多孔球负载催化剂的甲醇水蒸气重整制氢性能与反应机理

Hydrogen Production Performance and Reaction Mechanism of Methanol Steam Reforming over Porous Sphere-supported Catalysts

摘要

采用“自上而下”的设计思路，利用湿法成型技术和竞争浸渍吸附法制备了一种多孔碳球负载催化剂(Cu-Zn/CS)，并用于甲醇水蒸气重整(MSR)制氢反应.以商业化的Al₂O₃为对比研究载体，通过多种表征测试手段对比分析了Cu-Zn/Al₂O₃和Cu-Zn/CS两种催化剂形貌特征、晶相结构、理化性质、催化性能以及反应机理的差异.表征测试结果表明，Cu-Zn/CS结构具有丰富的多形态多尺度指状孔和龟裂纹结构，不仅为活性物质的多尺度均匀锚定提供了必要的空间基础，而且增加了催化反应中活性位点和反应物的接触几率.催化性能测试表明，在甲醇完全转化的前提下，相较于Cu-Zn/Al₂O₃，Cu-Zn/CS的CO选择性降低一个数量级，H₂选择性增加近一倍，高温催化活性更佳.原位实验表明，在高反应温度下，气态反应物质在Cu-Zn/Al₂O₃表面不仅存在甲醇催化转化为CO₂和H₂的主反应，还存在产生CO的副反应.而在Cu-Zn/CS表面则主要发生主反应，即CH₃OH+H₂O→^*OCH₃+^*OH→^*HCHO→^*CHOO→^*CO₂+^*H₂.

Abstract

A "top-down" design concept was adopted in this paper. herein, a porous carbon sphere-supported catalyst (Cu-Zn/CS) was fabricated by means of a wet spinning technique and a competitive impregnation adsorption method and applied for the hydrogen (H₂) production via methanol steam reforming (MSR) reaction. Taking commercial Al₂O₃ as the comparative support, the morphological characteristics, crystal phase structure, physicochemical properties, catalytic performance, and reaction mechanism of Cu-Zn/Al₂O₃ and Cu-Zn/CS were compared and analyzed through a series of complementary characterizations and tests. The characterization results showed that the constructed Cu-Zn/CS had abundant multi-morphological and multi-scale pores and craquelure structures, which not only provided the necessary spatial foundation for the multiscale anchoring of active substances but also increased the contact probability between active sites and reactants during the reactions. Catalytic performance showed that, compared with Cu-Zn/Al₂O₃, the CO selectivity of Cu-Zn/CS was reduced by one order of magnitude, the H₂ selectivity was nearly doubled, and the high-temperature catalytic activity was improved under the condition of complete methanol conversion. In addition, in-situ DRIFTS experiments indicated that at high reaction temperatures, gaseous reactants on the surface of Cu-Zn/Al₂O₃ not only involved the main reaction of methanol catalytic conversion to CO₂ and H₂ but also concerned the side reaction of generating CO. On the surface of Cu-Zn/CS, the main reaction occurs, that is, the reaction path can be described as CH₃OH+H₂O→^*OCH₃+^*OH→*HCHO→*CHOO→*CO2+*H2.

关键词

指状孔 / 龟裂纹 / 竞争吸附 / 甲醇水蒸气重整 / 反应机理

Key words

Finger-shaped pore / Craquelure / Competitive adsorption / Methanol steam reforming / Reaction mechanism

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基金资助

贵州省基础研究计划(自然科学)项目(黔科合基础QN[2025]270)

毕节市科学技术局-贵州工程应用技术学院科学技术联合基金项目(毕科联合[2025]128)

毕节市科学技术局-贵州工程应用技术学院科学技术联合基金项目(毕科联合[2025]127)

毕节市科学技术项目(毕科联合[2023]9)

毕节市科学技术项目(毕科联合[2023]43)

贵州省高等学校自然科学研究项目(黔教技[2023]047)