• 论文
主办单位:煤炭科学研究总院有限公司、中国煤炭学会学术期刊工作委员会
蒸气重整轻质生物油催化制氢研究进展
  • Title

    Research progress on catalytic hydrogen production based on steam reforming of light bio-oil

  • 作者

    单明玄王坤杨美玲赵荣洋梁文政王凤印王翠苹

  • Author

    SHAN Mingxuan,WANG Kun,YANG Meiling,ZHAO Rongyang,LIANG Wenzheng,WANG Fengyin,WANG Cuiping

  • 单位

    山东科技大学土木工程与建筑学院清洁能源实验室青岛大学机电工程学院

  • Organization
    Clean Energy Laboratory,College of Civil Engineering and Architecture,Shandong University of Science and Technology;School of Mechanical and Electrical Engineering,Qingdao University
  • 摘要

    H2作为一种高能量密度且环境友好型能源而备受关注,目前主要的制氢方法有化石燃料制氢、电解水制氢、生物质制氢等。生物质为碳中性资源,对实现我国“双碳”目标具有推动作用。生物质通过中温热解或水热解制得的生物油具有热值低、酸性强、黏度大等缺点,生物油中轻重组分须分别重整以生产高附加值的产品。生物油的轻质组分相对简单且成本低廉、转化途径经济可行,因此蒸气重整并催化制氢是很有前景的制氢方法。其中,催化剂的选择是影响轻质生物油制氢效率和稳定性最关键因素。综述了近年来基于蒸气重整的轻质生物油催化制氢的研究进展,重点介绍了传统蒸气重整、吸附增强的蒸气重整、自热蒸气重整、化学链蒸气重整和吸附增强的化学链蒸气重整等技术原理,归纳比较了催化剂、CO2吸附剂对制氢性能的影响。传统蒸气重整技术中,相比贵金属催化剂高昂的制氢成本,Ni基催化剂因其低成本和较高制氢性能一直受到青睐,但仍需通过复合活性金属改性等方式改善其易烧结和积碳的缺陷。而吸附增强蒸气重整技术可通过CO2原位吸附一定程度上提高制氢的产率和纯度。类水滑石化合物CO2吸附剂碱性强、比表面积大,但需改性提高CO2吸附温度以适应轻质生物油蒸气重整的温度。碱金属CO2吸附剂稳定性强但成本较高。而CaO吸附剂成本低并在中高温下具有优良的CO2吸附特性,成为最有应用前景的吸附剂之一。自热重整过程结合了蒸气重整与部分氧化制氢的优势,但需消耗O2且易导致催化剂失活。吸附增强的化学链蒸气重整技术是载氧、载热和催化多功能颗粒的化学链路线耦合CO2吸附,将化学链的自热优势以及吸附CO2增强H2产率的优点相结合,具有广泛的应用潜力。但其催化、吸附过程热质流率不匹配、吸附剂碳酸化速率影响催化作用规律等问题需进一步研究解决。

  • Abstract

    Hydrogen, as a high energy density and environment-friendly energy, has attracted much attention. At present, the main sources of hydrogen production include fossil fuels, water, biomass, etc. Biomass is a carbon neutral resource, which can promote the realization of China′s "Dual Carbon"goal. The bio-oil produced by biomass pyrolysis or hydrolysis has the disadvantages of low calorific value, strong acidity and high viscosity. The light and heavy components in bio-oil should be reformed separately to produce high value-added products. The components in light bio-oil are relatively simple, cheap and the conversion route is economical and feasible, the catalytical steam reforming of bio-oil is generally considered to be a promising hydrogen production way and the selection of catalyst is the most key factor affecting the efficiency and stability of hydrogen production. In this paper, the recent researches on hydrogen production from catalytic with steam reforming of light bio-oil were reviewed. The process principles of traditional steam reforming, adsorption enhanced steam reforming, autothermal steam reforming, chemical looping steam reforming and sorption-enhanced chemical looping steam reforming were emphatically introduced, and the effects of catalysts and CO2 adsorbents on hydrogen production performance were summarized and compared. Compared with expensive noble metal catalysts in the traditional steam reforming technology, the Ni-based catalyst has been widely recognized because of its low cost and high hydrogen production performance. However, the defects of easy sintering and carbon deposition still need to be improved by composite active metal modification. The adsorption-enhanced steam reforming technology can improve the yield and purity of hydrogen production through CO2 in-situ adsorption to a certain extent. The hydrotalcite like compound CO2 adsorbent has strong alkalinity and large specific surface area, but it needs to be modified to increase the CO2 adsorption temperature to meet the temperature needs of light bio oil steam reforming. Alkali metal CO2 adsorbent has strong stability but high cost. And CaO has become one of the most promising adsorbent due to its low cost and excellent CO2 adsorption characteristics at medium and high temperature. The autothermal reforming process combines the advantages of traditional and partial oxidation steam reforming to produce hydrogen, but it consumes O2 and easily leads to catalyst deactivation. The sorption-enhanced chemical looping steam reforming technology is the route of applying the oxygen carrying, heat carrying and catalytic multifunctional particles coupling CO2 adsorption, which combines the self-thermal advantages of chemical looping and enhanced adsorption advantages for high H2 purity, and has the potential of wide application. However, the mismatch of heat and mass flow rate in the catalytic and adsorption process, and the influence of carbonation process on catalysis need to be further studied. 

  • 关键词

    轻质生物油催化制氢蒸气重整CO2吸附化学链

  • KeyWords

    light bio-oil;catalytic hydrogen production;steam reforming;CO2 adsorption;chemical looping

  • 基金项目(Foundation)
    国家自然科学基金资助项目(52076125)
  • 文章目录

    0 引言

    1 传统蒸气重整轻质生物油

       1.1 贵金属催化剂

       1.2 过渡金属催化剂

    2 CO2吸附增强的生物油水蒸气重整

       2.1 CaO吸附剂

       2.2 类水滑石化合物吸附剂

       2.3 碱金属吸附剂

    3 自热型生物油重整制氢

    4 生物油化学链重整制氢

    5 吸附增强的化学链重整

       5.1 热力学分析

       5.2 载氧体与吸附剂物理混合物性能

       5.3 多功能载氧/吸附/催化材料

    6 结语与展望

  • 引用格式
    单明玄,王坤,杨美玲,等.蒸气重整轻质生物油催化制氢研究进展[J].洁净煤技术,2022,28(7):120-133.
    SHAN Mingxuan,WANG Kun,YANG Meiling,et al.Research progress on catalytic hydrogen production based on steam reforming of light bio-oil[J].Clean Coal Technology,2022,28(7):120-133.
  • 相关文章
  • 图表
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    • 不同金属氧化物吸收CO2的热力学性质

    图(7) / 表(0)

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