Study on application of CuZn/CeO<sub>2</sub> catalysts in CO<sub>2 </sub>hydrogenation to methanol

ZHANG Lan; CHEN Biaohua; WANG Ning

doi:10.12434/j.issn.2097-2547.20240205

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Study on application of CuZn/CeO₂ catalysts in CO₂hydrogenation to methanol

- Study on application of CuZn/CeO₂ catalysts in CO₂hydrogenation to methanol
- Vol. 49, Issue 8, Pages: 100-106(2024)
- 作者机构：
  
  北京工业大学环境科学与工程学院，北京 100124
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20240205
  CLC： TQ072;X701;O643.3
- Published：25 August 2024，
  
  Received：09 May 2024，
  
  Revised：20 May 2024，
- 稿件说明：
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张兰,陈标华,王宁.CuZn/CeO₂催化剂在CO₂加氢制甲醇中的应用研究[J].低碳化学与化工,2024,49(08):100-106.

ZHANG Lan,CHEN Biaohua,WANG Ning.Study on application of CuZn/CeO₂ catalysts in CO₂hydrogenation to methanol[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):100-106.
张兰,陈标华,王宁.CuZn/CeO₂催化剂在CO₂加氢制甲醇中的应用研究[J].低碳化学与化工,2024,49(08):100-106. DOI： 10.12434/j.issn.2097-2547.20240205.

ZHANG Lan,CHEN Biaohua,WANG Ning.Study on application of CuZn/CeO₂ catalysts in CO₂hydrogenation to methanol[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):100-106. DOI： 10.12434/j.issn.2097-2547.20240205.

摘要

加氢制甲醇反应过程中产生的大量副产物水会加速催化剂中CuZn物种的聚集和烧结，导致催化剂严重失活。而CeO

亲水性较弱，具有较高的水热稳定性，可以增强CuZn物种的分散。因此，通过水热合成法制备了一系列CeO

载体晶面可调控的CuZn基催化剂，并在其中引入了适当浓度的氧空位。采用TEM、XRD和H

-TPR等表征手段研究了合成的CeO

载体及CuZn/CeO

催化剂（

为rod、cube 或otca）的形貌、结构和还原性能等物理化学性质，并考察了CuZn/CeO

催化剂在CO

加氢制甲醇反应中的催化性能。结果表明，暴露(110)晶面的纳米棒结构的CeO

载体（CeO

-rod）更有利于CuZn基物种的分散，并且CeO

-rod与Cu物种形成了Cu—O—Ce界面，增强了催化剂同时吸附和活化CO

和H

的性能。因此，CuZn/CeO

-rod表现出较高的CO

转化率和甲醇选择性，在260 ℃、3 MPa的条件下，甲醇时空收率为433.4 g/(kg·h)，甲醇选择性高达68.5%。同时，利用原位漫反射傅立叶变换红外光谱对CO

加氢制甲醇的反应路径和重要中间物种的演变进行了详细研究，发现在CuZn/CeO

催化剂的作用下，反应主要遵循甲酸盐路径，载体的晶面效应没有改变反应路径，但是提高了重要中间物种达到平衡的速率。

Abstract

The presence of by-product water produced during the CO

hydrogenation to methanol reaction will accelerate the aggregation and sintering of CuZn species

resulting in serious deactivation of the catalyst. CeO

has weak hydrophilicity and high hydrothermal stability

which can enhance the dispersion of CuZn species. Consequently

a series of CuZn-based catalysts with controllable crystal planes of CeO

carriers were synthesized by hydrothermal method

and appropriate concentrations of oxygen vacancy were strategically introduced. The physicochemical properties such as morphologies a

nd structures and reduction performances of the synthesized CeO

carriers and CuZn/CeO

catalysts (

represents rod、cube or otca) were studied by characterization methods such as TEM

XRD and H

-TPR. The catalytic performances of CuZn/CeO

catalysts in CO

hydrogenation to methanol were also investigated. The results show that the CeO

carrier with nanorod structure and exposed (110) crystal plane (CeO

-rod) is more conducive to the dispersion of CuZn-based species. Moreover

CeO

-rod and Cu species form Cu—O—Ce interface

which enhances the ability of the catalyst to adsorb and activate CO

and H

simultaneously. Therefore

CuZn/CeO

-rod catalyst exhibits high CO

conversion and methanol selectivity. Under the conditions of 260 °C and 3 MPa

the space-time yield of methanol is up to 433.4 g/(kg·h)

and methanol selectivity is up to 68.5%. Simultaneously

the reaction paths and evolution of intermediates in CO

hydrogenation to methanol were thoroughly delineated by in situ diffuse reflectance infrared Fourier transform spectroscopy. It is found that under the action of CuZn/CeO

catalysts

the reaction mainly follow the formate path. The crystal plane effect of the carrier does not change the reaction paths

but it increases the equilibrium rate of important intermediate species.

关键词

CuZn/CeO2催化剂CO2加氢甲醇选择性氧空位

Keywords

CuZn/CeO2 catalystCO2 hydrogenationmethanol selectivityoxygen vacancy

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Study on application of CuZn/CeO2 catalysts in CO2 hydrogenation to methanol

DOI：10.12434/j.issn.2097-2547.20240205

摘要

Abstract

关键词

Keywords

references

Study on application of CuZn/CeO₂ catalysts in CO₂hydrogenation to methanol