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废弃生物质催化热解制富氢燃气:催化剂性能的影响

李学琴 刘鹏 卢岩 王志伟 吴幼青 雷廷宙

李学琴, 刘鹏, 卢岩, 王志伟, 吴幼青, 雷廷宙. 废弃生物质催化热解制富氢燃气:催化剂性能的影响[J]. 燃料化学学报(中英文), 2024, 52(7): 976-987. doi: 10.19906/j.cnki.JFCT.2024011
引用本文: 李学琴, 刘鹏, 卢岩, 王志伟, 吴幼青, 雷廷宙. 废弃生物质催化热解制富氢燃气:催化剂性能的影响[J]. 燃料化学学报(中英文), 2024, 52(7): 976-987. doi: 10.19906/j.cnki.JFCT.2024011
LI Xueqin, LIU Peng, LU Yan, WANG Zhiwei, WU Youqing, LEI Tingzhou. Catalytic pyrolysis of waste biomass to produce hydrogen-rich gas:Influence of catalyst performance[J]. Journal of Fuel Chemistry and Technology, 2024, 52(7): 976-987. doi: 10.19906/j.cnki.JFCT.2024011
Citation: LI Xueqin, LIU Peng, LU Yan, WANG Zhiwei, WU Youqing, LEI Tingzhou. Catalytic pyrolysis of waste biomass to produce hydrogen-rich gas:Influence of catalyst performance[J]. Journal of Fuel Chemistry and Technology, 2024, 52(7): 976-987. doi: 10.19906/j.cnki.JFCT.2024011

废弃生物质催化热解制富氢燃气:催化剂性能的影响

doi: 10.19906/j.cnki.JFCT.2024011
基金项目: 国家重点研发计划(2022YFB4201901)和江苏省碳达峰碳中和科技创新专项资金项目(BE2022426)资助
详细信息
    通讯作者:

    E-mail: wyq@ecust.edu.cn

    China_newenergy@163.com

  • 中图分类号: TK6

Catalytic pyrolysis of waste biomass to produce hydrogen-rich gas:Influence of catalyst performance

Funds: The project was supported by the National Key Reasearch & Development Program of China (2022YFB4201901) and Carbon Reaches Peak and Carbon Neutrality Scientific and Technological Innovation of Jiangsu Province (BE2022426).
  • 摘要: 本研究通过超声波辅助过量浸渍法将活性组分镍、助剂铁与HZSM-5分子筛结合来提高富氢燃气的产率;进一步以废弃铝灰(ASA)与HZSM-5分子筛作为共载体制备铝灰与HZSM-5分子筛符合共载镍-铁催化剂,并将其用于强化生物质催化热解产富氢燃气的过程。结果表明,在热解温度700 ℃下,Ni-Fe/HZSM-5可使富氢燃气的产率提高到56.49%(约为230.59 mL/g),氢气产率提高到63.12%,产氢效率提高到0.71%,CO得率增加到65.77 mL/g;足够的Ni-Fe/HZSM-5催化剂量强化了生物质热解的产氢路径,促进了积炭气化反应,起到提高H2和CO产率的双重作用。不同种类生物质的组成差异导致催化热解的产物分布不同,Ni-Fe/HZSM-5催化生物质热解气体产率的顺序为PR(74.21%)>WSt(54.71%)>CR(53.5%)>MCh(52.47%)>WSh(52.10%)>CS(46.49%)。HZSM-5和ASA载体间的协同作用强化了CH4与CO2的重整过程,抑制了逆水气变换反应,获得了53.37%和41.56%的气体和焦油产率;并加速了积炭气化反应从而减少了积炭量(0.05 g/g),获得了5.07%的半焦产率;Ni-Fe/ASA@HZSM-5具有较好的热裂化能力和脱氧能力,有助于促进HZSM-5催化剂上富氢燃气的生成;为开发高温热解气深度净化与高效利用技术提供理论支撑,有效指导多级催化重整的新型双催化床层的开发。
  • 图  1  新鲜催化剂的SEM谱图

    Figure  1  SEM images of fresh catalyst

    图  2  生物质热解反应的装置

    Figure  2  Device for the pyrolysis reaction of biomass

    图  3  不同升温速率下玉米秸秆(a)、麻栗壳(b)、椿木屑(c)、核桃壳(d)、麦秸秆(e)、杨木屑(f)的TG/DTG曲线

    Figure  3  TG/DTG curves of CS (a), MCh (b), CR (c), WSh (d), WSt (e), PR (f) at different heating rates

    图  4  热解温度对产物分布规律的影响

    Figure  4  Effect of pyrolysis temperature on product distribution ((a) three-phase product distribution, (b) gas yield)

    图  5  催化剂量对玉米秸秆热解释放气体速率的影响

    Figure  5  Effect of catalytic dosage on the gas release from the pyrolysis of CS

    图  6  催化剂量对产物分布的影响

    Figure  6  Effect of catalytic dosage on products distribution ((a) Gas yield, (b) distribution of liquid products)

    图  7  催化剂类型对热解产物分布的影响

    Figure  7  Effect of catalyst types on the distribution of pyrolysis products

    图  8  HZSM-5分子筛的多孔道结构

    Figure  8  Porous structure of HZSM-5

    图  9  催化剂类型对玉米秸秆热解气体产物及氢碳转化率的影响

    Figure  9  Effects of catalyst types on gas products and conversion of H, C ((a) gas yield, (b) yield of H and C)

    图  10  不同催化剂催化玉米秸秆热解的液体产物分布

    Figure  10  Liquid product distribution of the pyrolysis of CS catalyzed by different catalysts

    图  11  不同催化剂催化玉米秸秆热解的产物分布

    Figure  11  Effect of different catalysts on the product distribution from the pyrolysis of CS

    图  12  催化生物质热解的产物分布

    Figure  12  Product distribution of the catalytic pyrolysis of biomass ((a) three-phase product distribution, (b) gas yield)

    图  13  催化生物质热解的产物分布

    Figure  13  Product distribution from the catalytic pyrolysis of biomass

    表  1  新鲜催化剂的物理特性及孔道特性

    Table  1  Physical properties and pore distribution of fresh catalysts

    Fresh catalyst BET surface area/(m2·g−1) t-plot micropore area/(m2·g−1) t-plot external surface area/(m2·g−1) Total pore
    volume/(cm3·g−1)
    Pore size
    /nm
    ASA 262.13 0.44 6.75
    HZSM-5 276.21 145.49 130.72 0.23 3.26
    Ni/HZSM-5 241.83 155.48 86.35 0.19 3.16
    Ni-Fe/HZSM-5 219.50 133.02 84.48 0.17 3.11
    Ni-Fe/ASA@HZSM-5 195.90 107.59 88.31 0.16 3.17
    下载: 导出CSV

    表  2  不同升温速率下玉米秸秆热解反应动力学参数

    Table  2  Kinetic parameters of CS pyrolysis under different heating rates

    β/(mL·min−1) CS MCh CR
    E/(kJ·mol−1) A/min−1 E/(kJ·mol−1) A/min−1 E/(kJ·mol−1) A/min−1
    10 74.96 1498.02 74.88 1474.39 73.04 1237.76
    20 73.21 1253.56 73.50 1290.48 72.27 1150.18
    30 72.81 1210.30 74.60 1430.49 72.44 1169.72
    40 72.61 1186.40 73.75 1316.83 71.77 1099.88
    β/(mL·min−1) WSh WSt PR
    E/(kJ·mol−1) A/min−1 E/(kJ·mol−1) A/min−1 E/(kJ·mol−1) A/min−1
    10 71.33 1059.17 72.48 1178.61 73.89 1341.81
    20 71.51 1073.74 72.20 1143.25 72.22 1144.56
    30 71.69 1093.54 72.18 1143.54 71.69 1091.38
    40 71.95 1119.70 72.48 1179.23 71.63 1084.02
    下载: 导出CSV

    表  3  生物质热解的反应动力学参数

    Table  3  Reaction kinetic parameters of biomass pyrolysis

    SampleE/(kJ·mol−1)A/min−1SampleE/(kJ·mol−1)A/min−1
    CS73.391237.27WSh71.621061.48
    MCh74.181379.27WSt72.341142.08
    CR72.381147.11PR72.361144.39
    下载: 导出CSV

    表  4  反应后催化剂的孔道特性

    Table  4  Pore characteristics of reacted catalysts

    Reacted catalyst ASA HZSM-5 Ni/HZSM-5 Ni-Fe/HZSM-5 Ni-Fe/ASA@HZSM-5
    BET surface area/(m2·g−1) 48.95 219.99 235.49 214.4 136.12
    t-plot micropore area/(m2·g−1) 33.09 157.67 167.17 172.84 104.48
    t-plot external surface area/(m2·g−1) 15.86 62.32 68.32 41.56 31.64
    Total pore volume/(cm3·g−1) 0.09 0.15 0.18 0.15 0.10
    Pore size/nm 7.13 2.75 3.03 2.72 2.94
    Average nanoparticle size/nm 122.58 27.27 25.48 27.99 44.08
    下载: 导出CSV
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  • 收稿日期:  2023-12-25
  • 修回日期:  2024-01-31
  • 录用日期:  2024-03-20
  • 网络出版日期:  2024-03-30
  • 刊出日期:  2024-07-01

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