成孔增强型载磷温敏微球对水中U(VI)的去除性能与机制

Removal performance and mechanism of U(VI) in water by pore forming enhanced phosphorus loaded thermosensitive microspheres

  • 摘要: 为了解决海藻酸钠微球溶胀性差、吸附剂和被吸附物间的传质阻力大和干燥后吸附位点少的问题,采用自由基聚合和离子交联法制备了一种热响应互穿聚合物网络水凝胶微球,并对其进行“造孔+磷酸基团功能化”改性(简称P/PF@TR-IPN)。通过单因素试验研究了铀初始浓度、ZnO的含量、投加量、pH值、温度、干扰离子和吸附时间等对U(VI)吸附的影响,探究了其再生性能。在U(VI)初始浓度为10 mg∙L−1,pH值为4,P/PF@TR-IPN的投加量为0.4 g∙L−1,温度为25℃的条件下,6 h内P/PF@TR-IPN对U(VI)的去除率为94.8%,比造孔微球(PF@TR-IPN)和空白微球(TR-IPN)分别提高了18.5%和30.03%。随着温度从20℃增加到50℃,温敏微球P/PF@TR-IPN的溶胀率从6.98%降至5.14%。P/PF@TR-IPN的BET比表面积比TR-IPN增大了28.5倍。当pH值为4,温度为30℃和20℃时,P/PF@TR-IPN对U(VI)的最大吸附量分别为76.99 mg∙g−1和85.62 mg∙g−1。U(VI)的去除遵循单分子层化学吸附过程,拟二级动力学模型和Langmuir模型可以较好拟合P/PF@TR-IPN对U(VI)的吸附过程。试验表明,3D多孔结构和磷酸基团新活性吸附位点的形成是U(VI)去除效率增加的两个主要因素,P/PF@TR-IPN去除U(VI)的主要机制包括磷酸基团共沉淀的化学吸附作用和海藻酸钠含氧官能团的表面络合作用。

     

    Abstract: In order to solve the problems of poor swelling property of sodium alginate microspheres, large mass transfer resistance between adsorbent and adsorbate, and few adsorption sites after drying, a thermal-responsive interpenetrating polymer network hydrogel microspheres were prepared by free radical polymerization and ionic crosslinking, and modified by "pore forming+phosphate group functionalization" (P/PF@TR-IPN). The effects of initial uranium concentration, ZnO content, dosage, pH value, temperature, interfering ions and adsorption time on U(VI) adsorption were studied by single factor experiment, and its regeneration performance was explored. When the initial concentration of U(VI) is 10 mg∙L−1, the pH value is 4, the dosage of P/PF@TR-IPN is 0.4 g∙L−1, and the temperature is 25℃, the removal rate of U (VI) by P/PF@TR-IPN is 94.8% within 6 h, which is 18.5% and 30.03% higher than that of PF@TR-IPN and TR-IPN, respectively. With the increase of temperature from 20 ℃ to 50℃, the swelling rate of temperature-sensitive microspheres P/PF@TR-IPN decreases from 6.98% to 5.14%. The BET specific surface area of P/PF@TR-IPN is 28.5 times larger than that of TR-IPN. When pH value is 4 and the temperature is 30℃ and 20℃, the maximum adsorption capacity of P/PF@TR-IPN for U(VI) is 76.99 mg∙g−1 and 85.62 mg∙g−1, respectively. The removal of U(VI) follows the monolayer chemical adsorption process, and the pseudo-second-order kinetic model and Langmuir model can better fit the adsorption process of U(VI) by P/PF@TR-IPN. The results show that the 3D porous structure and the formation of new active adsorption sites of phosphate groups are the two main factors for the increase of U(VI) removal efficiency, the main mechanisms of U(VI) removal by P/PF@TR-IPN include the chemical adsorption of phosphate group coprecipitation and the surface complexation of sodium alginate oxygen-containing functional groups.

     

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