可用于工业污水处理的功能复合材料制备、表征及相关性能

发布时间：2018-06-21 12:36

本文选题：凹凸棒土 + 八羧基酞菁铁　；参考：《东华大学》2017年博士论文

【摘要】：近年来,随着环境保护意识、可持续发展概念的不断深入,水资源问题的关注度日益提高。愈来愈多的研究开始关注如何实现对污水进行环境友好型处理,实现对水资源的保护及循环利用。近年来随着研究的不断深入,越来越多的新方法层出不穷。但与此同时对于污水处理的要求也不断提高,因此仍需不断完善、改进污水处理方法。本文针对染料污水处理,利用超声共沉淀法将四氧化三铁负载到凹凸棒土表面,制备了一系列磁性凹凸棒土基功能复合材料。这种纳米复合材料具有优异的吸附性能并且可以利用磁分离技术解决凹凸棒土的回收再利用问题。在此基础上,本文引入具有光催化氧化性的金属酞菁衍生物,制备了磁性凹凸棒土/金属酞菁功能复合材料,探讨了该纳米复合材料对染料污水的光催化降解性能。基于满足对污水处理材料智能化的要求,本文研究了将多重响应智能水凝胶体系应用于染料污水处理,通过智能水凝胶的不同响应性实现了对处理过程的智能化控制。此外,本文还研究了表面分子印迹功能复合材料对重金属污水中特定组分的选择识别处理性能,主要研究内容如下:(1)利用超声共沉淀法,制备了磁性凹凸棒土(AT/Fe3O4)纳米复合材料,通过红外光谱、X射线粉末衍射、场发射扫描电镜、比表面积以及磁滞回线分析对其进行了一系列的表征。结果表明Fe3O4纳米粒子能均匀分散在AT表面,形成磁性纳米复合粒子,在赋予其顺磁性的同时依然保留着AT本身良好的吸附性能。染料吸附性能测试结果表明,AT/Fe3O4纳米复合粒子对染料具有优异的吸附去除效果,去除率在短时间内即可达到90%以上,其吸附过程符合二级动力学模型。随着pH值的增大,对于阳离子型染料的化学吸附作用显著提高。通过磁分离技术,实现了对AT/Fe3O4纳米粒子在水相中的分离回收。经四次循环再利用后,其对染料的去除率依然可达60%以上。通过模拟连续化动态吸附过程,进一步探讨了AT/Fe3O4纳米复合粒子在工业化连续处理染料污水应用中的可行性。(2)利用具有光催化氧化性的八羧基金属酞菁铁(FeOCAP)与磁性凹凸棒土相复合,制备了AT/Fe3O4-FeOCAP纳米复合粒子,通过红外光谱、紫外可见光谱、x射线光电子能谱以及光催化降解实验等对其进行了一系列的表征与测试。结果表明feocap结构成功地引入到了这种纳米复合粒子中。通过采用at/fe3o4作为载体材料,避免了feocap平面大环结构的聚集,从而提高了光催化活性。根据带隙能与费米能级计算结果可知,随着feocap含量的增加,这种纳米粒子的光催化降解活性不断增加。所制备的纳米复合材料对rhb染料分子具有优异的光催化降解作用,避免了传统吸附材料的最大饱和吸附量以及复杂的再生过程,符合langmuir-hinshelwood动力学模型。(3)利用具有温度、ph值以及磁场响应性的磁性凹凸棒土基聚乙二醇(pmoa-at/fe3o4)多重响应智能凝胶体系,实现了对染料污水处理的智能化要求,通过染料吸附测试对其性能进行了一系列的分析。结果表明pmoa-at/fe3o4多重响应智能凝胶对染料具有良好的去除效果,符合准二级吸附动力学模型以及langmuir等温吸附模型,因而吸附过程倾向于复杂非均质体系吸附。通过改变外界环境,使得智能凝胶结构产生不同的响应,对染料污水表现出了不同的去除效果,实现对染料处理过程的智能化控制。进一步利用凝胶的这种智能响应性,可以通过简单操作实现对该凝胶吸附材料重复再生处理,重复循环再生4次之后,对染料污水仍具有较好的处理效果。(4)利用具有优异光催化性能的at/fe3o4-feocap纳米粒子,进一步设计制备了具有光催化降解性的feocap/mat-pmoa多重响应智能凝胶,通过红外光谱等对其结构进行了表征。结果表明,该多重响应智能凝胶体系中存在有氢键作用力,因此避免了at/fe3o4-feocap纳米粒子在凝胶网络中的相分离,提高了光催化活性。光催化降解性能测试结果表明,feocap/mat-pmoa多重响应智能凝胶对染料污水的去除率接近100%,依然符合langmuir-hinshelwood动力学模型。重复循环测试结果表明,水凝胶网络结构的引入,显著增加了金属酞菁的稳定性,避免了其向溶液中的迁移,重复再生五次后,对染料的去除效率依然可以接近100%,且溶液呈无色状,没有任何金属酞菁扩散的痕迹。随着外界环境的改变,feocap/mat-pmoa复合凝胶依旧能产生多种智能响应性,表现出了不同的染料处理效果。(5)以磁性凹凸棒土为基体,cu2+为模板,利用表面分子印迹技术,制备了具有ph值智能响应性的cu(ii)分子印迹智能凝胶,应用于对重金属污水中特定离子的选择识别处理。红外光谱测试结果表明,通过1.0M HNO3溶液洗脱,可以成功地将印迹模板洗脱,留下印迹位点用于后续的选择识别过程。该分子印迹凝胶对模板Cu2+具有优异的选择识别性能,整个吸附过程符合Freundlich等温吸附模型。经5次重复再生循环测试后,依然对Cu2+具有优异的吸附性能,同时保留良好的选择识别性能。随pH值的变化,该印迹凝胶可以对Cu2+表现出不同的选择识别性。
[Abstract]:In recent years, with the awareness of environmental protection and the continuous development of the concept of sustainable development, the attention of water resources is increasing. More and more studies have begun to pay attention to how to realize environmental friendly treatment of sewage and realize the protection and recycling of water resources. In recent years, more and more new methods have been developed with the deepening of research. But at the same time, the demand for sewage treatment is increasing, so it is still necessary to improve and improve the method of sewage treatment. In this paper, a series of magnetic attapulgite based functional composite materials are prepared by using the method of ultrasonic coprecipitation to prepare a series of magnetic attapulgite based functional composite. The material has excellent adsorption properties and can use magnetic separation technology to solve the recycling and reuse of attapulgite. On this basis, this paper introduces a metallic phthalocyanine derivative with photocatalytic oxidation, and the magnetic Palygorskite / metal phthalocyanine composite material is prepared, and the photocatalytic reaction of the nano composite to dye wastewater is discussed. Based on the requirements for the intellectualization of the sewage treatment materials, this paper studies the application of the multi response intelligent hydrogel system to the treatment of dyestuff wastewater, and realizes the intelligent control of the treatment process through the different responsiveness of the intelligent hydrogel. In addition, this paper also studied the heavy gold of the surface molecularly imprinted functional composite. The main research contents are as follows: (1) magnetic attapulgite (AT/Fe3O4) nanocomposites were prepared by ultrasonic co precipitation method, and a series of characterizations were carried out by infrared spectroscopy, X ray powder diffraction, field emission scanning electron microscopy, surface product and hysteresis loop analysis. It is shown that the Fe3O4 nanoparticles can be dispersed evenly on the surface of AT to form magnetic nanocomposite particles, which still retain the good adsorption properties of AT itself while giving it paramagnetic. The results of the dye adsorption performance test show that the AT/Fe3O4 nanocomposite particles have excellent adsorption and removal effect on the dye, and the removal rate can reach 9 in a short time. More than 0%, the adsorption process conforms to the two stage kinetic model. With the increase of pH value, the chemical adsorption of cationic dyes is significantly improved. The separation and recovery of AT/Fe3O4 nanoparticles in the aqueous phase is realized by magnetic separation technology. After four cycles, the removal rate of dyes can still be over 60%. The feasibility of continuous dynamic adsorption of AT/Fe3O4 nanocomposite particles in the industrial continuous treatment of dyestuff wastewater was further discussed. (2) the composite of eight carboxyl metal phthalocyanine (FeOCAP) with photocatalytic oxidation and magnetic attapulgite was prepared. The AT/ Fe3O4-FeOCAP nanocomposite particles were prepared by infrared spectroscopy and ultraviolet. The visible spectra, the X ray photoelectron spectroscopy and the photocatalytic degradation experiment have been characterized and tested. The results show that the feocap structure has been successfully introduced into the nanocomposite particles. By using at/fe3o4 as the carrier material, the aggregation of the large ring structure in the feocap plane is avoided and the photocatalytic activity is improved. According to the results of band gap energy and Fermi energy level calculation, with the increase of feocap content, the photocatalytic degradation activity of the nanoparticles is increasing. The prepared nanocomposites have excellent photocatalytic degradation of the RHB dye molecules, avoiding the maximum saturated adsorption capacity of the traditional adsorbents and the complex regeneration process. Langmuir-Hinshelwood dynamic model. (3) using the multi response intelligent gel system with magnetic palygorskite (pmoa-at/fe3o4) with temperature, pH and magnetic field responsiveness, the intelligent requirement for the treatment of dyestuff wastewater is realized. The performance of the dye adsorption test is analyzed by a series of dye adsorption tests. The results show that pmoa-at/ The Fe3O4 multi response intelligent gel has a good removal effect on the dye, which conforms to the quasi two stage adsorption kinetic model and the Langmuir isothermal adsorption model. Therefore, the adsorption process is inclined to the adsorption of complex heterogeneous systems. By changing the environment, the intelligent gel structure has a different response, and the dye sewage is different. The intelligent control of the dye treatment process is realized by removing the effect. Further using this intelligent responsiveness of the gel, the gel adsorption material can be regenerated by a simple operation. After repeated recycling for 4 times, the dye sewage still has a good treatment effect. (4) using at/fe3o with excellent photocatalytic performance. 4-feocap nanoparticles were further designed and prepared for the photocatalytic degradation of feocap/mat-pmoa multiple response intelligent gel. The structure was characterized by infrared spectroscopy. The results showed that the hydrogen bond force existed in the multi response intelligent gel system, thus avoiding the at/fe3o4-feocap nanoparticles in the gel network. The photocatalytic activity was enhanced by phase separation. The results of photocatalytic degradation test showed that the removal rate of feocap/mat-pmoa multiple response intelligent gel was close to 100% and still conformed to the Langmuir-Hinshelwood kinetic model. The results of repeated cycle test showed that the structure of hydrogel network increased the stability of metal phthalocyanine significantly. After five times of repeated regeneration, the removal efficiency of the dye can still be close to 100%, and the solution is colorless, and there is no trace of any metal phthalocyanine diffusion. With the change of the environment, the feocap/mat-pmoa composite gel can still produce many kinds of intelligent responsiveness, showing different dye treatment effects. (5) using magnetic palygorskite as the matrix and cu2+ as a template, the Cu (II) molecularly imprinted intelligent gel with pH value intelligent responsiveness is prepared by surface molecularly imprinted technique. It is applied to the selection recognition of specific ions in heavy metal sewage. The infrared spectrum test results show that the imprinting can be successfully carried out through 1.0M HNO3 solution elution. Template elution and left imprinting loci are used for the subsequent selection recognition process. The molecularly imprinted gel has excellent selection recognition performance for template Cu2+, and the whole adsorption process conforms to the Freundlich isothermal adsorption model. After 5 repeated recycling tests, the molecular imprinting gel still has excellent adsorption properties for Cu2+, while preserving good selection recognition With the change of pH value, the imprinted gel can show different selective recognition to Cu2+.
【学位授予单位】：东华大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TB33;X703

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