生物质气化过程中焦油减量研究进展

doi:10.16085/j.issn.1000-6613.2024-1532

摘要/Abstract

摘要：

生物质气化作为清洁能源技术，因其可高效转化生物质为高热值合成气而受到关注。然而，焦油的产生严重影响气化效率和合成气质量。本文介绍了生物质焦油的定义、分类及其形成机理，综述了现阶段通过调整生物质特性、操作条件和添加催化剂来减少焦油的研究进展。文献调研表明：生物质的木质素含量、粒径及含水率均影响焦油产生；气化炉型优化、气化温度提高和蒸汽、氧气等气化剂的使用都有助于减少焦油并提高合成气质量；加压操作在大规模气化中表现出潜力，但在小规模气化中可能会增加焦油产生。催化剂（如白云石、橄榄石和镍基催化剂）虽在焦油裂解中效果显著，但面临失活和成本高的挑战。此外，本文还介绍了微波辅助与化学链气化结合技术及碳化硅膜与催化剂联用的新方法，这些创新技术展现出显著的减焦优势和潜在应用前景。未来研究应专注于催化剂的长效性、低成本制备及新型技术的开发，以高效减少焦油并推动生物质气化的可持续发展。

关键词: 生物质, 气化, 焦油, 合成气, 焦油减量

Abstract:

Biomass gasification, as a clean energy technology, has garnered significant attention for its efficient conversion of biomass into high-calorific-value syngas. However, the generation of tar severely affects the gasification efficiency and syngas quality. This paper introduces the definition, classification, and formation mechanism of biomass tar and reviews current research progress on tar reduction strategies through modifications in biomass properties, operational conditions, and the addition of catalysts. Literature review indicates that biomass characteristics, including lignin content, particle size, and moisture content, influence tar production. Optimization of gasifier types, increasing gasification temperature, and the use of gasifying agents such as steam and oxygen contribute to tar reduction and improved syngas quality. Pressurized operation has shown potential in large-scale gasification but may increase tar production in small-scale systems. Catalysts, such as dolomite, olivine, and nickel-based catalysts, have demonstrated remarkable efficiency in tar cracking, yet face challenges of deactivation and high cost. Additionally, this paper discusses innovative methods, such as microwave-assisted gasification combined with chemical looping and the integration of silicon carbide membranes with catalysts, which exhibit significant tar reduction advantages and promising application prospects. Future research should focus on the durability and cost-effective preparation of catalysts, as well as the development of novel technologies, to efficiently reduce tar and promote the sustainable development of biomass gasification.

Key words: biomass, gasification, tar, syngas, tar reduction

中图分类号:

S216.2

徐乃光, 刘涛涛, 宋薇, 聂文文, 王雪可, 严兆晨, 王昌松. 生物质气化过程中焦油减量研究进展[J]. 化工进展, 2025, 44(11): 6174-6186.

XU Naiguang, LIU Taotao, SONG Wei, NIE Wenwen, WANG Xueke, YAN Zhaochen, WANG Changsong. Research progress on tar reduction in biomass gasification process[J]. Chemical Industry and Engineering Progress, 2025, 44(11): 6174-6186.

图/表 9

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方法	种类	描述	典型化合物
基于形成过程	初级焦油	400~700℃下低分子量含氧化合物及衍生物	甲醇、乙醛、呋喃
	次级焦油	700~850℃下酚类和烯烃类转化成的化合物	苯酚、丙烯
	三级焦油	850~1000℃下无分支的芳香化合物	苯、甲苯、萘、蒽、菲
基于芳环的数量	Ⅰ类	GC检测不到的重焦油，高温下冷凝	—
	Ⅱ类	含有杂原子的有机化合物，高水溶性	吡啶、苯酚、喹啉
	Ⅲ类	单环芳香烃类，通常不会冷凝和水溶	甲苯、苯乙烯
	Ⅳ类	2~3环芳香烃类，中温、高浓度下冷凝	菲、萘、芴
	Ⅴ类	4~5环芳香烃类，高温、低浓度下冷凝	荧蒽、冠烯

方法	种类	描述	典型化合物
基于形成过程	初级焦油	400~700℃下低分子量含氧化合物及衍生物	甲醇、乙醛、呋喃
	次级焦油	700~850℃下酚类和烯烃类转化成的化合物	苯酚、丙烯
	三级焦油	850~1000℃下无分支的芳香化合物	苯、甲苯、萘、蒽、菲
基于芳环的数量	Ⅰ类	GC检测不到的重焦油，高温下冷凝	—
	Ⅱ类	含有杂原子的有机化合物，高水溶性	吡啶、苯酚、喹啉
	Ⅲ类	单环芳香烃类，通常不会冷凝和水溶	甲苯、苯乙烯
	Ⅳ类	2~3环芳香烃类，中温、高浓度下冷凝	菲、萘、芴
	Ⅴ类	4~5环芳香烃类，高温、低浓度下冷凝	荧蒽、冠烯

序号	原料	生物质成分（质量分数）	工艺描述	气化剂	焦油含量	参考文献
#1	微晶纤维素	99.0%纤维素	下吸式固定床气化炉1000℃	氮气	1.2mg/g	[19]
	小麦木聚糖	99.0%半纤维素			1.4mg/g
	硫酸盐木质素	98.0%木质素			3.9mg/g
#2	松木	36.7%纤维素 26.1%半纤维素 27.5%木质素	固定床气化炉500℃	氮气	338mg/g	[20]
#3	芒草	45.7%纤维素 22.8%半纤维素 20.2%木质素			211mg/g
#4	小麦秸秆	33.8%纤维素 21.7%半纤维素 20.5%木质素			159mg/g
#5	秸秆	40.5%纤维素 24.9%半纤维素 17.6%木质素	下吸式固定床气化炉1000℃	氮气	2mg/g	[19]
#6	松木	46.8%纤维素 18.5%半纤维素 27.3%木质素	下吸式固定床气化炉1000℃	氮气	8mg/g	[19]
#7	木材颗粒	含水率6.9%	流化床气化炉700℃，粒径20.0mm	蒸汽	190mg/g	[21]
#7	木材颗粒	含水率6.9%	粒径5.0mm	蒸汽	80mg/g	[21]
#8	木材残留物	47.6%纤维素 39.0%半纤维素 11.2%木质素	上吸式固定床气化炉480℃，粒径30.0mm	氮气	145mg/g	[22]
			粒径20.0mm		200mg/g
			粒径10.0mm		260mg/g
#9	玉米秸秆	27.9%纤维素 18.1%半纤维素 23.4%木质素	流化床气化炉700℃，ER=0.21	空气	6.2g/m³	[23]
			820℃，ER=0.31	空气	4.0g/m³
			700℃，S/B=0.6	蒸汽	3.5g/m³
#10	松木屑	含水率10.0%	上吸式固定床气化炉840℃，粒径2.0mm	空气	79.4g/m³	[24]
			粒径7.0mm		13.0g/m³
			粒径30.0mm		93.0g/m³
		含水率22.0%	粒径7.0mm		6.2g/m³
#11	木片	含水率6.0%	流化床气化炉810℃	空气	8.3g/m³	[25]
		含水率19.0%			5.2g/m³
		含水率30.0%			5.6g/m³
#12	干化污水污泥	含水率7.3%	鼓泡流化床，ER=0.26，659℃	蒸汽和氧气	98.0g/m³	[26]
			778℃		31.0g/m³
			894℃		21.0g/m³
#13	干化污水污泥	—	流化床气化炉，818℃，ER=0.22	空气	296.0mg/m³	[27]
#13	干化污水污泥	—	821℃，ER=0.50	空气	76.0mg/m³	[27]
#14	沼渣	含水率10.0%~20.0%	循环流化床气化炉，810℃，ER=0.32	空气	8.6g/m³	[28]
#14	沼渣	含水率10.0%~20.0%	ER=0.36，S/B=0.79	空气和蒸汽	3.7g/m³	[28]
#15	松木锯末	—	流化床气化炉，900℃	氮气	154.0g/m³	[29]
#15	松木锯末	—	S/B=1.0	蒸汽	142.0g/m³	[29]
#16	稻壳、稻草和聚乙烯	—	鼓泡流化床气化炉，850℃，ER=0.2	蒸汽和空气	12.5g/m³	[30]
#16	稻壳、稻草和聚乙烯	—	鼓泡流化床气化炉，850℃，ER=0.2	蒸汽和60%富氧空气	9.0g/m³	[30]
#17	桉树木片	—	上吸式固定床气化炉，ER=0.24，S/B=0.20	空气和蒸汽	31.6g/m³	[31]
#17	桉树木片	—	ER=0.23，S/B=0.21	氧气和蒸汽	11.2g/m³	[31]
#18	云杉	—	流化床气化炉0.1MPa，ER=0.22，S/B=1.6	空气和蒸汽	0.5%（质量分数）	[32]
#18	云杉	—	1MPa，ER=0.24，S/B=1.7	空气和蒸汽	1.6%（质量分数）	[32]
#19	煤	—	高压反应器，2MPa	氧气和蒸汽	3078.5mg/m³	[33]
#19	煤	—	4MPa	氧气和蒸汽	556.5mg/m³	[33]

序号	原料	生物质成分（质量分数）	工艺描述	气化剂	焦油含量	参考文献
#1	微晶纤维素	99.0%纤维素	下吸式固定床气化炉1000℃	氮气	1.2mg/g	[19]
	小麦木聚糖	99.0%半纤维素			1.4mg/g
	硫酸盐木质素	98.0%木质素			3.9mg/g
#2	松木	36.7%纤维素 26.1%半纤维素 27.5%木质素	固定床气化炉500℃	氮气	338mg/g	[20]
#3	芒草	45.7%纤维素 22.8%半纤维素 20.2%木质素			211mg/g
#4	小麦秸秆	33.8%纤维素 21.7%半纤维素 20.5%木质素			159mg/g
#5	秸秆	40.5%纤维素 24.9%半纤维素 17.6%木质素	下吸式固定床气化炉1000℃	氮气	2mg/g	[19]
#6	松木	46.8%纤维素 18.5%半纤维素 27.3%木质素	下吸式固定床气化炉1000℃	氮气	8mg/g	[19]
#7	木材颗粒	含水率6.9%	流化床气化炉700℃，粒径20.0mm	蒸汽	190mg/g	[21]
#7	木材颗粒	含水率6.9%	粒径5.0mm	蒸汽	80mg/g	[21]
#8	木材残留物	47.6%纤维素 39.0%半纤维素 11.2%木质素	上吸式固定床气化炉480℃，粒径30.0mm	氮气	145mg/g	[22]
			粒径20.0mm		200mg/g
			粒径10.0mm		260mg/g
#9	玉米秸秆	27.9%纤维素 18.1%半纤维素 23.4%木质素	流化床气化炉700℃，ER=0.21	空气	6.2g/m³	[23]
			820℃，ER=0.31	空气	4.0g/m³
			700℃，S/B=0.6	蒸汽	3.5g/m³
#10	松木屑	含水率10.0%	上吸式固定床气化炉840℃，粒径2.0mm	空气	79.4g/m³	[24]
			粒径7.0mm		13.0g/m³
			粒径30.0mm		93.0g/m³
		含水率22.0%	粒径7.0mm		6.2g/m³
#11	木片	含水率6.0%	流化床气化炉810℃	空气	8.3g/m³	[25]
		含水率19.0%			5.2g/m³
		含水率30.0%			5.6g/m³
#12	干化污水污泥	含水率7.3%	鼓泡流化床，ER=0.26，659℃	蒸汽和氧气	98.0g/m³	[26]
			778℃		31.0g/m³
			894℃		21.0g/m³
#13	干化污水污泥	—	流化床气化炉，818℃，ER=0.22	空气	296.0mg/m³	[27]
#13	干化污水污泥	—	821℃，ER=0.50	空气	76.0mg/m³	[27]
#14	沼渣	含水率10.0%~20.0%	循环流化床气化炉，810℃，ER=0.32	空气	8.6g/m³	[28]
#14	沼渣	含水率10.0%~20.0%	ER=0.36，S/B=0.79	空气和蒸汽	3.7g/m³	[28]
#15	松木锯末	—	流化床气化炉，900℃	氮气	154.0g/m³	[29]
#15	松木锯末	—	S/B=1.0	蒸汽	142.0g/m³	[29]
#16	稻壳、稻草和聚乙烯	—	鼓泡流化床气化炉，850℃，ER=0.2	蒸汽和空气	12.5g/m³	[30]
#16	稻壳、稻草和聚乙烯	—	鼓泡流化床气化炉，850℃，ER=0.2	蒸汽和60%富氧空气	9.0g/m³	[30]
#17	桉树木片	—	上吸式固定床气化炉，ER=0.24，S/B=0.20	空气和蒸汽	31.6g/m³	[31]
#17	桉树木片	—	ER=0.23，S/B=0.21	氧气和蒸汽	11.2g/m³	[31]
#18	云杉	—	流化床气化炉0.1MPa，ER=0.22，S/B=1.6	空气和蒸汽	0.5%（质量分数）	[32]
#18	云杉	—	1MPa，ER=0.24，S/B=1.7	空气和蒸汽	1.6%（质量分数）	[32]
#19	煤	—	高压反应器，2MPa	氧气和蒸汽	3078.5mg/m³	[33]
#19	煤	—	4MPa	氧气和蒸汽	556.5mg/m³	[33]

气化炉	焦油浓度/g·m^-3	优点	缺点
上吸式固定床气化炉	10~150	结构简单、热效率高、可处理高含水率原料	气体产率低、启动耗时长、焦油含量高
下吸式固定床气化炉	0.015~0.5	结构简单、碳转化率高、焦油含量低	热效率低、需要低含水率的原料
横吸式固定床气化炉	—	启动时间短、气化炉高度低	热效率低、出口气体温度高
鼓泡流化床气化炉	3~40	能适应多种原料、高热负荷、操作灵活	对粒径有要求、气体净化需求高
循环流化床气化炉	5~12	气化效率高、适应大规模工业化	设备投资大，工艺控制难度大
夹带流气化炉	几乎没有	高效连续气化、规模大、气体洁净	设计和运行复杂，设备投资最高