Progress in co-pyrolysis technology of agricultural biomass and plastics

doi:10.16085/j.issn.1000-6613.2021-2511

Abstract

Abstract:

Co-pyrolysis technology is an important means to convert a variety of raw materials into clean energy through thermochemical methods. This paper reviewed mainly about the co-pyrolysis technology development status and the research progress of the agricultural biomass resources and plastics such as polypropylene (PP), high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyvinyl chloride (PVC), polystyrene (PS) and polyethylene terephthalate (PET), etc, in recent years. The kinetic model and the law of synergy between the components of co-pyrolysis of common agricultural biomass with plastics were analyzed and the co-pyrolysis mechanism of agricultural biomass and plastics was claimed. The influence of temperature, heating rate, residence time, the mixing ratio of raw materials and other factors on co-pyrolysis were concluded. The characteristics and distribution law of co-pyrolysis products of biomass and plastics were analyzed in this paper. In terms of solid products, biochar obtained from co-pyrolysis of biomass and plastics had high calorific value and high porosity, which can be used as cheap absorbent, carbon coating, solid fuel and soil amendment, etc. In terms of liquid products, liquid obtained from co-pyrolysis of biomass and plastics had lower water content, oxygen content, acid content and higher calorific value, and the viscosity coefficient of liquid products can be changed. The liquid can be used as aviation fuel by upgrading. In terms of gas products, syngas obtained from co-pyrolysis of biomass and plastics had higher heating value, which can be used as energy for daily life. Consequently, the advantages and disadvantages of the co-pyrolysis technology of biomass and plastics were summarized and the future development direction of biomass and plastic co-pyrolysis technology was prospected. This paper can provide a theoretical reference for the co-pyrolysis of biomass and plastic to prepare high value-added products, and new methods and new ideas for the treatment of agricultural biomass and agricultural film.

Key words: agricultural biomass, plastics, co-pyrolysis, technical progress, agricultural film

摘要：

共热解技术是将多种原料通过热化学方法转化为清洁能源的重要手段。本文综述了以农业生物质为主要原料与塑料（聚丙烯PP、高密度聚乙烯HDPE、低密度聚乙烯LDPE、聚氯乙烯PVC、聚苯乙烯PS、聚对苯二甲酸乙二醇酯PET等）共热解技术的发展现状和研究进展。分析农业生物质与塑料共热解的动力学模型以及各组分之间的协同效应，阐述农业生物质与塑料的共热解机理；总结了温度、升温速率、滞留时间、原料混配比等因素对共热解协同作用的影响规律；探究生物质与塑料共热解固、液、气三相产物特性及分布规律，总结共热解技术优势及存在问题，展望未来发展方向，可为生物质与塑料共热解制备高附加值产品提供参考，同时也为农业生物质和农膜处理问题提供新方法、新思路。

关键词: 农业生物质, 塑料, 共热解, 技术进展, 农膜

CLC Number:

XIE Teng, ZHAO Lixin, YAO Zonglu, HUO Lili, JIA Jixiu, ZHANG Peizhen, TIAN Liwei, FU Guohao. Progress in co-pyrolysis technology of agricultural biomass and plastics[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5306-5315.

谢腾, 赵立欣, 姚宗路, 霍丽丽, 贾吉秀, 张沛祯, 田利伟, 傅国浩. 农业生物质与塑料共热解技术进展[J]. 化工进展, 2022, 41(10): 5306-5315.

Figures/Tables 4

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原料	活化能E/kJ·mol^-1	指前因子A/min^-1	参考文献
纤维素	127~157.32	7.89×10¹²	［17， 27］
棉花秸秆	38.9~79.48	1.26×10⁴~6.63×10⁹	［13］
小麦秸秆	44.9~250.6	—	［25， 27］
木屑	97.9（E_m）	4.5×10⁷	［28］
玉米秸秆	26.13~177.3	2.39×10⁵~2.76×10⁷	［19，23，26］
PP	100.43~294.62	6.88×10¹⁵	［16］
PVC	108.12~246.78	8.3×10⁸~1.8×10²³	［13］
PS	273.74	3.42×10²⁰	［16，24］
HDPE	212.8~302.81	1.14×10¹⁴~5.29×10²⁰	［16，24，26］
LDPE	213.78~306.6	3.95×10¹⁴~2.59×10¹⁹	［16-17，24，28］
棉花秸秆/PVC=1/1	51.08~190.13	6.13×10⁷~1.75×10¹³	［13］
纤维素/LDPE=1/1	134.59	5.3×10⁷	［17］
纤维素/LDPE=1/1（催化）	89.51	6.73×10⁵	［17］
木屑/LDPE=1/1	250~380℃时116.5~132.9； 380~480℃时143.7~202.2； 480~530℃时293.6~486.8	5.5×10⁸； 5.3×10²¹； 5.5×10²⁷	［28］
玉米秸秆/HDPE=4/1	170.7（E_m）	—	［19，26］
玉米秸秆/HDPE=3/2	208.1（E_m）	—
玉米秸秆/HDPE=2/3	211.5（E_m）	—
玉米秸秆/HDPE=1/4	220.3（E_m）	—
玉米秸秆/HDPE=1/1	98.35~392.67	3.26×10⁴~9.19×10²³

原料	活化能E/kJ·mol^-1	指前因子A/min^-1	参考文献
纤维素	127~157.32	7.89×10¹²	［17， 27］
棉花秸秆	38.9~79.48	1.26×10⁴~6.63×10⁹	［13］
小麦秸秆	44.9~250.6	—	［25， 27］
木屑	97.9（E_m）	4.5×10⁷	［28］
玉米秸秆	26.13~177.3	2.39×10⁵~2.76×10⁷	［19，23，26］
PP	100.43~294.62	6.88×10¹⁵	［16］
PVC	108.12~246.78	8.3×10⁸~1.8×10²³	［13］
PS	273.74	3.42×10²⁰	［16，24］
HDPE	212.8~302.81	1.14×10¹⁴~5.29×10²⁰	［16，24，26］
LDPE	213.78~306.6	3.95×10¹⁴~2.59×10¹⁹	［16-17，24，28］
棉花秸秆/PVC=1/1	51.08~190.13	6.13×10⁷~1.75×10¹³	［13］
纤维素/LDPE=1/1	134.59	5.3×10⁷	［17］
纤维素/LDPE=1/1（催化）	89.51	6.73×10⁵	［17］
木屑/LDPE=1/1	250~380℃时116.5~132.9； 380~480℃时143.7~202.2； 480~530℃时293.6~486.8	5.5×10⁸； 5.3×10²¹； 5.5×10²⁷	［28］
玉米秸秆/HDPE=4/1	170.7（E_m）	—	［19，26］
玉米秸秆/HDPE=3/2	208.1（E_m）	—
玉米秸秆/HDPE=2/3	211.5（E_m）	—
玉米秸秆/HDPE=1/4	220.3（E_m）	—
玉米秸秆/HDPE=1/1	98.35~392.67	3.26×10⁴~9.19×10²³

原料	试验条件	质量混配比	固态产物		液态产物（A+T）		参考文献
原料	试验条件	质量混配比	产率/%	热值/MJ·kg^-1	产率/%	热值/MJ·kg^-1	参考文献
纤维素/LDPE	竖式固定床：10℃∙min^-1；550℃；30min；N₂；外管道保温140~160℃	1∶0	22.0	33.9	33.0+9	17.8	［35］
纤维素/LDPE		0∶1	—		70.0	46.3
纤维素/LDPE		1∶1	8.0	34.8	66	37.8
木屑/PS	固定床：10℃∙min^-1；500℃；N₂	1∶0	31.3	—	48.8	17.8	［61］
木屑/PS		0∶1	4.9	—	77.8	41.7
木屑/PS		1∶3			39.2	39.7
棕榈壳/HDPE	固定床：5℃∙min^-1；550℃；30min；N₂	1∶0	28.2	—	21.1+18.0		［47］
棕榈壳/HDPE		0∶1			56
棕榈壳/HDPE		1∶2	9.3		50.9+15.4
棕榈壳/HDPE		1∶1	15.6		41.4+10.0
棕榈壳/HDPE		2∶1	20.0		37.9+13.9
核桃壳/PET	固定床：10℃∙min^-1；500℃；30min；N₂	1∶1	25.9	32.0	28.9	25.1	［62］
核桃壳/PVC		1∶1	20.0	31.3	17.6（T）	40.5
核桃壳/PS		1∶1		27.1	44.8	31.5
核桃壳			30.6	28.9	20.8	24.4
废报纸/HDPE	固定床：10℃∙min^-1；500℃；N₂	1∶2	8.0		54.7+13.8		［60］
废报纸/HDPE		1∶1	14.5		55.5	26.8~34.8
废报纸/HDPE		2∶1	16.5		52.0
废报纸/HDPE		1∶0	29.8	—	40.5	17.0
废报纸/HDPE		0∶1	1.0	—	52.8	43.8
棕榈壳/PS	固定床：10℃∙min^-1；600℃，60min；N₂ 2L·min^-1	1∶1			61.6	38.0	［59］
棕榈壳/PS		4∶1	27.8		47.7
棕榈壳/PS		7∶3	23.2		49.9
棕榈壳/PS		3∶2	20.2		59.1
棕榈壳/PS		1∶0	31.7	—	46.1	11.9
棕榈壳/PS	固定床：600℃，45min	2∶3			68.3	40.3	［58］

原料	试验条件	质量混配比	固态产物		液态产物（A+T）		参考文献
原料	试验条件	质量混配比	产率/%	热值/MJ·kg^-1	产率/%	热值/MJ·kg^-1	参考文献
纤维素/LDPE	竖式固定床：10℃∙min^-1；550℃；30min；N₂；外管道保温140~160℃	1∶0	22.0	33.9	33.0+9	17.8	［35］
纤维素/LDPE		0∶1	—		70.0	46.3
纤维素/LDPE		1∶1	8.0	34.8	66	37.8
木屑/PS	固定床：10℃∙min^-1；500℃；N₂	1∶0	31.3	—	48.8	17.8	［61］
木屑/PS		0∶1	4.9	—	77.8	41.7
木屑/PS		1∶3			39.2	39.7
棕榈壳/HDPE	固定床：5℃∙min^-1；550℃；30min；N₂	1∶0	28.2	—	21.1+18.0		［47］
棕榈壳/HDPE		0∶1			56
棕榈壳/HDPE		1∶2	9.3		50.9+15.4
棕榈壳/HDPE		1∶1	15.6		41.4+10.0
棕榈壳/HDPE		2∶1	20.0		37.9+13.9
核桃壳/PET	固定床：10℃∙min^-1；500℃；30min；N₂	1∶1	25.9	32.0	28.9	25.1	［62］
核桃壳/PVC		1∶1	20.0	31.3	17.6（T）	40.5
核桃壳/PS		1∶1		27.1	44.8	31.5
核桃壳			30.6	28.9	20.8	24.4
废报纸/HDPE	固定床：10℃∙min^-1；500℃；N₂	1∶2	8.0		54.7+13.8		［60］
废报纸/HDPE		1∶1	14.5		55.5	26.8~34.8
废报纸/HDPE		2∶1	16.5		52.0
废报纸/HDPE		1∶0	29.8	—	40.5	17.0
废报纸/HDPE		0∶1	1.0	—	52.8	43.8
棕榈壳/PS	固定床：10℃∙min^-1；600℃，60min；N₂ 2L·min^-1	1∶1			61.6	38.0	［59］
棕榈壳/PS		4∶1	27.8		47.7
棕榈壳/PS		7∶3	23.2		49.9
棕榈壳/PS		3∶2	20.2		59.1
棕榈壳/PS		1∶0	31.7	—	46.1	11.9
棕榈壳/PS	固定床：600℃，45min	2∶3			68.3	40.3	［58］

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