生物质油重整制氢的积炭机制及类水滑石型高效催化剂的研究

As a carbon-neutral solution for industrial scale of hydrogen production, steam reforming of bio-oil has been attracting much attention for decades. Among the concerns involving in the reforming process, the coke deposition is the main obstacle to the industrialization of bio-oil steam reforming. The present project focuses on the mechanism of coke formation, as well as the gasification of coke formed over hydrotalcite-like catalysts. The in-situ characterizations and dynamic methods are employed to find the activation of the typical components of bio-oil, for example, acetic acid, acetone, etc. To address the endothermicity of the reforming process, the autothermal reforming (ATR) process, in which oxygen is introduced, can balance the net heat need with a relatively high hydrogen yield by adjusting the ratio of oxygen in feed. The activation of bio-oil is supposed to be modified with oxygen as well. To obtain high resistance to coke deposition, sintering and oxidation in ATR, catalysts with hydrotalcie-like structure will be extensively studied the pilot research of bio-oil reforming for hydrogen production.

以廉价生物质油为原料催化转化制取氢气，是一个碳中性的规模化获取氢能源的解决方案。针对现有生物质油水蒸气催化重整制氢过程中的严重积炭失活问题，本项目以类水滑石型镍基催化剂为研究对象，采用原位和动态、瞬态表征技术，在分子水平上研究乙酸、丙酮等典型生物质油分子的活化和过渡态中间产物的控制转化，揭示该过程的积炭失活机制及消炭再生机制。针对水蒸气重整的吸热反应特点，引入自热重整过程，以氧分子强化对反应物分子的活化，并研究活性氧物种对反应中间产物生成及其控制转化的影响等关键科学问题，探索自热重整过程中的耐烧结、耐氧化的催化活性位结构，设计和可控制备高活性自热重整用类水滑石型催化剂，实现生物质油分子控制活化和选择转化并抑制积炭的目标，为生物质油催化转化制氢过程的工业应用提供实验依据。

依据项目书开展了生物质油催化转化过程的积炭失活机制和应用于该过程的类水滑石型高效催化剂的研究，探索了生物质油催化重整过程中的乙酸等典型组分活化及其控制转化反应机制和积炭形成机制，获得了Mg-Al系列、Zn-Al系列和Ca-Al系列类水滑石型结构衍生的高效镍基和钴基催化剂，以及具有层状结构钙钛矿型、橄榄石型等多型高效催化剂，并对所获得催化剂开展了生物质油转化制氢的活性研究，探讨了组分配比、温度、压力和空速等变量对催化制氢过程的影响，通过优化工艺条件，筛选出了具有活性高、氢气产率高、耐烧结和抗积炭性能好的高效镍基和钴基催化剂，为生物质油催化重整反应用催化剂的工业应用提供了实验依据。