纤维素生物质与废塑料共催化热解制取富烃液体燃料的研究进展

马中青; 丁紫霞; 李逍然; 朱亮; 岑珂慧; 黄明; 陈登宇

doi:10.19906/j.cnki.JFCT.2023070

纤维素生物质与废塑料共催化热解制取富烃液体燃料的研究进展

doi: 10.19906/j.cnki.JFCT.2023070

马中青^1,,
丁紫霞^1,,
李逍然^2,,
朱亮^1,,
岑珂慧^2,,
黄明^1,,
陈登宇^2, ,

1.
浙江农林大学化学与材料工程学院, 浙江杭州 311300
2.
南京林业大学材料科学与工程学院, 江苏南京 210037

基金项目: 国家自然科学基金（52076112），浙江省自然科学基金（LY21E060001）和浙江省 “领雁”研发攻关计划（2022C03092）资助

详细信息

作者简介:
马中青，男，博士，副教授，主要从事生物质热化学转化研究工作，Email: mazq@zafu.edu.cn

通讯作者:
E-mail: chendy@njfu.edu.cn

中图分类号: TK6
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- 被引次数: 0
出版历程
- 收稿日期: 2023-05-26
- 修回日期: 2023-06-27
- 录用日期: 2023-07-14
- 网络出版日期: 2023-09-18

Recent progress on co-catalytic fast pyrolysis of biomass and waste plastics to produce hydrocarbon-rich liquid fuels

MA Zhongqing^1
,,
DING Zixia^1
,,
LI Xiaoran^2
,,
ZHU Liang^1
,,
CEN Kehui^2
,,
Huang Ming^1
,,
CHEN Dengyu^{2
, ,}

1.
College of Chemistry and Materials Engineering, Zhejiang A & F University, Hangzhou, 311300, China
2.
College of Materials Science and Engineering, Nanjing Forestry University, Nanjing, 210037, China

Funds: The project was supported by the National Natural Science Foundation of China (52076112), the Natural Science Foundation of Zhejiang Province (LY21E060001), the Key R & D Program of Zhejiang Province (2022C03092).

摘要

摘要: 生物质能是国际公认的零碳可再生能源，其高效利用成为缓解能源与环境危机的关键，并对中国实现“碳达峰”和 “碳中和”的目标具有重要意义。纤维素生物质与废塑料的共催化热解技术，不仅能制备高附加值的富烃液体燃料，还可达到“以废治废”的目的，进而实现生物质与废塑料的高效资源化利用。本工作从生物质与废塑料高值化利用的角度出发，对生物质和废塑料共催化热解制备富烃液体燃料的研究现状进行了综述，介绍了纤维素生物质和废塑料的基础化学特性差异，论述了废塑料种类、催化剂种类、物料和催化剂比例、催化热解温度等因素对生物质和废塑料共催化热解生物油产率和品质的影响；阐述了生物质和废塑料单独催化热解过程中的化学反应机理；并揭示了共催化热解过程中的协同反应机理；展望了该领域未来的发展方向。为生物质与废塑料的高附加值利用提供参考与思路。
- 生物质 /
- 塑料 /
- 共催化热解 /
- 催化剂 /
- 富烃液体燃料
Abstract: Biomass energy is recognized as a zero carbon renewable energy source, and the efficient utilization of biomass has become the key to address the energy and environmental crises. It is of great important for China to achieve the goals of “carbon peaking” and “carbon neutrality”. The co-catalytic pyrolysis technology (co-CFP) of biomass and waste plastics can not only produce the value-added hydrocarbon-rich liquid fuels, but achieve the goal of “treating waste with waste” as well, thereby achieving efficient resource utilization of biomass and waste plastics. From the perspective of high value utilization of biomass and waste plastics, this work reviewed the research progress of the co-CFP of biomass and waste plastics to produce hydrocarbon-rich liquid fuels. First, the basic chemical characteristics of cellulose biomass and waste plastics were introduced. The influence of the catalytic pyrolysis temperature, the types of waste plastics, the types of catalyst, the mass ratio of feedstock-to- catalyst on the yield and quality of bio-oil during the co-CFP of biomass and waste plastics was systematically discussed. The synergistic reaction mechanism between biomass and waste plastics was elucidated. Finally, the work forecasted the future development direction of the co-CFP of biomass and waste plastics, and provided reference and ideas for the high value-added utilization of biomass and waste plastics.
- biomass /
- plastic /
- co-catalytic fast pyrolysis /
- catalyst /
- hydrocarbon-rich liquid fuels

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图 1 纤维素生物质和废塑料的基本化学结构

Figure 1 Chemical structure of lignocellulosic biomass and waste plastics

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图 2 生物质和废塑料共催化热解过程中不同种类的催化剂

Figure 2 Different types of catalysts employed in the co-catalytic fast pyrolysis of lignocellulosic biomass and waste plastics

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图 3 纤维素生物质和废塑料的两段式催化热解机理示意图

Figure 3 Chemical reaction mechanism of the dual-catalyst CFP of lignocellulosic biomass and waste plastics

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图 4 纤维素生物质和LDPE在HZSM-5催化剂作用下的协同反应机理

Figure 4 Synergistic reaction mechanism during Co-CFP of lignocellulosic biomass and LDPE by using HZSM-5 as catalyst

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表 1 纤维素生物质和塑料的元素分析和工业分析

Table 1 Elemental and proximate analysis of lignocellulosic biomass and waste plastics

Sample	Ultimate analysis w/%						Proximate analysis w/%			H/C_eff	HHV/ (MJ·kg⁻¹)
Sample	C	H	O	N	S	Cl	V	FC	A	H/C_eff	HHV/ (MJ·kg⁻¹)
Lignocellulosic biomass
Woody biomass, pine wood^[12]‎‪	49.33	6.06	44.57	0.04	0.00	0.00	73.40	16.70	0.50	0.12	19.80
Woody biomass, poplar wood^[13]	47.21	6.04	46.74	0.01	0.00	0.00	87.95	10.93	1.12	0.05	18.58
Woody biomass, fir wood^[14]	49.07	6.70	44.18	0.02	0.03	0.00	81.93	17.75	0.32	0.29	20.29
Herbaceous biomass, rice straw^[15]	36.07	5.20	57.83	0.64	0.26	0.00	78.07	6.93	15.00	−0.67	12.53
Herbaceous biomass, wheat straw^[15]	38.34	5.47	55.22	0.60	0.37	0.00	83.08	10.29	6.63	−0.45	13.96
Fruit shell biomass, palm kernel shell^[14]	48.44	6.23	44.99	0.31	0.03	0.00	71.72	25.21	3.07	0.15	20.30
Fruit shell biomass, walnut shell^[16]	47.30	6.10	42.00	0.50	0.10	0.00	76.60	19.40	4.00	0.22	19.11
Waste plastics
Polyethylene (PE)^[17]	85.50	14.50	0.00	0.00	0.00	0.00	99.96	0.04	0.00	2.04	46.01
High density polyethylene (HDPE)^[6]	85.16	14.48	0.31	0.02	0.03	0.00	99.85	0.06	0.09	2.03	49.63
Low density polyethylene (LDPE)^[13]	84.21	14.29	1.47	0.03	0.00	0.00	99.79	0.21	0.00	2.01	48.83
Linear low density polyethylene (LLDPE)^[18]	85.61	14.29	0.02	0.05	0.03	0.00	99.85	0.07	0.05	2.00	46.17
Polypropylene (PP)^[19]	84.70	15.30	0.00	0.00	2.10	0.00	96.90	0.00	1.00	2.17	45.23
Polystyrene (PS)^[17]	92.20	7.80	0.00	0.00	0.00	0.00	99.50	0.50	0.00	1.02	40.49
Polyvinyl chloride (PVC)^[20]	38.70	4.80	0.00	0.00	0.00	56.5	95.80	4.20	0.00	1.49	19.30
Polyethylene terephthalate (PET)^[19]	64.10	3.70	34.20	0.00	0.00	0.00	84.10	13.90	0.00	−0.01	24.15
H/C_eff: hydrogen-to-carbon effective ratio

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表 2 基于HZSM-5分子筛催化剂的生物质与废塑料共催化热解的相关研究

Table 2 Catalytic co-pyrolysis of biomass and waste plastics by using HZSM-5 as catalyst

Biomas	Plastic	Mass ratio of biomass-to-plastic	Catalyst	Pyrolysis Temperature /℃	Pyrolysis device	Main conclusion
Corn stalk	HDPE	1:1	HZSM-5	400−800	Py–GC/MS	The H/C_eff ratio of feedstock should be adjusted to be >1.0 so that achieved high content of aromatics^[21]
Switchgrass	HDPE	1:1	HZSM-5	650	Py–GC/MS	The addition of HDPE is beneficial for the generation of aromatics and reduces coke deposition^[22]
Red oak	PE	1:1	HZSM-5	500−700	Py–GC/MS	Higher pyrolysis or catalyst temperatures promoted the yield of aromatic hydrocarbons monotonically^[23]
Pine sawdust	PE	1:1	HZSM-5	400−650	Fluidized bed reactor	The maximum carbon yield of petrochemicals (71%) was obtained at 600 ℃ and polyethylene/ pine sawdust ratio of 4:1^[24]
Cellulose	LDPE	1:1	HZSM-5	650	Py–GC/MS	CFP of the cellulose and LDPE mixture produced a much higher aromatic carbon yield (47.46%)^[25]
Walnut shell	LDPE	1:1	HZSM-5	550	Py–GC/MS	The selectivity toward aromatics is as high as 82.5% during TSCCP process^[16]
Laminaria japonica	PP	1:1	HZSM-5	600	Py–GC/MS	MFI type catalyst showed high catalytic upgrading capability during catalytic co-pyrolysis of polypropylene and Laminaria japonica^[26]
Cellulose	PP	1:3	HZSM-5	550	Py-GC/MS/TCD/FID	The maximum BTEXs yield (33.4%) achieved at the ratio of 3:1 with samples and the ratio of 1:3 with catalyst^[27]
Pine wood	PVC	3:1, 1:1, 1:3	HZSM-5	600	Fixed bed reactor	The interaction of biomass and plastic materials decreased the H/C atomic ratio of char, which resulted in a higher chemical stability of char^[28]
olive pomace / almond shell	PVC	1:2	HZSM-5	650	Py-GC/MS-FGA	BTX yields enhanced up to 25% at biomass/plastic ratio of 1:1.5 with the presence of HZSM-5^[29]
Poplar wood	PET	1:1	HZSM-5	600	TG-GC/MS	The two-stage catalytic co-pyrolysis over in-situ calcium oxide and ex-situ HZSM-5 produced the much larger amounts of BTEXs^[30]
Sugarcane bagasse pith	PET	1:0, 1:1, 1:2, 1:3, 1:4	HZSM-5	400−800	Py–GC/MS	The catalyst combination as well as biomass/plastic mixtures used in this work can lead to both high yields of valuable aromatic chemicals^[31]
Karanja and Niger seeds	PS	1:1, 2:1, 4:1, 8:1	HZSM-5	500−600	Cylindrical furnace	Co-pyrolysis of waste polystyrene and biomass altered the composition of pyrolytic oil which had a positive influence on the quality of co-pyrolytic oil^[32]
Pine sawdust	PS	1:1	HZSM-5	400−650	Fluidized bed reactor	Catalytic co-pyrolysis of polystyrene and pine sawdust produced the highest and lowest yields of aromatics (47%) and olefins (11.4%), respectively^[24]

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