剩余污泥为燃料的微生物燃料电池产电特性及污泥减量化研究
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摘要
微生物燃料电池(MFC)是一种利用附着在阳极电极表面微生物的代谢过程,将蕴含在有机物中的化学能转化成电能的装置。由于其可在处理废水的同时产生电能,已成为环境科学与工程领域的一个重要研究方向。剩余活性污泥主要由悬浮的污泥絮体构成,而絮体是由大量的分散微生物细菌通过胞外聚合物(EPS)、阳离子和其他细颗粒架桥而组成,其中有机物占污泥总量的60%以上。这些均可作为MFC的潜在基质。采用剩余污泥为燃料,通过MFC技术实现在污泥厌氧消化处理的同时实现电能回收,将成为一种新颖的剩余污泥处理技术。剩余污泥中有机物大部分为细胞物质,产电微生物要利用这些物质,首先必须进行破胞,将胞内物质释放出来,使之转化为溶解性物质。而对于MFC体系内的污泥水解过程和产电规律的关系目前未有研究,同时污泥强化水解作用和产电特性的关系仍有待探讨。据此,本研究采用城市污水处理厂剩余污泥作为燃料,结合污泥水解方法(厌氧水解、微波强化水解和外加酶强化水解)和MFC技术进行产电特性和污泥减量化研究。
剩余污泥为燃料MFC (SMFC)获得了成功的启动。SMFC最大功率输出为294.5mW/m2,内阻为247.85Ω,库仑效率(CE)为4.7%。经处理后,污泥中TCOD去除率为26.2%,TSS去除率为24.7%,VSS去除率为32.5%。随着氯化钠投加量的增加,SMFC内阻逐步降低,功率密度则逐步增加。当污泥稀释比增加时,SMFC内阻降低,但功率密度为先上升后下降,功率密度输出下降主要是由于稀释比例过大,导致基质浓度过低,影响了阳极微生物的生长。搅拌有利于改善SMFC内物质的传递,从而增加功率输出。温度对SMFC的产电特性影响较明显,但在一定区间内(如20℃和25℃；30℃和40℃；45℃和50℃)变化不明显,说明产电微生物有一定的温度适应范围,这也可能是在不同温度下产电微生物也不同导致。污泥中的微生物竞争作用是影响SMFC产电效率的主要因素。SMFC运行过程中阴极氧向溶液中的传递并没有对功率输出产生明显影响,主要是由于系统中非产电微生物的作用和阳极附着物的保护作用。研究表明,SMFC中污泥厌氧消化主要控制在水解阶段。SMFC内阻组成主要由阳极电阻、阴极电阻和电解液电阻组成。
微波强化剩余污泥为燃料MFC (MSMFC)电压输出先上升后缓慢下降,产电周期为666h。MSMFC最大功率输出为343.41mW/m2,内阻为146.80Ω。微波时间和微波功率的延长均促进了污泥中SCOD增加,MSMFC功率密度随着微波时间的延长而增加,但随着微波功率的增加先增加后下降。CE随着微波时间或微波功率的增加而减小。在微波时间为300s,功率为720W,微波对污泥的破解能力最强(SCOD为1194mg/L),产生的功率密度最大(163.33mW/m2),且其CE居中(76.7%)。MSMFC系统内阳极表面微生物和电解液微生物均以球状细菌为主。MSMFC中阳极内阻占主要部分,其次为阴极内阻,电解液电阻最小。MSMFC内微量的溶解氧水平将有利于有机物的分解(发酵分解和好氧氧化),抑制产甲烷化过程,提高功率密度和CE。
研究外加酶强化污水为燃料MFC (ESMFC)产电特性时,外加酶(蛋白酶、淀粉酶)的投加促进了污泥水解,提高了MFC产电特性,投加蛋白酶、淀粉酶时ESMFC能量密度增加分别在52%、8%以上。而在酶投加10mg/g的情况下,相对于参照组ESMFC最大功率密度输出增加最大,投加蛋白酶、淀粉酶时分别增加174%、36%。运行温度对ESMFC产电性能的提高也较明显,但相对于酶的促进作用来说,40℃时投加淀粉酶和蛋白酶对ESMFC功率密度输出的促进作用最为明显,投加蛋白酶、淀粉酶时分别增加174%、66%。在外加酶强化作用下,污泥水解效果明显,TCOD去除率均在60%以上,VSS去除率在70%以上,处理后的污泥中VSS/TSS值均明显降低。当蛋白酶：淀粉酶比例为2：3时,ESMFC最大功率密度输出最大,为775.21mW/m2,CE也最大,为10.58%。
在研究三种不同处理方式污泥为燃料MFC产电特性对比分析时发现,ESMFC产电周期最长,为41d,功率密度最大,为775.21mW/m2。 MSMFC库仑效率最大,为84.6%。SMFC中TCOD去除率为26.2%,VSS去除率为32.5%,采用污泥预处理手段有利于促进污泥的减量化,MSMFC中TCOD去除率增加到58.5%,VSS去除率增加到73.9%;MSMFC中TCOD去除率增加到63.2%,VSS去除率增加到77.1%。ESMFC能源效率最高,MSMFC次之,SMFC最小。
Microbial fuel cell (MFC) can transform the chemical energy of the organic matter to electrical energy during microorganism in the anode electrode surface metabolic reaction. MFC has become one of the important research directions in environment science and engineering because it can treat wastewater and generate electricity synchronously. The surplus sludge is made of the suspended floc that includes the microbial cell, extracellular polymeric substances (EPS), cation and other fine particles. The content of organic mater in sludge is above60%and it can be used as potential fuel of MFC. MFC using surplus sludge, which achieves the sludge disposal of anaerobic digestion and the recycling of electrical power, would become a new technique of sludge disposal. Most of the organic matters in sludge are microbial cell, and the microbial cell walls must be hydrolyzed before those organics can be used by exoelectrogenic bacteria. However, so far there is no study reported in MFC on the relationship between sludge hydrolysis and produce electricity. Moreover, the relationship between sludge strengthening hydrolysis and electrical characteristics is not clear. Therefore, in this paper, the surplus sludge from the urban sewage treatment plants was selected as the studied material. The electrogenesis property and the decrement of sludge were investigated based on the MFC techniques and different sludge hydrolysis methods (Anaerobic hydrolysis, microwave strengthening hydrolysis and enzyme strengthening hydrolysis).
MFC using surplus sludge (SMFC) was successfully started up. In SMFC, the maximum power density, internal resistance and coulombic efficiency (CE) were294.5mW/m2,247.85Ω,4.7%, respectively. The TCOD, TSS and VSS in the sludge were removed by26.2%,24.7%and32.5%, respectively.(Here should provide the full names for TCOD, TSS and VSS.) With the increasing NaCl addition, the internal resistance decreased and the maximum power density increased. When the sludge dilution ratio increased, the internal resistance decreased. But the maximum power density firstly arose and then dropped with the increasing sludge dilution ratio. The decrease of the power density may be attributed to the lack of nutrients in MFCs, which affected the anode microbial growth when the sludge dilution ratio is too high. The churning increased the power output because it improved the material transmission in SMFC. The influence of temperature on the produce electrical characteristics of SMFC was generally obvious. However, the power output did not change significantly in the certain temperature interval (such as20℃～25℃,30℃～40℃, and45℃～50℃). This indicates that exoelectrogenic bacteria have appropriate temperature range. It may be attributed to the production of different exoelectrogenic bacteria at different temperatures. The microbial competition in the sludge was the major factor in MFC electric efficiency. In SMFC, the transmission of cathodic oxgen had no obvious influences on the power output, which is due to the consumption of inelectrogenic bacteria and the protection of anode attachments. This study suggests that the hydrolyzing stage is dominating in sludge anaerobic digestion of SMFC. The internal resistance of SMFC consists of anode resistance, cathode resistance and electrolyte resistance.
In MFC using surplus sludge with microwave treatment (MSMFC), the voltage output firstly arose, then dropped slowly. And the cycle was666h. The maximum power density and internal resistance of MSMFC were343.41mW/m2and146.80Ω, respectively. With the increasing microwave power and treatment time, SCOD (provide the full name) of sludge increased. The maximum power density of MSMFC increased with the microwave treatment time. But it firstly arose and then dropped with the microwave power. CE decreased with the increasing microwave treatment time or power. When the microwave time and power were300s and720W, respectively, the cracking capacity of sludge was strongest by microwave (SCOD was1194mg/L), the power density of MSMFC was biggest (163.33mW/m2), and CE was better (76.7%). The dominant microorganism of anode surface and electrolyte were the globular bacteria in MSMFC. The anode resistance in MSMFC was the main part, the cathode resistance was second, and the electrolyte resistance was lowest. This study suggests that the trace dissolved oxygen is conducive to decompose the organic matter (fermentation and aerobic oxidation), restrain methanogenesis process, and improve the power density and CE.
Production of electricity in MFC using surplus sludge by enzymes (ESMFC) was investigated. With the addition of enzymes (protease and amylase), the sludge hydrolysis was promoted and MFC electrogenesis characteristics were improved. The energy density with addition of protease and amylase was increased by52%and8%, respectively. When the enzyme addition was10mg/g, the maximum power density increased maximally. The power density with addition of protease and amylase was increased by174%and36%, respectively. Temperature has significant effects on the electrogenesis characteristics. The effect of addition of protease and amylase at40℃ was the most significant to improve power density if only considering the enzyme action. The power density with addition of protease and amylase was increased by174%and66%, respectively. The hydrolyzing effect of sludge with addition of enzyme was obvious. TCOD and VSS removal efficiencies were above60%and70%, respectively. VSS/TSS in sludge was reduced significantly. When the mixture ratio of protease and amylase was2:3, the largest maximum power density and CE were obtained (775.21mW/m2and10.58%).
Production of electricity in MFC using surplus sludge by three different treatments was investigated. The longest electricity cycle (41d) and the largest power density (775.21mW/m2) were achieved by ESMFC. The largest CE (84.6%) was obtained by MSMFC. TCOD and VSS removal efficiencies by SMFC were26.2%and32.5%, respectively. The sludge reduction can be promoted by using sludge pretreatment method. TCOD and VSS removal efficiencies by MSMFC were increased to58.5%and73.9%, respectively. TCOD and VSS removal efficiencies by ESMFC were increased to63.2%and77.1%, respectively. The energy efficiency of ESMFC was the biggest, MSMFC was the second, and SMFC was the lowest.
剩余污泥为燃料MFC (SMFC)获得了成功的启动。SMFC最大功率输出为294.5mW/m2,内阻为247.85Ω,库仑效率(CE)为4.7%。经处理后,污泥中TCOD去除率为26.2%,TSS去除率为24.7%,VSS去除率为32.5%。随着氯化钠投加量的增加,SMFC内阻逐步降低,功率密度则逐步增加。当污泥稀释比增加时,SMFC内阻降低,但功率密度为先上升后下降,功率密度输出下降主要是由于稀释比例过大,导致基质浓度过低,影响了阳极微生物的生长。搅拌有利于改善SMFC内物质的传递,从而增加功率输出。温度对SMFC的产电特性影响较明显,但在一定区间内(如20℃和25℃；30℃和40℃；45℃和50℃)变化不明显,说明产电微生物有一定的温度适应范围,这也可能是在不同温度下产电微生物也不同导致。污泥中的微生物竞争作用是影响SMFC产电效率的主要因素。SMFC运行过程中阴极氧向溶液中的传递并没有对功率输出产生明显影响,主要是由于系统中非产电微生物的作用和阳极附着物的保护作用。研究表明,SMFC中污泥厌氧消化主要控制在水解阶段。SMFC内阻组成主要由阳极电阻、阴极电阻和电解液电阻组成。
微波强化剩余污泥为燃料MFC (MSMFC)电压输出先上升后缓慢下降,产电周期为666h。MSMFC最大功率输出为343.41mW/m2,内阻为146.80Ω。微波时间和微波功率的延长均促进了污泥中SCOD增加,MSMFC功率密度随着微波时间的延长而增加,但随着微波功率的增加先增加后下降。CE随着微波时间或微波功率的增加而减小。在微波时间为300s,功率为720W,微波对污泥的破解能力最强(SCOD为1194mg/L),产生的功率密度最大(163.33mW/m2),且其CE居中(76.7%)。MSMFC系统内阳极表面微生物和电解液微生物均以球状细菌为主。MSMFC中阳极内阻占主要部分,其次为阴极内阻,电解液电阻最小。MSMFC内微量的溶解氧水平将有利于有机物的分解(发酵分解和好氧氧化),抑制产甲烷化过程,提高功率密度和CE。
研究外加酶强化污水为燃料MFC (ESMFC)产电特性时,外加酶(蛋白酶、淀粉酶)的投加促进了污泥水解,提高了MFC产电特性,投加蛋白酶、淀粉酶时ESMFC能量密度增加分别在52%、8%以上。而在酶投加10mg/g的情况下,相对于参照组ESMFC最大功率密度输出增加最大,投加蛋白酶、淀粉酶时分别增加174%、36%。运行温度对ESMFC产电性能的提高也较明显,但相对于酶的促进作用来说,40℃时投加淀粉酶和蛋白酶对ESMFC功率密度输出的促进作用最为明显,投加蛋白酶、淀粉酶时分别增加174%、66%。在外加酶强化作用下,污泥水解效果明显,TCOD去除率均在60%以上,VSS去除率在70%以上,处理后的污泥中VSS/TSS值均明显降低。当蛋白酶：淀粉酶比例为2：3时,ESMFC最大功率密度输出最大,为775.21mW/m2,CE也最大,为10.58%。
在研究三种不同处理方式污泥为燃料MFC产电特性对比分析时发现,ESMFC产电周期最长,为41d,功率密度最大,为775.21mW/m2。 MSMFC库仑效率最大,为84.6%。SMFC中TCOD去除率为26.2%,VSS去除率为32.5%,采用污泥预处理手段有利于促进污泥的减量化,MSMFC中TCOD去除率增加到58.5%,VSS去除率增加到73.9%;MSMFC中TCOD去除率增加到63.2%,VSS去除率增加到77.1%。ESMFC能源效率最高,MSMFC次之,SMFC最小。
Microbial fuel cell (MFC) can transform the chemical energy of the organic matter to electrical energy during microorganism in the anode electrode surface metabolic reaction. MFC has become one of the important research directions in environment science and engineering because it can treat wastewater and generate electricity synchronously. The surplus sludge is made of the suspended floc that includes the microbial cell, extracellular polymeric substances (EPS), cation and other fine particles. The content of organic mater in sludge is above60%and it can be used as potential fuel of MFC. MFC using surplus sludge, which achieves the sludge disposal of anaerobic digestion and the recycling of electrical power, would become a new technique of sludge disposal. Most of the organic matters in sludge are microbial cell, and the microbial cell walls must be hydrolyzed before those organics can be used by exoelectrogenic bacteria. However, so far there is no study reported in MFC on the relationship between sludge hydrolysis and produce electricity. Moreover, the relationship between sludge strengthening hydrolysis and electrical characteristics is not clear. Therefore, in this paper, the surplus sludge from the urban sewage treatment plants was selected as the studied material. The electrogenesis property and the decrement of sludge were investigated based on the MFC techniques and different sludge hydrolysis methods (Anaerobic hydrolysis, microwave strengthening hydrolysis and enzyme strengthening hydrolysis).
MFC using surplus sludge (SMFC) was successfully started up. In SMFC, the maximum power density, internal resistance and coulombic efficiency (CE) were294.5mW/m2,247.85Ω,4.7%, respectively. The TCOD, TSS and VSS in the sludge were removed by26.2%,24.7%and32.5%, respectively.(Here should provide the full names for TCOD, TSS and VSS.) With the increasing NaCl addition, the internal resistance decreased and the maximum power density increased. When the sludge dilution ratio increased, the internal resistance decreased. But the maximum power density firstly arose and then dropped with the increasing sludge dilution ratio. The decrease of the power density may be attributed to the lack of nutrients in MFCs, which affected the anode microbial growth when the sludge dilution ratio is too high. The churning increased the power output because it improved the material transmission in SMFC. The influence of temperature on the produce electrical characteristics of SMFC was generally obvious. However, the power output did not change significantly in the certain temperature interval (such as20℃～25℃,30℃～40℃, and45℃～50℃). This indicates that exoelectrogenic bacteria have appropriate temperature range. It may be attributed to the production of different exoelectrogenic bacteria at different temperatures. The microbial competition in the sludge was the major factor in MFC electric efficiency. In SMFC, the transmission of cathodic oxgen had no obvious influences on the power output, which is due to the consumption of inelectrogenic bacteria and the protection of anode attachments. This study suggests that the hydrolyzing stage is dominating in sludge anaerobic digestion of SMFC. The internal resistance of SMFC consists of anode resistance, cathode resistance and electrolyte resistance.
In MFC using surplus sludge with microwave treatment (MSMFC), the voltage output firstly arose, then dropped slowly. And the cycle was666h. The maximum power density and internal resistance of MSMFC were343.41mW/m2and146.80Ω, respectively. With the increasing microwave power and treatment time, SCOD (provide the full name) of sludge increased. The maximum power density of MSMFC increased with the microwave treatment time. But it firstly arose and then dropped with the microwave power. CE decreased with the increasing microwave treatment time or power. When the microwave time and power were300s and720W, respectively, the cracking capacity of sludge was strongest by microwave (SCOD was1194mg/L), the power density of MSMFC was biggest (163.33mW/m2), and CE was better (76.7%). The dominant microorganism of anode surface and electrolyte were the globular bacteria in MSMFC. The anode resistance in MSMFC was the main part, the cathode resistance was second, and the electrolyte resistance was lowest. This study suggests that the trace dissolved oxygen is conducive to decompose the organic matter (fermentation and aerobic oxidation), restrain methanogenesis process, and improve the power density and CE.
Production of electricity in MFC using surplus sludge by enzymes (ESMFC) was investigated. With the addition of enzymes (protease and amylase), the sludge hydrolysis was promoted and MFC electrogenesis characteristics were improved. The energy density with addition of protease and amylase was increased by52%and8%, respectively. When the enzyme addition was10mg/g, the maximum power density increased maximally. The power density with addition of protease and amylase was increased by174%and36%, respectively. Temperature has significant effects on the electrogenesis characteristics. The effect of addition of protease and amylase at40℃ was the most significant to improve power density if only considering the enzyme action. The power density with addition of protease and amylase was increased by174%and66%, respectively. The hydrolyzing effect of sludge with addition of enzyme was obvious. TCOD and VSS removal efficiencies were above60%and70%, respectively. VSS/TSS in sludge was reduced significantly. When the mixture ratio of protease and amylase was2:3, the largest maximum power density and CE were obtained (775.21mW/m2and10.58%).
Production of electricity in MFC using surplus sludge by three different treatments was investigated. The longest electricity cycle (41d) and the largest power density (775.21mW/m2) were achieved by ESMFC. The largest CE (84.6%) was obtained by MSMFC. TCOD and VSS removal efficiencies by SMFC were26.2%and32.5%, respectively. The sludge reduction can be promoted by using sludge pretreatment method. TCOD and VSS removal efficiencies by MSMFC were increased to58.5%and73.9%, respectively. TCOD and VSS removal efficiencies by ESMFC were increased to63.2%and77.1%, respectively. The energy efficiency of ESMFC was the biggest, MSMFC was the second, and SMFC was the lowest.
引文
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