【作者】 唐星华；

【导师】 郭灿城；

【作者基本信息】 湖南大学 ， 应用化学， 2008， 博士

【摘要】 本论文对壳聚糖（CTS）交联或接枝化学改性进行比较系统的研究,包括用三乙烯四胺对壳聚糖进行交联、在壳聚糖分子中接枝上具有螯合作用的官能团、对壳聚糖进行接枝共聚等,研究了壳聚糖化学改性产物的吸附性能或阻垢性能。以丙烯酰胺（AM）、甲基丙烯酰氧乙基三甲基氯化铵（DMC）为改性剂对壳聚糖进行阳离子改性,制得一种新型壳聚糖衍生物吸附剂（CAD）。用FTIR、SEM及XRD对产物结构进行了表征,通过正交实验优化了合成CAD的最佳反应条件。吸附研究表明:CAD对Cu²⁺、Zn²⁺、Cd²⁺的吸附符合Langmuir方程;在Cu²⁺-Zn²⁺-Cd²⁺三元体系中,能选择性吸附Cu²⁺和Zn²⁺,在分离、萃取、富集、回收和纯化Cu²⁺和Zn²⁺方面具有潜在的应用前景。CAD处理模拟印染废水的试验结果表明:在弱酸性条件下CAD对直接耐兰GL染料有较好的吸附去除率,且去除率随CAD质量浓度的增加而增大。合成了一种对重金属离子具有高吸附容量,并且易于回收利用的三乙烯四胺交联壳聚糖吸附剂CCTS,用FTIR、SEM、XRD及元素分析等对CCTS及其中间产物进行了表征。通过用吸附模型分析其对各重金属离子吸附的动力学,发现CCTS对Pb²⁺、Cu²⁺、Cd²⁺、Ni²⁺吸附与准二级吸附公式更为吻合。通过与Langmuir理论公式及Freundlich经验公式分析,发现与Langmuir理论公式更为吻合。CCTS对各重金属离子的吸附热力学分析结果表明:CCTS对各重金属离子吸附熵变△adsS为正值,并且吸附自由能改变量△adsG均为负值,说明CCTS对各重金属离子的吸附是自发进行的,但其吸附焓变△adsH为正值,说明CCTS对重金属离子的吸附不仅仅是化学吸附的过程,还伴随着其他如物理吸附、吸附剂溶胀等吸热过程。在由Cu²⁺,Cd²⁺、Ni²⁺俩俩组成的双组份及其三组份重金属离子溶液中,研究表明:CCTS对Cu²⁺,Cd²⁺,Ni²⁺不具备选择吸附性能。通过对CCTS对各重金属离子的再生性能研究表明:CCTS具有较好的再生性能。杯[6]芳烃改性壳聚糖的制备与吸附性能研究。与杯[4]芳烃相比,杯[6]芳烃空穴有更大的调节空间,选择性地吸附某些体积较大的金属离子能力应该更强。通过单取代对叔丁基杯[6]芳烃溴丙氧基衍生物与预处理的壳聚糖发生交联,合成了杯[6]芳烃-壳聚糖聚合物,研究了其对Mn²⁺ , Pb²⁺ , Cr³⁺和Cu²⁺等离子的吸附性能。研究了改性壳聚糖的阻垢性能。通过静态阻垢法对阻垢率的测定,评定阻垢剂的阻垢性能。研究改性壳聚糖的阻垢性能,如马来酸酐、丙烯酸、丙烯酰胺等改性壳聚糖的阻垢性能,探讨其阻垢率与阻垢剂用量、Ca²⁺浓度、溶液pH值之间的关系,从而筛选出性能优异的阻垢剂。更多还原

【Abstract】 In this paper,we made a systematic research on the chitosan grafting or cross-linking modification , including cross-linking of chitosan with trimethyl ammonium,introducing chelate agent into chitosan,grafting copolymer on chitosan etc. The adsorption properties and the scale inhibitive performance of the chemical modified chitosan were also investigated.A kind of new modified chitosan absorbent was synthesized with chitosan （CTS）, acrylamide（AM） and methacryloyloxyethyl trimethyl ammonium chloride（DMC） as raw materials.The structure of product was confirmed by FTIR, SEM and XRD.The reaction condition was optimized through the orthogonal experiment. The adsorption behavior to Cu²⁺,Zn²⁺,Cd²⁺ was confirmed to obey the Langmuir equation.Because of its good selective adsorption ability of Cu²⁺ and Zn²⁺ in the Cu²⁺-Zn²⁺-Cd²⁺ ternary system,the absorbent has latent application prospect in the aspects of separation, extraction, enrichment and recovery of Cu²⁺ and Zn²⁺.The results of the simulated treatment of printing waste water indicated that CAD had a strong adsorption ability to Direct Fast Blue GL under weak acid conditions, and the removing rate increased with increasing the CAD mass concentration.A novel crosslinked chitosan absorbent CCTS was synthesized,which is more efficient than chitosan and could be reused.The structure of CCTS and intermediate products were characterized by IR, XRD, SEM and element analysis.Adsorption kinetics have been tested and fitted to adsorption model. The adsorption behavior of CCTS to Pb²⁺,Cu²⁺,Cd²⁺,Ni²⁺ was well fitted to the pseudo-second-order equation. The data were analyzed by the Langmuir and Freundlich model, showing that best fit was obtained with the Langmuir equation.The thermodynamic investigation of adsorptions shows that adsorption of CCTS to Pb²⁺,Cu²⁺,Cd²⁺,Ni²⁺ is spontaneous.Because the values of Gibbs free energy （△adsG） are negative and the calculated entropy values （△adsS） of interactions are positive.However the positive values of the variation in enthalpy （△adsH） show that besides chemisorption, other processes of decalescence, such as physical adsorption and swelling of CCTS were also involved.The adsorption ability of CCTS to metal ions in binary or ternary solutions composed of Cu²⁺, Ni²⁺, and Cd²⁺ was researched. The results show that no selective adsorption ability of CCTS to Cu²⁺,Ni²⁺ and Cd²⁺.The recycling investigation shows that CCTS can be used to remove metal ions repeatedly.Synthesis and adsorption properties of calix[6]arene derivatives modified chitosan. Comparing with calix[4]arene, calix[6]arene has the bigger adjustment space, thus stronger selective adsorption ability to big metallic ion was shown. The calix[6]arene-chitosan polymer was synthesized by the reaction of mono-substituted calix[6]arene derivative with pretreated chitosan. The absorption properties of polymer towards Mn²⁺ ,Pb²⁺ ,Cr³⁺ and Cu²⁺ were studied.The scale inhibitive performance of modified chitosan was studied. Scale inhibitive performance was evaluated by determining scale inhibitive rate using static anti-scaling method.Through the test of scale inhibitive performance of maleic anhydride, acrylic acid or acrylamide modified chitosan, the effect of the scale inhibitor amount, Ca²⁺ concentration, and pH value to scaling inhibition rate was investigated. Therefore, the superior scale inhibitor can be obtained.更多还原