微波诱导热解废旧印刷电路板（WPCB）的实验和机理研究
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摘要
科学技术和信息产业的飞速发展,加快了各种电子和电器产品的升级换代或淘汰,致使全球电子废弃物数量升幅惊人,成为目前增长速度最快的固体废弃物。作为电子电器产品生产和消费的大国,同时又有欧美地区电子废弃物的非法流入,我国正面临着前所未有的电子废弃物浪潮。电子废弃物作为一种危险废弃物的同时又富含多种金属和贵金属,是宝贵的待用资源。日趋严格的政策法规和日益增长的环境保护和资源回收的意识推动了电子废弃物的回收处理工作的开展。高效而环境友好的处置与回收技术,无论从环境保护还是从宝贵资源的回收利用角度来看,都是电子废弃物完全蜕变为资源的关键,而目前研究和应用还亟待深入。
作为电子废弃物的典型代表,废弃印刷电路板(WPCB)的合理处置与回收是一个相当复杂的问题,引起世界各国研究人员的高度重视。但是由于WPCB自身的材料特性和结构特点,处置和回收过程中存在着一些不利因素,如：基板层压结构韧性强、强度大,破碎不易；稀贵金属往往被非金属材料包裹,回收率低；破碎过程中高温导致有机聚合物分解,引发环境问题；非金属材料利用不足；常规热解因物料尺寸比较大、孔隙率比较多、导热系数比较小等因素而效率不高等,目前相关资源化技术的研发还很不成熟。为此,本文以WPCB为研究对象,对其高效资源化技术展开研究。
微波加热具有选择性、整体性、即时性和高效性等特点,已在生物质、医疗垃圾、生活垃圾等领域得到广泛的研究和应用,将其应用于WPCB热解,可以有效解决WPCB破碎难的问题,并能够实现有价成分的全面回收,而且热解后稀贵金属不存在被非金属材料包裹而难以完全解离的问题,增加产品的附加值。因此,WPCB的微波热解技术日益受到重视。但由于WPCB富含金属的材料特性以及微波加热对于金属材料的规避常识,微波热解WPCB的相关研究还不多。目前已有的研究也是仅仅基于微波作用强吸波介质产生的快速升温特性,通过被率先加热至高温的吸波介质这一热媒的热传导将WPCB热解,从物料被加热方式上看仍属于外部加热,或者说是外部加热和微波加热的混合加热方式,微波整体性加热的优势没有被充分发挥。而微波直接作用WPCB诱导其高效热解的研究还几乎处于空白。
综合国内外微波热解技术在固体废弃物处理和能源转化领域的研究现状,结合WPCB的材料组成和结构特点,尤其是富含金属丝、线、引脚等的材料特性,以及微波作用不同介质的作用机理,尤其是金属尖端在微波作用下能够引发电晕放电乃至剧烈的弧光放电的深入思考,本文提出了微波诱导热解WPCB的研究。本研究是基于微波加热和电晕放电的原理,发挥WPCB本身或掺加介质的微波吸收作用,发挥废弃物中金属部分的放电特性,通过二者的有机耦合,实现WPCB以内部加热为特征的直接热解。基于该思想本文开展了以下研究：
在工业微波热解实验装置上,对两种废旧印刷电路板(电路板基板生产过程中产生的残次品,未安装任何电子元器件,记为WPCB-A;废电脑主板,拆除电阻、电容元件,记为WPCB-B)微波热解的升温特性和失重特性进行了系统的研究,并对废旧印刷电路板在微波加热和常规加热体系下的热分解动力学进行了系统的研究,得到以下结论：微波功率是影响物料升温特性和热解失重特性的重要因素,微波功率较低,只能实现物料的部分热解,总失重较低,物料所能达到的最高温度也相对较低,微波功率超过一定限值后,物料能够实现快速完全热解,热解反应为一阶反应；在相同微波功率下,WPCB-B热解过程伴有频繁的电火花现象,致使升温速率和失重速率都要优于鲜能观察到电火花现象的WPCB-A的热解过程,暗示金属放电对微波加热过程和热解反应的促进作用；对WPCB-A而言,添加合适的微波吸收剂,特别是热解残炭和活性炭,能够显著加快热解反应的进程；对WPCB-B而言,微波吸收剂的添加需谨慎,可能会导致介质吸波与微波-金属放电产生竞争作用机制,以致吸波介质的加入削弱了微波-金属放电的激发及其热效应,产生不利于热解反应进行的影响；WPCB-B微波热解和常规热解的动力学过程存在明显的不同：相同升温速率下,微波加热条件下的活化能显著低于常规加热条件下,表明在微波加热和金属放电的耦合作用下可能存在某种特殊效应(如,非热效应)。
热解产物的有效分离回收和分析表征是本文的另一重要内容。通过对热解产物的有效分离回收,获得WPCB在微波加热条件下热解的产物分布规律；通过采用先进的分析仪器和科学的分析方法对WPCB热解产物的元素组成、分子结构、化学组成、物理性质等进行了全面的分析,对不同产物的资源化利用途径进行全方面、多角度的探讨。此外,针对热解产物中因普遍含有有毒的溴化物而影响产物品质的弊端,本文对微波热解WPCB过程中溴的迁移规律及固化脱除途径进行研究,并针对溴元素在WPCB及热解产物中的存在形式建立了一套完整的、系统的溴元素含量的测试方法。研究结果表明：升温速率和热解终温是影响产物分布的重要因素,升温速率和热解终温的提高在一定范围内有助于缩短挥发分的停留时间,降低了挥发分的二次分解反应,致使液体产物产率升高,同时有助于气体产物中H2含量的提升。热解残炭或活性炭作为性能优良的微波吸收剂,其添加比例的增加,在一定范围内,能促进热分解反应的进行,缩短挥发分的停留时间,致使液体产物产率提高,然而,当添加量达到一定程度致使热解物料床层温度显著提高时,热解释放的挥发分经过炙热的物料床层时便被二次分解为小分子的气体,致使液体产率降低,气体产率升高。由此可见,添加剂的选用一方面应考虑热解效率的提高,同时也要兼顾理想产品的获得。溴元素在WPCB热解过程中,～30%迁移到液体产物中；-50%迁移到气体产物中；仅～20%留在固体产物中。通过提高加热速率促进有机溴化物向HBr的转化后采用CaCO3进行产物脱溴,可实现溴的固化脱除率达到50%以上,液体产物中溴的脱除率达到95%以上,大大提升了热解产品的品质,降低了对管路的腐蚀。
介质吸波和金属放电的耦合作用机制是微波诱导热解WPCB的核心机理问题,只有揭示金属放电与介质吸波的关系,才能明确了WPCB中各主要成分在微波辐照下的作用过程与机理。本文对金属放电和介质吸波的耦合作用进行剥离和叠加分析：首先,本文通过把金属置于微波透射并保温材料——石英砂中进行微波辐照,通过间接水量热法以热量形式对金属放电热效应进行表征；其次,采用同样方式将不同质量的吸波介质置于石英砂中进行微波辐照,考察吸波介质的微波加热效应；最后,将一定质量的金属和不同质量的吸波介质混合后同时进行微波辐照,考察金属放电和介质吸波的叠加热效应。综合以上实验结果和分析获得对介质吸波和金属放电耦合作用的总体描述。研究表明：微波作用下介质吸波与金属放电的耦合作用机制随着吸波介质的添加量的变化既可以是合作又可以是竞争的。当微波吸收介质的量相对较小,微波-金属放电现象几乎不受吸波介质的影响,耦合热效应是两种热效应之间的协同,随着吸波介质量的增加,微波-金属放电激发变得困难,热效应减弱。被加热样品的总体热效应,在很大程度上取决于吸波介质对微波能量的吸收。继续增加吸波介质的量将导致微波金属放电完全不能够被激发,一方面,被加热样品将以介质吸波为主对微波能量进行转化；另一方面,金属可能会对微波传输造成干扰,致使耦合热效应低于相同条件下吸波介质自身产生的热效应。
通过对微波加热过程的模拟研究,进一步从金属和吸波介质引入后空间和物料内部电磁场和温度场的变化规律的角度,对微波作用下金属与吸波介质的耦合作用机制进行进一步的阐释。试验是宏观表征,计算则能具体到点和局部,获得理论层面的深度剖析。本文首先选取物性参数为温变函数并且数据比较完整可靠的水作为吸波介质,对其加热过程电磁场和温度场进行模拟,并对模型的可靠性进行实验验证。然后,对吸波介质(活性炭)在微波辐照下的电磁场和温度场进行模拟,并考察介电参数对能量转化效率的影响,通过理论计算与试验结果的相互检验和印证,完善微波场下吸波介质加热机制的系统描述。最后,对微波辐照下金属和电介质共同存在时电磁场进行了模拟,将电介质分为弱吸波介质和强吸波介质两个情况,分别对叠加作用下的电磁场进行模拟计算,并从负载的平均介电损耗角度对耦合作用机制进行深入的剖析,从理论上完善介质吸波和金属放电耦合作用的系统描述。模拟结果与实验结果能够相互验证,并取得了很好的一致性规律。
通过对热解固体产物进行破碎分离,对金属和非金属组分进行分离回收。通过对气体和液体产物热值和回收的金属组分的市场价值的评估,进行微波辐照废旧印刷电路板回收工艺的经济性的初步分析,发现经济效益显著。因此,采用微波诱导热解的方式处置电子废弃物,特色高效,效益突出,是一种极具潜力的资源回收技术。考虑到规模放大和工业推广的需求,本文针对电子废弃物进行连续生产工艺的设计,并结合国家政策、设备投资、运行成本等方面进行了较为全面的经济性分析,并提出了合理化的建议。
通过本文研究,对微波诱导热解WPCB的过程和机制有了较为全面、深入的透析,对微波热解在不同场合的原理与机制有了进一步的认识和剖析,为微波热解电子废弃物乃至类似固体废弃物的工艺设计和系统优化提供了理论参考和系统参照。最后,对全文的研究内容和研究结论进行总结,指出研究不足,明确下一步研究工作的主要内容。
With the rapid technology innovation, the upgrade and replacement of electrical and electronic equipments (EEE) have been immensely accelerated in the last two decades, resulting in the ever-increasing generation of waste electrical and electronic equipments (WEEE) or so-called e-waste. WEEE has become the fastest growing solid waste. As a big country of the production and consumption of electrical and electronic products, meanwhile with the illegal flow of electronic waste from Europe and America, China is facing an unprecedented wave of electronic waste. As a kind of hazardous waste, WEEE is also very valuable because it is rich in a variety of metals and precious metals. Increasingly stringent policies and the growing awareness of environmental protection and resource recycling have greatly promoted the launching of e-waste recycling. Thus, the efficient and environment-friendly disposal and recycling technology is of great significance not only as regards environmental protection but also for the recovery of valuable materials. However, present research and applications are not deep enough. More work is also urgently needed.
As one of the most important branches of the WEEE stream, waste printed circuit boards (WPCB) are generally considered to be representative of WEEE, and have received increasing attention from the public and researchers worldwide because the reasonable disposal and effective recycling of WPCB is a very complicated issue. Due to complex material properties and structural features of WPCB, the disposal and recycling process are limited by some unfavorable factors, such as:WPCB can not be crushed easily due to its tough substrate laminated structure; the recovery rate of rare metals is low because they are often wrapped in non-metallic materials; environmental problems will be caused in the crushing process because high temperatures cause the decomposition of organic polymer; nonmetallic materials are often underutilized; the efficiency of conventional pyrolysis is not high enough due to the large material size, porosity, low thermal conductivity, and other factors. Currently, the research and development on the recovery technology of WPCB is still immature. In this paper, WPCB is targeted as research object and its efficient recycling technology is widely researched.
Microwave heating is characterized by selective, holistic, real-time and efficient. On basis of these characteristics, microwave heating has been widely used in the field of biomass, medical waste, living garbage and so on. When microwave heating is applied to WPCB pyrolysis, the difficult crushing problem of WPCB can be effectively solved. Moreover, a comprehensive recovery of valuable components can be achieved; rare metals can be easily dissociated from the non-metallic materials; the value of the pyrolysis products can be increased, among others. Thus, microwave pyrolysis technologies of WPCB have received increasing attentions. However, due to the metal-rich material property of WPCB and the common avoidance of the application of microwave heating to metal materials, research on microwave prolysis of WPCB is very rare. The existing researches are solely based on the rapid heating characteristics of microwave absorbers which can be instantly heated to a high temperature. Through the heat conduction of the preheated absorbers, WPCB can be pyrolyzed. From the perspective of heating mode, it is still external heating, or hybrid heating of external heating and microwave heating. Thus, the advantages of microwave overall heating have not been fully explored. While research on the direct exertion of microwaves to WPCB to induce its pyrolysis is still nearly blank.
Based on the research status of microwave pyrolysis technology applied in the field of the solid waste recycling and energy conversion, combined with the material composition and structural characteristics of WPCB, in particular, its metal-rich material property and the microwave heating mechanism, especially discharge phenomenon can be triggered by the exposure of metal tips to microwaves, the research on microwave induced pyrolysis of WPCB is put forward in this paper. This research is based on the principle of microwave heating and corona discharge, aiming to fully utilize the microwave heating effect of WPCB itself or added absorbers and the heating effect of corona discharge caused by microwave-metal interaction. Through the coupling of these two kinds of heating effect, direct pyrolysis of WPCB characterized by internal heating style can be achieved. On the basis of this thinking, the following studies have been carried out:
Systematic research on the dynamics of temperature rising and weight-loss during the microwave-induced pyrolysis of two kinds of WPCB (waste circuit board substrates without any electronic components, denoted as WPCB-A; waste computer motherboard with the removal of resistors and capacitors, denoted as WPCB-B) have been carried out in the industrial microwave pyrolysis apparatus. Moreover, the kinetic study of the thermal decomposition of WPCB under both conventional and microwave heating schemes have been studied by using thermogravimetric analyzer (TGA) and above-mentioned industrial microwave pyrolysis apparatus respectively. The following conclusions can be obtained. Microwave power is an important factor to affect the characteristics of temperature rising and weight-loss. When microwave power is low, only partial pyrolysis of the material can be achieved; the total weight-loss rate is very low; and the highest temperature that the material can reach is also relatively low. When the microwave power exceeds a certain limit, material can be pyrolyzed rapidly and completely and the pyrolysis reactions can be described by a one-phase reaction. At the same microwave power, the pyrolysis process of WPCB-B is accompanied by frequent spark phenomena, resulting in accelerated heating rate and weight-loss rate when compared to WPCB-A, who is pyrolyed with rare spark phenomenon. These results indicate that the metal discharge can promote the microwave heating process and pyrolysis reaction. As regards WPCB-A, the pyrolysis process can be significantly accelerated by adding a suitable microwave absorber, especially pyrolytic char and activated carbon. While, for WPCB-B, the addition of microwave absorbers should be cautious because it may weaken the heating effect caused by microwave-metal discharge, lead to the competition between dielectric heating and microwave-metal discharge which may be inferior to WPCB-B pyrolysis. The kenetics of microwave-induced pyrolysis of WPCB-B is different from its conventional pyrolysis kinetics. Under the same heating rate, the activation energy in microwave-induced pyrolysis is significantly smaller than that in conventional heating scheme, indicating that there may be some kind of special effects (such as non-thermal effects).
The effective separation and recovery as well as analytical characterization of the pyrolysis products is another important part of this paper. Through the effective separation and recovery of the pyrolyzed products, the distribution rules of WPCB under microwave heating conditions can be obtained. Based on the advanced analytical instruments and scientific analytical methods, the elemental composition, molecular structure, chemical composition, and physical properties of the pyrolysis products are analyzed comprehensively. And then the resource utilization of different products has been discussed from multiple perspectives. In addition, with respect to the drawbacks that pyrolysis products generally contain toxic bromides that are unsuitable for reuse, the transference rules of bromine in microwave pyrolysis process of WPCB was studied to explore effective removal pathway. Meanwhile, a complete set of analytical method for the elemental bromine content in the WPCB and pyrolysis products was established. The following conclusion can be obtained. The heating rate and the final pyrolysis temperature are two important factors to affect products distribution; high heating rate and final pyrolysis temperature is beneficial to shorten the residence time of the volatiles and reduce the secondary decomposition reaction, resulting in an increase in the liquid product, also contributing to the enhancement of the H2content in the gaseous product at the same time. With the increased addition of pyrolytic char or activated carbon, the pyrolysis process can be promoted with reduced residence time of the volatiles, leading to the increase of pyrolysis product. However, when the addition of microwave absorber was increased to a certain amount, the reaction temperature can be greatly improved. Thus, the volatile was decomposed secondly when they escape from the material bed, leading to a decrease in the liquid products and an increase of pyrolysis gas. Therefore, the addition of microwave absorber should consider both the pyrolysis efficiency and the expected products. In the microwave-induced pyrolysis of WPCB,～30%Br was transferred into the liquid and～50%Br was transferred into gaseous products while only about one fifth was left in the solid residues. Under the high temperature and rapid pyrolysis process induced by microwave, more than50wt.% bromine in WPCBs can be transformed into HBr and captured by CaCO3. As a result, the pyrolysis oils can achieve a debromination of over95%, improving its quality greatly as well as reducing corrosion to connecting pipes.
The coupling mechanism between microwave-metal discharge and microwave dielectric heating is the core mechanism of microwave-induced pyrolysis of WPCB. Only the relationship between microwave-metal discharge and the dielectric heating is revealed, the performance mechanism of every part of the main ingredients in the WPCB under microwave irradiation can be clear. In this paper, the heating effect of microwave-metal discharge and dielectric heating was studied respectively and then together. Firstly, metal strips were inserted in microwave-transparent and insulated materials-quartz sand, and then irradiated by the microwaves. The heating effect was obtained through an indirect calorimetric method. Secondly, different amounts of microwave absorbers were placed in the quartz sand to obtain their heating effect as the same way. Finally, the mixture of metal strips and microwave absorbers were mixed together and placed in the quartz sand to study their combined heating effect. Based on the above experimental results and analysis, the coupling mechanism of microwave absorption and microwave-metal discharge generation was described. The following conclusion can be obtained. To a certain amount of metals strips, the stimulation and intensity of the discharge are very sensitive to the amount of absorber, with the variation of which, the heating mechanism can be collaborative as well as competitive. When the amount of microwave absorber is small relative to a certain amount of metals strips, the microwave-metal discharge phenomenon is largely unaffected by the absorber, and the heating mechanism between the two effects is collaborative, and the total heat generated could be essentially the sum of the heat produced in each type of interaction. With the increase in the amount of microwave absorber material, microwave-metal discharges become harder to trigger. Thus, the importance of microwave-metal discharges is reduced, and the total heating in the sample is largely dependent on the wave absorption in the absorber. When the amount of microwave absorber is large enough to prevent microwave-metal discharges completely, the total heat generation in the sample is mainly attributable to the wave absorption of absorber. Furthermore, the dispersed metal strips may disturb the wave propagation due to the "skin effect" and reflection of waves, leading to a reduced total heating effect when compared with that of microwave absorber alone.
Through the simulation of microwave heating process, the coupling mechanism between microwave absorber and metal under microwave can be viewed theoretically. The experimental test can characterize their coupling rules from a macroscopic view, while calculation can be specific to the point and detail to obtain their coupling mechanism theoretically. Firstly, due to complete information about the variation of the physical parameters as a function of temperature-change, water was selected as microwave absorber to simulate the electromagnetic field and temperature field during its microwave heating process. The simulation results were tested by the temperature measurement experiments after a certain period of time to validate the reliability of the model. Then, the electromagnetic field and temperature field of microwave absorber (activated carbon) during microwave heating process were simulated. The influence of dielectric parameters on the energy conversion ratio was studied. By the mutual inspection and confirmation between the theoretical calculations and experimental results, the mechanism of microwave dielectric heating can be described more completely. Finally, the electromagnetic field when metal strips and dielectric medium were co-existed under microwave irradiation was simulated to complete the systematic and theoretical description of the coupling mechanism. Dielectric medium was classified into two kinds:one is microwave transparent medium, the other is strong microwave absorber. The calculation results and the experimental results can be mutually verified.
The economic assessment of the recovery process by microwave-induced pyrolysis was carried out by crushing and separating the pyrolysis solid products to recover metals and assess their value and assessing the calorific value of the gas and liquid products. The economic assessment reveals that the combined treatment is amazingly profitable and very promising to tackle the challenges posed by the electronic scraps. Taking into account the demand for scale-up and industrial promotion, a continuous recycling process was designed for WEEE recycling and reasonable proposal has been put forward for the improvement of pyrolysis efficiency and economic benefits.
Through this study, a more comprehensive and in-depth understanding of the microwave-induced pyrolysis process of WPCB can be obtained, enriching the understanding of the principles and mechanisms of microwave pyrolysis in different occasions. It will provide theoretical reference for the process design and system optimization for the microwave-induced pyrolysis of electronic waste and even other similar solid waste. Finally, a summary of the content and conclusions of the full text were presented, the inadequate points of my research were pointed out, and the further research work was indicated.
作为电子废弃物的典型代表,废弃印刷电路板(WPCB)的合理处置与回收是一个相当复杂的问题,引起世界各国研究人员的高度重视。但是由于WPCB自身的材料特性和结构特点,处置和回收过程中存在着一些不利因素,如：基板层压结构韧性强、强度大,破碎不易；稀贵金属往往被非金属材料包裹,回收率低；破碎过程中高温导致有机聚合物分解,引发环境问题；非金属材料利用不足；常规热解因物料尺寸比较大、孔隙率比较多、导热系数比较小等因素而效率不高等,目前相关资源化技术的研发还很不成熟。为此,本文以WPCB为研究对象,对其高效资源化技术展开研究。
微波加热具有选择性、整体性、即时性和高效性等特点,已在生物质、医疗垃圾、生活垃圾等领域得到广泛的研究和应用,将其应用于WPCB热解,可以有效解决WPCB破碎难的问题,并能够实现有价成分的全面回收,而且热解后稀贵金属不存在被非金属材料包裹而难以完全解离的问题,增加产品的附加值。因此,WPCB的微波热解技术日益受到重视。但由于WPCB富含金属的材料特性以及微波加热对于金属材料的规避常识,微波热解WPCB的相关研究还不多。目前已有的研究也是仅仅基于微波作用强吸波介质产生的快速升温特性,通过被率先加热至高温的吸波介质这一热媒的热传导将WPCB热解,从物料被加热方式上看仍属于外部加热,或者说是外部加热和微波加热的混合加热方式,微波整体性加热的优势没有被充分发挥。而微波直接作用WPCB诱导其高效热解的研究还几乎处于空白。
综合国内外微波热解技术在固体废弃物处理和能源转化领域的研究现状,结合WPCB的材料组成和结构特点,尤其是富含金属丝、线、引脚等的材料特性,以及微波作用不同介质的作用机理,尤其是金属尖端在微波作用下能够引发电晕放电乃至剧烈的弧光放电的深入思考,本文提出了微波诱导热解WPCB的研究。本研究是基于微波加热和电晕放电的原理,发挥WPCB本身或掺加介质的微波吸收作用,发挥废弃物中金属部分的放电特性,通过二者的有机耦合,实现WPCB以内部加热为特征的直接热解。基于该思想本文开展了以下研究：
在工业微波热解实验装置上,对两种废旧印刷电路板(电路板基板生产过程中产生的残次品,未安装任何电子元器件,记为WPCB-A;废电脑主板,拆除电阻、电容元件,记为WPCB-B)微波热解的升温特性和失重特性进行了系统的研究,并对废旧印刷电路板在微波加热和常规加热体系下的热分解动力学进行了系统的研究,得到以下结论：微波功率是影响物料升温特性和热解失重特性的重要因素,微波功率较低,只能实现物料的部分热解,总失重较低,物料所能达到的最高温度也相对较低,微波功率超过一定限值后,物料能够实现快速完全热解,热解反应为一阶反应；在相同微波功率下,WPCB-B热解过程伴有频繁的电火花现象,致使升温速率和失重速率都要优于鲜能观察到电火花现象的WPCB-A的热解过程,暗示金属放电对微波加热过程和热解反应的促进作用；对WPCB-A而言,添加合适的微波吸收剂,特别是热解残炭和活性炭,能够显著加快热解反应的进程；对WPCB-B而言,微波吸收剂的添加需谨慎,可能会导致介质吸波与微波-金属放电产生竞争作用机制,以致吸波介质的加入削弱了微波-金属放电的激发及其热效应,产生不利于热解反应进行的影响；WPCB-B微波热解和常规热解的动力学过程存在明显的不同：相同升温速率下,微波加热条件下的活化能显著低于常规加热条件下,表明在微波加热和金属放电的耦合作用下可能存在某种特殊效应(如,非热效应)。
热解产物的有效分离回收和分析表征是本文的另一重要内容。通过对热解产物的有效分离回收,获得WPCB在微波加热条件下热解的产物分布规律；通过采用先进的分析仪器和科学的分析方法对WPCB热解产物的元素组成、分子结构、化学组成、物理性质等进行了全面的分析,对不同产物的资源化利用途径进行全方面、多角度的探讨。此外,针对热解产物中因普遍含有有毒的溴化物而影响产物品质的弊端,本文对微波热解WPCB过程中溴的迁移规律及固化脱除途径进行研究,并针对溴元素在WPCB及热解产物中的存在形式建立了一套完整的、系统的溴元素含量的测试方法。研究结果表明：升温速率和热解终温是影响产物分布的重要因素,升温速率和热解终温的提高在一定范围内有助于缩短挥发分的停留时间,降低了挥发分的二次分解反应,致使液体产物产率升高,同时有助于气体产物中H2含量的提升。热解残炭或活性炭作为性能优良的微波吸收剂,其添加比例的增加,在一定范围内,能促进热分解反应的进行,缩短挥发分的停留时间,致使液体产物产率提高,然而,当添加量达到一定程度致使热解物料床层温度显著提高时,热解释放的挥发分经过炙热的物料床层时便被二次分解为小分子的气体,致使液体产率降低,气体产率升高。由此可见,添加剂的选用一方面应考虑热解效率的提高,同时也要兼顾理想产品的获得。溴元素在WPCB热解过程中,～30%迁移到液体产物中；-50%迁移到气体产物中；仅～20%留在固体产物中。通过提高加热速率促进有机溴化物向HBr的转化后采用CaCO3进行产物脱溴,可实现溴的固化脱除率达到50%以上,液体产物中溴的脱除率达到95%以上,大大提升了热解产品的品质,降低了对管路的腐蚀。
介质吸波和金属放电的耦合作用机制是微波诱导热解WPCB的核心机理问题,只有揭示金属放电与介质吸波的关系,才能明确了WPCB中各主要成分在微波辐照下的作用过程与机理。本文对金属放电和介质吸波的耦合作用进行剥离和叠加分析：首先,本文通过把金属置于微波透射并保温材料——石英砂中进行微波辐照,通过间接水量热法以热量形式对金属放电热效应进行表征；其次,采用同样方式将不同质量的吸波介质置于石英砂中进行微波辐照,考察吸波介质的微波加热效应；最后,将一定质量的金属和不同质量的吸波介质混合后同时进行微波辐照,考察金属放电和介质吸波的叠加热效应。综合以上实验结果和分析获得对介质吸波和金属放电耦合作用的总体描述。研究表明：微波作用下介质吸波与金属放电的耦合作用机制随着吸波介质的添加量的变化既可以是合作又可以是竞争的。当微波吸收介质的量相对较小,微波-金属放电现象几乎不受吸波介质的影响,耦合热效应是两种热效应之间的协同,随着吸波介质量的增加,微波-金属放电激发变得困难,热效应减弱。被加热样品的总体热效应,在很大程度上取决于吸波介质对微波能量的吸收。继续增加吸波介质的量将导致微波金属放电完全不能够被激发,一方面,被加热样品将以介质吸波为主对微波能量进行转化；另一方面,金属可能会对微波传输造成干扰,致使耦合热效应低于相同条件下吸波介质自身产生的热效应。
通过对微波加热过程的模拟研究,进一步从金属和吸波介质引入后空间和物料内部电磁场和温度场的变化规律的角度,对微波作用下金属与吸波介质的耦合作用机制进行进一步的阐释。试验是宏观表征,计算则能具体到点和局部,获得理论层面的深度剖析。本文首先选取物性参数为温变函数并且数据比较完整可靠的水作为吸波介质,对其加热过程电磁场和温度场进行模拟,并对模型的可靠性进行实验验证。然后,对吸波介质(活性炭)在微波辐照下的电磁场和温度场进行模拟,并考察介电参数对能量转化效率的影响,通过理论计算与试验结果的相互检验和印证,完善微波场下吸波介质加热机制的系统描述。最后,对微波辐照下金属和电介质共同存在时电磁场进行了模拟,将电介质分为弱吸波介质和强吸波介质两个情况,分别对叠加作用下的电磁场进行模拟计算,并从负载的平均介电损耗角度对耦合作用机制进行深入的剖析,从理论上完善介质吸波和金属放电耦合作用的系统描述。模拟结果与实验结果能够相互验证,并取得了很好的一致性规律。
通过对热解固体产物进行破碎分离,对金属和非金属组分进行分离回收。通过对气体和液体产物热值和回收的金属组分的市场价值的评估,进行微波辐照废旧印刷电路板回收工艺的经济性的初步分析,发现经济效益显著。因此,采用微波诱导热解的方式处置电子废弃物,特色高效,效益突出,是一种极具潜力的资源回收技术。考虑到规模放大和工业推广的需求,本文针对电子废弃物进行连续生产工艺的设计,并结合国家政策、设备投资、运行成本等方面进行了较为全面的经济性分析,并提出了合理化的建议。
通过本文研究,对微波诱导热解WPCB的过程和机制有了较为全面、深入的透析,对微波热解在不同场合的原理与机制有了进一步的认识和剖析,为微波热解电子废弃物乃至类似固体废弃物的工艺设计和系统优化提供了理论参考和系统参照。最后,对全文的研究内容和研究结论进行总结,指出研究不足,明确下一步研究工作的主要内容。
With the rapid technology innovation, the upgrade and replacement of electrical and electronic equipments (EEE) have been immensely accelerated in the last two decades, resulting in the ever-increasing generation of waste electrical and electronic equipments (WEEE) or so-called e-waste. WEEE has become the fastest growing solid waste. As a big country of the production and consumption of electrical and electronic products, meanwhile with the illegal flow of electronic waste from Europe and America, China is facing an unprecedented wave of electronic waste. As a kind of hazardous waste, WEEE is also very valuable because it is rich in a variety of metals and precious metals. Increasingly stringent policies and the growing awareness of environmental protection and resource recycling have greatly promoted the launching of e-waste recycling. Thus, the efficient and environment-friendly disposal and recycling technology is of great significance not only as regards environmental protection but also for the recovery of valuable materials. However, present research and applications are not deep enough. More work is also urgently needed.
As one of the most important branches of the WEEE stream, waste printed circuit boards (WPCB) are generally considered to be representative of WEEE, and have received increasing attention from the public and researchers worldwide because the reasonable disposal and effective recycling of WPCB is a very complicated issue. Due to complex material properties and structural features of WPCB, the disposal and recycling process are limited by some unfavorable factors, such as:WPCB can not be crushed easily due to its tough substrate laminated structure; the recovery rate of rare metals is low because they are often wrapped in non-metallic materials; environmental problems will be caused in the crushing process because high temperatures cause the decomposition of organic polymer; nonmetallic materials are often underutilized; the efficiency of conventional pyrolysis is not high enough due to the large material size, porosity, low thermal conductivity, and other factors. Currently, the research and development on the recovery technology of WPCB is still immature. In this paper, WPCB is targeted as research object and its efficient recycling technology is widely researched.
Microwave heating is characterized by selective, holistic, real-time and efficient. On basis of these characteristics, microwave heating has been widely used in the field of biomass, medical waste, living garbage and so on. When microwave heating is applied to WPCB pyrolysis, the difficult crushing problem of WPCB can be effectively solved. Moreover, a comprehensive recovery of valuable components can be achieved; rare metals can be easily dissociated from the non-metallic materials; the value of the pyrolysis products can be increased, among others. Thus, microwave pyrolysis technologies of WPCB have received increasing attentions. However, due to the metal-rich material property of WPCB and the common avoidance of the application of microwave heating to metal materials, research on microwave prolysis of WPCB is very rare. The existing researches are solely based on the rapid heating characteristics of microwave absorbers which can be instantly heated to a high temperature. Through the heat conduction of the preheated absorbers, WPCB can be pyrolyzed. From the perspective of heating mode, it is still external heating, or hybrid heating of external heating and microwave heating. Thus, the advantages of microwave overall heating have not been fully explored. While research on the direct exertion of microwaves to WPCB to induce its pyrolysis is still nearly blank.
Based on the research status of microwave pyrolysis technology applied in the field of the solid waste recycling and energy conversion, combined with the material composition and structural characteristics of WPCB, in particular, its metal-rich material property and the microwave heating mechanism, especially discharge phenomenon can be triggered by the exposure of metal tips to microwaves, the research on microwave induced pyrolysis of WPCB is put forward in this paper. This research is based on the principle of microwave heating and corona discharge, aiming to fully utilize the microwave heating effect of WPCB itself or added absorbers and the heating effect of corona discharge caused by microwave-metal interaction. Through the coupling of these two kinds of heating effect, direct pyrolysis of WPCB characterized by internal heating style can be achieved. On the basis of this thinking, the following studies have been carried out:
Systematic research on the dynamics of temperature rising and weight-loss during the microwave-induced pyrolysis of two kinds of WPCB (waste circuit board substrates without any electronic components, denoted as WPCB-A; waste computer motherboard with the removal of resistors and capacitors, denoted as WPCB-B) have been carried out in the industrial microwave pyrolysis apparatus. Moreover, the kinetic study of the thermal decomposition of WPCB under both conventional and microwave heating schemes have been studied by using thermogravimetric analyzer (TGA) and above-mentioned industrial microwave pyrolysis apparatus respectively. The following conclusions can be obtained. Microwave power is an important factor to affect the characteristics of temperature rising and weight-loss. When microwave power is low, only partial pyrolysis of the material can be achieved; the total weight-loss rate is very low; and the highest temperature that the material can reach is also relatively low. When the microwave power exceeds a certain limit, material can be pyrolyzed rapidly and completely and the pyrolysis reactions can be described by a one-phase reaction. At the same microwave power, the pyrolysis process of WPCB-B is accompanied by frequent spark phenomena, resulting in accelerated heating rate and weight-loss rate when compared to WPCB-A, who is pyrolyed with rare spark phenomenon. These results indicate that the metal discharge can promote the microwave heating process and pyrolysis reaction. As regards WPCB-A, the pyrolysis process can be significantly accelerated by adding a suitable microwave absorber, especially pyrolytic char and activated carbon. While, for WPCB-B, the addition of microwave absorbers should be cautious because it may weaken the heating effect caused by microwave-metal discharge, lead to the competition between dielectric heating and microwave-metal discharge which may be inferior to WPCB-B pyrolysis. The kenetics of microwave-induced pyrolysis of WPCB-B is different from its conventional pyrolysis kinetics. Under the same heating rate, the activation energy in microwave-induced pyrolysis is significantly smaller than that in conventional heating scheme, indicating that there may be some kind of special effects (such as non-thermal effects).
The effective separation and recovery as well as analytical characterization of the pyrolysis products is another important part of this paper. Through the effective separation and recovery of the pyrolyzed products, the distribution rules of WPCB under microwave heating conditions can be obtained. Based on the advanced analytical instruments and scientific analytical methods, the elemental composition, molecular structure, chemical composition, and physical properties of the pyrolysis products are analyzed comprehensively. And then the resource utilization of different products has been discussed from multiple perspectives. In addition, with respect to the drawbacks that pyrolysis products generally contain toxic bromides that are unsuitable for reuse, the transference rules of bromine in microwave pyrolysis process of WPCB was studied to explore effective removal pathway. Meanwhile, a complete set of analytical method for the elemental bromine content in the WPCB and pyrolysis products was established. The following conclusion can be obtained. The heating rate and the final pyrolysis temperature are two important factors to affect products distribution; high heating rate and final pyrolysis temperature is beneficial to shorten the residence time of the volatiles and reduce the secondary decomposition reaction, resulting in an increase in the liquid product, also contributing to the enhancement of the H2content in the gaseous product at the same time. With the increased addition of pyrolytic char or activated carbon, the pyrolysis process can be promoted with reduced residence time of the volatiles, leading to the increase of pyrolysis product. However, when the addition of microwave absorber was increased to a certain amount, the reaction temperature can be greatly improved. Thus, the volatile was decomposed secondly when they escape from the material bed, leading to a decrease in the liquid products and an increase of pyrolysis gas. Therefore, the addition of microwave absorber should consider both the pyrolysis efficiency and the expected products. In the microwave-induced pyrolysis of WPCB,～30%Br was transferred into the liquid and～50%Br was transferred into gaseous products while only about one fifth was left in the solid residues. Under the high temperature and rapid pyrolysis process induced by microwave, more than50wt.% bromine in WPCBs can be transformed into HBr and captured by CaCO3. As a result, the pyrolysis oils can achieve a debromination of over95%, improving its quality greatly as well as reducing corrosion to connecting pipes.
The coupling mechanism between microwave-metal discharge and microwave dielectric heating is the core mechanism of microwave-induced pyrolysis of WPCB. Only the relationship between microwave-metal discharge and the dielectric heating is revealed, the performance mechanism of every part of the main ingredients in the WPCB under microwave irradiation can be clear. In this paper, the heating effect of microwave-metal discharge and dielectric heating was studied respectively and then together. Firstly, metal strips were inserted in microwave-transparent and insulated materials-quartz sand, and then irradiated by the microwaves. The heating effect was obtained through an indirect calorimetric method. Secondly, different amounts of microwave absorbers were placed in the quartz sand to obtain their heating effect as the same way. Finally, the mixture of metal strips and microwave absorbers were mixed together and placed in the quartz sand to study their combined heating effect. Based on the above experimental results and analysis, the coupling mechanism of microwave absorption and microwave-metal discharge generation was described. The following conclusion can be obtained. To a certain amount of metals strips, the stimulation and intensity of the discharge are very sensitive to the amount of absorber, with the variation of which, the heating mechanism can be collaborative as well as competitive. When the amount of microwave absorber is small relative to a certain amount of metals strips, the microwave-metal discharge phenomenon is largely unaffected by the absorber, and the heating mechanism between the two effects is collaborative, and the total heat generated could be essentially the sum of the heat produced in each type of interaction. With the increase in the amount of microwave absorber material, microwave-metal discharges become harder to trigger. Thus, the importance of microwave-metal discharges is reduced, and the total heating in the sample is largely dependent on the wave absorption in the absorber. When the amount of microwave absorber is large enough to prevent microwave-metal discharges completely, the total heat generation in the sample is mainly attributable to the wave absorption of absorber. Furthermore, the dispersed metal strips may disturb the wave propagation due to the "skin effect" and reflection of waves, leading to a reduced total heating effect when compared with that of microwave absorber alone.
Through the simulation of microwave heating process, the coupling mechanism between microwave absorber and metal under microwave can be viewed theoretically. The experimental test can characterize their coupling rules from a macroscopic view, while calculation can be specific to the point and detail to obtain their coupling mechanism theoretically. Firstly, due to complete information about the variation of the physical parameters as a function of temperature-change, water was selected as microwave absorber to simulate the electromagnetic field and temperature field during its microwave heating process. The simulation results were tested by the temperature measurement experiments after a certain period of time to validate the reliability of the model. Then, the electromagnetic field and temperature field of microwave absorber (activated carbon) during microwave heating process were simulated. The influence of dielectric parameters on the energy conversion ratio was studied. By the mutual inspection and confirmation between the theoretical calculations and experimental results, the mechanism of microwave dielectric heating can be described more completely. Finally, the electromagnetic field when metal strips and dielectric medium were co-existed under microwave irradiation was simulated to complete the systematic and theoretical description of the coupling mechanism. Dielectric medium was classified into two kinds:one is microwave transparent medium, the other is strong microwave absorber. The calculation results and the experimental results can be mutually verified.
The economic assessment of the recovery process by microwave-induced pyrolysis was carried out by crushing and separating the pyrolysis solid products to recover metals and assess their value and assessing the calorific value of the gas and liquid products. The economic assessment reveals that the combined treatment is amazingly profitable and very promising to tackle the challenges posed by the electronic scraps. Taking into account the demand for scale-up and industrial promotion, a continuous recycling process was designed for WEEE recycling and reasonable proposal has been put forward for the improvement of pyrolysis efficiency and economic benefits.
Through this study, a more comprehensive and in-depth understanding of the microwave-induced pyrolysis process of WPCB can be obtained, enriching the understanding of the principles and mechanisms of microwave pyrolysis in different occasions. It will provide theoretical reference for the process design and system optimization for the microwave-induced pyrolysis of electronic waste and even other similar solid waste. Finally, a summary of the content and conclusions of the full text were presented, the inadequate points of my research were pointed out, and the further research work was indicated.
引文
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