CN101967017A - Electrochemical device for wastewater treatment and method for treating wastewater by using same - Google Patents
Electrochemical device for wastewater treatment and method for treating wastewater by using same Download PDFInfo
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Abstract
本发明涉及一种用于废水处理的电化学装置及使用所述装置处理废水的方法。本发明的电化学装置由电源、初级电解槽B、电解槽A、电解槽C、阴极、透过性隔离材料部分、阳极、原水池、净水收集器与浓缩溶液收集池组成。使用本发明的电化学装置可同时除去硝酸根、磷酸根、氯离子、氟离子等常见阴离子和有机物，无需投加任何药剂，可以避免对出水产生二次污染、操作方便、处理效率高、能耗较低。The invention relates to an electrochemical device for wastewater treatment and a method for treating wastewater using the device. The electrochemical device of the present invention is composed of a power supply, a primary electrolytic cell B, an electrolytic cell A, an electrolytic cell C, a cathode, a part of a permeable isolation material, an anode, a raw water pool, a clean water collector and a concentrated solution collection pool. The electrochemical device of the present invention can simultaneously remove common anions and organic substances such as nitrate, phosphate, chloride, and fluoride, without adding any chemicals, and can avoid secondary pollution to the effluent, with convenient operation, high treatment efficiency, and high energy efficiency. lower consumption.
Description
[technical field]
The invention belongs to technical field of waste water processing.More specifically, the present invention relates to a kind of electrochemical appliance that is used for wastewater treatment, also relate to the method for using described device to handle waste water.
[background technology]
At present, the effluent quality index that obtains through sewage work's conventional processing has reached innoxious emission standards such as total nitrogen＜35ppm, COD＜50ppm, total phosphorus＜10ppm, suspended substance＜30ppm, yet but its index still has bigger gap apart from recyclings such as urban look water, flowers and plants irrigation and river and lake moisturizings.Major cause at first is that total nitrogen, total phosphorus equal size are still higher, causes the water quality eutrophication more outstanding, occurs serial problems such as wawter bloom, peculiar smell easily; Next is that negatively charged ion such as common fluorine, chlorine, bromine in the water body are difficult to remove.In order to satisfy the resource utilization requirement of sewage disposal water outlet, must develop the advanced water purifying technology, the nitrogen phosphorus equal size in the water is reduced to below the emission standard restriction, and makes anion-contents such as fluorine, chlorine that remarkable reduction be arranged.Yet conventional sewage disposal technologies such as existing flocculation, sedimentation, biochemical treatment are difficult to realize the lower concentration nitrate radical in the water body, phosphate radical, chlorion, fluorion and organism are reduced the requirement that reaches recycling of water resource.
For nitrogen, phosphorus and the organism removed in the sewage, using very widely, treatment technology is biological process and chemical precipitation method; For negatively charged ion such as the fluorine in the water body, chlorine, commonly used and efficient ways is that water carries out dilution process.But these technology exist many shortcomings in actual applications, long as the current residence time, floor space is big, produce and to be difficult to the mud disposed in a large number, the less stable of biological treatment process, conventional denitrification process need add carbon source or chemical agent, and cost is higher, and the complicated operation management is loaded down with trivial details etc.
Nitrate radical degree of depth removal method in a kind of sewage is to utilize directly to carry out electrochemical reduction degradation under electric field action.
For example, Chinese patent CN200410098590.2, " metal modified active carbon fiber electrode and remove the method for nitrate with this electrode " disclose a kind of carrier band in a kind of and base metals such as copper, tin, copper and zinc that utilize in precious metal such as the metals such as palladium, platinum and gold is made nitrate in the reducible water on modified active carbon fiber activated cathode electrode, and utilize inactive, conductive material such as graphite, plumbic oxide to be anode, separate with proton exchange membrane between the anode and cathode, under the situation of energising, with nitrate reduction.Negative electrode is the place that the nitrate catalytic reduction reaction takes place in this invention, because Ka band negative electricity, can produce the effect of electrically repelling each other with same electronegative nitrate ion, nitrate radical adheres on the cathod catalyst surface like this, and then with negative electrode on the H2 that produces of electrolysis that the chance of catalytic reduction reaction takes place is just comparatively limited, so reaction efficiency, the effect of removing nitrate radical are difficult to raising.
Phosphate radical, fluorion and the organism in the sewage removed in flocculation about electricity, Chinese patent CN1986435A proposes to utilize the combination process of electricity flocculation and micro-filtration, promptly adopting aluminium sheet or iron plate is that electrolysis produces aluminium salt or molysite, fluorion in the combination water and organism form bigger flco, then the flco that forms is filtered removal in follow-up micro-filtration membrane module, from tap water, removes fluorine and organic purpose thereby reach.This technology needs to increase processing cost in conjunction with micro-filtration, and electrode surface easily forms oxide film and passivation, and treatable pollutant kind is single, and target compound concentration is less in the water body, and electrochemical efficiency is lower.Chinese patent CN 101269863A proposes to utilize the combination process of electricity flocculation and membrane bioreactor, adopting iron plate or aluminium sheet is that anode electrolysis produces iron ion or aluminum ion, form flco with hydroxide ion, phosphate anion in the sewage, organism forms mud after the interior microbiological deterioration of membrane bioreactor is arranged, be removed through the micro-filtrate membrane filtration pollutent, from sewage, remove phosphorus and organic purpose thereby reach.The electrochemical efficiency of this system is lower, and processing cost is bigger, produce to be difficult to the mud disposed in a large number, and the less stable of biological treatment, it is single to handle pollutant kind.
Chinese patent CN02146020.5 " activated carbon fiber and electrodynamics synergistic purification tap water method and device ", a kind of activated carbon fiber and electrodynamics synergistic purification tap water method and device have been announced, promptly on the activated carbon fiber filtrate, applied electric field, there is electric current to exist in the fiber, the motion of harmful ion and bacterium is no longer only determined by the flow field, but be subjected to the acting in conjunction in electric field and flow field, the electromigration that under electric field action, produces, galvanic actions such as electrophoresis can effectively improve the water pollutant ion, the collision frequency of particle and bacterium and activated carbon fiber, thus adsorption rate and adsorption effect improved.Yet the shortcoming of this device is regularly to carry out the regeneration of electrode, and complicated operating process is loaded down with trivial details, the processing cost height.
Employed electrodialysis or reverse osmosis technology in the tap water system because efficient is low and use expensive ion-exchange membrane, are not suitable for the advanced treatment of sewage.
[summary of the invention]
[technical problem that will solve]
The purpose of this invention is to provide a kind of electrochemical appliance that is used for wastewater treatment.
Another object of the present invention provides a kind ofly uses described electrochemical appliance to handle the method that contains negatively charged ion and organic waste water.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of electrochemical appliance that is used for wastewater treatment.
Shown in the accompanying drawing 1 is the most basic electrochemical appliance that is used for wastewater treatment, this device is made up of with concentrated solution collecting tank 4 power supply 1, primary electrolysis groove B, electrolyzer A, electrolyzer C, negative electrode 5, perviousness isolated material part 6, anode 7, former pond 2, water purification collector 3, and described each electrolyzer comprises cell body, anode, negative electrode and perviousness isolated material part; Described perviousness isolated material partly is a kind of parts that described cell body are separated into positive column and cathodic area;
Staying water in former pond 2 is entered by the bottom, cathodic area of primary electrolysis groove B, more respectively from being flowed out by its cathodic area and top, positive column;
Enter from the bottom, cathodic area of the effusive water body in primary electrolysis groove B positive column by electrolyzer A, flow out from the top in its positive column and cathodic area respectively again, enter concentrated solution collecting tank 4 from its effusive water body in top, positive column, and enter former pond 2 from its effusive water body in top, cathodic area;
Enter from the bottom, cathodic area of the effusive water body in primary electrolysis groove B cathodic area, flow out from the top in its positive column and cathodic area respectively again by electrolyzer C; Enter water purification collector 3 from its effusive water body in top, cathodic area, and enter former pond 2 from its effusive water body in top, positive column.
A preferred embodiment of the invention, the described electrochemical appliance (referring to accompanying drawing 2) that is used for wastewater treatment is made up of with concentrated solution collecting tank 4 power supply 1, primary electrolysis groove B, electrolyzer A1, electrolyzer A2, electrolyzer C1, electrolyzer C2, negative electrode 5, perviousness isolated material part 6, anode 7, former pond 2, water purification collector 3, and described each electrolyzer comprises cell body, anode, negative electrode and perviousness isolated material part; Described perviousness isolated material partly is a kind of parts that described cell body are separated into positive column and cathodic area;
Staying water in former pond 2 is entered by the bottom, cathodic area of primary electrolysis groove B, more respectively from being flowed out by its cathodic area and top, positive column;
Enter from the bottom, cathodic area of the effusive water body in primary electrolysis groove B positive column, flow out from the top in its positive column and cathodic area respectively again by electrolyzer A1; Enter the cathodic area bottom of electrolyzer A2 from the effusive water body in top, electrolyzer A1 positive column, then from its positive column and the outflow of top, cathodic area; Enter bottom, electrolyzer A1 cathodic area from the effusive water body in top, electrolyzer A2 cathodic area; Enter concentrated solution collecting tank 4 from the effusive water body in top, electrolyzer A2 positive column, this moment, the nitrate concentration of concentrated solution collecting tank 4 interior water bodys can reach the higher concentration that is fit to carry out biochemical treatment, or reached the higher concentration of higher Faradaic current efficient; And still return former pond 2 from the effusive water body in top, electrolyzer A1 cathodic area, carry out cyclic electrolysis;
Enter from the bottom, cathodic area of the effusive water body in primary electrolysis groove B cathodic area, flow out from the top in its positive column and cathodic area respectively again by electrolyzer C1;
Enter the cathodic area bottom of electrolyzer C2 from the effusive water body in top, electrolyzer C1 cathodic area, then from its positive column and the outflow of top, cathodic area; Enter water purification collector 3 from the effusive water body in top, electrolyzer C2 cathodic area, but this moment, water purification collector 3 interior water quality can reach the requirement that resource utilization is utilized again; Flow into the bottom in electrolyzer C1 cathodic area again from the effusive water body in top, electrolyzer C2 positive column; And still return former pond 2 from the effusive water body in top, positive column of electrolyzer C1, carry out cyclic electrolysis.
According to another kind of preferred implementation of the present invention, described cell body is plastic containers, process is anti-corrosion and iron ware or other corrosion-resistant insulation container of insulation processing.
According to another kind of preferred implementation of the present invention, described anode is made up of soluble anode or insolubility anode, perhaps
Described anode is connected to form with parallel way by soluble anode and insolubility anode.
According to another kind of preferred implementation of the present invention, described negative electrode is made up of metal or nonmetal electrode.
According to another kind of preferred implementation of the present invention, described soluble anode is netted, strip, the tabular or block type electrode of being made by iron, aluminium and alloy thereof; Described insolubility anode is netted, strip, the tabular or block type electrode of being made by platinum, iridium, ruthenium, palladium, titanium/ruthenium dioxide or titanium/iridium dioxide.
According to another kind of preferred implementation of the present invention, described negative electrode is by palladium, copper, nickel, iron or aluminium and alloy thereof or by nonmetal netted, the strip of making of graphite, tabular or block type electrode.
The invention still further relates to a kind of negatively charged ion and organic method of wastewater treatment of containing, it is characterized in that using described electrochemical appliance to carry out the processing of described waste water, apply DC electric field between described anode and described negative electrode, the current density of described primary electrolysis groove B is controlled at 0.5-50mA/cm
2, the current density of described electrolyzer A is controlled at 2.5-100mA/cm
2The current density of described electrolyzer C is controlled at 0.1-30mA/cm
2
A preferred embodiment of the invention applies DC electric field between described anode and described negative electrode, the current density of described primary electrolysis groove B is controlled at 5-30mA/cm
2, the current density of described electrolyzer A is controlled at 30-80mA/cm
2, and when adopting the mode of a plurality of electrolyzer A coupling, below the current density of adjacent electrolyzer A greater than the current density of the adjacent electrolyzer A in front; The current density of described electrolyzer C is controlled at 0.5-20mA/cm
2, and when adopting the mode of a plurality of electrolyzer couplings, below the current density of adjacent electrolyzer C less than the current density of the adjacent electrolyzer C in front.
Below the present invention will be described in more detail.
The present invention relates to a kind of electrochemical appliance that is used for wastewater treatment.
Electrochemical appliance of the present invention is the combined action that realizes electromigration, electricity flocculation and electrochemical degradation in this device simultaneously, remove common negatively charged ion and organism such as the nitrate radical that exists in the water, phosphate radical, chlorion, fluorion simultaneously, this electrochemical appliance can improve degradation efficiency, cuts down the consumption of energy and reduce the treatment time.
This device (accompanying drawing 1) is made up of with concentrated solution collecting tank 4 power supply 1, primary electrolysis groove B, electrolyzer A, electrolyzer C, negative electrode 5, perviousness isolated material part 6, anode 7, former pond 2, water purification collector 3.
Described power supply 1 is a direct supply, and its voltage request is the 0-36 volt, electric current 0-1000 peace.Described DC power supply device for example is the direct supply that the surely rich Electrical Appliances Co., Ltd in Shanghai produces, its input voltage, and single-phase AC220V ± 10%, three-phase 380V, output voltage, 0 to the maximum adjustable value; Outward current, 0 to maximum adjustable value, frequency, 50Hz/60Hz.
According to the present invention, described each electrolyzer comprises cell body, anode, negative electrode and perviousness isolated material part.
In the present invention, described cell body is plastic containers, process is anti-corrosion and iron ware or other erosion resisting insulation container of insulation processing.
For example, described plastic containers are resol container, furane resin container or glass reinforced plastic container.Described iron ware is at the inner Steel Vessel with Resins, epoxy, furane resin, vibrin, resol or rubber anti-corrosive lining of steel tank.Described erosion resisting insulation container is the erosion resisting insulation container made from cement or stupalith.What these electrolytic vessels had can directly buy from the market, and what have can be according to concrete dimensional requirement processing or customization.
In the present invention, described anode is made up of soluble anode or insolubility anode.
Described anode also can be connected to form with parallel way by soluble anode and insolubility anode.
According to the present invention, described soluble anode is netted, strip, the tabular or block type electrode of being made by iron, carbon steel, aluminium and alloy thereof.
Described insolubility anode is netted, strip, the tabular or block type electrode of being made by platinum, iridium, ruthenium, palladium, titanium/ruthenium dioxide or titanium/iridium dioxide.The electrode of titanium/ruthenium dioxide electrode wherein for being composited in titanium matrix and ruthenium dioxide coating, this alloy is the alloy product of selling in the market, for example the auspicious prosperous titanium in Baoji already company limited with trade(brand)name sewage disposal anode product sold.The electrode of titanium/iridium dioxide electrode for being composited in titanium matrix and iridium dioxide coating, this alloy are that for example oxygen titanium electrode product sold is analysed with trade(brand)name by the abundant non-ferrous metal in Baoji company limited at the alloy product of sale in the market.
According to the present invention, described negative electrode is made up of metal or nonmetal electrode.
Described metal for example is nickel, iron, aluminium and alloy thereof, copper and alloy thereof.Described copper base alloy for example is according to copper 64.5%-66.5%, nickel 16.5%-18.5%, surplus is the alloy that zinc is formed, and this alloy is the alloy product of selling in the market, and for example Dongguan City Yi Mei metal Materials Co., Ltd is with trade(brand)name C7521 product sold.Described nonmetal for example be graphite.
Described negative electrode is netted, strip, tabular or lumphy structure.
Described perviousness isolated material partly is a kind of parts that described cell body are separated into positive column and cathodic area.
According to the present invention, described perviousness isolated material for example is the isolated material of dry goods.Described perviousness isolated material part mainly plays and had both limited catholyte and anolyte mixed flow, keeps again conducting between the two, allows the both sides charged ion to carry out electromigration again under the electrical forces effect.Described perviousness isolated material can be various dense cloth fabrics, and these cloth fabrics for example can be various chemical ﹠ blended fabrics, as woven dacron or nylon cloth, and various cottons or filter cloth.Described perviousness isolated material part can be a kind of cloth tissue layer, also can be by the stacked composite bed that forms of two or more cloth fabric.
In this composite bed, adjacent cloth fabric warp thread intersect angle should＞45.
According to the present invention, in described cell body, described anode, negative electrode and perviousness isolated material part be the good combination coupling dimensionally.
Two interpolars at above-mentioned electrolyzer apply DC electric field, can realize electromigration, electricity flocculation and electrochemical degradation effect simultaneously.Wherein common negatively charged ion such as nitrate radical, phosphate radical, fluorion, chlorion under the DC electric field effect, see through described isolated material part from the cathodic area electromigration to the positive column, and described iron, aluminium and alloy soluble anode thereof can discharge Fe under DC electric field
2+And Al
3+Ion, they can form the bigger flocks of molecular weight with phosphate anion, fluorion, can remove through sedimentation; In addition, electrochemical reduction degradation can take place and be removed in nitrate radical near negative electrode.The oxygenant institute oxidation that is can be on anode directly oxidized or that produced by anode electrolysis of organic pollutant in the water body, or transform and generate charged group, in electrolyzer, be removed by electromigration and throwing out.
When using electrochemical appliance of the present invention, contain described negatively charged ion and organic staying water in former pond 2 are entered by the bottom, cathodic area of primary electrolysis groove B, again according to velocity ratio 3: 1～5: 1 respectively from by its cathodic area and the outflow of top, positive column.Between anode and negative electrode, apply DC electric field, current density can be controlled at 0.5-50mA/cm according to the kind and the concentration of pollutent
2In the scope.Electromigration, electricity flocculation and electrochemical reduction effect take place in negatively charged ion in staying water simultaneously under electric field action.The control flow rate, make described water body in electrolyzer, stop 1-5min, fully allow common negatively charged ion such as nitrate radical, phosphate radical, fluorion under the DC electric field effect, see through isolated material, therefore, nitrate ion concentration from the effusive water body in positive column water inlet has remarkable increase, phosphate anion, fluorion and iron, aluminium plasma interact, and generate throw out and settle down; Anion concentration in cathodic area outflow water body is than the remarkable minimizing of water inlet.
Enter from the bottom, cathodic area of the effusive water body in primary electrolysis groove B positive column by electrolyzer A, flow out from the top in its positive column and cathodic area respectively according to the certain flow rate ratio again, enter concentrated solution collecting tank 4 from its effusive water body in top, positive column, the anion concentration in its positive column outflow water body further increases than the anode water outlet of previous electrolyzer B.And entering former pond 2 from its effusive water body in top, cathodic area, the anion concentration from cathodic area outflow water body reduces to some extent than the anode water outlet of previous electrolyzer B.
In order to improve degradation efficiency, to cut down the consumption of energy, can adopt the mode of a plurality of electrolyzer couplings.
Adopt the electrochemical appliance of five electrolyzer couplings as shown in Figure 2, this device is made up of with concentrated solution collecting tank 4 power supply 1, primary electrolysis groove B, electrolyzer A1, electrolyzer A2, electrolyzer C1, electrolyzer C2, negative electrode 5, perviousness isolated material part 6, anode 7, former pond 2, water purification collector 3.
Staying water in former pond 2 is entered by the bottom, cathodic area of primary electrolysis groove B, more respectively from being flowed out by its cathodic area and top, positive column;
Enter from the bottom, cathodic area of the effusive water body in primary electrolysis groove B positive column, flow out from the top in its positive column and cathodic area respectively again by electrolyzer A1; Enter the cathodic area bottom of electrolyzer A2 from the effusive water body in top, electrolyzer A1 positive column, then from its positive column and the outflow of top, cathodic area; Enter bottom, electrolyzer Al cathodic area from the effusive water body in top, electrolyzer A2 cathodic area; Enter concentrated solution collecting tank 4 from the effusive water body in top, electrolyzer A2 positive column, this moment, the nitrate concentration of concentrated solution collecting tank 4 interior water bodys can reach the higher concentration that is fit to carry out biochemical treatment, or reached the higher concentration of higher Faradaic current efficient; And still return former pond 2 from the effusive water body in top, electrolyzer A1 cathodic area, carry out cyclic electrolysis;
Enter from the bottom, cathodic area of the effusive water body in primary electrolysis groove B cathodic area, flow out from the top in its positive column and cathodic area respectively again by electrolyzer C1;
Enter the cathodic area bottom of electrolyzer C2 from the effusive water body in top, electrolyzer C1 cathodic area, then from its positive column and the outflow of top, cathodic area; Enter water purification collector 3 from the effusive water body in top, electrolyzer C2 cathodic area, but this moment, water purification collector 3 interior water quality can reach the requirement that resource utilization is utilized again; Flow into the bottom in electrolyzer C1 cathodic area again from the effusive water body in top, electrolyzer C2 positive column; And still return former pond from the effusive water body in top, positive column of electrolyzer C1, carry out cyclic electrolysis.
The invention still further relates to a kind of negatively charged ion and organic method of wastewater treatment of containing, it is characterized in that using described electrochemical appliance to carry out the processing of described waste water, apply DC electric field between described anode and described negative electrode, the current density of described primary electrolysis groove B is controlled at 0.5-50mA/cm
2, described electrolyzer A current density is controlled at 2.5-100mA/cm
2The current density of described electrolyzer C is controlled at 0.1-30mA/cm
2
A preferred embodiment of the invention applies DC electric field between described anode and described negative electrode, the current density of described primary electrolysis groove B is controlled at 5-30mA/cm
2, the current density of described electrolyzer A is controlled at 30-80mA/cm
2, and when adopting the mode of a plurality of electrolyzer A (A, A1 and A2) coupling, below the current density of adjacent electrolyzer A greater than the current density of the adjacent electrolyzer A in front; The current density of described electrolyzer C (C, C1 and C2) is controlled at 0.5-20mA/cm
2, and when adopting the mode of a plurality of electrolyzer couplings, below the current density of adjacent electrolyzer C less than the current density of the adjacent electrolyzer C in front.
Use electrochemical appliance of the present invention can handle common negatively charged ion and organic waste water such as containing nitrate radical, nitrite anions, phosphate radical, sulfate radical, chlorion, bromide anion, fluorion simultaneously.Described waste water for example is urban domestic wastewater, the middle water of Sewage Plant through obtaining after the conventional processing.
Contain the waste water of a large amount of solid waste in processing, need carry out pre-treatment, reach the manageable level of electrochemical appliance of the present invention so that the solid waste in its waste water or other suspended substances reduced, for example solid waste should be controlled at below the 200mg/L.
In addition, it is below horizontal that the pH value should be controlled at 6～8, waste water viscosity should be controlled at 1.2 centipoises in the time of 25 ℃.
Nitrate radical, phosphate radical, chlorion, fluorinion concentration and organic measuring method before and after handling in the water body are to write according to State Environmental Protection Administration's water and effluent monitoring analytical procedure editorial committee; " water and effluent monitoring analytical procedure " (the 4th edition; [), measuring method of stipulating in China Environmental Science Press's publication (2002) carries out assay determination.
By a large amount of evidences, nitrate concentration can be reduced to below the 1ppm by 40ppm.Phosphate concentration can be reduced to below the 0.1ppm by 3ppm.Chlorine ion concentration can be reduced to below the 20ppm by 150ppm.Fluorinion concentration can be reduced to below the 0.2ppm by 2ppm.Organic concentration can be reduced to below the 40ppm by 300ppm.
[beneficial effect]
The present invention compared with prior art has following beneficial effect:
First, the present invention is by using the anode group and applying electric field, realize the combined action of electromigration, electricity flocculation and electrochemical degradation in a device simultaneously, the pollutant kind that can remove simultaneously is many, as common negatively charged ion and organism such as nitrate radical, phosphate radical, chlorion, fluorion in the water;
The second, use the class isolated material of weaving cotton cloth among the present invention, compare with ion-exchange membrane commonly used, cheap, and the pollution problem of film can not take place, be easy to safeguard;
The 3rd, the present invention utilizes negatively charged ion and the organism in electromigration, electricity flocculation and the electrochemical degradation combined removal water, need not to add any medicament, can avoid to go out the water generates secondary pollution, easy to operate, processing efficiency is high, energy consumption is lower.
[description of drawings]
Fig. 1 is an electrochemical appliance synoptic diagram of the present invention.
1-power supply, the former pond of 2-, 3-water purification collector, 4-concentrated solution collecting tank, primary electrolysis groove B, electrolyzer A, electrolyzer C, 5-negative electrode, 6-perviousness isolated material part, 7-anode, 8-return line.
Fig. 2 is a kind of preferred electrochemical appliance synoptic diagram of the present invention.
1-power supply, the former pond of 2-, 3-water purification collector, 4-concentrated solution collecting tank, primary electrolysis groove B, electrolyzer A1, electrolyzer C1, electrolyzer A2, electrolyzer C2,5-negative electrode, 6-perviousness isolated material part, 7-anode, 8-return line
[embodiment]
Below in conjunction with embodiment technical scheme of the present invention is further described.
As shown in Figure 1, electrochemical appliance of the present invention is made up of power supply, primary electrolysis groove B, electrolyzer A, electrolyzer C, negative electrode, perviousness isolated material part, anode, former pond, water purification collector and concentrated solution collecting tank.Described each electrolyzer comprises the rectangle cell body made from resol, netted (rhombus size, 12.5 * 4.5mm) Ti-IrO
2(matrix is Ti, and coating is the thick IrO of 20-50 μ m
2) anode, copper base alloy plate (surplus is a zinc for copper 64.5%-66.5%, nickel 16.5%-18.5%) negative electrode and the thick 0.1mm nylon cloth of perviousness isolated material part., its electrode area 238cm
2(14cm * 17cm), interelectrode distance is 8mm.The direct supply that uses the surely rich Electrical Appliances Co., Ltd in Shanghai to produce applies direct current between anode and negative electrode, current density is 5mA/cm
2
Material solution is the sodium nitrate aqueous solution of autogamy, its nitrogen content is 20.2ppm, flows into from the cathodic area of primary electrolysis groove B with flow velocity 30ml/min, extracts the positive column water body out with the 5ml/min flow velocity behind 10min, inject the cathodic area of electrolyzer A, the current density of electrolyzer A is 8mA/cm
2The solution in primary electrolysis groove B cathodic area is with the cathodic area of flow velocity 25ml/min injection electrolyzer C, and the current density of electrolyzer C is 1.5mA/cm
2Behind the 20min, the water body of each electrolyzer reaches stable, and volume is basic identical, measures the nitrate concentration of each electrolyzer negative and positive polar region water body, and test-results is listed in table 1.
Table 1: the nitrate concentration of each electrolyzer negative and positive polar region water body
By the result of table 1 as can be seen, use electrochemical appliance of the present invention to handle, the water body of about 1/3 volume (wherein nitrate concentration is reduced to 1.9ppm) is up to standard in 20min, produce the dense water (wherein nitrate concentration is 140ppm) of about 1/3 volume simultaneously, all the other water bodys of about 1/3 circulate in system.
Present embodiment adopts with the same manner of embodiment 1 and removes nitrate in the water, but current density changes to some extent.In the present embodiment, the current density of primary electrolysis groove B is 40mA/cm
2, the current density of electrolyzer A is 80mA/cm
2, the current density of electrolyzer C is 20mA/cm
2, 10min measures the nitrate concentration of each electrolyzer negative and positive district water body afterwards, and test-results is as shown in table 2.
Table 2: the nitrate concentration of each electrolyzer negative and positive polar region water body
As can be seen, along with the increase of current density, the concentration that the concentration of nitrate nitrogen can be reduced to the following positive column of 1ppm can be concentrated to 160ppm, but current density is big, can cause energy consumption to increase.
As shown in Figure 2, adopt 5 electrolyzer couplings, i.e. primary electrolysis groove B, electrolyzer A1 and A2, electrolyzer C1 and C2.
Enter from the bottom, cathodic area of the effusive water body in primary electrolysis groove B positive column, flow out from the top in its positive column and cathodic area respectively again by electrolyzer A1; Return former pond 2 from the effusive water body in top, electrolyzer A1 cathodic area, carry out cyclic electrolysis; Enter the cathodic area bottom of electrolyzer A2 from the effusive water body in top, electrolyzer A1 positive column, then from its positive column and the outflow of top, cathodic area; Enter bottom, electrolyzer A1 cathodic area from the effusive water body in top, electrolyzer A2 cathodic area; Enter concentrated solution collecting tank 4 from the effusive water body in top, electrolyzer A2 positive column.
Enter from the bottom, cathodic area of the effusive water body in primary electrolysis groove B cathodic area, flow out from the top in its positive column and cathodic area respectively again by electrolyzer C1; Return former pond 2 from the effusive water body in top, positive column of electrolyzer C1, carry out cyclic electrolysis; Enter the cathodic area bottom of electrolyzer C2 from the effusive water body in top, electrolyzer C1 cathodic area, then from its positive column and the outflow of top, cathodic area; Enter water purification collector 3 from the effusive water body in top, electrolyzer C2 cathodic area; Flow into the bottom in electrolyzer C1 cathodic area again from the effusive water body in top, electrolyzer C2 positive column.
The current density of primary electrolysis groove B is 10mA/cm
2, the current density of electrolyzer A1 and A2 is respectively 22mA/cm
2And 35mA/cm
2, the current density of electrolyzer C1 and electrolyzer C2 is respectively 5mA/cm
2And 2mA/cm
2
Use netted (rhombus size, 12.5 * 4.5mm) Ti-IrO
2(matrix is Ti, and coating is the thick IrO of 20-50 μ m
2) and the iron plate parallel connection as the anode group, copper base alloy (surplus is a zinc for copper 64.5%-66.5%, nickel 16.5%-18.5%) as negative electrode, is shaped as tabular.Electrode area 0.63m
2(70cm * 90cm), polar plate spacing is 6mm, and the thick nylon cloth of 0.1mm is as sealing coat.Flow velocity is 10L/h.
Material solution is the second pond water outlet of some sewage works, and the anion concentration of second pond water outlet is listed in table 3.
After using electrochemical appliance of the present invention to handle, adopt the detection method of describing in this specification sheets to measure water outlet water body anion concentration, its analytical results is listed in table 3.
Table 3: use the water outlet water body anion concentration after electrochemical appliance of the present invention is handled
Shown in table 3 result, after the second pond water outlet of sewage work uses electrochemical appliance of the present invention to handle, three kinds of indexs of the effluent quality of negative electrode have all satisfied surface water III class standard, the total phosphorus in the anode water outlet and the concentration of fluorion have dropped to very low level, need not to handle once more, can directly discharge; Nitrate radical then has higher concentration, can carry out biochemical treatment.As seen, advanced water purifying technology of the present invention all has significant removal effect to the nitrogen in the sewage, phosphorus, fluorine and chlorion.
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