林产化学与工业 ›› 2021, Vol. 41 ›› Issue (6): 127-138.doi: 10.3969/j.issn.0253-2417.2021.06.016
• 综述评论 • 上一篇
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
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基金资助:
Qiuhao WU1,2, Yunpu WANG1,2,*(), Shumei ZHANG1,2, Yuan ZENG1,2, Yuhuan LIU1,2, Roger RUAN3
Received:
2020-08-26
Online:
2021-12-28
Published:
2021-12-31
Contact:
Yunpu WANG
E-mail:wangyunpu@ncu.edu.cn
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。
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.
表1
共热解中电加热与微波加热液体产物的对比"
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% | [ |
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% | [ |
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%) | [ | |
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%) | [ | |
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%) | [ | ||
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%) | [ | |
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%) | [ | |
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%*) | [ |
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%) | [ | |
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%) | [ | |
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 | [ |
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%) | [ | |
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%) | [ |
表3
6种金属氧化物与HZSM-5共催化结果对比"
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. | |||
总烃/% hydrocarbon | 芳烃/% aromatics | BTEXS/ (g·L-1) | 羰基化合物/% carbonyl compound | |||||
CaO | 500 | 5∶1 | 废白土油 waste clay oil | 68.85 | / | / | 23.37 | [ |
CaO/HZSM-5(1∶1) | 500 | 5∶2 | 废食用油 waste cooking oil | 91.36 | 88.28 | 167.54 | 0.84 | [ |
SrO/HZSM-5(1∶1) | 500 | 5∶2 | 废食用油 waste cooking oil | 83.38 | 73.47 | 192.36 | 2.45 | [ |
ZrO2/HZSM-5(1∶1) | 500 | 5∶2 | 废食用油 waste cooking oil | 85.67 | 73.02 | 174.19 | 1.93 | [ |
CoO/HZSM-5(1∶1) | 500 | 5∶2 | 废食用油 waste cooking oil | 81.77 | 72.54 | 155.70 | 2.89 | [ |
NiO/HZSM-5(1∶1) | 500 | 5∶2 | 废食用油 waste cooking oil | 79.01 | 65.78 | 84.26 | 2.47 | [ |
CeO2 /HZSM-5(1∶1) | 500 | 5∶2 | 废食用油 waste cooking oil | 85.02 | 81.38 | 153.44 | 2.51 | [ |
表4
微波驱动催化剂在不同加热方式下的产物对比"
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. | ||
烃/% hydrocarbon | 芳烃/% aromatic | 含氧化合物/% oxygen-containing compound | ||||||
皂脚/秸秆(1∶1) soapstock/straw | ZSM-5@SiC | 电加热 electric heating | 54 | 82.23 | 62.00 | [ | ||
皂脚/秸秆(1∶1) soapstock/straw | ZSM-5@SiC | 微波加热 microwave heating | 46 | 84.88 | 73.56 | |||
乌桕籽油 tallow kernel oil | MCM-41@SiC | 电加热 electric heating | 61.15 | 86.571 | 13.429 | 4.4 | [ | |
乌桕籽油 tallow kernel oil | MCM-41@SiC | 微波加热 microwave heating | 59.38 | 94.833 | 5.167 | 3.16 | ||
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 | [ |
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 |
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