制备方法对CuZnAl-ZrO<sub>2</sub>双功能催化剂合成气制C<sub>4</sub>烃类性能的影响

瞿凡; 殷富; 魏宇学; 孙松; 王飞; 常强; 张成华

doi:10.12434/j.issn.2097-2547.20240492

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制备方法对CuZnAl-ZrO₂双功能催化剂合成气制C₄烃类性能的影响

更新时间：2025-03-10

- 制备方法对CuZnAl-ZrO₂双功能催化剂合成气制C₄烃类性能的影响
- Influences of preparation methods on performances of CuZnAl-ZrO₂ bifunctional catalysts for production of C₄ hydrocarbons from syngas
- 低碳化学与化工 2025: 1-9.
- 作者机构：
  
  1.安徽大学化学化工学院，安徽合肥 230601
  2.中国科学院山西煤炭化学研究所，山西太原 030001
  3.中科合成油技术股份有限公司国家能源煤基液体燃料研发中心，北京 101407
- 作者简介：
  
  瞿凡（1999—），硕士研究生，研究方向为多相催化，E-mail：qf88882022@163.com。
  常强（1989—），博士，高级工程师，研究方向为多相催化，E-mail：changqiang12@mails.ucas.ac.cn；
  张成华（1975—），博士，教授级高级工程师，研究方向为多相催化，E-mail：zhangchh@sxicc.ac.cn。
- 基金信息：
  
  国家重点研发计划(2022YFB4101204);国家自然科学基金(22302219;22179001;22308001;21902001);安徽省高校杰出青年科研项目(2022AH020007);安徽省高校协同创新项目(GXXT-2023-009);安徽省高等学校自然科学基金(2023AH050114)
- DOI：10.12434/j.issn.2097-2547.20240492
  中图分类号： TQ426;O643.36
- 收稿日期：2024-12-13，
  
  修回日期：2025-01-12，
  
  网络出版日期：2025-03-07，
- 稿件说明：
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瞿凡,殷富,魏宇学等.制备方法对CuZnAl-ZrO₂双功能催化剂合成气制C₄烃类性能的影响[J].低碳化学与化工,

QU Fan,YIN Fu,WEI Yuxue,et al.Influences of preparation methods on performances of CuZnAl-ZrO₂ bifunctional catalysts for production of C₄ hydrocarbons from syngas[J].Low-carbon Chemistry and Chemical Engineering,
瞿凡,殷富,魏宇学等.制备方法对CuZnAl-ZrO₂双功能催化剂合成气制C₄烃类性能的影响[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20240492.

QU Fan,YIN Fu,WEI Yuxue,et al.Influences of preparation methods on performances of CuZnAl-ZrO₂ bifunctional catalysts for production of C₄ hydrocarbons from syngas[J].Low-carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20240492.

摘要

异构合成是由合成气（CO + H

）直接合成异丁烯和异丁烷的反应，目前该反应主要使用ZrO

基催化剂，但反应条件普遍较为苛刻，并且催化剂的CO转化率和C

烃类选择性均较低。为了解决单一ZrO

活化CO生成C1物种性能较弱的问题，对CuZnAl催化剂与ZrO

耦合形成的双功能催化剂进行了研究。分别以共沉淀法、浸渍法和物理混合法制备了双功能催化剂，并对其织构性质、氧化物质量分数和晶相结构等进行了表征。在合成气组成为

(CO):

) = 1:1、温度为260 °C、压力为2 MPa和空速为6000 mL/(g·h)的条件下反应72 h评价了催化剂生成C

烃类的性能。结果表明，浸渍法所得CZA-ZrO

(im)的表面ZrO

与CuZnAl产生了强相互作用且表面酸碱性适宜，有利于在CuZnAl上生成CH

O*等物种，并在ZrO

作用下生成C

烃类异构体。CZA-ZrO

(im)的CO转化率、C

烃类选择性和C

烃类异构体在C

烃类中的占比分别为5.9%、15.1%和79.7%。

Abstract

Heterogeneous synthesis is the reaction for direct synthesis of isobutene and isobutane from syngas (CO + H

). Currently

the reaction is performed using ZrO

-based catalysts

but the reaction conditions are generally harsh and the catalysts have low CO conversion rate and C

hydrocarbon selectivity. In order to solve the problem of weak performance of CO

activation to generate C1 species of single ZrO

the bifunctional catalysts formed by coupling CuZnAl catalyst with ZrO

was investigated. The bifunctional catalysts were prepared by co-precipitation

impregnation and physical mixing methods

respectively

and their texture properties

oxide mass fractions and crystalline phase structures were characterized. The performances of catalysts for production of C

hydrocarbons were evaluated under syngas composition of

(CO):

) = 1:1

temperature of 260 °C

pressure of 2 MPa and air velocity of 6000 mL/(g·h) for 72 h. The results show that the surface ZrO

of CZA-ZrO

(im) obtained by impregnation method produced strong interaction with CuZnAl

and the surface of CZA-ZrO

(im) has suitable acidity and alkalinity

which were favorable for generation of CH

O* species on CuZnAl

and generation C

hydrocarbon isomers under the action of ZrO

. The CO conversion rate

hydrocarbon selectivity and the proportion of C

hydrocarbon isomers in C

hydrocarbons are 5.9%

15.1% and 79.7%

respectively.

关键词

Keywords

references

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DOI：10.12434/j.issn.2097-2547.20240492

摘要

Abstract

关键词

Keywords

references

制备方法对CuZnAl-ZrO₂双功能催化剂合成气制C₄烃类性能的影响

Influences of preparation methods on performances of CuZnAl-ZrO₂ bifunctional catalysts for production of C₄ hydrocarbons from syngas