高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

甲醇氧化羰基化反应中水对Cu/C催化剂结构与性能的影响

张文胜,孟凡会,李浩杰,李忠   

  1. 太原理工大学，化学与化工学院，省部共建煤基能源清洁高效利用国家重点实验室
  • 收稿日期:2026-01-24 修回日期:2026-03-02 网络首发:2026-04-29 发布日期:2026-04-29
  • 通讯作者: 李忠 E-mail:lizhong@tyut.edu.cn
  • 基金资助:
    国家自然科学基金面上项目（批准号: 22278293）和国家重点研发计划项目（批准号: 2023YFB4103302）资助

Effect of water on structure and performance of Cu/C catalyst in methanol oxidative carbonylation reaction

Zhang Wensheng，Meng Fanhui，Li Haojie，Li Zhong   

  1. State Key Laboratory of Clean and Efficient Coal Utilization, College of Chemical Engineering and Technology, Taiyuan University of Technology
  • Received:2026-01-24 Revised:2026-03-02 Online First:2026-04-29 Published:2026-04-29
  • Contact: Zhong Li E-mail:lizhong@tyut.edu.cn
  • Supported by:
    Supported by the National Natural Science Foundation of China (No. 22278293) and National Key Research and Development Program of China (No. 2023YFB4103302)

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摘要： 在甲醇氧化羰基化合成碳酸二甲酯（DMC）反应中，炭材料负载铜Cu/C催化剂展现出良好的催化活性与选择性，但副产物水对其催化剂性能具有显著的影响. 本文考察了原料甲醇中的水含量对Cu/C催化剂性能的影响规律. 研究结果表明，随水含量的增加，催化剂的反应活性显著下降，但水含量对反应产物DMC选择性无明显影响. 气相副产物中CO2含量随水含量的增加而显著上升；在不同水含量条件下，催化剂的反应活性呈相同的变化规律，且甲醇转化率均在反应15 h时达到最大值，随着反应时间的进行，活性逐渐下降并在150~250 h时达到相对稳定. 在相同反应时间条件下，水含量增加导致催化剂活性显著下降的主要原因是水分子在Cu/C催化剂上与反应物甲醇发生竞争吸附，水分子优先占据活性物种导致反应物甲醇分子与活性Cu物种的接触减少，直接且快速地抑制了催化剂活性. 随着反应持续进行，活性Cu物种与反应物O2和副产物水以及CO2的共同作用下转化无催化活性的Cu2(OH)2CO3. 同时，CO2溶于水形成酸性环境促使Cu2(OH)2CO3溶解流失，造成活性Cu物种的不可逆的流失. 此外，水的存在加剧了Cu物种的氧化与团聚，加速了催化剂失活. 该工作可指导氧化羰基化反应中铜基催化剂的设计并为副产物水对Cu/C催化剂的影响提供了理论依据.

关键词: Cu基催化剂, 水, 活性, 稳定性, 甲醇氧化羰基化, 碳酸二甲酯

Abstract: Copper-based catalysts exhibit high activity and selectivity in the oxidation and carbonylation of methanol to dimethyl carbonate (DMC), however, the presence of water as a byproduct can significantly affect the catalytic performance. This study investigated the effect of water in the methanol feedstock on the conversion of methanol to DMC using a copper-based catalyst supported on carbon material (Cu/C) catalyst. The results indicate that, as the water content in the methanol feedstock increases, the initial catalytic activity decreases significantly, the water content has no apparent effect on the selectivity of DMC; however, the CO2 content in the gas-phase products increases remarkably as the water content increases. Under different water content conditions, the catalyst exhibits identical patterns of reactivity variation. Methanol conversion reaches its maximum value at 15 hours into the reaction. As reaction time progresses, activity gradually declines and stabilizes between 150 and 250 hours. Increasing water content significantly reduces the initial catalytic activity. This is mainly due to that the competitive adsorption of water molecules on the Cu/C catalyst with reactant methanol molecules, which reduces contact between active Cu species and reactant methanol. Under the reaction conditions with a constant water content, the active Cu reacts with the reactant O2 and the by-products water and CO2, and thus converted into Cu2(OH)2CO3. Moreover, the acidic environment created by CO2 dissolving in water promotes the dissolution and loss of Cu2(OH)2CO3, which reduces the content of active Cu species in the catalyst and leads to the decrease in catalytic activity and stability. Furthermore, the oxidation and agglomeration of Cu species, induced by water, exacerbate the catalyst deactivation. This work may inform the design of Cu-based catalysts for oxidative carbonylation reactions and provide a theoretical basis for understanding the impact of by-product water on Cu/C catalysts.

Key words: Cu-based catalyst, water, activity, stability, methanol oxidative carbonylation; dimethyl carbonate

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