沉淀法对CuZnAl催化剂催化1， 4-丁二醇脱氢制<italic style="font-style: italic">γ</italic>-丁内酯性能的影响

张思琦; 孟令臣; 吴慧玲; 李浩东; 刘博帆; 王德辰; 袁胜华

doi:10.12434/j.issn.2097-2547.20260086

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沉淀法对CuZnAl催化剂催化1， 4-丁二醇脱氢制γ-丁内酯性能的影响

更新时间：2026-04-27

- 沉淀法对CuZnAl催化剂催化1， 4-丁二醇脱氢制γ-丁内酯性能的影响
- Effect of Precipitation Method on the Performance of CuZnAl Catalyst for Catalytic Dehydrogenation of 1, 4-Butanediol to γ-Butyrolactone
- 低碳化学与化工 2026: 1-11.
- 作者机构：
  
  中石化（大连）石油化工研究院有限公司，辽宁大连 116041
- 作者简介：
  
  张思琦（1993—），女，博士，助理研究员，研究方向为铜基脱氢催化剂，E-mail: zhangsiqi.fshy@sinopec.com
  袁胜华（1970—），男，博士，正高级工程师，研究方向为渣油加氢催化剂与低碳化工催化剂，E-mail: yuanshenghua.fshy@sinopec.com。
- 基金信息：
  
  中国石化青年博士支持计划课题(224084)
- DOI：10.12434/j.issn.2097-2547.20260086
  中图分类号： TQ42
- 收稿：2026-02-26，
  
  修回：2026-03-20，
  
  网络首发：2026-04-22，
- 稿件说明：
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张思琦,孟令臣,吴慧玲等.沉淀法对CuZnAl催化剂催化1， 4-丁二醇脱氢制γ-丁内酯性能的影响[J].低碳化学与化工,

ZHANG Siqi,MENG Lingchen,WU Huiling,et al.Effect of Precipitation Method on the Performance of CuZnAl Catalyst for Catalytic Dehydrogenation of 1, 4-Butanediol to γ-Butyrolactone[J].Low-Carbon Chemistry and Chemical Engineering,
张思琦,孟令臣,吴慧玲等.沉淀法对CuZnAl催化剂催化1， 4-丁二醇脱氢制γ-丁内酯性能的影响[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20260086.

ZHANG Siqi,MENG Lingchen,WU Huiling,et al.Effect of Precipitation Method on the Performance of CuZnAl Catalyst for Catalytic Dehydrogenation of 1, 4-Butanediol to γ-Butyrolactone[J].Low-Carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20260086.

摘要

针对铜基催化剂在1

4-丁二醇（BDO）脱氢制

-丁内酯（GBL）反应中，不同制备方法所得催化剂缺乏系统性对比、构效关系不明确及反应网络不完善等关键科学问题，本文采用分步沉淀法制备了一系列CuZnAl催化剂（记作CZ

-ZA），并与共沉淀法制备的CZA进行

对比。系统考察了工艺条件对BDO脱氢制备GBL催化性能的影响，筛选出最优催化剂CZ

-ZA及其最佳工艺条件：220 °C、空速1.0 h

-1

、气体/醇摩尔比5.0，N

氛围中BDO转化率达99.94%，GBL产率达99.00%，且240 h长周期测试中稳定性优异。通过XRD、TEM、N

物理吸附、N

O滴定、XPS、H

-TPR及NH

-TPD等多维度表征手段，系统研究了催化剂结构、织构性质、电子态、还原行为及表面酸性与催化性能之间的构效关系。实验结果表明，分步沉淀法有效优化了催化剂的织构性质与电子结构，使CZ

-ZA具有适中的比表面积、最小的孔径和最高的铜分散度，增强了Cu-ZnO相互作用与铜物种可还原性；分步沉淀法实现了对催化剂酸强度分布的精准调控，使酸中心集中于弱酸和中强酸区域，有效避免了强酸位点过多引发的脱水副反应。构建的BDO脱氢反应网络明确了主副反应之间的路径竞争机制。本研究为高性能BDO脱氢制GBL催化剂的设计开发提供了理论依据。

Abstract

Addressing the key scientific issues in the dehydrogenation of 1

4-butanediol (BDO) to

-butyrolactone (GBL) over copper-based catalysts

including the lack of systematic comparison among catalysts prepared by different methods

unclear structure-activity relationships

and the incomplete reaction network

this study employed a stepwise precipitation method to prepare a series of CuZnAl catalysts (denoted as CZ

-ZA). Their performance was compared with a CZA catalyst synthesized by the conventional coprecipitation method. The influence of reaction parameters on catalytic performance for BDO dehydrogenation to GBL was systematically investigated. The optimal CZ

-ZA catalyst exhibited excellent performance under the optimized conditions (220℃

space velocity of 1.0 h

-1

gas/alcohol molar ratio of 5.0

atmosphere)

achieving a BDO conversion of 99.94% and a GBL yield of 99.00%

along with outstanding stability during a 240 h long-term test. Multiple characterization techniques

including XRD

TEM

physisorption

O titration

XPS

-TPR

and NH

-TPD

were employed to systematically investigate the structure-activity relationship between the structure of catalysts

textural properties

electronic states

reducibility

surface acidity and its catalytic performance. The experimental results demonstrate that the stepwise precipit

ation method effectively optimizes the textural properties and electronic structure of the catalyst. The resulting CZ

-ZA catalyst possesses a moderate specific surface area

the smallest average pore diameter

and the highest copper dispersion

which enhances Cu-ZnO interaction and the reducibility of copper species. Furthermore

stepwise precipitation enables precise regulation of the acid strength distribution

concentrating acid sites in the weak and medium-strong acid regions

thereby effectively avoiding dehydration side reactions caused by excessive strong acid sites. A comprehensive reaction network for BDO dehydrogenation was constructed

elucidating the competitive pathways between the main reaction and side reactions. This study provides a theoretical basis for the rational design and development of high-performance catalysts for the dehydrogenation of BDO to GBL.

关键词

Keywords

references

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DOI：10.12434/j.issn.2097-2547.20260086

摘要

Abstract

关键词

Keywords

references