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n (Cu)/n (Zn)对Cu/ZnO/Al2O3催化剂CO2加氢制甲醇催化性能的影响Effect of
n (Cu)/n (Zn) on performance of Cu/ZnO/Al2O3 catalyst for CO2 hydrogenation to methanol- 低碳化学与化工 2025, 50(5): 132-141.
- 作者机构：
1.天津大学分子+研究院，天津 300110
2.中国天辰工程有限公司，天津 300400
- 作者简介：
刘大李（1991—），博士，高级工程师，研究方向为工业催化及碳资源高效转化， E-mail：liudali@cntcc.cn。
于一夫（1986—），博士，教授，研究方向为环境及能源催化，E-mail：yyu@tju.edu.cn。
- 基金信息：
DOI：10.12434/j.issn.2097-2547.20240361
中图分类号： TQ072;X701;O643.3收稿日期：2024-08-29，
修回日期：2024-10-22，
纸质出版日期：2025-05-25
- 稿件说明：
移动端阅览
刘大李,王聪,刘新伟等.n(Cu)/n(Zn)对Cu/ZnO/Al2O3催化剂CO2加氢制甲醇催化性能的影响[J].低碳化学与化工,2025,50(05):132-141.
LIU Dali,WANG Cong,LIU Xinwei,et al.Effect of n(Cu)/n(Zn) on performance of Cu/ZnO/Al2O3 catalyst for CO2 hydrogenation to methanol[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(05):132-141.
刘大李,王聪,刘新伟等.n(Cu)/n(Zn)对Cu/ZnO/Al2O3催化剂CO2加氢制甲醇催化性能的影响[J].低碳化学与化工,2025,50(05):132-141. DOI： 10.12434/j.issn.2097-2547.20240361.
LIU Dali,WANG Cong,LIU Xinwei,et al.Effect of n(Cu)/n(Zn) on performance of Cu/ZnO/Al2O3 catalyst for CO2 hydrogenation to methanol[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(05):132-141. DOI： 10.12434/j.issn.2097-2547.20240361.
摘要
CO
2
加氢制甲醇（CH
3
OH）不仅减少了CO
2
排放，而且缓解了能源短缺，是实现“碳中和”的有效手段之一。Cu/ZnO/Al
2
O
3
（CZA）催化剂因其成本低、催化活性高而广泛应用于CH
3
OH合成，其组分结构和表面特性对催化性能具有重要影响。为了探究
n
(Cu)/
n
(Zn)对CZA催化剂物化特性和催化性能的影响，采用共沉淀-焙烧法制备了一系列不同
n
(Cu)/
n
(Zn)的CZA催化剂，采用XRD、SEM、HRTEM、XPS、ICP-MS、H
2
-TPR和CO
2
-TPD等多种表征手段对催化剂进行了表征，并将其用
于催化CO
2
加氢制CH
3
OH反应。结果表明，
n
(Cu)/
n
(Zn)会影响催化剂的Cu颗粒粒径、比表面积、表面Cu
+
与Cu
0
数量之比（
N
(Cu
+
)/
N
(Cu
0
)）、还原性能和表面碱度等理化性质。CZA-R-2（
n
(Cu)/
n
(Zn)为2）的Cu颗粒粒径为5.32 nm，比表面积达到53.5 m
2
/g，表面
N
(Cu
+
)/
N
(Cu
0
)为0.900。在220 ℃、2 MPa和气体空速为7500 mL/(h·g)条件下，CZA-R-2具有最佳的CO
2
转化率（15.5%）和CH
3
OH选择性（67.0%），且此时CH
3
OH产率达到10.4%。此外
CZA-R-2在此条件下平稳运行超200 h，具有良好的稳定性。
Abstract
CO
2
hydrogenation to methanol (CH
3
OH) not only reduces CO
2
emissions but also relieves energy shortage
which is considered one of the effective means to achieve “carbon neutrality”. Cu/ZnO/Al
2
O
3
(CZA) catalysts are widely used in CH
3
OH synthesis due to their low cost and high catalytic activity and their component structure and surface characteristics have a significant impact on catalytic performance. In order to investigate the effect of
n
(Cu)/
n
(Zn) on the physicochemical properties and catalytic performance of CZA catalysts
a series of CZA catalysts with different
n
(Cu)/
n
(Zn) were prepared by coprecipitation-calcination method and characterized by XRD
SEM
HRTEM
XPS
ICP-MS
H
2
-TPR
CO
2
-TPD and other characterization methods
and they were used for catalytic CO
2
hydrogenation to CH
3
OH reaction. The results indicate that the
n
(Cu)/
n
(Zn) affects the physicochemical properties of catalysts
such as Cu particle size
specific surface area
ratio of numbers of Cu
0
and Cu
+
(
N
(Cu
0
)/
N
(Cu
+
)) on the surface
reducibility and surface alkalinity. The Cu particle size of CZA-R-2 (
n
(Cu
)/
n
(Zn) is 2) is 5.32 nm
and the specific surface area is 53.5 m
2
/g
and the surface
N
(Cu
+
)/
N
(Cu
0
) is 0.9. At 220 ℃
2 MPa and volume space velocit
y
of 7500 mL/(h·g)
CZA-R-2 exhibits the best CO
2
conversion rate (15.5%) and CH
3
OH selectivity (67.0%). At the same time
the CH
3
OH yield reaches 10.4%. In addition
CZA-R-2 runs smoothly for over 200 h under the same conditions and shows good stability.
关键词
Keywords
references
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