基于环糊精聚合物的平衡被动采样器的设计

发布时间：2018-06-08 08:27

本文选题：环糊精聚合物 + 平衡被动采样器　；参考：《大连理工大学》2015年硕士论文

【摘要】：水中有机污染物种类和数量与日俱增,给自然生态系统和人类健康造成一定影响。对这些有机污染物快速采集具有重要意义。通常目标污染物的前处理工作量占整个分析工作量的70%-90%。被动采样不受突发污染事件影响,可以方便、快捷的进行采样。目前平衡型被动采样技术主要有被动扩散袋式采样技术、半透膜被动采样技术、固相微萃取技术、薄膜扩散平衡技术。它们存在着平衡时间较长,多针对于疏水性有机污染物等问题。环糊精聚合物作为吸附剂具有水凝胶结构,吸附平衡时间短,有多种吸附位点,且具有结构多样性。本研究通过反相乳液聚合法合成环糊精聚合物,表征其形貌结构,通过拟合等温吸附方程、研究环境因素对吸附的影响、计算目标物洗脱回收率,从而考察材料的吸附性能,基于以上背景设计加工以环糊精聚合物为吸附剂的平衡被动采样器,用于实际水体采样。研究结果如下：(1)通过反相乳液聚合法合成β-环糊精聚合物,筛选出80-120目的材料。材料呈均匀的球形形貌,溶胀后粒径呈对数正态分布,平均粒径371.00 gm,粒径分布集中。材料溶胀率8.67 g/g,环糊精单元含量68.81%,孔尺寸5.60 nm,属介孔范围。(2)对p-环糊精聚合物吸附性能进行研究。选定26种目标化合物(如阿特拉津、苯线磷、噻菌灵、氢氯噻嗪、磺胺噻唑、磺胺吡啶等)通过序批式等温吸附实验,拟合等温吸附方程,这些目标化合物均符合Freundlich等温吸附方程(R20.96)。考察离子强度(Ca2+、Mg2+)、溶解性有机质(DOM)对吸附的影响,结果发现这些物质吸附不受环境因素影响。考察目标污染物的洗脱回收率,得到对于大多数物质回收率在70-110%之间,且相对偏差在10%以内。(3)考虑到环糊精聚合物溶胀后不易凸附在采样器表面,将采样器设计成椭球形状。选择抗腐蚀、机械性能良好、对污染物无吸附作用的不锈钢304材质用于后续加工。根据材料溶胀后体积1.3 cm3和椭球体积计算公式,得到采样器长半轴0.85 cm,短半轴0.85cm,半高0.43 cm。通过模具制造、冲压、包边、锁扣焊接加工成成品用于实际水体测试。选定磺胺嘧啶、磺胺噻唑、磺胺吡啶、林可霉素、磺胺地索辛五种抗生素,结果表明磺胺噻唑、磺胺吡啶Ce,pred精确度在93%-116%。磺胺嘧啶、林可霉素、磺胺地索辛Ce,pred精确度在54%-62%。由于是初步设计采样器,它有待进一步的优化完善。
[Abstract]:The species and quantity of organic pollutants in water are increasing day by day, which has a certain impact on natural ecosystem and human health. It is of great significance for the rapid collection of these organic pollutants. Usually, the pre-treatment of target pollutants accounts for 70-90% of the total analytical work. Passive sampling is not affected by sudden pollution events, so it is convenient and fast to sample. At present, the balanced passive sampling technology mainly includes passive diffusion bag sampling, semi-permeable membrane passive sampling, solid-phase microextraction and film diffusion balance. They have many problems, such as long equilibrium time and hydrophobic organic pollutants. As an adsorbent, cyclodextrin polymer has hydrogel structure, short adsorption equilibrium time, multiple adsorption sites and structural diversity. In this study, cyclodextrin polymer was synthesized by inverse emulsion polymerization, and its morphology and structure were characterized. By fitting the isothermal adsorption equation, the influence of environmental factors on adsorption was studied, and the recovery rate of elution was calculated. Based on the above background, a balanced passive sampler with cyclodextrin polymer as adsorbent was designed and manufactured for practical water sampling. The results are as follows: (1) 尾 -cyclodextrin polymer was synthesized by inverse emulsion polymerization and 80-120 target materials were selected. After swelling, the particle size is logarithmic normal distribution, the average particle size is 371.00 gmm, the particle size distribution is concentrated. The adsorption properties of p-cyclodextrin polymer were studied with the swelling ratio of 8.67 g / g, the content of cyclodextrin in 68.81 and the pore size of 5.60 nm. 26 target compounds (such as atrazine, benzophosphorus, thiabendazole, hydrochlorothiazide, sulfathiazole, sulfampyridine, etc.) were selected to fit the isothermal adsorption equation. These target compounds all accord with Freundlich isotherm adsorption equation, R20.96. The effect of ionic strength, Ca 2 + mg 2 +, dissolved organic matter (DOM) on adsorption was investigated. The results showed that the adsorption of these substances was not affected by environmental factors. The elution recovery of the target pollutants was investigated. The results showed that the recovery rate of most substances was 70-110% and the relative deviation was less than 10%. Considering that cyclodextrin polymer swelling was not easy to protrude onto the surface of the sampler, the sampler was designed into an ellipsoid shape. Corrosion resistant, good mechanical properties, no adsorption to pollutants of stainless steel 304 material for subsequent processing. According to the formula of material swelling volume of 1. 3 cm3 and ellipsoid volume, the sampler's long half axis 0. 85 cm, short half axis 0. 85 cm and half height 0. 43 cm were obtained. Through die manufacturing, stamping, wrapping, locking welding finished products for actual water testing. Five antibiotics, sulfadiazine, sulfathiazole, sulfampyridine, lincomycin and sulfadioxacin, were selected. The results showed that the accuracy of sulfathiazole and sulfampyridine Cepred was 93-116. The accuracy of sulfadiazine, lincomycin, and sulfamethoxine is 54-62. Because it is a preliminary design sampler, it needs further optimization and improvement.
【学位授予单位】：大连理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X832

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