新型离子交换树脂的合成及其高酸吸附镓基础理论研究

With the development of high and new technology in our country, Gallium is in great demand as the foundational support materials and has been listed strategic reserve metal. Gallium is mainly associated in monohydrallite and Lead-Zinc ore. At present, more than 90% Gallium is extracted from the alumina production process. Restricted by extraction technology in high acid solution system, Gallium in Lead-Zinc ore is barely used. According to the above current situation and combining with the base work, applicants use chlorine methyl styrene resin (Chlorine ball) as matrix, phenol as graft material, P2O5 as phosphorylation modification, agenting grafted, phosphorylation reaction and synthesizing a novel poly phenyl phosphate ester- poly styrene resin which has high adsorption capacity and good selectivity of Gallium from high acidity sulfuric acid system.The structure-activity relationship between molecular structure of phenol grafting material, resin electronic effect and space steric hindrance and characteristics of Gallium adsorption are studied. The adsorption characteristics, adsorption mechanism, adsorption process kinetics, adsorption thermodynamics of the novel resin are studied. And the adsorption, stripping, regeneration properties and behavior rules of the novel resin in the process of extraction and separation Gallium from coexisting ions in the high acidity leaching liquid of zinc metallurgical slag are researched. Through the establishment of these theories, a green and efficient extraction technology in view of Gallium in high acidity of sulfate solution system is developed and the efficient use of Gallium associated in Lead-Zinc ore resources is implemented.

随着我国高新技术领域发展，镓作为基础支撑材料，已被列为战略储备金属，需求旺盛。镓主要伴生于铝土矿和铅锌矿中，目前90%以上的镓从氧化铝生产工艺中提取。受高酸溶液体系提取技术限制，铅锌矿中镓几乎未被利用。针对上述现状，结合已有的工作基础，申请者设计采用以氯甲基苯乙烯树脂（氯球）为基体，以酚类为接枝物、P2O5为磷酸化改性剂发生接枝、磷酸化反应，合成在高酸体系下对镓具有优良吸附特性、高吸附容量的聚苯基磷酸酯—聚苯乙烯离子交换树脂，系统研究酚类接枝物分子结构—树脂的电子效应、空间位阻—镓吸附特性间的构效关系、树脂吸附特性、吸附机理、吸附过程动力学、吸附热力学以及树脂在锌冶炼渣高酸度硫酸浸出液中提取分离镓与共存竞争离子过程的吸附、脱附、再生性能及行为规律。通过这些理论的建立，开发出一种针对高酸度硫酸溶液中镓的绿色、高效提取技术，实现铅锌矿中伴生镓资源的高效利用。

稀散金属镓是当代高新技术领域的重要基础支撑材料。近年来，随着我国对高新技术产业的大力发展，镓的战略地位将更显突出，镓资源的开发利用受到广泛关注。镓主要伴生于铝土矿和铅锌矿中，多作为副产物在主金属冶炼过程提取回收。目前90%以上的镓从氧化铝生产工艺碱性体系中提取，受高酸溶液体系提取技术限制，铅锌矿中镓几乎未被利用。随着铝产量的相对饱和和产能过剩，镓产量难以提升。在此背景下，本项目开展了新型离子交换树脂的合成与表征及其高酸吸附镓基础研究，树脂从锌冶炼渣高酸度硫酸浸出液吸附镓应用研究，锌冶炼渣高酸度硫酸浸出液中选择性提取镓应用研究以及锌冶炼渣高效浸出镓、锗研究。取得的主要研究进展有：1）开展完成了树脂合成过程接枝反应、磷酸化反应的技术路线优化、参数设计及工艺基础研究，制备得到了新型聚苯基磷酸酯—聚苯乙烯离子交换树脂，并完成表征，建立了新型树脂的合成基础理论；开展完成了树脂吸附基础实验研究及其从锌冶炼渣高酸度浸出液吸附镓应用研究，分析了树脂未达到预期吸附效果的原因并开展了优化探索；2）完成了从锌冶炼渣高酸度硫酸浸出液中选择性分离提取镓技术优化与应用研究，开发出了苯基磷酸酯直接萃取法从高酸度低铁锌冶炼渣硫酸浸出液中选择性提镓新工艺，以及“N235+Cyanex272”两步萃取法从高酸度高铁锌冶炼渣硫酸浸出液中选择性提镓新工艺，完成了工艺方案优化与应用基础研究，实现了锌冶炼渣高酸度硫酸溶液中镓的提取分离。3）针对锌冶炼渣硫酸浸出过程中酸度高、浸出效率低等问题，开展完成了锌冶炼渣表征及物相分析，开发了“酸+碱”分段浸出法从锌冶炼渣中选择性高效浸出镓、锗新工艺，完成了工艺方案优化与应用基础研究，实现了锌冶炼渣中镓、锌，铅与锗的高效浸出和分离。