Kurley J Matthew, Halstenberg Phillip W, McAlister Abbey, Raiman Stephen, Dai Sheng, Mayes Richard T
Chemical Sciences Division, Oak Ridge National Laboratory Oak Ridge TN 37831 USA
Materials Science & Technology Division, Oak Ridge National Laboratory Oak Ridge TN 37831 USA.
RSC Adv. 2019 Aug 15;9(44):25602-25608. doi: 10.1039/c9ra03133b. eCollection 2019 Aug 13.
Molten salts for use as heat transfer fluids in concentrated solar or nuclear power plants have experienced a resurgence over the past decade with a special focus on chloride-based salt mixtures, particularly for use in concentrating solar power and fast-spectrum nuclear reactors. Salt purification, specifically oxide removal, is required even for high purity commercial salts and can be achieved using many different methods. Carbochlorination, however, proves most effective according to thermodynamics and produces a gaseous byproduct easily removed from the salt. A variety of carbochlorinating reagents and reagent combinations were evaluated for thermodynamic favorability in the removal of common impurities in MgCl-based feedstock or coverage gases used in industrial systems. Carbon tetrachloride exhibited superior purification thermodynamics above the melting point of common MgCl-based salt compositions. Salt with composition of 68 : 32 mol% KCl : MgCl was purified on the kilogram scale by sparging with carbon tetrachloride, reducing dissolved oxide to trace levels (42 μmol MgO/kg salt). Interestingly, the lower purity salts exhibited magnesium and oxygen presence along grain boundaries in the corrosion layers while the purified salts did not, highlighting the need for decreased oxide content. The lessened corrosivity of the highly purified salt suggests a proper salt treatment may reduce dependence on specialized materials for use with molten salts.
在过去十年中,用作聚光太阳能或核电站传热流体的熔盐再度兴起,特别关注基于氯化物的盐混合物,尤其是用于聚光太阳能发电和快中子谱核反应堆。即使对于高纯度商业盐,也需要进行盐净化,特别是去除氧化物,这可以通过许多不同方法实现。然而,根据热力学原理,碳氯化法被证明是最有效的,并且会产生易于从盐中去除的气态副产物。对多种碳氯化试剂和试剂组合进行了评估,以确定其在去除基于MgCl的原料或工业系统中使用的覆盖气体中的常见杂质方面的热力学优势。在常见的基于MgCl的盐组合物的熔点以上,四氯化碳表现出优异的净化热力学性能。通过用四氯化碳鼓泡,对组成为68:32摩尔% KCl:MgCl的盐进行了千克规模的纯化,将溶解的氧化物降低到痕量水平(42 μmol MgO/kg盐)。有趣的是,纯度较低的盐在腐蚀层的晶界处存在镁和氧,而纯化后的盐则没有,这突出了降低氧化物含量的必要性。高纯度盐腐蚀性的降低表明,适当的盐处理可能会减少对用于熔盐的特殊材料的依赖。