在氯盐介质中同时电解铅和二氧化锰的研究
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摘要
从氯化铅水溶液中电解提取铅和从氯化锰水溶液中电解提取二氧化锰是湿法冶金的两个研究热点。为了实现电解槽的阳极上不析出氯气的铅电解过程,本文首次研究了从氯化铅和氯化锰混合溶液中同时电解铅和二氧化锰的过程。这种铅和二氧化锰同时电解过程不仅能避免氯气在阳极上析出,而且还能同时得到两种电解产品,并导致电解过程电能消耗的降低。
本研究首先开展了从氯化铅溶液中电解提取铅和从氯化锰溶液中电解提取二氧化锰两组单独电解试验,然后进行了在氯盐介质中铅和二氧化锰同时电解的试验工作。铅和二氧化锰同时电解包括两种方法：电解槽中阴、阳极之间有隔膜和没有隔膜两种电解。试验结果表明,铅和二氧化锰同时电解,特别是有隔膜的同时电解过程是可行的。
无隔膜同时电解的最佳工艺条件概括如下：电解液中Pb2+和Mn2+浓度分别为15g/L和50g/L,电解液中HCl和NaCl浓度分别为4g/L和2mol/L,电解液温度为90℃,电流密度为80A/m2。在最佳工艺条件下电解2h的阴、阳极的电流效率分别为98%和92%,电极上产生的铅和二氧化锰的重量之比为2.61：1,平均槽电压为1.667V,产生2.61kg铅和1kg二氧化锰的直流电消耗为1.131kWh,与铅和二氧化锰单独电解相比,电能节省55.47%。阳极产物为γ-MnO2,产物中二氧化锰的含量大于91%。
有隔膜同时电解的最佳工艺条件被确定为：隔膜材质为涤棉布,阳极液面比阴极液面高20mm,阴极液中Pb2+和NaCl浓度分别为25g/L和4.5mol/L,阳极液中Mn2+和HCl浓度分别为50g/L和8g/L。在最佳工艺条件下电解2h,阴、阳极电流效率均达到99%,电解5h的阴、阳极电流效率分别达到96%和99%,平均槽电压为1.701V,电极上得到的铅和二氧化锰的重量之比为2.39：1,产生2.39kg铅和1kg二氧化锰的直流电耗为1.056kWh,与铅和二氧化锰单独电解相比,节省电能56.58%。阳极产物为γ-MnO2,二氧化锰含量达92%以上。
虽然基于试验结果,无隔膜和有隔膜两种电解方法都是可行的,但无隔膜电解过程的阳极电流效率只达92%。这表明,必然有一些氯气从阳极上析出。因此,有隔膜电解过程是在氯盐介质中电解提取铅和二氧化锰的最佳工艺方案。扩大试验结果与小型试验结果基本相同。根据本研究的结果,本文的第五章给出了从铅精矿和碳酸锰矿提取铅和二氧化锰的推荐原则工艺流程。
Electrowinning of lead from aqueous solution of PbCl2 and electrowinning of manganese dioxide from aqueous solution of MnCl2 are two research focuses in hydrometallurgy. To realize the electrowinning of lead without liberation of chlorine at anodes in cell, simultaneous electrowinning of lead and manganese dioxide from a mixture solution of PbCl2 and MnCl2 was investigated for the first time. This simultaneous electrowinning of lead and manganese dioxide not only can prevent chlorine from liberating at anodes but also obtain two electrolysis products simultaneously, which result in decrease of electric energy consumption for the electrowinning process.
Firstly two separate electrowinning tests, electrowinning of lead from PbCl2 solution and electrowinning of manganese dioxide from MnCl2 solution, were carried out. And then, tests for simultaneous electrowinning of lead and manganese dioxide in chloride medium were conducted. The simultaneous electrowinning of lead and manganese dioxide includes two methods:electrowinning processes without and with diaphragm between anode and cathode in cell. Experimental results indicated that simultaneous electrowinning process, especially the simultaneous electrowinning process with diaphragm is feasible.
The optimum process conditions of simultaneous electrowinning without diaphragm are summarized as follows:concentration of Pb2+and Mn2+in electrolyte is 15 g/L and 50g/L respectively, concentration of HCl and NaCl in electrolyte is 4g/L and 2mol/L respectively, temperature of electrolyte is 90℃, and current density is 80A/m2. By electrowinning for 2 hours under the optimum process conditions, current efficiency of cathode and anode is 98% and 92% respectively, weight ratio of lead and manganese dioxide produced at electrodes is 2.61:1, average cell voltage is 1.667V, direct current consumption to produce 2.61 kg of lead and lkg of manganese dioxide is 1.131kWh, the save of electric energy reaches 55.47% by comparison with the separate electrowinning of lead and manganese dioxide. Anode products are y-MnO2, content of MnO2 in the products is more than 91%.
The optimum process conditions of simultaneous electrowinning with diaphragm are determined as:material of diaphragm is polyster cotton, height difference between surface of anolyte and surface of catholyte is 20mm, concentration of Pb2+ and NaCl in the catholyte is 25g/L and 4.5mol/L respectively, concentration of Mn2+and HCl in the anolyte is 50g/L and 8g/L respectively, temperature of electrolyte is 80℃, current density is 80A/m2. By electrowinning for 2 hours under the optimum process conditions, current efficiency of cathode and anode is both more than 99%, current efficiency of cathode and anode for 5 hours is 96% and 99% respectively, the average cell voltage is 1.701V, the weight ratio of lead and manganese dioxide produced in electrodes is 2.39:1, direct current consumption to produce 2.39 kg of lead and lkg of manganese dioxide is 1.056kWh, the save of electric energy reaches 56.58% by comparison with the separate electrowinning of lead and manganese dioxide, anode products are y-MnO2, content of which is more than 92%.
Although two electrowinning process without and with diaphragm are both feasible on the basis of the experimental results, current efficiency of anode for electrowinning process without diaphragm is only 92%, which show that there must be some chlorine liberating from anodes. Therefore, electrowinning process with diaphragm is the optimum technology for extraction of lead and manganese dioxide in chloride medium. The results of expanding test are basically the same with that of laboratory experiment. According to results of present work, a suggested principle flow sheet for the extraction of lead and manganese dioxide from lead concentrate and manganese carbonate ore is given in the fifth chapter of this paper.
本研究首先开展了从氯化铅溶液中电解提取铅和从氯化锰溶液中电解提取二氧化锰两组单独电解试验,然后进行了在氯盐介质中铅和二氧化锰同时电解的试验工作。铅和二氧化锰同时电解包括两种方法：电解槽中阴、阳极之间有隔膜和没有隔膜两种电解。试验结果表明,铅和二氧化锰同时电解,特别是有隔膜的同时电解过程是可行的。
无隔膜同时电解的最佳工艺条件概括如下：电解液中Pb2+和Mn2+浓度分别为15g/L和50g/L,电解液中HCl和NaCl浓度分别为4g/L和2mol/L,电解液温度为90℃,电流密度为80A/m2。在最佳工艺条件下电解2h的阴、阳极的电流效率分别为98%和92%,电极上产生的铅和二氧化锰的重量之比为2.61：1,平均槽电压为1.667V,产生2.61kg铅和1kg二氧化锰的直流电消耗为1.131kWh,与铅和二氧化锰单独电解相比,电能节省55.47%。阳极产物为γ-MnO2,产物中二氧化锰的含量大于91%。
有隔膜同时电解的最佳工艺条件被确定为：隔膜材质为涤棉布,阳极液面比阴极液面高20mm,阴极液中Pb2+和NaCl浓度分别为25g/L和4.5mol/L,阳极液中Mn2+和HCl浓度分别为50g/L和8g/L。在最佳工艺条件下电解2h,阴、阳极电流效率均达到99%,电解5h的阴、阳极电流效率分别达到96%和99%,平均槽电压为1.701V,电极上得到的铅和二氧化锰的重量之比为2.39：1,产生2.39kg铅和1kg二氧化锰的直流电耗为1.056kWh,与铅和二氧化锰单独电解相比,节省电能56.58%。阳极产物为γ-MnO2,二氧化锰含量达92%以上。
虽然基于试验结果,无隔膜和有隔膜两种电解方法都是可行的,但无隔膜电解过程的阳极电流效率只达92%。这表明,必然有一些氯气从阳极上析出。因此,有隔膜电解过程是在氯盐介质中电解提取铅和二氧化锰的最佳工艺方案。扩大试验结果与小型试验结果基本相同。根据本研究的结果,本文的第五章给出了从铅精矿和碳酸锰矿提取铅和二氧化锰的推荐原则工艺流程。
Electrowinning of lead from aqueous solution of PbCl2 and electrowinning of manganese dioxide from aqueous solution of MnCl2 are two research focuses in hydrometallurgy. To realize the electrowinning of lead without liberation of chlorine at anodes in cell, simultaneous electrowinning of lead and manganese dioxide from a mixture solution of PbCl2 and MnCl2 was investigated for the first time. This simultaneous electrowinning of lead and manganese dioxide not only can prevent chlorine from liberating at anodes but also obtain two electrolysis products simultaneously, which result in decrease of electric energy consumption for the electrowinning process.
Firstly two separate electrowinning tests, electrowinning of lead from PbCl2 solution and electrowinning of manganese dioxide from MnCl2 solution, were carried out. And then, tests for simultaneous electrowinning of lead and manganese dioxide in chloride medium were conducted. The simultaneous electrowinning of lead and manganese dioxide includes two methods:electrowinning processes without and with diaphragm between anode and cathode in cell. Experimental results indicated that simultaneous electrowinning process, especially the simultaneous electrowinning process with diaphragm is feasible.
The optimum process conditions of simultaneous electrowinning without diaphragm are summarized as follows:concentration of Pb2+and Mn2+in electrolyte is 15 g/L and 50g/L respectively, concentration of HCl and NaCl in electrolyte is 4g/L and 2mol/L respectively, temperature of electrolyte is 90℃, and current density is 80A/m2. By electrowinning for 2 hours under the optimum process conditions, current efficiency of cathode and anode is 98% and 92% respectively, weight ratio of lead and manganese dioxide produced at electrodes is 2.61:1, average cell voltage is 1.667V, direct current consumption to produce 2.61 kg of lead and lkg of manganese dioxide is 1.131kWh, the save of electric energy reaches 55.47% by comparison with the separate electrowinning of lead and manganese dioxide. Anode products are y-MnO2, content of MnO2 in the products is more than 91%.
The optimum process conditions of simultaneous electrowinning with diaphragm are determined as:material of diaphragm is polyster cotton, height difference between surface of anolyte and surface of catholyte is 20mm, concentration of Pb2+ and NaCl in the catholyte is 25g/L and 4.5mol/L respectively, concentration of Mn2+and HCl in the anolyte is 50g/L and 8g/L respectively, temperature of electrolyte is 80℃, current density is 80A/m2. By electrowinning for 2 hours under the optimum process conditions, current efficiency of cathode and anode is both more than 99%, current efficiency of cathode and anode for 5 hours is 96% and 99% respectively, the average cell voltage is 1.701V, the weight ratio of lead and manganese dioxide produced in electrodes is 2.39:1, direct current consumption to produce 2.39 kg of lead and lkg of manganese dioxide is 1.056kWh, the save of electric energy reaches 56.58% by comparison with the separate electrowinning of lead and manganese dioxide, anode products are y-MnO2, content of which is more than 92%.
Although two electrowinning process without and with diaphragm are both feasible on the basis of the experimental results, current efficiency of anode for electrowinning process without diaphragm is only 92%, which show that there must be some chlorine liberating from anodes. Therefore, electrowinning process with diaphragm is the optimum technology for extraction of lead and manganese dioxide in chloride medium. The results of expanding test are basically the same with that of laboratory experiment. According to results of present work, a suggested principle flow sheet for the extraction of lead and manganese dioxide from lead concentrate and manganese carbonate ore is given in the fifth chapter of this paper.
引文
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