Oyola Yatsandra, Vukovic Sinisa, Dai Sheng
Oak Ridge National Laboratory, Chemical Sciences Division, 1 Bethel Valley Rd, Oak Ridge, TN 37831-6119, USA.
Dalton Trans. 2016 May 28;45(20):8532-40. doi: 10.1039/c6dt00347h. Epub 2016 Apr 27.
Amidoxime-based polymer adsorbents have attracted interest within the last decade due to their high adsorption capacities for uranium and other rare earth metals from seawater. The ocean contains an approximated 4-5 billion tons of uranium and even though amidoxime-based adsorbents have demonstrated the highest uranium adsorption capacities to date, they are still economically impractical because of their limited recyclability. Typically, the adsorbed metals are eluted with a dilute acid solution that not only damages the amidoxime groups (metal adsorption sites), but is also not strong enough to remove the strongly bound vanadium, which decreases the adsorption capacity with each cycle. We resolved this challenge by incorporating Le Chatelier's principle to recycle adsorbents indefinitely. We used a solution with a high concentration of amidoxime-like chelating agents, such as hydroxylamine, to desorb nearly a 100% of adsorbed metals, including vanadium, without damaging the metal adsorption sites and preserving the high adsorption capacity. The method takes advantage of knowing the binding mode between the amidoxime ligand and the metal and mimics it with chelating agents that then in a Le Chatelier's manner removes metals by shifting to a new chemical equilibrium. For this reason the method is applicable to any ligand-metal adsorbent and it will make an impact on other extraction technologies.
在过去十年中,基于偕胺肟的聚合物吸附剂因其对海水中铀和其他稀土金属的高吸附能力而备受关注。海洋中大约含有40亿至50亿吨铀,尽管基于偕胺肟的吸附剂迄今为止已展现出最高的铀吸附能力,但由于其有限的可回收性,在经济上仍然不实用。通常,用稀酸溶液洗脱吸附的金属,这不仅会破坏偕胺肟基团(金属吸附位点),而且其强度不足以去除紧密结合的钒,从而导致每个循环的吸附容量下降。我们通过运用勒夏特列原理来无限期地循环利用吸附剂,解决了这一难题。我们使用了一种含有高浓度偕胺肟类螯合剂(如羟胺)的溶液,以解吸几乎100%的吸附金属,包括钒,同时不破坏金属吸附位点并保持高吸附容量。该方法利用了对偕胺肟配体与金属之间结合模式的了解,并用螯合剂进行模拟,然后以勒夏特列方式通过转移到新的化学平衡来去除金属。因此,该方法适用于任何配体 - 金属吸附剂,并且将对其他萃取技术产生影响。