Selective hydrogenation of CO<sub>2</sub> to CO over Co/ZrO<sub>2</sub> catalysts regulated by Sn promoter

YUAN Jinbiao; CHEN Jie; XU Yuebing; LIU Bing; LIU Xiaohao

doi:10.12434/j.issn.2097-2547.20240079

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Selective hydrogenation of CO₂ to CO over Co/ZrO₂ catalysts regulated by Sn promoter

- Selective hydrogenation of CO₂ to CO over Co/ZrO₂ catalysts regulated by Sn promoter
- Vol. 49, Issue 11, Pages: 21-27(2024)
- 作者机构：
  
  江南大学化学与材料工程学院，江苏无锡 214122
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20240079
  CLC： TQ426
- Published：25 November 2024，
  
  Received：02 March 2024，
  
  Revised：18 March 2024，
- 稿件说明：
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袁金标,陈杰,胥月兵等.Sn助剂调控Co/ZrO₂催化剂用于CO₂选择性加氢制CO[J].低碳化学与化工,2024,49(11):21-27.

YUAN Jinbiao,CHEN Jie,XU Yuebing,et al.Selective hydrogenation of CO₂ to CO over Co/ZrO₂ catalysts regulated by Sn promoter[J].Low-carbon Chemistry and Chemical Engineering,2024,49(11):21-27.
袁金标,陈杰,胥月兵等.Sn助剂调控Co/ZrO₂催化剂用于CO₂选择性加氢制CO[J].低碳化学与化工,2024,49(11):21-27. DOI： 10.12434/j.issn.2097-2547.20240079.

YUAN Jinbiao,CHEN Jie,XU Yuebing,et al.Selective hydrogenation of CO₂ to CO over Co/ZrO₂ catalysts regulated by Sn promoter[J].Low-carbon Chemistry and Chemical Engineering,2024,49(11):21-27. DOI： 10.12434/j.issn.2097-2547.20240079.

摘要

将CO

通过逆水煤气变换（RWGS）反应转化为CO能够有效缓解因CO

排放引发的环境问题，然而CO

的有效活化以及抑制副产物CH

的生成是RWGS反应的关键难点。将不同掺杂量（质量分数，下同）的Sn引入5Co/ZrO

（Co质量分数为5%）中进行修饰，制备了5Co

Sn/ZrO

（

= 1、3或5，分别对应Sn掺杂量为1%、3%或5%）催化剂，并对5Co/ZrO

和5Co

Sn/ZrO

的催化CO

加氢反应性能评价过程中的各项实验参数进行了调节和筛选，用于探究Sn助剂对活性组分以及催化性能的影响。其中，5Co5Sn/ZrO

具有最佳的RWGS催化性能，其在600 °C下预还原2 h后，在反应温度为500 ℃、压力为0.1 MPa和体积空速为36000 mL/(g·h)的反应条件下，CO

转化率达到11.9%，CO选择性为99.4%。采用XRD、H

-TPR和H

-TPD等表征方法综合分析了Sn助剂在CO

加氢反应过程中的作用。结果表明，Sn助剂的引入将CO

加氢反应从甲烷化调控为RWGS反应。经过还原预处理后，Sn与Co物种形成了Co-Sn合金，新的活性位点减弱了催化剂表面吸附CO

、H

和CO的性能。与5Co/ZrO

相比，5Co5Sn/ZrO

的H

吸附和活化性能减弱，CO

和CO吸附量大幅降低，降低了CO

加氢的活性并抑制了CO

深度加氢，使得催化剂的催化性能降低，CH

选择性降低，CO选择性升高至

约100%。

Abstract

The conversion of CO

to CO via reverse water gas transformation (RWGS) reaction can present a promising strategy to mitigate the environmental impact of CO

emission. However

the RWGS reaction encounters notable challenges

such as the efficient activation of CO

and the suppressed generation of CH

. Different doping contents (mass fractions

the same below) of Sn were introduced into 5Co/ZrO

(Co mass fraction of 5%) for modification

and 5Co

Sn/ZrO

(

= 1

3 or 5

corresponding to Sn doping content of 1%

3% or 5%) catalysts were prepared. The experimental parameters for evaluating the catalytic performances of 5Co/ZrO

and 5Co

Sn/ZrO

in CO

hydrogenation reaction were adjusted and screened to explore the influence of Sn additives on the active components and catalytic performance. Among them

5Co5Sn/ZrO

shows the best RWGS catalytic performance. After pre-reduction for 2 h at 600 ℃

under reaction conditions of temperature of 500 ℃

pressure of 0.1 MPa and space velocity of 36000 mL/(g·h)

the CO

conversion rate reaches 11.9%

and the CO selectivity is 99.4%. The role of Sn promoter in CO

hydrogenation reaction was comprehensively analyzed by characterization methods such as XRD

-TPR

and H

-TPD. The results indicate that the introduction of Sn regulates the CO

hydrogenation reaction from methanation to RWGS. After reduction

Sn and Co species form Co-Sn alloy

and new active sites reduce the ability of the catalyst surface to adsorb CO

and CO. Compared with 5Co/ZrO

5Co5Sn/ZrO

shows weaker adsorption and activation ability of H

and much lower adsorption amount of CO

and CO

which reduces the activity of CO

hydrogenation a

nd inhibits the deep CO

hydrogenation

resulting in a decrease in the catalytic performance of the catalyst

a decrease in CH

selectivity and an increase in CO selectivity to about 100%.

关键词

CO2加氢RWGS选择性转换Co-Sn合金化学吸附

Keywords

CO2 hydrogenationRWGSselectivity switchCo-Sn alloychemisorption

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Selective hydrogenation of CO2 to CO over Co/ZrO2 catalysts regulated by Sn promoter

DOI：10.12434/j.issn.2097-2547.20240079

摘要

Abstract

关键词

Keywords

references

Selective hydrogenation of CO₂ to CO over Co/ZrO₂ catalysts regulated by Sn promoter