RCEES OpenIR  > 中国科学院环境生物技术重点实验室
过滤-电芬顿催化膜原位去除难降解有机物及界面作用机制研究
Alternative TitleIn situ removal of refractory organics by electro-Fenton catalytic membrane and mechanism analysis of interface reaction
姜雯丽
Subtype博士
Thesis Advisor王爱杰
2020-12
Degree Grantor中国科学院生态环境研究中心
Place of Conferral北京
Degree Name工学博士
Degree Discipline环境工程
Keyword二级出水,低浓度污染物,电芬顿催化膜,非金属电芬顿,截留增浓-催化降解模型 Secondary Effluent, Low-concentration Of Pollutants, Electro-fenton Catalytic Membrane (Efcm), Metal-free Electro-fenton (Mf-ef), Concentration-degradation Model.
Abstract

    污水回用是缓解水资源短缺的一条重要途径,然而,污水经过二级处理后,其中残留的难降解有机物仍然具有潜在的环境和健康风险。 膜过滤 技术能够有效截留难降解有机物,是一项较有前景的污水深度处理技术。本研究针对 膜过滤浓液处置困难、膜污染等问题,将电芬顿的原理引入膜过滤体系,并借助石墨烯等碳材料的 导电、催化、稳定、成本低等方面的特性,提出石墨烯介导的 过滤电芬顿催化膜技术。利用电芬顿反应对难降解有机物的原位降解,去除 过 滤浓液中的污染物,并提高膜的抗污染性能。同时,利用微界面上浓差极化对难降解有机物的富集作用提高 电 芬顿反应速率。重点研究复合膜的制备方法及可控化组装,考察复合膜对典型难降解有机物的去除效果及抗污染性能,揭示 过 滤和电芬顿过程在复合膜微界面上的作用机制,为难降解有机物在复合膜体系中的高效去除提供理论依据和技术基础。
    提出制备石墨烯介导的过滤电芬顿催化膜( EFCM ),原位催化降解低浓度抗生素污染物。这种电芬顿催化膜具有以下优势:可截留低浓度小分子污染物,利于增大膜表面的污染物浓度,提高其被氧化降解的效率及速率;过 滤式膜催化电极的三维多层绕流构型,延长流体在膜电极表面的路径,增大污染物与电极的接触,促进对流与扩散传质,提高污染物降解速率;与非过滤式电芬顿过程相比,可促进传质效率,提高污染物降解过程的矿化电流效率和体系能耗;催化膜制备方法简单可控,可根据水处理过程需求制备不同性能的膜,易于放大加工制造。与前期报道的电化学滤器不同的是,本研究中电芬顿催化膜不仅作为连续流模式下电芬顿氧化降解污染物反应的阴极,同时可作为一道膜屏障截留增浓污染物。因此,被浓缩污染物的反应速率得到提高。膜截留增浓与电芬顿催化氧化过程的耦合,可有 效缓解污染物堆积引起的膜污染。同时,以抗生素氟苯尼考为目标污染物,研究了电芬顿催化膜在双氧水产生、抗生素降解和矿化等方面的性能。以单纯过滤、单纯电芬顿及电化学过滤过程作为对照实验,揭示 了 电芬顿催化反应与膜过滤过程的耦合协同作用。
    首次研究开发新型紫外光驱动的电芬顿催化膜(UV-EFCM)过滤系统,即光-电耦合催化过滤体系,以TiO2改性的石墨毡过滤器(TiO2/GF)作为光电阳极,以EFCM为阴极,耦合紫外光辐射、电芬顿催化与膜过滤过程处理低浓度抗生素污染物。该耦合体系可有效利用光阳极、降低铂电极成本、通过利用光生电子降低电芬顿反应的能量需求、有效降解低浓度抗生素、并通过光催化预处理加后续电芬顿氧化降解去除抗生素抗菌活性以控制抗生素抗性的发展和扩散。我们还综合评估了光电化学/电芬顿(PEC/EF)耦合过滤体系的性能,并将其与光电化学/电化学(PEC/EC)耦合过滤、光电化学(PEC)过滤、电芬顿过滤和单纯过滤等过程进行了比较。随后,对处理后出水的抗菌活性进行测定分析,并将其与氟苯尼考结构的变化相关联。
    研发了一种用于高效降解药物等微污染物的RGO-CCNT-Fe 电芬顿催化膜,通过调控RGO与CCNT的比例,制备出兼具高透水性、高截留率和高催化活性的复合催化膜,提供了一种有效减少药物污染物流入环境水体中的方法。考察了不同RGO/CCNT比例的系列催化膜的性能,并重点探讨了催化膜对不同荷电药物微污染物的去除效率与污染物物化性质参数间的相关性分析。
    碳基纳米材料RGO-CCTN-Fe介导的电芬顿催化膜可同时具备高透水性、高截留率、高催化性能,为解决其中铁催化剂流失的问题,开发了一种新型非金属电芬顿催化膜。通过调整RGO和掺氮碳纳米管(N-CNT)的比例,控制膜的孔径大小、表面荷电、催化剂比例及活性,在保留复合催化膜本身具备的高透水性和高截留率的前提下,同时实现N-CNT作为催化剂催化分解原位还原产生的H2O2,生成羟基自由基,从而避免了金属离子流失导致的催化膜性能损失及环境二次污染问题。并构建表面增浓-催化降解模型探究催化膜对污染物降解的界面作用机制。

Other Abstract

     Sewage reuse is an important way to alleviate the shortage of water resources. However, after the secondary treatment of sewage, the residual refractory organics in it still pose potential environmental and health risks. Membrane filtration technology can effectively intercept refractory organics and is a promising advanced wastewater treatment technology. Aiming at the problems of difficult disposal of membrane concentrate and membrane fouling, this research introduces the principle of electro-Fenton into the membrane system, and uses the characteristics of graphene to conduct electricity, catalysis, stability, and low cost, and propose graphene-mediated Nanofiltration-electric Fenton composite membrane technology. The electro-Fenton reaction is used to degrade the refractory organic matter in situ, remove the pollutants in the nanofiltration concentrate, and improve the anti-pollution performance of the membrane. At the same time, the enrichment of refractory organics by the concentration polarization on the microinterface is used to increase the Fenton reaction rate. It is planned to focus on the preparation method and controllable assembly of the composite membrane, investigate the removal effect and anti-pollution performance of the composite membrane on typical refractory organics, and reveal the mechanism of nanofiltration and electro-Fenton processes on the microinterface of the composite membrane. The efficient removal of organic matter in the composite membrane system provides a theoretical basis and technical basis.
     It is proposed to prepare graphene-mediated filtration electro-Fenton catalytic membrane (EFCM) to catalyze the degradation of low-concentration antibiotic pollutants in situ. This electro-Fenton catalytic membrane has the following advantages: it can retain low-concentration small-molecule pollutants, which is beneficial to increase the concentration of pollutants on the membrane surface, and improve the efficiency and rate of oxidation and degradation; the three-dimensional multi-layer winding of the filter membrane catalytic electrode The flow configuration extends the path of the fluid on the surface of the membrane electrode, increases the contact between the pollutants and the electrode, promotes convection and diffusion mass transfer, and increases the pollutant degradation rate; compared with the non-filtered electro-Fenton process, it can promote mass transfer Efficiency, improve the mineralization current efficiency of the pollutant degradation process and the system energy consumption; the preparation method of the catalytic membrane is simple and controllable, and membranes with different properties can be prepared according to the requirements of the water treatment process, which is easy to scale up and manufacture. Different from the electrochemical filter reported in the previous period, the electro-Fenton catalytic membrane in this study is not only used as the cathode for the electro-Fenton oxidation and degradation of pollutants in continuous flow mode, but also as a membrane barrier to retain concentrated pollutants. Therefore, the reaction rate of the concentrated contaminants is increased. The coupling of membrane retention enrichment and electro-Fenton catalytic oxidation process can effectively alleviate membrane pollution caused by pollutant accumulation. At the same time, with the antibiotic florfenicol as the target pollutant, the performance of the electro-Fenton catalytic membrane in hydrogen peroxide production, antibiotic degradation and mineralization was studied. Simple filtration, simple electric Fenton and electrochemical filtration process were used as control experiments to reveal the coupling and synergy of electro-Fenton catalytic reaction and membrane filtration process.
    The first research and development of a new type of ultraviolet light-driven electro-Fenton catalytic membrane (UV-EFCM) filter system, using TiO2 modified graphite felt filter (TiO2/GF) as the photoanode, EFCM as the cathode, coupling ultraviolet radiation, electricity Fenton's catalytic and membrane filtration process treats low concentrations of antibiotic contaminants. The coupling system can effectively use the photoanode, reduce the cost of platinum electrodes, reduce the energy requirement of the electro-Fenton reaction by using photogenerated electrons, effectively degrade low-concentration antibiotics, and remove the antibiotic antibacterial activity through photocatalytic pretreatment and subsequent electro-Fenton oxidation degradation To control the development and spread of antibiotic resistance. We also comprehensively evaluated the performance of the PEC/EF coupled filtration system and compared it with the photoelectrochemical/ electrochemical (PEC/EC) coupled filtration, PEC filtration, EF filtration and pure filtration processes. Subsequently, the antibacterial activity of the treated effluent was measured and analyzed, and it was correlated with the change in the structure of florfenicol.
     A RGO-CCNT-Fe electro-Fenton catalytic membrane for high-efficiency degradation of pharmaceutical micro-pollutants has been developed, which provides an effective method to reduce the influx of pharmaceutical pollutants into environmental water bodies. The performance of a series of catalytic membranes with different RGO/CCNT ratios was investigated, and the correlation between the removal efficiency of the catalytic membranes on micro-pollutants of different charged drugs and the correlation between the physical and chemical properties of the pollutants was discussed.
    The carbon-based nanomaterial RGO-CCTN-Fe-mediated electro Fenton catalytic membrane can simultaneously have high water permeability, high rejection rate, and high catalytic performance. In order to solve the problem of iron catalyst loss, a new type of non-metallic electro Fenton has been developed Dayton catalytic film. By adjusting the ratio of RGO and nitrogen-doped carbon nanotubes (N-CNT), the pore size, surface charge, catalyst ratio and activity of the membrane can be controlled, while retaining the high water permeability and high rejection rate of the composite catalytic membrane itself. At the same time, N-CNT can be used as a catalyst to catalyze the decomposition of H2O2 produced by in-situ reduction, avoiding the loss of catalytic membrane performance and secondary environmental pollution caused by metal ion loss.

Pages198
Document Type学位论文
Identifierhttp://ir.rcees.ac.cn/handle/311016/43587
Collection中国科学院环境生物技术重点实验室
Recommended Citation
GB/T 7714
姜雯丽. 过滤-电芬顿催化膜原位去除难降解有机物及界面作用机制研究[D]. 北京. 中国科学院生态环境研究中心,2020.
Files in This Item:
File Name/Size DocType Version Access License
姜雯丽_过滤-电芬顿催化膜原位去除难降解(9397KB)学位论文 开放获取CC BY-NC-SAApplication Full Text
Related Services
Recommend this item
Bookmark
Usage statistics
Export to Endnote
Google Scholar
Similar articles in Google Scholar
[姜雯丽]'s Articles
Baidu academic
Similar articles in Baidu academic
[姜雯丽]'s Articles
Bing Scholar
Similar articles in Bing Scholar
[姜雯丽]'s Articles
Terms of Use
No data!
Social Bookmark/Share
All comments (0)
No comment.
 

Items in the repository are protected by copyright, with all rights reserved, unless otherwise indicated.