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硝酸介质中合成硫化物精矿的溶解动力学

Synthetic Sulfide Concentrate Dissolution Kinetics in HNO Media.

作者信息

Dizer Oleg, Karimov Kirill, Kritskii Aleksei, Rogozhnikov Denis

机构信息

Laboratory of Advanced Technologies in Non-Ferrous and Ferrous Metals Raw Materials Processing, Department of Non-Ferrous Metals Metallurgy, Ural Federal University, 620002 Yekaterinburg, Russia.

出版信息

Materials (Basel). 2022 Nov 17;15(22):8149. doi: 10.3390/ma15228149.

Abstract

The nature of tennantite (Cu12As4S13), chalcopyrite (CuFeS2) and sphalerite (ZnS) particles’ mixture dissolution in nitric acid (HNO3) media was investigated in this study. The effects of temperature (323−368 K), HNO3 (1−8 mol/L) and Fe3+ (0.009−0.036 mol/L) concentrations, reaction time (0−60 min) and pyrite (FeS2) additive (0.5/1−2/1; FeS2/sulf.conc.) on the conversion of the minerals were evaluated. It has been experimentally shown that the dissolution of the mixture under optimal conditions (>353 K; 6 mol/L HNO3; FeS2/synt. conc = 1/1) allows Cu12As4S13, CuFeS2 and ZnS conversion to exceed 90%. The shrinking core model (SCM) was applied for describing the kinetics of the conversion processes. The values of Ea were calculated as 28.8, 33.7 and 53.7 kJ/mol, respectively, for Cu12As4S13, CuFeS2 and ZnS. Orders of the reactions with respect to each reactant were calculated and the kinetic equations were derived to describe the dissolution rate of the minerals. It was found that the interaction between HNO3 solution and Cu12As4S13, CuFeS2 and ZnS under the conditions investigated in this are of a diffusion-controlled nature. Additionally, the roles of Fe(III) in the initial solution and FeS2 in the initial pulp as catalysts were studied. The results indicated that the increase in Fe3+ concentration significantly accelerates the dissolution of the mixture, while the addition of FeS2 forms a galvanic coupling between FeS2, and Cu12As4S13 and CuFeS2, which also accelerates the reaction rate. The results of the study are considered useful in developing a hydrometallurgical process for polymetallic sulfide raw materials treatment.

摘要

本研究考察了黝铜矿(Cu₁₂As₄S₁₃)、黄铜矿(CuFeS₂)和闪锌矿(ZnS)颗粒混合物在硝酸(HNO₃)介质中的溶解情况。评估了温度(323 - 368 K)、HNO₃浓度(1 - 8 mol/L)、Fe³⁺浓度(0.009 - 0.036 mol/L)、反应时间(0 - 60分钟)以及黄铁矿(FeS₂)添加剂(0.5/1 - 2/1;FeS₂/硫浓度)对矿物转化率的影响。实验表明,在最佳条件下(>353 K;6 mol/L HNO₃;FeS₂/合成浓度 = 1/1)混合物的溶解可使Cu₁₂As₄S₁₃、CuFeS₂和ZnS的转化率超过90%。采用收缩核模型(SCM)描述转化过程的动力学。对于Cu₁₂As₄S₁₃、CuFeS₂和ZnS,计算得到的Ea值分别为28.8、33.7和53.7 kJ/mol。计算了各反应物的反应级数,并推导了动力学方程以描述矿物的溶解速率。发现在本研究考察的条件下,HNO₃溶液与Cu₁₂As₄S₁₃、CuFeS₂和ZnS之间的相互作用具有扩散控制的性质。此外,研究了初始溶液中的Fe(III)和初始矿浆中的FeS₂作为催化剂的作用。结果表明,Fe³⁺浓度的增加显著加速了混合物的溶解,而添加FeS₂会在FeS₂与Cu₁₂As₄S₁₃和CuFeS₂之间形成电偶,这也加速了反应速率。该研究结果对于开发多金属硫化物原料处理的湿法冶金工艺具有重要意义。

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