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Ni/CeO2催化剂上CO2甲烷化反应本征动力学研究
Study on intrinsic kinetics of CO2 methanation on Ni/CeO2 catalyst
- 低碳化学与化工 2024, 49(8): 123-130.
- 作者机构：
郑州大学 化工学院，河南 郑州 450001
- 作者简介：
范志辉（1998—），硕士研究生，研究方向为催化反应动力学，E-mail：17856509754@163.com。
涂维峰（1986—），博士，教授，研究方向为CO2资源化高值利用，E-mail：weifengtu@zzu.edu.cn；
韩一帆（1968—），博士，教授，研究方向为工业催化剂动态构-效关系，E-mail：yifanhan@e.edu.cn。
- 基金信息：国家自然科学基金面上项目(22278379);河南省科技研发计划联合基金(222301420010)
DOI：10.12434/j.issn.2097-2547.20240104
中图分类号： TQ211;TQ426纸质出版日期：2024-08-25，
收稿日期：2024-03-15，
修回日期：2024-04-21，
- 稿件说明：
移动端阅览
范志辉,岳燕燕,张笑楠等.Ni/CeO2催化剂上CO2甲烷化反应本征动力学研究[J].低碳化学与化工,2024,49(08):123-130.
FAN Zhihui,YUE Yanyan,ZHANG Xiaonan,et al.Study on intrinsic kinetics of CO2 methanation on Ni/CeO2 catalyst[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):123-130.
范志辉,岳燕燕,张笑楠等.Ni/CeO2催化剂上CO2甲烷化反应本征动力学研究[J].低碳化学与化工,2024,49(08):123-130. DOI： 10.12434/j.issn.2097-2547.20240104.
FAN Zhihui,YUE Yanyan,ZHANG Xiaonan,et al.Study on intrinsic kinetics of CO2 methanation on Ni/CeO2 catalyst[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):123-130. DOI： 10.12434/j.issn.2097-2547.20240104.
摘要
CO
2
加氢合成CH
4
（CO
2
甲烷化）是CO
2
高效、清洁转化的重要途径之一。尽管CO
2
甲烷化的催化体系研究已较深入，但特定条件下CO
2
甲烷化本征动力学的研究较少。采用燃烧法制备了Ni/CeO
2
催化剂（Ni质量分数为10%），并通过加入内稀释剂（
α
-Al
2
O
3
）制备了不同
m
(
α
-Al
2
O
3
):
m
(Ni/CeO
2
)的样品。考察了在温度为300 ℃、压力为1 MPa和空速为3 × 10
6
mL/(g·h)的条件下，
m
(
α
-Al
2
O
3
):
m
(Ni/CeO
2
) = 25:1样品（样品A）的CO
2
甲烷化本征动力学。结合本征动力学测试、漫反射红外光谱、H
2
-程序升温还原和H
2
-程序升温脱附等对CO
2
甲烷化本征反应动力学方程进行了深入分析。结果表明，样品A作用下的CH
4
生成速率最高可达41.4 mmol/(g·h)（H
2
分压为400 kPa，CO
2
分压为120 kPa）。当CO
2
分压为30~120 kPa时，CH
4
生成速率随H
2
分压的增大线性增长，并且不受CO
2
分压或CO分压变化的影响。在该CO
2
分压范围内，富氢环境可以显著提高催化剂的CO
2
甲烷化催化活性。
Abstract
Hydrogenation of CO
2
to synthesize CH
4
(CO
2
methanation) is one of the crucial pathways for the efficient and clean conversion of CO
2
. Despite extensive researches on the catalytic system for CO
2
methanation
the intrinsic kinetics of CO
2
methanation under specific conditions have not been thoroughly investigated. Ni/CeO
2
catalyst (Ni mass fraction of 10%) was prepared using the combustion method
and samples with varying
m
(
α
-Al
2
O
3
):
m
(Ni/CeO
2
) were produced by incorporating
α
-Al
2
O
3
as the internal diluent. The intrinsic kinetics of CO
2
methanation of sample A with
m
(
α
-Al
2
O
3
):
m
(Ni/CeO
2
) = 25:1 were examined
under the conditions of temperature of 300 ℃
pressure of 1 MPa and gas hourly space velocity of 3 × 10
6
mL/(g·h). An in-depth analysis of the kinetic equations for the intrinsic CO
2
methanation reaction was conducted through a combination of intrinsic kinetic tests
diffuse reflection infrared spectrum
H
2
-temperature programmed reaction and H
2
-temperature programmed desorption
etc. The results show that the CH
4
generation rate under action of sample A can reach up to 41.4 mmol/(g·h)(H
2
partial pressure is 400 kPa
and CO
2
partial pressure is 120 kPa). When CO
2
partial pressure is 30 kPa to 120 kPa
the CH
4
generation rate exhibits linear increases with the rises of the H
2
partial pressure
and is not affected by variation of the CO
2
or CO partial pressure. Within this CO
2
partial pressure range
the hydrogen-rich environment significantly enhances the catalytic activity of the catalyst for CO
2
methanation.
关键词
CO2甲烷化Ni/CeO2催化剂本征动力学
Keywords
CO2 methanationNi/CeO2 catalystintrinsic dynamics
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