高纯阴极铜电解精炼过程中电化学振荡行为的研究

The copper of electrorefining is high energy in hydrometallurgical industry. The new and key method of energy-saving electrolytic for high purity cathode copper is developed to reduce the power consumption, which caused by the electrochemical oscillation. It has been difficult to explain this electrochemical oscillation phenomenon based on the traditional equilibrium thermodynamic theory. In this work, based on the nonlinear dynamics theory, the electrochemical oscillation behavior during the electrolysis system was studied, and characterized regularity was summarized; information about electrode reactions was obtained by temporal self-organizing behavior, and primitive steps and the coupling nature between the various primitive steps were realized, to speculate the possibility of reaction course; the mathematical model of the electrochemical oscillation characteristics was established, which was calculated to get threshold by a way of linear stability analysis. The evolution of electrochemical oscillation behavior was simulated by using Matlab software, to improve constantly its electrochemical oscillation mechanism combining with experimental testing; based on the above electrochemical oscillation theory, it indicated the intrinsic link of electrochemical oscillation between its external control parameters (voltage, current, temperature, concentration, agitation, etc.) and its characteristic variables of the theoretical model; the electrochemical oscillation was adjusted by improving anodes, optimizing field, adding inhibitors, filling with bubbles and so on. Hence, it could improve the electrolytic process by this special electrochemical oscillation behavior far from equilibration conditions. All these offered a new work zone for electrolytic of energy-saving and environmental protection far from equilibrium.

电解精炼铜生产是高能耗湿法冶金产业，研发高纯阴极铜节能电解新方法的关键是减少耗于电化学振荡引起的电能。基于传统平衡态热力学理论已无法解释这一现象。本项目拟基于非平衡非线性动力学理论，研究在电解体系中出现的电化学振荡行为及其变化规律；通过这些时空自组织行为获得电极反应的信息和基元步骤及其之间的耦联本质，推测可能的反应历程；建立电化学振荡特征数学模型，借助线性稳定性分析进行阈值计算，利用Matlab模拟电化学振荡行为的演化过程，并结合实验测试不断完善其电化学振荡机制；基于已建立的电化学振荡理论，找出电化学振荡外控参数（电压、电流、温度、浓度、搅拌等）与理论模型特征变量之间的内在联系；采用改进阳极、优化电场、添加抑制剂或通入气体等措施调控电化学振荡，进而有效利用这种在远离平衡条件下的特殊电化学振荡行为来改善电解过程，在远离平衡区找出新的节能环保电解工作区间。

电解精炼铜生产是高能耗湿法冶金产业，研发高纯阴极铜节能电解新方法的关键是减少耗于非线性行为引起的电能，研究电解体系中非线性行为特征及其机理。首先，研究了电解体系中阳极的电化学振荡行为及变化规律，系统地研究了电极电势、电解质组成和浓度、温度、搅拌速率和扫描速度对电化学振荡的影响。建立了电化学振荡耦合的数学理论模型，理论结合试验推测电化学振荡的机理。发现了理论模拟参数与实验的影响因素之间的联系。提出了调控电化学振荡的方法，研究为微观化学机制与宏观非线性现象间的关系提供理论，为冶金中高效电解提出了新的概念。其次，建立了分形生长的试验参数与模型参数相对应的计算体系，研究分形生长对电解产品质量的影响及生长机制。模拟了电沉积过程中电解池内部电流密度和镀液分布情况，分析电解池内部电化学特性参数变化规律。提出了调控电沉积产品质量的方法，为全面分析电解过程中的非线性特征提供方法。再次，在已建立的电沉积非平衡态热力学及非线性动力学理论基础上，结合电化学振荡和分形生长对电解影响的特征规律，找出电沉积外控参数（电压、电流、温度、浓度、搅拌等）与理论模型特征变量之间的内在联系。采用改进阳极、添加抑制剂、优化电场等措施调控电化学振荡等非线性行为。进而有效利用这种在远离平衡条件下的特殊电化学振荡行为来改善电解过程。实现降低电化学振荡能耗、避免电沉积铜产品分形生长的目的，在远离平衡区建立节能电解操作模式。最后，作为研究拓展，将电化学分析方法应用于铜合金的电沉积过程中，提出节能电沉积金属及合金的方法。此外，在项目的执行期间，在国内外学术期刊上发表学术论文10篇，其中SCI 论文8篇；申报国家发明专利3项，授权3项；培养在读硕士研究生3名。圆满完成了项目任务书的各项内容，达到了项目任务书的各项指标。

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