CN101048349A - Method and apparatus for treating aqueous medium - Google Patents
Method and apparatus for treating aqueous medium Download PDFInfo
- Publication number
- CN101048349A CN101048349A CNA2005800365527A CN200580036552A CN101048349A CN 101048349 A CN101048349 A CN 101048349A CN A2005800365527 A CNA2005800365527 A CN A2005800365527A CN 200580036552 A CN200580036552 A CN 200580036552A CN 101048349 A CN101048349 A CN 101048349A
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- water
- bearing media
- treatment
- cod
- diamond electrode
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- 239000012736 aqueous medium Substances 0.000 title abstract description 8
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- 238000007781 pre-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 230000008439 repair process Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
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- 238000007789 sealing Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000010530 solution phase reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- AAKBLFQBZDFKMP-UHFFFAOYSA-H trimagnesium azane diphosphate Chemical compound N.[Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O AAKBLFQBZDFKMP-UHFFFAOYSA-H 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009280 upflow anaerobic sludge blanket technology Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
Abstract
There are provided a method and apparatus according to which an aqueous medium, in particular a poorly biodegradable aqueous medium, can be treated efficiently through electrolytic treatment using a special conductive electrode. In one embodiment of the present invention, there is provided a method for treating an aqueous medium, which comprises subjecting an aqueous medium to an electrolytic step (2) using a special conductive electrode, and then to a water treatment step (4).
Description
Technical field
The present invention relates to a kind of method that is used to handle any no matter form various water-bearing medias of the aqueous solution, mud, emulsion, micella, suspension, concentrated solution and mud form, particularly a kind of method that the water-bearing media of difficult for biological degradation is effectively handled as how about.
Background technology
Understand the various waste water (this specification sheets, these are generically and collectively referred to as " water-bearing media ") of discharging any form such as the aqueous solution, mud, emulsion, micella, suspension, concentrated solution and mixing mud from corporate sector facility, communal facility, half public joint facility etc.Such waste water must make it harmless through water treatment procedure before being discharged into public waters.The most frequently used water treatment method that waste water is handled is a biological treatment, the just widespread use long ago because processing cost is cheap relatively.Biological treatment broad sense is categorized as aerobic treatment method and anaerobic treatment method.The chemical oxygen demand (COD) (COD) that the former is mainly used in water-bearing media is tens to several thousand mg/L or situation still less, and the latter is mainly used in COD to be the situation of 1000mg/L at least.And, ight soil is handled, sewage disposal or similar treating processes, in case single can not finish denitrogenation with aerobic treatment or anaerobic treatment means the time, but then coupling aerobe facture and anaerobic biological treatment method so that both characteristics can both be applied.Under any circumstance, when pending water-bearing media mainly comprises biodegradable material, then extensively adopt biological treatment.Comprise many material Tathagata that come from natural origin under the situation of waste water, vinasse, food residual, animal residue, sewage, ight soil or the biological waste of food, beverage or brew-house at water-bearing media, often adopt biological treatment.
But, biological treatment is difficult to be applied to comprise the water-bearing media of a lot of recalcitrant substances, comprise the chemical substance that is derived from petroleum chemicals or the situation of chemosynthesis material as water-bearing media, perhaps water-bearing media comprises the situation in the organic sludge of the situation of the microorganism with sclereid wall such as methane fermentation mud or sewage work.In addition, even come from natural origin such as xylogen and humin substances, if macromole has phenyl ring functional group in molecule, its biodegradable can be extremely low.That is, biological treatment is difficult to be applied to the situation that water-bearing media comprises much the material that can not be digested by the biological treatment microorganism used therefor basically.In addition, even when being applied to comprise the water-bearing media of biodegradable material, also can not in the practical time limit, finish treating processes sometimes.In addition, even water-bearing media is when mainly comprising biodegradable material, even if if water-bearing media comprises and microorganism is poisoned or causes the biological material that suppresses, then biological treatment is may effect bad.For example, well-known, ammonia, benzene and phenol can suppress many microbic activity.Also have, acetate itself has very high biodegradable, but can understand that from its effect of serving as pickle cure food if water-bearing media comprises high-concentration acetic acid, then microorganism will no longer can breed, thus water-bearing media self difficult for biological degradation that will become.Equally, sucrose or analogue also are highly biodegradable, if but such sugar is the red syrup that has comprised high density, then, solute concentration missionary society between microorganism cells and the water-bearing media rises owing to causing osmotic pressure, microorganism will no longer can breed, so the water-bearing media difficult for biological degradation that will become.This is equally applicable to have the pickled slurry or the analogue of high salt concentration.For such concentrating spent liquor, by the dilution eliminate difficult for biological degradation after, it is feasible that biological treatment becomes.Yet in this case, the amount of the water-bearing media that must handle can become a lot, thereby handle the needed cost of a large amount of water-bearing medias, equipment, space or the like and will become problem, therefore to successfully formulate and utilize the water technology of biological treatment to have difficulty.
In addition, if water-bearing media comprises as the coloring agent component in the dyeing waste water, biological treatment may be extremely difficult.Coloring agent component is difficult to be degraded by microorganisms usually.When the water-bearing media that comprises coloring agent component is carried out a biological disposal upon, have the situation that some fully remove COD composition (some time is also referred to as COD hereinafter) and BOD composition (some time is also referred to as BOD hereinafter), but almost without any decolorizing effect.
In addition, except judging well that biological treatment is whether feasible and be criterion not only that also having some water-bearing medias of desiring to carry out a biological disposal upon is dangerous originally with difficult for biological degradation thing and the contained ratio of readily biodegradable thing.Specifically, the antibiotic waste water/waste liquid of locating from pharmaceutical factory, hospital etc. that contains just ranges this class water-bearing media.In biological treatment, cultivate aerobic microbiological or anaerobion so that purifying aqueous medium.It is extremely weak point that such aerobic microbiological or the generation of anaerobion are changed, from a few hours by several days, if water-bearing media treatment plant has microbiotic to continuously flow into thus, then be easy to generate microorganism and breed with antibiotic antibody.It is believed that and be pernicious to people and MRSA (methicillin resistant staphylococcus aureus) that microbiotic is invalid is occurring by same principle excessively using in the antibiotic hospital.Therefore, if such waste water uses biological treatment to handle, then water-bearing media treatment plant has to become and has antigen microbial reproduction base and these microorganisms and can be discharged into danger in the surrounding environment.
Usually and in this manual, recalcitrant substance refers to be not easy the material that decomposed by organism.As mentioned above, even water-bearing media comprises biodegradable material or comes from the material of natural origin, mean not necessarily that also in fact these water-bearing medias can handle by biological treatment.In this manual, " water-bearing media of difficult for biological degradation " is not limited to the water-bearing media that contains recalcitrant substance, toxic substance or suppress the biological treatment material, generally more is meant aforesaid being difficult to the water-bearing media of biological treatment as water treatment method.And the form of difficult for biological degradation water-bearing media can be the aqueous solution or mud, emulsion, micella, suspension, concentrated solution or the mud that contains solids.
Comprise mixing mud liquid by the example of the difficult for biological degradation water-bearing media of this definition from water treatment plant such as sewage work, various mud from methane fermentation process and similar procedure, waste water/liquid from refinery and petroleum products factory, waste water/liquid from the chemical plant, waste water/liquid from pharmaceutical factory and hospital, from each step of semiconductor fabrication processes (photoresist step, rinse step, plating step) waste water/liquid, the photograph development waste liquid, from any useless machining oil of engineering shop (oil soluble or water-soluble) waste liquid, wash-down water and waste water from the paint manufacturing processed, from canning factory, the wash-down water and the waste water of body plant and metal sheet factory coating procedure, waste water/liquid from the agrochemistry production process, dyeing waste water, dye processing plant waste water, from power station ion-exchange recycling waste water (condensate demineralizer waste water) with from the electroplating effluent that comprises organism or ammoniacal liquor of plating shop with electroplate wash-down water.But be not limited to this, also have many other water-bearing medias that are difficult to carry out a biological disposal upon.
The water-bearing media of these difficult for biological degradation must adopt other method such as physico-chemical process to handle.At the COD of water-bearing media is under hundreds of mg/L or the situation still less, and available ozone, ultraviolet ray, hydrogen peroxide, hypochlorous acid etc. are handled water-bearing media.And, can adopt the advanced oxidation processes (AOP) of ozone or hydrogen peroxide and ultraviolet coupling.Known AOP or ultraviolet irradiation method can be effective to handle and contain the particularly water-bearing media of two English of trace chlorinated organic cpd.The treatment process that the situation that contains lower concentration coloring agent component or dyestuff at water-bearing media places an order with ozone also is effective.Water-bearing media needs under the situation of disinfection before entering surrounding environment, and the hypochlorous acid facture is more suitable.
Under the situation that colored component content is high in that the COD of water-bearing media concentration is low, adopt granulated active carbon adsorption treatment method can remove colored component well.If but water-bearing media comprises the COD composition of higher concentration, the absorption property of gac can descend at short notice.The cost of gac also may not be always cheap, and exhausted gac itself must also must dispose, and it is limited therefore to remove the difficult for biological degradation water-bearing media of colored component wherein with gac.
In addition, comprise at water-bearing media under the situation of a large amount of suspended substances, can effectively carry out water treatment by carrying out flocculation treatment.When with aluminium base or iron-based flocculation agent such as polymerize aluminum chloride (PAC) or Tai-Ace S 150 adding water-bearing media, electronegative suspended substance is neutralized, and by the Van der Waals force flocculation together.After throwing out formation throw out, can remove the method processing water-bearing media of throw out by sedimentation or filtration means.Yet, for example comprise under the situation of a large amount of solutes completely at water-bearing media, such as flocculation and sedimentation or flocculation and filtering method with nearly unavailable.Yet, the method for using flocculation agent is also arranged, promptly before carrying out processed, sewage sludge, methane fermentation mud etc. adds flocculation agent, be easier to from mud, extrude filtrate like this.Yet, under the situation of organic sludge, comprise big water gaging in the microorganism wall, therefore be difficult to sludge dewatering to water ratio is lower than 80% with flocculation agent.Therefore the flocculation treatment method may be effectively to the suspended substance in the water-bearing media only, therefore is as preprocessing means rather than final treatment process under most of occasions.
With regard to the mud method of disposal, before more than ten years, also adopt the method for ocean tipping, but owing to reasons such as London treaty valids, legal restraint is more severe, therefore ocean tipping has now become infeasible.In addition, also have the method for landfill, but polluted underground water resource for fear, local resident's Environmental awareness improves, and disposal site such as exhausts at reason, and this disposal method has become and has been difficult to implement.
In addition, concerning the water-bearing media of difficult for biological degradation, combustion method is a kind of effective physical chemistry treatment process.During burning, water-bearing media stands heating and burn processing under 800 to 900 ℃ temperature, and water becomes water vapor thus, organism becomes carbonic acid gas and water and inorganics and becomes ash, and the refuse amount therefore and significantly reduces.Combustion method is used to handle some mud, concentrating spent liquor and various other water-bearing medias of can not applying biological handling.By under the situation of burn processing water-bearing media, normally in having the incinerator of incendiary material of kerosene, town gas or analogue, a confession handles, perhaps can burn with refuse in the incinerator of burning solid refuse with high heating value.Water-bearing media such as photograph development waste liquid and waste water from pesticide factory are to handle in a confession has the incinerator of kerosene incendiary material.
But, handle in combustion method under the situation of water-bearing media, unless water-bearing media comprises the combustiblematerials at least about 40%, otherwise can not the self-heating burning.The calorific value insufficient section must be compensated by above-mentioned kerosene or analogue, thereby if having only seldom combustiblematerials in the water-bearing media, fuel cost will be very high so.In addition, carry out under the incendiary situation in the stove that water-bearing media is sprayed into a burning high heating value refuse such as waste plastic product, the problem of appearance is to descend or similar reason has unburnt tendency takes place because of furnace temperature.In addition, in recent years, the combustion waste way itself there are very big opposing views, can not obtain agreeing with of local resident.Because at the regulation limitations of special measurement standards such as two English, incinerator is out of service on a small scale legally, does not also obtain local resident's agreement or has been subjected to regulation limitations and build new burning facility.In order to safeguard the operation of incinerator, must carry out statutory audit to two English concentration in the waste gas etc., and this concentration of circular relevant authorities is within the emission standard scope.As a result, burning operation there is strict demand,, thereby keeps small-sized and medium-sized incinerator and become very difficult so that related problems such as incomplete combustion, high-temp combustion are carried out general management.Present trend is to abandon small incinerator, with waste delivery to place far away, concentrate and in large-scale incinerator, burn.In large-scale incinerator, operation control and to control waste gas fully relatively easy, but processing costs might not be cheap, because the processing of large-scale emission-control equipment, incineration residue and flying dust and transportation cost etc. will be installed.
In recent years, the novel method that the electrochemical water treating method of use electrolytic reaction is handled water-bearing media as a kind of physical chemistry has caused people's attention.The electro-chemical water facture is because of easy handling, when opening, electric current begins to handle and electric current stops to handle when closing, do not need pharmaceutical chemicals, can in compact devices, handle, electronics is as the substitute of pharmaceutical chemicals, can handle at normal temperature and normal pressure, or the like, thereby itself established model into so-called " Green Chemistry ".
If water-bearing media comprises chlorion, locate to produce hypochlorous acid at noble metal electrode such as DSA (dimensional stabilizing electrode), ammonia and coloring agent component contained in the water-bearing media can be decomposed by this hypochlorous acid.Ammonia in the water-bearing media can be nitrogen by being converted into inorganics with hypochlorous breakpoint reaction.Yet except ammonia and coloring agent component, it is almost like water off a duck's back that these precious metals DSA electrode pair decomposes the COD composition.Therefore, proposed to use the electro-chemical water facture of plumbic oxide or similar electrode with high oxygen evolution overvoltage.Adopt this electrode, it seems the decomposition reaction that the COD composition directly takes place on the surface of electrode to make the COD composition change into inorganics thus.But, use the electrochemical treatment method of this electrode not necessarily high aspect the efficient of decomposing the COD composition, because electrode is made of heavy metal, can worry to constitute the heavy metal stripping of electrode in treating water in addition.
Recent years, utilize the electro-chemical water facture of conductive diamond to cause concern.Greatly before 10 years, have and report that effect except that COD is arranged when diamond being made conductor and carrying out electrochemical reaction with conductive diamond as electrode.But, although confirmed the phenomenon that COD is decomposed in this report, be still unclearly in reaction mechanism at that time, can not produce the electrode of practical application in addition.Yet owing to adopted the development of the coating technology of CVD method in recent years, the manufacturing technology of conductive diamond electrode has obvious improvement.In addition, in recent years, report in addition when conductive diamond electrode is used for the electrochemical treatment process of water-bearing media, height (Ghrardini et al.:Electrochemicaloxidation of 4-chlorophenol for wastewater treatment when the removal efficiency ratio of COD is used lead dioxide electrode, J.Electrochemical Society, 148, D78-D82,2001).Under the conductive diamond electrode situation, different with plumbic oxide is that even some meeting strippings are arranged in water-bearing media, unique composition also is a carbon, does not therefore have the problem of heavy metal stripping.Because electrode surface produces the OH root, the decomposition efficiency of COD is high in addition.In addition, go back the OH root that produces on the known conductive diamond electrode high sterilization effect is arranged.
Natural diamond is an isolator, but diamond the same with silicon be the element of IV family.If mix with iii group element such as boron, diamond can become the p-N-type semiconductorN, if perhaps mix with V group element such as nitrogen then become the n-N-type semiconductorN.When increasing dopant dose, diamond becomes conductor, presents the low resistance of amount of metal level, as 10m Ω cm.If this conductive diamond is used as electrode in electrochemical reaction, then conductive diamond presents a wide thermodynamics window (for liberation of hydrogen overvoltage and the gesture window of analysing the oxygen overvoltage), and this is that other electrode materials be can't see.If promptly be used for electrolysis, conductive diamond electrode is the electrode that does not produce oxygen and hydrogen tendency.Therefore, it is believed that when conductive diamond electrode when the anode, generation be the OH root rather than separate out oxygen that these OH roots can decompose COD.The OH root has high oxidation capacity, thereby can decompose nearly all COD composition as organism being decomposed into carbonic acid gas and water.
Utilize conductive diamond electrode that water-bearing media is carried out electrochemical treatment and have aforesaid advantage, but concerning prior art, also there are many problems in the treating processes that make the electrochemical treatment method that adopts conductive diamond electrode be suitable for applying to the difficult for biological degradation water-bearing media..
Handle the difficult for biological degradation water-bearing media by electrolytic process utilizing conductive diamond electrode, be dissolved in the COD constituent concentration of water-bearing media fully when higher, particularly solvable COD concentration is at least under the situation of thousands of mg/L, the COD composition is converted into inorganics, promptly be converted into carbonic acid gas, water, nitrogen etc., current efficiency almost 100%.Yet in case the COD density loss in the water-bearing media, current efficiency begins significant decline.The difficult for biological degradation water-bearing media that the inventor will discharge from factory carried out electrolysis treatment with conductive diamond electrode, studied the relation between the current efficiency that COD concentration and COD are decomposed in the water-bearing media.The results are shown in Figure 1.
Though the current density when operating with conductive diamond electrode is relevant, within the conventional current density range, if the COD in the water-bearing media is at least 500 to 2000mg/L, the current efficiency that is used for the conductive diamond electrode of COD decomposition almost is 100%.Yet when being lower than this COD, current efficiency begins remarkable decline.For the COD composition is converted into inorganics, the COD composition in the water-bearing media must touch the OH root that produces on the conductive diamond electrode surface.The OH root is that successive produces on the conductive diamond electrode surface, but has only the very short life-span.Because of rather than be discharged into from electrode surface that to carry out oxidative decomposition the solution be so-called solution-phase reaction.That is, the reaction that is converted into inorganics of COD composition is only carried out at electrode surface.Therefore, if COD concentration becomes very low in the water-bearing media, then the mass transfer to electrode surface becomes speed limit, thereby the current efficiency that COD decomposes descends greatly.In this case, even increase Reynolds number (it is laminar flow or turbulent non-dimensional number that representative is flowed),, thereby be difficult to keep the current efficiency that COD decomposes because of limited speed makes the mass transfer degree limited by water-bearing media being carried out measures such as mechanical agitation.If the current efficiency that COD decomposes descends, then the required electric weight for the treatment of processes will increase greatly, the problem that processing costs increases therefore occur.
If mass transfer is subjected to speed limit, the OH root that then produces on the conductive diamond electrode surface can consume in vain.What take place on the conductive diamond electrode surface is not COD decomposition reaction but OH root self-decomposition reaction etc., thereby begins to produce oxygen.The oxygen that this place produces reacts (be lower than reaction hardly under 150 ℃ at least, and this being the normal condition that electrode uses) hardly with the COD composition.The product of anodic reaction is oxygen rather than carbonic acid gas in this case.
On the other hand, as the reduction of cathodic reaction generation water, carry out evolving hydrogen reaction.No matter whether be that conductive diamond electrode is used as negative electrode or with other DSA electrode or platinum, titanium or stainless steel electrode the hydrogen evolution reaction takes place normally.If oxygen and hydrogen are to produce in same electrolysis compartment simultaneously, the explosive mixture that then probably has oxygen and hydrogen produces, and this is a problem at the technological process secure context.Concerning the used electrolysis compartment of soda industry, use a demarcation membrane that the electrolysis compartment is divided into anolyte and catholyte usually, thereby the gas that produces can not be mixed with each other.The fluorinated ionic exchange membrane has higher wearing quality, is commonly used for such demarcation membrane.But this fluorinated ionic exchange membrane is comparatively expensive, the OH root corrosive problem that also has anti-conductive diamond electrode to produce.If demarcation membrane contacts with conductive diamond electrode in the electrolysis compartment in operation, then the possibility of the remarkable deterioration of demarcation membrane is very big.And as the situation of soda industry, although do not have what problem when only pure saturated brine being introduced the electrolysis compartment under controlling condition of water quality fully, demarcation membrane will be easy to deterioration when processing difficult for biological degradation water-bearing media is dirty waste water or waste liquid.Concerning the difficult for biological degradation water-bearing media, water-bearing media comprises various materials, stops up demarcation membrane thus, and degradation problem under the ion-exchange capacity then takes place easily in adhering to of this type of material etc.Demarcation membrane is applicable to processing " water-bearing media of cleaning " usually, but the difficult for biological degradation water-bearing media that intractable this invention is intended to handle.
If adopting the electrolysis compartment of conductive diamond electrode is to operate continuously under the state of above-mentioned mass transfer speed limit, the more serious problems of conductive diamond electrode self stability aspect then can appear relating to.COD concentration is higher in water-bearing media, thereby when the mass transfer of COD composition was not rate-limiting factor on the electrode surface, the OH root that is produced on the electrode surface consumed by decomposing the COD composition.So, in case on electrode surface the mass transfer of COD composition become limited speed and when making the COD composition no longer arrive conductive diamond electrode, the OH root that produces on the electrode surface finally becomes oxygen.But before being converted into oxygen, still have active OH root can with the conductive diamond electrode id reaction.OH root that conductive diamond electrode produced can the most of organism of oxygenolysis, therefore can not guarantee the OH root not can with adamantine highly stable carbon (sp
3) reaction.The inventor uses conductive diamond electrode to carry out test by the electrolytic reaction decomposing organic matter under above-mentioned mass transfer velocity constrained state.Electron photomicrograph shown in Figure 2 (SEM figure) shows the conductive diamond electrode surface at the state that is used for the electrolytic reaction front and back.Before using as can be seen polycrystalline diamond particulate uniform deposition on the conductive diamond electrode surface (Fig. 2 a), but these diamond crystalses have eroded (Fig. 2 b) after using for some time.It is believed that this is the result that carbon causes of the OH root oxidation conductive diamond electrode that do not consume in the decomposition reaction of COD composition.
The conductive diamond film of conductive diamond electrode is to make by the CVD method as carbon source as methane with cheap organism.Therefore can expect and to make more cheap conductive diamond electrode future.Yet on state-of-the art, conductive diamond electrode is still not cheap, and the running cost of the CVD coating method that carries out under the high temperature is very high.Thereby do not have a situation that conductive diamond electrode was just replaced after the some months deterioration every several days.If must after the short like this time, just change a conductive diamond electrode, then can and keep in repair the artificial cost that makes and rise, thereby be difficult to make the treatment process of this difficult for biological degradation water-bearing media feasible because of servicing time.
Under the situation that dissolved COD constituent concentration is low in the water-bearing media, the problems referred to above can occur, also can occur the problem that current efficiency descends under the situation of the suspended substance that is insoluble to water-bearing media but promptly exist at mud situation passing stool like mud.This is because solid/suspended substance contacts poor causing with electrode surface.
In addition, make in the harmless fully process of water-bearing media using conductive diamond electrode to handle by treatment with electrolytic method, even the limited problem of aforesaid mass transfer velocity does not take place, also have some problems as described below when water-bearing media comprises the solubilized COD composition of high density.
About the electrochemical reaction that on the conductive diamond electrode surface, takes place, may relate to following electrochemical reaction formula by the reduction potential table.
From water, produce the OH root:
H
2O→OH·+H
++e
- E
0＝2.8V (1)
From water, produce oxygen:
H
2O→1/2O
2+2H
++2e
- E
0＝1.2V (2)
The molecular weight of oxygen is 16, and therefore according to Faraday's law, the chemical oxygen demand (COD) of decomposing 1g in the water-bearing media is that the desired electric charge of COD is given by the following formula.
(2×F)/16＝(2×96485C)/16g
＝(192.970As)/16g＝53.6Ah/16g
＝3.4Ah/g-COD
That is to say,, need the electric charge of 3.4Ah to decompose the COD of 1g in theory even current efficiency is 100%.The known conductive diamond electrode has wide thermodynamics window and the high oxygen overvoltage of analysing.If produced the OH root before oxygen is separated out, then the diamond electrode electromotive force must be the 2.8V of formula (1) at least in electrolytic process.Be used to carry out the cell voltage of the conductive diamond electrode of electrolytic reaction, in practice should at least 4 to 5V, because except this electrode overvoltage,, electrolyte solution and electrode place can make its increase because producing the resistance of gas.Although the current density during with operation, the temperature of electrolytic solution, the specific conductivity of water-bearing media etc. are relevant, can the cell voltage typical operation value that proposes (the interior electrode voltage of monocell) is about 7V.
Therefore the desired electric weight of COD that decomposes 1g is 3.4Ah * 7V=23.8VAh, just about 24Wh/g-COD or about 24kWh/kg-COD.
Use conductive diamond electrode to handle 1m by treatment with electrolytic method
3Concentrated aqueous medium is as containing 5% (50kg/m
3) the needed electric weight of water-bearing media of COD composition is 50 * 24kWh=1200kWh; Calculate by this, processing costs must not be said so cheap.Promptly, if COD concentration is lower, the mass transfer limited speed that becomes so, thereby the problem that has electricity to waste, if and COD concentration is higher, then the current efficiency of COD decomposition is good, but the electrolysis cost will be directly proportional with the absolute value of COD, therefore has the per unit volume desire to handle the higher shortcoming of electric cost of water-bearing media.
Summary of the invention
As mentioned above, utilize conductive diamond electrode water-bearing media to be handled a lot of problems fully by electrolytic process.The inventor carries out diligent in one's studies to address these problems, and the result at first finds to use conductive diamond electrode that water-bearing media is carried out the biodegradable that electrolysis treatment is improved water-bearing media.
The inventor has at first carried out various tests at BOD/COD, and with its index as the water-bearing media biodegradable, found that by using conductive diamond electrode to carry out electrolysis treatment has increased the BOD/COD value.In addition, the inventor finds that the reason that the water-bearing media biodegradable improves is to have increased voltaile fatty acid (VFA ' s) and the quantity of soluble sugar by carry out electrolysis treatment with conductive diamond electrode.That is,, be converted into voltaile fatty acid and soluble sugar makes the COD composition be converted into the BOD composition by the COD composition because voltaile fatty acid and soluble sugar have high biological degradability.In addition, be to handle by electrolytic process if the inventor finds water-bearing media with conductive diamond electrode, then the character such as viscosity of water-bearing media can change, so the flocculence of water-bearing media, settleability, filterableness etc. also improve.The inventor notices that then the improvement of character such as the improvement of the water-bearing media biodegradable that is taken place and flocculence, precipitation threshold, filterableness, adsorptivity, crystallinity is to remove fully in the water-bearing media before the COD composition by electrolysis with conductive diamond electrode, so just finishing the invention of handling the water-bearing media method according to the present invention.
Promptly, in a specific embodiment of the present invention, a kind of method of handling water-bearing media is provided, it is included in and utilizes conductive diamond electrode to handle water-bearing media in the electrolysis step, be water treatment steps then, one of biological example processing, flocculating settling processing, filtration treatment, oil/water sepn processing, adsorption treatment and crystallization treatment, or biological treatment and one of flocculating settling processing, filtration treatment, oil/water sepn processing, adsorption treatment and crystallization treatment or at least two kinds of couplings.
As mentioned above, discovery according to the inventor, significantly improved the water-bearing media biodegradable by carrying out electrolysis treatment with conductive diamond electrode, thereby make biological treatment handle water-bearing media to become and be more prone to, and the processing of finishing water-bearing media by biological treatment makes it innoxious, and the cost of total treatment process also can significantly reduce.
Equally, the flocculence of suspended substance is also improved greatly in the water-bearing media, has therefore improved the efficient of flocculating settling, only need use a spot of flocculation agent by utilizing conductive diamond electrode to carry out electrolysis treatment in addition.When the flocculence of suspended substance in the water-bearing media was hanged down, the viscosity composition that contains in the water-bearing media often was an influence factor.These viscosity compositions are decomposed by utilizing conductive diamond electrode to carry out electrolysis treatment, thereby make the water-bearing media non-sticky.Therefore, after flocculence improves, water-bearing media is carried out flocculating settling and handle and the COD composition is removed as throw out, can reduce with conductive diamond electrode and carry out the electric weight that electrolysis treatment consumed.
In addition, because the viscosity of water-bearing media is reduced by carry out electrolysis treatment with conductive diamond electrode, thereby any filter operation such as micro-filtration (MF), ultrafiltration (UF), reverse osmosis (RO), sand filtration, strainer press filtration or belt press filtration all become possibility, remove pollutent in the water-bearing media by this filter operation in addition, can economize on conductive diamond electrode and carry out the electric weight that electrolysis treatment needs, therefore can reduce the cost of total treatment process.In addition, for as organic mud in microorganism cells in contained water, available conductive diamond electrode is carried out electrolysis treatment and is destroyed cell walls, and the water separation capability of mud is improved.
In addition, if with conductive diamond electrode the water-bearing media of emulsion form is carried out electrolysis treatment, the broken phenomenon of breakdown of emulsion and micella then takes place, thereby phase boundary occurs between oil phase and water, oil/water sepn just becomes possibility like this.
In addition, in the present invention, can be with biological treatment and one of flocculating settling processing, filtration treatment, oil/water sepn processing, adsorption treatment and crystallization treatment or at least two kinds of couplings, the leading portion that the back segment water treatment steps and then uses the diamond electrode electrolysis to handle.For example with conductive diamond electrode carry out electrolysis treatment improve can handle by flocculating settling after the water-bearing media biodegradable, filtration treatment etc. removes suspended substance or solid matter in the water-bearing media, carry out a biological disposal upon then, thereby water-bearing media is carried out effective disaggregating treatment.Flocculating settling and to filter be the inexpensive method that removes suspended substance or floating solids from water-bearing media, and the suspended substance in the water-bearing media or solid COD composition quilt utilizing the conductive diamond electrode electrolysis treatment after can be removed.In addition, can not be in the water-bearing media as for being dissolved in by the COD composition that filters or sedimentation removes, because by utilizing the conductive diamond electrode electrolysis treatment to increase biodegradable, it is more easy that biological treatment also can become.Under the situation of this external handling oil/water mixing water-bearing media, make oil/water sepn become possibility by utilizing the conductive diamond electrode electrolysis treatment, therefore can remove oil phase carries out effective water disaggregating treatment by biological treatment then.
In the method for the invention, anaerobic biological treatment method or aerobe facture can be used as biological treatment step.Difficult for biological degradation COD composition in the water-bearing media is converted into organic acid and soluble sugar by utilizing the conductive diamond electrode electrolysis treatment, and these materials can be converted into biogas fast by anaerobic treatment then.This method is special under the COD of water-bearing media concentration condition with higher, and effectively and the biogas of making can be used as the energy, and therefore recovered energy becomes possibility from refuse.In addition, because the processing costs of aerobic treatment is cheap, also can after utilizing conductive diamond electrode electrolysis treatment increase water-bearing media biodegradable, carry out aerobic treatment.When the COD concentration in the water-bearing media when not being very high this method effective especially.Have low COD concentration at water-bearing media, can effectively adopt biological treatment when hanging down with conductive diamond electrode electrolysis treatment efficient.Using energy seldom just can improve biological degradability and coupling biological treatment, can improve the efficient of total treating processes with following of conductive diamond electrode electrolysis treatment condition.
In the method for the invention, do not stop under the leading portion that the utilizes conductive diamond electrode electrolysis treatment step state that preferably the COD composition decomposes fully in water-bearing media, carry out the back segment water treatment steps then.If the COD composition in the water-bearing media is by decomposing fully with the conductive diamond electrode electrolysis treatment, then under the situation that the COD concentration in water-bearing media is high, there is the high problem of per unit volume current consumption, under the situation that COD concentration is low in water-bearing media, there is the problem that current efficiency is low and electricity is wasted.But, according to a preferred embodiment of the invention, provide a kind of at water-bearing media processing cost and efficient aspect splendid method, wherein in the water-bearing media COD composition be not all but only some by handling with the conductive diamond electrode treatment with electrolytic method, improve its biological degradability and/or filterableness, settleability etc. whereby, in back segment, carry out water treatment steps then as biological treatment or flocculating settling processing.In addition, in case the leading portion with the conductive diamond electrode electrolysis treatment only carries out under high COD concentration range, surpass the excellent in efficiency of this scope with the conductive diamond electrode electrolysis treatment, the OH root that can avoid being produced because of conductive diamond electrode itself is attacked the conductive diamond electrode oneself deterioration problem that causes, and the wearing quality of conductive diamond electrode is improved like this.
Method of the present invention can be specially adapted to handle the water-bearing media of difficult for biological degradation.
In of the present invention one preferred specific embodiment, cause the BOD/COD of water-bearing media to be at least 0.2 by in the leading portion electrolysis treatment, using conductive diamond electrode, to improve the water-bearing media biodegradable.If the BOD/COD of water-bearing media is 0.2 or littler, then biological degradability is lower, so the back segment biological treatment will become difficult.Under the situation of aerobe facture as the back segment biological treatment step, by the means that promptly prolong the residence time as dilution water-bearing media, prolongation biological treatment time, even the BOD/COD of water-bearing media is 0.2 or still less also can handles water-bearing media, but processing efficiency will be lower.In addition, even the BOD/COD of water-bearing media is 0.2 or still less, even it takes place to change so that the means that microorganism is tamed can make biological treatment become feasible from generation to generation by long-time culturing micro-organisms.Yet, in this way, will form a special selected microorganism phase.Although can not have problems under the situation of water-bearing media of identical water quality is supplied in the biological treatment chamber always, if the water quality of water-bearing media fluctuates at short notice, the ability of biological treatment may significantly descend.For the back segment biological treatment process is carried out smoothly, preferably by leading portion with conductive diamond electrode carry out electrolysis treatment make the BOD/COD of water-bearing media be at least 0.2, more preferably at least 0.3, also more preferably at least 0.5.If the BOD/COD of water-bearing media is at least 0.5, it is easy then to use gasification to be that the anaerobic treatment method also will become.
In the method for the invention, preferably utilize in the step of conductive diamond electrode electrolysis treatment, the every gram COD in the water-bearing media is applied the electric charge that is no more than 34Ah at leading portion.Be low to moderate under the situation of hundreds of mg/L per unit volume water-bearing media (for example every m in the initial COD concentration of water-bearing media
3) the charge consumption amount also will be lower, surpass the above-mentioned quantity of electric charge even therefore apply, this facture also is feasible aspect cost, but in either case, will in the lower zone of current efficiency, carry out with conductive diamond electrode electrolysis treatment step, therefore electric charge will be wasted, and this is undesirable.In a preferred embodiment, with applying the electric charge that is no more than 17Ah/g-COD in the conductive diamond electrode electrolysis treatment step, more preferably use and be no more than 3.4Ah/g-COD, this is theoretical electric charge, more preferably apply electric charge and drop to and be no more than 95% of theoretical electric charge, also more preferably no more than 90% of theoretical electric charge.The lower limit that applies electric charge in utilizing the electrolysis treatment of conductive diamond electrode is 0.034Ah/g-COD at least preferably.If this is few for charge ratio, then is difficult to water quality by changing water-bearing media or physical properties and the back segment water treatment is carried out smoothly as the means of improving the water-bearing media biodegradable or improving similarities such as precipitation threshold, filterableness.The more preferably value of electric charge lower limit is 0.34Ah/g-COD at least, promptly 10% of theoretical electric charge or more than.And one more preferably value be 0.68Ah/g-COD at least, promptly 20% of theoretical electric charge or more than.
Description of drawings
Fig. 1 illustrates when utilizing the conductive diamond electrode electrolysis treatment from difficult for biological degradation water-bearing media that factory discharges, the COD concentration of water-bearing media and decompose relation between the instantaneous current efficiency of COD.
Fig. 2 comprises that electron microscopic that conductive diamond electrode condition of surface before and after the electrolysis is shown is according to (SEM ' s).Fig. 2-(a) illustrates the condition of surface of conductive diamond electrode before the electrolysis, and Fig. 2-(b) illustrates the state after the electrolysis.
Fig. 3 is the schema of method that is used to handle water-bearing media of the specific examples according to the present invention.
Fig. 4 illustrates the COD of sample liquids of electric charge (transverse axis) that every 1g COD contained in the sample liquids applied and embodiment 1 experiment and the relation curve between the BOD (longitudinal axis).
Fig. 5 illustrates the relation curve between the COD decreasing ratio and BOD/COD (per-cent) in embodiment 1 experiment.
Fig. 6 illustrates the relation curve between the organic acid of the electric charge of input in embodiment 1 experiment and generation.
Fig. 7 illustrates the relation curve between the gaseous constituent of the electric charge of input in embodiment 1 experiment and generation.
Fig. 8 illustrates the methane content trend map in time that produces in embodiment 2 experiments.
Fig. 9 illustrates the electric charge of input in embodiment 3 experiments and the relation curve between COD, BOD and the colour-change.
Figure 10 illustrates the relation curve between the COD decreasing ratio and decolouring per-cent in embodiment 3 experiment.
Figure 11 illustrates the relation curve between the COD decreasing ratio and ammonia concentration nitrogen decreasing ratio in embodiment 3 experiment.
Figure 12 is illustrated in the electric charge and the COD of input in embodiment 4 experiments, the relation curve between MLSS and the viscosity.
Figure 13 is the detail flowchart that specific examples according to the present invention is used to handle a kind of method of water-bearing media.
Figure 14 is the detail flowchart that specific examples according to the present invention is used to handle a kind of method of water-bearing media, and the difficult water-bearing media that decomposes adopts leading portion to handle with diamond electrode treatment step and back segment flocculating settling step in the method that relates to.
Figure 15 and the relevant schema of another specific examples of the present invention are wherein with biological treatment and the flocculating settling combination of leading portion with diamond electrode electrolysis treatment and back segment.
Figure 16 is and the relevant schema of another specific examples of the present invention, wherein with biological treatment and the flocculating settling combination of leading portion with diamond electrode electrolysis treatment and back segment.
Figure 17 is and the relevant schema of another specific examples of the present invention wherein leading portion to be handled and the filtration treatment combination with the flocculating settling of diamond electrode electrolysis treatment and back segment.
Figure 18 is and the relevant schema of another specific examples of the present invention, wherein with the crystallization dephosphorization treatment combination of leading portion with diamond electrode electrolysis treatment and back segment.
In Figure 18, the following implication of each symbolic representation.The water-bearing media (raw water) of 1 expression difficult degradation; 2 expressions utilize the electrolysis treatment step of diamond electrode; 3 expression brine electrolysis; 4 expression water treatment steps; 5 expression treated waters; 16 expression teeter columns; 21 expressions are regulated with chemical liquid (ph conditioning agent, Ca
2+, Mg
2+, NH
4 +); 22 expression crystallization-adjusted treating water; 23 expression dephosphorization towers; 24 expression phosphorated crystalline materials (HAP or MAP).
Detailed description of the invention
Used term in this specification sheets is described now.
" water-bearing media " is the wherein medium of main component of a kind of water conduct, and can be any form, and for example mud, emulsion or the aqueous solution are not limited in this respect.In addition, the formation of each composition of water-bearing media can be any in the materials like that such as organism, inorganics, salt.
As described in previous, " difficult for biological degradation water-bearing media " refers to utilize traditional water treatment method such as biological treatment that it is handled the relatively water-bearing media of difficulty.Comprise under the situation of many low biological degradability materials at water-bearing media especially, for example comprising with the petroleum chemicals at water-bearing media is under the situation of chemosynthesis material of raw material, perhaps comprise under the situation of the microorganism with sclereid wall at water-bearing media, under the situation as organic mud or methane fermentation mud, water-bearing media will be a kind of difficult for biological degradation water-bearing media.In addition, water-bearing media contains the virulent material of microorganism, perhaps microorganism is caused biological material such as ammonia, benzene or the phenol that suppresses, and will also can become the difficult for biological degradation water-bearing media.In addition, comprising the acetate of high density or the water-bearing media of sugar, also to can be described as be the difficult for biological degradation water-bearing media, because microorganism inside can not breed.In addition, the water-bearing media that comprises coloring agent component etc. also is the difficult for biological degradation water-bearing media, and the problematic water-bearing media of carrying out a biological disposal upon in addition also is included in " the difficult for biological degradation water-bearing media " among the present invention as comprising antibiotic water-bearing media.
COD in this manual, " " (chemical oxygen demand (COD)) refer to the chemical oxygen demand (COD) (COD of the water-bearing media determined as oxygenant with potassium bichromate
Cr).And COD
CrThe same as the physical chemistry oxygen requirement, also exist with the COD of potassium permanganate as oxygenant
Mn, TOD (total oxygen demand) determines by the numerical value of oxygen-consumption under the combustion conditions, and ThOD (theoretical oxygen demand) determines by the chemical equation of complete oxidation.Therefore the measuring method difference of these physical chemistry oxygen requirements, even for identical water-bearing media, these values also can there are differences.With COD in this manual
CrValue and other physical chemistry oxygen requirements between have ThOD 〉=TOD 〉=COD
Cr〉=COD
MnRelation.That is, because the chemical oxygen demand value of the water-bearing media that provides in this specification sheets is COD
CrIf determine chemical oxygen demand (COD) with ThOD or TOD then can obtain the situation of a higher value usually, if with COD
MnDetermine that chemical oxygen demand (COD) then will obtain a more situation of low value." BOD " refers to biochemical oxygen demand (BOD) in this manual, and is BOD
5, promptly be through 5 days definite values.The value of BOD/COD is to use BOD in this manual as the index of water-bearing media biological degradability
5Value divided by COD
CrValue obtain, write by from 0 to 1 or from 0 to 100% numerical value.
One embodiment of the invention will utilize Fig. 3 to be described now.According to this embodiment of the present invention, water-bearing media 1 at first utilizes conductive diamond electrode to handle in leading portion electrolysis treatment step 2, then the brine electrolysis 3 that generates is handled in back segment water treatment steps 4, discharges treated water 5.
According to the present invention, can be particularly suitable for handling the difficult for biological degradation water-bearing media.The example of the difficult for biological degradation water-bearing media that available the present invention handles comprises the mud from sewage work and water treatment plant, various mud from methane fermentation process etc., waste water/liquid from refinery and petroleum products factory, waste water/liquid from the chemical plant, waste water/liquid from pharmaceutical factory and hospital, from each step of semiconductor fabrication processes (photoresist step, rinse step, plating step) waste water/liquid, the photograph development waste liquid, any useless machining oil (oil soluble or water-soluble) waste liquid from engineering shop, wash-down water and waste water from the paint manufacturing processed, from canning factory, the wash-down water and the waste water of body plant and metal sheet factory coating procedure, waste water/liquid from the agrochemistry production process, dyeing waste water, dye processing plant waste water, from power station ion-exchange recycling waste water (condensate demineralizer waste water), from the electroplating effluent that comprises organism or ammoniacal liquor of plating shop with electroplate wash-down water and from the membrane filtration condensed water of tap water treatment plant.In addition, the present invention is not limited thereto, but can be applied to the water-bearing media of any biological treatment difficulty usually.
To the form of pending water-bearing media 1 without limits.For example pending water-bearing media 1 may be the consoluet aqueous solution, perhaps mud, emulsion, micella, suspension, concentrated solution or contain the mud of solid matter.In addition, pending water-bearing media 1 may be a kind of difficult for biological degradation water-bearing media that various film processing, various distillation processing, flocculating settling are handled or filtration treatment has concentrated that utilized.In the present invention, be effectively to the pending water-bearing media that is concentrated to thousands of mg/L COD concentration, but to this concentration without limits.Contained solid matter is not with form of suspension but has under the situation of several at least mm sizes in pending water-bearing media, utilizing before conductive diamond electrode carries out the leading portion electrolysis treatment, preferably water-bearing media is handled by filter screen, sieve or analogue.Not emulsion at pending water-bearing media but obviously under the situation of separated oil phase or oil film, preferably remove these oil phases by the separation or the similar means of fluid level.In addition, have turbidity or just have under the situation that solid matter settles, preferably remove sedimentation material or stirring in advance so that water-bearing media can be transported to smoothly with in the conductive diamond electrode electrolysis treatment step from beginning at pending water-bearing media 1.Have at pending water-bearing media under the situation of low conductivity, preferably utilize conductive diamond electrode to add various electrolytic solution such as sodium-chlor or sodium sulfate before carrying out electrolysis treatment step 2 at leading portion.In pending water-bearing media specific conductivity is under 0.1mS/cm or the lower situation, preferably adds electrolytic solution to water-bearing media.This is because if the specific conductivity of water-bearing media is low, then utilizes the cell voltage in the electrolysis treatment step 2 of conductive diamond electrode to increase, and therefore electrolytic cost will rise.The specific conductivity that preferably makes pending water-bearing media is 1mS/cm at least.In this case, chemical electrolysis liquid can be added in the water-bearing media, perhaps can obtain easily under the situation of water-bearing media that another kind has high conductivity, this water-bearing media with high conductivity can mix with pending water-bearing media, afterwards the mixture that obtains is sent into in the conductive diamond electrode electrolysis treatment step 2.For example, obtaining easily under the situation of seawater, seawater can mixed with pending water-bearing media, then the mixture that obtains is being sent in the usefulness conductive diamond electrode electrolysis treatment step.
In the present invention, at first, pending water-bearing media is handled by the method for utilizing the conductive diamond electrode electrolysis treatment.The conductive diamond of any structure known in the art can both be as the conductive diamond electrode of this electrolysis treatment step.For example, make electrode by depositing one deck conductive diamond film as matrix and on the surface of these matrix with conductive metallic material such as nickel, tantalum, titanium, molybdenum, tungsten or zirconium, by utilizing semiconductor material such as silicon wafer as matrix, and on the surface of this matrix, form one deck conductive diamond film and make electrode, perhaps also can be used as conductive diamond electrode in the present invention by the material of sedimentary conduction polycrystalline diamond being made the acquisition of writing board shape or analogous shape.Conductive diamond film is that the method that is used on the matrix doping agent of doping specified quantity when forming diamond thin such as boron, nitrogen is made electric conductor, makes doping agent with boron usually.In leading portion electrolysis treatment step of the present invention, conductive diamond electrode can be used to do simultaneously anode and negative electrode, and perhaps conductive diamond electrode can be used to do one of anode and negative electrode.As the electrode materials of non-conductive diamond electrode, available typical electrode materials such as platinum or titanium.Preferred anodes and negative electrode all are made up of conductive diamond electrode in the electrolysis treatment step.
In the present invention, the COD composition that comprises in the preferred water-bearing media 1 is in leading portion incomplete decomposing in the electrolysis treatment step 2 of conductive diamond electrode.This is because if COD is removed completely in the electrolysis treatment step, then under the situation of the COD of water-bearing media concentration height (tens thousand of at least mg/L, i.e. at least percent order of magnitude), and then per unit volume (L or m in the electrolysis treatment step
3) processing cost of water-bearing media will be high, on the other hand under the low situation of the COD of water-bearing media concentration, will become to the lip-deep mass transfer of conductive diamond electrode is subjected to speed limit, thereby will be wasted with electric charge in the conductive diamond electrode electrolysis treatment step 2.
Have at the initial COD of pending water-bearing media under the order of magnitude situation of several percentage ratios at least as mentioned above, use in the conductive diamond electrode electrolysis treatment step 2 at leading portion, the COD decreasing ratio preferably reaches the COD value that makes brine electrolysis 3 and is at least 500mg/L, preferred 1000mg/L at least, more preferably 2000mg/L at least.Initial COD value height and COD composition at water-bearing media are under the soluble situation, and the current efficiency that COD decomposes in utilizing the electrolysis treatment of conductive diamond electrode can remain on 100%.Yet if COD concentration is at these below value in the water-bearing media, the current efficiency of electrolysis treatment of utilizing conductive diamond electrode is with step-down.For example under the situation that the initial COD concentration of water-bearing media 1 is 10000mg/L (1%), be no more than 95%, preferably be no more than 90%, more preferably no more than 80% with the preferred COD percentage ratio that is removed in the conductive diamond electrode electrolysis treatment step; If COD concentration is lower than this, then the COD composition mass transfer of water-bearing media will begin to become limited speed to electrode, so processing efficiency is with step-down.But be not if the initial COD concentration difference of water-bearing media, then under mass transfer begins to become the COD concentration of limited speed the decreasing ratio of COD also with difference.For example, getting initial COD concentration is 50000mg/L, and the concentration range of COD does not reach mass transfer begin the to become value of limited speed yet when 96% to 99% COD has decomposed.Even the limited speed yet mass transfer does not become if reached high COD decreasing ratio for such high concentration aqueous medium, utilizes the processing cost of conductive diamond electrode electrolysis treatment step 2 also will uprise; Therefore preferably make and utilize the COD decreasing ratio of conductive diamond electrode electrolysis treatment step to be no more than 95%, preferably be no more than 90%, more preferably no more than 80%.
The preferred minimum value that removes per-cent with COD in the conductive diamond electrode electrolysis treatment step 2 is at least 1%, more preferably at least 5%, also more preferably at least 10%, also more preferably at least 15%, also more preferably at least 20%.Removing all COD in utilizing the conductive diamond electrode electrolysis treatment is not that the present invention is desired, if but COD concentration does not reduce fully, then can not change the physical values of water quality and each side and then influence suchlike character such as water-bearing media biodegradable, flocculence, precipitation threshold, filterableness.Therefore in back segment water treatment steps 4, to carry out water treatment in order making, preferably to make COD concentration be reduced by at least 1% in conductive diamond electrode electrolysis treatment step at leading portion.Therefore preferably keep above-mentioned COD decreasing ratio lower value in conductive diamond electrode electrolysis treatment step at leading portion.By in utilizing the conductive diamond electrode electrolysis treatment COD decreasing ratio being remained within such scope, (describing) water-bearing media biodegradable (BOD/COD) as shown in Figure 5 subsequently in detail can be improved by electrolysis treatment.
Be in several thousand mg/L or when lower at the low order of magnitude of the above-mentioned value of initial COD concentration ratio of water-bearing media 1, COD concentration has been in the COD composition within the mass transfer on conductive diamond electrode surface begins to become the scope of limited speed.Even COD concentration is low, the charge number that the COD concentration that a water-bearing media also arranged is imported with the conductive diamond electrode electrolysis treatment time is the scope that linear scaling descends.Certainly the mass transfer velocity of COD composition is limited in this scope, therefore can not keep current efficiency 100%, and drops to when being lower than hundreds of mg/L as COD, and current efficiency is poorer.For example, initial COD is the situation of water-bearing media by handling with the conductive diamond electrode electrolysis of 1300mg/L shown in Fig. 9.In Fig. 9, current efficiency approximately is 56% when the electric charge that applies is 2.6Ah/g-COD, in case but COD drops to more that current efficiency descends when being lower than 500mg/L.Is easily to decompose composition by preferentially being decomposed with the conductive diamond electrode electrolysis in initial period current efficiency than higher reason.Different with the electrolytic easy decomposition composition of conductive diamond electrode with the material of readily biodegradable in the biological treatment.From Fig. 9, know and find out that colored component is easily by decomposing with the conductive diamond electrode electrolytic processing method.Low many of the electric charge that color suppression ratio COD density loss is used.Usually just can remove colored component fully at 10% to 90% place that decomposes electric charge that COD requires fully.In case when generally being difficult to remove colored component, preferably in electrolysis treatment 2, remove colored component with conductive diamond electrode as much as possible, although COD does not decompose fully by conventional water treating method such as biological treatment.
Even the COD concentration of pending water-bearing media 1 is the order of magnitude of percentum, comprise microbial biomass in solid COD composition such as the mud situation at pending water-bearing media 1, may will descend in the efficient that COD arrives electrolysis treatment before 500 to 2000mg/L, this be because as mentioned above this moment the COD composition mass transfer begin the limited speed that becomes.For example, Figure 12 illustrates the situation of methane fermentation mud being carried out electrolysis treatment with conductive diamond electrode.As shown in figure 12, in case the COD density loss in the water-bearing media to being lower than 6000mg/L, the decline that the decomposition efficiency of COD can be unexpected.It is believed that this is because the contact efficiency between solid COD composition and the electrode surface descends.If attempt under such state, to remove 100% COD by the electrolysis treatment step, then will expend huge electric power with conductive diamond electrode.Therefore carry out in leading portion electrolysis treatment step that minimum COD decomposes and task be placed on as much as possible making in the back segment water treatment that the cost of whole process is more cheap.
The mechanism that by the method for carrying out the leading portion electrolysis treatment with conductive diamond electrode the back segment water treatment steps is carried out smoothly in the present invention will be described now.This mechanism began to play a role before by electrolytic process COD being decomposed fully.
At first, in one embodiment of this invention, can increase the water-bearing media biodegradable by the method for utilizing conductive diamond electrode to carry out electrolysis treatment.BOD/COD is used as the index of water-bearing media biodegradable, and the COD composition of difficult degradation is converted into the BOD composition is important in order to increase this value (promptly strengthening biological degradability).In utilizing the conductive diamond electrode electrolysis treatment, the OH root that produces on the conductive diamond electrode is not directly organism and similar substance to be converted into carbonic acid gas and water, but with organism at first through intermediate product such as organic acid, these organic acids are converted into carbonic acid gas and water then.Such organic acid, exemplary are VFA, and high biological degradability is arranged, and therefore producing under the high density organic acid situation with the conductive diamond electrode electrolytic processing method by leading portion, can effectively carry out methane fermentation in the back segment anaerobic biological treatment.Therefore use in the conductive diamond electrode electrolysis treatment at leading portion, the water-bearing media biodegradable increased before the COD composition decomposed fully.Comprise at water-bearing media under the situation of larger molecular organics, such larger molecular organics generally has difficult for biological degradation, so the water-bearing media biodegradable is very poor.Yet by utilizing the reaction of conductive diamond electrode electrolysis treatment generation larger molecular organics molecular weight and molecular weight, so the water-bearing media biodegradable can increase.It is believed that larger molecular organics such as xylogen, humin substances and be not directly to resolve into carbonic acid gas and water, but become carbonic acid gas and water after progressively reducing through molecular weight as the polysaccharide of cellulosic cpd.
In addition, the common very poor colored component of biodegradable also can easily be decomposed by utilizing conductive diamond electrode to carry out electrolysis treatment.Be used to decompose the possible machine-processed as described below of colored component, at first, have a kind of mechanism of decomposing colored component by the direct reaction of OH root.This decomposition may not be to decompose fully, disappears but color may be the variation of the part molecule by colored component.Comprise at water-bearing media under the situation of dyestuff composition, the key in the colorific molecular structure may be caused color to disappear by the OH fracture.The destruction of coloured molecule may be taken place by various colored components or as the tinting material of azo-compound and the reaction between the OH root.This external water-bearing media comprises under the situation of chlorion or sulfate ion, they are oxygenants, by the reaction on conductive diamond electrode, these ions are converted into hypochlorous acid or persulfuric acid, and these oxygenants are made/coloring agent component coloured in order to decompose then.
For as the water-bearing media of organic mud, wherein the microbial cell wall has comprised big water gaging and owing to the viscosity that has increased makes the water separation capability extreme difference, has been easy to decompose the viscosity composition by the method for utilizing conductive diamond electrode to carry out electrolysis treatment.In addition, the microbial cell wall is damaged, can significantly improves the water separation capability of mud then by the OH root that produces on the conductive diamond electrode surface.
Except that improving water separation capability, by the ruined mud of cell walls is incorporated in the aerobe treatment chamber, promptly solarization air cell can construct the water treatment system that does not produce mud.Promptly by utilizing conductive diamond electrode to adopt the residue mud of water treatment plant's generation of aerobe facture to carry out electrolysis treatment to all or part, to return the aerobe treatment chamber by the brine electrolysis that electrolysis treatment obtains then, and can construct in view of the above and not produce mud or the extremely low water treatment system of mud generation.That is,, then can reach the purpose that mud dissolving and volume reduce if structure of the present invention is introduced the aerobe treatment system as its part.This idea not only can be used to the aerobe facture, and can be used to the anaerobic biological treatment method.That is,, return all or part brine electrolysis then, can construct one in view of the above and not produce mud or the extremely low methane fermentation system of mud generation to the methane fermentation chamber by utilizing conductive diamond electrode to carry out electrolysis treatment to the mud that originates from methane fermentation.As mentioned above, producing organic acid when water-bearing media being utilized conductive diamond electrode carry out electrolysis treatment.These organic acids are a kind of good substrate for the methane fermentation microorganism has served as, and therefore the biogas amount itself that produces can be increased.Notice that not the already treated liq in will all conductive diamond electrode electrolysis treatment steps 2 of using by oneself turns back to methane fermentation chamber or aerobe treatment chamber.What return methane fermentation chamber or biological treatment chamber can only be by the filtrate that electrolytic solution is transported to after filtration or the solid/liquid separation process of similar means obtains.The microbial cell wall is destroyed by the electrolytic processing method that utilizes conductive diamond electrode.Although by the solid shell spended time of microorganism digestion microbe, comprise that the aqueous solution part of materials like that such as organic acid, soluble sugar is easier to be digested by aerobic or anaerobic biological treatment.
As another mechanism of improving the water-bearing media processing efficiency by the present invention, under the situation that pending water-bearing media exists with the form of suspension, emulsion or analogue, relate to by utilizing the conductive diamond electrode electrolytic processing method to change the electric charge or the analogue of emulsion, and then improve flocculence and separability.If pending water-bearing media comprises paint, resin or the analogue that is dissolvable in water water, then can flocculate by changing change pH values.Shown in the electrochemical reaction formula that on the conductive diamond electrode surface, takes place (1) and (2) that provide previously, when by electrolytic reaction after anode produces OH root or oxygen, produce proton (H simultaneously
+), so electrode surface becomes strongly-acid.On the other hand, OH
-Produced at negative electrode, so negative electrode becomes strong basicity.The particle of water soluble resin, paint or analogue is in suspension or emulsive equilibrium state in water-bearing media; With strongly-acid with during alkaline electrode surface contacts repeatedly, begin flocculation immediately.Especially when near the pH value electrode is acidity, the electric charge that then is suspended on the particle of water soluble resin in the water-bearing media or paint is neutralized, so particle repels no longer mutually and therefore flocculation.
In addition, when utilizing conductive diamond electrode electrolysis treatment water-bearing media, make the pH value become acidity because of producing organic acid, water-soluble paint or resin may flocculate and precipitate whereby.This external pending water-bearing media is in oil and emulsifying water state together down as water-soluble machining oil, and the effect by electrolytic reaction produces micella and breaks and demulsifying phenomenon, the oil particles accumulation formation agglomerate oil that is bonded together.Between oil phase and water, form phase boundary clearly like this, therefore can produce the state of oil/water sepn.As mentioned above, such effect appears at leading portion and utilizes the conductive diamond electrode electrolysis treatment to remove fully before the COD, and the characteristic of water-bearing media becomes and is suitable for the back segment water treatment thus.
Structure or form with conductive diamond electrode electrolysis treatment step 2 equipment used among the present invention is not particularly limited.Tank room can be batch-type or continous way operation.Under batch-wise situation, anode and negative electrode that conductive diamond forms are mounted in pending that chamber that water-bearing media was transported to, electrolysis treatment is carried out for some time, then in case after reaching the COD decreasing ratio of regulation, brine electrolysis is sent into the back segment water treatment steps.In addition, can be used for a kind of circulation batch mode with conductive diamond electrode electrolysis treatment step 2.In the circulation batch-type, provide and the isolating electrolyzer of water-bearing media groove, water-bearing media is sent in the electrolyzer with pump or analogue from groove, and treated water is returned to the water-bearing media groove in electrolyzer then.In this case, because, therefore keeping electrolytic efficiency with pump delivery and then form the forced-flow of water-bearing media between the anode of electrolyzer and negative electrode, water-bearing media is better than only electrode being immersed in situation in the water-bearing media.Also be in this circulation batch-type, when the water-bearing media COD concentration in the groove had dropped to preset value, water-bearing media can be admitted to the back segment water treatment steps.In addition, be used for batch-type or the batch-wise treatment facility that circulates, utilize the electrolytic processing apparatus of conductive diamond electrode to form, but may have multistage structure by a groove and an electrolyzer for above-mentioned.That is, can take to have the equipment of following structure, wherein water-bearing media is sent to next section tank room after first section tank room is processed, and utilizes diamond electrode to carry out similar electrolysis treatment in this tank room.In equipment, from the tank room of back segment conductive diamond electrode, obtain brine electrolysis and be sent to water treatment steps 4 with such structure.Advantage with equipment of such structure is to set the operational condition of each section electrolyzer according to the COD concentration of water-bearing media.Set the more valid function of electrolysis treatment that low current density can use conductive diamond electrode by in the tank room at water-bearing media place, setting high current density and having in the tank room at water-bearing media place of low COD concentration range with high COD concentration range.The OH root density that produces on the conductive diamond electrode surface is by the current density decision, and therefore the OH radical amount that produces can be according to being regulated by electrolytic water-bearing media COD concentration.If such structure is used, then can reduce the generation of excessive OH root, the loss of the conductive diamond electrode that causes because of the OH root can reduce, and therefore can increase the life-span of electrode.In addition, the generation that reduces excessive OH root also can cause the saving of the electricity that uses in the electrolysis.
Also can use continous way with conductive diamond electrode electrolysis treatment step 2.Under the situation of carrying out the continous way electrolysis treatment, have the tank room of conductive diamond electrode to be installed in series together with a plurality of, and the regulation residence time of each tank room should be safe.In addition, need not handle by such tank room, also can adopt a kind of filter pressure type electrolyzer that uses in soda industry to handle, wherein anode and negative electrode alternately are placed in the multistage operation.In addition, as in each electrolyzer by the method for electric current, can adopt the monopolar electrode method, perhaps also can adopt the bipolar electrode method.Under the situation that requires the large electrode zone, bipolar method has the compact more advantage of equipment.
In tank room, the temperature of the water-bearing media of contact conductive diamond electrode is preferably set to 40 to 100 ℃.The specific conductivity of water-bearing media is along with temperature variation is huge, and specific conductivity is also higher when comparatively high temps.In addition, can keep low cell voltage by the high conductivity that keeps water-bearing media.By the electrolytic reaction that utilizes conductive diamond electrode the temperature of water-bearing media is risen, and preferred high as far as possible this temperature of maintenance.A kind of is being 50 to 90 ℃ with the preferred working temperature of conductive diamond electrode electrolysis treatment step, more preferably 60 to 85 ℃.In order to keep such temperature, to settle heat exchanger particularly preferably in the import and the outlet of tank room, and do like this to make between this and can carry out heat exchange, the heat that tank room is produced can be used effectively again.As the method for in tank room, settling conductive diamond electrode, the structure that preferred employing can effectively outgas therein.If can not effectively outgas well, then between electrode with residual bubble, and cause the voltage of internal electrode to rise.Therefore preferably in tank room the positioned vertical electrode be better than placed horizontally.But under the situation of placed horizontally electrode in tank room, preferably at least one negative electrode or have as the anodic conductive diamond electrode and can promote the structure that outgases for example is a mesh, porous plate, the perhaps form of net metal.
Form according to the water-bearing media that desire is handled, the gas that produces in electrolytic reaction can form the tiny bubble that size is no more than 1 millimeter.For example, under the situation of handling a kind of very sticking water-bearing media, because the decreasing ratio of COD is lower, promptly in the initial period of electrolysis step, not having bubble increases, and therefore effusive treated water wherein may be mixed with tiny bubble from tank room.Under these circumstances, before brine electrolysis is sent to back segment water treatment steps 4, effusive water-bearing media (brine electrolysis) will be through the froth breaking operation from tank room, and this is manipulated de-gassing vessel or mechanical deaeration's equipment or a kind of froth breaking equipment is provided in another chamber.In this froth breaking operation, it is effective using a spot of chemical defoamer.What notice is to produce this tiny bubble in that lower section of COD decreasing ratio.Though depend on the initial viscosity of processed water-bearing media, in case the COD decreasing ratio reaches at least 5 to 15% o'clock in the electrolysis treatment, the foamy problem has generally just disappeared.
In one embodiment of this invention, biological treatment can be used as the back segment water treatment steps and is carried out.Biological treatment is the most cheap in several water treatment method, and can be used for effectively handling the water-bearing media that is difficult to the low COD concentration range of conductive diamond electrode electrolysis treatment.In addition, greatly increased the water-bearing media biodegradable, therefore made high effect biological treatment become possibility by utilizing conductive diamond electrode to carry out electrolysis treatment.
Biological treatment step 4 may be the anaerobic biological treatment step in the method for the invention.Particularly preferably the anaerobic biological treatment method is used for pending water-bearing media COD concentration higher system, and produce a large amount of organic acids or soluble sugar with the conductive diamond electrode electrolysis treatment by leading portion.The anaerobic biological treatment method can be 20 days gasifications of standard, perhaps can be the high temperature gasification that carries out under about 55 ℃ of temperature.Under the situation of high temperature methane fermentation, advantage is that biological treatment speed is very fast, so the treatment time can reduce to 10 to 15 days.In the present invention; as biological treatment; alternative way is a kind of high speed UASB (upper reaches (up flow) anaerobism mud bed) gasification that particle mud (the methane fermentation microorganism caking of granulation) is housed, and perhaps also can use EGSB (the expanded granular mud bed) gasification that a kind of reaction is faster, the processing load is higher.If anaerobic treatment is carried out as the back segment biological treatment in the method for the invention, then having for example can be with biogas form recovered energy, the advantage that the amount of sludge of generation is lower.The gas that utilizes methane fermentation to produce can directly be acted as a fuel, and perhaps can be converted into the energy derive that hydrogen is used as fuel cell or analogue then by reforming.Certainly in utilizing the electrolysis treatment step of conductive diamond electrode, also can produce hydrogen, and this hydrogen can be used as the energy of fuel cell equally.
In another embodiment of the present invention, the back segment water treatment steps may be the aerobe facture.Have at the brine electrolysis that obtains by the electrolysis treatment of utilizing conductive diamond electrode under the situation of low COD value, preferably use the aerobe facture to handle as back segment.In the present invention, have no particular limits for the aerobe facture of handling as back segment, for example, can adopt a kind of floating activated sludge treatment process (wherein mud swims in the solarization air cell) of standard aerobe facture, the biofilm filtration method that perhaps a kind of microorganism is fixed on the film can be used.In addition, aerobic microbiological is fixed on as the aerobe facture on the carrier of gac, hard coal (based on the carbon of coal) or sand and can be used.In addition, as a kind of distortion of floating method, the method that microorganism is fixed on the carrier of granulous PEG (polyoxyethylene glycol) or gac also can be used.The biological contact aeration that mode as an alternative, microorganism are fixed on string shape, the netted or honeycomb support is handled and can be used.Mode as an alternative is not to carry out aeration but the carousel-type aerobe facture of directly getting oxygen from air can be used.Carousel-type aerobe facture is that the dish that will have sponge or analogue is arranged to that its upper part is exposed in the outer air of water-bearing media and directly oxygen is brought into aerobe facture method in the water-bearing media by rotating-disk from air.
In addition, in another embodiment of the present invention, anaerobic biological treatment method and the combination of aerobe facture can be used for the back segment biological treatment step.In this case, nitrogen, the phosphorus composition of staying in the brine electrolysis is removed.Under the situation that adopts this method, need not in the electrolysis treatment step of leading portion, remove nitrogen all in the water-bearing media, phosphorus composition with conductive diamond electrode.
Describe below with reference to accompanying drawings according to of the present invention with the conductive diamond electrode electrolysis treatment leading portion and the various embodiment of the processing water-bearing media method of arbitrary back segment water treatment coupling.In the following description, provided the several specific exampless among the various embodiment that can be used for processing water-bearing media method of the present invention, but the present invention is not limited thereto.
Figure 13 is the schema according to the specific examples of the processing water-bearing media method of embodiment of the present invention, wherein is with leading portion and the back segment coupling that comprises anaerobic treatment and aerobic treatment combination with the conductive diamond electrode electrolysis treatment.Embodiment shown in Figure 13 is preferred for the water-bearing media that pending water-bearing media is a difficult for biological degradation, and comprises many ammonia and nitric nitrogen but do not contain many chlorions.For example, embodiment shown in Figure 13 is preferred for handling that to comprise 3 to 3000mg/L be the water-bearing media of the difficult for biological degradation of total nitrogen with ammonia and nitric nitrogen.Under the nitrogen concentration of the water-bearing media situation higher, preferably in conductive diamond electrode electrolysis treatment step, add chlorion to realize removing of nitrogen to water-bearing media before by the electrolysis treatment of utilizing conductive diamond electrode than this.The water-bearing media 1 of difficult for biological degradation utilizes conductive diamond electrode to carry out electrolysis treatment in leading portion electrolysis treatment step 2.In with conductive diamond electrode electrolysis treatment step 2, preferably the residue mud 15 that back segment aerobe treatment step 10 is produced carries out this processing after sneaking into pending water-bearing media 1.By utilizing conductive diamond electrode that residue mud 15 is carried out electrolysis treatment, make to make up a kind of organic sludge or extremely low water technology of mud generation of not producing.It should be noted that for keeping the low cost of entire treatment process, incomplete decomposing COD composition is very important in conductive diamond electrode electrolysis treatment step 2.In addition, if water-bearing media comprises chlorion hardly, then the ammonia nitrogen in the water-bearing media 1 of difficult for biological degradation is converted into nitric nitrogen in conductive diamond electrode electrolysis treatment step 2.Secondly, the brine electrolysis 3 of the conductive diamond electrode electrolysis treatment of using by oneself step 2 is sent to settling bowl 6, is removed at this solid matter 8.Note in the present embodiment, settling bowl 6 illustrates as the means of carrying out solid/liquid separation, but also can use any of means of other various solid/liquid separation, for example membrane filtering method, sand filtration method, press filtration method, belt press filtration method or flocculation sediment separation method.Suchlike material such as undecomposed cell walls removes in settling bowl 6 in the solid materials that does not have in the electrolysis treatment with conductive diamond electrode in the water-bearing media 1 to decompose, the mud.The solid matter that comprises in the brine electrolysis 3 is not the solid matter of difficult dehydration, and as the residue organic sludge from activated sludge, but therefore the non-sticky solid matter is easy to remove by precipitation process, filtration treatment or similar processing.Then, to be sent to anaerobic be in the anaerobic biological treatment chamber 9 to the supernatant liquor in the settling bowl 7.Though do not show, after can mixing with another labile water-bearing media, supernatant liquor 7 delivers in the anaerobic biological treatment chamber 9 at Figure 13.Because biological treatment is at back segment, therefore do not wish in supernatant liquor 7, to increase the water-bearing media of difficult for biological degradation, the water-bearing media of difficult for biological degradation preferably at first utilizes conductive diamond electrode to carry out electrolysis treatment.Nitric nitrogen in the water-bearing media is converted into nitrogen in anaerobic biological treatment chamber 9.In anaerobic biological treatment chamber 9, denitrifying bacteria attracts nitric nitrogen to replace oxygen as hydrogen acceptor, and nitric nitrogen or nitrite nitrogen are reduced into nitrogen.Notice that ammonia nitrogen is not to decompose here.Otherwise if water-bearing media comprises protein nitrogen or analogue, ammonia concentration may increase in anaerobic biological treatment chamber 9.In addition, denitrifying bacteria uses the organism that comprises the BOD composition as hydrogen donor, so the BOD composition for example is used for nitric nitrogen and nitrite nitrogen are converted into nitrogen in anaerobic biological treatment chamber 9 with the organic acid that the conductive diamond electrode electrolysis treatment produces.Undec ammonia nitrogen in anaerobic biological treatment chamber 9 is converted into nitric nitrogen and nitrite nitrogen in next stage aerobe treatment chamber 10.Be converted in the step of nitric nitrogen and nitrite nitrogen at ammonia nitrogen, the nitrite bacterium (Nitrosomonas or the like) of aerobic microbiological is converted into nitrite nitrogen with ammonia nitrogen, and the nitrate bacterium (bacterium nitrobacter) that is present in aerobe treatment chamber 10 then is converted into nitric nitrogen with nitrite nitrogen." B " among Figure 13 is the aeration pump that air is fed aerobe treatment chamber 10.The digestive fluid that contains nitric nitrogen and nitrite nitrogen is returned in the anaerobic biological treatment chamber 9 through circulating line 11, is converted into nitrogen at this nitric nitrogen and nitrite nitrogen.Return the mud ratio of anaerobic biological treatment chamber 9 by adjusting, can be controlled at total denitrogenation ratio in the biological treatment process 4 by circuit 11 round-robin Digestive system ratios with by pipeline 14.The water 12 of discharging from aerobe treatment chamber 10 has the residue mud that therefrom removes in settling bowl 13, be recovered as treated water 5 then.Residue mud turns back to anaerobic biological treatment chamber 9 respectively and with the electrolysis treatment chamber 2 of conductive diamond electrode through pipeline 14 and 15.More than describe and only provided denitrogenation method, but for example also decomposition in biological treatment step 4 of organism of BOD composition, so treated water 5 is well purified.Attention is in Figure 13, the structure that adopts an anaerobic biological treatment chamber 9 and an aerobe treatment chamber 10 is shown, but for example uses the two-part biological denitrificaion treatment process of first anaerobic room, first aerobic room, second anaerobic room and second aerobic room to can be used as the alternative method of biological treatment step 4 successively.In addition, methyl alcohol can be added to second anaerobic room so that strengthen denitrogenation speed.
Now with the example that further describes about diamond electrode treatment step of the present invention and other back segment water treatment method couplings.Be used for the method for back segment water treatment steps after carrying out as the electrolysis treatment of utilizing diamond electrode at leading portion, the flocculating settling facture is suitable as phosphorus removing method, and SS, number of C OD, colored component etc. also remove simultaneously.In the present invention, being contemplated to leading portion carries out the supplementary result of partially disposed and this method with the treatment with electrolytic method of diamond electrode to be used to handle water-bearing media extremely effective.
As the method for implementing the flocculating settling step, have and use settling bowl or flotation separator to carry out the method for flocculation treatment, a kind of method is directly to add flocculation agent in biological treatment solarization air cell (activated sludge method), a kind of method is that the flocculating settling operation is placed on biological treatment afterwards as degree of depth water treatment steps, a kind of method is that filtration step adds flocculation agent as degree of depth water treatment steps before, or the like.The flocculation agent that this flocculation treatment step is used preferably uses molysite (ferric iron muriate, ferric iron vitriol or the like), aluminium salt (Tai-Ace S 150, PAC or the like) or calcium salt (lime or the like).For each flocculation agent, be useful on the optimum pH of flocculation reaction, and can regulate the pH value by the alkalescence or the acidic solution that add necessary amount.In addition, can add polymer flocculant and increase the floc size that is generated.
Except dephosphorization, at water-bearing media is from electroplating effluent or from the waste water of chemical industry or analogue and comprise under the situation of a large amount of metal ions, if before with diamond electrode electrolysis treatment step with the flocculation sediment treatment step as pre-treatment step, then can avoid on electrode, precipitating metal, salt or analogue, so this is another useful embodiment of the present invention.
Figure 14 to 17 is schemas of handling the specific examples of water-bearing media method according to an embodiment of the present invention, wherein the flocculating settling treatment combination with diamond electrode electrolysis treatment and back segment of leading portion uses, and it is difficult for biological degradation water-bearing media and the situation that comprises many phosphorus that this embodiment can be preferred for pending water-bearing media.
Figure 14 illustrates the schema of the specific examples of embodiment of the present invention, and wherein the flocculating settling treatment combination with diamond electrode electrolysis treatment and back segment of leading portion uses.Difficult for biological degradation water-bearing media 1 carries out electrolysis treatment with diamond electrode in leading portion electrolysis treatment step 2.Then, handle the brine electrolysis 3 that step produced through this and be sent to teeter column 16, and inject flocculation agent 17 and stirring, mix with brine electrolysis 3 at this point, mixture is delivered in the flocculating settling pond 18 then, and be separated into treated water 5 and solids 8, according to the characteristic of throw out, flocculating settling pond 18 can be the flotation separation chamber.
Figure 15 illustrates the schema of the specific examples of handling the water-bearing media method according to an embodiment of the present invention, and wherein the biological treatment and the flocculating settling treatment combination with diamond electrode electrolysis treatment and back segment of leading portion use.Difficult for biological degradation water-bearing media 1 leading portion with diamond electrode electrolysis treatment step 2 in carry out electrolysis treatment.Then, be sent to back segment aerobe treatment step 10, inject flocculation agent 17 during aeration, mix with brine electrolysis 3 at this point by this brine electrolysis 3 of handling the step generation.The treated water of handling through aerobe 12 is sent in the flocculating settling pond 18, is separated into treated water 5 and solid matter 8.Part solid matter 8 can be used as feed back mud 14 and turns back to the aerobe treatment step.In addition, before back segment aerobe treatment step 10, can add the anaerobic biological treatment step, thereby can reach higher levels of biological treatment.
Figure 16 illustrates the schema of the specific examples of handling the water-bearing media method according to an embodiment of the present invention, and wherein the biological treatment and the flocculating settling treatment combination with diamond electrode electrolysis treatment and back segment of leading portion use.Difficult for biological degradation water-bearing media 1 is handled with diamond electrode electrolysis treatment step 2 through leading portion.Then, handling the brine electrolysis 3 that produces through this is sent in the back segment aerobe treatment step 10, to deliver to teeter column 16 and inject flocculation agent 17 through the treated water 12 that aerobe is handled, mix with treated water 12 at this point, then mixture is delivered in the flocculating settling pond 18, be separated into treated water 5 and solid matter 8.In addition, before back segment aerobe treatment step 10, can add the anaerobic biological treatment step, thereby can reach higher levels of biological treatment, and can add settling bowl as subsequent step, a part of mud returns biological treatment step and/or joins in the electrolysis treatment step 2.
Figure 17 illustrates the schema of the specific examples of handling the water-bearing media method according to an embodiment of the present invention, and wherein the flocculating settling processing and the filtration treatment with diamond electrode electrolysis treatment and back segment of leading portion are used in combination.Difficult for biological degradation water-bearing media 1 carries out electrolysis treatment at leading portion in diamond electrode electrolysis treatment step 2.Then, handle the brine electrolysis 3 that produces through this and be sent in the teeter column 16, and under agitation inject flocculation agent 17, mix with brine electrolysis 3 at this point, then mixture is delivered in the flocculating settling pond 18, be separated into treating water 19 and solid matter 8 through flocculation separation.Treating water 19 through flocculation separation is sent in the filtration chamber 20, obtains treated water 5 at this.The filter method of any type still can be adopted as required as the filtration chamber in preferred sand filtration chamber 20.
Figure 18 shows the flow process of another embodiment of the present invention, wherein provides diamond electrode electrolysis treatment step and back segment to utilize the crystallizing-dephosphorizing step.The dephosphorization step that is provided in this flow process is in back segment, but under the high situation that thousands of mg/L are arranged of the phosphorus concentration of water-bearing media, also can in leading portion, provide the dephosphorization step, the degree that the dephosphorization step is carried out should with can not be on the pipeline of diamond electrode device or electrode degree of being precipitated as.As a kind of method of the back segment water treatment steps that adopts after leading portion is with the diamond electrode electrolysis treatment, the crystallizing-dephosphorizing method is very effective in the present invention.When promoting crystallization by the amount that reduces organism and other obstruction crystalline material with diamond electrode electrolysis treatment step, phosphorus can be used as the resource recovery and does not produce mud simultaneously.The crystal type that can be used for crystallizing-dephosphorizing has HAP (hydroxylapatite, Ca
5(OH) (PO
4)
3) and MAP (trimagnesium phosphate ammonia, Mg (NH
4) PO
4).Select a kind of in these crystallization types according to each composition in the water-bearing media and ionic balance.These type crystals any one, are added the ionic species that lacks and regulated pH, in the dephosphorization tower, remove phosphorus then, and obtain treated water as crystallising part.Figure 18 illustrates the schema of the specific examples of handling the water-bearing media method according to an embodiment of the present invention, and wherein the crystallizing-dephosphorizing treatment combination with diamond electrode electrolysis treatment and back segment of leading portion uses.This can be preferred for pending water-bearing media is that difficult for biological degradation water-bearing media and brine electrolysis 3 comprise the phosphorus (PO of 50mg/L at least
3-P) situation.Difficult degradation water-bearing media 1 is handled in diamond electrode electrolysis treatment step at leading portion, then brine electrolysis 3 is delivered in the teeter column 16, add modulability chemical liquid 21 (comprising the pH regulator agent and the chemical liquid of the ionic species that lacks) at this, adjust the required condition of crystallization like this.Then the adjusted crystalline treating water 22 that obtains is delivered to dephosphorization tower 23, remove dephosphorization by the crystal (HAP or MAP) of in dephosphorization tower 23, growing.From dephosphorization tower 23, take out phosphorous crystalline material 24, obtain treated water 5 at this point.24 1 kinds of valuable phosphorus of phosphorous crystalline material source can be used as fertilizer and uses or be mixed in the fertilizer.
Below be various embodiments of the present invention.
1, a kind of method of handling water-bearing media, this method comprises carries out electrolytic step with water-bearing media with conductive diamond electrode, is water treatment steps then.
2, the method for 1 processing water-bearing media as stated above, its posterior segment water treatment steps comprises one of biological treatment, flocculating settling processing, filtration treatment, oil/water sepn processing, adsorption treatment and crystallization treatment.
3, the method for 1 processing water-bearing media as stated above, its posterior segment water treatment steps comprise biological treatment and one of flocculating settling processing, filtration treatment, oil/water sepn processing, adsorption treatment and crystallization treatment or at least two couplings.
4, the method for 1 to 3 arbitrary processing water-bearing media as stated above, wherein biological treatment is that anaerobic biological treatment or aerobe are handled.
5, the method for 1 to 4 arbitrary processing water-bearing media does not as stated above wherein stop under the situation that leading portion electrolysis step COD composition therein decomposes fully, carries out the back segment water treatment steps then.
6, the method for 1 to 5 arbitrary processing water-bearing media as stated above, wherein pending water-bearing media is a kind of difficult for biological degradation water-bearing media.
7, the method for 6 processing water-bearing media as stated above wherein through the leading portion electrolysis step, makes the BOD/COD value of water-bearing media be at least 0.2.
8, the method for 1 to 7 arbitrary processing water-bearing media as stated above, wherein in the leading portion electrolysis step, the electric charge that is applied on each the gram COD in the water-bearing media is no more than 34Ah.
9, handle the equipment of water-bearing media, this equipment comprises the tank room that uses conductive diamond electrode, pending water-bearing media is introduced into wherein to carry out electrolysis treatment and at least one water treatment room, and the brine electrolysis of having handled in the tank room is introduced wherein to carry out water treatment.
10, the equipment of 9 processing water-bearing media as stated above, its posterior segment water treatment room comprise one of biological treatment chamber, flocculating settling treatment chamber, filtration treatment chamber, oil/water sepn treatment chamber, adsorption treatment chamber and crystallization treatment chamber.
11, the equipment of 9 described processing water-bearing medias as stated above, its posterior segment water treatment room comprise biological treatment chamber and one of flocculating settling treatment chamber, filtration treatment chamber, oil/water sepn treatment chamber, adsorption treatment chamber and crystallization treatment chamber or at least two s' combination.
12, the equipment of 9 to 11 arbitrary processing water-bearing medias as stated above, the chamber of wherein carrying out a biological disposal upon is by anaerobic biological treatment chamber or aerobe treatment chamber or their array configuration constitutes.
Embodiment
In the present embodiment, the water-bearing media of discharging from factory has water quality as shown in table 1 below, by with the method for conductive diamond electrode electrolysis treatment it being handled.
Table 1: the water quality of processed water-bearing media in embodiment 1
| Analysis project | Unit | Numerical value | |
| COD cr | mg/L | 10600 | |
| BOD 5 | mg/L | 1630 | |
| BOD/COD | ％ | 15.3 | |
| Colourity (PtCo spectrophotometry) | - | 400 | |
| | FAU | 12 | |
| pH | - | 5.10 | |
| EC (specific conductivity) | mS/cm | 6.72 | |
| Cl- | mg/L | 1610 | |
| SO 4 2- | mg/L | 106 | |
| NH 4-N | mg/L | nd | |
| VFA | mg/L | 518 | |
| Formic acid | mg/L | 155 | |
| Acetate | mg/L | 248 | |
| Lactic acid | mg/L | 109 | |
| Propionic acid | mg/ | 6 |
Pending water-bearing media has the COD value up to 10600mg/L, and BOD/COD is 15.3%, so biological degradability is lower, therefore is a kind of difficult for biological degradation water-bearing media of utilizing conventional biological method to handle of being difficult to.Get 3 liters of this water-bearing medias as liquid sample, use conductive diamond electrode at current density 140mA/cm
2With carry out the electrolysis treatment experiment under the electrolytic condition of average battery voltage 7.5V.The temperature of water-bearing media is elevated to 46 ℃ because of the heat that electrode reaction produces in the electrolysis treatment process.In electrolyzer, anode is a conductive diamond electrode, and the titanium plate is set to negative electrode, and interelectrode distance is 2mm and demarcation membrane is not set between electrode.Diamond electrode utilizes heated filament CVD method that conductive diamond is deposited on 6 inches silicon chip matrix and obtains.Electrolysis treatment adopts the circulation batch-type to carry out, and with pump liquid sample is sent into electrolyzer from the sealing reservoir of 5 liters of cumulative volumes, and the liquid of discharging from electrolyzer turns back to reservoir.The air of reservoir upper space is replaced with inert argon in advance, and periodically emits the gas that produces in the reservoir in the electrolytic process, and carries out quantitative analysis by vapor-phase chromatography.The result shows in Fig. 4,5,6 and 7.Fig. 4 illustrates electric charge (transverse axis) and the COD of sample liquids and the relation curve between the BOD (longitudinal axis) that every 1g COD contained in the sample liquids is applied.When the COD of liquid sample still was higher than about 2000mg/L, the current efficiency of COD decomposition approached 100% as shown in Figure 4.Dotted line among Fig. 4 is a straight line, is illustrated in current efficiency and is the minimizing situation of COD under 100% the situation.Yet in case COD becomes 2000mg/L or still less, the mass transfer of COD composition begins the limited speed that becomes in the water-bearing media, so COD concentration reduces curve and begins crooked and the dotted line in the slip chart 4 far away.In addition, the initial BOD of liquid sample is 1630mg/L, and when applying the electric charge of 1Ah/g-COD, BOD becomes 2.8 times and mostly is 4600mg/L.That is, the BOD concentration in the water-bearing media reaches maximum when the theoretical electric charge that applies about 29%.When electric charge was higher than this value, BOD concentration descended again.Fig. 5 shows the relation between the COD decreasing ratio and BOD/COD in the present embodiment.BOD/COD is by using BOD
5Divided by COD
CrThe value that obtains and represent with percentage ratio.The biodegradable of the COD composition in the high more then water-bearing media of this value is just high more.The BOD/COD of contrast raw water is 15.4%, and BOD/COD reaches 50% when the COD decreasing ratio is 15%, and when COD decreasing ratio from 30% to 75% BOD/COD greater than 60%.When the COD decreasing ratio with the conductive diamond electrode electrolysis treatment surpassed 95%, it is also lower than the value in the raw water that BOD/COD becomes on the contrary.Under the situation of anaerobic biological treatment method as the back segment water treatment steps, preferably make COD composition residue to improve the biogas amount that reclaims, therefore use in the conductive diamond electrode electrolysis treatment step at leading portion, preferred COD decreasing ratio is at 10% stopped reaction between 60% time.In addition, under the situation of aerobe facture as the back segment water treatment steps, preferred COD is low, thus leading portion with the conductive diamond electrode electrolysis treatment in preferred COD decreasing ratio higher, for example 30% to 95%.Fig. 6 illustrates the relation between the organic acid of the electric charge imported in the present embodiment and generation.The maximum organic acid that produces in the conductive diamond electrode electrolysis treatment is a formic acid, secondly is lactic acid, acetate, is a spot of propionic acid then.These organic acid total concns are presented among Fig. 6 as VFA (voltaile fatty acid) concentration.By make the water-bearing media biodegradable just increase generation with the conductive diamond electrode electrolysis treatment owing to VFA.Notice that in the present embodiment when the electric charge that applies was 1.8Ah/g-COD (be about 53% theoretical electric charge), VFA concentration was the highest.When electric charge was higher than this value, VFA was by further being decomposed with the conductive diamond electrode electrolysis treatment, so its density loss.In with conductive diamond electrode electrolysis treatment process owing to organic partial oxidation produces VFA.Decompose fully up to COD if be continuously applied more electric charge in electrolysis treatment, then VFA will be converted into carbonic acid gas and water.Fig. 7 illustrates the concentration that produces gas in the present embodiment and forms.Can find out that therefrom by carrying out the gas main component that electrolytic reaction produced with conductive diamond electrode be hydrogen, secondly be carbonic acid gas.In addition, when the electric charge that applies surpassed 3.2Ah/g-COD, the electric charge that promptly applies surpassed 94% o'clock of theoretical electric charge, begins to produce oxygen.This is that the COD mass transfer on electrode surface begins the limited speed that becomes because therefore the COD of water-bearing media tails off, thereby begins to take place oxygenous water oxidizing reaction, has replaced the decomposition reaction of COD composition.In this way, when the COD decreasing ratio was low, producing hydrogen and carbonic acid gas was without a doubt.In case but the COD decreasing ratio uprises, when hydrogen and oxygen produce simultaneously, the danger of hydrogen gas explosion is just arranged in this case.
The COD decreasing ratio that obtains by present embodiment is that the brine electrolysis between 15% to 95% can fully be handled by conventional water treatment method such as biological treatment.
For embodiment 1 resulting COD decreasing ratio is shown is that brine electrolysis between 15% and 95% has been transformed into and is enough to the water handled with conventional water treatment method such as biological treatment, the brine electrolysis (be VFA reach maximum, COD decreasing ratio be 55% brine electrolysis) that applies the 1.8Ah/g-COD electric charge among the embodiment 1 as sample, is carried out anaerobic biological treatment (methane fermentation).In addition, experiment as a comparison, the raw material waste water that has water quality as shown in table 1 from factory carries out the methane fermentation test also as sample.The total amount that makes methane fermentation kind mud and each sample after the adjustment is 40mL, and is sealed in the bottle of a 100mL with rare gas element.In addition, the blank sample that kind of mud obtains of also preparing only to pack in the bottle.Each bottle is put into 55 ℃ constant temperature vibrating trough, carry out the test of high temperature methane fermentation.The result is presented among Fig. 8.The biogas amount (having deducted the biogas amount (blank) that kind of mud produces) that every gram COD produces in the longitudinal axis show sample in Fig. 8.Carry out at undressed raw water under the situation of methane fermentation, increase gradually, even in the time of 14 days, have only very a spot of methane to produce at lasting methane fermentation though see the methane generation.In undressed raw water being carried out methane fermentation test, notice,, observe a phenomenon beginning two days, deduct the methane content that blank test produces after, resulting methane generation is a negative value.It is believed that this is because comprise the composition that some suppress methane fermentation in the untreated water.On the other hand, under the situation of the brine electrolysis that obtains with the conductive diamond electrode electrolysis treatment being carried out the methane fermentation processing, just can't see the biogas generation later on increased from the 7th day, but was higher than the biogas output of comparison test.That is, this shows under the situation of the brine electrolysis that obtains with the conductive diamond electrode electrolysis treatment, because VFA has accounted for the major part of COD composition, methane fermentation carries out with high speed, thereby finishes within about 7 days.
In the present embodiment, used water sample is by biological treatment ight soil and concentrated making, and sample is handled with the conductive diamond electrode treatment with electrolytic method.Pending water is the difficult for biological degradation water-bearing media that water quality as shown in table 2 is arranged.
The water quality of the water-bearing media of handling among table 2: the embodiment 3
| Analysis project | Unit | Numerical value | |
| COD cr | mg/L | 1300 | |
| BOD 5 | mg/ | 80 | |
| BOD/ | ％ | 6 | |
| Colourity (PtCo spectrophotometry) | - | 6200 | |
| pH | - | 6.4 | |
| EC (electricity is led) | mS/cm | 22 | |
| Cl - | mg/L | 2900 | |
| SO 4 2- | mg/L | 860 | |
| NH 4-N | mg/L | 302 |
The COD concentration of water sample is 1300mg/L, be not very high, but BOD hangs down and has only 80mg/L, therefore biodegradable extremely low (BOD/COD:6%) in addition, water sample comprises and is considered to derive from biliary colored component in a large number (colourity: 6200), and this colored component almost can not remove by biological treatment at all.Processed water also comprises the ammonia nitrogen of about 300mg/L.Get 3 liters of these difficult for biological degradation water-bearing medias as sample, use conductive diamond electrode at current density 40mA/cm
2With carry out the electrolysis treatment experiment under the condition of average battery voltage 4.8V.Because of electrolytic reaction produces heat, so the temperature of water-bearing media is elevated to 40 ℃ in the electrolysis treatment process.The structure of electrolyzer with handle operation and example 1 in use identical.The diamond electrolysis treatment the results are shown in Fig. 9,10 and 11.As shown in Figure 9, the initial COD of water sample is 1300mg/L, because of being in the mass transfer velocity limited range, so initial current efficient approximately has only 56%.Current efficiency descends along with the minimizing of water-bearing media COD, and observes that current efficiency further descends when the electric charge that applies surpasses theoretical electric charge.When BOD aspect, maximum appear at and apply electric charge and be 1.3Ah/g-COD (38% of theoretical electric charge, COD decreasing ratio are 22%).This moment, BOD/COD was 39%, was that 6.5 times of raw water BOD/COD are high.The color aspect along with the increase color of importing electric charge descends significantly, when the input electric charge is 2.6Ah/g-COD (76% theoretical electric charge), can realize 100% effective elimination.This moment, the per-cent that removes of COD was 56%, therefore, was 100% in order to remove that color do not need to make the decreasing ratio of COD obviously.Relation between COD decreasing ratio and the percent of decolourization is that the data computation by Fig. 9 draws, and is painted among Figure 10.Clearly again from Figure 10 see that in order to remove that color do not need to make the decreasing ratio of COD be 100%.In addition, Figure 11 illustrates the relation between the ammonia nitrogen concentration and COD decreasing ratio in the present embodiment.When the COD decreasing ratio was 80%, ammonia nitrogen was effectively decomposed by 100%.It is believed that this is because raw water comprises chlorion, so some chlorions are by being converted into hypochlorous acid with the conductive diamond electrode electrolytic processing method, and hypochlorous acid makes the ammonia nitrogen decomposition by the breakpoint reaction.
When the COD decreasing ratio reaches 22%,, carry out aerobe then and handle ten times of dilutions of brine electrolysis water.Employing activated sludge method is carried out the test of aerobe facture with the load of 0.2g-BOD/g-VSS-mud every day.The COD concentration of final treating water is 10mg/L or still less, colourity is 2.
In the present embodiment, will handle the resulting methane fermentation of ight soil and food waste factory mud, it be handled with the conductive diamond electrode treatment with electrolytic method as sample.Pending liquid is a kind of difficult degradation water-bearing media with water quality as shown in table 3.
Table 3: the water quality of processed water-bearing media in embodiment 4
| Analysis project | Unit | Numerical value |
| T-COD cr | mg/L | 11100 |
| T-BOD 5 | mg/L | 976 |
| BOD/COD | ％ | 8.8 |
| MLSS | mg/L | 7290 |
| pH | - | 7.9 |
| EC (electricity is led) | mS/cm | 2.7 |
| Cl - | mg/L | 450 |
| Viscosity | mPa·s | 195 |
Methane fermentation mud is the residue after a kind of anaerobic biological treatment, therefore has low biological degradability (BOD/COD:8.8%), and constitute by the microorganism that comprises many water in the microorganism cells, in addition viscosity number than higher be 195mPas, therefore be the relatively poor water-bearing media of water separation capability.T-COD (COD that comprises solid matter) concentration is higher to be 11100mg/L, and about 90% COD can not dissolve, and comprises main solid COD composition from microorganism.The MLSS (mixed liquor suspended solid) that comprises 7290mg/L in this solid matter.Getting 3 liters of this water-bearing medias as sample, is 120mA/cm in current density
2With carry out electrolysis treatment with conductive diamond electrode under the condition of average battery voltage 13.5V.In the electrolysis treatment process, because of electrolytic reaction produces heat, the temperature of water-bearing media rises to about 55 ℃.The structure of electrolyzer with handle operation and example 1 in use identical.The electrolysis treatment of methane fermentation mud the results are shown in Figure 12.Observing the downtrending of T-COD can find out, when the electric charge that applies was 1.85Ah/g-COD (theoretical electric charge 54%), the decomposition of COD was carried out to approach 100% current efficiency.This moment, the COD decreasing ratio was 48%.Yet can find out electric charge when input during greater than above-mentioned value the COD decomposing efficiency descend significantly.Though in Figure 12, do not show, for obtain 96% or higher COD decreasing ratio need import the electric charge of 276Ah/g-COD (81 times of theoretical electric charges) at least.Can extrapolate processing 1m according to this value
3The electric weight that needs of methane fermentation mud be 2060kWh at least.Obviously must expend a large amount of electricity by decomposing COD fully, therefore the cost performance that can not obtain with the method for conductive diamond electrode electrolysis treatment.It is believed that the high reason of current efficiency of decomposing at electrolysis treatment initial period COD is to exist with the preferential decomposition of conductive diamond electrode electrolysis treatment to the composition of increase viscosity or the solubility COD composition that is easy to decompose.In addition, when the electric charge that applies was 1.85Ah/g-COD, MLSS was 3760mg/L (the SS decreasing ratio is 52%), and viscosity is 43mPas (viscosity degradation rate 77%), and this moment, the COD decreasing ratio was 48%.Being used for electrolytic electric weight heretofore is 138kWh/m
3-mud is to obtain 1/15 of 96% COD electric weight that decreasing ratio requires.In addition,, it is believed that the cell walls of OH root attack micro organisms is broken cytolemma by using the conductive diamond electrode electrolytic processing method, and the volume of organic sludge is reduced because MLSS descends.Microorganism is dissolved in the water-bearing media if cell walls is broken simultaneously, and then these microorganisms also will be decomposed successively with the conductive diamond electrode electrolysis treatment.Attention is relatively poor by the decomposition efficiency of the residue sclereid wall handled with the conductive diamond electrode electrolysis.Especially, will bring problems such as contact efficiency if attempt so at this solid cell wall composition of electrode surface oxidation.It is believed that Here it is when applying electric charge and surpass 1.85Ah/g-COD, the decline of MLSS is reason slowly.
The brine electrolysis that the COD decreasing ratio is reached at 48% o'clock filters through one 0.45 μ m film filter.Raw material mud is carried out same filtration test.For raw material mud, just occurred the phenomenon of blocking filter soon, thereby almost can't filter, and being 48% brine electrolysis, the COD decreasing ratio can filter easily.In addition, the solid in the raw material mud is very slimy, and the COD decreasing ratio that to be 48% brine electrolysis filter back residual solids material is relatively sticking.
Industrial applicibility
The invention provides a kind of method of processing water-bearing media. In the present invention, the leading portion electrolytic treatments of conductive diamond electrode, back segment comprises biological treatment, flocculating setting processing, filtration treatment, oil/moisture from the water treatment steps of at least one of processing, adsorption treatment, crystallization treatment etc., thereby makes whole processing procedure efficient and low-cost. In the methods of the invention, only be responsible for the effective part processing procedure for the treatment of with electrolytic method with conductive diamond electrode electrolytic treatments step, the back segment water treatment steps only is responsible for the effective part treatment process of biological treatment, and whole processing procedure is carried out smoothly. In addition, according to the present invention, can greatly improve the life-span of conductive diamond electrode.
Claims (12)
1, a kind of method of handling water-bearing media, this method comprises carries out electrolytic step with water-bearing media with conductive diamond electrode, is water treatment steps then.
2, press the method for the processing water-bearing media of claim 1, its posterior segment water treatment steps comprises one of biological treatment, flocculating settling processing, filtration treatment, oil/water sepn processing, adsorption treatment and crystallization treatment.
3, press the method for the processing water-bearing media of claim 1, its posterior segment water treatment steps comprises biological treatment and one of flocculating settling processing, filtration treatment, oil/water sepn processing, adsorption treatment and crystallization treatment or at least two couplings.
4, by the method for the arbitrary processing water-bearing media of claim 1 to 3, wherein biological treatment is that anaerobic biological treatment or aerobe are handled.
5, by the method for the arbitrary processing water-bearing media of claim 1 to 4, wherein stop under the leading portion electrolysis step situation that the COD composition does not decompose fully therein, carry out the back segment water treatment steps then.
6, by the method for the arbitrary processing water-bearing media of claim 1 to 5, wherein pending water-bearing media is a kind of difficult for biological degradation water-bearing media.
7, press the method for the processing water-bearing media of claim 6,, make the BOD/COD value of water-bearing media be at least 0.2 wherein through the leading portion electrolysis step.
8, by the method for the arbitrary processing water-bearing media of claim 1 to 7, wherein in the leading portion electrolysis step, the electric charge that is applied on each the gram COD in the water-bearing media is no more than 34Ah.
9, handle the equipment of water-bearing media, this equipment comprises the tank room that uses conductive diamond electrode, and pending water-bearing media is introduced into wherein to carry out electrolysis treatment; With at least one water treatment room, the brine electrolysis of having handled in the tank room is introduced wherein to carry out water treatment.
10, press the equipment of the processing water-bearing media of claim 9, its posterior segment water treatment room comprises one of biological treatment chamber, flocculating settling treatment chamber, filtration treatment chamber, oil/water sepn treatment chamber, adsorption treatment chamber and crystallization treatment chamber.
11, by the equipment of the described processing water-bearing media of claim 9, its posterior segment water treatment room comprises biological treatment chamber and one of flocculating settling treatment chamber, filtration treatment chamber, oil/water sepn treatment chamber, adsorption treatment chamber and crystallization treatment chamber or at least two s' combination.
12, by the equipment of the arbitrary processing water-bearing media of claim 9 to 11, the chamber of wherein carrying out a biological disposal upon is by anaerobic biological treatment chamber or aerobe treatment chamber or their array configuration constitutes.
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| JP2004253946A JP2006068617A (en) | 2004-09-01 | 2004-09-01 | Method and apparatus for treating water medium |
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| EP (1) | EP1805109A1 (en) |
| JP (1) | JP2006068617A (en) |
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| CN101648761B (en) * | 2009-09-11 | 2011-05-11 | 陈明功 | Device for purifying and emulsifying oily wastewater by low temperature plasma synergetic flocculating agent |
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| JP5004427B2 (en) * | 2005-03-11 | 2012-08-22 | 三井造船株式会社 | Processing method of methane fermentation digestive juice |
| JP2007000838A (en) * | 2005-06-27 | 2007-01-11 | Fujifilm Holdings Corp | Method for treating waste water containing ammonia |
| JP4956016B2 (en) * | 2006-02-28 | 2012-06-20 | 水ｉｎｇ株式会社 | Apparatus and method for treating organic wastewater containing hardly biodegradable substances |
| JP2008093569A (en) * | 2006-10-12 | 2008-04-24 | Ebara Corp | Water medium treatment method and apparatus using ultrasonic treatment and diamond electrode |
| JP2008259930A (en) * | 2007-04-10 | 2008-10-30 | Hitachi Plant Technologies Ltd | Method for treating organic solvent-containing waste water |
| EP2276877B1 (en) * | 2008-05-14 | 2011-11-09 | Basf Se | Method for electrochemically cleaving lignin on a diamond electrode |
| WO2010011927A1 (en) | 2008-07-25 | 2010-01-28 | Noventis, Inc. | Compositions and methods for the prevention and treatment of cardiovascular diseases |
| US8266736B2 (en) | 2009-07-16 | 2012-09-18 | Watkins Manufacturing Corporation | Drop-in chlorinator for portable spas |
| EP2595636A4 (en) | 2010-07-22 | 2014-01-15 | Reven Pharmaceuticals Inc | Methods of treating or ameliorating diseases and enhancing performance comprising the use of a magnetic dipole stabilized solution |
| WO2012054812A2 (en) * | 2010-10-21 | 2012-04-26 | Packaging Corporation Of America | Method for biological treatment of hydrolyzate from pulp washing by balancing chemical oxygen demand |
| CN102491516A (en) * | 2011-11-25 | 2012-06-13 | 天津工业大学 | Method for treating wastewater difficult to be biodegraded by electric microorganism and membrane filtration coupled technology |
| CN103496821B (en) * | 2013-09-18 | 2015-12-09 | 广西丽桂环保科技有限公司 | Administration of papermaking black liquid recoverying and utilizing method |
| CN106006821B (en) * | 2016-07-12 | 2019-04-09 | 河南永泽环境科技有限公司 | One kind removing ammonia dephosphorization compound drug |
| KR102130071B1 (en) * | 2018-12-12 | 2020-07-03 | 한국과학기술원 | Method for simultaneous removal of ammonia, hydrogen sulfide and heavy metal in wastewater |
| CN110040910B (en) * | 2019-04-29 | 2022-03-18 | 北部湾大学 | Waste water treatment device for biodiesel production and treatment method thereof |
| WO2023175719A1 (en) * | 2022-03-15 | 2023-09-21 | 株式会社ジェイテクト | Biogas production system and method for producing biogas |
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| DE19708296A1 (en) * | 1997-02-28 | 1998-09-03 | Eastman Kodak Co | Process for the treatment of liquid residues from photographic processes |
| TW200306954A (en) * | 2002-04-23 | 2003-12-01 | Kurita Water Ind Ltd | Methods and apparatuses for treating wastewater containing organic compounds |
| JP2004344806A (en) * | 2003-05-23 | 2004-12-09 | Fuji Photo Film Co Ltd | Photographic waste solution treatment method |
| JP2004344805A (en) * | 2003-05-23 | 2004-12-09 | Fuji Photo Film Co Ltd | Method and apparatus for electrolytic oxidation treatment of photographic waste solution and silver recovering method |
| JP2005087860A (en) * | 2003-09-17 | 2005-04-07 | Fuji Photo Film Co Ltd | Treatment method for leachate from industrial waste disposal plant |
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