纤维增强树脂复合材料化学回收技术研究进展

doi:10.11949/0438-1157.20221489

化工学报 ›› 2023, Vol. 74 ›› Issue (3): 981-994.DOI: 10.11949/0438-1157.20221489

纤维增强树脂复合材料化学回收技术研究进展

陈瑞哲¹^,²^,³(), 程磊磊¹^,²^,³, 顾菁²^,³, 袁浩然¹^,²^,³(), 陈勇¹^,²^,³

^1.中国科学技术大学能源科学与技术学院，安徽合肥 230026
^2.中国科学院广州能源研究所，广东广州 510640
^3.广东省新能源和可再生能源研究开发与应用重点实验室，广东广州 510640

收稿日期:2022-11-15 修回日期:2023-02-11 出版日期:2023-03-05 发布日期:2023-04-19
通讯作者: 袁浩然
作者简介:陈瑞哲（1999—）男，硕士研究生，crz4212@163.com
基金资助:
广东省基础与应用基础研究基金项目(2021B1515020068);中国科学院稳定支持基础研究领域青年团队计划项目(YSBR-044)

Research progress in chemical recovery technology of fiber-reinforced polymer composites

Ruizhe CHEN¹^,²^,³(), Leilei CHENG¹^,²^,³, Jing GU²^,³, Haoran YUAN¹^,²^,³(), Yong CHEN¹^,²^,³

^1.School of Energy Science and Engineering, University of Science and Technology of China, Hefei 230026, Anhui, China
^2.Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^3.Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, Guangdong, China

Received:2022-11-15 Revised:2023-02-11 Online:2023-03-05 Published:2023-04-19
Contact: Haoran YUAN

摘要/Abstract

摘要：

纤维增强树脂复合材料(fiber-reinforced polymer composites，FRPC)具有强度高、易加工、成本低等优异性能，成为风机叶片、线路板等典型工业产品的首选结构材料。随着FRPC产量逐年增加以及工业产品退役期的来临，废弃复合材料的累积将导致严重的环境污染和能源资源浪费，亟需研发高效清洁回收技术。化学回收技术不仅能够回收高质纤维材料，而且可实现树脂定向转化为燃料和有机化学品。本文在分析复合废材组成特性以及化学回收技术的基础上，对再生产品应用、技术经济性以及环境效益进行了评价。进一步提出基于有机树脂官能团特性，在温和条件下定向解聚升级循环制备精细化学品的同时，实现纤维材料无损再生利用。

关键词: 纤维增强树脂复合材料, 化学回收, 热解, 溶剂法, 再生, 经济环境评价

Abstract:

Fiber-reinforced polymer composites (FRPC) which have excellent properties such as high strength, easy processing and low cost are the preferred structural materials for typical industrial products such as wind turbines and circuit boards. With the increase in FRPC production year by year and the arrival of decommissioning period of industrial products, the accumulation of discarded composite materials will lead to serious environmental pollution and waste of energy and resources, thus it is urgent to develop efficient and clean recycling technologies. Chemical recovery technology can not only recover high-quality fiber materials, but also realize the targeted conversion of resin into fuel and organic chemicals. Based on the analysis of composition characteristics of composites wasted and chemical recovery technologies, this article evaluates the application of recycled products, technical economy and environmental benefits. It is further proposed that based on the characteristics of the functional groups of organic resins, the non-destructive recycling of fiber materials can be realized while producing fine chemicals through directional depolymerization and upgrading cycle under mild conditions.

Key words: fiber-reinforced polymer composites, chemical recovery, pyrolysis, solvolysis method, regeneration, economic and environmental assessment

中图分类号:

X 783.2

陈瑞哲, 程磊磊, 顾菁, 袁浩然, 陈勇. 纤维增强树脂复合材料化学回收技术研究进展[J]. 化工学报, 2023, 74(3): 981-994.

Ruizhe CHEN, Leilei CHENG, Jing GU, Haoran YUAN, Yong CHEN. Research progress in chemical recovery technology of fiber-reinforced polymer composites[J]. CIESC Journal, 2023, 74(3): 981-994.

图/表 13

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回收技术	优势	劣势
填埋处理	过程简单，处理成本低	危害环境，浪费废弃物资源
能量回收	不限制材料种类	碳排放量大，无法回收高性能纤维
物理回收	可回收得到短纤维制品，适合大规模生产应用	回收产物价值较低，对可回收的废弃物种类有限制
化学回收	有效回收树脂并较大程度地保持回收纤维的性能，对环境危害小	处理程序复杂，成本较高，产物较为复杂，缺乏低耗高效的全资源化回收技术

回收技术	优势	劣势
填埋处理	过程简单，处理成本低	危害环境，浪费废弃物资源
能量回收	不限制材料种类	碳排放量大，无法回收高性能纤维
物理回收	可回收得到短纤维制品，适合大规模生产应用	回收产物价值较低，对可回收的废弃物种类有限制
化学回收	有效回收树脂并较大程度地保持回收纤维的性能，对环境危害小	处理程序复杂，成本较高，产物较为复杂，缺乏低耗高效的全资源化回收技术

树脂			纤维
种类	聚合物类型	结构特性	种类	结构特性
环氧树脂	热固性	含两个或两个以上环氧基团	玻璃纤维	含有SiO₂、Na₂O、CaO、Al₂O₃
酚醛树脂	热固性	酚类与醛类（苯酚、甲醛）聚合而成	碳纤维	含碳量高于90%
不饱和聚酯树脂	热固性	单体为二元酸与二元醇	硼纤维	芯材为金属丝（钨丝），中间层为硼，表层为涂层
聚烯烃	热塑性	烯烃分子聚合而成	玄武岩纤维	玄武岩石料高温熔融后拉制而成连续纤维
聚酰胺	热塑性	含有酰胺基团	芳纶纤维	间位芳纶纤维：锯齿状分子链对位芳纶纤维：直线状分子链
聚碳酸酯	热塑性	含碳酸酯基	芳纶纤维	间位芳纶纤维：锯齿状分子链对位芳纶纤维：直线状分子链
聚碳酸酯	热塑性	含碳酸酯基	聚乙烯纤维	聚乙烯熔融纺丝制成

树脂			纤维
种类	聚合物类型	结构特性	种类	结构特性
环氧树脂	热固性	含两个或两个以上环氧基团	玻璃纤维	含有SiO₂、Na₂O、CaO、Al₂O₃
酚醛树脂	热固性	酚类与醛类（苯酚、甲醛）聚合而成	碳纤维	含碳量高于90%
不饱和聚酯树脂	热固性	单体为二元酸与二元醇	硼纤维	芯材为金属丝（钨丝），中间层为硼，表层为涂层
聚烯烃	热塑性	烯烃分子聚合而成	玄武岩纤维	玄武岩石料高温熔融后拉制而成连续纤维
聚酰胺	热塑性	含有酰胺基团	芳纶纤维	间位芳纶纤维：锯齿状分子链对位芳纶纤维：直线状分子链
聚碳酸酯	热塑性	含碳酸酯基	芳纶纤维	间位芳纶纤维：锯齿状分子链对位芳纶纤维：直线状分子链
聚碳酸酯	热塑性	含碳酸酯基	聚乙烯纤维	聚乙烯熔融纺丝制成

化学名称	结构特性	回收利用	文献
玻璃纤维增强聚丙烯	改性GF表面会发生化学反应，产生接枝共聚物，共聚物分散纠缠于聚丙烯高分子链中，形成复杂结构	聚丙烯热解可得热解油或蜡，回收GF可做增强材料	[17-19]
玻璃纤维增强酚醛树脂	固化过程首先进行凝胶化，再进行交联固化。固化时，在酚核之间形成亚甲基键和醚键	在含碳热解气中，钴基催化剂可催化酚醛树脂生成 CF和碳纳米管	[20-21]
碳纤维增强环氧树脂	CF力学性能优良，改性可进一步提高增强体与基体间的浸润性，有利于化学键形成，提高增强体与基体间的固化交联度	化学回收法可以得到干净的CF，回收CF的拉伸强度保持率可达95%，环氧树脂可以降解为苯或苯酚的衍生物	[22]
芳纶纤维增强环氧树脂	芳纶纤维经过表面改性可以提高机械绞合程度，表面官能团增多，表面能增大，纤维与树脂的结合强度提高	热解得到热解气和热解油	[23]

纤维增强树脂复合材料化学回收技术研究进展

Research progress in chemical recovery technology of fiber-reinforced polymer composites

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Metrics

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热解气	含量/%
热解气	500℃	550℃	600℃
H₂	5.8	7.5	11.5
CH₄	10.6	15.4	20.7
CO	24.2	24.0	21.8
CO₂	32.6	26.0	20.4
C₂H₄	4.8	5.0	5.2
C₂H₆	2.8	3.3	3.7
C₃	1.4	1.4	1.3
C₄	2.6	2.7	2.5
其他	15.2	14.7	12.9

热解油	含量/（g/L）
热解油	500℃	550℃	600℃
苯	3.4	9.5	6.8
甲苯	15.0	31.1	27.3
乙苯	16.7	30.0	21.5
苯乙烯	7.9	13.7	13.6

流体	临界温度/℃	临界压力/ MPa
水	373.95	22.06
甲醇	239.45	8.10
乙醇	240.85	6.14
丙醇	263.65	5.20
丙酮	234.85	4.80
CO₂	31.26	7.38

回收方法	试剂、设备	工艺参数	纤维性能	文献
高温热解	固定床反应器	N₂气氛500℃下热解，保持1 h；空气气氛500℃下氧化	抗拉强度：3270 MPa 模量：230000 MPa 抗拉强度保持率：93%	[55]
流化床热解	流化床反应器， 0.85 mm沙粒	空气气氛450℃下热解	抗拉强度：285 MPa 模量：（227100±32300） MPa 抗拉强度保持率：73%	[38]
微波热解	微波炉	N₂气氛3 kW功率下通电8 s	抗拉强度：3260 MPa 模量：210000 MPa 抗拉强度保持率：80%	[56]
超临界流体	正丙醇	压力5.2 MPa，温度310℃，保持20 min	抗拉强度：4325 MPa 模量：（213200±11600） MPa 抗拉强度保持率：99%	[57]
溶剂溶解	硝酸、聚乙二醇、KOH	室温下硝酸预处理，然后在160℃下的聚乙二醇和 KOH混合液中反应200 min	抗拉强度：3890 MPa 模量：173790 MPa 抗拉强度保持率：96%	[51]
电化学回收	KOH、NaCl电解液	75℃，电流40 mA，反应36 h	抗拉强度：4152 MPa 抗拉强度保持率：89.83%	[54]

公司	地点	回收方法	回收能力/(t/a)
Carbon Conversions Inc	美国	高温热解法	2000
CFK Valley Stade Recycling GmbH & Co. KG	德国	高温热解法	1000
ELG Carbon Fibre	英国	高温热解法	2000
KARBOREK RCF	意大利	高温热解法	1000
SGL Automotive Carbon Fibres	美国	高温热解法	1500
Toray Industries	日本	高温热解法	1000
University of Nottingham	英国	流化床热解法	12
Hitachi Chemical	日本	超临界流体法	12
V-Carbon	美国	溶剂溶解法	1.7

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