根据质量守恒和同时平衡原理,以Me(Co、Ni、Fe、Mn)为金属元素,建立Me-OH?、Me-OH?-CO32?、Me-OH?-S2?、Me-OH?-NH3和 Me-OH?-NH3-CO32?等多个配合?沉淀体系的热力学平衡模型.结果表明:Fe3+可以在Me-OH?、Me-OH?-NH3体系中通过调节pH=3预先沉淀分离,而Co、Ni、Mn仅在Me-OH?-NH3-CO32?体系中有分离效果.Me-OH?-NH3-CO32?体系热力学计算表明:Co、Ni、Mn在溶液中的行为受pH值、配合剂、沉淀剂浓度共同影响,碳酸根初始总浓度[C]增大和氨初始总浓度[N]减小有利于Co、Ni、Mn形成沉淀.当[C]=1 mol/L、[N]=2 mol/L、pH值为9~10时,大部分Ni以高级氨配离子[Ni(NH3)42+]、[Ni(NH3)52+]、[Ni(NH3)62+]的形式保留在溶液中,而Co、Mn以MnCO3、CoCO3的形式沉淀出来.Co可在Me-OH?-S2?体系中通过调节pH<6从溶液中与Mn分离.研究结果可为钴镍二次资源综合回收钴镍、制备钴镍产品提供理论指导.
@@@@Based on mass balance principle and simultaneous equilibrium principle, the metal element Me (Co, Ni, Fe, Mn), complexing agent of OH? and NH3, and precipitant of OH?, S2? and CO32? were chosen to form the complexation–precipitation systems of Me-OH?, Me-OH?-CO32?, Me-OH?-S2?, Me-OH?-NH3 and Me-OH?-NH3-CO32?. The thermodynamic equilibriums of these systems were studied. The results show that Fe3+in systems of Me-OH? and Me-OH?-NH3 can be separated by precipitation through adjusting the pH value to 3. However, Co, Ni and Mn can be separated only in Me-OH?-NH3-CO32?system. The theoretical calculations show that the behavior of Co, Ni and Mn in Me-OH?-NH3-CO32?system is affected by pH value, complexing agent concentration and precipitant concentration. The increase of the total concentration of carbonate [C] is in favor of the precipitation of Ni, Co and Mn, but the increase of the total ammonia concentration [N] has the opposite effect. When [C]=1 mol/L, [N]=2 mol/L and pH value of 9?10, most Ni is complexed in the solution in the form of senior ammonia complexes [Ni(NH3)42+] and [Ni(NH3)52+], [Ni(NH3)62+], while Co and Mn precipitate in MnCO3 and CoCO3. Finally, Co can be separated with Mn from the solution in Me-OH?-S2? system when pH<6. The results provide a theoretical guidance for cobalt and nickel recovery from secondary resources and the preparation of cobalt and nickel products.
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