HZSM-5分子筛催化木质素热解制芳烃研究进展

doi:10.16085/j.issn.1000-6613.2023-2158

化工进展 ›› 2024, Vol. 43 ›› Issue (S1): 517-532.DOI: 10.16085/j.issn.1000-6613.2023-2158

HZSM-5分子筛催化木质素热解制芳烃研究进展

万震¹^,²(), 王绍庆², 李志合²(), 赵天生¹()

^1.宁夏大学化学化工学院省部共建煤炭高效利用与绿色化工国家重点实验室，宁夏银川 750021
^2.山东理工大学农业工程与食品科学学院，山东省清洁能源工程技术研究中心，山东淄博 255000

收稿日期:2023-12-06 修回日期:2024-07-23 出版日期:2024-11-20 发布日期:2024-12-06
通讯作者: 李志合,赵天生
作者简介:万震（1997—），男，博士研究生，研究方向为应用催化。E-mail：wanzhen202108@163.com。
基金资助:
国家自然科学基金(52176192)

Advances in HZSM-5 catalyzed pyrolysis of lignin to aromatic hydrocarbons

WAN Zhen¹^,²(), WANG Shaoqing², LI Zhihe²(), ZHAO Tiansheng¹()

^1.State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry & Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China
^2.Shandong Research Center of Engineering and Technology for Clean Energy, School of Agricultural Engineering and Food Science, Shandong University of Technology, Zibo 255000, Shandong, China

Received:2023-12-06 Revised:2024-07-23 Online:2024-11-20 Published:2024-12-06
Contact: LI Zhihe, ZHAO Tiansheng

摘要/Abstract

摘要：

芳烃是重要的有机化工产品原料，也是汽油的重要混合组分，传统获取途径来自石油路线。石油的持续消耗与日渐枯竭迫使人们从可再生生物质资源路线获取芳烃。生物质中的木质素具有丰富的芳香结构组成，是生产芳烃的潜在原料。HZSM-5分子筛催化木质素热解转化制芳烃受到关注，然而存在产物选择性差、催化剂易积炭失活等问题。本文分析了HZSM-5理化特性、反应条件对芳烃产物分布影响；综述了金属改性、脱硅改性、复合介孔催化剂、辅助催化等改性方式，通过调变催化剂的酸性、孔道、传质扩散等提高生物油产物中单环芳烃的分布以及催化剂的稳定性。提出了该催化热解转化过程研究的未来方向，如根据目标芳烃产物选择HZSM-5改性策略、深入揭示其催化作用和积炭机理等。

关键词: HZSM-5, 改性, 辅助催化, 木质素, 热解, 芳烃

Abstract:

Aromatic hydrocarbons (AHCs) are important raw materials of organic chemicals and blending components of gasoline, which are traditionally derived from petroleum route. Obtaining AHCs from renewable biomass resources is demanded due to the growing consumption of petroleum. Lignin, one of the components of biomass with rich aromatics, is a potential raw material for the production of AHCs. Efficient transformation of lignin to AHCs by catalyzed pyrolysis over HZSM-5 molecular sieve has attracted increasing attention, although this process faces low selectivity of target products, easy coke deposition on HZSM-5, and so on. The influences of HZSM-5 physicochemical properties and reaction conditions on the distribution of aromatic products were analyzed. Regulating the acidity, porosity, and mass transfer/diffusion of the catalysts, by metal addition, desilication, combining mesoporous catalysts, and assisted catalysis, enhanced the distribution of mono-aromatic hydrocarbons in bio-oils and the catalytic stability. Future development directions for this catalytic pyrolysis transformation were proposed including rational selection of the HZSM-5 modification strategy according to the target aromatic products, in-depth understanding of the catalysis and the carbon-accumulation mechanism.

Key words: HZSM-5, modification, assisted catalysis, lignin, pyrolysis, aromatic hydrocarbons

中图分类号:

万震, 王绍庆, 李志合, 赵天生. HZSM-5分子筛催化木质素热解制芳烃研究进展[J]. 化工进展, 2024, 43(S1): 517-532.

WAN Zhen, WANG Shaoqing, LI Zhihe, ZHAO Tiansheng. Advances in HZSM-5 catalyzed pyrolysis of lignin to aromatic hydrocarbons[J]. Chemical Industry and Engineering Progress, 2024, 43(S1): 517-532.

图/表 16

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85	WANG Shaoqing, LI Zhihe, BAI Xueyuan, et al. Catalytic pyrolysis of lignin in a cascade dual-catalyst system of modified red mud and HZSM-5 for aromatic hydrocarbon production[J]. Bioresource Technology, 2019, 278: 66-72.
86	WANG Shaoqing, LI Zhihe, YI Weiming, et al. Renewable aromatic hydrocarbons production from catalytic pyrolysis of lignin with Al-SBA-15 and HZSM-5: Synergistic effect and coke behaviour[J]. Renewable Energy, 2021, 163: 1673-1681.
87	FAN Liangliang, CHEN Paul, ZHANG Yaning, et al. Fast microwave-assisted catalytic co-pyrolysis of lignin and low-density polyethylene with HZSM-5 and MgO for improved bio-oil yield and quality[J]. Bioresource Technology, 2017, 225: 199-205.
88	Sumin RYU, LEE Hyung Won, KIM Young-Min, et al. Catalytic fast co-pyrolysis of organosolv lignin and polypropylene over in situ red mud and ex-situ HZSM-5 in two-step catalytic micro reactor[J]. Applied Surface Science, 2020, 511: 145521.
89	WAN Zhen, LI Zhihe, YI Weiming, et al. Lignin and spent bleaching clay into mono-aromatic hydrocarbons by a cascade dual catalytic pyrolysis system: Critical role of spent bleaching clay[J]. International Journal of Biological Macromolecules, 2023, 236: 123879.

木质素来源	原料∶催化剂	催化剂接触方式	Si/Al	温度 /℃	活性评价方式	芳烃产率/%	文献
碱性	1∶4	原位	15	650	Py-GC/MS	34^①	[20]
			25			32^①
			55			22^①
			210			8^①
黑液	1∶2	非原位	25	650	Py-GC/MS	35.5^②	[21]
			50			41.4^②
			210			50.8^②
麦草	1∶2	原位	25	500	连续式热解	30^④	[22]
有机溶剂	—	原位	25	550	Py-GC/MS	26^②	[23]
秸秆	—	非原位	23	600	连续式热解	70^①	[24]
Kraft	1∶1	原位	30	500	固定床	7^③	[25]
醋酸	1∶2	非原位	25	500	固定床	93^②	[26]
碱性	1∶5	原位	23	600	Py-GC/MS/FID	7.63^③	[27]
			50			2.27^③
			80			1.32^③
杉木	1∶2	非原位	25	650	Py-GC/MS	63.72^②	[28]
			50			49.19^②
			210			17.82^②
稻草			25			67.27^②
			50			66.62^②
			210			21.42^②
杨木磨木	1∶1	非原位	30	600	Py-GC/MS/FID	2.62^③	[29]
杨木磨木	1∶1	非原位	280	600	Py-GC/MS/FID	0.76^③	[29]
糠醛渣	1∶1	原位	—	500	Py-GC/MS	27.00^②	[31]
			—	650		59.20^②
			—	800		62.28^②
磨木	1∶5	非原位	25	650	Py-GC/MS	6.3×10^⑤	[32]
碱性						3.5×10^⑤
Klason						3.1×10^⑤
醇解						4.0×10^⑤
碱性	7∶3	非原位	80	550	微波固定床	37^②	[33]
碱性	7∶3	原位	80	550	微波固定床	23^②	[33]
有机溶剂	1∶4	非原位	30	600	Py-GC/MS	16.4^③	[34]
有机溶剂	1∶3	原位	30	600	Py-GC/MS	23^③	[34]

木质素来源	原料∶催化剂	催化剂接触方式	Si/Al	温度 /℃	活性评价方式	芳烃产率/%	文献
碱性	1∶4	原位	15	650	Py-GC/MS	34^①	[20]
			25			32^①
			55			22^①
			210			8^①
黑液	1∶2	非原位	25	650	Py-GC/MS	35.5^②	[21]
			50			41.4^②
			210			50.8^②
麦草	1∶2	原位	25	500	连续式热解	30^④	[22]
有机溶剂	—	原位	25	550	Py-GC/MS	26^②	[23]
秸秆	—	非原位	23	600	连续式热解	70^①	[24]
Kraft	1∶1	原位	30	500	固定床	7^③	[25]
醋酸	1∶2	非原位	25	500	固定床	93^②	[26]
碱性	1∶5	原位	23	600	Py-GC/MS/FID	7.63^③	[27]
			50			2.27^③
			80			1.32^③
杉木	1∶2	非原位	25	650	Py-GC/MS	63.72^②	[28]
			50			49.19^②
			210			17.82^②
稻草			25			67.27^②
			50			66.62^②
			210			21.42^②
杨木磨木	1∶1	非原位	30	600	Py-GC/MS/FID	2.62^③	[29]
杨木磨木	1∶1	非原位	280	600	Py-GC/MS/FID	0.76^③	[29]
糠醛渣	1∶1	原位	—	500	Py-GC/MS	27.00^②	[31]
			—	650		59.20^②
			—	800		62.28^②
磨木	1∶5	非原位	25	650	Py-GC/MS	6.3×10^⑤	[32]
碱性						3.5×10^⑤
Klason						3.1×10^⑤
醇解						4.0×10^⑤
碱性	7∶3	非原位	80	550	微波固定床	37^②	[33]
碱性	7∶3	原位	80	550	微波固定床	23^②	[33]
有机溶剂	1∶4	非原位	30	600	Py-GC/MS	16.4^③	[34]
有机溶剂	1∶3	原位	30	600	Py-GC/MS	23^③	[34]

木质素来源	金属	负载量/%	制备方法	芳烃产率/%	芳烃选择性/%					文献
木质素来源	金属	负载量/%	制备方法	芳烃产率/%	MAHCs	B	T	X	PAHCs	文献
杉木	Mg	2	浸渍	—	—	12	19.5	20.82	—	[42]
杨木				—	—	14.5	21	18	—
玉米秸秆				—	—	15	22	17	—
工业	Zn	1	浸渍	48.9	43.35	—	14.11	26.18	56.65	[46]
杉木		2		—	—	22.34	24.40	18	—	[42]
杨木				—	—	18.61	25.89	19.5	—
玉米秸秆				—	—	23.84	22.5	17.5	—
工业	Fe	1	浸渍	43.7	44.62	—	9.38	30.66	55.38	[43]
柳枝		1.4	离子交换	5.5^①	72.24	9.99	36.97	21.57	27.76	[44]
		2.4		2.9^①	72.02	8.79	33.80	25.84	27.98
		4.2		3.2^①	71.38	11.37	34.46	22.35	28.62
工业	Co	0.5	浸渍	41.8	63.40	—	19.86	38.04	36.60	[43]
		1		51.1	54.01	—	19.18	31.31	45.99
		2		37.3	59.25	—	10.99	39.14	40.75
		5		28.4	44.01	—	9.51	24.30	55.99
工业	Ni	1	浸渍	41.3	31.96	—	10.90	16.95	68.04
玉米秸秆		2		19.23^①	78.46	28.34	22.78	7.45	21.54	[45]
火炬松				14.19^①	82.73	26.88	27.92	11.10	17.27
红橡木				14.96^①	83.50	23.72	27.30	14.02	16.50
玉米秸秆	Mo	2	混合煅烧	27.06^①	91.68	37.54	32.01	9.74	8.32
火炬松				22.86^①	94.48	34.97	37.96	14.30	5.52
红橡木				20.67^①	94.54	26.62	39.48	18.32	5.46
工业	Cu	1	浸渍	46.6	40.99	—	10.52	26.82	59.01	[46]
工业	Ga	1	浸渍	49.4	40.08	—	11.94	25.10	59.92	[46]
杉木		2		—	—	17	22.5	17	—	[42]
杨木				—	—	17.5	21.5	19	—
玉米秸秆				—	—	10	25.74	23.83	—

木质素来源	金属	负载量/%	制备方法	芳烃产率/%	芳烃选择性/%					文献
木质素来源	金属	负载量/%	制备方法	芳烃产率/%	MAHCs	B	T	X	PAHCs	文献
杉木	Mg	2	浸渍	—	—	12	19.5	20.82	—	[42]
杨木				—	—	14.5	21	18	—
玉米秸秆				—	—	15	22	17	—
工业	Zn	1	浸渍	48.9	43.35	—	14.11	26.18	56.65	[46]
杉木		2		—	—	22.34	24.40	18	—	[42]
杨木				—	—	18.61	25.89	19.5	—
玉米秸秆				—	—	23.84	22.5	17.5	—
工业	Fe	1	浸渍	43.7	44.62	—	9.38	30.66	55.38	[43]
柳枝		1.4	离子交换	5.5^①	72.24	9.99	36.97	21.57	27.76	[44]
		2.4		2.9^①	72.02	8.79	33.80	25.84	27.98
		4.2		3.2^①	71.38	11.37	34.46	22.35	28.62
工业	Co	0.5	浸渍	41.8	63.40	—	19.86	38.04	36.60	[43]
		1		51.1	54.01	—	19.18	31.31	45.99
		2		37.3	59.25	—	10.99	39.14	40.75
		5		28.4	44.01	—	9.51	24.30	55.99
工业	Ni	1	浸渍	41.3	31.96	—	10.90	16.95	68.04
玉米秸秆		2		19.23^①	78.46	28.34	22.78	7.45	21.54	[45]
火炬松				14.19^①	82.73	26.88	27.92	11.10	17.27
红橡木				14.96^①	83.50	23.72	27.30	14.02	16.50
玉米秸秆	Mo	2	混合煅烧	27.06^①	91.68	37.54	32.01	9.74	8.32
火炬松				22.86^①	94.48	34.97	37.96	14.30	5.52
红橡木				20.67^①	94.54	26.62	39.48	18.32	5.46
工业	Cu	1	浸渍	46.6	40.99	—	10.52	26.82	59.01	[46]
工业	Ga	1	浸渍	49.4	40.08	—	11.94	25.10	59.92	[46]
杉木		2		—	—	17	22.5	17	—	[42]
杨木				—	—	17.5	21.5	19	—
玉米秸秆				—	—	10	25.74	23.83	—

供氢原料	催化剂	反应装置	芳烃产率/%	芳烃选择性/%					文献
供氢原料	催化剂	反应装置	芳烃产率/%	MAHCs	B	T	X	PAHCs	文献
四氢化萘	HZSM-5	Py-GC/MS	35.93^①	59.50	43.33	11.33	3.92	40.50	[74]
废油	ZSM-5/MCM-41	微波固定床	50^①	75.81	—	—	—	24.19	[75]
废弃食用油	HZSM-5	Py-GC/MS	86.3^①	83.78	8	20	20	16.22	[76]
丙酮	Co/HZSM-5	固定床	24.25^②	95.05	49.24	35.63	6.06	4.95	[77]
丙酮	Fe/HZSM-5	固定床	36.51^②	96.80	—	—	—	3.2	[77]
聚乙烯	HZSM-5	Py-GC/MS	26.3^①	—	—	—	—	—	[78]

HZSM-5分子筛催化木质素热解制芳烃研究进展

Advances in HZSM-5 catalyzed pyrolysis of lignin to aromatic hydrocarbons

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