Research progress on synergistic catalytic conversion of biomass gasification tar by non-thermal plasma

doi:10.16085/j.issn.1000-6613.2024-0664

Abstract

Abstract:

Biomass, as a renewable energy source, holds a significant position in the global energy due to its potential for producing syngas through thermochemical conversion processes. However, tar formation during this process severely hampers the quality of synthesis gas and impedes the commercialization of biomass gasification technology. Among various tar removal methods, catalytic reforming has garnered substantial attention because it can effectively decompose tar into valuable gaseous products. Notwithstanding, catalyst deactivation under high-temperature conditions remains a critical challenge to be addressed. The synergistic use of non-thermal plasma (NTP) catalysis stands out as particularly promising due to its capability to efficiently decompose tar at lower temperatures. By coupling with heterogeneous catalysts, NTP can significantly enhance catalyst activity and stability, reduce the formation of unfavorable byproducts, and improve product selectivity. This paper systematically reviews the optimization of tar reforming catalysts in conventional catalytic systems, including their deactivation mechanisms, and further delves into the synergistic effects of different combinations of NTP and catalyst systems on tar reforming efficiency and mechanisms. Ultimately, the paper discusses the prospects of applying NTP catalytic technology in the field of biomass gasification tar reforming, emphasizing the importance of catalyst design and preparation, as well as the optimization of practical operating parameters, in order to propel the sustainable development and technological advancement of the biomass gasification industry.

Key words: biomass, gasification tar, non-thermal plasma, catalytic reforming, synergistic effect

摘要：

生物质作为一种可再生能源，在全球能源结构中占据重要地位，其通过热化学转化过程生产合成气极具应用价值，但过程中产生的焦油问题严重制约了合成气品质和生物质气化技术的商业化进程。在多种焦油去除方法中，催化重整因其能有效将焦油分解为有价值的气体产物而备受关注。然而，高温条件下的催化剂失活问题仍是亟待解决的关键挑战。低温等离子体（non-thermal plasma，NTP）处理技术因其能够在较低温度下进行高效的焦油分解而显得尤为具有吸引力。通过与非均相催化剂结合形成耦合体系，NTP可以显著增强催化剂活性和稳定性，减少不利副产物生成并提升产物选择性。本文系统阐述了单纯催化体系中焦油重整催化剂的优化及其失活机理，深入探讨了不同NTP与催化剂催化耦合体系对焦油重整效率及机理的优化作用。最后，本文讨论了未来NTP催化技术在生物质气化焦油重整领域的应用前景，强调了从催化剂设计与制备到实际操作工艺参数优化的重要性，以期推动生物质气化产业的持续发展和技术升级。

关键词: 生物质, 气化焦油, 低温等离子体, 催化重整, 协同作用

CLC Number:

X784

XU Zhicheng, GAO Ningbo, QUAN Cui, SONG Qingbin. Research progress on synergistic catalytic conversion of biomass gasification tar by non-thermal plasma[J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3432-3442.

许志成, 高宁博, 全翠, 宋庆彬. 低温等离子体协同催化转化生物质气化焦油研究进展[J]. 化工进展, 2025, 44(6): 3432-3442.

Figures/Tables 9

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应用场景	焦油最高含量/mg·m^-3	参考文献
压缩机	50~500	[10]
内燃机	50~100	[11]
直燃燃气轮机	<5	[12]
甲醇合成	<0.1	[13]
燃料电池	<1.0	[13]

应用场景	焦油最高含量/mg·m^-3	参考文献
压缩机	50~500	[10]
内燃机	50~100	[11]
直燃燃气轮机	<5	[12]
甲醇合成	<0.1	[13]
燃料电池	<1.0	[13]

等离子体反应器	焦油模拟物	焦油浓度/g·m^-3	载气种类	转化率/%	能量效率/g·kW^-1·h^-1	参考文献
旋转滑动弧等离子体	甲苯	10.0	N₂/H₂O	85.2	11.7	[22]
滑动弧等离子体	甲苯	16.1	N₂/CO₂/H₂O	63.3	40.7	[23]
滑动弧等离子体	甲苯/萘	2	N₂/CO₂/H₂O	85.9/68.9	2.6	[24]
滑动弧等离子体	萘	1.1	N₂/H₂O	84.8	5.7	[25]
滑动弧等离子体	甲苯/萘	0.49	N₂/CO₂/H₂O	约80	53.6	[26]
滑动弧等离子体	甲苯	23.5	N₂/H₂O	35.8	16	[27]
介质阻挡放电等离子体	甲苯	261	N₂/O₂	78.0	34	[28]
介质阻挡放电等离子体	萘	90	N₂/H₂/CO/CO₂	60.0	2.2	[29]
介质阻挡放电等离子体	甲苯	20	H₂	99.0	4.79	[30]
电晕放电等离子体	甲苯	261	He/H₂O	35.0	25.3	[31]
电晕放电等离子体	甲苯	70	空气	50.0	2.5	[32]
电晕放电等离子体	真实焦油	0.7	气化尾气	62.0	11.2	[33]
微波等离子体	甲苯	10	N₂/H₂O	98.0	5.8	[34]
微波等离子体	甲苯	4.2	Ar/N₂	99.0	4.5	[35]

等离子体反应器	焦油模拟物	焦油浓度/g·m^-3	载气种类	转化率/%	能量效率/g·kW^-1·h^-1	参考文献
旋转滑动弧等离子体	甲苯	10.0	N₂/H₂O	85.2	11.7	[22]
滑动弧等离子体	甲苯	16.1	N₂/CO₂/H₂O	63.3	40.7	[23]
滑动弧等离子体	甲苯/萘	2	N₂/CO₂/H₂O	85.9/68.9	2.6	[24]
滑动弧等离子体	萘	1.1	N₂/H₂O	84.8	5.7	[25]
滑动弧等离子体	甲苯/萘	0.49	N₂/CO₂/H₂O	约80	53.6	[26]
滑动弧等离子体	甲苯	23.5	N₂/H₂O	35.8	16	[27]
介质阻挡放电等离子体	甲苯	261	N₂/O₂	78.0	34	[28]
介质阻挡放电等离子体	萘	90	N₂/H₂/CO/CO₂	60.0	2.2	[29]
介质阻挡放电等离子体	甲苯	20	H₂	99.0	4.79	[30]
电晕放电等离子体	甲苯	261	He/H₂O	35.0	25.3	[31]
电晕放电等离子体	甲苯	70	空气	50.0	2.5	[32]
电晕放电等离子体	真实焦油	0.7	气化尾气	62.0	11.2	[33]
微波等离子体	甲苯	10	N₂/H₂O	98.0	5.8	[34]
微波等离子体	甲苯	4.2	Ar/N₂	99.0	4.5	[35]

等离子体耦合体系	作用机理	优势	劣势
传统热催化体系	通过催化剂在高温条件下催化焦油分子的裂解及重整反应，包括扩散、吸附、活化转化以及脱附，催化剂能够降低反应活化能，促进反应进行生成产物	反应转化高效、产物选择性控制较好、应用广泛	高温操作、催化剂易失活导致成本较高、能耗较高、反应条件限制较多
单纯等离子体体系	利用等离子体产生的高能粒子能够在较低温度条件下活化焦油分子，打破热力学限制，促进化学反应	反应在相对较低温度下发生、无需催化剂即可催化反应进行、反应控制灵活	催化效率有限、对特定产物选择性较差、能量利用率较低
等离子体预处理体系	利用等离子体技术对催化剂进行表面改性或激活以改善催化剂的性能，后将催化剂用于传统热催化体系催化焦油重整反应	增强催化剂活性并提升其选择性及稳定性、适用范围较广	成本相对较高、参数控制复杂、等离子体无法直接催化重整反应
等离子体后催化体系	在等离子体体系后连接传统催化剂体系，等离子体与催化剂在各段分别发挥作用，反应物先经等离子体催化后经催化剂催化	促进副产品的分解、提高产物的纯度、等离子体与催化剂段反应条件可分开控制	等离子体段产生的短寿命活性物质无法到达催化剂段协助反应、反应器设计较复杂
等离子体协同催化体系	在等离子体放电区域填充催化剂，二者能够产生相互作用，等离子体产生的活性物种可以直接参与反应，共同催化焦油重整反应	等离子体与催化剂能产生协同作用、在较低的温度下实现高效反应、提高产物选择性及催化剂稳定性	反应机理较为复杂、能量转换效率有待提高、需设计高效协同催化剂