CN201358182Y - Device for carrying out water treatment to field-generated Fenton reagents - Google Patents

Abstract

The utility model relates to a device for carrying out water treatment to field-generated Fenton reagents, which is easy to carry out biochemical treatment and has good processing effect; the device is provided with an adjusting tank (1), a mixer (2), a reactor (3) and a solid-liquid separator (4) which are sequentially connected, and a hydrogen peroxide field generator (5) and an iron ion field generator (6) are arranged for connecting with the mixer. The device is suitable for purifying treatment of waste water which is hard to carry out biochemical treatment.

Description

The device that the Fenton reagent that takes place with the scene carries out water treatment

Technical field

The utility model relates to a kind of device of water treatment, relates in particular to a kind of device that carries out water treatment with the on-the-spot Fenton reagent that takes place, and belongs to field of environment protection.

Background technology

Current, in existing wastewater treatment equipment, be a kind of device that cost is minimum, effect is best for the waste water biochemical treatment apparatus of easy biochemical treatment.Yet, it is the requirement that does not reach biochemical treatment that a lot of waste water its biochemicals is arranged, such as dyeing waste water, coking chemical waste water, phenolic wastewater, pharmacy waste water, garbage leachate etc., these contain in the organic waste water of high-concentration hardly-degradable and contain the inhibition microorganism growth, even to the poisonous and hazardous composition of microorganism, microorganism can't survive under such environment substantially, just can't handle such waste water with biochemical device.For such waste water, adopt emerging " high-level oxidation technology " and device thereof to obtain good effect, and obtained very swift and violent development in recently, be subjected to efforts at environmental protection person's attention deeply.

" high-level oxidation technology " is by chemistry or physicochemical method the pollutent in the water body to be direct oxidation into inorganics, or is translated into the intermediate product of the readily biodegradable of low toxicity.Along with the fast development of pharmacy and fine chemistry industry industry, the processing of some high-concentration hardly-degradable poisonous and harmful organic wastewaters is a difficult problem that is perplexing the environmental protection scientific worker always.Therefore, adopt " high-level oxidation technology " and these water pollution problemss of device solves thereof to become the current hot subject of water treatment research field both at home and abroad.

" high-level oxidation technology " of water treatment comprises chemical oxidation, wet type (catalysis) oxidation, photochemistry (catalysis) oxidation etc.A characteristic feature of " high-level oxidation technology " has produced hydroxyl radical free radical (OH) exactly in water treatment procedure.OH is a kind of very strong oxygenant, and the normal potential of (pH=0) is in acidic solution $E_{\mathrm{OH}\&CenterDot;/H_{2}O}=2.72V,$ In basic solution (pH=14) be $E_{\mathrm{OH}\&CenterDot;/{\mathrm{OH}}^{-}}=1.89V,$ Because of having the normal potential of extremely strong oxidation susceptibility ozone well known in acidic solution also only be ${\mathrm{<figure-callout\; id="3"\; label="E\; O"\; filenames="Y2009201126310015H1.png"\; state="\{\{state\}\}">E</figure-callout>}}_{O_{}}=2.07V,$ In basic solution be ${\mathrm{<figure-callout\; id="3"\; label="E\; O"\; filenames="Y2009201126310015H1.png"\; state="\{\{state\}\}">E</figure-callout>}}_{O_{}}=1.24V.$ So, OH even the oxidisability stronger than ozone arranged, that is to say, it is easier to react with organism than ozone, this is for the organic pollutant molecule that destroys in the water body, it is very favorable making its degraded and last mineralising become carbonic acid gas and water, and in other words, it has better processing power and performance than ozone aspect water treatment.

OH is a kind of very strong oxidising agent, and it can be with the mode (1) of hydrogen substitution reaction, the mode (2) of redox reaction, perhaps mode (3) the deoxidation organic molecule of electrophilic addition reaction on the π key.

RH+OH·→R·+H ₂O (1)

RX+OH·→RX ⁺·+OH ^- (2)

The result of these reactions has generated organic free radical, if dissolved oxygen is arranged in the reaction system, molecular oxygen just can add to organic molecule and get on, become peroxy-radical (equation 4 and 5), peroxy-radical can cause the chain reaction of carbochain fracture degraded, finally causes being degraded into carbonic acid gas and water.

R·+O ₂→RO ₂· (4)

That is to say that the OH aromatics of both can having degraded also can the degrading aliphatic compound, this method degradation capability is very strong, and can not leave over new problem to environment.Now, the key of problem is how to find a kind of i.e. cheapness convenient, and the device that can obtain the OH of q.s again is used for water treatment.

In these " high-level oxidation technologies ", from required design factors, wet type (catalysis) oxidation need (carry out under 0.5～20MPa), the operational condition harshness be to the equipment requirements height at high temperature (150～350 ℃) high pressure.Photochemistry (catalysis) oxidation must be disposed a considerable amount of ultraviolet sources in water body, the equipment requirements height because the optical density(OD) of ultra-violet lamp is low at present, is difficult to handle a large amount of waste water.Because be subjected to the restriction of auto levelizer, these technology also are applied in actual production.Chemical oxidation is because the reaction conditions gentleness is not high to equipment requirements, and speed of response obtains favor soon.According to the oxygenant difference, chemical oxidization method can be divided into ozone oxidation, dioxide peroxide oxidation, potassium permanganate oxidation and Fenton reagent (Fenton ' sreagent) oxidation etc.In these oxygenants, the oxidisability of Fenton reagent is the strongest, and treatment effect is best, therefore receives maximum concern, and the applied research in water treatment is also popular to Fenton reagent and device thereof.

Fenton reagent is exactly hydrogen peroxide and Fe ²⁺Combination, hydrogen peroxide is at Fe ²⁺Katalysis produce down OH, this reaction is referred to as Fenton's reaction:

H ₂O ₂+Fe ²⁺→Fe ³⁺+OH ^-+OH· (6)

Therefore, the essence of Fenton reagent oxidation style (being called for short Fenton oxidation style or Fenton process) is exactly hydrogen peroxide and Fe ²⁺, promptly Fenton reagent has produced OH by Fenton's reaction, utilizes the strong oxidizing property of OH to come the organic pollutant in the oxidative degradation water body or the poisonous inorganics of reductibility.Obviously, in these " high-level oxidation technologies ", it is the method that a kind of most convenient also has most application prospect from device that Fenton reagent obtains OH by reaction formula (6).

In fact, the Fenton oxidation style is used widely at field of environment protection in order to the difficult oxidized waste water of degrading, and just handles high density difficulty oxidized organic wastewater with this method as the Chinese patent ZL 96110517.8 of Liu Faqiang etc.But commercially available hydrogen peroxide and ferrous sulfate are higher because of price, and the cost that is directly used in water treatment is too high and can't be applied.On the other hand, well-known, hydrogen peroxide is a kind of unsettled oxygenant, contacts the hidden danger that blast is all arranged with organism or reductive agent, and its transportation and storage all are serious problems.Similarly, ferrous sulfate also is a unstable compounds, can be oxidized to ferric sulfate and lose katalysis in air.

For a transportation and a storage difficult problem that solves Fenton reagent, and reduce processing cost, a kind of on-the-spot technology and device thereof that Fenton reagent takes place arises at the historic moment.This technology and device thereof are directly to generate hydrogen peroxide and Fe with electrochemical method in pending water ²⁺Ion is referred to as electricity-Fenton oxidation style or electricity-Fenton process.Concrete way is that pending water is added a certain amount of sodium sulfate or sodium oxide as conducting salt, to improve electrical conductivity of water, and the pH value of adjusting water is about 3.0, to regulate pH value water afterwards then feeds in the electrolyzer of a built-in iron anode and graphite cathode, and near negative electrode bubbling air, when after feeding direct current on the anode and cathode, anode generation iron stripping reaction obtains Fe ²⁺:

Fe→Fe ²⁺+2e (7)

Simultaneously, two electronic reduction reactions take place at negative electrode and obtain hydrogen peroxide in airborne oxygen:

O ₂+2H ⁺+2e→H ₂O ₂ (8)

So, the on-the-spot H that takes place ₂O ₂And Fe ²⁺Produce OH by Fenton's reaction, be used for direct oxidation some intractable organism of degrading, as 2,4-D (2,4 dichloro benzene acetate), aniline, chloro aminobenzen, organic dye and other aromatics etc.These have all obtained extraordinary effect in the laboratory, but have all run into unsurmountable obstacle in the actual industrial application.Mainly show three aspects: at first, hydrogen peroxide is that the dissolved oxygen from pending water obtains through two electron reductions, and under barometric point, the dissolved oxygen concentration that balances each other with air in the water approximately has only 10 ^-4The order of magnitude of mol/L, even under the experiment condition of violent aeration-agitation, current density is also necessary＜10m A/cm ², produce hydrogen peroxide and Fe ²⁺Speed very slow, efficient is also extremely low; Secondly, hydrogen peroxide and Fe in electrochemical reactor ²⁺All one's life, achievement produced OH by Fenton's reaction immediately, and this OH must react with organic pollutant at once, otherwise OH will be reduced by other materials in a short period of time, and this just requires pending water directly to pass through electrochemical reactor.But if pending water directly flows through from electrochemical reactor, the organism of contained complicated component and inorganics will inevitably contaminated electrode in the pending water, make electrochemical reactor be difficult to the work of stable for extended periods of time; At last, because actual pending water constituent is complicated and fluctuation is big, can't keep a stable electrochemical system, just can't guarantee that also the generation of OH can keep stable, make the effect of water treatment very unstable, this is very disadvantageous for actual production.

In sum, existing electricity-Fenton device all can't be applied in actual production.

Summary of the invention

It all is to obtain hydrogen peroxide and Fe through the electrochemical method scene in water treatment system that the utility model will solve existing electricity-Fenton device ²⁺, have that working current density is little, efficient is low, electrode easily pollutes and OH generation problem of unstable.A kind of device that carries out water treatment with the on-the-spot Fenton reagent that takes place of the present utility model is provided for this reason.This device not only can high-level efficiency and hydrogen peroxide and Fe is taken place apace ²⁺, and hydrogen peroxide and Fe ²⁺Generating capacity stable and controlled, can produce stable OH, the more important thing is that electrode can be not contaminated, can work steadily in the long term, solved the difficult problem that existing electricity-the Fenton device can't be used in practice.

For addressing the above problem, its special character of the technical scheme that the utility model provides is to be provided with equalizing tank, mixing tank, reactor and the solid-liquid separator that links to each other successively, is provided with on-the-spot producer of the hydrogen peroxide that links to each other with described mixing tank and the on-the-spot producer of iron ion.

The on-the-spot producer of described hydrogen peroxide is made up of electrolyzer, catholyte storage tank, anolyte storage tank, direct supply and oxygen-containing gas producer; Described electrolyzer is made up of air chamber, cathode compartment and built-in anodic anolyte compartment, between air chamber and the cathode compartment every being equipped with gas diffusion cathode, between cathode compartment and the anolyte compartment every being equipped with barrier film; Described anolyte storage tank links to each other with the lower interface of anolyte compartment through pump, and the last interface of anolyte compartment links to each other with the anolyte storage tank; The catholyte storage tank links to each other with the lower interface of cathode compartment through pump, and the last interface of cathode compartment links to each other with described mixing tank; The air outlet of oxygen-containing gas producer links to each other with the last interface of air chamber; The positive pole of direct supply is electrically connected with the anode of electrolyzer, and the negative pole of direct supply is connected with the cathodic electricity of electrolyzer.

The on-the-spot producer of described iron ion can be the on-the-spot producer of iron ion chemical method or electrochemical process;

The on-the-spot producer of the iron ion of described chemical method is made up of liquid storage vessel and filling type reactor, be filled with ferrous material in the filling type reactor, liquid storage vessel links to each other through the lower interface of pump with the filling type reactor, and the last interface of filling type reactor links to each other with described mixing tank;

The on-the-spot producer of the iron ion that described electrochemistry is worked as is made up of electrolyzer, acid solution storage tank and the direct supply of built-in negative electrode and iron anode, and the acid solution storage tank links to each other with the lower interface of electrolyzer through pump, and the last interface of electrolyzer is connected with mixing tank; The positive pole of direct supply is electrically connected with the iron anode of electrolyzer, and the negative pole of direct supply is connected with the cathodic electricity of electrolyzer.

Described anode is that nickel, iron, stainless steel, platinum, ruthenium titanium, ruthenium-iridium-tantalum, titanium carry at least a in platinum, the graphite; Described barrier film is at least a in ceramic diaphragm, polymer fiber barrier film, fibreglass diaphragm, the ion-exchange membrane; Described carbon is at least a in graphite, acetylene black, carbon black, the gac.

Described ferrous material is at least a in iron, carbon steel, steel alloy, iron ore, ferrous sulfate, iron protoxide, the ferric oxide, and the shape of described ferrous material is at least a in plate, grain, bits, piece, bar, silk, the net.

Described iron anode is at least a in iron, carbon steel, the steel alloy, and the shape of described iron anode is at least a in plate, grain, bits, piece, bar, silk, the net.

Described mixing tank is at least a in mechanical stirring mixing tank, waterpower mixing pit, pipeline static mixer, the water pump mixing tank.

Described reactor is at least a in partition plate reaction tank, eddy current reaction tank, automatic reaction pond, the flap reaction tank.

Described solid-liquid separator is at least a in settling bowl, filter tank, pressure filter, Microfilter, the plate-and-frame filter press.

Description of drawings

Fig. 1 is a structured flowchart of the present utility model;

Fig. 2 is the structural representation of the on-the-spot producer of hydrogen peroxide in the utility model;

Fig. 3 is the structural representation of the on-the-spot producer of iron ion in the utility model;

Fig. 4 is the structural representation of the on-the-spot producer of another kind of iron ion in the utility model.

Be labeled as among the figure: 1 equalizing tank; 2 mixing tanks; 3 reactors; 4 solid-liquid separators; The on-the-spot producer of 5 hydrogen peroxide; The on-the-spot producer of 6 iron ions;

51 electrolyzers; 52 catholyte storage tanks; 53 anolyte storage tanks; 54 direct supplys; 55 oxygen-containing gas producers; 56 pumps; 57 pumps;

511 air chambers; 512 gas diffusion cathodes; 513 cathode compartments; 514 barrier films; 515 anolyte compartments; 516 anodes;

61 ferrous materials; 62 filling type reactors; 63 pumps; 64 liquid storage vessels;

601 negative electrodes; 602 electrolyzers; 603 pumps; 604 acid solution storage tanks; 605 direct supplys; 606 iron anodes.

The utility model is described in further detail below in conjunction with accompanying drawing.

The defects that existing electricity-Fenton device exists can't be pushed away it in the actual industrial water treatment The wide application, operating current in the existing apparatus is little, current efficiency is low, electrode is subject to pending in order to solve The pollution of the various pollutants in the water, the problem of job insecurity, key is the generation with Fenton reagent Device is independent from water treatment system, so that Fenton reagent can not be subjected in generating process is pending Contained pollutant effects in the water. The scheme that the utility model proposes as shown in Figure 1, regulating reservoir 1, mixed Close device 2, reactor 3 and solid-liquid separator 4 and link to each other successively, with the hydrogen peroxide scene of these device separates The on-the-spot generator 6 of generator 5 and iron ion is linked respectively blender 2. Waterpower between them flows and gets final product To rely on the gravity natural flow, also can rely on the equipment for liquid transportation forced flow such as pump. Because peroxidating The on-the-spot generator 5 of hydrogen separates with water treatment system with the on-the-spot generator 6 of iron ion, and their work is not subjected to The water quality impact of pending water can produce hydrogen peroxide and Fe with very high intensity²⁺, with these hydrogen peroxide and Fe²⁺Fully effectively mix by blender 2 with pending water. Hydrogen peroxide and Fe²⁺Fenton's reaction takes place and produces OH, Fe in a mixing immediately²⁺Itself is oxidized to Fe³⁺ OH is under slightly acidic condition Organic pollution in (pH 3-4) degradation water or the inorganic matter of reproducibility, Fe³⁺It also is a kind of function admirable Flocculant. Subsequently, the water after processing is adjusted to pH more than 4, make Fe³⁺Be converted into Fe (OH)₃Precipitation is because Fe (OH)₃Be flocculent deposit, can adsorb some remaining organic matters, particularly can inhale Be attached to the oligomer that polymerization reaction take place in the processing procedure generates, make contaminant degradation or with precipitate and separate Go out.

The preparation method of hydrogen peroxide has electrolysis, alkyl-anthraquinone method, isopropanol method, oxygen cathode reducing process With five kinds of hydrogen-oxygen the direct synthesis, wherein electrolysis and isopropanol method are eliminated. The alkyl-anthraquinone method is order The absolute main method of front suitability for industrialized production hydrogen peroxide, but complex technical process, the equipment investment scale is big, Therefore it is only applicable to large-scale production, and is not suitable for the utility model. The hydrogen-oxygen the direct synthesis is one Plant up-and-coming production method, half that production cost is low, equipment investment only is the alkyl-anthraquinone method, but It must operate under 2.9～17.3MPa pressure, and so high operating pressure obviously is not suitable on a small scale Ground in situ preparation hydrogen peroxide.

In sum, the preparation method of suitable hydrogen peroxide of the present utility model is the oxygen cathode reducing process. As shown in Figure 2 be to adopt a kind of typical structure of the on-the-spot generator of hydrogen peroxide of oxygen cathode reducing process to show Intention, this generator is by electrolytic cell 51, catholyte storage tank 52, anolyte storage tank 53, dc source 54 Form with oxygen-containing gas generator 55; Described electrolytic cell 51 is by air chamber 511, cathode chamber 513 and built-in sun The anode chamber 515 of the utmost point 516 forms, and uses by carbon and polytetrafluoroethylene (PTFE) between air chamber 511 and the cathode chamber 513 The gas diffusion cathode 512 of making separates, between cathode chamber 513 and the anode chamber 515 with barrier film 514 every Open; Described anolyte storage tank 53 links to each other through the lower interface of pump 57 with anode chamber 515, anode chamber 515 Upper interface link to each other with anolyte storage tank 53; Catholyte storage tank 52 connects through pump 56 and the lower of cathode chamber 513 Mouth links to each other, and the upper interface of cathode chamber 513 is linked blender 2; The gas outlet of oxygen-containing gas generator 55 with The upper interface of air chamber 511 links to each other; The positive pole of dc source 54 is by lead or conductive bus bar and electrolytic cell 51 Anode 516 link to each other, the negative pole of dc source 54 is by the moon of lead or conductive bus bar and electrolytic cell 51 The utmost point 512 links to each other.

Gas diffusion cathode 512 is prepared by technology known in the art by carbon and polytetrafluoroethylene (PTFE). Material with carbon element Be selected from graphite, carbon black, acetylene black and active carbon etc. These materials namely can use separately, preferred graphite And carbon black. In order to improve catalytic performance, also can two kinds and two or more material with carbon elements use after mixing, Preferred graphite and acetylene black, carbon black and active carbon, graphite, carbon black and acetylene black. Can also be at these carbon The catalyst that has identical catalytic action on the material in the load, such as alkyl-anthraquinone, azobenzene, Cobalt Phthalocyanine etc., Preferred 2-EAQ and azobenzene.

Anode 516 here has been electric action, itself does not participate in reaction, so long as anode does not dissolve Material can be used as anode, i.e. insoluble anode (DSA). For at acidity and neutral electrolyte In, the optional platinum of anode, titanium carry platinum, ruthenium titanium, ruthenium-iridium-tantalum, graphite etc., and preferred titanium carries platinum and ruthenium-iridium-tantalum sun The utmost point; And in alkaline electrolyte, except above-mentioned anode, also can select iron, stainless steel, nickel, preferred Stainless steel and nickel.

Oxygen-containing gas generator 55 is carried oxygen-containing gas to air chamber 511. Oxygen-containing gas comprises air, oxygen Or the gaseous mixture of oxygen and other inert gas, preferred air. The oxygen-containing gas generator can be air pump, Air compressor, air blast, tank of compressed air, oxygen bottle, PSA oxygen generator etc., preferred Air pump.

The effect of barrier film 514 is that catholyte and anolyte are separated, and avoids the hydrogen peroxide in the catholyte to exist The oxidized decomposition of anode also can be avoided the hydrogen peroxide in the leachable catalytic decomposition catholyte of anode. Every Film can be selected from ceramic diaphragm, polymer fiber barrier film, fibreglass diaphragm, amberplex, and is preferred Amberplex.

When anode chamber and cathode chamber are filled with respectively anolyte and catholyte, when being filled with oxygen-containing gas in the air chamber, Because gas diffusion cathode has the waterproof and breathable effect, the catholyte in the cathode chamber can not leak in the air chamber, Gas in the air chamber then can be spread to the inside of gas diffusion cathode, and at gas-diffusion electrode and negative electrode The intersection of liquid forms a gas-liquid-solid three-phase interface, and on this interface, the oxygen in the gas can be directly Flow under the effect of electricity, powering on the surface of material with carbon element is catalysed and reduced into hydrogen peroxide (reaction equation (8)), right After be diffused in the catholyte. So, just contain certain density peroxide in the catholyte in cathode chamber exit Change hydrogen, this part solution that contains hydrogen peroxide just flow in the blender.

The utility model is not limited in the on-the-spot generator of so a kind of hydrogen peroxide, and all can on-the-spotly produce The generator of giving birth to hydrogen peroxide all is applicable to the utility model.

The on-the-spot generator 6 of iron ion is much simpler than the on-the-spot generator of hydrogen peroxide 5. The iron ion scene Generator both can adopt chemical method also can adopt electrochemical process. The iron that shown in Figure 3 is adopts chemical method from The structural representation of the on-the-spot generator of son, it is made up of liquid storage vessel 64 and filled type reactor 62, fills out Fill and be filled with ferrous material 61 in the formula reactor 62, liquid storage vessel 64 is through pump 63 and filled type reactor 62 lower interface links to each other, and the upper interface of filled type reactor 62 is linked blender 2.

Ferrous material chosen from Fe, carbon steel, steel alloy, iron ore, ferrous sulfate, ferrous oxide, oxygen Change iron, the shape of these materials is not limit, can be plate, grain, bits, piece, bar, silk, net at least A kind of. Can prepare easily iron ion with pure water or these ferrous materials of acid fluid dissolves.

Adopt the electrochemical production iron ion to have higher efficient and speed faster than chemical method. Fig. 4 Shown is the structural representation that adopts the on-the-spot generator of iron ion of electrochemical process, and it is by built-in negative electrode 601 Form with electrolytic cell 602, the acid solution storage tank 605 of iron anode 606, acid solution storage tank 605 is through pump 603 and electricity The lower interface of separating groove 602 links to each other, and the upper interface of electrolytic cell 602 is linked blender 2; Dc source 605 Positive pole link to each other dc source 605 by lead or conductive bus bar with the iron anode 606 of electrolytic cell 602 Negative pole link to each other with the negative electrode 601 of electrolytic cell 602 by lead or conductor wire busbar.

Iron anode must be ferruginous metallic substance, can chosen from Fe, carbon steel, steel alloy, its shape does not have special requirement, can be at least a in plate, grain, bits, piece, bar, silk, the net, can directly hang on the electrolyzer for large-sized iron anode, then need be loaded in the frame or basket made from the inert metal material for undersized iron anode with conductive hook.Negative electrode only plays electric action here, any conductive metallic material all can, but consider the cost of material and the degree of polarization of anticathode liberation of hydrogen, preferred stainless steel and iron.

Certain density acid solution in acid solution storage tank 604 is squeezed into electrolyzer 602 with pump 603, and behind the logical direct current, and the iron in the iron anode will be at anode generation solubilizing reaction [reaction formula (7] and obtained iron ion.So on electrolyzer interface effusive be the iron content ion solution, flow in the mixing tank 2.

Pending waste water is regulated pH at the pH value place that helps Fenton's reaction most with acid or alkali earlier in equalizing tank 1, be generally about 3.Then in mixing tank 2 and from the solution that contains hydrogen peroxide of the on-the-spot producer 5 of hydrogen peroxide with from reaction in reactor 3 behind the iron content ion solution thorough mixing of the on-the-spot producer of iron ion, regulate pH to 6～9 with alkali again after reaction finishes, allow Fe in the waste water ³⁺All be converted into Fe (OH) ₃Precipitation, leave standstill cohesion then, also can add coagulating agent in case of necessity, as polymerize aluminum chloride, polyacrylamide etc., make precipitation more abundant effectively, and some organic pollutants in the absorption waste water, use solid-liquid separator 4 with precipitate and separate at last, water qualified discharge or handle in addition again after the processing of gained.

Mixing tank 2 must can be selected from mechanical stirring mixing tank, waterpower mixing pit, pipeline static mixer, water pump mixing tank with pending waste water, the solution that contains hydrogen peroxide and iron content ion solution thorough mixing.The partition plate reaction tank of widespread usage, eddy current reaction tank, automatic reaction pond, flap reaction tank etc. in the reactor 3 optional comfortable water treatments.The settling bowl of using always in solid-liquid separator 4 optional comfortable water treatments or the Chemical Manufacture, filter tank, pressure filter, Microfilter, plate-and-frame filter press etc.

Use separately device that the utility model provides can pending wastewater treatment to meeting national relevant emission standard, but say it might not is suitable from processing efficiency and processing cost angle.Because the processing of the device that pending waste water process the utility model provides, can significantly improve the biodegradability of waste water, therefore device provided by the utility model is used for the pre-treatment that some is difficult to biodegradable waste water, carry out biochemical treatment again after improving its biochemical, can widen the use range of the utility model institute generator greatly.

The device that provides with the utility model with the factory effluent of Acid Rose Red B is treated to example embodiment of the present utility model is described below, but the scope of the invention is not limited in this.

Embodiment

Embodiment 1

The device that the Fenton reagent that takes place with the scene carries out water treatment is provided with the equalizing tank 1, mixing tank 2, reactor 3 and the solid-liquid separator 4 that link to each other successively, is provided with on-the-spot producer 5 of the hydrogen peroxide that links to each other with described mixing tank and the on-the-spot producer 6 of iron ion;

The on-the-spot producer 5 of described hydrogen peroxide is made up of electrolyzer 51, catholyte storage tank 52, anolyte storage tank 53, direct supply 54 and oxygen-containing gas producer 55; Described electrolyzer 51 is made up of the anolyte compartment 515 and the direct supply 54 of air chamber 511, cathode compartment 513, built-in anode 516, between air chamber 511 and the cathode compartment 513 every being equipped with gas diffusion cathode 512, between cathode compartment 513 and the anolyte compartment 515 every being equipped with barrier film 514; Described anolyte storage tank 53 links to each other through the lower interface of pump 57 with anolyte compartment 515, and the last interface of anolyte compartment 515 links to each other with anolyte storage tank 53; Catholyte storage tank 52 links to each other through the lower interface of pump 56 with cathode compartment 513, and the last interface of cathode compartment 513 links to each other with described mixing tank 2; The air outlet of oxygen-containing gas producer 55 links to each other with the last interface of air chamber 511; The positive pole of direct supply 54 is electrically connected with the anode 516 of electrolyzer 51, and the negative pole of direct supply 54 is electrically connected with the negative electrode 512 of electrolyzer 51;

The on-the-spot producer of iron ion that the on-the-spot producer 6 of described iron ion is a chemical method, it is made up of liquid storage vessel 64 and filling type reactor 62, be filled with ferrous material 61 in the filling type reactor 62, liquid storage vessel 64 links to each other through the lower interface of pump 63 with filling type reactor 62, and the last interface of filling type reactor 62 links to each other with described mixing tank 2.

The NaOH solution that adds 0.5mol/L in the catholyte storage tank 52 in the on-the-spot producer 5 of hydrogen peroxide, the sulphuric acid soln that in anolyte storage tank 53, adds 0.5mol/L, electrolyzer 51 adopts ionic membrane as barrier film 514, when catholyte is squeezed into cathode compartment 513 through pump 56, anolyte is squeezed into anolyte compartment 515 through pump 57, air is made oxygen-containing gas producer 55 with air pump and is filled into air chamber 511, applies 750A/m at anode and negative electrode ²Direct current, the solution that contains the 0.5mol/L hydrogen peroxide is approximately flowed out in the exit of cathode compartment 513.

The sulphuric acid soln that in the liquid storage vessel 64 of the on-the-spot producer 6 of iron ion, adds 0.5mol/L, in filling type reactor 62, fill waste iron filing, scrap iron piece etc., sulphuric acid soln in the acid solution storage tank is squeezed in the filling type reactor through pump 63, and the control flow velocity makes in the reactor exit solution and contains iron concentration about 0.45mol/L.

With the factory effluent of Acid Rose Red B, wherein COD is 340.4mg/L, and pH 2.5, colourity 4000 degree, BOD ₅/ COD is 0.06, squeezes in the equalizing tank 1, and the pH value of regulating waste water is about 3.The waste water that to regulate then after the pH value is squeezed in the mechanical stirring mixer 2, with squeeze into partition plate reaction tank 3 after above-mentioned solution that contains hydrogen peroxide and iron content ion solution are mixed, about the pH to 7 that reaction finishes to transfer waste water in the back, leave standstill, make solid-liquid separator 4 with plate-and-frame filter press, filter the filtrate obtain by analysis, the COD clearance is 67.3%, percent of decolourization 77.5%, BOD ₅/ COD is 0.31.

Embodiment 2

Repeat embodiment 1, difference is to change the on-the-spot producer of iron ion into the iron ion that adopts electrochemical process on-the-spot producer, it is made up of electrolyzer 602, acid solution storage tank 604 and the direct supply 605 of built-in negative electrode 601 and iron anode 606, acid solution storage tank 604 links to each other through the lower interface of pump 603 with electrolyzer 602, and the last interface of electrolyzer 602 is connected with mixing tank 2; The positive pole of direct supply 605 is electrically connected with the iron anode 606 of electrolyzer 602, and the negative pole of direct supply 605 is electrically connected with the negative electrode 601 of electrolyzer 602.

In electrolyzer 602, place a pair of iron plate as negative electrode and anode, between cathode and anode, apply 1000A/m ²Direct current, control acid solution flow velocity makes the iron ion that contains about 0.45mol/L in the acid solution in exit.Other change is that mixing tank adopts the waterpower mixing pit, and reactor adopts the eddy current reaction tank, and solid-liquid separator adopts the filter tank, the water quality of water outlet by analysis, the COD clearance is 75.4%, percent of decolourization 83.2%, BOD ₅/ COD is 0.35.

Embodiment 3

Repeat embodiment 1, difference is that mixing tank adopts pipeline static mixer, and reactor adopts the automatic reaction pond, and solid-liquid separator adopts settling bowl, the clear liquid that drains from settling bowl by analysis, the COD clearance is 52.4%, percent of decolourization 73.8%, BOD ₅/ COD is 0.28.

Embodiment 4

Repeat embodiment 1, difference is that mixing tank adopts water pump mixing tank, reactor to adopt the flap reaction tank, and solid-liquid separator adopts pressure filter, filtrate by analysis, the COD clearance is 77.1%, percent of decolourization is 92.8%, BOD ₅/ COD is 0.42.

Claims (9)

1, the device that carries out water treatment with the on-the-spot Fenton reagent that takes place, it is characterized in that being provided with the equalizing tank (1), mixing tank (2), reactor (3) and the solid-liquid separator (4) that link to each other successively, be provided with on-the-spot producer (5) of the hydrogen peroxide that links to each other with described mixing tank and the on-the-spot producer (6) of iron ion.

2, device as claimed in claim 1 is characterized in that the on-the-spot producer of described hydrogen peroxide (5) is made up of electrolyzer (51), catholyte storage tank (52), anolyte storage tank (53), direct supply (54) and oxygen-containing gas producer (55); Described electrolyzer (51) is made up of the anolyte compartment (515) of air chamber (511), cathode compartment (513) and built-in anode (516), between air chamber (511) and the cathode compartment (513) every being equipped with gas diffusion cathode (512), between cathode compartment (513) and anolyte compartment (515) every being equipped with barrier film (514); Described anolyte storage tank (53) links to each other through the lower interface of pump (57) with anolyte compartment (515), and the last interface of anolyte compartment (515) links to each other with anolyte storage tank (53); Catholyte storage tank (52) links to each other through the lower interface of pump (56) with cathode compartment (513), and the last interface of cathode compartment (513) links to each other with described mixing tank (2); The air outlet of oxygen-containing gas producer (55) links to each other with the last interface of air chamber (511); The positive pole of direct supply (54) is electrically connected with the anode (516) of electrolyzer (51), and the negative pole of direct supply (54) is electrically connected with the gas diffusion cathode (512) of electrolyzer (51).

3, device as claimed in claim 1 is characterized in that the on-the-spot producer of described iron ion (6) is the on-the-spot producer of iron ion chemical method or electrochemical process;

The on-the-spot producer of the iron ion of described chemical method is made up of liquid storage vessel (64) and filling type reactor (62), be filled with ferrous material (61) in the filling type reactor (62), liquid storage vessel (64) links to each other through the lower interface of pump (63) with filling type reactor (62), and the last interface of filling type reactor (62) links to each other with described mixing tank (2);

The on-the-spot producer of the iron ion of described electrochemical process is made up of electrolyzer (602), acid solution storage tank (604) and the direct supply (605) of built-in negative electrode (601) and iron anode (606), acid solution storage tank (604) links to each other through the lower interface of pump (603) with electrolyzer (602), and the last interface of electrolyzer (602) is connected with mixing tank (2); The positive pole of direct supply (605) is electrically connected with the iron anode (606) of electrolyzer (602), and the negative pole of direct supply (605) is electrically connected with the negative electrode (601) of electrolyzer (602).

4, device as claimed in claim 2 is characterized in that described anode (516) is that nickel, iron, stainless steel, platinum, ruthenium titanium, ruthenium-iridium-tantalum, titanium carry at least a in platinum, the graphite; Described barrier film (514) is at least a in ceramic diaphragm, polymer fiber barrier film, fibreglass diaphragm, the ion-exchange membrane; Described carbon is at least a in graphite, acetylene black, carbon black, the gac.

5, device as claimed in claim 3, it is characterized in that described ferrous material (61) is at least a in iron, carbon steel, steel alloy, iron ore, ferrous sulfate, iron protoxide, the ferric oxide, the shape of described ferrous material (61) is at least a in plate, grain, bits, piece, bar, silk, the net.

6, device as claimed in claim 3 is characterized in that described iron anode (606) is at least a in iron, carbon steel, the steel alloy, and the shape of described iron anode (606) is at least a in plate, grain, bits, piece, bar, silk, the net.

7, device as claimed in claim 1 is characterized in that described mixing tank (2) is at least a in mechanical stirring mixing tank, waterpower mixing pit, pipeline static mixer, the water pump mixing tank.

8, device as claimed in claim 1 is characterized in that described reactor (3) is at least a in partition plate reaction tank, eddy current reaction tank, automatic reaction pond, the flap reaction tank.

9, device as claimed in claim 1 is characterized in that described solid-liquid separator (4) is at least a in settling bowl, filter tank, pressure filter, Microfilter, the plate-and-frame filter press.

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