仲钨酸铵蒸发结晶过程中杂质元素的析出行为

Precipitation behavior of impurity elements during evaporation crystallization of ammonium paratungstate

  • 摘要: 仲钨酸铵(APT)主要采用蒸发钨酸铵溶液的方式制取,是钨冶炼中最重要的中间产品,其化学质量将直接影响后续钨产品的质量。以硫磷混酸协同分解白钨所得钨酸铵溶液为原料,通过研究APT蒸发结晶过程中主要杂质离子的析出规律,获得了制备APT-0级产品所要满足的钨酸铵原料液中各杂质的浓度上限,既为钨酸铵净化工序提供了除杂深度的数据依据,又确保了蒸发结晶工序产品质量的达标。结果表明:对于杂质Na和K,K比Na更易析出;杂质Cu和Mg的析出率和在APT中的含量均随其浓度的增加而增大;杂质Mo在蒸发结晶前、后期的析出方式有所不同;杂质P和Si的析出率随其浓度增大而降低,且P的析出率比Si要大;杂质S以溶解度很大的(NH4)2SO4形式存在,故除了被吸附、夹带以外很少析出。根据GB/T 10116—2007,当溶液中c(Na)<52 mg/L,c(Cu)<18 mg/L,c(Mg)<17 mg/L,c(Mo)<30 mg/L时,制得的APT产品可满足零级要求,而对溶液中杂质K,P,Si,S的要求须更加苛刻才可能达到产品标准。

     

    Abstract: Ammonium paratungstate (APT), mainly made by evaporation of ammonium tungstate solution, is the most important intermediate product in tungsten smelting. Its chemical quality directly affects the quality of subsequent tungsten products. With ammonium tungstatesolution obtained from the synergistic decomposition of scheelite by sulfur-phosphorus mixed acid as raw material, we studied the precipitation law of main impurity ions during the evaporation and crystallization process of APT. The concentration upper limits for each impurity in the ammonium tungstate raw material liquid for the preparation of APT-0 grade products were determined. It not only provides a data basis for impurity removal for the ammonium tungstate purification process, but also ensures that the product quality of the evaporation crystallization process meets the standard. The impurity K is easier to be precipitated than Na. The precipitation rate of impurities Cu and Mg and their contents in APT increased with the growth of their concentrations. The precipitation mode of impurity Mo was different at initial and later stages of evaporation crystallization. The precipitation rate of impurities P and Si decreased with the increase of their concentrations, and the precipitation rate of P was higher than that of Si. Impurity S existed in the form of (NH4)2SO4 with high solubility, so it is rarely precipitated except for being adsorbed and entrained. According to GB/T 10116-2007, when c(Na) < 52 mg/L, c(Cu) < 18 mg/L, c(Mg) < 17 mg/L and c(Mo) < 30 mg/L in the solution, APT product can meet the zero-order requirements. However, the requirements for impurities K, P, Si and S in the solution must be more stringent in order to reach the product standard.

     

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