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

Effect of Water on the Structure and Performance of Cu/C Catalyst in Methanol Oxidative Carbonylation Reaction

摘要

在甲醇氧化羰基化合成碳酸二甲酯（DMC）的反应中，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，但副产物水对催化剂性能有显著影响.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，随着水含量的增加，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；当水含量不同时，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.当反应时间不同时，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的共同作用下转化为无催化活性的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.

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). 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 h into the reaction. As reaction time progresses, activity gradually declines and stabilizes between 150 and 250 h. Increasing water content significantly reduces the initial catalytic activity. This is mainly due to 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 converts 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 a 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.

关键词

Cu基催化剂 / 水 / 稳定性 / 甲醇氧化羰基化 / 碳酸二甲酯

Key words

Cu-based catalyst / Water / Stability / Methanol oxidative carbonylation / Dimethyl carbonate (DMC)

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基金资助

国家重点研发计划项目(2023YFB4103302)

国家自然科学基金(22278293)