功能基修饰超高交联吸附树脂的制备及其对生物丁醇发酵废水中有机酸的吸附机理研究

The environmental pollution caused by large quantities of biobutanol fermentation wastewater is extraordinary serious, which needs to be solved. In recent years, adsorption as an efficient separation technology has been greatly developed for the treatment of organic chemical wastewater pollution and become the hotspot of the current research. However, the major problem in practical application of cyclic utilization of biobutanol fermentation wastewater is the inhibitory effect of organic acid and color to the Clostridium acetobutylicum. Firstly, this project aims at synthesizing a series of novel modified hyper-cross-linked adsorption resins in terms of uniform size, high selectivity, high adsorption capacity, controllable pore structures and surface properties by chemically binding different polar functional groups onto host polymeric matrixes. Subsequently, the quantitative structure-activity relationship between organic acids in biobutanol fermentation wastewater and these modified resin adsorbents will be explored in terms of matrix composition, pore size distribution, and surface properties. Furthermore, we will systematically investigate the effect of adsorption thermodynamics, dynamics, in order to clarify the diffusion and mass transfer mechanism of organic acids in biobutanol fermentation wastewater in the pore of modified resin adsorbent. Then we will establish a chromatographic column model to predict the separation of biobutanol fermentation wastewater in the column. This research will develop integral process on the basis of new modified resin adsorbent for effective removal and recovery of organic acids from biobutanol fermentation wastewater. All the results available are believed to open a new field to design new polymeric adsorbents and provide the theoretical basis and technical support for biobutanol fermentation wastewater treatment.

发酵法生产丁醇排出的废水不仅量大且污染非常严重，需亟待解决。近年来吸附分离技术在有机化工废水污染治理方面有很大的发展，是当前研究的热点。本项目针对生物丁醇发酵废水直接循环利用时废水中有机酸、色素等抑制剂对丙酮丁醇梭菌发酵产生抑制的关键问题，拟从微球介质结构的定向设计和控制方面入手，研制尺寸均一、高吸附选择性、高吸附容量、且孔结构和表面性质可控的功能基修饰超高交联吸附树脂。探索改性树脂骨架结构、孔分布、表面性质与生物丁醇发酵废水中有机酸等抑制剂吸附性能之间的“构效关系”。通过吸附热力学和动力学研究，阐明生物丁醇发酵废水中有机酸等抑制剂在树脂内部的扩散与传质机理；建立色谱柱内的模型，预测生物丁醇发酵废水中有机酸等抑制剂在色谱柱内的分离结果，开发以树脂吸附为核心的生物丁醇发酵废水中有机酸等抑制剂的高效净化与回用集成技术，为树脂吸附法在工业废水处理及资源化领域中的应用拓展提供理论基础与技术支持。

吸附分离技术是一种集有机物去除和资源回收为一体的实用技术，并满足“4-E” 标准：高效、经济、环保和容易操作。新型吸附剂的合成和应用已成为环保领域的重要研究方向之一。本项目以提高吸附剂对亲水性强、低碳数的有机酸吸附/脱附性能为目标，具体解析功能基修饰超高交联吸附树脂骨架结构、表面性质和孔分布与废水中有机酸、色素等抑制剂吸附性能之间“构效关系”的基础上，通过引入酯基、酰胺基进行修饰，利用氢键作用力的方向性和短程性提高超高交联吸附树脂的吸附/脱附性能。重点研究超高交联吸附树脂吸附有机酸的热力学及动力学模拟，阐明了扩散传质机制，同时构建色谱柱内动态柱吸附数学模型，预测有机酸等抑制剂在色谱柱内的分离结果。本项目根据生物丁醇发酵废水中组分的特性，系统考察了不同单体/交联剂比例、致孔剂用量、致孔剂中良/非良溶剂比、非良溶剂的类型对聚苯乙烯二乙烯苯树脂结构以及对稻草秸秆水解液（用于制备生物丁醇）、生物丁醇发酵废水中糖、有机酸、呋喃衍生物、色素和酸溶木质素的吸附性能的影响。研究发现，聚苯乙烯二乙烯苯树脂的比表面积对色素、呋喃衍生物和酸溶木质素的吸附起着关键的作用，而孔径分布对有机酸和糖的吸附至关重要。相关研究结果发表在Ind. Eng. Chem. Res. ( 2018，补充封面文章，他引1次)，申请4项中国发明专利。构建了描述SY-01单组分及多组分固定床柱吸附分离有机酸的模型，模拟不同操作条件下有机酸在SY-01树脂固定床柱上的吸附行为，相关研究结果发表在Sep. Purif. Tech. (2017，他引10次)、Chemosphere (2017，他引14次)、Ind. Eng. Chem. Res. ( 2018，补充封面文章，他引4次)。