微生物燃料电池处理有机废水过程中的产电特性研究
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摘要
随着全世界范围内的能源紧缺和环境污染问题的加剧,研发新的环境友好处理工艺从有机废水中回收有价能源已经成为环境工程领域一个重要的方向,是实现废水处理能源化与可持续性发展的重要途径之一。微生物燃料电池(Microbial fuel cell,MFC)能够利用微生物作为催化剂将有机化合物氧化分解,同时产生电流,将有机物中的化学能直接转化为电能,是一种全新的废水处理技术。目前,MFC在全世界范围内的研究尚处于起步阶段,大量的工作集中在技术的可行性和基础研究的水平上,而限制该技术应用于商业化和工程应用的主要问题是产电功率密度低,材料造价昂贵,MFC型式的不确定。
针对MFC研究目前存在的问题,本文以典型的双室MFC和单室MFC为研究对象,系统研究了MFC的基本特性、阳极底物溶液性质的影响、阴极强化、空气阴极MFC结构的改进及相关机制。论文取得了一些创新性的研究成果。
使用厌氧污泥能够成功启动双室MFC和单室MFC,在间歇运行方式下,使用乙酸钠作为单一的有机底物能够获得稳定的电压输出和COD去除。最大功率密度的顺序为:K3[Fe(CN)6]阴极MFC>空气阴极MFC>曝气阴极MFC。K3[Fe(CN)6]阴极MFC、曝气阴极MFC和空气阴极MFC的库仑效率CE与COD去除率分别为49 %、28.2 %、33.8 %和60 %、45.3 %、80 %。控制双室MFC性能的关键因素是阳极特性,而控制单室MFC性能的关键因素是空气阴极的催化反应动力学和氧传质特性。导致K3[Fe(CN)6]阴极MFC和空气阴极MFC库仑损失的主要原因分别是厌氧菌与产电菌争夺有机底物和氧气的阴极扩散。这些结果表明,MFC能够实现产电和同步有机废水处理;此外,在对MFC反应器进行设计和运行优化时要充分考虑到不同形式MFC功率密度和库伦效率的主要限制因素不同。
单糖、多糖以及一些常见的小分子有机挥发酸盐和醇类物质均可作为MFC产电的有机底物,功率密度随有机底物浓度的变化具有“饱和效应”,可以用经典的Monod方程式进行描述和非线性回归分析。底物浓度较高时,搅拌的影响不明显;底物浓度较低时,搅拌的影响十分显著。在双室MFC中,阳极电解液具有良好的缓冲能力能够维持pH处在一个稳定的水平,是保证MFC稳定运行的重要条件。适当地提高离子强度能够降低MFC的内阻,提高电流密度和功率密度。无论对于双室MFC还是单室MFC,高浓度的NH3-N对MFC产电都没有影响。单室MFC中的NH3-N转化与好氧氨氧化有关,与产电无关。双室MFC中阳极的一部分NH3-N在产电过程中以NH4+的形式扩散进入阴极,以维持电荷平衡。这些结果都表明,在对MFC进行基础研究和运行优化时,要充分考虑到有机物、水力条件及电解液缓冲能力对系统的影响和限制作用。
通过对比研究发现,在双室MFC中,酸性KMnO4阴极MFC的开路电位能够达到1.48 V,最大功率密度远高于K3[Fe(CN)6]和氧气。在使用酸性KMnO4阴极时,阴极的电极电位主要受控于KMnO4浓度和pH,但对pH更加敏感。在[KMnO4]=20 mg·L-1和pH=3.5的条件下,环式MFC的最大功率密度能够达到3986.72 mW·m-2。SEM和XPS分析表明,KMnO4的主要还原产物是沉积在电极表面的固相MnO2,这是KMnO4阴极MFC具有高电位的主要原因。对于单室空气阴极MFC来说,阴极的性能是影响功率输出的重要因素。缩短电极距离、增大阴极的面积都能够降低电池内阻。空气阴极的Pt负载量对功率输出的影响与Nafion溶液的使用密切相关。这些结果都充分表明,提高阴极的电化学氧化性能是强化MFC功率输出的重要途径。
开发了更适于废水处理的升流式空气阴极MFC(UAMFC)。随着有机负荷率的增加,功率密度先升高再降低;COD去除率、CE、EE和pH均呈现出下降的趋势。电化学阻抗谱(EIS)分析表明,电荷转移内阻Rc、欧姆内阻Rohm和扩散内阻Rd分别占总内阻的22.6 %、50.2 %和26.3 %,欧姆内阻占主导作用,主要由UAMFC的结构形式决定。高有机负荷下,回流比影响不显著;低有机负荷下,提高回流比能显著提高功率密度。氮的去除与产电过程无关,主要受到有机负荷的影响。通过对UAMFC的长期行为进行观察,发现功率以0.051 W·m-3·d-1的速率降低,欧姆内阻Rohm和扩散内阻Rd有升高的趋势。通过对空气阴极MFC的设计进行改进,能够实现连续产电及有机物和氮元素的去除。该种设计模式的显著优点是尽最大限度减少了电极距离,降低内阻,提高功率输出,进而为优化空气阴极MFC的设计与运行提供了切实可行的依据。
World-wide depletion of energy reservers and environmental contamination are inspiring the search for renewable and environment-friendly technologies to recover useful energy and materials from organic wastes. This has been particularly emphasised as a significant approach so as to make the wastewater treatment more sustainable and economical in the field of environmental engineering. Microbial fuel cell (MFC) has been addressed able to generate electrical currents via oxidizing orgianic compounds by using microorganisms as the bio-catalysts. Electricity generation during organic degradation represents a process of directly converting chemical energy within organic matters to electrical energy, which gives rise to a potential for MFC to produce electricity from organic wastewater along with wastewater treatment. Currently, MFC is still in its infant and majority of works have been emerged only focusing on its technical feasibility and fundamental characteristics. It has been taken into account that three bottlenecks in terms of low power density, high costs of materials and indetermination of available MFC configuration should be the main limiting elements for MFC technology to apply commercially.
This study systematically investigated the feature and corresponding mechanisms of two-chambered MFC and single-chambered MFC, including the basic characteristics of power generation, the effects of anodic substrate, cathode enhancement as well as improvements of air-cathode MFC design mode. Some innovative findings have been made as follows.
The results demonstrated that both the two-chambered and single-chambered MFC after being started up by using anaerobic activated sludge as inoculated source could stably generate power with simultaneous COD removal when acetate was offered as the single carbon source. The maximum power density produced followed the order of K3[Fe(CN)6]-cathode MFC>air-cathode MFC>aeration-cathode MFC. CE and COD in such three MFCs was 49 %, 28.2 %, 33.8 % and 60 %, 45.3 %, 80 %, respectively. Besides, the performance of the two-chambered MFC was limited by the anode while the performance of the single-chambered MFC was mainly limited by the cathode, which was determined by the inherent nature of the MFC configuration. The main reason for Coulombic loss occurring in the two-chambered MFC and single-chambered MFC should be anaerobic loss and aerobic loss, respectively.
Additionally, MFC was demonstrated capable of using a wide variety of organic compounds for power generation, including single-sugar, multi-sugar as well as several types of small molecular organic fatty acid and ethanol. The dependence of power density on initial COD concentration exhibited“saturation effect”, which could be described and explained with traditional Monod equation. The mixing was observed to have different impact on the MFC performance, depending upon the COD concentrtion, which was most likely due to the difference in diffusion of substrate into the biofilm. In the two-chambered MFC, buffering capacity of the anodic electrolyte played an important role in maintaining pH within a stable level. Increasing ion strength could result in a decrease of internal resistance as well as an increase of power density. High concentration of NH3-N was observed to have no obvious adverse influence on MFC performance. The oxidation of partial NH3-N in single-chambered MFC was achieved with oxygen as electron acceptor and independent on current output. In the two-chamber MFC, NH3-N could be transferred with the form of NH4+ cation into the cathode through PEM in order to balance the charge.
Using acidic permanganate as the cathodic electron acceptor could increase the open circuit potential (OCP) of the two-chambered MFC up to 1.48 V with a higher corresponding maximum power density than that using ferricyanide and oxygen. Unlike permanganate concentration, the cathode potential was shown more sensitive to pH value. At permanganate concentration of 20 mg·L-1 and pH=3.5, the maximum power density produced in bushing MFC could reach a level as high as 3986.72 mW·m-2. Both SEM and XPS analysis confirmed the mechanisms that the main reduced product of permanganate was solid-state MnO2 deposited on the electrode surface. Its redox potential as great as +1.70 V could explain the most probable reason for high OCP in the permanganate-cathode MFC, which was well consistent with the experimental results shown above. For single-chambered MFC, power density could be apparently increased by means of either reducing the electrode spacing or increasing the cathode area because of the corresponding decrease of internal resistance of the cell. The Pt loading and Nafion content were revealed to have a co-effect on power output, i. e., power density was substantially increased with the increase of Pt loading in the absence of Nafion binder solution, while such effect was absent in the presence of Nafion solution.
An up-flow air-cathode MFC (UAMFC) was designed for more available applications for wastewater treatment. As the organic loading rate (OLR) increased, COD removing efficiency, CE, EE and pH tended to decline and power density revealed a setpoint, which might be attributed to the limitation of treating capacity and acid accumulation. As indicated by electrochemical impedance spectroscopy (EIS) analysis, charge transfer resistance (Rc), ohmic resistance (Rohm) and diffusion resistance (Rd) accounted for 22.6 %,50.2 % and 26.3 % of total internal resistance Large fraction of ohmic resistance mainly originated from the inherent limitation of the system in relation to the reactor design structure and electrolyte characteristics. Recirculation was found to have a substantial impact on electrochemical performance (power, Rohm and Rd) at low OLR, while such effect was absent at high OLR. Removal of nitrogen compounds in the UAMFC was obtained along with power generation. It was also shown here that the long-term operation might lead to the performance degradation of the UAMFC, as indicated by a decrease of power density at a rate of 0.051 W·m-3·d-1 and an increase of Rohm and Rd. Such design is more advantageous by its virtue of low internal resistance and high power density, which provides a proof-in-concept and new approach to optimize the air-cathode MFC design and operation.
针对MFC研究目前存在的问题,本文以典型的双室MFC和单室MFC为研究对象,系统研究了MFC的基本特性、阳极底物溶液性质的影响、阴极强化、空气阴极MFC结构的改进及相关机制。论文取得了一些创新性的研究成果。
使用厌氧污泥能够成功启动双室MFC和单室MFC,在间歇运行方式下,使用乙酸钠作为单一的有机底物能够获得稳定的电压输出和COD去除。最大功率密度的顺序为:K3[Fe(CN)6]阴极MFC>空气阴极MFC>曝气阴极MFC。K3[Fe(CN)6]阴极MFC、曝气阴极MFC和空气阴极MFC的库仑效率CE与COD去除率分别为49 %、28.2 %、33.8 %和60 %、45.3 %、80 %。控制双室MFC性能的关键因素是阳极特性,而控制单室MFC性能的关键因素是空气阴极的催化反应动力学和氧传质特性。导致K3[Fe(CN)6]阴极MFC和空气阴极MFC库仑损失的主要原因分别是厌氧菌与产电菌争夺有机底物和氧气的阴极扩散。这些结果表明,MFC能够实现产电和同步有机废水处理;此外,在对MFC反应器进行设计和运行优化时要充分考虑到不同形式MFC功率密度和库伦效率的主要限制因素不同。
单糖、多糖以及一些常见的小分子有机挥发酸盐和醇类物质均可作为MFC产电的有机底物,功率密度随有机底物浓度的变化具有“饱和效应”,可以用经典的Monod方程式进行描述和非线性回归分析。底物浓度较高时,搅拌的影响不明显;底物浓度较低时,搅拌的影响十分显著。在双室MFC中,阳极电解液具有良好的缓冲能力能够维持pH处在一个稳定的水平,是保证MFC稳定运行的重要条件。适当地提高离子强度能够降低MFC的内阻,提高电流密度和功率密度。无论对于双室MFC还是单室MFC,高浓度的NH3-N对MFC产电都没有影响。单室MFC中的NH3-N转化与好氧氨氧化有关,与产电无关。双室MFC中阳极的一部分NH3-N在产电过程中以NH4+的形式扩散进入阴极,以维持电荷平衡。这些结果都表明,在对MFC进行基础研究和运行优化时,要充分考虑到有机物、水力条件及电解液缓冲能力对系统的影响和限制作用。
通过对比研究发现,在双室MFC中,酸性KMnO4阴极MFC的开路电位能够达到1.48 V,最大功率密度远高于K3[Fe(CN)6]和氧气。在使用酸性KMnO4阴极时,阴极的电极电位主要受控于KMnO4浓度和pH,但对pH更加敏感。在[KMnO4]=20 mg·L-1和pH=3.5的条件下,环式MFC的最大功率密度能够达到3986.72 mW·m-2。SEM和XPS分析表明,KMnO4的主要还原产物是沉积在电极表面的固相MnO2,这是KMnO4阴极MFC具有高电位的主要原因。对于单室空气阴极MFC来说,阴极的性能是影响功率输出的重要因素。缩短电极距离、增大阴极的面积都能够降低电池内阻。空气阴极的Pt负载量对功率输出的影响与Nafion溶液的使用密切相关。这些结果都充分表明,提高阴极的电化学氧化性能是强化MFC功率输出的重要途径。
开发了更适于废水处理的升流式空气阴极MFC(UAMFC)。随着有机负荷率的增加,功率密度先升高再降低;COD去除率、CE、EE和pH均呈现出下降的趋势。电化学阻抗谱(EIS)分析表明,电荷转移内阻Rc、欧姆内阻Rohm和扩散内阻Rd分别占总内阻的22.6 %、50.2 %和26.3 %,欧姆内阻占主导作用,主要由UAMFC的结构形式决定。高有机负荷下,回流比影响不显著;低有机负荷下,提高回流比能显著提高功率密度。氮的去除与产电过程无关,主要受到有机负荷的影响。通过对UAMFC的长期行为进行观察,发现功率以0.051 W·m-3·d-1的速率降低,欧姆内阻Rohm和扩散内阻Rd有升高的趋势。通过对空气阴极MFC的设计进行改进,能够实现连续产电及有机物和氮元素的去除。该种设计模式的显著优点是尽最大限度减少了电极距离,降低内阻,提高功率输出,进而为优化空气阴极MFC的设计与运行提供了切实可行的依据。
World-wide depletion of energy reservers and environmental contamination are inspiring the search for renewable and environment-friendly technologies to recover useful energy and materials from organic wastes. This has been particularly emphasised as a significant approach so as to make the wastewater treatment more sustainable and economical in the field of environmental engineering. Microbial fuel cell (MFC) has been addressed able to generate electrical currents via oxidizing orgianic compounds by using microorganisms as the bio-catalysts. Electricity generation during organic degradation represents a process of directly converting chemical energy within organic matters to electrical energy, which gives rise to a potential for MFC to produce electricity from organic wastewater along with wastewater treatment. Currently, MFC is still in its infant and majority of works have been emerged only focusing on its technical feasibility and fundamental characteristics. It has been taken into account that three bottlenecks in terms of low power density, high costs of materials and indetermination of available MFC configuration should be the main limiting elements for MFC technology to apply commercially.
This study systematically investigated the feature and corresponding mechanisms of two-chambered MFC and single-chambered MFC, including the basic characteristics of power generation, the effects of anodic substrate, cathode enhancement as well as improvements of air-cathode MFC design mode. Some innovative findings have been made as follows.
The results demonstrated that both the two-chambered and single-chambered MFC after being started up by using anaerobic activated sludge as inoculated source could stably generate power with simultaneous COD removal when acetate was offered as the single carbon source. The maximum power density produced followed the order of K3[Fe(CN)6]-cathode MFC>air-cathode MFC>aeration-cathode MFC. CE and COD in such three MFCs was 49 %, 28.2 %, 33.8 % and 60 %, 45.3 %, 80 %, respectively. Besides, the performance of the two-chambered MFC was limited by the anode while the performance of the single-chambered MFC was mainly limited by the cathode, which was determined by the inherent nature of the MFC configuration. The main reason for Coulombic loss occurring in the two-chambered MFC and single-chambered MFC should be anaerobic loss and aerobic loss, respectively.
Additionally, MFC was demonstrated capable of using a wide variety of organic compounds for power generation, including single-sugar, multi-sugar as well as several types of small molecular organic fatty acid and ethanol. The dependence of power density on initial COD concentration exhibited“saturation effect”, which could be described and explained with traditional Monod equation. The mixing was observed to have different impact on the MFC performance, depending upon the COD concentrtion, which was most likely due to the difference in diffusion of substrate into the biofilm. In the two-chambered MFC, buffering capacity of the anodic electrolyte played an important role in maintaining pH within a stable level. Increasing ion strength could result in a decrease of internal resistance as well as an increase of power density. High concentration of NH3-N was observed to have no obvious adverse influence on MFC performance. The oxidation of partial NH3-N in single-chambered MFC was achieved with oxygen as electron acceptor and independent on current output. In the two-chamber MFC, NH3-N could be transferred with the form of NH4+ cation into the cathode through PEM in order to balance the charge.
Using acidic permanganate as the cathodic electron acceptor could increase the open circuit potential (OCP) of the two-chambered MFC up to 1.48 V with a higher corresponding maximum power density than that using ferricyanide and oxygen. Unlike permanganate concentration, the cathode potential was shown more sensitive to pH value. At permanganate concentration of 20 mg·L-1 and pH=3.5, the maximum power density produced in bushing MFC could reach a level as high as 3986.72 mW·m-2. Both SEM and XPS analysis confirmed the mechanisms that the main reduced product of permanganate was solid-state MnO2 deposited on the electrode surface. Its redox potential as great as +1.70 V could explain the most probable reason for high OCP in the permanganate-cathode MFC, which was well consistent with the experimental results shown above. For single-chambered MFC, power density could be apparently increased by means of either reducing the electrode spacing or increasing the cathode area because of the corresponding decrease of internal resistance of the cell. The Pt loading and Nafion content were revealed to have a co-effect on power output, i. e., power density was substantially increased with the increase of Pt loading in the absence of Nafion binder solution, while such effect was absent in the presence of Nafion solution.
An up-flow air-cathode MFC (UAMFC) was designed for more available applications for wastewater treatment. As the organic loading rate (OLR) increased, COD removing efficiency, CE, EE and pH tended to decline and power density revealed a setpoint, which might be attributed to the limitation of treating capacity and acid accumulation. As indicated by electrochemical impedance spectroscopy (EIS) analysis, charge transfer resistance (Rc), ohmic resistance (Rohm) and diffusion resistance (Rd) accounted for 22.6 %,50.2 % and 26.3 % of total internal resistance Large fraction of ohmic resistance mainly originated from the inherent limitation of the system in relation to the reactor design structure and electrolyte characteristics. Recirculation was found to have a substantial impact on electrochemical performance (power, Rohm and Rd) at low OLR, while such effect was absent at high OLR. Removal of nitrogen compounds in the UAMFC was obtained along with power generation. It was also shown here that the long-term operation might lead to the performance degradation of the UAMFC, as indicated by a decrease of power density at a rate of 0.051 W·m-3·d-1 and an increase of Rohm and Rd. Such design is more advantageous by its virtue of low internal resistance and high power density, which provides a proof-in-concept and new approach to optimize the air-cathode MFC design and operation.
引文
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