电子废弃物的预处理以及铜的电积制备
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摘要
电子废弃物中除了含有卤素阻燃剂、汞、硒、镍、铅、铬等污染物，还含有多种贵金属，如金、铜和银等，如果将其作为垃圾直接进行处理，不仅造成大量宝贵资源的浪费，而且给环境造成严重的危害。如何处理这些电子废弃物，已经成为整个人类共同面临的课题。
在本文中，笔者以废弃电脑中的线路板为例，总结了电子废弃物的特点及国内外从电子废弃物中回收铜的技术，在分析线路板经过拆卸分离后的金属混合物中的成分和各种元素含量的基础上，研究了如何从废弃线路板中回收高品质的铜，并对整个工艺进行了初步的工艺设计和效益分析。在这个工艺中，主要分为三个阶段：电子废弃物的预处理；从预处理液中选择性萃取铜；从经过萃取浓缩的硫酸铜溶液中电积制备铜。
本文分别用电感耦合等离子体原子发射光谱(ICP-AES)法和火焰原子吸收(AAS)法测定了线路板经过拆卸分离后的金属混合物中的成分以及各种元素的含量。测量结果表明，线路板中元素的种类多样，含量相差很大。主要含有的金属有：铜、金、银、镁、铅、锌、锰、铝、铁、锡、铂、钯、铬、镍、钛等等。其中铜占金属总重量的90％，将线路板中的铜进行回收，具有很可观的经济效益，同时也避免了其中的重金属给环境带来的危害。
根据印刷线路板中元素的成分及其含量，决定其预处理和资源化工艺。在预处理工艺中，设计两种实验方案：第一种是采用H_2SO_4-HNO_3-H_2O-NaOH回收体系对电子废弃物进行预处理；第二种是采用H_2SO_4-HNO_3-H_2O-O_2-NO_x循环使用体系对电子废弃物进行预处理，这是在第一种体系的基础上，在体系中通入氧气，并加入气体吸收装置，将反应过程中产生的氮氧化物转化为硝酸而加以回用。通过实验，笔者摸索出预处理工艺的最佳运行条件：原料20g，硫酸35mL，硝酸18mL，水200mL，氧气流量3L／h，温度60℃，反应时间2小时，金属的浸取率可达到93％以上，铜的溶解率达到99％以上，硝酸在现有设备上的回收率可达94％以上。
对经过预处理的溶液进行三级萃取、一级反萃取，就可以得到符合电积要求的硫酸铜溶液。在萃取、反萃取工艺中，摸索出该工艺的一级萃取的最佳运行条件：温度20℃，pH值2.0、相比2：1、萃取时间3min、搅拌速度910r／min、萃取剂浓度80％。按照最优化条件(萃取剂的浓度取30％)对原溶液进行三级萃取，萃取率可以达到99.2％。按照O／A的比值为3进行一级反萃取，反萃率也可以达到99％以上。
将符合电积要求的硫酸铜溶液进行电积就可以得到高品质的铜。在电积工艺中，重点考察了pH值、温度、电流密度、槽电压、铜离子浓度、搅拌速度、对电流效率的影响。实验表明：pH值4，温度60℃，电流密度200A／m~2，槽电压2.2V，铜离子浓度在18g／L以上，搅拌速度600r／min，电流效率、电耗、铜的表面质量和纯度都能够取得比较理想的效果。
在实验的基础上，对整个工艺进行了初步的工艺设计和经济效益分析，结果表明：该工艺具有很好的经济效益和环境效益。
ABSTRACTThe electronic wastes still contained various metals, such as gold, copper and silver except for some pollutants, such as halogen flame retardants, mercury, selenium, nickel, lead and chrome. If the electronic wastes are directly disposed as garbage, this would not only be a waste of amount of metals, but result in serious damage to environment. How to deal with these electronic wastes has become a universal subject faced by the humankind.In this paper, the author took the circuit board of the discarded computer as example, summaried the characteristics of electronic wastes and the technology of recovering copper from electronic wastes at home and abroad. On the basis of determining element component and content in circuit board, the way of recovering high-quality copper from discarded circuit board had been studied, and the preliminary processing design and benefit analysis about the entire process had been carried out. There were three main steps in this process: the pretreatment of electronic wastes, selective extraction of copper from the pretreated solution, and preparing copper from copper sulfate solution which had been extracted and condensed.The element component and content in circuit board were deter-mined by IGP-AES and AAS methods, respectively. Result indicated that there were many type of elements in circuit board, and the element content varied widely. The main metals contained in circuit board were copper, aurum, silver, magnesium, lead, zinc, manganese, aluminum, iron, stannum, platinum, palladium, chrome, nickel, titanium etc. Because copper content was 90%, recovering copper from circuit board may not only bring forth considerable economic benefit, but avoid resulting in harm to environment.The pretreatment on circuit board was carried out on the basis of determining the component and content of element in circuit board. There were two alternative schemes for pretreatment process. The first was HSO-HNO-HO-NaOH system, and the second was HSO-HNO-HO-O-NOx System, which was on the basis of the first system. oxygen was added into the entire system, together with the gas absorption setup which was used for turning nitrogen oxide produced by metal-oxidized reactions into nitric acid for recycling. The best operating conditions of pretreat-ment process had been found out through experiment: Raw material, 20g; sulfuric acid, 35ml; nitric acid, 18ml; water, 200ml; flow rate of oxygen, 3L/h; temperature, 60(?); time of reaction ,2 hours. The dissolution rate of metal mixture was over 93%, and that of copper was also over 99%. At the same time, the recycling rate of nitric acid was at least 94% with the use of the equipment available.By the pretreatment, the original copper sulfate could be gained. The pure copper sulfate solution which meet the need of electrodeposition could be prepared through tri-stage extraction and single stage re-extraction. The best operating conditions of single stage extraction were: temperature, 20(?); pH, 2．0; O/A, 2:1; extraction time, 3min; stirring velocity, 910r/min; extractant concentration, 80%. The extraction efficiency was high to 99．2% provided that the tri-stage extraction was carried out to the original solution under the optimized condition (extractant concentration, 30%). The re-extraction efficiency could be higher than 99% by single re-extraction with the operating parameter (O/A, 3:1) .High-quality copper could be prepared by electrodeposition of copper sulfate solution. The effect of pH, temperature, current density, cell voltage, reaction time, stirring velocity and concentration of copper sulfate on current efficiency was studied, the result of experiment demonstrated that high current efficiency, low electricity consumption, good surface characteristic and high purity of copper could be gained under the following operating conditions:pH,4;temperature,60(?);currentdensity,200A/m; cell voltage,2．2V; concentration copper sulfate, 18g/L;stirring velocity,600r/min. Based on the experiment, the preliminary precessing design and theeconomic benefit analysis about the entire process had been carried out.The result demonstrated that this process of preparing high-quality copperhad both economic and environmental benefit.Name: Zhangwuxue (environmental engineering) Supervised by: Lidengxin(professor)
在本文中，笔者以废弃电脑中的线路板为例，总结了电子废弃物的特点及国内外从电子废弃物中回收铜的技术，在分析线路板经过拆卸分离后的金属混合物中的成分和各种元素含量的基础上，研究了如何从废弃线路板中回收高品质的铜，并对整个工艺进行了初步的工艺设计和效益分析。在这个工艺中，主要分为三个阶段：电子废弃物的预处理；从预处理液中选择性萃取铜；从经过萃取浓缩的硫酸铜溶液中电积制备铜。
本文分别用电感耦合等离子体原子发射光谱(ICP-AES)法和火焰原子吸收(AAS)法测定了线路板经过拆卸分离后的金属混合物中的成分以及各种元素的含量。测量结果表明，线路板中元素的种类多样，含量相差很大。主要含有的金属有：铜、金、银、镁、铅、锌、锰、铝、铁、锡、铂、钯、铬、镍、钛等等。其中铜占金属总重量的90％，将线路板中的铜进行回收，具有很可观的经济效益，同时也避免了其中的重金属给环境带来的危害。
根据印刷线路板中元素的成分及其含量，决定其预处理和资源化工艺。在预处理工艺中，设计两种实验方案：第一种是采用H_2SO_4-HNO_3-H_2O-NaOH回收体系对电子废弃物进行预处理；第二种是采用H_2SO_4-HNO_3-H_2O-O_2-NO_x循环使用体系对电子废弃物进行预处理，这是在第一种体系的基础上，在体系中通入氧气，并加入气体吸收装置，将反应过程中产生的氮氧化物转化为硝酸而加以回用。通过实验，笔者摸索出预处理工艺的最佳运行条件：原料20g，硫酸35mL，硝酸18mL，水200mL，氧气流量3L／h，温度60℃，反应时间2小时，金属的浸取率可达到93％以上，铜的溶解率达到99％以上，硝酸在现有设备上的回收率可达94％以上。
对经过预处理的溶液进行三级萃取、一级反萃取，就可以得到符合电积要求的硫酸铜溶液。在萃取、反萃取工艺中，摸索出该工艺的一级萃取的最佳运行条件：温度20℃，pH值2.0、相比2：1、萃取时间3min、搅拌速度910r／min、萃取剂浓度80％。按照最优化条件(萃取剂的浓度取30％)对原溶液进行三级萃取，萃取率可以达到99.2％。按照O／A的比值为3进行一级反萃取，反萃率也可以达到99％以上。
将符合电积要求的硫酸铜溶液进行电积就可以得到高品质的铜。在电积工艺中，重点考察了pH值、温度、电流密度、槽电压、铜离子浓度、搅拌速度、对电流效率的影响。实验表明：pH值4，温度60℃，电流密度200A／m~2，槽电压2.2V，铜离子浓度在18g／L以上，搅拌速度600r／min，电流效率、电耗、铜的表面质量和纯度都能够取得比较理想的效果。
在实验的基础上，对整个工艺进行了初步的工艺设计和经济效益分析，结果表明：该工艺具有很好的经济效益和环境效益。
ABSTRACTThe electronic wastes still contained various metals, such as gold, copper and silver except for some pollutants, such as halogen flame retardants, mercury, selenium, nickel, lead and chrome. If the electronic wastes are directly disposed as garbage, this would not only be a waste of amount of metals, but result in serious damage to environment. How to deal with these electronic wastes has become a universal subject faced by the humankind.In this paper, the author took the circuit board of the discarded computer as example, summaried the characteristics of electronic wastes and the technology of recovering copper from electronic wastes at home and abroad. On the basis of determining element component and content in circuit board, the way of recovering high-quality copper from discarded circuit board had been studied, and the preliminary processing design and benefit analysis about the entire process had been carried out. There were three main steps in this process: the pretreatment of electronic wastes, selective extraction of copper from the pretreated solution, and preparing copper from copper sulfate solution which had been extracted and condensed.The element component and content in circuit board were deter-mined by IGP-AES and AAS methods, respectively. Result indicated that there were many type of elements in circuit board, and the element content varied widely. The main metals contained in circuit board were copper, aurum, silver, magnesium, lead, zinc, manganese, aluminum, iron, stannum, platinum, palladium, chrome, nickel, titanium etc. Because copper content was 90%, recovering copper from circuit board may not only bring forth considerable economic benefit, but avoid resulting in harm to environment.The pretreatment on circuit board was carried out on the basis of determining the component and content of element in circuit board. There were two alternative schemes for pretreatment process. The first was HSO-HNO-HO-NaOH system, and the second was HSO-HNO-HO-O-NOx System, which was on the basis of the first system. oxygen was added into the entire system, together with the gas absorption setup which was used for turning nitrogen oxide produced by metal-oxidized reactions into nitric acid for recycling. The best operating conditions of pretreat-ment process had been found out through experiment: Raw material, 20g; sulfuric acid, 35ml; nitric acid, 18ml; water, 200ml; flow rate of oxygen, 3L/h; temperature, 60(?); time of reaction ,2 hours. The dissolution rate of metal mixture was over 93%, and that of copper was also over 99%. At the same time, the recycling rate of nitric acid was at least 94% with the use of the equipment available.By the pretreatment, the original copper sulfate could be gained. The pure copper sulfate solution which meet the need of electrodeposition could be prepared through tri-stage extraction and single stage re-extraction. The best operating conditions of single stage extraction were: temperature, 20(?); pH, 2．0; O/A, 2:1; extraction time, 3min; stirring velocity, 910r/min; extractant concentration, 80%. The extraction efficiency was high to 99．2% provided that the tri-stage extraction was carried out to the original solution under the optimized condition (extractant concentration, 30%). The re-extraction efficiency could be higher than 99% by single re-extraction with the operating parameter (O/A, 3:1) .High-quality copper could be prepared by electrodeposition of copper sulfate solution. The effect of pH, temperature, current density, cell voltage, reaction time, stirring velocity and concentration of copper sulfate on current efficiency was studied, the result of experiment demonstrated that high current efficiency, low electricity consumption, good surface characteristic and high purity of copper could be gained under the following operating conditions:pH,4;temperature,60(?);currentdensity,200A/m; cell voltage,2．2V; concentration copper sulfate, 18g/L;stirring velocity,600r/min. Based on the experiment, the preliminary precessing design and theeconomic benefit analysis about the entire process had been carried out.The result demonstrated that this process of preparing high-quality copperhad both economic and environmental benefit.Name: Zhangwuxue (environmental engineering) Supervised by: Lidengxin(professor)
引文
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