生物质水蒸气催化重整制氢研究进展

doi:10.3969/j.issn.1673-5854.2023.04.008

摘要/Abstract

摘要：

生物质能是一种理想的清洁能源, 具有可再生、多样性并能够实现二氧化碳零排放的优点。生物质催化重整制氢是生物质热化学转换利用的一种高效、环保、经济的方式。本文从生物质催化重整过程中的关键反应参数: 反应温度、水碳比、反应空速和催化剂等方面综述了生物质催化重整制氢相关研究进展, 总结了反应参数、催化剂的选择和应用对热解产物的影响, 梳理了天然矿石催化剂、碱金属催化剂、过渡金属催化剂和尖晶石催化剂在生物质水蒸气转化特性的影响机制, 总结了通过定向调控开发稳定的高活性催化剂以提高重整反应的效率和稳定性的有效利用途径。指出了明晰催化机理还需从生物质与催化剂的交互作用机制和热解气化反应机理的角度进一步探究。

关键词: 生物质, 制氢, 催化剂, 重整, 热解

Abstract:

Biomass energy was an ideal clean energy, with the advantages of renewable, diversity and could achieve zero carbon dioxide emissions. Biomass catalytic reforming to produce hydrogen was an effective, environmentally friendly and economical way of biomass thermochemical conversion and utilization. In this paper, the research progress of biomass catalytic reforming for hydrogen production was reviewed from the aspects of key reaction parameters in the process of biomass catalytic reforming: reaction temperature, ratio of water to carbon, reaction space velocity and catalyst. The effects of reaction parameters, catalyst selection and application on pyrolysis products were reviewed. The influence mechanism of natural ore catalyst, alkali metal catalyst, transition metal catalyst and spinel catalyst on the water vapor conversion characteristics of biomass was combed. The effective utilization way of improving the efficiency and stability of reforming reaction by developing stable catalyst with high activity through directional control was summarized. It was pointed out that the clear catalytic mechanism should be further explored from the perspective of the interaction mechanism between biomass and catalyst and the reaction mechanism of pyrolysis and gasification.

Key words: biomass, hydrogen production, catalyst, reforming, pyrolysis

中图分类号:

TQ35
TK6

郭恒涛, 王学涛, 邢利利, 李浩杰, 翟好山. 生物质水蒸气催化重整制氢研究进展[J]. 生物质化学工程, 2023, 57(4): 60-70.

Hengtao GUO, Xuetao WANG, Lili XING, Haojie LI, Haoshan ZHAI. Research Advance in Biomass Steam Catalytic Reforming for Hydrogen Production[J]. Biomass Chemical Engineering, 2023, 57(4): 60-70.

图/表 4

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图3

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催化剂 catalyst	生物质原料 biomass raw material	反应条件 reaction condition	结果 result	文献 ref.
Fe-Ce/白云石	松木屑	反应温度900 ℃，水流量1 g/min	与无催化剂的气化试验相比，产气率增加0.15 m³/kg，产氢率增加16.27 g/kg，V(H₂)由39.02%升至46.95%	[28]
橄榄石	松木屑	解耦双回路气化系统，气化反应器700 ℃，重整反应器850 ℃，n(H₂O)∶n(C)=1.2	相比于石英砂，气体产率由0.8 m³/kg增至1.0 m³/kg, 焦油由77.1 g/m³降至13.9 g/m³，H₂ 38.8%	[29]
褐铁矿	松木颗粒	气化温度700 ℃，蒸汽流量0.9 kg/h	V(H₂)64.8%	[30]
碱金属成分	玉米芯炭	反应温度900 ℃，水蒸气流量0.4 g/min	KOH 6%时玉米芯炭的产氢率为197.8 g/kg	[31]
Ni基催化剂	乙酸	反应温度为700 ℃，n(H₂O)∶n(C)=2.5，液时空速(LHSV)=10 h^-1	KOH碱化耦合HNO₃酸化制备的Ni/biochar催化剂碳转化率91.2%, 氢气产率71.2%	[32]
MFe₂O₄(M=Ni，Co，Mn)尖晶石	乙醇	反应温度250~700 ℃	650 ℃时MnFe₂O₄的最大氢产率达94.6%	[33]
CoFe₂O₄、CuFe₂O₄和MgFe₂O₄	沼气	V(CH₄)∶V(CO₂)=1∶1 GHSV=6 000 h^-1，反应温度800 ℃	3种催化剂中CuFe₂O₄的催化性能最佳，获得氢气和一氧化碳选择性分别为87.60%和89.79%	[34]

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