生物质热解气中含氮化合物形成与控制的研究进展

王凤超; 朱虹宇; 阴秀丽; 徐彬; 李伟振; 刘华财

doi:10.19906/j.cnki.JFCT.2023090

生物质热解气中含氮化合物形成与控制的研究进展

doi: 10.19906/j.cnki.JFCT.2023090

中国科学院广州能源研究所中国科学院可再生能源重点实验室广东省新能源和可再生能源研发重点实验室, 广东广州 510640

基金项目: 中国科学院战略性先导科技专项课题（XDA29010400），国家自然科学基金（52106282），吉林省与中国科学院科技合作项目（2021SYHZ0014），长春市科技发展计划项目（22SH20）和工业源生物质原料燃料化应用调配成型关键技术及示范(执行)（E339010101）资助

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通讯作者:
Tel: 19928370279, E-mail: liuhc@ms.giec.ac.cn

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出版历程
- 收稿日期: 2023-11-30
- 修回日期: 2024-01-07
- 录用日期: 2024-01-10
- 网络出版日期: 2024-03-02

The research progress of formation and control on the N-containing compound of biomass pyrolysis gas

Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, CAS Key Laboratory of Renewable Energy, Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, China

Funds: The project was supported by the Strategic Priority Research Program of Chinese Academy of Sciences (XDA29010400), National Natural Science Foundation of China (52106282), Science and Technology Co-operation Project between Jilin Province and Chinese Academy of Sciences （2021SYHZ0014），Changchun Science and Technology Development Plan Project (22SH20) and The Key Technology and Demonstration of Blending and Moulding for Fuel Applications of Biomass Feedstocks from Industrial Sources (Implementation) ( E339010101).

摘要

摘要: 热解是利用生物质能的一种高效且经济的方式，但生物质热解气中的含氮化合物使热解气品质低且燃烧导致空气二次污染。本工作总结了生物质热解气中的含氮化合物研究现状，主要综述了典型生物质热失重行为，探讨了生物质热解气中含氮化合物的生成机理，分析了含氮化合物的分布状况和控制的研究进展。同时，指出了含氮化合物控制在实际应用中面临的困难挑战，进一步展望了含氮化合物控制工艺优化及经济性分析的重点研究方向，为生物质热解气净化提供理论依据和技术支持。
- 生物质 /
- 热解 /
- 含氮化合物 /
- 生成机理 /
- 脱除
Abstract: Biomass energy plays an important role in combating global warming and the depletion of fossil energy sources. Although different recovery technologies of biomass energy were utilized industrially, the development level of different recovery technologies varies. The application of biomass energy includes technologies such as combustion, pyrolysis, gasification, and fermentation. The pyrolysis technology is an efficient and economical method to utilize biomass energy, which combines the advantage of energy recovery and product diversification. However, the N-containing compounds in the biomass pyrolysis gas make the pyrolysis gas of low quality, which combustion leads to secondary pollution of air. This review summaries the research status of N-containing compounds in the biomass pyrolysis gas, mainly reviewing the differences in the thermos-gravimetric behavior of typical biomass and the four compositions in biomass (cellulose, hemicellulose, lignin, and proteins). There were significant differences in the thermos-gravimetric behavior of biomass with different material compositions, but the whole TG curve can be divided into three stages: in the first stage, the pyrolysis of easily decomposable components in biomass releases small molecule gases and steam; in the second stage, the pyrolysis of cellulose, hemicellulose, and lignin in biomass released a large amount of O-containing bio-oil; in the third stage, the volatile components attached to the surface of the bio-char were cracked again and condensation reaction occurs. The nitrogen content in biomass was high, and during the pyrolysis process, nitrogen migrated into the solid-liquid-gas three-phase, and the migration transformation process was extremely complex. This review also discussed the generation mechanism of N-containing compounds in biomass pyrolysis gas and analyzed the distribution and control research of N-containing compounds. The NH₃ in the low-temperature pyrolysis gas was mainly derived from the direct pyrolysis of protein in biomass. With the increase of pyrolysis temperature, the biomass pyrolysis volatiles were cracked secondly to generate N-containing heterocyclic substances, nitriles, and cyclic amides, and further cracked to produce HCN. Under the high-temperature atmosphere, partial HCN reacts with ·H and generates NH₃ with the biomass char catalysis, leading to a decrease in the concentration of HCN. The N-containing heterocyclic substances from the second cracking of volatiles were the main resource of HCNO, and HCNO has a relatively lower concentration and is easily reduced to HCN and NO. Thus, with the pyrolysis temperature increase, the main components of N-containing compounds in the pyrolysis gas were gradually converted from NH₃ and HCNO to NO and HCN. When the temperature was 800 ℃, the concentration of NO accounted for 40% of the N-containing compounds in pyrolysis gas. While, at 900 ℃, NH₃ and HNCO were barely detectable. At the same time, it pointed out the difficulties and challenges faced in the practical application of N-containing compound removal. It is necessary to establish a generalized mechanism for nitrogen conversion during the thermal conversion of biomass. The nitrogen transport and control mechanisms during biomass pyrolysis need to be further improved. And, the key research directions in the process optimization and economic analysis of N-containing control are further anticipated. This review aims to provide a theoretical basis and technology support for biomass pyrolysis gas purification.
- biomass /
- pyrolysis /
- N-containing compound /
- generation mechanism /
- removal

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图 1 生物质热失重行为曲线

Figure 1 Thermogravimetric curves of biomass (a): pine sawdust (PS), cow dung (CD), kidney bean stura (KS) and bamboo (BA)^[13]; (b): palm kernel shell^[18]

(with permission from Elsevier)

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图 2 生物质中纤维素、半纤维素、木质素和蛋白质的热失重（a）及红外光谱谱图（b）

Figure 2 TG (a) and FT-IR (b) curves of cellulose, hemicellulose, lignin and protein in biomass

(with permission from Elsevier)

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图 3 蘑菇糠（MB）和玉米秸秆（CS）热失重过程中HCN和NH₃的演变曲线^[29]

Figure 3 The evolution curves of HCN and NH₃ during the weight loss of mushroom bran (MB) and corn stover (CS)^[29]

(with permission from Elsevier)

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图 4 含N气体分布

Figure 4 N-containing gas distribution

(with permission from Elsevier)

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图 5 生物质热解燃料-N转化途径（a）^[53]和藻类蛋白质热解氮转化路径（b）^[55]

Figure 5 Fuel-N conversion pathway(a)^[53] of biomass pyrolysis and algal protein pyrolysis nitrogen conversion pathway(b)^[55]

(with permission from Elsevier)

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图 6 生物质热解过程中氮迁移转化路径示意图

Figure 6 Nitrogen migration pathway in biomass pyrolysis process

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图 7 Cu-K金属椰壳活性炭脱除NO的能力（a），（b）^[68]及反应机理（c），（ d）^[69−70]

Figure 7 Ability of Cu-K metal coconut shell activated carbon to remove NO (a), (b)^[68] and reaction mechanism (c), (d)^[69−70]

(with permission from Elsevier)

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图 8 金属Cu和Co促进炭脱除NO的影响^[71]

Figure 8 Effect of metal Cu and Co on promoting carbon removal of NO^[71]

(with permission from Elsevier)

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图 9 铁和钙催化剂转化NH₃的循环机制^[75]

Figure 9 Cycling mechanism of iron and calcium catalysts for NH₃ conversion^[75]

(with permission from Elsevier)

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图 10 大豆蛋白热解氮的迁移转化路径^[76]

Figure 10 The migration and transformation pathway of pyrolytic nitrogen of soybean protein^[76]

(with permission from Elsevier)

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表 1 部分典型生物质化学组成

Table 1 chemical composition of partial typical biomass

Material	Proximate analysis/%				Ultimate analysis/%					Q_HHV/(MJ·kg⁻¹)	Reference
Material	M	V	A	FC	N	C	H	S	O^a	Q_HHV/(MJ·kg⁻¹)	Reference
Almond shell (ar)	11.0	69.6	1.30	18.10	0.50	49.38	5.23	−	44.76	17.92	[12]
Pine sawdust (ar)	1.67	84.27	1.02	13.04	0.72	34.65	4.13	−	45.8	−	[13]
Cow dung (ar)	4.35	73.71	21.40	0.54	1.53	24.39	3.08	−	40.2	−
Kidney bean stura (ar)	4.25	82.4	1.84	11.51	1.67	38.19	6.10	−	54.01	−
Bamboo (ar)	3.37	71.81	16.58	8.24	0.90	27.22	3.42	−	43.8	−
Penicillin residue（db）	−	78.51	8.09	13.40	8.04	48.07	6.96	0.57	36.36	19.28	[14]
Hygromycin residue（db）	−	73.09	14.85	11.25	10.93	50.60	7.17	0.81	30.49	19.33	[14]
Soybean straw（db）		77.77	5.32	16.91	1.40	46.74	6.59	0.06	45.21	−	[15]
Fibreboard（db）		83.56	0.30	16.13	7.49	44.79	6.16	0.01	41.55	−	[15]
Cellulose (ar)	4.76	96.66	0.05	3.34	0.00	43.44	6.42	0.00	50.14	−	[16]
Hemicellulose (ar)	4.32	90.81	0.12	9.19	0.01	41.76	6.72	0.00	51.51	−
Lignin (ar)	5.33	65.74	16.40	34.26	0.03	61.48	5.86	3.08	29.55	−
Protein (ar)	8.78	83.25	4.59	16.75	14.90	51.07	7.72	1.12	25.19	−
-: no tested，^a: indicated difference calculation, ar: as received，db: dry basis.

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