生物质三组分与低密度聚乙烯共催化热解制取轻质芳烃的协同作用机理

doi:10.11949/0438-1157.20211387

化工学报 ›› 2022, Vol. 73 ›› Issue (2): 699-711.DOI: 10.11949/0438-1157.20211387

• 催化、动力学与反应器 • 上一篇下一篇

生物质三组分与低密度聚乙烯共催化热解制取轻质芳烃的协同作用机理

黄明(),朱亮,丁紫霞,毛一婷,马中青()

浙江农林大学化学与材料工程学院，国家木质资源综合利用工程技术研究中心，浙江杭州 311300

收稿日期:2021-09-27 修回日期:2021-10-22 出版日期:2022-02-05 发布日期:2022-02-18
通讯作者: 马中青
作者简介:黄明（1996—），男，博士研究生，huangmingzafu@163.com
基金资助:
浙江省自然科学基金项目(LY21E060001);浙江省属高校基本科研业务费专项资金项目(2020YQ006);中国科协“青年人才托举工程”项目(2018QNRC001);国家林业和草原局科技创新青年拔尖人才项目(2019132617);浙江大学能源清洁利用国家重点实验室开放基金项目(ZJU-CEU2020021);中国博士后科学基金项目(2021M692868)

Synergistic interactions of biomass three-component and low-density polyethylene during co-catalytic fast pyrolysis for the production of light aromatics

Ming HUANG(),Liang ZHU,Zixia DING,Yiting MAO,Zhongqing MA()

College of Chemistry and Materials Engineering, National Engineering Research Center of Wood-based Resources Comprehensive Utilization, Zhejiang A & F University, Hangzhou 311300, Zhejiang, China

Received:2021-09-27 Revised:2021-10-22 Online:2022-02-05 Published:2022-02-18
Contact: Zhongqing MA

摘要/Abstract

摘要：

生物质与废塑料共催化快速热解是制取轻质芳烃的重要途径。采用不同种类的分子筛催化剂，首先研究了分子筛种类对杨木、生物质三组分和低密度聚乙烯（LDPE）单独催化快速热解轻质芳烃产率的影响，其次研究了生物质三组分与LDPE在共催化热解过程中的协同作用机理。结果表明：在杨木、生物质三组分和LDPE单独催化快速热解时，HZSM-5（25）催化剂体现出最高的轻质芳烃产率；在杨木和LDPE共催化快速热解时，随着LDPE质量的增加，轻质芳烃的产率呈先升高后降低趋势；在生物质三组分和LDPE共催化快速热解时，纤维素和半纤维素热解的呋喃类中间产物与LDPE热解的轻烯烃中间产物易发生“双烯合成”反应，表现出较强的协同催化作用，促进轻质芳烃的生成，而木质素则抑制轻质芳烃生成。

关键词: 生物质三组分, 低密度聚乙烯, 催化热解, 轻质芳烃, 生物能源, 催化剂, 化学反应

Abstract:

Co-catalytic fast pyrolysis (Co-CFP) of biomass and waste plastics is an important way to produce light aromatics. In this work, co-catalytic fast pyrolysis of three major component in biomass (cellulose, hemicellulose, and lignin) and low density polyethylene (LDPE) was carried out in Py-GC/MS by using different zeolite catalysts (HZSM-5 (25), HZSM-5 (85), HY, USY and MCM-41). The effect of catalytic pyrolysis parameters on the yield of light aromatics and the synergistic interactions between biomass three major components and LDPE were investigated. The results showed that, among the five types of zeolite catalysts, HZSM-5 (25) presented highest yield of light aromatics during single CFP of poplar, biomass three major components, and LDPE. During Co-CFP of poplar and LDPE, the yield of light aromatics increased first, and then decreased with the increase of mass of LDPE. During Co-CFP of biomass three major components and LDPE, Diels-Alder reaction occurred between the pyrolysis intermediates of the furans from cellulose/hemicellulose and the light olefins from LDPE, promoting the formation of light aromatics. However, the Co-CFP of lignin and LDPE hindered the formation of light aromatics.

Key words: biomass three major components, LDPE, catalytic pyrolysis, light aromatics, bioenergy, catalyst, chemical reaction

中图分类号:

TK 6

黄明, 朱亮, 丁紫霞, 毛一婷, 马中青. 生物质三组分与低密度聚乙烯共催化热解制取轻质芳烃的协同作用机理[J]. 化工学报, 2022, 73(2): 699-711.

Ming HUANG, Liang ZHU, Zixia DING, Yiting MAO, Zhongqing MA. Synergistic interactions of biomass three-component and low-density polyethylene during co-catalytic fast pyrolysis for the production of light aromatics[J]. CIESC Journal, 2022, 73(2): 699-711.

图/表 8

表1 杨木、生物质三组分和LDPE的元素分析、工业分析和热值

Table 1 Ultimate and proximate analysis， and calorific value of poplar wood， three major components of biomass， and LDPE

原料	元素分析/%					工业分析/%			有效氢碳比	低位热值/ (MJ/kg)
原料	C	H	O	N	S	挥发分	固定碳	灰分	有效氢碳比	低位热值/ (MJ/kg)
杨木	47.21	6.04	46.74	0.01	0.00	87.95	10.93	1.12	0.050	16.25
木质素	63.58	5.35	30.52	0.55	0.00	66.24	33.70	0.06	0.289	23.72
纤维素	43.21	6.30	50.33	0.00	0.16	94.41	5.59	0.00	0.002	14.62
木聚糖	42.99	6.43	50.40	0.00	0.18	93.30	6.70	0.00	0.036	14.73
LDPE	84.21	14.29	1.47	0.03	0.00	99.79	0.21	0.00	2.010	48.83

图1 杨木、生物质三组分和LDPE的红外光谱图

Fig.1 FTIR analysis of poplar wood, three major components of biomass, and LDPE

图2 杨木、生物质三组分和LDPE的TG和DTG曲线

Fig.2 TG and DTG curves of poplar wood, three major components of biomass, and LDPE

图3 分子筛种类对杨木及生物质三组分单独催化快速热解生物油组分的影响

Fig.3 Effect of the types of catalyst on the product distribution of bio-oil derived from catalytic fast pyrolysis of poplar wood and three major components of biomass

图4 分子筛种类对LDPE单独催化热解生物油组分的影响

Fig.4 Effect of different zeolite catalysts on the product distribution of bio-oil derived from catalytic fast pyrolysis of LDPE

图5 杨木与LDPE共催化热解过程中生物油组分分布和协同效果

Fig.5 Distribution of bio-oil components and synergistic reaction abundance derived from co-catalytic fast pyrolysis of poplar wood and LDPE

图6 生物质三组分与LDPE共催化热解过程中生物油组分分布和协同效果

Fig.6 Distribution of bio-oil components and synergistic reaction abundance derived from co-catalytic fast pyrolysis of three major components of biomass and LDPE

图7 生物质三组分与LDPE共催化热解制取轻质芳烃的机理

Fig.7 Formation mechanism of the aromatic hydrocarbon derived from co-catalytic fast pyrolysis of three major components of biomass and LDPE

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生物质三组分与低密度聚乙烯共催化热解制取轻质芳烃的协同作用机理

Synergistic interactions of biomass three-component and low-density polyethylene during co-catalytic fast pyrolysis for the production of light aromatics

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