CN106299431B

CN106299431B - A kind of electrochemical appliance and its method for river sediment in-situ reparation

Info

Publication number: CN106299431B
Application number: CN201610864528.2A
Authority: CN
Inventors: 李中坚; 李刚; 张兴旺; 杨彬; 雷乐成; 郑展望
Original assignee: Zhejiang University ZJU
Current assignee: Zhejiang University ZJU
Priority date: 2016-09-29
Filing date: 2016-09-29
Publication date: 2019-02-01
Anticipated expiration: 2036-09-29
Also published as: CN106299431A

Abstract

The invention discloses a kind of electrochemical appliances and its method for river sediment in-situ reparation, different and traditional no film deposit microbiological fuel cell (SMFC), it increases one layer of exchange membrane on the basis of deposit microbiological fuel cell and the two poles of the earth isolation is got up and increases aeration in cathode, simultaneously with power supply instead of the resistance between the two poles of the earth, organic matter is deposited indigenous microorganism oxygenolysis in object near anode region in deposit, the electron transmission of generation is to anode, cathode is reached using external circuit, water is generated in conjunction with the oxygen in cathodic region and from the proton that anode block transitive comes, to realize the removal of the organic pollutant in removal deposit, it is big that the device effectively improves traditional SMFC electrode distance, the high disadvantage of internal resistance, it is low to solve water body conductivity, the low problem of rate of oxygen, effectively mention The high repair ability of the device, contaminant removal efficiency and operation stability, expand its application range.

Description

A kind of electrochemical appliance and its method for river sediment in-situ reparation

Technical field

The present invention relates to environmental protection industry (epi), especially a kind of electrochemical appliance and its side for river sediment in-situ reparation Method.

Background technique

However as the quickening of economic fast development and urbanization process, many urban river water quality pollutions in China and life State degenerate problem is very prominent, and since long-term external source pollutes input, substrate habitat deteriorates, and ecosystem degradation is unable to complete Output, transfer and the catharsis of pollutant, lead to pollutant serious accumulation and vicious circle, and water quality deterioration simultaneously generates black smelly existing As；Meanwhile urban river, due to long-term viscous flow, the bed mud largely containing polluters such as organic matter, nitrogen, phosphorus, heavy metals is heavy Product also forms endogenous pollution, and traditional administering method lacks systematicness and continuity, and slow effect, that is lasting, and low efficiency is controlled Mark does not effect a permanent cure, and after water remediation, bed mud can still discharge pollutant, therefore river regulation as endogenous pollution into water body, administers Bed mud is only at all.Deposit microbiological fuel cell (SMFC), using bacterium in bed mud to the degradation of organic pollutant, The improvement to pollutant can be thus achieved, and can be realized the recycling of energy, be a kind of very promising technology, but traditional For SMFC by water body dissolved oxygen, the influence of bed mud situation is big, and internal resistance is high, and low efficiency is very restricted in practical applications.

Summary of the invention

Problem to be solved by this invention is just to provide a kind of model electrochemical device for combining aeration with electrochemistry, It realizes and improves cathode nearby dissolved oxygen, the purpose for reducing internal resistance, improving efficiency, allow to the water project situation for adapting to various complexity.

In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme:

A kind of electrochemical appliance for river sediment in-situ reparation includes anode, amberplex, cathode chamber and power supply, The power supply is connected with the cathode in anode, cathode chamber respectively, and amberplex is described between anode and cathode room Cathode chamber includes several supports, cathode, aerators；The amberplex is fastened around in support and constitutes cathode chamber The electrolyte of high conductivity is added in periphery, inside, and cathode is submerged into electrolyte, and the aeration opening of aerator is located under cathode Portion.

Preferably, the aerator includes that air pump, aeration tube and aeration outlet, air pump are connected with aeration tube, is exposed Tracheae gos deep into electrolyte, and the aeration opening of aeration tube is located at cathode lower part, and aeration outlet is located at cathode chamber liquid level or more and outside Environment is connected.

Preferably, which is 0.1-2dm³, cathode chamber volume is 0.05-1dm³。

Preferably, the amberplex is proton exchange membrane, anion-exchange membrane or cation-exchange membrane.

Preferably, material used in the cathode and anode is carbon felt, carbon brush, carbon foam, stainless steel cloth filler Or metal foam, anode surface area 2-40dm², cathodic surface area 1-20dm², the distance between two electrodes are 1-3cm.

Preferably, the power supply is constant voltage dc source, supply voltage 1-5V.

Preferably, the electrolyte is the PBS solution of 100mM or the NaCl solution of 0.5mol/L, the PBS solution Group become 0.62g/L NH₄Cl、4.904g/L NaH₂PO₄、9.152g/L Na₂HPO₄With 0.26g/L KCl.

The river sediment in-situ remediation method of the electrochemical appliance is: wait administer in river, by several claims 1 The electrochemical appliance is completely submerged in river bottom mud, and the spacing distance controlled between electrochemical appliance is 5-30cm, is opened It opens air pump and carries out cathode aeration, control gas velocity in 30ml/min, while opening external power supply, apply 1-5V's between the two poles of the earth Voltage；Because dissolved oxygen concentration is very low in polluted river channel bed mud, microorganism to the degradation of Organic Pollutants in Sedimentary Mud by Limitation, degradation rate is very slow, and after being inserted into the device, near anode, anode sinks instead of the electron acceptor that is used as of oxygen For organic matter in product object by native bacterium oxygenolysis, the electronics of generation is passed to anode, reaches cathode using external circuit, Generation water is combined with the proton that oxygen and anode region that cathode nearby dissolves transmit, while outside in alive situation, Driving force is increased for microbial degradation organic pollutant, greatly accelerates degradation rate, to realize organic dirt in deposit The removal of object is contaminated, the voltage and current of continuous operation and monitoring device illustrates this after device electric current is significantly raised and keeps stablizing Device has successfully started up, and by adjusting voltage and aeration quantity, so that device is optimal state and guarantees device stable operation, The concentration of detection Organic Pollutants in Sedimentary Mud determines the treatment effect of the technology, further adjusts the operating condition of the device.

After adopting the above technical scheme, the present invention has the advantage that cathode, which exposes oxygen, greatly improves cathode water body nearby Oxyty improves cathode efficiency；Isolation cathode, additional electrolyte improve the conductivity between the two poles of the earth, reduce electrode Distance greatly reduces the internal resistance of the device, greatly improves the organic pollutant degradation rate and current efficiency of anode；And Administered river is not necessarily to dredging dirt-carrying, does not influence the other functions such as river beauty, i.e., in situ to administer；The device is designed to tightly simultaneously The entirety gathered is not easy to be influenced by environmental conditions, and can be applied to the water body of various complexity.

Detailed description of the invention

The following further describes the present invention with reference to the drawings:

Fig. 1 is the structural schematic diagram of electrochemical appliance of the invention.

Specific implementation method

Device generally seals cylinder, and inside is cathode, and surrounding is fixed on bracket and anode and outer with amberplex The isolation of portion's environment, the electrolyte that high conductivity is added in inside submerge cathode material, and aeration tube and escape pipe, aeration tube are accessed in top Cathode bottom is protruded into, escape pipe is located at liquid level or more, junction sealing, and aeration tube stretches out the water surface and connects external aerator, out Tracheae directly stretches out the water surface.

There are four supports, other parts to empty for four wall of device, and amberplex is fixed in support, with glue and cranse Sealing, prevents from leaking.

The device anode is coated on outside amberplex, is fixed with cranse, make with amberplex close contact, with reduce Electrode distance reduces internal resistance.

The two electrode connecting wire of device picks out the water surface, connects external power supply or resistance.

Wait administer in river, which is entirely insertable in river bottom mud, applies certain voltage between two electrodes, and Aerator is opened, the voltage and current of continuous operation and monitoring device enables devices to stable operation, anode surface forms stabilization Biomembrane, consume the organic pollutant in bed mud, and by adjusting voltage and aeration quantity, device is made to be optimal state.

Described device body volume is 0.1-2dm³, cathode volume 0.05-1dm³, specific surface area is, can be according to different realities Border situation selects different volume sizes, and used exchange membrane is proton exchange membrane and anion-exchange membrane and cation exchange Film can be selected according to the actual situation.Used sealant is the marine glues such as AB glue, resin glue.Described device cathode with Material used in anode be with high-specific surface area, high voidage, hydrophilic Carbon Materials and metal material such as: carbon felt, carbon Brush, carbon foam and stainless steel cloth filler, metal foam etc., anode surface area 2-40dm², cathodic surface area 1-20dm²。 The distance between two electrodes are 1-3cm.

Used external power supply is constant voltage dc source, and the voltage applied is 1-5V.The aerator used includes Air pump and underwater aerator such as micro-hole aerator, the aeration quantity of each device are maintained at 10-50ml/min, maintain catholyte DO concentration is in 4mg/L or more in liquid.It is uniformly distributed according to the river bottom mud repaired, the distance between similar SMFC is two-by-two 5-30cm, active area 10-700cm²/, processing capacity by described device volume size, electrode material and structure and Applying voltage is influenced.

In this example, microbiological fuel cell technology improve and be controlled applied to river drift organic pollutant In reason, near anode, for the organic matter in deposit by native bacterium oxygenolysis, the electronics of generation is passed to anode, Cathode is reached by external circuit, is combined with the proton that cathode zone oxygen and anode region transmit, to realize in deposit The removal of organic pollutant.Simulated experiment is carried out with the river bottom mud to be processed of acquisition, reactor is fully embedded in bed mud, It is spaced 10cm between each reactor, opens air pump and carry out cathode aeration, aeration rate 30ml/min is applied between anode and cathode Add the voltage of a 3V, after a week, electric current obviously starts to increase and gradually tend towards stability in 50mA continuous operation, illustrate SMFC at Function starting, Effects of Organic Matter in Sediments total amount reduces by 31% after one month.The spy extremely low for oxyty in water body, conductivity is low Point, we combine aeration with SMFC, to improve the dissolved oxygen solubility near cathode, improve cathode efficiency, thus that cathode is complete Full isolation sealing improves the stability of its operation to facilitate the electrolyte of aeration and the high conductivity of addition and improve aeration efficiency, The distance between but also substantially reduce the two poles of the earth, the internal resistance of battery is thus reduced, current efficiency is improved.In addition a whole set of dress Compact-sized, convenient transportation management and transfer are set, can adapt to more complicated water body situation, persistently keeps stability and high efficiency fortune Row is small by environmental influence.

In examples detailed above, the size of the electrochemical appliance and its arrangement in river and quantity can be according to realities Border situation and select, after the pollution of river obtains improvement, can suitably reduce reactor quantity or drop low applied voltage, with reduce Cost.In examples detailed above, the aeration connection type of multiple reactors improves aeration effect in such a way that parallel connection and serial connection combines Rate.

Claims

1. a kind of electrochemical appliance for river sediment in-situ reparation, it is characterised in that including anode, amberplex, cathode Room and power supply, the power supply are connected with the cathode in anode, cathode chamber respectively, amberplex be located at anode and cathode room it Between, the cathode chamber includes several supports, cathode, aerators；The amberplex is fastened around in support Cathode chamber periphery is constituted, the electrolyte of high conductivity is added in inside, and cathode is submerged into electrolyte, the aeration opening position of aerator In cathode lower part；

Material used in the cathode and anode be carbon felt, carbon brush, carbon foam, stainless steel cloth filler or metal foam, Anode surface area is 2-40 dm², cathodic surface area is 1-20 dm², the distance between two electrodes are 1-3 cm；

The power supply is constant voltage dc source, supply voltage 1-5V；

The electrolyte is that the PBS solution of 100mM or the NaCl solution of 0.5mol/L, the group of the PBS solution become 0.62g/L NH₄Cl、4.904g/L NaH₂PO₄、9.152g /L Na₂HPO₄With 0.26g/L KCl.

2. electrochemical appliance according to claim 1, it is characterised in that aerator includes air pump, aeration tube and aeration Outlet, air pump are connected with aeration tube, and aeration tube gos deep into electrolyte, and the aeration opening of aerator is located at cathode lower part, aeration Outlet is located at cathode chamber liquid level or more and is connected with external environment.

3. electrochemical appliance according to claim 1, it is characterised in that the apparatus main body volume is 0.1-2dm³, cathode chamber Volume is 0.05-1dm³。

4. electrochemical appliance according to claim 1, it is characterised in that the amberplex is anion-exchange membrane Or cation-exchange membrane.