Department of Civil and Environmental Engineering , Duke University , Durham , North Carolina 27708 , United States.
Center for Applied Energy Research , University of Kentucky , Lexington , Kentucky 40511 , United States.
Environ Sci Technol. 2019 Apr 16;53(8):4490-4499. doi: 10.1021/acs.est.9b00539. Epub 2019 Apr 5.
Coal combustion residues and other geological waste materials have been proposed as a resource for rare earth elements (REEs, herein defined as the 14 stable lanthanides, yttrium, and scandium). The extraction of REEs from residues often generate acidified leachates that require highly selective separation methods to recover the REEs from other major soluble ions in the leachates. Here, we studied two liquid membrane processes (liquid emulsion membranes, LEM, and supported liquid membranes, SLM) and compared them to standard solvent extraction techniques for selective recovery and concentration of REEs from a leachate of coal fly ash. All separation methods involved an organic solution of di(2-ethylhexyl)phosphoric acid dissolved in kerosene or mineral oil and an acid strippant solution of 5 M nitric acid for the liquid-based separations. The LEM configuration, which separated REEs by immersing an acid-in-oil emulsion in the ash leachate, resulted in similar recovery percentages of individual REEs as the conventional solvent extraction approach. The recovery of REEs in the SLM configuration, which involved the impregnation of the solvent in a hydrophobic membrane, was slower than the LEM process. However, the SLM process was notably more selective for the heavy (and higher value) REEs, while the conventional extraction and LEM processes were more selective for the light REEs. A flux-based model of the extraction processes suggested that recovery rates were limited by REE affinity for the solvent chelator in the SLM, while the rates of REEs separation via LEM were limited by diffusive mass transfer across the liquid membrane. Altogether, these results help to identify specific steps in the recovery process that future work should target in the development of scalable liquid membrane separations for REE recovery.
煤燃烧残渣和其他地质废料已被提议作为稀土元素(REEs,本文定义为 14 种稳定的镧系元素、钇和钪)的资源。从残渣中提取 REEs 通常会产生酸化的浸出液,需要高度选择性的分离方法才能从浸出液中的其他主要可溶性离子中回收 REEs。在这里,我们研究了两种液膜工艺(液体乳液膜(LEM)和支撑液膜(SLM)),并将其与标准溶剂萃取技术进行了比较,以从粉煤灰浸出液中选择性回收和浓缩 REEs。所有分离方法都涉及二(2-乙基己基)磷酸溶解在煤油或矿物油中的有机溶液和 5 M 硝酸的酸性剥离剂溶液,用于基于液体的分离。LEM 配置通过将油包酸乳液浸入粉煤灰浸出液中来分离 REEs,导致个别 REEs 的回收率与传统溶剂萃取方法相似。SLM 配置中溶剂的浸渍在疏水性膜中,REEs 的回收率比 LEM 过程慢。然而,SLM 过程对重(和高价值)REEs 的选择性明显更高,而传统萃取和 LEM 过程对轻 REEs 的选择性更高。萃取过程的通量模型表明,回收率受 SLM 中溶剂螯合剂对 REE 亲和力的限制,而通过 LEM 分离 REEs 的速率受通过液膜的扩散质量传递限制。总之,这些结果有助于确定回收过程中的特定步骤,未来的工作应针对可扩展的液膜分离技术的开发来针对 REE 回收。