CN108448144B - Microbial fuel cell - Google Patents
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Abstract
本发明提供一种微生物燃料电池,包括依次设置的第一阳极室、阴极室和第二阳极室,分别通过阳离子交换膜和阴离子交换膜隔开,第一阳极室和第二阳极室还相互连通,第一阳极、阴极以及第二阳极分别连接;第一阳极上接种有具有产电活性的微生物或活性污泥,阴极上设置有非生物催化剂,阴极室内的阴极液中接种有具有硝化活性的微生物或活性污泥,第二阳极上接种有同时具有产电和反硝化活性的微生物或活性污泥。本发明分别保证了产电效率、硝化效率和反硝化效率的最适环境,在废水中有机物有效去除的基础上,还确保了废水中氮素的有效去除。
The invention provides a microbial fuel cell, comprising a first anode chamber, a cathode chamber and a second anode chamber arranged in sequence, separated by a cation exchange membrane and an anion exchange membrane respectively, and the first anode chamber and the second anode chamber are also communicated with each other The first anode, the cathode and the second anode are respectively connected; the first anode is inoculated with microorganisms or activated sludge with electricity-generating activity, the cathode is provided with a non-biological catalyst, and the catholyte in the cathode chamber is inoculated with nitrification activity. Microorganisms or activated sludge, the second anode is inoculated with microorganisms or activated sludge that have both electricity production and denitrification activities. The invention guarantees the optimum environment for the power generation efficiency, the nitrification efficiency and the denitrification efficiency respectively, and on the basis of the effective removal of organic matter in the wastewater, the effective removal of nitrogen in the wastewater is also ensured.
Description
技术领域technical field
本发明涉及微生物电化学技术领域,具体涉及一种微生物燃料电池。The invention relates to the technical field of microbial electrochemistry, in particular to a microbial fuel cell.
背景技术Background technique
目前,随着我国经济的快速发展,日益频繁的工业生产活动和人类活动造成了严重的水体污染,同时也消耗了大量的能源;当今水体污染与能源紧缺已经成为制约我国可持续发展的关键问题。At present, with the rapid development of my country's economy, the increasingly frequent industrial production activities and human activities have caused serious water pollution, and also consumed a lot of energy; today's water pollution and energy shortage have become the key problems restricting my country's sustainable development .
微生物燃料电池(Microbial Fuel Cell,MFC),是一种新型的清洁能源技术,利用产电微生物降解水中有机污染物并将其化学能原位转化为电能。利用微生物燃料电池处理废水,不仅实现了有机物的有效去除,还能直接将化学能转化为电能,既解决了传统污水处理能耗高和污泥产量大的缺点,又可有效回收污水中大量有机物潜在的化学能,逐渐应用在废水处理领域中。Microbial Fuel Cell (MFC) is a new type of clean energy technology that uses electricity-generating microorganisms to degrade organic pollutants in water and convert their chemical energy into electricity in situ. The use of microbial fuel cells to treat wastewater not only achieves effective removal of organic matter, but also directly converts chemical energy into electrical energy, which not only solves the shortcomings of high energy consumption and large sludge output in traditional wastewater treatment, but also effectively recovers a large amount of organic matter in wastewater. Potential chemical energy is gradually applied in the field of wastewater treatment.
在实际应用中,传统的微生物燃料电池虽然实现了对废水中有机物的有效去除,但对废水中的氮素去除效果仍然不太理想,尤其是对硝酸根的去除,而且其去除速率也远远不能满足需求。In practical applications, although traditional microbial fuel cells can effectively remove organic matter in wastewater, the nitrogen removal effect in wastewater is still not ideal, especially the removal of nitrate, and its removal rate is far cannot meet demand.
发明内容SUMMARY OF THE INVENTION
本发明提供一种微生物燃料电池,以解决现有技术中的微生物燃料电池无法对废水中的氮素有效去除的问题。The present invention provides a microbial fuel cell to solve the problem that the microbial fuel cell in the prior art cannot effectively remove nitrogen in wastewater.
本发明实施例提供一种微生物燃料电池,包括依次设置的第一阳极室、阴极室和第二阳极室,所述第一阳极室和所述阴极室通过阳离子交换膜隔开,所述阴极室和所述第二阳极室通过阴离子交换膜隔开,所述第一阳极室和所述第二阳极室还相互连通;位于所述第一阳极室内的第一阳极、位于所述阴极室内的阴极以及位于所述第二阳极室内的第二阳极分别连接;An embodiment of the present invention provides a microbial fuel cell, comprising a first anode compartment, a cathode compartment and a second anode compartment arranged in sequence, the first anode compartment and the cathode compartment are separated by a cation exchange membrane, and the cathode compartment and the second anode chamber are separated by an anion exchange membrane, and the first anode chamber and the second anode chamber are also communicated with each other; the first anode in the first anode chamber, the cathode in the cathode chamber and the second anodes located in the second anode chamber are respectively connected;
所述第一阳极上接种有具有产电活性的微生物或活性污泥,所述阴极上设置有非生物催化剂,所述阴极室内的阴极液中接种有具有硝化活性的微生物或活性污泥,所述第二阳极上接种有同时具有产电和反硝化活性的微生物或活性污泥。The first anode is inoculated with microorganisms or activated sludge with electricity generating activity, the cathode is provided with non-biological catalysts, and the catholyte in the cathode chamber is inoculated with microorganisms or activated sludge with nitrification activity. The second anode is inoculated with microorganisms or activated sludge that have both electricity production and denitrification activities.
作为本发明的优选方式,所述第一阳极室包括第一进水口和第一出水口,所述第二阳极室包括第二进水口和第二出水口,其中所述第一出水口和所述第二进水口通过导管连接,所述第一进水口与外部的废水供给装置连接。As a preferred mode of the present invention, the first anode chamber includes a first water inlet and a first water outlet, the second anode chamber includes a second water inlet and a second water outlet, wherein the first water outlet and all The second water inlet is connected through a conduit, and the first water inlet is connected with an external waste water supply device.
作为本发明的优选方式,所述第一阳极室内的阳极液和所述第二阳极室内的阳极液中溶解氧的浓度均为0.05~0.1mg/L。As a preferred mode of the present invention, the concentrations of dissolved oxygen in the anolyte in the first anode chamber and in the anolyte in the second anode chamber are both 0.05 to 0.1 mg/L.
作为本发明的优选方式,所述阴极室内设置有曝气管,所述曝气管的另一端与外部的空气泵连接。As a preferred mode of the present invention, an aeration tube is provided in the cathode chamber, and the other end of the aeration tube is connected to an external air pump.
作为本发明的优选方式,所述曝气管与所述空气泵之间还设置有气体流量计,通过所述气体流量计控制曝气量为10~50ml/min。As a preferred mode of the present invention, a gas flow meter is further provided between the aeration pipe and the air pump, and the aeration rate is controlled to be 10-50 ml/min by the gas flow meter.
作为本发明的优选方式,所述阴极上设置的非生物催化剂为Pt或氮掺杂石墨烯催化剂。As a preferred mode of the present invention, the non-biological catalyst provided on the cathode is a Pt or nitrogen-doped graphene catalyst.
作为本发明的优选方式,所述阴极液为无机盐溶液或含氮无机盐溶液。As a preferred mode of the present invention, the catholyte is an inorganic salt solution or a nitrogen-containing inorganic salt solution.
作为本发明的优选方式,所述第一阳极室、所述阴极室和所述第二阳极室的培养温度为30℃。As a preferred mode of the present invention, the culture temperature of the first anode chamber, the cathode chamber and the second anode chamber is 30°C.
作为本发明的优选方式,所述第一阳极室、所述阴极室和所述第二阳极室的体积相同。As a preferred mode of the present invention, the volumes of the first anode chamber, the cathode chamber and the second anode chamber are the same.
作为本发明的优选方式,所述第一阳极、所述阴极和所述第二阳极由碳纸、碳布、碳毡、石墨毡或石墨板材料制成。As a preferred mode of the present invention, the first anode, the cathode and the second anode are made of carbon paper, carbon cloth, carbon felt, graphite felt or graphite plate material.
本发明提供的一种微生物燃料电池,采用两个阳极室和一个阴极室的结构,实现了在第一阳极室将氮素快速地从废水中分离以降低对第一阳极室内具有产电活性的微生物的毒害作用,同时将脱氮的硝化反应和反硝化反应进行分离,使得在阴极室内发生硝化反应,而在第二阳极室内发生反硝化反应,从而分别保证了产电效率、硝化效率和反硝化效率的最适环境,在废水中有机物有效去除的基础上,还确保了废水中氮素的有效去除。The microbial fuel cell provided by the invention adopts the structure of two anode chambers and one cathode chamber, and realizes the rapid separation of nitrogen from wastewater in the first anode chamber to reduce the electricity generation activity in the first anode chamber. At the same time, the nitrification reaction and denitrification reaction of denitrification are separated, so that the nitrification reaction occurs in the cathode chamber, and the denitrification reaction occurs in the second anode chamber, thereby ensuring the power generation efficiency, nitrification efficiency and reverse reaction respectively. The optimum environment for nitrification efficiency ensures the effective removal of nitrogen in wastewater on the basis of effective removal of organic matter in wastewater.
附图说明Description of drawings
为了更清楚地说明本发明实施例中的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。In order to illustrate the technical solutions in the embodiments of the present invention more clearly, the following briefly introduces the accompanying drawings used in the description of the embodiments. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained from these drawings without creative effort.
图1为本发明实施例提供的微生物燃料电池的结构示意图;1 is a schematic structural diagram of a microbial fuel cell provided by an embodiment of the present invention;
图2为本发明实施例提供的微生物燃料电池的电压输出示意图;FIG. 2 is a schematic diagram of a voltage output of a microbial fuel cell provided by an embodiment of the present invention;
图3为本发明实施例提供的微生物燃料电池中第一阳极室和第二阳极室的COD变化示意图;3 is a schematic diagram of COD changes of the first anode chamber and the second anode chamber in the microbial fuel cell provided by the embodiment of the present invention;
图4为本发明实施例提供的微生物燃料电池中第一阳极室、阴极室和第二阳极室的氨氮浓度变化示意图;4 is a schematic diagram of changes in ammonia nitrogen concentration in a first anode chamber, a cathode chamber and a second anode chamber in a microbial fuel cell provided by an embodiment of the present invention;
图5为本发明实施例提供的微生物燃料电池中第一阳极室、阴极室和第二阳极室的硝态氮浓度变化示意图。FIG. 5 is a schematic diagram showing the change of nitrate nitrogen concentration in the first anode chamber, the cathode chamber and the second anode chamber in the microbial fuel cell according to the embodiment of the present invention.
其中,1、第一阳极室,2、阴极室,3、第二阳极室,4、阳离子交换膜,5、阴离子交换膜,6、第一阳极,7、阴极,8、第二阳极,9、第一进水口,10、第一出水口,11、第二进水口,12、第二出水口,13、导管,14、曝气管,15、气体流量计。Among them, 1, the first anode chamber, 2, the cathode chamber, 3, the second anode chamber, 4, the cation exchange membrane, 5, the anion exchange membrane, 6, the first anode, 7, the cathode, 8, the second anode, 9 , The first water inlet, 10, the first water outlet, 11, the second water inlet, 12, the second water outlet, 13, the conduit, 14, the aeration pipe, 15, the gas flow meter.
具体实施方式Detailed ways
为了使本技术领域的人员更好地理解本发明方案,下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分的实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都应当属于本发明保护的范围。In order to make those skilled in the art better understand the solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only Embodiments are part of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
参照图1所示,本发明实施例公开了一种微生物燃料电池,包括依次设置的第一阳极室1、阴极室2和第二阳极室3,第一阳极室1和阴极室2通过阳离子交换膜4隔开,阴极室2和第二阳极室3通过阴离子交换膜5隔开,第一阳极室1和第二阳极室3还相互连通;位于第一阳极室1内的第一阳极6、位于阴极室2内的阴极7以及位于第二阳极室3内的第二阳极8分别连接;第一阳极6上接种有具有产电活性的微生物或活性污泥,阴极7上设置有非生物催化剂,阴极室2内的阴极液中接种有具有硝化活性的微生物或活性污泥,第二阳极8上接种有同时具有产电和反硝化活性的微生物或活性污泥。Referring to FIG. 1 , an embodiment of the present invention discloses a microbial fuel cell, comprising a first anode chamber 1, a
本实施例中,利用微生物燃料电池处理的废水指含有有机物和氮素的废水,这里的氮素一般是指废水中的氨氮,而氨氮是指水中以游离氨(NH3 -)和铵离子(NH4 +)形式存在的氮。传统的微生物燃料电池主要实现了废水中有机物的去除,但对废水中的氮素去除效果不太理想,尤其是对硝酸根的去除,而且其去除速率也远远不能满足需求。In this embodiment, the wastewater treated by the microbial fuel cell refers to wastewater containing organic matter and nitrogen, where nitrogen generally refers to ammonia nitrogen in wastewater, and ammonia nitrogen refers to free ammonia (NH 3 - ) and ammonium ions ( nitrogen in the form of NH 4 + ). Traditional microbial fuel cells mainly achieve the removal of organic matter in wastewater, but the removal effect of nitrogen in wastewater is not ideal, especially the removal of nitrate, and the removal rate is far from meeting the demand.
本发明实施例提供的微生物燃料电池,采用两个阳极室和一个阴极室的结构,废水进入第一阳极室后,其中的有机物在第一阳极室进行降解并释放电子,电子经外电路到达阴极,其中的氮素经阳离子交换膜快速进入阴极室,并在阴极室内微生物的硝化作用下形成硝酸根,阴极室中还在催化剂的作用下发生氧还原反应消耗来自阳极的电子;硝酸根进一步经阴离子交换膜进入第二阳极室,最终在第二阳极室内被还原为氮气,同时废水进一步进入第二阳极室内,有机物在第二阳极室中进行进一步的降解并释放电子,电子经外电路也到达阴极。The microbial fuel cell provided by the embodiment of the present invention adopts the structure of two anode chambers and one cathode chamber. After the waste water enters the first anode chamber, the organic matter in the first anode chamber is degraded and electrons are released, and the electrons reach the cathode through the external circuit , the nitrogen in it quickly enters the cathode chamber through the cation exchange membrane, and forms nitrate under the action of microorganisms in the cathode chamber, and the oxygen reduction reaction occurs in the cathode chamber under the action of the catalyst to consume the electrons from the anode; The anion exchange membrane enters the second anode chamber, and is finally reduced to nitrogen in the second anode chamber. At the same time, the waste water further enters the second anode chamber. The organic matter is further degraded in the second anode chamber and releases electrons, and the electrons also reach the external circuit. cathode.
该微生物燃料电池实现了在第一阳极室将氮素快速地从废水中分离以降低对第一阳极室内具有产电活性的微生物的毒害作用,同时将脱氮的硝化反应和反硝化反应进行分离,使得在阴极室内发生硝化反应,而在第二阳极室内发生反硝化反应,从而分别保证了产电效率、硝化效率和反硝化效率的最适环境,在废水中有机物有效去除的基础上,还确保了废水中氮素的有效去除。The microbial fuel cell realizes the rapid separation of nitrogen from wastewater in the first anode chamber to reduce the poisoning effect on microorganisms with electricity-generating activity in the first anode chamber, and simultaneously separates the nitrification reaction and denitrification reaction of denitrification. , so that the nitrification reaction occurs in the cathode chamber, and the denitrification reaction occurs in the second anode chamber, thereby ensuring the optimal environment for the power generation efficiency, nitrification efficiency and denitrification efficiency respectively. Effective removal of nitrogen from wastewater is ensured.
同时,废水的有机物得到充分的降解,并且转化成电能通过外部电路以供外部用电设备利用。At the same time, the organic matter in the wastewater is fully degraded and converted into electrical energy for use by external electrical equipment through an external circuit.
本实施例中,第一阳极上接种的具有产电活性的微生物或活性污泥、阴极液中接种的具有硝化活性的微生物或活性污泥以及第二阳极上接种的同时具有产电和反硝化活性的微生物或活性污泥,均采用现有技术中通常采用的微生物或活性污泥,本发明实施例对此不做具体限定。In this embodiment, the microorganisms or activated sludge with electricity-generating activity inoculated on the first anode, the microorganisms or activated sludge with nitrification activity inoculated in the catholyte, and the inoculated on the second anode have both electricity-generating and denitrifying properties The activated microorganisms or activated sludges all use microorganisms or activated sludges commonly used in the prior art, which are not specifically limited in the embodiment of the present invention.
进一步地,第一阳极室中的废水中的氮素通过阳离子交换膜快速迁移至阴极,降低了氮素对具有产电活性的微生物活性的抑制,从而可有效提高第一阳极室中第一阳极的产电性能。Further, the nitrogen in the wastewater in the first anode chamber quickly migrates to the cathode through the cation exchange membrane, which reduces the inhibition of nitrogen on the activity of microorganisms with electricity-generating activity, so that the first anode in the first anode chamber can be effectively improved. power generation performance.
进一步地,阴极采用非生物催化剂进行催化氧还原反应进行高效产电,同时采用阴极液中接种的具有硝化活性的微生物或活性污泥进行硝化反应,可释放质子中和阴极发生氧还原反应消耗的质子,有效缓解阴极液pH的升高,不影响微生物的催化活性,确保了氮素的有效去除;并且具有硝化活性的微生物可在非生物催化剂表面形成生物薄膜,有效防止非生物催化剂的脱落和流失,延长阴极的有效使用寿命,从而降低了微生物燃料电池的成本。而传统的微生物燃料电池中,阴极使用非生物催化剂时,由于在运行过程中常造成非生物催化剂的脱落和流失使得阴极的使用寿命大大缩短,从而增加了微生物燃料电池的成本;同时阴阳极室之间的分隔膜降低了质子的传输,导致长期运行过程中阴阳极室中的酸碱失衡,影响了微生物的催化活性,虽然通过缓冲液体系可有效缓解pH的变化,但是仍然不能从本质上解决酸碱失衡的问题。Further, the cathode uses non-biological catalysts to catalyze the oxygen reduction reaction to generate electricity efficiently, and at the same time, the nitrification reaction is carried out by using microorganisms with nitrification activity or activated sludge inoculated in the catholyte, which can release protons and neutralize the oxygen consumption at the cathode. Protons can effectively alleviate the increase of catholyte pH, do not affect the catalytic activity of microorganisms, and ensure the effective removal of nitrogen; and microorganisms with nitrification activity can form biofilms on the surface of abiotic catalysts, effectively preventing abiotic catalysts from falling off and loss, extending the effective life of the cathode, thereby reducing the cost of microbial fuel cells. In traditional microbial fuel cells, when abiotic catalysts are used in the cathode, the service life of the cathode is greatly shortened due to the shedding and loss of the abiotic catalysts during operation, thereby increasing the cost of the microbial fuel cell. The separation membrane between the two reduces the transport of protons, which leads to the acid-base imbalance in the cathode and anode chambers during long-term operation, which affects the catalytic activity of microorganisms. Although the pH change can be effectively alleviated by the buffer system, it still cannot be solved in essence. The problem of acid-base imbalance.
进一步地,第二阳极室主要进行反硝化反应,可快速还原硝酸根,产生的氢氧根中和了前期酸化的阳极液,有效缓解阴极液pH的升高,不影响微生物的催化活性,确保了氮素的有效去除;并且能够进一步降解阳极液中的有机物并释放电子至阴极,进一步提高产电性能。Further, the second anode chamber mainly conducts denitrification reaction, which can quickly reduce nitrate, and the generated hydroxide neutralizes the anolyte acidified in the early stage, effectively alleviates the increase of catholyte pH, does not affect the catalytic activity of microorganisms, and ensures It can effectively remove nitrogen; and can further degrade the organic matter in the anolyte and release electrons to the cathode, and further improve the power generation performance.
在上述实施例的基础上,第一阳极室1包括第一进水口9和第一出水口10,第二阳极室3包括第二进水口11和第二出水口12,其中第一出水口10和第二进水口11通过导管13连接,第一进水口9与外部的废水供给装置连接。On the basis of the above embodiment, the first anode chamber 1 includes a
本实施例中,废水由废水供给装置引入,并通过第一进水口进入第一阳极室中,在第一阳极室中进行有机物的降解并释放电子,其中的氮素经阳离子交换膜快速进入阴极室;在第一阳极室中经过处理的废水还依次通过第一出水口、导管和第二进水口进入第二阳极室中,进一步对废水中残留的有机物进行降解并产生电子,同时在阴极室中由氮素形成的硝酸根经阴离子交换膜也进入第二阳极室中进行反硝化反应,这样不仅能够有效去除废水中的有机物,还使硝化反应和反硝化反应的环境分离,从而有效去除废水中的氮素。最后,处理后达标的废水经第二出水口排出。In this embodiment, the waste water is introduced from the waste water supply device and enters the first anode chamber through the first water inlet, where the organic matter is degraded and electrons are released, and the nitrogen in it enters the cathode quickly through the cation exchange membrane The treated wastewater in the first anode chamber also enters the second anode chamber through the first water outlet, the conduit and the second water inlet in turn, further degrades the residual organic matter in the wastewater and generates electrons, while in the cathode chamber Nitrate formed by nitrogen also enters the second anode chamber through the anion exchange membrane for denitrification reaction, which can not only effectively remove organic matter in wastewater, but also separate the environment of nitrification reaction and denitrification reaction, so as to effectively remove wastewater nitrogen in. Finally, the treated wastewater that meets the standard is discharged through the second water outlet.
在上述实施例的基础上,第一阳极室1内的阳极液和第二阳极室3内的阳极液中溶解氧的浓度均为0.05~0.1mg/L。On the basis of the above embodiment, the concentration of dissolved oxygen in the anolyte in the first anode chamber 1 and the anolyte in the
本实施例中,第一阳极室和第二阳极室为厌氧的密闭环境,因此使第一阳极室和第二阳极室内的阳极液中溶解氧的浓度为0.05~0.1mg/L时,可使有机物在微生物的作用下较好地分解并释放出电子,提高阳极的产电性能。In this embodiment, the first anode chamber and the second anode chamber are anaerobic closed environments, so when the dissolved oxygen concentration in the anolyte in the first anode chamber and the second anode chamber is 0.05-0.1 mg/L, the Under the action of microorganisms, the organic matter is decomposed better and electrons are released, and the electricity generation performance of the anode is improved.
在上述实施例的基础上,阴极室2内设置有曝气管14,曝气管14的另一端与外部的空气泵连接。On the basis of the above embodiment, the
本实施例中,阴极室为好氧的曝气环境,因此在阴极室内设置了曝气管,并使曝气管的一端伸入阴极液中,另一端与外部的空气泵连接,可保证阴极室内阴极液中的溶解氧充足。In this embodiment, the cathode chamber is an aerobic aeration environment, so an aeration tube is set in the cathode chamber, and one end of the aeration tube extends into the catholyte, and the other end is connected to an external air pump, which can ensure the cathode The dissolved oxygen in the indoor catholyte is sufficient.
在上述实施例的基础上,曝气管14与空气泵之间还设置有气体流量计15,通过气体流量计15控制曝气量为10~50ml/min。On the basis of the above embodiment, a
本实施例中,为更好地控制曝气量,在曝气管与空气泵之间设置了气体流量计,并且通过气体流量计将曝气量控制为10~50ml/min时,可使阴极液中溶解氧的含量达到最佳,有利于阴极液中具有硝化活性的微生物对氮素的硝化作用。In this embodiment, in order to better control the aeration volume, a gas flow meter is set between the aeration pipe and the air pump, and when the aeration volume is controlled to 10-50ml/min by the gas flow meter, the cathode can be The content of dissolved oxygen in the liquid is optimal, which is beneficial to the nitrification of nitrogen by microorganisms with nitrification activity in the catholyte.
在上述实施例的基础上,阴极7上设置的非生物催化剂为Pt或氮掺杂石墨烯催化剂。On the basis of the above embodiment, the non-biological catalyst arranged on the
本实施例中,阴极上设置的非生物催化剂为Pt或氮掺杂石墨烯催化剂,其具有较好的催化性能,可以有效实现阴极在进行氧化还原反应时的催化作用。In this embodiment, the non-biological catalyst arranged on the cathode is a Pt or nitrogen-doped graphene catalyst, which has good catalytic performance and can effectively realize the catalytic effect of the cathode during redox reaction.
在上述实施例的基础上,阴极液为无机盐溶液或含氮无机盐溶液。On the basis of the above embodiments, the catholyte is an inorganic salt solution or a nitrogen-containing inorganic salt solution.
本实施例中,阴极液优选为无机盐溶液或含氮无机盐溶液,可以较好地提供具有硝化活性的微生物或活性污泥的接种环境和生长环境。In this embodiment, the catholyte is preferably an inorganic salt solution or a nitrogen-containing inorganic salt solution, which can better provide an inoculation environment and a growth environment for microorganisms or activated sludge with nitrification activity.
在上述实施例的基础上,第一阳极室1、阴极室2和第二阳极室3的培养温度为30℃。On the basis of the above embodiment, the incubation temperature of the first anode chamber 1 , the
本实施例中,将第一阳极室、阴极室和第二阳极室的培养温度控制为30℃,从而间接调节第一阳极和第二阳极表面的温度以及阴极液的温度为30℃,可为微生物提供最适宜的生长环境,提高微生物的生物活性,最终提高整个微生物燃料电池的性能。实际应用中,可将第一阳极室、阴极室和第二阳极室整体放入恒温培养箱中进行30℃恒温培养。In this embodiment, the culture temperature of the first anode chamber, the cathode chamber and the second anode chamber is controlled to be 30°C, thereby indirectly adjusting the temperature of the surfaces of the first anode and the second anode and the temperature of the catholyte to 30°C, which can be Microorganisms provide the most suitable growth environment, improve the biological activity of microorganisms, and ultimately improve the performance of the entire microbial fuel cell. In practical application, the whole of the first anode chamber, the cathode chamber and the second anode chamber can be put into a constant temperature incubator for constant temperature cultivation at 30°C.
在上述实施例的基础上,第一阳极室1、阴极室2和第二阳极室3的体积相同。On the basis of the above embodiment, the volumes of the first anode chamber 1 , the
本实施例中,由于阴阳离子交换膜对阴阳离子的迁移速率与极室腔体体积和离子浓度有关,因此阴极室的硝化反应速率由第一阳极室向阴极室的迁移速率决定,其产生的质子可作为阴极氧还原反应的质子来源;第二阳极室的反硝化反应速率取决于阴极室向第二阳极室的迁移速率与第一阳极室向第二阳极室迁移的有机物浓度有关;当三者体积相同时,有利于废水中氮素的硝化反应和反硝化反应,可保证排出的废水中有机物和氮素的去除率达95%以上。In this embodiment, since the migration rate of anions and cations by the anion and cation exchange membrane is related to the volume and ion concentration of the electrode chamber, the nitrification reaction rate of the cathode chamber is determined by the migration rate of the first anode chamber to the cathode chamber. Protons can be used as a source of protons for the cathode oxygen reduction reaction; the denitrification reaction rate of the second anode chamber depends on the migration rate of the cathode chamber to the second anode chamber and the concentration of organic matter migrated from the first anode chamber to the second anode chamber; when the three When the volume of the two is the same, it is beneficial to the nitrification and denitrification reactions of nitrogen in the wastewater, and the removal rate of organic matter and nitrogen in the discharged wastewater can be guaranteed to be more than 95%.
在上述实施例的基础上,第一阳极6、阴极7和第二阳极8由碳纸、碳布、碳毡、石墨毡或石墨板材料制成。On the basis of the above embodiments, the
本实施例中,第一阳极、阴极和第二阳极均采用碳纸、碳布、碳毡、石墨毡或石墨板材料制成,这些材料的导电效果较好,较易使微生物附着,而且这些材料成本低,容易获得。In this embodiment, the first anode, the cathode and the second anode are all made of carbon paper, carbon cloth, carbon felt, graphite felt or graphite plate materials. These materials have better electrical conductivity and are easier to attach to microorganisms. Material cost is low and easy to obtain.
为进一步阐述本发明的技术方案,本发明实施例还提供了一种微生物燃料电池的具体实施方式。To further illustrate the technical solution of the present invention, the embodiment of the present invention also provides a specific implementation of a microbial fuel cell.
本实施例中,该微生物燃料电池由体积均为100ml的第一阳极室和第二阳极室以及一个体积为100ml的阴极室组成,其中阴极室位于第一阳极室和第二阳极室的中间,且第一阳极室与阴极室由阳离子交换膜隔开,阴极室与第二阳极室由阴离子交换膜分隔开。位于第一阳极室内的第一阳极和位于第二阳极室内的第二阳极分别通过导线经由1kΩ的外电阻连接位于阴极室内的阴极,形成电流回路。In this embodiment, the microbial fuel cell consists of a first anode chamber and a second anode chamber with a volume of 100ml and a cathode chamber with a volume of 100ml, wherein the cathode chamber is located in the middle of the first anode chamber and the second anode chamber, And the first anode compartment and the cathode compartment are separated by a cation exchange membrane, and the cathode compartment and the second anode compartment are separated by an anion exchange membrane. The first anode located in the first anode chamber and the second anode located in the second anode chamber are respectively connected to the cathode located in the cathode chamber through wires through an external resistance of 1 kΩ to form a current loop.
第一阳极和第二阳极均采用碳毡材料制作,碳毡大小均为2×3×3cm,且在第一阳极上接种具有产电活性的活性污泥,在第二阳极上接种同时具有产电和反硝化活性的活性污泥,活性污泥接种量均为0.5mg/ml。阴极采用碳布材料制作,并负载0.5mg/cm2的Pt掺杂石墨烯催化剂,碳布大小为3×3cm,且在阴极室内的阴极液中接种具有硝化活性的活性污泥,活性污泥接种量为0.5mg/ml。第一阳极室和第二阳极室均为厌氧的密闭环境,其中的阳极液中溶解氧的浓度均为0.05~0.1mg/L。阴极室为好氧的曝气环境,曝气量由空气泵流经气体流量计控制在30-40ml/min。Both the first anode and the second anode are made of carbon felt material, and the size of the carbon felt is 2 × 3 × 3 cm, and the activated sludge with electricity-generating activity is inoculated on the first anode, and the activated sludge with electricity-producing activity is inoculated on the second anode. For activated sludge with electricity and denitrification activities, the inoculum amount of activated sludge is 0.5 mg/ml. The cathode is made of carbon cloth material, and is loaded with 0.5 mg/cm 2 of Pt-doped graphene catalyst. The size of the carbon cloth is 3 × 3 cm, and activated sludge with nitrification activity is inoculated in the catholyte in the cathode chamber. The inoculum was 0.5 mg/ml. Both the first anode chamber and the second anode chamber are anaerobic closed environments, and the concentration of dissolved oxygen in the anode solution is both 0.05-0.1 mg/L. The cathode chamber is an aerobic aeration environment, and the aeration volume is controlled at 30-40ml/min by an air pump flowing through a gas flow meter.
第一阳极室包括第一进水口和第一出水口,第二阳极室包括第二进水口和第二出水口,其中第一出水口和第二进水口通过导管连接,第一进水口与外部的废水供给装置连接。The first anode chamber includes a first water inlet and a first water outlet, the second anode chamber includes a second water inlet and a second water outlet, wherein the first water outlet and the second water inlet are connected by a conduit, and the first water inlet is connected to the outside connected to the waste water supply.
在第一阳极室和第二阳极室中添加模拟的含氮有机废水作为阳极液,其中第二阳极室的阳极液中各主要成份及配比为:二水合磷酸二氢钠(Na2HPO4·2H2O)0.8~8.1g/L,十二水合磷酸氢二钠(Na2HPO4·12H2O)2.1~22g/L,氯化钾(KCl)0~0.26g/L,乙酸钠(CH3COONa)0.5g/L,Wolfes矿物溶液10mL/L,并由HCl溶液或NaOH溶液调节其pH值至7。其中,Wolfes矿物溶液的具体组成为:氨基乙酸(NH2CH2COOH)1.5g/L,七水合硫酸镁(MgSO4·7H2O)3g/L,二水合硫酸锰(MnSO4·2H2O)0.5g/L,氯化钠(NaCl)1.0g/L,七水合硫酸亚铁(FeSO4·7H2O)0.1g/L,氯化钴(CoCl2)0.1g/L,氯化钙(CaCl2)0.1g/L,硫酸锌(ZnSO4)0.1g/L,五水合硫酸铜CuSO4·5H2O 0.01g/L,无水硫酸铝钾(AlK(SO4)2)0.01g/L,硼酸(H3BO3)0.01g/L,钼酸钠(Na2MoO4·2H2O)0.01g/L,并由KOH溶液调节其pH为至7。第一阳极室中的阳极液在第二阳极室中的阳极液的基础上,添加氯化铵(NH4Cl)0.42g/L作为氮源。In the first anode chamber and the second anode chamber, the simulated nitrogen-containing organic wastewater is added as the anolyte, wherein the main components and proportions of the anolyte in the second anode chamber are: sodium dihydrogen phosphate dihydrate (Na 2 HPO 4 2H 2 O) 0.8~8.1g/L, disodium hydrogen phosphate dodecahydrate (Na 2 HPO 4 12H 2 O) 2.1~22g/L, potassium chloride (KCl) 0~0.26g/L, sodium acetate (CH 3 COONa) 0.5 g/L,
在阴极室中的阴极液的主要成分及配比为:二水合磷酸二氢钠(Na2HPO4·2H2O)0.8~8.1g/L,十二水合磷酸氢二钠(Na2HPO4·12H2O)2.1~22g/L的磷酸盐缓冲溶液。The main components and proportions of the catholyte in the cathode compartment are: sodium dihydrogen phosphate dihydrate (Na 2 HPO 4 ·2H 2 O) 0.8-8.1 g/L, sodium hydrogen phosphate dodecahydrate (Na 2 HPO 4 ) 0.8-8.1 g/L ·12H 2 O) 2.1~22g/L phosphate buffer solution.
使用时,一次性将相应的溶液加入至各个腔室中,与活性污泥混合后,置于30℃恒温培养箱中培养,并在电极处连接数据采集卡以每5分钟一次记录采集电压。当电压先上升后再下降至20mV以下后,视为一个完整周期,需更换新的溶液。经过前3个周期的运行,整个微生物燃料电池的输出电压稳定,第四个周期运行过程中的电压输出如图2所示,第一阳极与阴极采集的最大输出电压高达620mV,该周期结束,更换溶液后电压迅速回升,第二阳极与阴极的电压变化与之一致。When using, the corresponding solution was added to each chamber at one time, mixed with activated sludge, placed in a 30°C constant temperature incubator for cultivation, and a data acquisition card was connected to the electrode to record the acquisition voltage every 5 minutes. When the voltage first rises and then drops below 20mV, it is regarded as a complete cycle and needs to be replaced with a new solution. After the first 3 cycles of operation, the output voltage of the entire microbial fuel cell is stable. The voltage output during the fourth cycle of operation is shown in Figure 2. The maximum output voltage collected by the first anode and cathode is as high as 620mV. After the solution was replaced, the voltage rose rapidly, and the voltage changes of the second anode and cathode were consistent with it.
图3为本发明实施例提供的微生物燃料电池中第一阳极室和第二阳极室的COD变化示意图,由图3可知,在第一阳极室和第二阳极室中的阳极液的初始COD(ChemicalOxygen Demand,化学需氧量)值均在500mg/L左右,随着整个运行过程的继续,第一阳极室中的COD值匀速下降,而等浓度下的第二阳极室中的COD值在前期快速下解。Fig. 3 is a schematic diagram of COD changes of the first anode chamber and the second anode chamber in the microbial fuel cell provided by the embodiment of the present invention. It can be seen from Fig. 3 that the initial COD ( ChemicalOxygen Demand) values are all around 500mg/L. As the whole operation process continues, the COD value in the first anode chamber decreases at a uniform speed, while the COD value in the second anode chamber under the same concentration is in the early stage. Quick solution.
图4为本发明实施例提供的微生物燃料电池中第一阳极室、阴极室和第二阳极室的氨氮浓度变化示意图,图5为本发明实施例提供的微生物燃料电池中第一阳极室、阴极室和第二阳极室的硝态氮浓度变化示意图。从图4和图5中的氮素变化可以看出,氨氮从第一阳极室迁移至阴极室,阴极室的氨氮并没有积累而是快速地转化为硝酸根。此外,硝酸根从阴极室迁移至第二阳极室时,同样快速地发生了硝酸根的还原反应,致使第二阳极室的硝酸根浓度维持在较低水平。从图4和图5中还可以看出,阴极室的硝化反应和第二阳极室的反硝化反应的速率较快,没有底物积累。Fig. 4 is a schematic diagram showing the change of ammonia nitrogen concentration in the first anode chamber, the cathode chamber and the second anode chamber in the microbial fuel cell provided by the embodiment of the present invention, and Fig. 5 is the first anode chamber and the cathode of the microbial fuel cell provided by the embodiment of the present invention Schematic diagram of the change of nitrate nitrogen concentration in the chamber and the second anode chamber. It can be seen from the nitrogen changes in Figures 4 and 5 that ammonia nitrogen migrates from the first anode chamber to the cathode chamber, and the ammonia nitrogen in the cathode chamber does not accumulate but is rapidly converted into nitrate. In addition, when nitrate migrates from the cathode compartment to the second anode compartment, the reduction reaction of nitrate also occurs rapidly, so that the nitrate concentration in the second anode compartment is maintained at a low level. It can also be seen from Figures 4 and 5 that the nitrification reaction in the cathode compartment and the denitrification reaction in the second anode compartment are at a faster rate without substrate accumulation.
本发明实施例提供的一种微生物燃料电池,结构简单,易操作,在废水中有机物有效去除的基础上,还确保了废水中氮素的有效去除,还可以有效防止非生物催化剂的脱落和流失,延长阴极的有效使用寿命,从而降低微生物燃料电池的成本。The microbial fuel cell provided by the embodiment of the present invention has a simple structure and is easy to operate. On the basis of the effective removal of organic matter in the wastewater, it also ensures the effective removal of nitrogen in the wastewater, and can also effectively prevent the abiotic catalyst from falling off and running off. , extending the effective life of the cathode, thereby reducing the cost of microbial fuel cells.
在本发明的上述实施例中,对各个实施例的描述都各有侧重,某个实施例中没有详述的部分,可以参见其他实施例的相关描述。In the above-mentioned embodiments of the present invention, the description of each embodiment has its own emphasis. For parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.
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