碳纤维增强聚合物(CFRP)凭借高强度、轻量化特性,广泛应用于风电叶片、航空航天、汽车及体育器材。全球CFRP年废弃量将超过50万吨,中国年均增长率达15%,当前处置手段主要依赖填埋或焚烧,造成资源浪费和碳排放。传统热固性树脂固化后形成永久交联结构,给碳纤维回收带来了巨大挑战。热化学技术通过在无氧环境中加热CFRP,能够使树脂分解为小分子油气,同时回收碳纤维。其作为当前最成熟的工业化路径,适合大规模处理风电叶片等废弃CFRP,但仍需优化热转化条件、设计新型催化剂来降低能耗和成本。因此,回顾了近年来基于常规热解、微波热解和熔盐热解的回收废弃CFRP技术的最新研究进展。总结提出热化学技术的优势与瓶颈,并展望未来研究方向。
Carbon fiber-reinforced polymer (CFRP) is widely used in wind turbine blades,aerospace,automotive,and sports equipment due to its high strength and lightweight characteristics.The annual global waste volume of CFRP will exceed 500,000 tons,with an average annual growth rate of 15% in China.Currently,the disposal methods mainly rely on landfilling or incineration,resulting in resource waste and carbon emissions.The traditional thermosetting resin forms a permanent cross-linked structure after curing,which poses a huge challenge to carbon fiber recycling.Thermochemical technology can decompose the resin into small-molecule oil and gas by heating CFRP in an oxygen-free environment while recycling carbon fibers.As the most mature industrial path at present,it is suitable for large-scale treatment of waste CFRP such as wind turbine blades.However,it is still necessary to optimize the thermal conversion conditions and design new catalysts to reduce energy consumption and costs.Therefore,this paper reviewed the latest research progress of waste CFRP recycling technologies based on conventional pyrolysis,microwave pyrolysis,and molten salt pyrolysis in recent years.The advantages and bottlenecks of thermochemical technology were summarized,and future research directions were prospected.
[1] Butenegro J A,Bahrami M,Swolfs Y,et al.Novel thermoplastic composites strengthened with carbon fiber-reinforced epoxy composite waste rods:development and characte rization[J].Polymers,2022,14(19):3951.
[2] 曹维宇,杨学萍,张藕生.我国高性能高分子复合材料发展现状与展望[J].中国工程科学,2020,22(5):112-120.
[3] Meng F,McKechnie J,Pickering S J.An assessment of financial viability of recycled carbon fibre in automotive applications[J].Composites Part A:Applied Science and Manufacturing,2018,109:207-220.
[4] Andersen N,Eriksson O,Hillman K,et al.Wind turbines' end-of-life:quantification and characterisation of future waste materials on a national level[J].Energies,2016,9(12):999.
[5] Zhang J,Lin G,Vaidya U,et al.Past,present and future prospective of global carbon fibre composite developments and applications[J].Composites Part B:Engineering,2023,250:110463.
[6] Lefeuvre A,Garnier S,Jacquemin L,et al.Anticipating in-use stocks of carbon fiber reinforced polymers and related waste flows generated by the commercial aeronautical sector until 2050[J].Resources,Conservation and Recycling,2017,125:264-272.
[7] Hermansson F,Janssen M,Svanström M.Prospective study of lignin-based and recycled carbon fibers in composites through meta-analysis of life cycle assessments[J].Journal of Cleaner Production,2019,223:946-956.
[8] Mishnaevsky L,Branner K,Petersen H N,et al.Materials for wind turbine blades:an overview[J].Materials,2017,10(11):1285.
[9] 郑波,颜春,祝颖丹,等.生物基可降解环氧树脂及其可回收碳纤维复合材料的研究进展[J].化工新型材料,2024,52(1):8-12,7.
[10] 布凤景.再生碳纤维的回收及应用现状[J].化工新型材料,2023,51(S2):60-64.
[11] Palola S,Laurikainen P,García-Arrieta S,et al.Towards sustainable composite manufacturing with recycled carbon fiber reinforced thermoplastic composites[J].Polymers,2022,14(6):1098.
[12] 张东致,万怡灶,罗红林,等.碳纤维复合材料的回收与再利用现状[J].中国塑料,2013,27(2):1-6.
[13] 周海琳,李国树,刘迎春,等.绿色高效回收碳纤维复合材料研究进展[J].化工新型材料,2022,50(10):1-4.
[14] Pickering S J.Recycling technologies for thermoset composite materials-current status[J].Composites Part A:Applied Science and Manufacturing,2006,37(8):1206-1215.
[15] Henry L,Schneller A,Doerfler J,et al.Semi-continuous flow recycling method for carbon fibre reinforced thermoset polymers by near-and supercritical solvolysis[J].Polymer Degradation and Stability,2016,133:264-274.
[16] Palmer J,Ghita O R,Savage L,et al.Successful closed-loop recycling of thermoset composites[J].Composites Part A:Applied Science and Manufacturing,2009,40(4):490-498.
[17] Yao Y,Zhao F,Wang B,et al.The designing of degradable unsaturated polyester based on selective cleavage activated hydrolysis and its application in recyclable carbon fiber composites[J].Composites Science and Technology,2022,229:109692.
[18] 胡侨乐,端玉芳,刘志,等.碳纤维增强聚合物基复合材料回收再利用现状[J].复合材料学报,2022,39(1):64-76.
[19] Yousef S,Eimontas J,Stasiulaitiene I,et al.Recovery of energy and carbon fibre from wind turbine blades waste (carbon fibre/unsaturated polyester resin) using pyrolysis process and its life-cycle assessment[J].Environmental Research,2024,245:118016.
[20] Guo L,Xu L,Ren Y,et al.Research on a two-step pyrolysis-oxidation process of carbon fiber-reinforced epoxy resin-based composites and analysis of product properties[J].Journal of Environmental Chemical Engineering,2022,10(3):107510.
[21] Deng J,Xu L,Zhang L,et al.Recycling of carbon fibers from CFRP waste by microwave thermolysis[J].Processes,2019,7(4):207.
[22] Shu J,Xu L,Ren Y,et al.Recovery of carbon fiber from carbon fiber reinforced polymer waste via microwave molten-carbonate pyrolysis[J].Journal of Analytical and Applied Pyrolysis,2024,183:106840.
[23] Overcash M,Twomey J,Asmatulu E,et al.Thermoset composite recycling-driving forces,development,and evolution of new opportunities[J].Journal of Composite Materials,2018,52(8):1033-1043.
[24] López F A,Rodríguez O,Alguacil F J,et al.Recovery of carbon fibres by the thermolysis and gasification of waste prepreg[J].Journal of Analytical and Applied Pyrolysis,2013,104:675-683.
[25] 马全胜,王宝铭.碳纤维复合材料回收及利用现状[J].纤维复合材料,2016,33(4):28-30,27.
[26] Nahil M A,Williams P T.Recycling of carbon fibre reinforced polymeric waste for the production of activated carbon fibres[J].Journal of Analytical and Applied Pyrolysis,2011,91(1):67-75.
[27] Mazzocchetti L,Benelli T,D'Angelo E,et al.Validation of carbon fibers recycling by pyro-gasification:the influence of oxidation conditions to obtain clean fibers and promote fiber/matrix adhesion in epoxy composites[J].Composites Part A:Applied Science and Manufacturing,2018,112:504-514.
[28] Yang J,Liu J,Liu W,et al.Recycling of carbon fibre reinforced epoxy resin composites under various oxygen concentrations in nitrogen-oxygen atmosphere[J].Journal of Analytical and Applied Pyrolysis,2015,112:253-261.
[29] Jiang G,Pickering S J.Structure-property relationship of recycled carbon fibres revealed by pyrolysis recycling process[J].Journal of Materials Science,2016,51:1949-1958.
[30] Lopez-Urionabarrenechea A,Gastelu N,Jiménez-Suárez A,et al.Secondary raw materials from residual carbon fiber-reinforced composites by an upgraded pyrolysis process[J].Polymers,2021,13(19):3408.
[31] 赵希强,宋占龙,王涛,等.微波技术用于热解的研究进展[J].化工进展,2008(12):1873-1877,1881.
[32] 许淳瑶,葛立超,冯红翠,等.风力发电现状及叶片组成与回收利用综述[J].热力发电,2022,51(9):29-41.
[33] Lester E,Kingman S,Wong K H,et al.Microwave heating as a means for carbon fibre recovery from polymer composites:a technical feasibility study[J].Materials Research Bulletin,2004,39(10):1549-1556.
[34] 阮芳涛,施建,徐珍珍,等.碳纤维增强树脂基复合材料的回收及其再利用研究进展[J].纺织学报,2019,40(6):153-158.
[35] Obunai K,Fukuta T,Ozaki K.Carbon fiber extraction from waste CFRP by microwave irradiation[J].Composites Part A:Applied Science and Manufacturing,2015,78:160-165.
[36] Deng J,Xu L,Liu J,et al.Efficient method of recycling carbon fiber from the waste of carbon fiber reinforced polymer composites[J].Polymer Degradation and Stability,2020,182:109419.
[37] Salas A,Berrio M E,Martel S,et al.Towards recycling of waste carbon fiber:strength,morphology and structural features of recovered carbon fibers[J].Waste Management,2023,165:59-69.
[38] 王学良.金属Ni、Cr和Fe在氯化物熔盐中的腐蚀行为及机理研究[D].上海:中国科学院大学(中国科学院上海应用物理研究所),2020.
[39] 魏慧卿,蒋元力,夏克东,等.熔盐法在碳纤维表面制备抗氧化SiC涂层[J].化工新型材料,2017,45(1):97-99,102.
[40] 石莉岩,梁精龙,张慧琳.生物质碳利用及制备电极材料研究进展[J].化工新型材料,2025,53(1):27-32,37.
[41] Ye S Y,Bounaceur A,Soudais Y,et al.Parameter optimization of the steam thermolysis:a process to recover carbon fibers from polymer-matrix composites[J].Waste and Biomass Valorization,2013,4:73-86.
[42] Nie W,Liu J,Liu W,et al.Decomposition of waste carbon fiber reinforced epoxy resin composites in molten potassium hydroxide[J].Polymer Degradation and Stability,2015,111:247-256.
[43] Wu T,Zhang W,Jin X,et al.Efficient reclamation of carbon fibers from epoxy composite waste through catalytic pyrolysis in molten ZnCl2[J].RSC Advances,2018,9(1):377-388.
[44] Ren Y,Hu H,Lin Z,et al.A novel method of reclaiming high-value carbon fiber from waste epoxy composite via molten salt thermal treatment[J].Chemical Engineering Journal,2024,496:153792.
[45] Chu Y,Yang X,Wu S,et al.Double-layer packed bed used for heating non-polar liquid under microwave irradiation[J].Chemical Engineering and Processing-Process Intensification,2020,149:107832.
基金资助
国家自然科学基金青年项目(52200143);武汉市自然科学基金探索计划(晨光计划)项目(2024040801020270);湖北省自然科学基金一般面上项目(2024AFB546);中央级公益性科研院所基本科研业务费(CKSF2025533/TG8);南水北调中线水源有限公司科研项目(ZSY/YG-SJ〈2024〉004)
PDF
(2047KB)
