for 2 hours, and then heat up to 650°C for 5 hours at the same heating rate to obtain ZrO 2 Loaded LaCo 0.7 Cu 0.3 o 3 . Among them, Cu is 1.34%, Co is 3.16%, La 2 o 3 11.52%, ZrO 2 It was 83.98%.

[0034] The catalyst precursor that gets 0.8g above-mentioned method preparation is packed in the reactor, with the volume space velocity being 2000h -1 Access to H 2 The mixed gas of hydrogen and argon with a volume fraction of 5% was raised to 550° at a rate of 10°C / min for reduction for 3 hours, cooled na...

Embodiment 2

[0037] 1.5258 g of lanthanum nitrate, 0.7106 g of cobalt nitrate, 0.2515 g of copper nitrate, 1.7450 g of citric acid, and 0.096 g of ethylene glycol were dissolved in 1.2 ml of deionized water. An equal volume of the above solution was immersed in 1.2g Al 2 o 3 on the carrier. The obtained solid was left to age for 24 hours, and then dried at 120° C. for 24 hours. Raise the temperature at 2°C / min to 300°C for 2 hours, and then use the same heating rate to 650°C for 5 hours to obtain Al 2 o 3 Loaded LaCo 0.7 Cu 0.3 o 3 . Among them, Cu is 3.36%, Co is 7.84%, La 2 o 3 28.8%, Al 2 o 3 60%.

[0038] Get 0.8g of the catalyst precursor prepared by the above-mentioned method, pack in the reactor, take volume space velocity as 2000h -1 Access to H 2 A mixture of hydrogen and nitrogen with a volume fraction of 5% was raised to 660°C at a rate of 10°C / min for reduction for 3 hours. Cool naturally to room temperature and pass through H 2 Syngas with CO in a molar ratio o...

Embodiment 3

[0040] The preparation process of the catalyst precursor is the same as in Example 2, except that the Al 2 o 3 The carrier is replaced by CeO 2 carrier; the drying temperature was changed from 120°C to 80°C to obtain CeO 2 Loaded LaCo 0.7 Cu 0.3 o 3 catalyst precursor.

[0041] Get this catalyst precursor of 0.8g and pack in the reactor, be placed in volume space velocity and be 1500h -1 , in a mixture of hydrogen and carbon monoxide with a volume fraction of 5%, rise to 450° at a rate of 2°C / min for reduction for 3 hours, then naturally cool down to room temperature and feed H 2 Syngas with CO in a molar ratio of 2:1. The pressure is increased to 3MPa, the temperature is set to 340°C, and the space velocity of the syngas is set to 3900h -1 . The measured conversion rate of carbon monoxide is 80.28%, the selectivity of low-carbon alcohol is 48.64%, and the space-time yield of total alcohol is 207.5g / kg cat .h. The conversion rate of CO on the catalyst and the distri...

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Abstract

The invention discloses a nano-copper-cobalt bimetallic catalyst as well as a preparation method and an application thereof. The catalyst takes SiO2, ZrO2, CeO2 or Al2O3 as a carrier and La2O3 as an aid, and is loaded with an active ingredient Cu[x]Co[1-x]. The preparation method comprises the following steps: soaking a mixed solution of lanthanum ions, copper ions, cobalt ions, citric acid and a chelating agent in the SiO2, ZrO2, CeO2 or Al2O3 carrier, drying and roasting to obtain a catalyst precursor; reducing the precursor through H2, CO or CH4 reducing gas or mixed gas containing the H2, CO or CH4 reducing gas and inert gas to obtain the loaded copper-cobalt bimetallic catalyst taking lanthanum oxide as the aid. The preparation method has the advantages that the interaction among Cu, Co and the lanthanum oxide is facilitated in the process of obtaining the catalyst through the precursor, and the components such as the Cu, the Co and the lanthanum oxide are high in dispersity and good in stability. The catalyst is used in reaction for preparing low-carbon alcohol from synthetic gas, and is relatively high in selectivity, activity and stability on alcohols each with 2-6 carbon atoms.

Description

technical field [0001] The invention relates to a nano-copper-cobalt bimetallic catalyst and its preparation and application, belonging to the technical field of metal catalysts. Background technique [0002] my country's energy structure has been in a state of "rich coal, poor oil and little gas" for a long time. Coal or biomass is used as raw material to prepare synthetic gas (CO+H 2 ). Then, the catalytic preparation of low-carbon alcohols (alcohols with 2-6 carbon atoms) through synthesis gas has important strategic significance and application prospects. [0003] Since South America banned the use of methyl tert-butyl ether and tetraethyl lead as additives, low-carbon alcohols have attracted widespread attention as gasoline additives, and the demand for their output has also increased sharply. At the same time, due to climate change, the consumption of fossil fuels, and the rise in crude oil prices, the development and utilization of clean and efficient energy has alw...

Claims

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Application Information

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IPC IPC(8): B01J23/83C07C29/156C07C31/02
Inventor 刘源刘贵龙潘东明曹昂
Owner TIANJIN UNIV
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