酸性蚀刻液电化学再生回用技术研究
摘要
随着中国改革开放不断的深化,全中国的印制电路板(Printed Circuit Board,简称PCB)生产企业发展迅速,自2003年以来,中国已经成为世界PCB工业的第二生产大国,并且每年还以20%左右的发展速度增加。在电路板的生产过程中,蚀铜是一个非常重要的过程,每年都要消耗大量精铜并排出数量庞大的含铜量高的蚀刻废液(含铜120-180 g/L)。大部分企业采用抛弃法,即廉价地将废液卖给有回收资质的单位,用化学法回收废液中的铜,这不仅造成企业本身的经济损失,污染源的转移还给环境造成了二次污染;还有部分企业采用化学试剂氧化再生法,虽然可以再生废液,但是会导致蚀刻液的体积不断增大,而且消耗了化学试剂,并且还是要面对废液的处理。因此,酸性蚀刻废液的的处理问题成为国内外研究的一项重要课题。
本文进行了运用电化学法电解再生回用酸性蚀刻液的研究。酸性蚀刻液的电化学再生,是一种在线的再生方法,不但可以使蚀刻液恢复原有的蚀刻效能,而且同时产出了具有商业价值的金属铜粉。电化学法再生的基本原理是电解时,在电解槽的阳极使Cu~+被氧化成Cu~(2+);同时在阴极首先是Cu~(2+)被还原成Cu~+,然后Cu~+被还原成Cu。
本文在总铜浓度不变或者Cu~(2+)浓度较Cu~+浓度很高且变化很小的情况下,用电位测量方法研究酸性蚀刻液中Cu~+浓度与ORP(氧化还原电位)的关系,结果表明,酸性蚀刻液的ORP随着Cu~+浓度的增加而不断降低,这遵循能斯特公式,即氧化还原电位与Cu~+浓度的对数成正比,这样就可以根据溶液ORP值自动控制电解过程的进行;酸性蚀刻液的蚀刻速度伴随着溶液ORP的增加而加快,电解再生中可以根据溶液的ORP确定再生溶液的蚀刻性能。
采用测量稳态极化曲线方法探讨酸性蚀刻液电解时阳极氧化过程的电化学行为,研究结果表明,酸性蚀刻液电化学行为受Cu~+扩散控制影响存在极限电流密度,且极限电流密度与Cu~+浓度及温度呈直线关系,极限电流密度内电解不会析出氯气。
运用隔膜电解方法分别研究酸性蚀刻液电解时阳极氧化过程、阴极还原过程的工艺参数,研究结果表明,阳极再生液的蚀刻速度与标准液的蚀刻速度相差不大,相对误差的范围在为-3.76% - 9.97%,因此阳极再生液可以满足蚀刻的需求;在同电流密度下电解,隔膜电解提铜比同槽电解提铜速度更快、效率更高。
With the constant deepening of China's reform and opening-up, the printed circuit board (Printed Circuit Board, referred to as PCB) manufacturer has developed rapidly around China. Since 2003, China has become the second largest producer of PCB industry in the world, and increased to 20% in the pace of development each year. In the circuit board manufacturing process, corrosion of copper is a very important process. Consumed amounts of refined copper annually and eliminated a huge number of the etching solution (copper 120 - 180 g/L) which were high content of copper. Most of the enterprises used abandon that sold a low-cost to the units which have qualified recovery. They recovered the copper from the waste by chemical method, that not only caused economic losses of the enterprises themselves, but also caused secondary pollution of the environment by the transfer of sources; there were some enterprises used by chemical reagent oxidation regeneration, which were renewable, but would result in increasing volume of etching solution, and the consumption of chemical reagents, and had also to face the waste water treatment. Therefore, the treatment of acid etching wastewater was an important topic in international research.
This paper was reserched about the regeneration and recycling of acid etching solution by electrochemical electrolysis. The electrochemical regeneration of acid etching solution, is an online method of regeneration, not only can restore the original etching performance, but also has produced the commercial value of copper. Basic principle of electrochemical regeneration is that Cu~+ is oxidized to Cu~(2+) in the anode in the cell; at the same time, firstly, Cu~(2+) is reduced to Cu~+ and then Cu~+ is reduced to Cu in the cathode.
This paper, in the case of that the total copper concentration is unchange or Cu~(2+) concentration is higher than Cu~+ concentration and small changes, was reserched the relationship of Cu~+ concentration and ORP (oxidation reduction potential) by the measurement of potential in the acid etching liquid, the results showed that the ORP of acid etching solution continuously decreased with increasing of Cu~+ concentration, which followed the Nernst equation, that was, redox potential and the logarithm of the Cu~+ concentration was proportional, so that could automatically control the conduct of the electrolysis process according to the ORP of the solution; the etching rate of acid etching solution accelerated along with the increase of ORP, that could the etching performance of the regeneration solution according to the ORP of solution in electrolytic regeneration.
By measuring steady-state polarization curves when acid etching solution electrolysed, discussed the electrochemical behavior of anodic oxidation process, the results showed that the electrochemical behavior of the acid etching solution controlled by Cu~+ diffusion and existed limiting current density, and there were linear relationship between the limiting current density and Cu~+ concentration, temperature. The chlorine would not be precipitated electrolysis in the limiting current density.
Were studied the parameters of the anodic oxidation process and the cathodic reduction process when acid etching solution electrolysed by using membrane electrolysis, the results showed that the etching rate of anodic renewable liquid was or less with the etching rate of the standard solution, which the range of relative error was for the -3.76% - 9.97%, the anodic regeneration fluid was to meet the needs of etching; in the same current density electrolysis, the mention copper of diaphragm electrolytic was faster and more efficient than the mention copper of simultaneous electrolysis.
本文进行了运用电化学法电解再生回用酸性蚀刻液的研究。酸性蚀刻液的电化学再生,是一种在线的再生方法,不但可以使蚀刻液恢复原有的蚀刻效能,而且同时产出了具有商业价值的金属铜粉。电化学法再生的基本原理是电解时,在电解槽的阳极使Cu~+被氧化成Cu~(2+);同时在阴极首先是Cu~(2+)被还原成Cu~+,然后Cu~+被还原成Cu。
本文在总铜浓度不变或者Cu~(2+)浓度较Cu~+浓度很高且变化很小的情况下,用电位测量方法研究酸性蚀刻液中Cu~+浓度与ORP(氧化还原电位)的关系,结果表明,酸性蚀刻液的ORP随着Cu~+浓度的增加而不断降低,这遵循能斯特公式,即氧化还原电位与Cu~+浓度的对数成正比,这样就可以根据溶液ORP值自动控制电解过程的进行;酸性蚀刻液的蚀刻速度伴随着溶液ORP的增加而加快,电解再生中可以根据溶液的ORP确定再生溶液的蚀刻性能。
采用测量稳态极化曲线方法探讨酸性蚀刻液电解时阳极氧化过程的电化学行为,研究结果表明,酸性蚀刻液电化学行为受Cu~+扩散控制影响存在极限电流密度,且极限电流密度与Cu~+浓度及温度呈直线关系,极限电流密度内电解不会析出氯气。
运用隔膜电解方法分别研究酸性蚀刻液电解时阳极氧化过程、阴极还原过程的工艺参数,研究结果表明,阳极再生液的蚀刻速度与标准液的蚀刻速度相差不大,相对误差的范围在为-3.76% - 9.97%,因此阳极再生液可以满足蚀刻的需求;在同电流密度下电解,隔膜电解提铜比同槽电解提铜速度更快、效率更高。
With the constant deepening of China's reform and opening-up, the printed circuit board (Printed Circuit Board, referred to as PCB) manufacturer has developed rapidly around China. Since 2003, China has become the second largest producer of PCB industry in the world, and increased to 20% in the pace of development each year. In the circuit board manufacturing process, corrosion of copper is a very important process. Consumed amounts of refined copper annually and eliminated a huge number of the etching solution (copper 120 - 180 g/L) which were high content of copper. Most of the enterprises used abandon that sold a low-cost to the units which have qualified recovery. They recovered the copper from the waste by chemical method, that not only caused economic losses of the enterprises themselves, but also caused secondary pollution of the environment by the transfer of sources; there were some enterprises used by chemical reagent oxidation regeneration, which were renewable, but would result in increasing volume of etching solution, and the consumption of chemical reagents, and had also to face the waste water treatment. Therefore, the treatment of acid etching wastewater was an important topic in international research.
This paper was reserched about the regeneration and recycling of acid etching solution by electrochemical electrolysis. The electrochemical regeneration of acid etching solution, is an online method of regeneration, not only can restore the original etching performance, but also has produced the commercial value of copper. Basic principle of electrochemical regeneration is that Cu~+ is oxidized to Cu~(2+) in the anode in the cell; at the same time, firstly, Cu~(2+) is reduced to Cu~+ and then Cu~+ is reduced to Cu in the cathode.
This paper, in the case of that the total copper concentration is unchange or Cu~(2+) concentration is higher than Cu~+ concentration and small changes, was reserched the relationship of Cu~+ concentration and ORP (oxidation reduction potential) by the measurement of potential in the acid etching liquid, the results showed that the ORP of acid etching solution continuously decreased with increasing of Cu~+ concentration, which followed the Nernst equation, that was, redox potential and the logarithm of the Cu~+ concentration was proportional, so that could automatically control the conduct of the electrolysis process according to the ORP of the solution; the etching rate of acid etching solution accelerated along with the increase of ORP, that could the etching performance of the regeneration solution according to the ORP of solution in electrolytic regeneration.
By measuring steady-state polarization curves when acid etching solution electrolysed, discussed the electrochemical behavior of anodic oxidation process, the results showed that the electrochemical behavior of the acid etching solution controlled by Cu~+ diffusion and existed limiting current density, and there were linear relationship between the limiting current density and Cu~+ concentration, temperature. The chlorine would not be precipitated electrolysis in the limiting current density.
Were studied the parameters of the anodic oxidation process and the cathodic reduction process when acid etching solution electrolysed by using membrane electrolysis, the results showed that the etching rate of anodic renewable liquid was or less with the etching rate of the standard solution, which the range of relative error was for the -3.76% - 9.97%, the anodic regeneration fluid was to meet the needs of etching; in the same current density electrolysis, the mention copper of diaphragm electrolytic was faster and more efficient than the mention copper of simultaneous electrolysis.
引文
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