摘要
随着社会的发展,水资源匮乏正严重影响着全世界的经济发展与生态环境。相关国际机构郑重指出“水将成为世界最严重的资源问题”、“供水不足将成为一个深刻的社会危机”。硼作为水体中的常见污染物,在海水、苦咸水、工业废水中广泛存在,目前的除硼方法存在操作压强高、通量低的缺点。硼酸与二羟基化合物如糖能进行高亲和性且可逆的反应,本论文基于硼酸和糖的亲和作用,综合聚丙烯微孔膜良好的物理机械性能和化学稳定性,设计并制备了具有除硼功能的糖基化聚丙烯亲和膜,能在较低的操作压强下有效去除水体中的硼污染物。
具体研究内容如下：用紫外光辐射接枝的方法在膜表面接枝甲基丙烯酸-2-氨乙酯盐酸盐(AEMA),在膜表面构建氨基活性接枝层(PAEMA),然后用三乙胺对氨基进行脱保护,EDC/NHS催化乳糖酸和氨基反应,固定糖基。接枝聚合过程可以通过改变单体浓度、紫外辐照时间来进行调控。接枝密度随单体浓度和光照时间的增加而增加。研究表明：温度、反应时间、溶液pH值等影响糖基化效率,最高糖基化效率为70%左右。FT-IR/ATR、XPS、染色法以及SEM对糖基化前后膜表面的化学结构以及形貌变化的表征,验证了糖基化各步的完成。水接触角和水通量实验揭示了糖基化改性接枝层对膜表面浸润和渗透性能的影响。
以乳糖糖基化聚丙烯微孔膜为亲和膜,以3-氨基苯硼酸为模型硼酸,进行硼酸分离实验。发现,最佳的吸附pH为9.1,且随着糖基密度的增加,除硼效率提高,其最高硼脱除率为39.64%。吸附硼酸后的糖基化聚丙烯亲和膜能用0.3 M的盐酸再生,重复使用性好。进一步考察了糖基化聚丙烯亲和膜对硼酸的吸附分离,结果表明,往溶液中添加金属镁离子能有效的提高分离效率,最高硼脱除率为66.01%。此外,考察了葡萄糖糖基化聚丙烯亲和膜对硼酸的吸附分离,结果表明,在同一条件下,乳糖糖基化亲和膜的分离效率是葡萄糖的3倍。测定了乳糖酸、葡萄糖-δ-内酯与硼酸的络合比,结果表明乳糖与硼酸的结合能力优于葡萄糖。
A novel affinity membrane is proposed for boron removal by microporous polypropylene membrane (MPPM) functionalized with glycopolymer containing saccharide polyols as ligands. The affinity is based on specific complexation between the saccharide ligand and boric acid. A two-step procedure was used to prepare this glycopolymer-functionalized affinity membrane. 2-Aminoethyl methacrylate hydrochloride (AEMA) was tethered on the surface and in the pores of MPPM by UV-induced graft polymerization. Grafting in the membrane pores was visualized by dying the cross-section of poly(AEMA)-grafted MPPM with fluorescein disodium and imaging with CLSM. It is reasonable to conclude that glycopolymer can also be formed both on the membrane surface and in the membrane pores by the subsequent coupling of the AEMA unit with lactobionic acid (LA). Physical and chemical properties of the affinity membrane were characterized by FESEM and FT-IR/ATR.
Boron removal from water was carried out by a single piece of glycopolymer-functionalized MPPM in a dynamic filtration system, and 3-aminophenylboronic acid was chosen as a typical model boric acid. The optimun operation condition was investigated. The results show that the highest removal efficiency is 39.64%. Regeneration of this affinity membrane was easily realized through washing with 0.3 M HCl. The membrane can thus be reused without significant loss of binding capability. Furthermore, the boron removal efficiency can be improved with the aid of magnesian ion, and the highest removal efficiency is 66.01%. The glycopolymer-functionalized MPPM with glucose pendant as the ligand was also applied to remove boron from water. The results show that the glucose-immobilized MPPM can not remove boron from water as effective as the lactose-immobilized MPPM. Complexometric titrition test was also carried out to confirm the results.
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