生物质气化制富氢合成气的研究进展

doi:10.3969/j.issn.1673-5854.2022.03.007

生物质化学工程 ›› 2022, Vol. 56 ›› Issue (3): 39-46.doi: 10.3969/j.issn.1673-5854.2022.03.007

生物质气化制富氢合成气的研究进展

任菊荣¹, 苏允泓², 应浩¹^,*(), 孙云娟¹, 徐卫¹, 尹航¹

1. 中国林业科学研究院林产化学工业研究所；生物质化学利用国家工程实验室；国家林业和草原局林产化学工程重点实验室；江苏省生物质能源与材料重点实验室，江苏南京 210042
2. 东南大学能源与环境学院，江苏南京 210096

收稿日期:2021-03-22 出版日期:2022-05-30 发布日期:2022-05-21
通讯作者: 应浩 E-mail:hy2478@163.com
作者简介:应浩，研究员，硕士生导师，研究领域：生物质能转化技术开发与工业应用；E-mail：hy2478@163.com
任菊荣(1997—)，女，宁夏石嘴山人，硕士生，研究方向：生物质热化学转化技术
基金资助:
国家自然科学基金资助项目(51976234);江苏省自然科学基金资助项目(BK20191135)

Research Progress of Biomass Gasification for Hydrogen-rich Syngas

Jurong REN¹, Yunhong SU², Hao YING¹^,*(), Yunjuan SUN¹, Wei XU¹, Hang YIN¹

1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China
2. School of Energy and Environment, Southeast University, Nanjing 210096, China

Received:2021-03-22 Online:2022-05-30 Published:2022-05-21
Contact: Hao YING E-mail:hy2478@163.com

摘要/Abstract

摘要：

生物质气化制取富氢合成气因其原料的清洁可再生性、产物应用方式的多样性被认为是最具发展前景的制氢方式之一。催化剂对调控生物质气化产物组成及焦油的裂解具有重要作用。本文综述了化石能源制氢、水分解制氢和生物质制氢方法，分析了生物质气化制氢的优势和局限性，以及存在的问题；重点介绍了生物质气化制氢的影响因素(气化剂、反应温度和催化剂)和用于生物质气化的主要催化剂种类(镍基、白云石和碱及碱土金属催化剂)及其特点，分析国内外生物质气化制取富氢合成气和催化剂的研究现状，探讨了催化气化制取富氢合成气的发展前景，提出有待解决的问题和研究方向。

关键词: 生物质, 气化, 催化, 富氢合成气

Abstract:

Hydrogen-rich syngas production from biomass gasification is considered as one of the most promising hydrogen production methods because of its clean and renewable raw materials and the diversity of product application. Catalysts play an important role in controlling the composition of biomass gasification products and the pyrolysis of tar. In this paper, the methods of hydrogen production from fossil energy, water decomposition, and biomass were reviewed, and the advantages, limitations, and existing problems of hydrogen production from biomass gasification were also analyzed. And, the influence factors of biomass gasification(gasification agent, reaction temperature, and catalyst) and the kinds of catalyst and its characteristics which used for biomass gasification(nickel-based, dolomite and alkali, and alkaline earth metal catalysts) were emphatically introduced. The research status of biomass gasification for making hydrogen rich syngas and catalysts in China and abroad were analyzed, and the prospects of the development of catalytic gasification for making hydrogen-rich syngas were discussed. The problems to be solved and the research direction were proposed.

Key words: biomass, gasification, catalysis, hydrogen-rich syngas

中图分类号:

TQ35

任菊荣, 苏允泓, 应浩, 孙云娟, 徐卫, 尹航. 生物质气化制富氢合成气的研究进展[J]. 生物质化学工程, 2022, 56(3): 39-46.

Jurong REN, Yunhong SU, Hao YING, Yunjuan SUN, Wei XU, Hang YIN. Research Progress of Biomass Gasification for Hydrogen-rich Syngas[J]. Biomass Chemical Engineering, 2022, 56(3): 39-46.

图/表 4

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气化剂类型gasification agent	优点advantage	缺点disadvantage
空气	气化剂廉价易得；焦油生成量和炭剩余量中等	产物中H₂体积分数低
氧气	焦油含量最低；可燃组分体积分数高	需要制氧设备，气化成本高
水蒸气	H₂体积分数可达40%~60%；气化剂廉价易得	产物中焦油含量高
二氧化碳	产物中CO₂体积分数低	产物中H₂体积分数低，能耗高

原料 raw material	最佳温度(范围)/℃ optimum temperature(range)	H₂体积分数/% H₂volume fraction	改变量 variable quantity	反应条件 reaction condition	参考文献 ref.
稻壳	850(750~850)	13.1	H₂体积分数较750 ℃时提升 42.4%；碳转化率86.1%，提升21.4%	空气-蒸汽混合物为气化剂；蒸汽与生物质质量比值为0.8	[19]
松木屑	900(700~950)	47.7	900 ℃之后H₂体积分数下降；碳转化率随温度升高而提高	水蒸气流量10 mL/min	[20]
玉米秸秆焦	950(750~950)	62.53	H₂体积分数由750 ℃时的37.68 %增加至62.53%	水蒸气流量5 mL/min	[21]

催化剂种类 catalyst type	催化剂代表 representative catalyst	优点 advantage	缺点 disadvantage	参考文献 ref.
Ni基催化剂		有效提高H₂体积分数，焦油去除率高	生物质气化在高温下迅速失活	[25]
天然矿石	白云石、橄榄石、石灰石	有效裂解焦油，吸收CO₂	在较高浓度的焦油下容易失活	[26]
碱及碱土金属	KOH、K₂CO₃、NaHCO₃	显著加快气化反应并有效降低结焦速率和CH₄含量	难以回收，价格昂贵	[27]

催化剂 catalyst	生物质原料 biomass	反应条件 reaction condition	合成气品质 syngas quality	催化效果 catalytic effect	参考文献 ref.
镍-铑/γ-Al₂O₃	绿豆残渣	温度650 ℃，碳与蒸气质量比为0.12	H₂体积分数65%， n(H₂)/n(CO)为10.9	气化效率为83%，无焦油生成	[46]
水滑石Ni/Mg/Al	雪松木	温度800 ℃，水蒸气流量0.02 mL/min，反应30 min	—	较高的抗积碳能力和催化剂稳定性	[47]
NiO/白云石	松木屑	900 ℃气化，730 ℃重整	H₂体积分数71.8%	最高产氢45.8 g/kg	[48]
Ni/CeO₂/Al₂O₃	木屑	温度900 ℃，反应60 min，催化剂负载量40%	—	焦油裂解率比没有催化剂时高196%	[49]
Rh/CeO₂/SiO₂	雪松木	空气流量20 mL/min，加热速率15 K/min(27~1 000 ℃)	—	碳转化率98%~99%，催化剂能够有效促进积碳燃烧	[50]
Ni-Fe/γ-Al₂O₃	藻类浒苔	加热速率为10 K/min，终温850 ℃，保持30 min	H₂体积分数74%	产氢率24.6 g/kg，促进生物质裂解	[51]
煅烧水泥 (86.44%CaO)	松木屑	温度800 ℃，反应45 min，水蒸气-空气为气化剂	H₂体积分数50.3%	焦油产率0.49 g/Nm³，焦油转化效率为71%~83%	[52]
K₂CO₃/Ca(OH)₂	纤维素粉	温度450~500 ℃，压力 24~26 MPa，反应20 min	产氢率分别比使用 K₂CO₃或Ca(OH)₂时高25%和45%	H₂产率是无催化剂的2.5倍	[27]

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生物质气化制富氢合成气的研究进展

Research Progress of Biomass Gasification for Hydrogen-rich Syngas

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