铁、锰、钴基复合材料的制备及其对水体污染物去除研究

发布时间：2018-01-15 18:27

  本文关键词：铁、锰、钴基复合材料的制备及其对水体污染物去除研究　出处：《中国科学技术大学》2017年博士论文　论文类型：学位论文

  更多相关文章： 铁掺杂二氧化锰 磷酸盐 砷 β-FeOOH纳米棒/泡沫炭 Fe_3O_4-氧化石墨烯/泡沫炭 钴基金属有机框架/泡沫炭

【摘要】：近年来,经济的快速发展导致污水排放量增加,给水体环境造成了严重的污染。其中,富营养化以及砷污染问题尤为突出。吸附是目前解决富营养化以及砷污染问题最有效的方法之一,因此开发新型、高效的吸附剂成为消除水污染的关键所在。然而现行的污染物吸附剂如生物吸附剂、活性炭、矿物材料等,存在吸附容量小、吸附选择性差、制备成本高、吸附后难以回收以及可能会引起二次污染等缺点,不能很好地解决日益严重的水体污染问题。基于以上分析,我们需要开发吸附量大、易于分离回收的吸附材料,充分暴露材料的吸附位点,旨在提高水体污染的处理能力。石油污染事故频发,给海洋生态环境带来了严重的后果。而常用的处理技术不能有效地消除石油泄漏带来的环境危害。因此,需要开发高性能的油水分离材料及技术,提高油水分离效率,降低油水分离成本,以期在实际石油污染水体处理中能够发挥效用。结合环境中砷污染以及富营养化特点,制备了铁掺杂二氧化锰微纳结构材料、β-FeOOH纳米棒/泡沫炭多孔分级结构材料以及Fe3O4-氧化石墨烯/泡沫炭复合材料用于去除水体污染物质,分别探究其对磷、砷的吸附性能及机理。同时由于全球石油资源日益枯竭,石油泄漏问题严重,给人类及生态环境带来严重的危害,开发了钴基金属有机框架/泡沫炭复合材料,将其碳化处理后用于油水分离,并与流动泵结合搭建了微小型油水分离装置,提高了油水分离的效率。本文的主要内容包括:(1)含磷废水的过度排放引起水体的富营养化问题被社会广泛关注。为了消除负面影响,开发三维微纳分级结构材料来处理水体富营养化污染是一种非常有效的方式。通过简单的一步无模板法制备三维花状的铁掺杂二氧化锰微纳米球处理磷酸盐污染水体。用扫描电镜和透射电镜表征样品,这种微纳米球由大量交织在一起的纳米片组装成,纳米片的厚度可以通过调节Fe/Mn摩尔比而控制在2～30 nm之间,并且随着纳米片厚度的减小,其对磷酸盐的去除效果显著提高。与未掺杂铁样品相比,铁掺杂二氧化锰微纳米球对磷酸盐吸附性能明显增强,同时随着铁掺杂量的增加,其去除效率也显著提高。当铁掺杂量为15%时,这种微纳米球可以完全将低浓度(少于10ppm)的磷酸盐从水体中去除。另外,制备的微纳米球对磷酸盐表现出较好的选择性,这可以归因于其独特的三维分级结构,以及磷与铁、锰之间较强的成键作用。更为重要的是,样品在五次循环再生后,其对磷酸盐的吸附量无明显降低。上述研究结果表明,所制备的铁掺杂二氧化锰微纳米球是一种理想的磷酸盐吸附剂。(2)其次,铁掺杂二氧化锰微纳米球对水体中As(Ⅲ)有很好的去除性能,其饱和吸附量为102.84 mg/g。这种微纳分级结构材料对As(Ⅲ)优良的吸附性能可归因于材料独特的结构特点以及其充分暴露的活性位点。另外,铁掺杂二氧化锰微纳米球对As(Ⅲ)氧化与吸附的协同进行是展现其良好吸附能力的另一关键原因,即二氧化锰首先将As(Ⅲ)氧化为As(V),而铁组分与氧化后的As(V)产生较强的键合作用,这可以通过X射线光电子能谱分析(XPS)进行证实。尤为重要的是材料在经过三次再生循环后对As(Ⅲ)的去除效率无显著的降低,并且因材料的颗粒尺寸相对较大,可以通过简单的过滤分离,降低了对环境的二次污染风险。因此,这种铁掺杂二氧化锰微纳米球是理想的As(Ⅲ)吸附剂。(3)水体砷污染问题已经引起了人们的广泛关注,给整个生态系统和人类健康带来严重的危害,因此迫切需要设计开发高性能的砷污染吸附剂。本文发展了一种简单、低成本的方法在三维泡沫炭材料表面生长β-FeOOH纳米棒来处理水体中砷污染。通过先碳化海绵随后水热反应制备这种多孔块体材料,并将其应用于水体中砷的去除,对As(Ⅲ)和As(Ⅴ)的饱和吸附量分别为103.4mg/g、172.9 mg/g。这种三维吸附剂材料对砷污染展现出优异的去除性能,可归因于其三维网状结构便于传质过程的进行,以及充分暴露的吸附位点,另外材料表面存在丰富羟基基团是提高水体中砷去除效率重要因素。样品对砷具有较好的选择性吸附,主要是由于材料的活性位与砷的亲和力更强,这种三维网状块体材料不仅有利于材料的分离回收,还有利于防止纳米颗粒对水体环境造成二次污染。另外,材料经过五次再生循环后无显著的吸附性能降低,表明这种材料具备优良的循环利用性。综上所述,这种三维块体吸附材料是一种理想的砷污染物去除吸附剂,有较好的实际应用前景。(4)具备丰富活性位点又便于磁性分离的三维块体复合材料在去除水体污染物中具有重要的意义。通过简单的一步法将氧化石墨烯包覆在四氧化三铁颗粒的表面,并锚定在三维大孔的泡沫炭框架上,用于水体中As(Ⅲ)的快速去除。这种三维复合材料对As(Ⅲ)的饱和吸附量为111 mg/g,其良好的吸附能力可归因于三维网状分级结构以及吸附活性位点的充分暴露。另外,材料的再生循环性能良好,利用材料的磁性和三维块体特点容易将材料进行分离回收,因此是一种理想的吸附材料。(5)频繁的石油泄漏逐渐成为一种严重的全球性环境污染问题,不仅会加剧全球能源危机,还会打破海洋生态系统平衡,这迫切需要开发良好的油水分离技术解决石油污染问题。本文利用气相水热法在泡沫炭表面合成了钴基金属有机框架,碳化后将其用于油水分离。这种复合材料展现出优异的油水分离性能,归因于复合材料较大的水接触角(156°)以及独特的三维网状结构,有利于液体在大孔通道传输。在此基础上,我们发展了基于Co@C/泡沫炭复合材料和流动泵结合的油水分离装置,可以原位高效收集油水混合物中的石油,不仅节省了材料而且还能提高分离效率。
[Abstract]:In recent years, the rapid development of economy led to the increased volume of sewage discharge, causing serious pollution to the water environment. The eutrophication and arsenic pollution problem is particularly prominent. The adsorption is one way to resolve the eutrophication and arsenic pollution in the most effective, so the development of new type high efficient adsorbent has become the key to eliminate water pollution. However, the existing pollutant adsorbent such as biological adsorbent, activated carbon, mineral materials, adsorption capacity, adsorption selectivity, high preparation cost, and is difficult to recover after adsorption may cause two pollution and other shortcomings, can not solve the water pollution problem is increasingly serious. Based on the above we need a large amount of analysis, the development of adsorption, adsorption materials, easy separation and recovery, fully exposed the adsorption sites of materials, in order to improve the processing capacity of the water pollution. Frequent oil pollution accidents, to the sea Ocean ecological environment has brought serious consequences. The processing technology can not be used to effectively eliminate oil spill pollution. Therefore, oil-water separation materials need to develop high performance and technology, improve the separating efficiency, reduce the cost of oil-water separation in order to be able to play, in the actual utility of oil pollution water treatment combined with environment. In the arsenic pollution and the eutrophication characteristics, preparation of iron doped manganese dioxide micro nano structure materials, beta -FeOOH Nanorods / carbon foam porous materials and the hierarchical structure of Fe3O4- graphene oxide / carbon foam composite material used for removing water pollutants, respectively, to explore their phosphorus adsorption properties and mechanisms of arsenic. At the same time as a result of global oil the increasing depletion of resources, the oil spill problem is serious, serious harm to human and ecological environment, the development of the cobalt based metal organic frameworks / carbon foam composite material, its carbon Used for oil-water separation processing, combined with the established micro oil-water separator and pump flow, improve the efficiency of oil-water separation. The main contents of this paper include: (1) the problem of eutrophication caused by excessive emissions of wastewater containing phosphorus water is widespread concern. In order to eliminate the negative effects, the development of three-dimensional micro nano hierarchical structure the material is a very effective way to deal with the water eutrophication pollution. Through the iron doped manganese dioxide simple one-step template free method for preparing three-dimensional flower like microspheres treatment of phosphate contaminated water. Using scanning electron microscopy and transmission electron microscopy characterization of samples, the micro nano spheres by nano film heavily intertwined assembled, the thickness of the nanosheets can be controlled in 2~30 nm by adjusting the molar ratio of Fe/Mn, and with the decrease of thickness of the nanosheets, and the removal efficiency of phosphate increased significantly. And not mixed Miscellaneous iron samples compared to iron doped manganese dioxide spheres on phosphate adsorption properties increase obviously, while with the increase of iron content, the removal efficiency is also improved significantly. When the iron content is 15%, the micro nano spheres could be the low concentration (less than 10ppm) the removal of phosphate from water. In addition, micro nano spheres on the preparation of phosphate showed good selectivity, which can be attributed to its unique three-dimensional hierarchical structure, and the phosphorus and iron, manganese between the strong bonding effect. More importantly, the sample in five cycles after regeneration, the adsorption of phosphate was not decreased. The above research the results show that the iron doped manganese dioxide prepared by micro nano spheres is an ideal phosphate adsorbent (2). Secondly, the iron doped MnO2 microspheres in water As (III) has good removal performance, the adsorption capacity is 102.84 mg/g. This micro nano hierarchical structures of As (III) excellent adsorption performance can be attributed to the unique structure characteristics of the material and its active site is fully exposed. In addition, the iron doped manganese dioxide micro nano spheres of As (III) and adsorption of CO oxidation is another key reason to show its good adsorption capacity, i.e. the As of manganese dioxide (III) oxide As (V), and the iron component and the oxidized As (V) have strong bonding effect, this can be done by X ray photoelectron spectroscopy (XPS) were confirmed. It is particularly important material after three regeneration cycles of As (III) removal efficiency significantly reduced, and due to the particle size is relatively large, can be separated by filtration is simple, reducing the risk of two pollution to the environment. Therefore, the iron doped MnO2 microspheres is ideal for As (III) adsorbent. (3) water arsenic pollution. The title has already aroused extensive attention, bring serious harm to the ecosystem and human health, so there is an urgent need for the design and development of high performance arsenic adsorbent. The paper presents the development of a simple, low cost method in the growth of beta -FeOOH nanorods to deal with arsenic pollution in the surface of carbon foam material. The first then the hydrothermal reaction carbonation sponge for preparation of the porous materials, and its application in the removal of arsenic in water body, the As (III) and As (V) of the saturated adsorption capacity of 103.4mg/g respectively, 172.9 mg/g. adsorbent material for the three-dimensional arsenic pollution show excellent removal performance, attributable to in the three-dimensional network structure is convenient for the mass transfer process, and fully exposed the adsorption sites, in addition there are abundant surface hydroxyl groups is to improve the efficiency of arsenic removal in water samples. An important factor has a good selection of arsenic Selective adsorption is mainly due to the activity of a material with arsenic affinity is stronger, the 3D mesh block material is not only conducive to the separation and recycling of materials, but also help prevent nanoparticles cause two pollution on the water environment. In addition, the material after five regeneration cycles after no adsorption decreased significantly, suggesting that this material has recycling of excellent. In summary, the 3D block adsorption material is an ideal adsorbent for arsenic removal of pollutants, which has good prospects of application. (4) have abundant active sites and easy magnetic separation of three-dimensional bulk composite materials play an important role in the removal of water pollutants by simple one step. The graphene oxide coated on the surface of Fe3O4 particles, carbon foam frame and anchor in three big hole, used for water As (III) the rapid removal of the 3D complex. The material of As (III) the saturated adsorption capacity is 111 mg/g, fully exposed its good adsorption ability can be attributed to the three-dimensional network structure and classification of adsorption sites. In addition, the regeneration cycle performance of materials, magnetic materials and the use of 3D block features easy to recover material, so it is the ideal adsorption material. (5) the frequent oil spill has gradually become a global serious problem of environmental pollution, not only exacerbate the global energy crisis, will break the balance of the marine ecosystem, it is urgent to develop oil water separation technology a good solution to oil pollution problems. This paper uses the vapor phase hydrothermal synthesis of cobalt metal organic frameworks in carbon foam surface, after the carbonation for oil-water separation. This composite material exhibits excellent water separation properties, due to the large composite water contact angle (156 degrees) and The three-dimensional network structure unique, is conducive to the liquid transmission in large pore channels. On this basis, we developed the oil-water separation device of Co@C/ carbon foam composite material and flow pump based on in situ can efficiently collect the oil-water mixture in the oil, not only saves materials but also improve the separation efficiency.

【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：X52;TB33

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