微波辅助/催化热解废油脂制取富烃生物油研究进展

doi:10.3969/j.issn.0253-2417.2021.06.016

林产化学与工业 ›› 2021, Vol. 41 ›› Issue (6): 127-138.doi: 10.3969/j.issn.0253-2417.2021.06.016

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微波辅助/催化热解废油脂制取富烃生物油研究进展

吴秋浩¹^,², 王允圃¹^,²^,*(), 张淑梅¹^,², 曾媛¹^,², 刘玉环¹^,², RUANRoger³

1. 南昌大学生物质转化教育部工程研究中心, 江西南昌 330047
2. 南昌大学食品科学与技术国家重点实验室, 江西南昌 330047
3. 生物精炼中心和生物制品与生物系统工程系, 明尼苏达大学, 圣保罗 55108, 美国

收稿日期:2020-08-26 出版日期:2021-12-28 发布日期:2021-12-31
通讯作者: 王允圃 E-mail:wangyunpu@ncu.edu.cn
作者简介:王允圃, 教授, 硕士生导师, 研究领域为生物质微波热解; E-mail: wangyunpu@ncu.edu.cn
吴秋浩(1996-), 男, 江西上饶人, 硕士生, 主要从事废弃油脂资源化利用研究工作
基金资助:
国家自然科学基金资助项目(21766019);江西省重点研发项目(20171BBF60023);中央引导地方科技发展专项(20202ZDB01012)

Research Progress on Microwave-assisted Catalytic Pyrolysis of Waste Oil for Hydrocarbon-rich Bio-oil

Qiuhao WU¹^,², Yunpu WANG¹^,²^,*(), Shumei ZHANG¹^,², Yuan ZENG¹^,², Yuhuan LIU¹^,², Roger RUAN³

1. Engineering Research Center of Biomass Conversion, Ministry of Education, Nanchang University, Nanchang 330047, China
2. State Key Laboratory of Food Science and Technology, Nanchang University, Nanchang 330047, China
3. Center for Biorefining and Department of Bioproducts and Biosystems Engineering, University of Minnesoa, St. Paul 55108, USA

Received:2020-08-26 Online:2021-12-28 Published:2021-12-31
Contact: Yunpu WANG E-mail:wangyunpu@ncu.edu.cn

摘要/Abstract

摘要：

结合微波辅助热解技术简述了微波加热原理及特性，讨论了废油脂原料特性及微波吸收剂等对产物分布及组成的影响，介绍了废油脂热解中常用的分子筛催化剂和金属氧化物催化剂，论述了微波驱动型催化剂的制备工艺和微波串联体系的搭建及其在废油脂微波热解中的应用研究，并总结了微波加热和电加热在催化体系的应用效果对比。最后，针对微波辅助/催化热解废油脂制备富烃生物油技术面临的挑战及未来研究方向提出了建议，为解决废油脂热解过程中催化剂易结焦失活、产物复杂等难题提供了新思路。

关键词: 微波辅助热解, 废油脂, 催化, 富烃生物油, 再生能源

Abstract:

Combined with the the microwave-assisted pyrolysis technology, microwave heating principle and characteristics were briefly described, and the effects of the characteristics of raw material waste oil and microwave absorbers on the product distribution and composition were discussed. Zeolite catalyst and metal oxide catalysts used in waste oil pyrolysis were introduced. The preparation process of microwave driven catalyst and the establishment of microwave tandem system and its application in microwave pyrolysis of waste oil were reviewed. The application of microwave heating and electrical heating in catalytic system were also discussed. The challenges and future research direction of microwave-assisted fast pyrolysis of waste oil for hydrocarbon-rich bio-oil were put forward, which provided a new idea for solving the problems such as the coking and deactivation of catalysts and the complex composition of bio-oil in the process of waste oil pyrolysis.

Key words: microwave-assisted pyrolysis, waste oil, catalysis, hydrocarbon-rich bio-oil, renewable energy

中图分类号:

吴秋浩, 王允圃, 张淑梅, 曾媛, 刘玉环, RUANRoger. 微波辅助/催化热解废油脂制取富烃生物油研究进展[J]. 林产化学与工业, 2021, 41(6): 127-138.

Qiuhao WU, Yunpu WANG, Shumei ZHANG, Yuan ZENG, Yuhuan LIU, Roger RUAN. Research Progress on Microwave-assisted Catalytic Pyrolysis of Waste Oil for Hydrocarbon-rich Bio-oil[J]. Chemistry and Industry of Forest Products, 2021, 41(6): 127-138.

图/表 8

图1

图2

表1

表2

催化剂在微波辅助热解废油脂中的催化性能对比"

类型¹⁾ type	催化剂 catalyst	温度/℃ temp.	原料与催化剂比例 material to catalyst ratio	原料 material	生物油产率/% bio-oil yield	主要组成²⁾ major component	参考文献 ref.
Ⅰ	ZSM-5	550	16.44∶1	橡胶籽油 rubber seed oil		芳烃aromatic 99.56%(BTX78.68%)	[54]
	ZSM-5	400	2∶1	皂脚 soapstock	22.66	单环芳烃monocyclic aromatic hydrocarbon(58.46%), 多环芳烃polycyclic aromatic hydrocarbon(28.24%)	[20]
	ZSM-5	550	3∶1	废油脂 waste oil		单环芳烃monocyclic aromatic hydrocarbon(58.7±2.6%), 多环芳烃polycyclic aromatic hydrocarbon(12.7±0.4%), 脂肪烃aliphatics(12.4±0.8%), 脂肪酸fatty acid(9.5±0.3%)	[3]
	MCM-41	400	1∶2	乌桕油 Sapium sebiferum kernel oil	63.99	C5-C12脂肪烃aliphatics(49.35%), 单环芳烃monocyclic aromatic hydrocarbon(34.05%), 含氧化合物oxygen-containing compound(8.81%), C12及以上脂肪烃C12 aliphatics and more(7.07%)	[55]
	MCM-41	500	5∶1	废白土油 waste clay oil	88.43±0.81	酸acid(58.22%)、总烃total hydrocarbon(31.40%), 醇alcohol(5.73%)、酮和醛aldehydes and ketones(2.37%)	[50]
Ⅱ	MgO@SBA-15	360	30∶1	废食用油 waste cooking oil	62.5	＜C9烃hydrocarbon(46%^), C10-C12烃hydrocarbon(16.5%^)	[57]
	K₂O/ Ba-MCM-41	420	50∶1	废食用油 waste cooking oil	63.2	十五烷pentadecane(22.75%), 十七烷heptadecane(12.45%), 十六烷cetane(10.10%), 1-十二烯1-laurylene(8.11%), 十四烷tetradecane(7.44%), 十三烷tridecane(7.06%), 十二烷dodecane(5.83%)	[58]
	CaO	500	5∶1	废白土油 waste clay oil	84.57±0.74	总烃total hydrocarbon(68.85%), 酮和醛aldehydes and ketones(23.37%), 酸acid(3.48%), 醇alcohol(1.22%)	[50]
Ⅲ	Na₂CO₃	450	20∶3	棕榈油 palm oil	60	烃hydrocarbon(92.84%), 含氧化合物oxygen-containing compound(7.16%)，不含羧酸non carboxylic acid	[59]
	K₂CO₃	420	50∶1	废食用油 waste cooking oil	57.4	8-十七烯8-heptadecene(14.13%), 十六烷cetane(7.88%), 2-庚烯2-heptylene(6.21%), 壬烷nonane(5.25%)	[58]
	Na₂CO₃	420	50∶1	废食用油 waste cooking oil	57.6	十六烷cetane(13.23%), 癸烷decane(11.71%), 壬烷nonane(11.67%), 1-十三烯1-tridecylene(9.63%), 十二烷dodecane(5.21%)	[58]

表2

表3

图3

表4

图4

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加热方式 heating mode	升温速率/ (℃·min^-1) heating rate	原料 feedstock	温度/℃ temp.	产率/% yield	主要组成¹⁾ major component	参考文献 ref.
微波加热 microwave heating	29	废聚乙烯/废油脂(1∶1)waste polyethylene/waste oil	400	78	烷烃alkane 68%，环烷烃cycloalkane 15%，烯烃alkene 14%，芳烃aromatic 1%，其他the others 2%	[29]
电加热 electric heating	10	废聚乙烯/废油脂(1∶1)waste polyethylene/waste oil	430	~61	烷烃alkane 65%，环烷烃cycloalkane 6%，芳烃aromatic 17%，烯烃alkene 5%，含氧oxygen-containing compound 4%	[49]

催化剂 catalyst	催化温度/℃ catalyst temperature	料比 feedstock to catalyst ratio	原料 feedstock	主要液体产物¹⁾major component of bio-oil				参考文献 ref.
催化剂 catalyst	催化温度/℃ catalyst temperature	料比 feedstock to catalyst ratio	原料 feedstock	总烃/% hydrocarbon	芳烃/% aromatics	BTEXS/ (g·L^-1)	羰基化合物/% carbonyl compound	参考文献 ref.
CaO	500	5∶1	废白土油 waste clay oil	68.85	/	/	23.37	[50]
CaO/HZSM-5(1∶1)	500	5∶2	废食用油 waste cooking oil	91.36	88.28	167.54	0.84	[56]
SrO/HZSM-5(1∶1)	500	5∶2	废食用油 waste cooking oil	83.38	73.47	192.36	2.45	[56]
ZrO₂/HZSM-5(1∶1)	500	5∶2	废食用油 waste cooking oil	85.67	73.02	174.19	1.93	[56]
CoO/HZSM-5(1∶1)	500	5∶2	废食用油 waste cooking oil	81.77	72.54	155.70	2.89	[56]
NiO/HZSM-5(1∶1)	500	5∶2	废食用油 waste cooking oil	79.01	65.78	84.26	2.47	[56]
CeO₂ /HZSM-5(1∶1)	500	5∶2	废食用油 waste cooking oil	85.02	81.38	153.44	2.51	[56]

原料 material	催化剂 catalyst	加热方式 heating mode	生物油产率 yield/%	主要液体产物 major comporent of bio-oil			催化剂结焦量/% coke	参考文献 ref.
原料 material	催化剂 catalyst	加热方式 heating mode	生物油产率 yield/%	烃/% hydrocarbon	芳烃/% aromatic	含氧化合物/% oxygen-containing compound	催化剂结焦量/% coke	参考文献 ref.
皂脚/秸秆(1∶1) soapstock/straw	ZSM-5@SiC	电加热 electric heating	54	82.23	62.00			[61]
皂脚/秸秆(1∶1) soapstock/straw	ZSM-5@SiC	微波加热 microwave heating	46	84.88	73.56			[61]
乌桕籽油 tallow kernel oil	MCM-41@SiC	电加热 electric heating	61.15	86.571		13.429	4.4	[15]
乌桕籽油 tallow kernel oil	MCM-41@SiC	微波加热 microwave heating	59.38	94.833		5.167	3.16	[15]
乌桕籽油 tallow kernel oil	MCM-41@SiC	微波加热 microwave heating	74.79	80.76	43.53	19.24	0.76	[55]
乌桕籽油 tallow kernel oil	MCM-41/SiC	微波加热 microwave heating	73.40	79.52	~37.50^*	20.48	0.87	[55]

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微波辅助/催化热解废油脂制取富烃生物油研究进展

Research Progress on Microwave-assisted Catalytic Pyrolysis of Waste Oil for Hydrocarbon-rich Bio-oil

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