U- \mathbfC\mathbfO_\boldsymbol3^\boldsymbol2- -H2O体系电位-pH图特征及其影响因素

Characteristics of Potential-pH Diagram of U-\bfC\bfO_\boldsymbol3^\boldsymbol2- -H2O System and Its Influencing Factors

  • 摘要: 为明确碳酸铀酰加氢还原四价铀的热力学特性及影响因素,本文通过热力学计算绘制了U- \mathrmCO_3^2- -H2O体系的电位-pH(E-pH)图,并对其影响因素进行了探讨。分析结果表明:在该体系中,采用加氢还原法将六价碳酸铀酰离子还原为四价二氧化铀沉淀物的过程在热力学上具有可行性,且二氧化铀的优势区域面积较大,体系中基本无其他形态铀化合物存在。尽管反应温度、溶液 \mathrmC\mathrmO_3^2- 浓度会对六价铀的还原电位有一定影响,但不会改变氢气对其的还原作用及二氧化铀沉淀的形成趋势。以某铀矿地浸采铀所得碱性合格液为研究对象进行加氢还原验证试验,所得结果与热力学分析结果一致。该U- \mathrmC\mathrmO_3^2- -H2O体系E-pH图可为碱性碳酸铀酰溶液中铀的加氢还原条件优选提供可靠的热力学依据。

     

    Abstract: Hydrogen reduction method has been widely studied and applied in the hydrometallurgy preparation of metal powders or oxides due to its simple operation, clean and environmental protection. A large number of research reports have emerged in the metallurgical processes and technologies of platinum group metals, nickel, cobalt, copper, vanadium and other metals. If the hexavalent uranyl ions in the solution are reduced to tetravalent by hydrogen reduction method, it is expected to achieve selective reduction and precipitation of uranium and produce high-quality uranium oxide products. However, the existence of uranium in alkaline solution is complex and changeable, with multiple valence states and hydrolysate products, and it is difficult to obtain the ideal hydroreduction effect without systematic research on the thermodynamics of hydroreduction precipitation of uranium. The potential-pH diagram is a phase diagram drawn according to the function relationship between the equilibrium potential of various reactions in the system and the pH value of the solution, which can be used to judge the possibility of the reaction under the system, the stability of the product, determine the chemical equilibrium conditions in the solution, the direction of the reaction and the dominant area and range of a certain component, provide a thermodynamic basis for the chemical reaction of the solution, and also carry out theoretical analysis, improvement and perfection of the production process. In order to determine the thermodynamic properties and influencing factors of uranyl carbonate hydroreduction, the potential-pH diagram of the U- \mathrmC\mathrmO_3^2- -H2O system was drawn by thermodynamic calculation, and its influencing factors were discussed. The diagram analyses show that under the U- \mathrmC\mathrmO_3^2- -H2O system, the reduction of uranium from hexavalent uranyl carbonate ions to tetravalent uranium dioxide precipitate is thermodynamically feasible, and the dominant area of uranium dioxide is large, and there are basically no other forms of uranium compounds. Although the reaction temperature and solution carbonate concentration have a certain effect on the reduction potential of hexavalent uranium, they do not affect the reduction of hydrogen and the formation of uranium dioxide precipitation as a whole. The hydroreduction verification test was carried out using the alkaline uranium qualified liquid obtained from a leaching mine, and the test results were consistent with the thermodynamic analysis results. The potential-pH map of this study can be used to guide the experimental research and industrial practice of uranium products prepared by hydroreduction of uranyl carbonate solution, which provides a new technical support for uranium mines to directly prepare high-quality uranium oxide products from alkaline uranyl carbonate qualified liquid.

     

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