无溴型环氧树脂电路板热解特性及动力学研究
摘要
随着电子电器行业的飞速发展,电子电器产品的更新换代频率日益加快,我国的电子废弃物数量也迅猛增加。电路板作为电子电器产品的核心部件,已经成为电子废弃物的重要来源。由于欧盟WEEE.RoHS.EuP三大绿色指令的推行,以及我国《电子信息产品污染防治管理办法》颁布实施,无溴型环氧树脂电路板的产量越来越大,报废量也与日俱增。因此,探索废旧无溴型环氧树脂电路板资源化利用技术具有重要的意义。
本文在国家科技支撑计划子课题“园区中再生利用技术集成与产业链链接技术研究”的支持下,研究电路板的热解回收技术。将电路板的热解回收技术作为电路板中非金属回收的单项技术与金属回收技术进行技术集成,作为废旧电路板再利用的集成技术模式,能够很好地实现电路板的资源化回收再利用。本文重点研究了无溴型环氧树脂电路板热解影响因素,热解产物组成,热解动力学三个方面的内容。
首先,研究了在氮气氛围下热解温度(300℃-900℃)、升温速率(10℃/min-40℃/min).保温时间(30 min-60min)对无溴型环氧树脂电路板热解产物产率的影响。结果表明：在300℃-900℃之间热解产物中热解残渣占61.74%-71.08%,热解油占22.52%-28.44%,热解气体占5.86%-12.81%。在热解温度700℃、升温速率20℃/min、保温时间40min时热解油产率最大。
其次,分别采用红外光谱、气质联用(GC/MS)分析官能团的变化和热解油成分。分别应用红外光谱、元素分析和扫描电子显微镜(SEM)分析了热解残渣的官能团、元素组成和微观外貌随热解温度的变化。结果表明：热解油中主要成分为苯酚、2-甲酚、对2,6-二异丙基苯酚以及双酚A等。热解过程中玻璃纤维外貌基本没有变化。
最后,采用热重分析法对无溴型环氧树脂电路板在氩气(Ar)条件下的热解反应进行动力学研究,并且研究了无溴型环氧树脂电路板的热解过程。通过TG曲线和DTG曲线分析了不同升温速率下的热稳定性及升温速率对热解反应的影响。利用Kissinger微分法和Flynn-Wall-Ozawa积分法研究其活化能E以相关动力学参数；采用Coats-Redfern方法研究得其反应动力学方程最为接近Valensi方程,推导出其反应级数n=2,并得到无澳型环氧树脂电路板的热分解机理函数为α+(1-α)·1n(1-α)。
As the rapid development of electrical and electronic equipment industry, the frequency of replacement electronic products is accelerated, the amount of waste Electrical and Electronic Equipment (WEEE) is rapidly increasing in China. As the key component of WEEE, waste printed circuit board (wPCB) has become an important kind of WEEE. Because of instruction of WEEE, ROHS, EUP and Regulation on contamination control and management of IT products, issued by the Ministry of Information Industry coming into effect, the amount of Anti-Br type epoxy resin printed circuit boards becomes larger. Therefore, it is of great significant to explore comprehensive utilization techniques of waste Anti-Br type epoxy resin printed circuit boards.
Based on the National Science and Technology Support Program sub-project, "recycling technology technology and industry chain linking technology", Pyrolysis recycling technology of wPCB was researched in the paper. As the single nonmetal recycling technology, pyrolysis recycling technology was integrated with many metal recycling technology. This can achieve good results. The anti-Br type epoxy resin printed circuit boards were investigated by pyrolysis experiment. This paper focuses on three aspects, including the influencing factors of pyrolysis, the analysing of the pyrolysis product and the pyrolysis kinetics.
Firstly, the effects of pyrolysis temperature (300℃-900℃), heating rate(10℃/min-40℃/min) and holding time (30 min-60min) on the yield of pyrolysis products in nitrogen were analyzed. Results show that solid residues account for about 61.74-71.08wt.%, liquid yields about 22.52-28.44wt.%and gas yields about 5.86-12.81wt.%. To get more pyrolysis oil, the optimal condition was obtained as follows:pyrolysis temperature at 700℃, heating rate of 20℃/min, holding time of 40 min.
Secondly, pyrolysis oil and residue were analyzed by Infrared spectroscopy, gas chromatography and mass spectroscopy (GC/MS), element analysis and scanning electron microscope. The main components of pyrolysis oil are phenol, 2-methylphenol,2,6-diisopropyl phenol, and bisphenol A,etc. In the process of pyrolysis, fibreglass appears unchanged.
In the end, pyrolysis kinetics of anti-Br type epoxy resin printed circuit boards was investigated with thermo gravimetric (TG) analysis in atmosphere of argon. The pyrolysis characteristics, stability analyses of anti-Br type epoxy resin printed circuit boards and the influence on pyrolysis were researched under various hearting rates(5,10,20,30℃·min-1). The pyrolysis activation energy E and other kinetic parameters were determined by Kissinger differentiation and Flynn-Wall-Ozawa integration. The reaction kinetics equation and the thermal decomposition mechanism function were investigated by Coats-Redfern method, the study shows that the proximal reaction kinetic equation is Valensi equation, and the reaction order is 2, and the thermal decomposition mechanism function isα+(1-α)·ln(1-α).
本文在国家科技支撑计划子课题“园区中再生利用技术集成与产业链链接技术研究”的支持下,研究电路板的热解回收技术。将电路板的热解回收技术作为电路板中非金属回收的单项技术与金属回收技术进行技术集成,作为废旧电路板再利用的集成技术模式,能够很好地实现电路板的资源化回收再利用。本文重点研究了无溴型环氧树脂电路板热解影响因素,热解产物组成,热解动力学三个方面的内容。
首先,研究了在氮气氛围下热解温度(300℃-900℃)、升温速率(10℃/min-40℃/min).保温时间(30 min-60min)对无溴型环氧树脂电路板热解产物产率的影响。结果表明：在300℃-900℃之间热解产物中热解残渣占61.74%-71.08%,热解油占22.52%-28.44%,热解气体占5.86%-12.81%。在热解温度700℃、升温速率20℃/min、保温时间40min时热解油产率最大。
其次,分别采用红外光谱、气质联用(GC/MS)分析官能团的变化和热解油成分。分别应用红外光谱、元素分析和扫描电子显微镜(SEM)分析了热解残渣的官能团、元素组成和微观外貌随热解温度的变化。结果表明：热解油中主要成分为苯酚、2-甲酚、对2,6-二异丙基苯酚以及双酚A等。热解过程中玻璃纤维外貌基本没有变化。
最后,采用热重分析法对无溴型环氧树脂电路板在氩气(Ar)条件下的热解反应进行动力学研究,并且研究了无溴型环氧树脂电路板的热解过程。通过TG曲线和DTG曲线分析了不同升温速率下的热稳定性及升温速率对热解反应的影响。利用Kissinger微分法和Flynn-Wall-Ozawa积分法研究其活化能E以相关动力学参数；采用Coats-Redfern方法研究得其反应动力学方程最为接近Valensi方程,推导出其反应级数n=2,并得到无澳型环氧树脂电路板的热分解机理函数为α+(1-α)·1n(1-α)。
As the rapid development of electrical and electronic equipment industry, the frequency of replacement electronic products is accelerated, the amount of waste Electrical and Electronic Equipment (WEEE) is rapidly increasing in China. As the key component of WEEE, waste printed circuit board (wPCB) has become an important kind of WEEE. Because of instruction of WEEE, ROHS, EUP and Regulation on contamination control and management of IT products, issued by the Ministry of Information Industry coming into effect, the amount of Anti-Br type epoxy resin printed circuit boards becomes larger. Therefore, it is of great significant to explore comprehensive utilization techniques of waste Anti-Br type epoxy resin printed circuit boards.
Based on the National Science and Technology Support Program sub-project, "recycling technology technology and industry chain linking technology", Pyrolysis recycling technology of wPCB was researched in the paper. As the single nonmetal recycling technology, pyrolysis recycling technology was integrated with many metal recycling technology. This can achieve good results. The anti-Br type epoxy resin printed circuit boards were investigated by pyrolysis experiment. This paper focuses on three aspects, including the influencing factors of pyrolysis, the analysing of the pyrolysis product and the pyrolysis kinetics.
Firstly, the effects of pyrolysis temperature (300℃-900℃), heating rate(10℃/min-40℃/min) and holding time (30 min-60min) on the yield of pyrolysis products in nitrogen were analyzed. Results show that solid residues account for about 61.74-71.08wt.%, liquid yields about 22.52-28.44wt.%and gas yields about 5.86-12.81wt.%. To get more pyrolysis oil, the optimal condition was obtained as follows:pyrolysis temperature at 700℃, heating rate of 20℃/min, holding time of 40 min.
Secondly, pyrolysis oil and residue were analyzed by Infrared spectroscopy, gas chromatography and mass spectroscopy (GC/MS), element analysis and scanning electron microscope. The main components of pyrolysis oil are phenol, 2-methylphenol,2,6-diisopropyl phenol, and bisphenol A,etc. In the process of pyrolysis, fibreglass appears unchanged.
In the end, pyrolysis kinetics of anti-Br type epoxy resin printed circuit boards was investigated with thermo gravimetric (TG) analysis in atmosphere of argon. The pyrolysis characteristics, stability analyses of anti-Br type epoxy resin printed circuit boards and the influence on pyrolysis were researched under various hearting rates(5,10,20,30℃·min-1). The pyrolysis activation energy E and other kinetic parameters were determined by Kissinger differentiation and Flynn-Wall-Ozawa integration. The reaction kinetics equation and the thermal decomposition mechanism function were investigated by Coats-Redfern method, the study shows that the proximal reaction kinetic equation is Valensi equation, and the reaction order is 2, and the thermal decomposition mechanism function isα+(1-α)·ln(1-α).
引文
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