钴白合金电解造液技术研究
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摘要
随着世界经济的快速发展,特别是电池功能材料、超细粉体材料和超硬材料的迅猛发展,导致相关有色金属材料的消费量也在快速增长,特别是中国十分缺乏并全球消费势头迅猛的钴资源。要确保我国有色金属工业的可持续发展和矿产资源的可持续开采,就要坚持国内国外两种资源并举,除了加大国内找矿的力度外,开发利用海外有色金属资源已十分紧迫。开发海外有色金属资源对我国经济的发展具有战略的、全局性的意义,是有色金属工业发展主要的、必然的选择。
非洲国家钴资源丰富,但非洲国家出台限制钴矿的出口,鼓励将钴矿加工成钴产品后再出售给国外,针对上述政策,必须研制一种低成本溶出钴白合金的技术。本论文主要研究了以非洲某国生产的钴白合金为原料,在1300~1500℃下熔化钴白合金,并浇铸成阳极块作阳极,铜片作阴极,以硫酸为电解液,在直流电的作用下,考查了含硅量不同的钴白合金的电化学溶解性能,根据电化学溶解中存大的问题加入适当的添加剂,使电化学溶解能正常进行。试验结果表明:含硅≤2.6%的钴白合金,电解液不外加任何添加剂,能在电流密度为700 A·m~(-2)下正常电化学溶解,含硅量越低,钴白合金能在越高的电流密度下电化学溶解;含硅≤2.6%的钴白合金,电解液外加添加剂A,用量为0.2mol·L~(-1)时,能在电流密度为1400 A·m~(-2)下正常电化学溶解;含硅≤2.6%的钴白合金,电解液外加添加剂A,用量为0.2mol·L~(-1)时,外加添加剂B,能提高电流密度,但提高的幅度不大;含硅量>2.6%的钴白合金,电解液不添加任何添加剂,随含硅量的增加,能正常电化学溶解的电流密度越小,电流密度不超过500 A·m~(-2),限制了在工业中的生产应用;含硅量>2.6%的钴白合金,电解液外加添加剂A,用量为0.2mol·L~(-1)时,能小幅度提高电流密度,继续增加添加剂A的用量,基本上不能提高钴白合金电化学溶解的电流密度;含硅量>2.6%的钴白合金,电解液外加添加剂A和B,用量分别为0.2mol·L~(-1)和0.12mol·L~(-1)时,钴白合金能在电流密度为1400 A·m~(-2)下进行电化学溶解;动态试验结果表明,含硅7.3%钴白合金的阳极效率为93.37%,溶解1t阳极耗电2.064kwh,铜粉成粉率为30.81%,钴一次电溶出率为87.45%,铜粉含铜99.5%,铜粉占原料含铜量80.85%,铁大部分进入溶液,初步分离了铜与钴铁。
本论文的最大特点是对含硅量不同的钴白合金电化学溶解性能进行了分类和加入新型添加剂B消除钴白合金溶解过程中的钝化现象。该法操作条件温和,初步实现了铜与钴铁的分离,生产成本低,与其它方法相比具有明显的优势。
With the rapid development of the world economy,especially the rapid development of the battery functional materials , ultra-fine powder materials and superhard material , the consumption of non-ferrous metals related to these materials are also rapid growth, particularly cobalt resources which were lack in China and were of vigorous consumption in world.In order to ensure the sustainable development and sustainable exploitation of mineral resources of China Nonferrous Metals Industry,we must adhere to both domestic and foreign resources.In addition to the efforts increasing domestic exploration,development and utilization of overseas non-ferrous metal resources had been very tight.It was inevitable for Non-ferrous industrial to explore overseas non-ferrous resourses.And it was a strategic,overall significance.
African countries were rich in cobalt resources . But African countries had introduced restrictions on the export of cobalt ore,and encourage the export of cobalt products after processing.In view of the above-mentioned policy,we must develop a low-cost technology for the dissolution of Co-Cu-Fe alloy.
This paper mainly studied the Co-Cu-Fe alloy from African.The Co-Cu-Fe alloy first were melt in 1300 ~ 1500℃and then casted into the anode.In electrochemical experiments,the cathode was sheet copper and the electrolyte was sulphuric acid.The experiments examined the eclectrochemical dissolution properties of different silicon content Co-Cu-Fe alloy.In accordance with the electrochemical dissolution properties,we added appropriate additives in order to be carried out normally in electrochemical dissolution.The experimental results showed that:The Co-Cu-Fe alloy which silicon content was less than 2.6% can be electrolyzed normally in te current density of 700 A·m-2 without any additives.And the lower the silicon content in Co-Cu-Fe alloy was ,the higher the current density was;The Co-Cu-Fe alloy which silicon content was less than 2.6% can be electrolyzed normally in te current density of 1400 A·m~(-2) with the additive A the amount of which is 0.2mol·L~(-1);The Co-Cu-Fe alloy which silicon content was less than 2.6% with the 0.2mol·L~(-1) additive A could increase the current density when adding additive B,but the current density increase was less;The Co-Cu-Fe alloy which silicon content was more than 2.6% had a smaller current density with the increase of silicon content in anode.And the current density was less than 500 A·m~(-2) which limited the industrial application;The Co-Cu-Fe alloy which silicon content was more than 2.6% can increase the current density smally with the amount of 0.2mol·L~(-1) additive A.But the effect is not obviously with the increase amount of additive A;The Co-Cu-Fe alloy which silicon content was more than 2.6% can be electrolyzed normally in te current density of 1400 A·m~(-2) with the amount of 0.2mol·L~(-1) additive A and 0.12mol·L~(-1) additive B;Dynamic experiment results showed that the anode efficiency of Co-Cu-Fe alloy which contained 7.3% silicon is 93.37%,the energy consumption was 2.064 kwh·t~(-1) Co-Cu-Fe alloy,copper power rate was 30.81%,the cobalt recovery rate into solution was 87.45%,the copper power contained 99.5% copper and the copper recovery rate into copper power was 80.85%.The majority of iron were in the solution.Through the electrochemical dissolution achieved the initial separation of copper and cobalt、iron.
The significant features in the whole technological process was classifying the electrochemical dissolution for the different silicon content Co-Cu-Fe alloy and adding new additive B in order to eliminate the passivation phenomenon in electrochemical dissolution.The operating conditions of this technology were mildness.And this technology achieved initial separation of copper and cobalt、iron and had a low production.Compared with other methods,it offered distinct advantages.
非洲国家钴资源丰富,但非洲国家出台限制钴矿的出口,鼓励将钴矿加工成钴产品后再出售给国外,针对上述政策,必须研制一种低成本溶出钴白合金的技术。本论文主要研究了以非洲某国生产的钴白合金为原料,在1300~1500℃下熔化钴白合金,并浇铸成阳极块作阳极,铜片作阴极,以硫酸为电解液,在直流电的作用下,考查了含硅量不同的钴白合金的电化学溶解性能,根据电化学溶解中存大的问题加入适当的添加剂,使电化学溶解能正常进行。试验结果表明:含硅≤2.6%的钴白合金,电解液不外加任何添加剂,能在电流密度为700 A·m~(-2)下正常电化学溶解,含硅量越低,钴白合金能在越高的电流密度下电化学溶解;含硅≤2.6%的钴白合金,电解液外加添加剂A,用量为0.2mol·L~(-1)时,能在电流密度为1400 A·m~(-2)下正常电化学溶解;含硅≤2.6%的钴白合金,电解液外加添加剂A,用量为0.2mol·L~(-1)时,外加添加剂B,能提高电流密度,但提高的幅度不大;含硅量>2.6%的钴白合金,电解液不添加任何添加剂,随含硅量的增加,能正常电化学溶解的电流密度越小,电流密度不超过500 A·m~(-2),限制了在工业中的生产应用;含硅量>2.6%的钴白合金,电解液外加添加剂A,用量为0.2mol·L~(-1)时,能小幅度提高电流密度,继续增加添加剂A的用量,基本上不能提高钴白合金电化学溶解的电流密度;含硅量>2.6%的钴白合金,电解液外加添加剂A和B,用量分别为0.2mol·L~(-1)和0.12mol·L~(-1)时,钴白合金能在电流密度为1400 A·m~(-2)下进行电化学溶解;动态试验结果表明,含硅7.3%钴白合金的阳极效率为93.37%,溶解1t阳极耗电2.064kwh,铜粉成粉率为30.81%,钴一次电溶出率为87.45%,铜粉含铜99.5%,铜粉占原料含铜量80.85%,铁大部分进入溶液,初步分离了铜与钴铁。
本论文的最大特点是对含硅量不同的钴白合金电化学溶解性能进行了分类和加入新型添加剂B消除钴白合金溶解过程中的钝化现象。该法操作条件温和,初步实现了铜与钴铁的分离,生产成本低,与其它方法相比具有明显的优势。
With the rapid development of the world economy,especially the rapid development of the battery functional materials , ultra-fine powder materials and superhard material , the consumption of non-ferrous metals related to these materials are also rapid growth, particularly cobalt resources which were lack in China and were of vigorous consumption in world.In order to ensure the sustainable development and sustainable exploitation of mineral resources of China Nonferrous Metals Industry,we must adhere to both domestic and foreign resources.In addition to the efforts increasing domestic exploration,development and utilization of overseas non-ferrous metal resources had been very tight.It was inevitable for Non-ferrous industrial to explore overseas non-ferrous resourses.And it was a strategic,overall significance.
African countries were rich in cobalt resources . But African countries had introduced restrictions on the export of cobalt ore,and encourage the export of cobalt products after processing.In view of the above-mentioned policy,we must develop a low-cost technology for the dissolution of Co-Cu-Fe alloy.
This paper mainly studied the Co-Cu-Fe alloy from African.The Co-Cu-Fe alloy first were melt in 1300 ~ 1500℃and then casted into the anode.In electrochemical experiments,the cathode was sheet copper and the electrolyte was sulphuric acid.The experiments examined the eclectrochemical dissolution properties of different silicon content Co-Cu-Fe alloy.In accordance with the electrochemical dissolution properties,we added appropriate additives in order to be carried out normally in electrochemical dissolution.The experimental results showed that:The Co-Cu-Fe alloy which silicon content was less than 2.6% can be electrolyzed normally in te current density of 700 A·m-2 without any additives.And the lower the silicon content in Co-Cu-Fe alloy was ,the higher the current density was;The Co-Cu-Fe alloy which silicon content was less than 2.6% can be electrolyzed normally in te current density of 1400 A·m~(-2) with the additive A the amount of which is 0.2mol·L~(-1);The Co-Cu-Fe alloy which silicon content was less than 2.6% with the 0.2mol·L~(-1) additive A could increase the current density when adding additive B,but the current density increase was less;The Co-Cu-Fe alloy which silicon content was more than 2.6% had a smaller current density with the increase of silicon content in anode.And the current density was less than 500 A·m~(-2) which limited the industrial application;The Co-Cu-Fe alloy which silicon content was more than 2.6% can increase the current density smally with the amount of 0.2mol·L~(-1) additive A.But the effect is not obviously with the increase amount of additive A;The Co-Cu-Fe alloy which silicon content was more than 2.6% can be electrolyzed normally in te current density of 1400 A·m~(-2) with the amount of 0.2mol·L~(-1) additive A and 0.12mol·L~(-1) additive B;Dynamic experiment results showed that the anode efficiency of Co-Cu-Fe alloy which contained 7.3% silicon is 93.37%,the energy consumption was 2.064 kwh·t~(-1) Co-Cu-Fe alloy,copper power rate was 30.81%,the cobalt recovery rate into solution was 87.45%,the copper power contained 99.5% copper and the copper recovery rate into copper power was 80.85%.The majority of iron were in the solution.Through the electrochemical dissolution achieved the initial separation of copper and cobalt、iron.
The significant features in the whole technological process was classifying the electrochemical dissolution for the different silicon content Co-Cu-Fe alloy and adding new additive B in order to eliminate the passivation phenomenon in electrochemical dissolution.The operating conditions of this technology were mildness.And this technology achieved initial separation of copper and cobalt、iron and had a low production.Compared with other methods,it offered distinct advantages.
引文
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[03]丰成友,张德全.中国钴资源开发及其开发利用概况.矿产与地质,2004,23(1):93~100
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