Process performance study of ZnZrO<italic style="font-style: italic"><sub>x</sub></italic> solid solution catalysts in the hydrogenation of carbon dioxide to methanol

WANG Muhan; ZHOU Yu; SHEN Kai; ZHANG Yaping

doi:10.19944/j.eptep.1674-8069.2025.03.006

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Process performance study of ZnZrO_x solid solution catalysts in the hydrogenation of carbon dioxide to methanol

Green Catalytic Technologies for the Power Sector in a Dual Carbon | 更新时间：2026-10-14

- Process performance study of ZnZrO_x solid solution catalysts in the hydrogenation of carbon dioxide to methanol
- Electric Power Technology and Environmental Protection Vol. 41, Issue 3, Pages: 405-412(2025)
- 作者机构：
  
  1.龙源（北京）碳资产管理技术有限公司北京 100034
  2.能源热转换及其过程测控教育部重点实验室（东南大学），江苏南京 210096
- 作者简介：
- 基金信息：
- DOI：10.19944/j.eptep.1674-8069.2025.03.006
  CLC： TK437;TQ223.121
- Received：20 January 2025，
  
  Accepted：12 May 2025，
  
  Published：15 June 2025
- 稿件说明：
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王霂晗,周宇,沈凯，等.ZnZrO_x催化二氧化碳加氢制甲醇的工艺性能研究[J].电力科技与环保,2025,41(3):405-412. DOI: 10.19944/j.eptep.1674-8069.2025.03.006.

WANG Muhan, ZHOU Yu, SHEN Kai, et al. Process performance study of ZnZrO_x solid solution catalysts in the hydrogenation of carbon dioxide to methanol[J]. Electric Power Technology and Environmental Protection, 2025, 41(3):405-412. DOI: 10.19944/j.eptep.1674-8069.2025.03.006.
王霂晗,周宇,沈凯，等.ZnZrO_x催化二氧化碳加氢制甲醇的工艺性能研究[J].电力科技与环保,2025,41(3):405-412. DOI: 10.19944/j.eptep.1674-8069.2025.03.006. DOI：

WANG Muhan, ZHOU Yu, SHEN Kai, et al. Process performance study of ZnZrO_x solid solution catalysts in the hydrogenation of carbon dioxide to methanol[J]. Electric Power Technology and Environmental Protection, 2025, 41(3):405-412. DOI: 10.19944/j.eptep.1674-8069.2025.03.006. DOI：

摘要

目的

甲醇作为工业化学品的关键原料，通过可再生氢能将温室气体CO₂转化为高附加值甲醇是实现“碳中和”的重要途径。为了给工业应用提供理论指导，开展ZnZrO

ₓ

固溶体催化剂在CO₂加氢制甲醇中的工艺条件优化研究，

方法

本文采用球磨法制备ZnZrO

ₓ

催化剂，通过固定床反应器系统考察不同反应温度、压力及空速对催化剂加氢性能的影响。结合原位红外光谱分析反应路径，分析最佳工况下不同H₂/CO₂摩尔比对催化剂加氢性能的影响，并引入疏水剂聚二乙烯基苯与催化剂物理混合，研究其对催化剂加氢性能的优化作用。

结果

结果表明，优化后的最佳工艺条件为：温度320 ℃、压力5 MPa、空速24 000 mL/（g

cat

·h），此时CO₂转化率为5.1%，CH

OH选择性72.2%，CH

OH产率约为80.0 mg/（g

cat

·h）。在最佳工艺条件下，H₂/CO₂摩尔比从3增至9时，CO₂转化率提高至12.9%，CH

OH产率提升145.8%；原位红外表明高氢碳比加速甲酸盐中间体形成，促进CH

OH生成。引入疏水剂聚二乙烯基苯（质量比1：1）后，催化剂疏水性增强，水产物快速排出，CH

OH产率在320 ℃下达到414.0 mg/（g

cat

·h），较未添加时提升显著。ZnZrO

ₓ

催化剂在优化工艺条件下表现出高效CO₂加氢性能，疏水剂聚二乙烯基苯的引入进一步提升了CH

OH产率。

结论

研究结果为工业中CO₂资源化利用及催化剂设计提供了重要参考。

Abstract

Objective

Methanol

a key industrial chemical

can be synthesized via CO

hydrogenation using renewable hydrogen

serving as an effective pathway toward carbon neutrality. This study aims to optimize the process conditions of ZnZrO

ₓ

solid solution catalysts for CO

hydrogenation to methanol

focusing on temperature

pressure

space velocity

/CO

ratio

and the role of a hydrophobic agent

providing guidance for industrial applications.

Methods

ZnZrO

ₓ

catalysts were prepared via ball milling. Catalytic performance was evaluated in a fixed-bed reactor under varied conditions (temperature

pressure

space velocity

/CO

molar ratio). In situ diffuse reflectance infrared Fourier transform spectroscopy was employed to analyze reaction intermediates. Additionally

hydrophobic polydivinylbenzene was physically mixed with the catalyst to enhance water removal and methanol synthesis.

Results

Optimal conditions were determined as 320 °C

5 MPa

and 24 000 mL/(g

cat

·h)

achieving a CO

conversion of 5.1%

methanol selectivity of 72.2%

and maximum methanol yield. Increasing the H

/CO

ratio from 3 to 9 improved CO

conversion to 12.9% and methanol yield by 145.8%

with DRIFTS revealing accelerated formate intermediate formation. Introducing PDVB (mass ratio 1:1) facilitated water removal

boosting methanol yield to 414.0 mg/(g

cat

·h) at 320 °C.

Conclusions

The ZnZrOₓ catalyst exhibited high efficiency under optimized conditions

while PDVB integration further enhanced methanol productivity. This study offers valuable insights for industrial CO

utilization and catalyst design in sustainable chemical synthesis.

关键词

Keywords

references

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Process performance study of ZnZrOx solid solution catalysts in the hydrogenation of carbon dioxide to methanol

DOI：10.19944/j.eptep.1674-8069.2025.03.006

摘要

Abstract

关键词

Keywords

references

Process performance study of ZnZrO_x solid solution catalysts in the hydrogenation of carbon dioxide to methanol