Pd掺杂方式对Cu/ZnO低温催化CO<sub>2</sub>加氢制甲醇性能的影响

张培培; 辛靖; 李思漩; 米晓彤; 杨国明; 刘影; 陈新国; 夏林

doi:10.12434/j.issn.2097-2547.20240469

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Pd掺杂方式对Cu/ZnO低温催化CO₂加氢制甲醇性能的影响

更新时间：2025-02-24

- Pd掺杂方式对Cu/ZnO低温催化CO₂加氢制甲醇性能的影响
- Effect of Pd doping method on low temperature catalytic performance of Cu/ZnO for CO₂ hydrogenation to methanol
- 低碳化学与化工 2025: 1-9.
- 作者机构：
  
  1.中海油化工与新材料科学研究院（北京）有限公司，北京 102219
  2.中国科学院上海高等研究院中国科学院低碳转化科学与工程重点实验室，上海 201210
- 作者简介：
  
  张培培（1989—），博士，副教授，研究方向为CO2加氢制高附加值化学品及其技术开发，E-mail：zhangpp15@cnooc.com.cn。
  夏林（1986—），本科，高级实验师，研究方向CO2加氢制甲醇及甲醇制氢，E-mail：xial@sari.ac.cn。
- 基金信息：
  
  国家自然科学基金(U23B6003;U22B20136);中国海洋石油有限公司CCUS重大专项(KJGG-2022-12-CCUS-030401)
- DOI：10.12434/j.issn.2097-2547.20240469
  中图分类号： TQ426
- 收稿日期：2024-11-27，
  
  修回日期：2024-12-25，
  
  网络出版日期：2025-02-21，
- 稿件说明：
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张培培,辛靖,李思漩等.Pd掺杂方式对Cu/ZnO低温催化CO₂加氢制甲醇性能的影响[J].低碳化学与化工,

ZHANG Peipei,XIN Jing,LI Sixuan,et al.Effect of Pd doping method on low temperature catalytic performance of Cu/ZnO for CO₂ hydrogenation to methanol[J].Low-carbon Chemistry and Chemical Engineering,
张培培,辛靖,李思漩等.Pd掺杂方式对Cu/ZnO低温催化CO₂加氢制甲醇性能的影响[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20240469.

ZHANG Peipei,XIN Jing,LI Sixuan,et al.Effect of Pd doping method on low temperature catalytic performance of Cu/ZnO for CO₂ hydrogenation to methanol[J].Low-carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20240469.

摘要

加氢制甲醇是CO

资源化利用的重要途径之一，Cu/ZnO催化剂因具有独特的催化性能而备受关注。采用共沉淀法、浸渍法和机械混合法制备了一系列掺杂Pd的Cu/ZnO催化剂，利用ICP-OES、N

物理吸/脱附和XRD等方法对催化剂进行了表征，并在温度为170~250 ℃、压力为5.0 MPa和气体空速为4000 mL/(g·h)的条件下对各催化剂催化性能进行了测试，深入研究了不同Pd掺杂方式对催化剂的结构、形貌和催化性能的影响。结果表明，共沉淀法制备的Pd-Cu/ZnO-C催化剂相对于未掺杂的Cu/ZnO催化剂，具有更高的CO

转化率、甲醇选择性和甲醇时空收率。共沉淀法促使Pd在催化剂中均匀分布且高度分散，贵金属Pd与Cu的协同催化作用有效增强了氢解离和溢流性能。此外，Pd-Cu/ZnO-C催化剂的粒径较小、比表面积较大且还原性能较为优异，从而有效降低了反应活化能。在170 ℃和190 ℃的低温下，Pd-Cu/ZnO-C催化剂的CO

转化率分别为5.5%和8.9%，甲醇选择性分别为82.2%和74.9%，甲醇时空收率分别为0.058 g/(g·h)和0.088 g/(g·h)。

Abstract

hydrogenation to methanol is one of promising route for CO

utilization. Cu/ZnO catalysts have garnered considerable attention due to their unique catalytic properties. A series of Pd doping Cu/ZnO catalysts were prepared by co-precipitation

impregnation

and mechanical mixing methods. The catalysts were characterized by ICP-OES

physical adsorption/desorption

XRD and so on. The catalytic performances of each catalyst were tested under the conditions of temperature from 170 ℃ to 250 ℃

pressure of 3.0 MPa and gas space velocity of 4000 mL/(g·h)

and the effects of different Pd doping methods on the structures

morphologies and performances of Cu/ZnO catalysts were studied. The results show that Pd-Cu/ZnO-C catalyst prepared by co-precipitation method exhibits hig

her CO

conversion rate

methanol selectivity and methanol space-time yield compared to the undoped Cu/ZnO catalyst. The co-precipitation method facilitates the uniform distribution and high dispersion of Pd in the catalyst. The synergistic catalysis between noble metal Pd and Cu effectively enhances hydrogen dissociation and spillover capabilities. Furthermore

the Pd-Cu/ZnO-C catalyst has small particle sizes

large specific surface areas and excellent reduction abilities

leading to a reduction of apparent activation energy. At low reaction temperatures of 170 ℃ and 190 ℃

conversion rates of Pd-Cu/ZnO-C catalysts are 5.5% and 8.9%

respectively

with methanol selectivities of 82.2% and 74.9% and methanol space-time yields of 0.058 g/(g·h) and 0.088 g/(g·h)

respectively.

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Pd掺杂方式对Cu/ZnO低温催化CO2加氢制甲醇性能的影响

Effect of Pd doping method on low temperature catalytic performance of Cu/ZnO for CO2 hydrogenation to methanol

DOI：10.12434/j.issn.2097-2547.20240469

摘要

Abstract

关键词

Keywords

references

Pd掺杂方式对Cu/ZnO低温催化CO₂加氢制甲醇性能的影响

Effect of Pd doping method on low temperature catalytic performance of Cu/ZnO for CO₂ hydrogenation to methanol