Effects of co-doping of Co and Zr on performances of In-based catalysts for carbon dioxide hydrogenation to methanol

ZHU Yicheng; MA Hongfang; QIAN Weixin; ZHANG Haitao; YING Weiyong

doi:10.12434/j.issn.2097-2547.20240110

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Effects of co-doping of Co and Zr on performances of In-based catalysts for carbon dioxide hydrogenation to methanol

- Effects of co-doping of Co and Zr on performances of In-based catalysts for carbon dioxide hydrogenation to methanol
- Vol. 49, Issue 8, Pages: 115-122(2024)
- 作者机构：
  
  1.华东理工大学化工学院大型工业反应器工程教育部工程研究中心化学工程联合国家重点实验室，上海 200237
  2.煤液化气化及高效低碳利用全国重点实验室，上海 200237
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20240110
  CLC： TQ21
- Published：25 August 2024，
  
  Received：18 March 2024，
  
  Revised：01 April 2024，
- 稿件说明：
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朱怡澄,马宏方,钱炜鑫等.钴、锆共掺杂对铟基催化剂二氧化碳加氢制甲醇性能的影响[J].低碳化学与化工,2024,49(08):115-122.

ZHU Yicheng,MA Hongfang,QIAN Weixin,et al.Effects of co-doping of Co and Zr on performances of In-based catalysts for carbon dioxide hydrogenation to methanol[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):115-122.
朱怡澄,马宏方,钱炜鑫等.钴、锆共掺杂对铟基催化剂二氧化碳加氢制甲醇性能的影响[J].低碳化学与化工,2024,49(08):115-122. DOI： 10.12434/j.issn.2097-2547.20240110.

ZHU Yicheng,MA Hongfang,QIAN Weixin,et al.Effects of co-doping of Co and Zr on performances of In-based catalysts for carbon dioxide hydrogenation to methanol[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):115-122. DOI： 10.12434/j.issn.2097-2547.20240110.

摘要

加氢制甲醇是CO

综合利用的重要途径之一。In基催化剂常用于CO

加氢合成甲醇反应，其甲醇选择性较高，但CO

转化率普遍较低。为研究添加不同比例的Co、Zr对In基催化剂性能的影响，在保持In总物质的量分数不变的情况下，采用共沉淀法制备了不同

(Zr):

(Co)的In基催化剂，通过Ar低温物

理吸附、X射线衍射（XRD）、高分辨率透射电镜（HRTEM）、X射线光电子能谱（XPS）和H

程序升温还原（H

-TPR）对催化剂进行了表征，并在温度为240~300 ℃、压力为3.0 MPa和气体空速为7200 mL/(h·g)的条件下对各催化剂的催化性能进行了测试。结果表明，在一定

(Zr):

(Co)范围内，Co、Zr同时添加的催化剂相对于单独添加Co或Zr的催化剂具有更高的CO

转化率和甲醇时空产率。

(Zr):

(Co)不同会产生不同程度的金属间相互作用，影响催化剂的比表面积、颗粒尺寸和还原性能。当

(Zr):

(Co)为1:3时，催化剂具有最优的甲醇合成性能，甲醇时空产率可达178 mg/(g·h)。催化剂的CO

转化率由高至低依次为Zr

In、Zr

2.5

17.5

In、Zr

7.5

12.5

In、Co

In、Zr

In和In

100

，与氧空位占比变化的趋势一致。Zr

In催化剂具有更小的颗粒尺寸与更大的比表面积，可以暴露更多的有效活性位点，因此具有更高的还原性和更强的金属间相互作用，其CO

转化率可达到13.63%，相比Co

In提升了19.9%，相比Zr

In提升了64.7%。

Abstract

hydrogenation to methanol is one of promising route for CO

utilization. In-based catalysts has high methanol selectivity but low CO

conversion rate for CO

hydrogenation to methanol. In order to investigate the effects of doping different proportions of Co and Zr on the performances of In-based catalysts

In-based catalysts doped with different

(Zr):

(Co) were synthesized by co-precipitation method while keeping the same mole fraction of In in the precursor. The catalysts were characterized by low-temperature Ar physical adsorption

X-ray diffraction (XRD)

high resolution transmission electron microscope (HRTEM)

X-ray photoelectron spectroscopy (XPS) and H

temperature-programmed reduction (H

-TPR). The catalytic performances of each catalyst were tested under the conditions of temperature from 240 ℃ to 300 ℃

pressure of 3.0 MPa and gas space velocity of 7200 mL/(h·g). The results show that the catalysts with Co and Zr at the same time has a higher CO

conversion rate and methanol time-sp

ace yield than the catalysts with Co or Zr alone in a certain

(Zr):

(Co) range.

(Zr):

(Co) will produce different degrees of metal-to-metal interactions

which will affect the specific surface area

particle size and reduction performance of the catalysts. When the doped

(Zr):

(Co) is 1:3

the catalyst has the best methanol synthesis ability and the methanol time-space yield is up to 178 mg/(g·h). The CO

conversion rate decreases in the order: Zr

2.5

17.5

7.5

12.5

In and In

100

which is consistent with the trend of oxygen vacancy ratio. The Zr

In catalyst has a smaller particle size with a larger specific surface area

which can expose more active sites

and has higher reducibility and stronger intermetallic interactions. The CO

conversion rate of Zr

In can reach 13.63%

which is 19.9% higher than Co

In and 64.7% higher than Zr

In.

关键词

甲醇In基催化剂二氧化碳加氢共沉淀

Keywords

methanolIn-based catalystscarbon dioxide hydrogenationco-precipitation

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Related Author

ZHU Yicheng

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Related Institution

Engineering Research Center of Large Scale Reactor Engineering and Technology, Ministry of Education, State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology

School of Chemical Engineering, East China University of Science and Technology-Shenergy Co., Ltd. Carbon Neutrality Joint Laboratory, East China University of Science and Technology

C1 Chemistry, Southwest Institute of Chemical Co., Ltd.

School of Chemistry and Chemical Engineering, North Minzu University

Key Laboratory for Chemical Engineering and Technology, State Ethnic Affairs Commission, North Minzu University

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