【作者】 翁延博；

【导师】 王静康；

【作者基本信息】 天津大学 ， 化学工程， 2008， 博士

【摘要】 本课题是国家“十一.五”科技支撑计划项目“钾镁盐矿生态化开发系统工程研究”中的应用基础研究一部分。为了最大限度地保护环境和提高资源利用率,将采用水采法进行开采,但其开采技术在国内外尚无大规模生产先例。为了避免在推进钾盐产业化进程中投资的盲目性,降低项目经济风险,本文对钾镁盐矿矿石进行了初步的溶浸试验探索性研究。采用盐矿真实岩心,对岩心特殊加工,制成防漏、防渗的几何体;室内模拟溶浸温度,注水采卤,分析卤水离子变化,找出合理采卤温度,了解矿藏溶腔模型变化。并且进一步测定了相关体系的相平衡数据,为钾镁盐矿的工业化开发提供了必需的基础数据。该钾镁盐矿是一个比较复杂的体系,由Na⁺、K⁺、Mg²⁺、Ca²⁺、Cl^-、Br^-、CO₃^2-、SO₄^2-等离子组成,其相平衡及平衡溶液物化性质的研究,对于开发该盐矿资源是必不可少的基础性研究工作。针对钾镁盐矿体系,在313K下采用等温溶解平衡法,测定了五元体系Na⁺,K⁺,Mg²⁺ // Cl^-,Br^--H₂O及其四个四元子体系、六个三元子体系相平衡关系和相应的平衡溶液的物化性质（密度、折光率、pH值、粘度）。绘制了三元子体系的相图,物化性质-组成图;绘制了四元子体系及五元体系的有关相图。填补了该体系溶解度数据和平衡溶液物化性质参数研究方面的空白。相平衡研究中,同时含有氯离子和溴离子的体系中生成了固体溶液,在所研究的三元、四元及五元体系中均有出现。三元体系KBr-MgBr₂-H₂O 313K时生成了一种复盐KBr·MgBr₂·6H₂O,在含该三元体系的四元、五元体系中也发现了该复盐的结晶区。将Pitzer理论应用到了高浓度、多组分的实际体系,采用三元体系溶解度数据,运用多元线性回归法拟合了Pitzer方程中313K时所涉及各种盐的单盐参数及混合离子作用参数,计算出了各种盐313K时溶解平衡常数。对于含固溶体的三元子体系,拟合了平衡固相与液相组成之间新的经验关系式,使该类相平衡的计算得到简化。运用Pitzer方程对简单四元体系及六个三元体系相平衡进行了理论计算,计算结果与实验结果基本吻合。本文研究成果尚未见国内外文献报道。更多还原

【Abstract】 The subject belongs to the application foundation research of the national eleventh five-year scientifical supporting and planning projects“study on systems engineering in ecotourism exploitation of potassium and magnesium salt deposit”. In order to protect environment and increase utilization as far as possible, a correct water exploitation program has been employed. However, this technology has not been applied in large-scale production at home and abroad. In order to avoid the bindness of the investment for advancing the process of industrialization of potassium and magnesium salt deposit and decrease the economic risk for the project, an exploratory research of Leaching-Experiment for K-Mg Salt-Deposit was performed in this work. Solid core of salt mine is treated with special method to be produced into leak-free and permeation-free geometrical body. Under the temperature simulated to that of the leaching, water is injected, extract brine and analyze ion change in brine. Reasonable brine extraction temperature is found for modeling in caverns in different period time in a view to learn the cavern modeling change.Further, in order to provide the necessary basic data for the industrialization of potassium and magnesium salt deposit, phase equilibrium data for related systems have been systematically measured. K-Mg Salt-Deposit is a complex chemical compound system, which is composed of many ions and molecule such as K⁺, Na⁺, Mg²⁺, Ca²⁺, Cl^-, Br^-, CO₃^2-, SO₄^2-, etc. So, the study of its phase equilibrium and the physico-chemical properties are in a dispensable elementary work for exploiting the resource of potassium salt mine.In accordance with the composition of the K-Mg Salt-Deposit, the reciprocal quinary system Na⁺, K⁺, Mg²⁺ // Cl^-, Br^--H₂O and its four quaternary sub-systems and six ternary sub-systems were studied at 313K with isothermal method at the present work. The solubilities and the physico-chemical properties of relevant equilibrium solutions, including density, refractivity index, pH value, viscosity, were determined. According to the experimental data, phase diagrams and physico-chemical property-composition diagrams of ternary systems were plotted; phase diagrams of four quaternary sub-systems and quinary system are also constructed. This work has filled the blank in this field of solubilities and the physico-chemical properties of relevant equilibrium solutions.It is founded that the system containing chloride and bromide is of solid solution type. A kind of complex salt KBr·MgBr₂·6H₂O was found in the ternary system KBr-MgBr₂-H₂O at 313K, and this complex salt also exists in the quaternary and quinary systems which contained the KBr-MgBr₂-H₂O system.Pitzer’s electrolyte solution model is employed for theoretically phase relations of the high concentration multicomponent systems in this work. Using the reliable solubility data of ternary systems at 313 K, the single salt Pitzer parameters and corresponding ion-interaction mixing parameters for Pitzer’s equations were fitted by multiple linear regress method. Equilibrium constant of salts for liquid-solid equilibrium at 313 K were evaluated with Pitzer’s model. To study the phase equilibrium of complex ternary salt-water system containing solid solution, the equilibrium relationship between liquid composition and solid composition was established to achieve the phase diagram by simple iterative calculation. Using the Pitzer’s equations, the solubilities of the simple quaternary sub-system and six ternary sub-systems were predicted. The calculated values are in agreement with experiment values on the whole.No same report to above study results has been published in literature at present.更多还原