Classification treatment of Cu-Al spinel for hydrogen production by methanol steam reforming: Effects of Cu species modulation on slow-release catalytic behaviors

ZHAO Zufeng; YANG Ming; WU Kunyun; HAN Jiao; LIU Daosheng; ZHANG Caishun; ZHANG Lei; GAO Zhixian

doi:10.12434/j.issn.2097-2547.20260084

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Classification treatment of Cu-Al spinel for hydrogen production by methanol steam reforming: Effects of Cu species modulation on slow-release catalytic behaviors

更新时间：2026-06-08

- Classification treatment of Cu-Al spinel for hydrogen production by methanol steam reforming: Effects of Cu species modulation on slow-release catalytic behaviors
- Pages: 1-10(2026)
- 作者机构：
  
  1.辽宁石油化工大学石油化工学院，辽宁抚顺 113001
  2.中石油昆仑燃气有限公司安徽分公司，安徽合肥 230041
  3.中石化（河南）炼化有限公司，河南洛阳 471012
  4.辽宁石油化工大学理学院，辽宁抚顺 113001
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20260084
  CLC： TQ426.8
- Received：24 February 2026，
  
  Revised：2026-03-20，
  
  Online First：05 June 2026，
- 稿件说明：
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赵祖锋,杨明,吴坤云等.甲醇水蒸气重整制氢中Cu-Al尖晶石分级处理：Cu物种调变对缓释催化行为的影响[J].低碳化学与化工,

ZHAO Zufeng,YANG Ming,WU Kunyun,et al.Classification treatment of Cu-Al spinel for hydrogen production by methanol steam reforming: Effects of Cu species modulation on slow-release catalytic behaviors[J].Low-Carbon Chemistry and Chemical Engineering,
赵祖锋,杨明,吴坤云等.甲醇水蒸气重整制氢中Cu-Al尖晶石分级处理：Cu物种调变对缓释催化行为的影响[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20260084.

ZHAO Zufeng,YANG Ming,WU Kunyun,et al.Classification treatment of Cu-Al spinel for hydrogen production by methanol steam reforming: Effects of Cu species modulation on slow-release catalytic behaviors[J].Low-Carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20260084.

摘要

为探究Cu-Al尖晶石催化剂在甲醇水蒸气重整制氢（MSR）反应中的缓释催化行为，以还原-氧化→酸洗→焙烧的方法对Cu-Al尖晶石催化剂进行了分级处理。通过XRD、H

-TPR和XPS等表征方法分析了催化剂物化性质，并评价了其MSR反应催化性能。结果表明，分级处理可实现催化剂中Cu物种（非尖晶石相、尖晶石相）的可控调变。还原-氧化使尖晶石相Cu含量降低，非尖晶石相CuO分散度提升；酸洗可高效脱除非尖晶石相CuO；焙烧则诱导部分尖晶石相Cu逆向转化为非尖晶石相CuO。同时，分级处理改变了催化剂织构性质，处

理后催化剂缓释特征显著增强。反应50 h后，未处理的CA作用下甲醇转化率升高了5.7%，反应68 h后，甲醇转化率稳定在90.5%。CA-300R-300O、CA-HNO

和CA-HNO

-500作用下初始甲醇转化率分别为57.3%、38.8%和42.8%，反应50 h后甲醇转化率分别升高了28.0%、39.2%和35.2%，并依次在90 h、55 h和60 h后稳定在87.5%、82.2%和83.6%左右。本研究可为高稳定性Cu-Al尖晶石缓释催化剂的结构设计与性能优化提供重要的实验数据与理论依据。

Abstract

To investigate the slow-release catalytic behaviors of Cu-Al spinel catalysts for hydrogen production by methanol steam reforming (MSR)

Cu-Al spinel catalysts were prepared via classification treatment including reduction-oxidation

acid washing and calcination. The physicochemical properties of the catalysts were characterized by XRD

-TPR and XPS

and their catalytic performances for MSR reaction were evaluated. The results demonstrate that classification treatment realizes the controllable modulation of Cu species (non-spinel phase and spinel phase). Reduction-oxidation reduces the content of spinel phase Cu and improves the dispersion of non-spinel phase CuO. Acid washing can efficiently remove non-spinel phase CuO

while calcination induces the reverse transformation of partial spinel phase Cu into non-spinel phase CuO. Meanwhile

classification treatment alters the textural properties of the catalysts

and the slow-release catalytic behaviors of modified catalysts are remarkably strengthened. After 50 hours of reaction

the methanol conversion of the untreated CA catalyst increases by 5.7% and stabilizes at 90.5% after 68 h. The initial methanol conversions of CA-300R-300O

CA-HNO

and CA-HNO

-500 are 57.3%

38.8% and 42.8%

respectively. After 50 hours of reaction

their methanol conversion rates increase by 28.0%

39.2% and 35.2%

and stabilize at about 87.5%

82.2% and 83.6% after 90 h

55 h and 60 h

respectively. This work will provide reliable experimental data and theoretical guidance for the structural design and performance optimization of high-stability Cu-Al spinel slow-release catalysts.

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