化工学报 ›› 2020, Vol. 71 ›› Issue (8): 3416-3427.DOI: 10.11949/0438-1157.20200191
仉利1,2(
),姚宗路2,赵立欣1,2(),李志合1,易维明1,付鹏1,袁超3
收稿日期:2020-02-27
修回日期:2020-03-26
出版日期:2020-08-05
发布日期:2020-08-05
通讯作者:
赵立欣
作者简介:仉利（1988—），女，博士研究生，基金资助:
Li ZHANG1,2(),Zonglu YAO2,Lixin ZHAO1,2(),Zhihe LI1,Weiming YI1,Peng FU1,Chao YUAN3
Received:2020-02-27
Revised:2020-03-26
Online:2020-08-05
Published:2020-08-05
Contact:
Lixin ZHAO
摘要：
生物质通过热化学转化制备高品质生物油和高附加值精细化工品是未来工业发展的重要方向，是解决能源短缺、实现碳的闭路循环的有效方式，如何提升生物质热化学转化品质和效率是目前学术界和工业界关注的热点。本文介绍了不同技术路径下的生物质热化学转化研究进展，重点阐述了催化热解、水热催化、化学链转化三种方式的反应机理及其催化剂类型，讨论了生物质热化学转化提质策略。最后，针对生物质热化学转化目前尚存在的问题提出建议，期望为生物质高值化利用提供参考和借鉴。
中图分类号:
仉利, 姚宗路, 赵立欣, 李志合, 易维明, 付鹏, 袁超. 生物质热化学转化提质及其催化剂研究进展[J]. 化工学报, 2020, 71(8): 3416-3427.
Li ZHANG, Zonglu YAO, Lixin ZHAO, Zhihe LI, Weiming YI, Peng FU, Chao YUAN. Research progress on thermochemical conversion of biomass to enhance quality and catalyst[J]. CIESC Journal, 2020, 71(8): 3416-3427.
| 转化路径 | 转化条件 | 转化产物 | 产物利用价值 | 转化特点 | 文献 |
|---|---|---|---|---|---|
| 燃烧 | 富氧、着火点 | 能量、CO2、H2O等 | 热力、电力等 | 能源利用率低，环境污染大 | [ |
| 催化热解 | 缺氧或少氧 高温（300~1500℃） | 热解气、生物油、生物炭 | 热力、电力、活性炭、燃气、 液体燃料、化学品等 | 设备要求低，转化效率高，技术成熟 | [ |
| 水热催化 | 缺氧或少氧 高压（5~25 MPa） 高温（200~600℃） | 热解气、生物油、生物炭 | 热力、电力、活性炭、燃气、 液体燃料、化学品等 | （1）水作为溶剂或催化反应介质，绿色环保无污染； （2）水热催化传质传热速率较快，反应迅速，节约能量； （3）生物质原材料无须脱水，经定向反应后产物收率较高 | [ |
| 化学链转化 | 高温（700~1000℃）氧载体 | 能量、CO2、H2O、合成 气等 | 热力、电力、干冰、燃气等 | （1）燃料反应器中产物为CO2和水蒸气，可通过冷凝实现CO2内分离； （2）空气反应器中温度较低避免了NOx的生成，降低了环境污染； （3）分步转化过程实现了能量梯级利用，提高了能量的利用率 | [ |
表1 生物质热化学转化路径及其特点
Table 1 Path and characteristics of biomass thermochemical conversion
| 转化路径 | 转化条件 | 转化产物 | 产物利用价值 | 转化特点 | 文献 |
|---|---|---|---|---|---|
| 燃烧 | 富氧、着火点 | 能量、CO2、H2O等 | 热力、电力等 | 能源利用率低，环境污染大 | [ |
| 催化热解 | 缺氧或少氧 高温（300~1500℃） | 热解气、生物油、生物炭 | 热力、电力、活性炭、燃气、 液体燃料、化学品等 | 设备要求低，转化效率高，技术成熟 | [ |
| 水热催化 | 缺氧或少氧 高压（5~25 MPa） 高温（200~600℃） | 热解气、生物油、生物炭 | 热力、电力、活性炭、燃气、 液体燃料、化学品等 | （1）水作为溶剂或催化反应介质，绿色环保无污染； （2）水热催化传质传热速率较快，反应迅速，节约能量； （3）生物质原材料无须脱水，经定向反应后产物收率较高 | [ |
| 化学链转化 | 高温（700~1000℃）氧载体 | 能量、CO2、H2O、合成 气等 | 热力、电力、干冰、燃气等 | （1）燃料反应器中产物为CO2和水蒸气，可通过冷凝实现CO2内分离； （2）空气反应器中温度较低避免了NOx的生成，降低了环境污染； （3）分步转化过程实现了能量梯级利用，提高了能量的利用率 | [ |
图1 生物质催化热解化学反应[23]
Fig.1 Schematic of chemical reactions for biomass catalytic pyrolysis[23]
图2 碱改性HZSM-5分子筛与木质素催化热解反应路线[41]
Fig.2 Reaction path of catalytic pyrolysis of lignin over hierarchical HZSM-5 zeolites prepared by post-treatment with alkaline solutions[41]
图3 木质素在赤泥与HZSM-5两级催化系统下的反应路径[52]
Fig.3 Reaction path of catalytic pyrolysis of lignin in a cascade dual-catalyst system of modified red mud and HZSM-5[52]
图4 木质素水热转化路径[53]
Fig.4 Hydrothermal conversion pathway of lignin[53]
图5 Ru-MC催化剂合成制备示意图[68]
Fig.5 Schematic illustration of preparation of incorporated Ru-MC catalyst[68]
图6 化学链重整制氢原理示意图
Fig.6 Schematic diagram of chemical-looping reforming hydrogen production principle
图7 氢电联合生产工艺路线示意图[83]
Fig.7 Schematic representation of integrated process[83](1 bar=105 Pa)
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