CN110451630B - A device and method for electrochemically assisted strengthening of biofilm formation with functions of generating electricity and removing organic chlorine - Google Patents

A device and method for electrochemically assisted strengthening of biofilm formation with functions of generating electricity and removing organic chlorine Download PDF

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CN110451630B
CN110451630B CN201910689179.9A CN201910689179A CN110451630B CN 110451630 B CN110451630 B CN 110451630B CN 201910689179 A CN201910689179 A CN 201910689179A CN 110451630 B CN110451630 B CN 110451630B
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titanium wire
anode
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graphite felt
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李浩然
王俊杰
冯雅丽
杜竹玮
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CHINA OCEAN MINERAL RESOURCES R&D ASSOCIATION
Institute of Process Engineering of CAS
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Abstract

本发明公开了一种电化学辅助强化具有产电和去除有机氯功能生物膜形成的装置及方法。所述装置中,阳极石墨毡置于电化学反应槽的槽底部,阴极石墨毡置于电化学反应槽的上端;阳极石墨毡与阳极钛丝相连,阴极石墨毡与阴极钛丝相连,阳极钛丝和阴极钛丝分别与外接电阻、电压数据采集系统和线性直流电源相连;外接电阻、电压数据采集系统和线性直流电源的三者之间采用并联结构;阳极钛丝或阴极钛丝与外接电阻的连接线上设置电阻开关;阳极钛丝或阴极钛丝与电压数据采集系统的连接线上设置电压数据采集系统开关;阳极钛丝或阴极钛丝与线性直流电源的连接线上设置电源开关;隔绝管套设于阳极钛丝上。本发明具有运行成本低、操作条件方便等优势。

Figure 201910689179

The invention discloses a device and a method for electrochemically assisted strengthening of biofilm formation with functions of generating electricity and removing organic chlorine. In the device, the anode graphite felt is placed at the bottom of the electrochemical reaction tank, and the cathode graphite felt is placed at the upper end of the electrochemical reaction tank; the anode graphite felt is connected to the anode titanium wire, the cathode graphite felt is connected to the cathode titanium wire, and the anode titanium felt is connected to the anode titanium wire. The wire and the cathode titanium wire are respectively connected with the external resistance, the voltage data acquisition system and the linear DC power supply; the external resistance, the voltage data acquisition system and the linear DC power supply adopt a parallel structure; the anode titanium wire or the cathode titanium wire is connected with the external resistance The resistance switch is set on the connection line of the anode titanium wire or the cathode titanium wire and the voltage data acquisition system switch is set on the connection line; the power switch is set on the connection line between the anode titanium wire or the cathode titanium wire and the linear DC power supply; The isolation tube is sleeved on the anode titanium wire. The invention has the advantages of low operating cost, convenient operating conditions and the like.

Figure 201910689179

Description

一种电化学辅助强化具有产电和去除有机氯功能生物膜形成 的装置及方法A device and method for electrochemically assisted strengthening of biofilm formation with functions of generating electricity and removing organic chlorine

技术领域technical field

本发明属于污水处理领域,具体涉及一种电化学辅助强化具有特定功能的微生物燃料电池阳极生物膜形成的装置及方法。The invention belongs to the field of sewage treatment, and in particular relates to a device and a method for electrochemically assisting the formation of an anode biofilm of a microbial fuel cell with specific functions.

背景技术Background technique

有机氯代化合物是一类有机物中的氢原子被氯原子取代,是以碳或烃为骨架、与氯原子相结合的一系列元素有机化合物的总称,包括氯代烷烃、氯代烯烃以及氯代芳香烃。这些有机氯代化合物具有独特的物理和化学性质,被广泛应用于化工、电子、制革、农药等行业。例如氯代烃(二氯甲烷、三氯乙烯、四氯乙烯等)作为一类重要的有机溶剂和产品中间体,被广泛应用于机械制造、电子元件清洗、化学化工等过程中。除此之外,氯代烃在有机合成中起着重要的桥梁作用。由于氯代烃化学性质比较活泼,能发生取代、消除反应,化合物中引入氯原子可以实现其分子性能的改变。最后,氯代化合物又具有一定的毒性,例如有机氯农药曾广泛应用于农业生产防治植物病及虫害,在一定时期内促进了我国农业的发展。然而,氯代化合物具有一定的抗降解性和毒性,其碳-氯键对水解非常稳定,并且氯取代(官能团)的数目越大,对生物降解和光解的抗性越大,在给人类造福的同时,也给人类的生存及生命质量带来了不良影响,甚至危害。Organochlorinated compounds are a class of organic compounds whose hydrogen atoms are replaced by chlorine atoms, and are a general term for a series of elemental organic compounds with carbon or hydrocarbon skeletons combined with chlorine atoms, including chlorinated alkanes, chlorinated alkenes, and chlorinated alkanes. Aromatic hydrocarbons. These organochlorinated compounds have unique physical and chemical properties and are widely used in chemical, electronic, leather, pesticide and other industries. For example, chlorinated hydrocarbons (dichloromethane, trichloroethylene, tetrachloroethylene, etc.), as a class of important organic solvents and product intermediates, are widely used in machinery manufacturing, electronic component cleaning, chemical and chemical processes. Besides, chlorinated hydrocarbons play an important bridge role in organic synthesis. Due to the relatively active chemical properties of chlorinated hydrocarbons, substitution and elimination reactions can occur, and the introduction of chlorine atoms into compounds can change their molecular properties. Finally, chlorinated compounds have certain toxicity. For example, organochlorine pesticides have been widely used in agricultural production to control plant diseases and insect pests, which has promoted the development of my country's agriculture for a certain period of time. However, chlorinated compounds have certain resistance to degradation and toxicity, their carbon-chlorine bonds are very stable to hydrolysis, and the greater the number of chlorine substitutions (functional groups), the greater the resistance to biodegradation and photolysis, which is beneficial to human beings. At the same time, it also brings adverse effects and even harm to human survival and quality of life.

有机氯污染物的去除方法有很多种,主要包括物理方法、化学方法和生物方法。物理法并不能实现氯代有机物的降解,仅是将污染物从一相转移到另一相,同时还会造成二次污染,成本高,不适合实际应用。化学方法条件严苛,且易产生二次污染;生物方法受pH、温度环境因素的影响较大,因此对水质及环境条件要求较高。There are many methods for the removal of organochlorine pollutants, including physical methods, chemical methods and biological methods. The physical method cannot achieve the degradation of chlorinated organics, but only transfers the pollutants from one phase to another, and also causes secondary pollution, which is costly and unsuitable for practical applications. Chemical methods have harsh conditions and are prone to secondary pollution; biological methods are greatly affected by pH and temperature environmental factors, so they have higher requirements on water quality and environmental conditions.

生物电化学系统是环境工程领域近年来新兴的废水处理手段,微生物燃料电池通过微生物作为催化剂,将废水中的有机底物进行分解代谢,同时将底物中的化学能转化为电子、质子和阴极的最终电子受体进行结合,完成最终的反应过程。然而单纯微生物燃料电池的启动时间较长,微生物燃料电池的启动需要在阳极表面形成具有产电功能的生物膜,对于需要进行特殊废水处理的微生物燃料电池,还需要对阳极的产电微生物进行驯化,使其具有某种特殊功能。本发明采用电化学辅助方法强化具有特定功能的阳极生物膜的形成、缩短微生物燃料电池启动周期。利用形成的阳极生物膜构建微生物燃料电池处理难降解的有机氯废水,可有效地实现有机氯的去除。Bioelectrochemical system is an emerging wastewater treatment method in the field of environmental engineering in recent years. Microbial fuel cells use microorganisms as catalysts to catabolize organic substrates in wastewater, and at the same time convert chemical energy in substrates into electrons, protons and cathodes. The final electron acceptor binds to complete the final reaction process. However, the start-up time of a simple microbial fuel cell is long, and the start-up of a microbial fuel cell requires the formation of a biofilm with electricity-generating function on the surface of the anode. For microbial fuel cells that require special wastewater treatment, it is also necessary to domesticate the electricity-producing microorganisms on the anode. , so that it has some special function. The invention adopts the electrochemical auxiliary method to strengthen the formation of the anode biofilm with specific functions, and shorten the start-up period of the microbial fuel cell. Using the formed anode biofilm to construct a microbial fuel cell to treat refractory organochlorine wastewater can effectively remove organochlorine.

发明内容SUMMARY OF THE INVENTION

本发明的目的在于,提供一种电化学辅助强化具有产电和去除有机氯功能生物膜形成的装置及方法,采用电化学辅助强化具有产电、去除有机氯功能的生物膜的形成并将其应用于处理难降解的有机含氯废水。The purpose of the present invention is to provide a device and method for electrochemically assisted strengthening of the biofilm formation with functions of generating electricity and removing organic chlorine, using electrochemical assistance to strengthen the formation of biofilms with functions of generating electricity and removing organic chlorine and making its It is applied to the treatment of refractory organic chlorine-containing wastewater.

为达到上述目的,本发明采用了如下的技术方案:To achieve the above object, the present invention has adopted the following technical scheme:

一种电化学辅助强化具有产电和去除有机氯功能生物膜形成的装置,所述装置包括电化学反应槽1、阳极石墨毡2、阴极石墨毡3、阴极钛丝4、外接电阻5、电压数据采集系统6、线性直流电源7、阳极钛丝8、隔绝管9、电源开关11、电压数据采集系统开关12和电阻开关13;A device for electrochemically assisted strengthening of biofilm formation with functions of generating electricity and removing organic chlorine, the device comprising an electrochemical reaction tank 1, an anode graphite felt 2, a cathode graphite felt 3, a cathode titanium wire 4, an external resistor 5, a voltage Data acquisition system 6, linear DC power supply 7, anode titanium wire 8, isolation tube 9, power switch 11, voltage data acquisition system switch 12 and resistance switch 13;

所述阳极石墨毡2置于电化学反应槽1的槽底部,所述阴极石墨毡3置于电化学反应槽1的上端;所述阳极石墨毡2与阳极钛丝8相连,所述阴极石墨毡3与阴极钛丝4相连,所述阳极钛丝8分别与外接电阻5、电压数据采集系统6和线性直流电源7相连,所述阴极钛丝4分别与外接电阻5、电压数据采集系统6和线性直流电源7相连;外接电阻5、电压数据采集系统6和线性直流电源7的三者之间采用并联结构;The anode graphite felt 2 is placed at the bottom of the electrochemical reaction tank 1, and the cathode graphite felt 3 is placed at the upper end of the electrochemical reaction tank 1; the anode graphite felt 2 is connected with the anode titanium wire 8, and the cathode graphite felt The felt 3 is connected to the cathode titanium wire 4, the anode titanium wire 8 is respectively connected to the external resistor 5, the voltage data acquisition system 6 and the linear DC power supply 7, and the cathode titanium wire 4 is respectively connected to the external resistor 5 and the voltage data acquisition system 6. It is connected with the linear DC power supply 7; the external resistor 5, the voltage data acquisition system 6 and the linear DC power supply 7 adopt a parallel structure;

所述阳极钛丝8或阴极钛丝4与外接电阻5的连接线上设置电阻开关13;A resistance switch 13 is provided on the connection line between the anode titanium wire 8 or the cathode titanium wire 4 and the external resistor 5;

所述阳极钛丝8或阴极钛丝4与电压数据采集系统6的连接线上设置电压数据采集系统开关12;A voltage data acquisition system switch 12 is provided on the connection line between the anode titanium wire 8 or the cathode titanium wire 4 and the voltage data acquisition system 6;

所述阳极钛丝8或阴极钛丝4与线性直流电源7的连接线上设置电源开关11;A power switch 11 is provided on the connection line between the anode titanium wire 8 or the cathode titanium wire 4 and the linear DC power supply 7;

所述隔绝管9套设于阳极钛丝8上。The isolation tube 9 is sleeved on the anode titanium wire 8 .

优选地,所述电化学反应槽1的上端敞口,槽底部密封。Preferably, the upper end of the electrochemical reaction tank 1 is open, and the bottom of the tank is sealed.

优选地,电化学反应槽采用有机玻璃制作,也可以采用其他制作材料。Preferably, the electrochemical reaction tank is made of plexiglass, and other materials may also be used.

优选地,隔绝管采用塑料制作,也可以采用其他制作材料。Preferably, the insulating tube is made of plastic, but other materials may also be used.

本发明还提供了一种电化学辅助强化具有产电和去除有机氯功能生物膜形成的方法,所述方法包括以下步骤:The present invention also provides a method for electrochemically assisted strengthening of biofilm formation with functions of generating electricity and removing organic chlorine, the method comprising the following steps:

1)将菌源和无机盐培养基配制为含菌无机盐培养液,含菌无机盐培养液加入电化学反应槽中,生物电化学体系pH为6~10,温度为15~45℃;1) The bacteria source and the inorganic salt medium are prepared into a bacteria-containing inorganic salt culture solution, and the bacteria-containing inorganic salt culture solution is added to an electrochemical reaction tank, the pH of the bioelectrochemical system is 6-10, and the temperature is 15-45°C;

2)微生物电解池体系条件下,在外加电压0.1V~0.8V条件下运行3~5天,在阳极石墨毡上形成具有产电功能的生物膜;2) Under the conditions of the microbial electrolysis cell system, run for 3 to 5 days under the condition of an applied voltage of 0.1V to 0.8V, and a biofilm with electricity generation function is formed on the anode graphite felt;

3)微生物燃料电池体系条件下,观测电池电压情况,待电压稳定,逐步提高含菌无机盐培养液中的有机氯浓度,重复步骤2)和3),对阳极石墨毡上形成的生物膜进行驯化,直至形成具有产电和去除有机氯功能的生物膜。3) Under the conditions of the microbial fuel cell system, observe the cell voltage, and when the voltage is stable, gradually increase the organic chlorine concentration in the bacterial-containing inorganic salt culture solution, repeat steps 2) and 3), and carry out the biofilm formed on the anode graphite felt. acclimatized until the formation of biofilms capable of generating electricity and removing organochlorine.

本发明中,所述菌源为海洋热液沉积物NO.21Ⅲ-S10-TVG6。In the present invention, the bacterial source is marine hydrothermal sediment NO.21III-S10-TVG6.

本发明中,所述有机氯为2,4,6-三氯苯酚。In the present invention, the organic chlorine is 2,4,6-trichlorophenol.

根据本发明的优选实施例,一种电化学辅助强化具有产电和去除有机氯功能的生物膜形成的方法,具体步骤如下:According to a preferred embodiment of the present invention, a method for electrochemically assisted strengthening of biofilm formation with functions of generating electricity and removing organic chlorine, the specific steps are as follows:

1)测量生物电化学装置体积,将菌源和无机盐培养基按1/4~1/3接入生物电化学装置,并加入10~20mM乙酸钠,生物电化学体系pH为6~10,温度为15~45℃;1) Measure the volume of the bioelectrochemical device, connect the bacterial source and inorganic salt medium to the bioelectrochemical device at 1/4 to 1/3, and add 10 to 20 mM sodium acetate, and the pH of the bioelectrochemical system is 6 to 10. The temperature is 15~45℃;

2)微生物电解池体系下,设置外加电压0.1V~0.8V,外加电压运行时间为3~5天;2) Under the microbial electrolysis cell system, the applied voltage is set to 0.1V-0.8V, and the operating time of the applied voltage is 3-5 days;

3)微生物燃料电池体系下观测电池电压情况,待电压稳定,提高无机盐培养基中的有机氯浓度,重复步骤2)、3),对正极石墨毡上形成的生物膜进行驯化,直至形成具有产电和去除一定浓度有机氯的生物膜。3) The cell voltage is observed under the microbial fuel cell system. After the voltage is stabilized, the concentration of organic chlorine in the inorganic salt medium is increased, and steps 2) and 3) are repeated to domesticate the biofilm formed on the positive electrode graphite felt until a Biofilms that generate electricity and remove certain concentrations of organic chlorine.

本发明中,当废水中2,4,6-三氯苯酚浓度为10~150mg/L,经本发明所述装置处理后的水体中的2,4,6-三氯苯酚的去除率可达85%以上,当废水中2,4,6-三氯苯酚浓度为150~600mg/L时,经本发明所述装置处理后的水体中的2,4,6-三氯苯酚的去除率可达45%以上。In the present invention, when the concentration of 2,4,6-trichlorophenol in the wastewater is 10-150 mg/L, the removal rate of 2,4,6-trichlorophenol in the water body treated by the device of the present invention can reach More than 85%, when the concentration of 2,4,6-trichlorophenol in the wastewater is 150-600 mg/L, the removal rate of 2,4,6-trichlorophenol in the water body treated by the device of the present invention can be improved. more than 45%.

本发明中,以海洋热液沉积物NO.21Ⅲ-S10-TVG6作为菌源,生物电化学体系pH为6~10,温度为15~45℃,闭合电源开关11,启动的微生物电解池系统,外加电压0.1V~0.8V,运行时间为3~5天;断开电源开关11,闭合电压数据采集系统开关12和电阻开关13监测系统的电压输出情况,当输出电压稳定运行后依次增加有机含氯化合物浓度30mg/L、50mg/L、150mg/L、300mg/L,闭合电源开关11,外加电压0.1V~0.8V,运行时间为3~5天,进一步筛选耐高浓度含氯有机化合物且能降解该含氯有机化合物的产电细菌;断开电源开关11,闭合电压数据采集系统开关12和电阻开关13监测系统的电压输出情况当输出电压稳定运行,即形成具有产电和去除有机氯功能的生物膜。利用微生物燃料电池系统对不同温度、不同初始pH、不同初始浓度的三氯苯酚溶液进行降解实验。表明温度为15~45℃条件,初始pH为6~10时,三氯苯酚溶液初始浓度为10~600mg/L,该生物电化学装置均可实现对三氯苯酚的高效降解。In the present invention, the marine hydrothermal sediment NO.21III-S10-TVG6 is used as the bacterial source, the pH of the bioelectrochemical system is 6-10, the temperature is 15-45°C, the power switch 11 is closed, and the microbial electrolysis cell system is activated, The applied voltage is 0.1V ~ 0.8V, and the running time is 3 ~ 5 days; disconnect the power switch 11, close the voltage data acquisition system switch 12 and the resistance switch 13 to monitor the voltage output of the system, and increase the organic content in turn when the output voltage is stable. The concentration of chlorine compounds is 30mg/L, 50mg/L, 150mg/L, 300mg/L, the power switch 11 is closed, the applied voltage is 0.1V~0.8V, and the running time is 3~5 days. The electricity-producing bacteria that can degrade the chlorine-containing organic compound; disconnect the power switch 11, close the voltage data acquisition system switch 12 and the resistance switch 13 to monitor the voltage output of the system. functional biofilm. The microbial fuel cell system was used to degrade trichlorophenol solutions with different temperatures, different initial pH and different initial concentrations. It is shown that when the temperature is 15-45 ℃, the initial pH is 6-10, and the initial concentration of trichlorophenol solution is 10-600 mg/L, the bioelectrochemical device can achieve high-efficiency degradation of p-trichlorophenol.

本发明通过对微生物燃料电池施加一定的电压,利用微生物等电点较低(通常为2~5),在pH高于等电点的条件下带负电的性质,可以有效实现微生物在正极石墨毡上的富集,促进产电微生物的代谢繁殖,从而在与外接电源正极相连的石墨毡上形成具有产电功能的生物膜。逐步提高氯代有机物的浓度,在微生物电解池体系对正极石墨毡上形成的生物膜进行驯化。利用形成生物膜的石墨毡作为阳极构建微生物燃料电池降解有机含氯化合物可有效地实现有机氯的去除。根据上述方法,形成了具有产电和降解2,4,6-三氯苯酚的生物膜的微生物燃料电池,在pH为6~10,温度为15~45℃,三氯苯酚浓度在10~600mg/L条件下,实现对2,4,6-三氯苯酚的高效降解。In the present invention, by applying a certain voltage to the microbial fuel cell, the microorganisms have a low isoelectric point (usually 2 to 5) and are negatively charged under the condition that the pH is higher than the isoelectric point, so that the microorganisms can effectively realize the positive electrode graphite felt. The enrichment on the surface promotes the metabolic reproduction of electricity-producing microorganisms, thereby forming a biofilm with electricity-producing function on the graphite felt connected to the positive electrode of the external power supply. The concentration of chlorinated organics was gradually increased, and the biofilm formed on the cathode graphite felt was acclimated in the microbial electrolysis cell system. The organic chlorine-containing compounds can be effectively removed by constructing a microbial fuel cell using the graphite felt forming the biofilm as the anode to degrade the organic chlorine-containing compounds. According to the above method, a microbial fuel cell with a biofilm that generates electricity and degrades 2,4,6-trichlorophenol is formed. Under the condition of /L, the efficient degradation of 2,4,6-trichlorophenol was achieved.

与现有技术相比,本发明具有如下优点:Compared with the prior art, the present invention has the following advantages:

1.外加电压有利于石墨毡上生物膜的快速富集形成,缩短启动周期。1. The applied voltage is conducive to the rapid enrichment and formation of biofilms on the graphite felt and shortens the start-up period.

2.形成的具有产电和去除有机氯功能的生物膜后,可直接在微生物燃料电池体系下对含氯有机废水进行降解。2. After the formed biofilm with the functions of generating electricity and removing organic chlorine, the chlorine-containing organic wastewater can be degraded directly under the microbial fuel cell system.

3.利用本发明中的装置和方法驯化具有产电和去除2,4,6-三氯苯酚的生物膜并构建微生物燃料电池,150mg/L的三氯苯酚废水的去除率可达89%以上,600mg/L的三氯苯酚废水的去除率可达45%以上。3. Using the device and method of the present invention to domesticate a biofilm with electricity generation and removal of 2,4,6-trichlorophenol and construct a microbial fuel cell, the removal rate of 150 mg/L trichlorophenol wastewater can reach more than 89% , the removal rate of 600mg/L trichlorophenol wastewater can reach more than 45%.

附图说明Description of drawings

图1本发明电化学辅助强化具有产电和去除有机氯功能生物膜形成的装置的结构示意图;1 is a schematic structural diagram of the device of the present invention for electrochemically assisted strengthening of the biofilm formation with the functions of generating electricity and removing organic chlorine;

图2为实施例2中不同外加电压条件下微生物燃料电池的电压变化情况;Fig. 2 is the voltage change situation of microbial fuel cell under different applied voltage conditions in Example 2;

图3为实施例6中不同温度对2,4,6-三氯苯酚降解的影响曲线图;3 is a graph showing the effect of different temperatures on the degradation of 2,4,6-trichlorophenol in Example 6;

图4为实施例6中不同初始pH对2,4,6-三氯苯酚降解的影响曲线图;4 is a graph showing the effect of different initial pH on the degradation of 2,4,6-trichlorophenol in Example 6;

图5为实施例6中不同2,4,6-三氯苯酚初始浓度对2,4,6-三氯苯酚降解的影响曲线图;Figure 5 is a graph showing the effect of different initial concentrations of 2,4,6-trichlorophenol on the degradation of 2,4,6-trichlorophenol in Example 6;

附图标记:Reference number:

1、电化学反应槽;2、阳极石墨毡;3、阴极石墨毡;4、阴极钛丝;5、外接电阻;6、电压数据采集系统;7、线性直流电源;8、阳极钛丝;9、隔绝管;10、含菌无机盐培养液;11、电源开关;12、电压数据采集系统开关;13、电阻开关。1. Electrochemical reaction tank; 2. Anode graphite felt; 3. Cathode graphite felt; 4. Cathode titanium wire; 5. External resistor; 6. Voltage data acquisition system; 7. Linear DC power supply; 8. Anode titanium wire; 9 , isolation tube; 10, bacteria-containing inorganic salt culture solution; 11, power switch; 12, voltage data acquisition system switch; 13, resistance switch.

具体实施方式Detailed ways

本说明书中公开得任一特征,除非特别叙述,均可被其他等效或具有类似目的的替代特征加以替换。除非特别叙述,每个特征只是一系列等效或者类似特征中的一个例子而已。所述仅仅是为了帮助理解本发明,不应该视为对本发明的具体限制。Any feature disclosed in this specification, unless expressly stated otherwise, may be replaced by other equivalent or alternative features serving a similar purpose. Unless stated otherwise, each feature is only one example of a series of equivalent or similar features. The description is only for helping understanding of the present invention and should not be regarded as a specific limitation of the present invention.

下面以附图和具体实施方式对本发明作进一步详细的说明。The present invention will be described in further detail below with the accompanying drawings and specific embodiments.

实施例1Example 1

如图1所示,一种电化学辅助强化具有产电和去除有机氯功能生物膜形成的装置,所述装置包括电化学反应槽1、阳极石墨毡2、阴极石墨毡3、阴极钛丝4、外接电阻5、电压数据采集系统6、线性直流电源7、阳极钛丝8、隔绝管9、电源开关11、电压数据采集系统开关12和电阻开关13;As shown in Figure 1, a device for electrochemically assisted strengthening of biofilm formation with functions of generating electricity and removing organic chlorine, the device comprises an electrochemical reaction tank 1, an anode graphite felt 2, a cathode graphite felt 3, and a cathode titanium wire 4 , external resistor 5, voltage data acquisition system 6, linear DC power supply 7, anode titanium wire 8, isolation tube 9, power switch 11, voltage data acquisition system switch 12 and resistance switch 13;

所述阳极石墨毡2置于电化学反应槽1的槽底部,所述阴极石墨毡3置于电化学反应槽1的上端;所述阳极石墨毡2与阳极钛丝8相连,所述阴极石墨毡3与阴极钛丝4相连,所述阳极钛丝8分别与外接电阻5、电压数据采集系统6和线性直流电源7相连,所述阴极钛丝4分别与外接电阻5、电压数据采集系统6和线性直流电源7相连;外接电阻5、电压数据采集系统6和线性直流电源7的三者之间采用并联结构;The anode graphite felt 2 is placed at the bottom of the electrochemical reaction tank 1, and the cathode graphite felt 3 is placed at the upper end of the electrochemical reaction tank 1; the anode graphite felt 2 is connected with the anode titanium wire 8, and the cathode graphite felt The felt 3 is connected to the cathode titanium wire 4, the anode titanium wire 8 is respectively connected to the external resistor 5, the voltage data acquisition system 6 and the linear DC power supply 7, and the cathode titanium wire 4 is respectively connected to the external resistor 5 and the voltage data acquisition system 6. It is connected with the linear DC power supply 7; the external resistor 5, the voltage data acquisition system 6 and the linear DC power supply 7 adopt a parallel structure;

所述阳极钛丝8或阴极钛丝4与外接电阻5的连接线上设置电阻开关13;A resistance switch 13 is provided on the connection line between the anode titanium wire 8 or the cathode titanium wire 4 and the external resistor 5;

所述阳极钛丝8或阴极钛丝4与电压数据采集系统6的连接线上设置电压数据采集系统开关12;A voltage data acquisition system switch 12 is provided on the connection line between the anode titanium wire 8 or the cathode titanium wire 4 and the voltage data acquisition system 6;

所述阳极钛丝8或阴极钛丝4与线性直流电源7的连接线上设置电源开关11;A power switch 11 is provided on the connection line between the anode titanium wire 8 or the cathode titanium wire 4 and the linear DC power supply 7;

所述隔绝管9套设于阳极钛丝8上。The isolation tube 9 is sleeved on the anode titanium wire 8 .

所述电化学反应槽1的上端敞口,槽底部密封,电化学反应槽采用有机玻璃制作,隔绝管采用塑料制作。The upper end of the electrochemical reaction tank 1 is open, the bottom of the tank is sealed, the electrochemical reaction tank is made of plexiglass, and the isolation tube is made of plastic.

本发明电化学反应槽内装有含菌无机盐培养液(或含有机氯废水)10,本发明装置当电源开关11处于闭合而电压数据采集系统开关12和电阻开关13处于断开状态时为微生物电解池,有利于生物膜的强化;当电源开关11处于断开而电压数据采集系统开关12和电阻开关13处于闭合状态时为微生物燃料电池,用于处理难降解的有机氯废水。The electrochemical reaction tank of the present invention is equipped with a bacterial-containing inorganic salt culture solution (or waste water containing organic chlorine) 10. When the power switch 11 of the present invention is closed and the voltage data acquisition system switch 12 and the resistance switch 13 are in an open state, the microorganisms are The electrolytic cell is beneficial to the strengthening of the biofilm; when the power switch 11 is turned off and the voltage data acquisition system switch 12 and the resistance switch 13 are turned on, it is a microbial fuel cell, which is used to treat the refractory organochlorine wastewater.

以下实施例中以海洋热液沉积物NO.21Ⅲ-S10-TVG6作为菌源(该菌源为已知菌源,在中国专利CN104894004B中已公开),闭合电源开关11,启动的微生物电解池系统,两极间的恒定电压0.2V,在该电压条件下运行3天;断开电源开关11,闭合电压数据采集系统开关12和电阻开关13监测系统的电压输出情况,当输出电压稳定运行后依次增加有机含氯化合物浓度30mg/L、50mg/L、150mg/L、300mg/L,闭合电源开关11,在电压0.1~0.8V条件下运行3~5天,进一步筛选耐高浓度含氯有机化合物且能降解该含氯有机化合物的产电细菌;断开电源开关11,闭合电压数据采集系统开关12和电阻13监测系统的电压输出情况,当输出电压稳定运行,即形成具有产电和去除有机氯功能的生物膜。利用形成的生物膜在微生物燃料电池体系对有机含氯废水进行降解。In the following examples, the marine hydrothermal sediment NO.21III-S10-TVG6 is used as the bacterial source (this bacterial source is a known bacterial source, which has been disclosed in Chinese patent CN104894004B), the power switch 11 is closed, and the microbial electrolysis cell system is activated. , the constant voltage between the two poles is 0.2V, and it will run for 3 days under this voltage condition; disconnect the power switch 11, close the voltage data acquisition system switch 12 and the resistance switch 13 to monitor the voltage output of the system, and increase in turn when the output voltage runs steadily. The concentration of organic chlorine-containing compounds is 30mg/L, 50mg/L, 150mg/L, 300mg/L, close the power switch 11, and run for 3-5 days under the condition of voltage 0.1-0.8V, and further screen the resistance to high-concentration chlorine-containing organic compounds and The electricity-producing bacteria that can degrade the chlorine-containing organic compound; turn off the power switch 11, close the voltage data acquisition system switch 12 and the resistor 13 to monitor the voltage output of the system, when the output voltage runs stably, it forms a power generation and removal of organic chlorine. functional biofilm. The formed biofilm is used to degrade organic chlorine-containing wastewater in a microbial fuel cell system.

实施例2Example 2

采用实施例1生物电化学的装置,测量生物电化学装置体积,将菌源和无机盐培养基按体积比1:3接入生物电化学装置,并加入20mM乙酸钠。在微生物电解池体系下,分别设置外加电压0.1V条件下运行5天、0.4V条件下运行4天、0.8V条件下运行3天,运行相应时间后在微生物燃料电池体系下运行并观察微生物燃料电池电压变化情况。不同外加电压条件下微生物燃料电池的电压变化情况如图2所示。The bioelectrochemical device of Example 1 was used, the volume of the bioelectrochemical device was measured, the bacterial source and the inorganic salt medium were connected to the bioelectrochemical device in a volume ratio of 1:3, and 20 mM sodium acetate was added. Under the microbial electrolysis cell system, set the applied voltage to run for 5 days under the condition of 0.1V, 4 days under the condition of 0.4V, and 3 days under the condition of 0.8V. Changes in battery voltage. The voltage changes of the microbial fuel cell under different applied voltage conditions are shown in Figure 2.

结果表明,电化学辅助强化有利于石墨毡上生物膜的快速富集形成,缩短微生物燃料电池启动周期。The results show that electrochemical-assisted strengthening is beneficial to the rapid enrichment and formation of biofilms on graphite felt and shortens the start-up period of microbial fuel cells.

实施例3Example 3

采用实施例1生物电化学的装置,测量生物电化学装置体积,将菌源和无机盐培养基按体积比1:3接入生物电化学装置,并加入20mM乙酸钠。在微生物电解池体系下,设置外加电压0.1V,运行时间为5天。微生物燃料电池体系下观测电池电压情况,待电压稳定,提高无机盐培养基中的2,4,6-三氯苯酚浓度,在微生物电解池体系下,设置外加电压0.1V,运行时间为5天,对正极石墨毡上形成的生物膜进行驯化,微生物燃料电池体系下观测电池电压情况,待电压稳定,即形成具有产电和去除一定浓度2,4,6-三氯苯酚的生物膜。生物电化学装置控制温度为25℃,初始pH为7。三氯苯酚初始浓度控制为10mg/L。The bioelectrochemical device of Example 1 was used, the volume of the bioelectrochemical device was measured, the bacterial source and the inorganic salt medium were connected to the bioelectrochemical device in a volume ratio of 1:3, and 20 mM sodium acetate was added. Under the microbial electrolysis cell system, the applied voltage was set to 0.1V, and the running time was 5 days. The cell voltage was observed under the microbial fuel cell system. After the voltage was stable, the concentration of 2,4,6-trichlorophenol in the inorganic salt medium was increased. Under the microbial electrolysis cell system, the applied voltage was set to 0.1V, and the running time was 5 days. , domesticate the biofilm formed on the cathode graphite felt, observe the cell voltage under the microbial fuel cell system, and when the voltage stabilizes, a biofilm with electricity generation and removal of a certain concentration of 2,4,6-trichlorophenol is formed. The bioelectrochemical device was controlled at a temperature of 25 °C and an initial pH of 7. The initial concentration of trichlorophenol was controlled at 10 mg/L.

结果表明,电化学辅助强化具有产电和脱氯功能的生物膜在微生物燃料电池系统对2,4,6-三氯苯酚有较好的降解效果,降解效果可达90%以上。The results show that electrochemically assisted biofilms with the functions of electricity generation and dechlorination have a good degradation effect on 2,4,6-trichlorophenol in the microbial fuel cell system, and the degradation effect can reach more than 90%.

实施例4Example 4

采用实施例1生物电化学的装置,测量生物电化学装置体积,将菌源和无机盐培养基按体积比1:3接入生物电化学装置,并加入10mM乙酸钠。在微生物电解池体系下,设置外加电压0.4V,运行时间为4天。微生物燃料电池体系下观测电池电压情况,待电压稳定,提高无机盐培养基中的2,4,6-三氯苯酚浓度,在微生物电解池体系下,设置外加电压0.4V,运行时间为4天,对正极石墨毡上形成的生物膜进行驯化,微生物燃料电池体系下观测电池电压情况,待电压稳定,即形成具有产电和去除一定浓度2,4,6-三氯苯酚的生物膜。生物电化学装置控制温度为25℃,初始pH为7。三氯苯酚初始浓度控制为150mg/L。The bioelectrochemical device of Example 1 was used, the volume of the bioelectrochemical device was measured, the bacterial source and the inorganic salt medium were connected to the bioelectrochemical device in a volume ratio of 1:3, and 10 mM sodium acetate was added. Under the microbial electrolysis cell system, the applied voltage was set to 0.4V, and the running time was 4 days. The cell voltage was observed under the microbial fuel cell system. After the voltage was stable, the concentration of 2,4,6-trichlorophenol in the inorganic salt medium was increased. Under the microbial electrolysis cell system, the applied voltage was set to 0.4V, and the running time was 4 days. , domesticate the biofilm formed on the cathode graphite felt, observe the cell voltage under the microbial fuel cell system, and when the voltage stabilizes, a biofilm with electricity generation and removal of a certain concentration of 2,4,6-trichlorophenol is formed. The bioelectrochemical device was controlled at a temperature of 25 °C and an initial pH of 7. The initial concentration of trichlorophenol was controlled at 150 mg/L.

结果表明,电化学辅助强化具有产电和脱氯功能的生物膜在微生物燃料电池系统对2,4,6-三氯苯酚有较好的降解效果,降解效果可达80%以上。The results show that electrochemically assisted biofilm with the functions of electricity generation and dechlorination has a good degradation effect on 2,4,6-trichlorophenol in the microbial fuel cell system, and the degradation effect can reach more than 80%.

实施例5Example 5

采用实施例1生物电化学的装置,测量生物电化学装置体积,将菌源和无机盐培养基按体积比1:4接入生物电化学装置,并加入20mM乙酸钠。在微生物电解池体系下,设置外加电压0.8V,运行时间为3天。微生物燃料电池体系下观测电池电压情况,待电压稳定,提高无机盐培养基中的2,4,6-三氯苯酚浓度,在微生物电解池体系下,设置外加电压0.8V,运行时间为3天,对正极石墨毡上形成的生物膜进行驯化,微生物燃料电池体系下观测电池电压情况,待电压稳定,即形成具有产电和去除一定浓度2,4,6-三氯苯酚的生物膜。生物电化学装置控制温度为25℃,初始pH为7。三氯苯酚初始浓度控制为300mg/L。The bioelectrochemical device of Example 1 was used, the volume of the bioelectrochemical device was measured, the bacterial source and the inorganic salt medium were connected to the bioelectrochemical device in a volume ratio of 1:4, and 20 mM sodium acetate was added. Under the microbial electrolysis cell system, the applied voltage was set to 0.8V, and the running time was 3 days. The cell voltage was observed under the microbial fuel cell system. After the voltage was stable, the concentration of 2,4,6-trichlorophenol in the inorganic salt medium was increased. Under the microbial electrolysis cell system, the applied voltage was set to 0.8V, and the running time was 3 days. , domesticate the biofilm formed on the cathode graphite felt, observe the cell voltage under the microbial fuel cell system, and when the voltage stabilizes, a biofilm with electricity generation and removal of a certain concentration of 2,4,6-trichlorophenol is formed. The bioelectrochemical device was controlled at a temperature of 25 °C and an initial pH of 7. The initial concentration of trichlorophenol was controlled at 300 mg/L.

结果表明,电化学辅助强化具有产电和脱氯功能的生物膜在微生物燃料电池系统对2,4,6-三氯苯酚有较好的降解效果,降解效果可达45%以上。The results show that electrochemically assisted biofilms with the functions of electricity generation and dechlorination have a good degradation effect on 2,4,6-trichlorophenol in the microbial fuel cell system, and the degradation effect can reach more than 45%.

实施例6Example 6

采用实施例1生物电化学的装置,测量生物电化学装置体积,将菌源和无机盐培养基按体积比1:3接入生物电化学装置,并加入20mM乙酸钠。在微生物电解池体系下,设置外加电压0.2V,运行时间为5天。微生物燃料电池体系下观测电池电压情况,待电压稳定,提高无机盐培养基中的2,4,6-三氯苯酚浓度,在微生物电解池体系下,设置外加电压0.2V,运行时间为5天,对正极石墨毡上形成的生物膜进行驯化,微生物燃料电池体系下观测电池电压情况,待电压稳定,即形成具有产电和去除一定浓度2,4,6-三氯苯酚的生物膜。生物电化学装置控制温度为15~45℃,初始pH为6~10。三氯苯酚初始浓度控制为30~600mg/L。分别考察不同温度、不同初始pH条件、不同三氯苯酚初始浓度对三氯苯酚降解的影响,结果如图3-5所示。The bioelectrochemical device of Example 1 was used, the volume of the bioelectrochemical device was measured, the bacterial source and the inorganic salt medium were connected to the bioelectrochemical device in a volume ratio of 1:3, and 20 mM sodium acetate was added. Under the microbial electrolysis cell system, the applied voltage was set to 0.2V, and the running time was 5 days. The cell voltage was observed in the microbial fuel cell system. After the voltage was stable, the concentration of 2,4,6-trichlorophenol in the inorganic salt medium was increased. In the microbial electrolysis cell system, the applied voltage was set to 0.2V, and the running time was 5 days. , domesticate the biofilm formed on the cathode graphite felt, observe the cell voltage under the microbial fuel cell system, and when the voltage stabilizes, a biofilm with electricity generation and removal of a certain concentration of 2,4,6-trichlorophenol is formed. The temperature of the bioelectrochemical device was controlled to be 15-45 °C, and the initial pH was 6-10. The initial concentration of trichlorophenol is controlled to be 30-600 mg/L. The effects of different temperatures, different initial pH conditions, and different initial concentrations of trichlorophenol on the degradation of trichlorophenol were investigated, and the results are shown in Figure 3-5.

从图3-5可以看出,对于初始浓度为50mg/L的三氯苯酚溶液,生物电化学装置温度为15~45℃、初始pH为6~10时,对三氯苯酚的降解率均在80%以上。在生物电化学装置温度在25℃、初始pH为7时,当三氯苯酚初始浓度低于150mg/L时三氯苯酚废水的去除率可达89%以上,当三氯苯酚初始浓度为600mg/L的三氯苯酚废水的去除率可达45%以上。As can be seen from Figure 3-5, for the trichlorophenol solution with an initial concentration of 50 mg/L, when the temperature of the bioelectrochemical device is 15-45 °C and the initial pH is 6-10, the degradation rates of p-trichlorophenol are all in the more than 80%. When the temperature of the bioelectrochemical device is 25℃ and the initial pH is 7, when the initial concentration of trichlorophenol is lower than 150mg/L, the removal rate of trichlorophenol wastewater can reach more than 89%, and when the initial concentration of trichlorophenol is 600mg/L The removal rate of L trichlorophenol wastewater can reach more than 45%.

本发明的工艺参数(如温度、时间等)区间上下限取值以及区间值都能实现本法,在此不一一列举实施例。The process parameters (such as temperature, time, etc.) of the present invention can implement the method by setting the upper and lower limits of the interval and the interval value, and the embodiments are not listed one by one here.

本发明未详细说明的内容均可采用本领域的常规技术知识。For the content not described in detail in the present invention, conventional technical knowledge in the field can be used.

最后所应说明的是,以上实施例仅用以说明本发明的技术方案而非限制。尽管参照实施例对本发明进行了详细说明,本领域的普通技术人员应该理解,对本发明的技术方案进行修改或者等同替换,都不脱离本发明技术方案的精神和范围,其均应涵盖在本发明的权利要求范围当中。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the embodiments, those of ordinary skill in the art should understand that any modification or equivalent replacement of the technical solutions of the present invention will not depart from the spirit and scope of the technical solutions of the present invention, and should be included in the present invention. within the scope of the claims.

Claims (5)

1.一种电化学辅助强化具有产电和去除有机氯功能生物膜形成的方法,其特征在于,所述方法采用如下装置形成具有产电和去除有机氯功能生物膜,所述装置包括电化学反应槽(1)、阳极石墨毡(2)、阴极石墨毡(3)、阴极钛丝(4)、外接电阻(5)、电压数据采集系统(6)、线性直流电源(7)、阳极钛丝(8)、隔绝管(9)、电源开关(11)、电压数据采集系统开关(12)和电阻开关(13);1. a kind of electrochemically assisted strengthening has the method for generating electricity and removing organic chlorine function biofilm, it is characterized in that, described method adopts following device to form biofilm with electricity generating and removing organic chlorine function, and described device comprises electrochemical Reaction tank (1), anode graphite felt (2), cathode graphite felt (3), cathode titanium wire (4), external resistor (5), voltage data acquisition system (6), linear DC power supply (7), anode titanium wire (8), isolation tube (9), power switch (11), voltage data acquisition system switch (12) and resistance switch (13); 所述阳极石墨毡(2)置于电化学反应槽(1)的槽底部,所述阴极石墨毡(3)置于电化学反应槽(1)的上端;所述阳极石墨毡(2)与阳极钛丝(8)相连,所述阴极石墨毡(3)与阴极钛丝(4)相连,所述阳极钛丝(8)分别与外接电阻(5)、电压数据采集系统(6)和线性直流电源(7)相连,所述阴极钛丝(4)分别与外接电阻(5)、电压数据采集系统(6)和线性直流电源(7)相连;外接电阻(5)、电压数据采集系统(6)和线性直流电源(7)的三者之间采用并联结构;The anode graphite felt (2) is placed at the bottom of the electrochemical reaction tank (1), and the cathode graphite felt (3) is placed at the upper end of the electrochemical reaction tank (1); the anode graphite felt (2) and the The anode titanium wire (8) is connected, the cathode graphite felt (3) is connected with the cathode titanium wire (4), and the anode titanium wire (8) is respectively connected with an external resistor (5), a voltage data acquisition system (6) and a linear A DC power supply (7) is connected, and the cathode titanium wire (4) is respectively connected with an external resistor (5), a voltage data acquisition system (6) and a linear DC power supply (7); the external resistor (5), the voltage data acquisition system ( 6) A parallel structure is adopted between the three of the linear DC power supply (7); 所述阳极钛丝(8)或阴极钛丝(4)与外接电阻(5)的连接线上设置电阻开关(13);A resistance switch (13) is arranged on the connection line between the anode titanium wire (8) or the cathode titanium wire (4) and the external resistor (5); 所述阳极钛丝(8)或阴极钛丝(4)与电压数据采集系统(6)的连接线上设置电压数据采集系统开关(12);A voltage data acquisition system switch (12) is provided on the connection line between the anode titanium wire (8) or the cathode titanium wire (4) and the voltage data acquisition system (6); 所述阳极钛丝(8)或阴极钛丝(4)与线性直流电源(7)的连接线上设置电源开关(11);A power switch (11) is provided on the connection line between the anode titanium wire (8) or the cathode titanium wire (4) and the linear DC power supply (7); 所述隔绝管(9)套设于阳极钛丝(8)上;The isolation tube (9) is sleeved on the anode titanium wire (8); 所述方法包括以下步骤:The method includes the following steps: 1)将菌源和无机盐培养基配制为含菌无机盐培养液,含菌无机盐培养液加入电化学反应槽中,生物电化学体系pH为6~10,温度为15~45℃;1) The bacteria source and the inorganic salt medium are prepared into a bacteria-containing inorganic salt culture solution, the bacteria-containing inorganic salt culture solution is added to the electrochemical reaction tank, the pH of the bioelectrochemical system is 6~10, and the temperature is 15~45℃; 2)微生物电解池体系条件下,在外加电压0.1V~0.8V条件下运行3~5天,在阳极石墨毡上形成具有产电功能的生物膜;2) Under the condition of microbial electrolysis cell system, under the condition of applied voltage of 0.1V~0.8V for 3~5 days, a biofilm with electricity generation function is formed on the anode graphite felt; 3)微生物燃料电池体系条件下,观测电池电压情况,待电压稳定,逐步提高含菌无机盐培养液中的有机氯浓度,重复步骤2)和3),对阳极石墨毡上形成的生物膜进行驯化,直至形成具有产电和去除有机氯功能的生物膜。3) Under the conditions of the microbial fuel cell system, observe the voltage of the cell, and after the voltage is stable, gradually increase the concentration of organic chlorine in the bacterial-containing inorganic salt culture solution, repeat steps 2) and 3), and carry out the biofilm formed on the anode graphite felt. acclimatized until the formation of biofilms capable of generating electricity and removing organochlorine. 2.根据权利要求1所述的方法,其特征在于,所述电化学反应槽(1)的上端敞口,槽底部密封。2 . The method according to claim 1 , wherein the upper end of the electrochemical reaction tank ( 1 ) is open, and the bottom of the tank is sealed. 3 . 3.根据权利要求1所述的方法,其特征在于,所述菌源取自海洋热液沉积物NO.21Ⅲ-S10-TVG6。3 . The method according to claim 1 , wherein the bacterial source is obtained from marine hydrothermal sediment NO.21III-S10-TVG6. 4 . 4.根据权利要求1所述的方法,其特征在于,所述有机氯为2,4,6-三氯苯酚。4. The method according to claim 1, wherein the organic chlorine is 2,4,6-trichlorophenol. 5.根据权利要求1所述的方法,其特征在于,菌源和无机盐培养基按体积比1:4~1:3的配比配制含菌无机盐培养液。5 . The method according to claim 1 , wherein the bacteria source and the inorganic salt medium are prepared in a volume ratio of 1:4 to 1:3 to prepare a bacteria-containing inorganic salt culture solution. 6 .
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