CN101041522A - Treating method and treating apparatus of waste water containing organic material - Google Patents
Treating method and treating apparatus of waste water containing organic material Download PDFInfo
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- CN101041522A CN101041522A CNA2007100882810A CN200710088281A CN101041522A CN 101041522 A CN101041522 A CN 101041522A CN A2007100882810 A CNA2007100882810 A CN A2007100882810A CN 200710088281 A CN200710088281 A CN 200710088281A CN 101041522 A CN101041522 A CN 101041522A
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Water Treatment By Sorption (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a treating method of waste water containing organic material, which can prevent flux reduction and bio contamination resulted from organism adsorbing on membrane in RO membrane separation device, when trating and recovering the RO membrane separation device for waste water containing organic material, and can effectively reduce the TOC value containing COD value of RO concentrated water, and prevent adverse effect such as effluent treatment of RO concentrated water. In the said method, the scale inhibitor is added into the waste water containing organic material, and the base reagent is added to ajust the pH to above 9.5, and then the water goes through the RO membrane separation device. The RO concentrated water is trough ozone oxidation in ozone reaction tower. The pH of RO feed water is adjusted to above 9.5 to prevent bio contaminating in the RO membrane separation device, nonionic surfactant adsorbing on membrane, and flux reducting. The scale inhibitor is added to inhibit membrane jamming due to calcium carbonate sacling at high pH. The concentrated TOC containing COD in RO concentrated water is taken away trough ozone oxygenolysis.
Description
Technical field
The present invention relates to will from discharges such as electronics manufacturing works contain high density to the draining of low-concentration organic (TOC) with reverse osmosis (RO) membrane separation unit handle, when reclaiming, prevent that flux that RO membrane separation unit internal cause organism is caused in face absorption from reducing or biological pollution and carry out stable treated for a long time, and, reduce TOC concentration in the water effectively and obtain the treating water of high water quality, in addition, also handle the treatment process that contains the organism draining and the treatment unit of the condensed water of RO membrane separation unit easily and effectively.
Background technology
In recent years, environmental criteria and water quality benchmark have more and more stricter tendency, also wish to carry out the purification of height for discharge water.On the other hand,, utilize again, also wish the water technology of exploitation height in order to reclaim various drainings from eliminating hydropenic purpose.
Under such situation, because handling, the impurity in the water (ionic species, organism, micropartical etc.) can be removed effectively the RO membrane sepn, so in a lot of fields, be used in recent years.For example, extensively adopt following method: in the time of will utilizing again from the draining recovery that contains high density TOC or lower concentration TOC that contains acetone, Virahol etc. that semiconductor fabrication is discharged, at first it is carried out a biological disposal upon, remove the TOC composition, and biological treatment of water is carried out the RO film handle, the method that purifies (for example, the spy opens the 2002-336886 communique).
But in recent years, following problem begins obviousization: when the RO membrane separation unit was arrived in the draining water flowing of will carrying out a biological disposal upon, because the organism that is undertaken by microorganism decomposes the generation biological metabolite, it made the face of RO film stop up, cause the flux reduction.
On the other hand, under the situation of RO membrane separation unit,, in the RO membrane separation unit, form the microorganism environment of breeding easily in the direct water flowing of draining of not using biological treatment, these being contained TOC owing to flow into the TOC concentration height of RO membrane separation unit.Therefore, from suppressing the purpose of the biological pollution in the RO membrane separation unit, usually in the draining that contains TOC, add a large amount of foundry loam control agents (slime control agent), but because foundry loam control agent price height, so seek the method for more cheap inhibition biological pollution.
In addition, from the draining that electronics manufacturing works discharge, be adsorbed in the face of RO membrane separation unit, the nonionic surfactant that flux is reduced is sneaked into sometimes, in the past, for such draining that contains nonionic surfactant, can not use the RO membrane sepn and handle.
In order to solve such problem, will be from electronics manufacturing works, high density to the draining of low-concentration organic that contains that discharge in other various fields is handled with the RO membrane separation unit, during recovery, preventing that RO membrane separation unit internal cause organism from reducing at the flux that face absorption is caused, biological pollution and when carrying out stabilizing treatment for a long time, TOC concentration in the water reduced effectively and obtain the treating water of high water quality, as such technology, the inventor has proposed following scheme: at first, in containing the organism draining, add these 5 times of foulings more than the weight of calcium ion that contain in the organism draining and prevent agent, and before the interpolation fouling prevents agent, afterwards or simultaneously, in containing the organism draining, add alkali reagent, pH is adjusted to more than 9.5, carry out the method and the device (spy opens the 2005-169372 communique) of RO separating treatment then.
Like this, prevent agent by the fouling of in the processed water that imports to the RO membrane separation unit (following title " RO feedwater " sometimes), adding specified amount, and adjust to more than 9.5 pH back to the water flowing of RO membrane separation unit, can obtain following action effect: prevent flux reduction that RO membrane separation unit internal cause organism is caused in face absorption or biological pollution and when carrying out stabilizing treatment for a long time, TOC concentration in the water is reduced effectively, thereby can obtain the treating water of high water quality.
(1) adjusts to more than 9.5 by pH, can obtain following effect the RO feedwater.
Microorganism can not survive under alkaline environment.Therefore, adjust to more than 9.5 by pH, in the RO membrane separation unit the RO feedwater, though nutritious source, but can create the inviable environment of microorganism, there is no need as in the past, to add expensive foundry loam control agent, can suppress the biological pollution in the RO membrane separation unit.
In addition, known might make nonionic surfactant that flux reduces under alkaline environment from the face desorb, adjust to more than 9.5 by pH the RO feedwater, can suppress of the absorption of these compositions to the RO face.
(2) prevent agent by add fouling in RO feedwater, its amount is 5 times of the calcium ion of RO in feeding water more than the weight, can obtain following effect.
From the draining that contains TOC of discharges such as electronics manufacturing works, few situation that exists the calcium ion that becomes the fouling reason etc. to sneak into.Adjust under the RO working conditions of the high pH more than 9.5 at pH,, also can generate foulings such as lime carbonate, cause the RO film directly to stop up even the calcium ion of denier is sneaked into the RO feedwater.Therefore, from the purpose that suppresses to cause face to stop up by such fouling, add fouling and prevent agent in the RO feedwater, its amount is 5 times of the calcium ion of RO in feeding water more than the weight, to prevent the generation of fouling.
Patent documentation 1: the spy opens the 2002-336886 communique
Patent documentation 2: the spy opens the 2005-169372 communique
Summary of the invention
Open the technology of 2005-169372 communique record according to the spy, the draining that containing of will discharging from electronics manufacturing works, other various fields, high density to the draining of low-concentration organic, particularly contained nonionic surfactant with the RO membrane separation unit handle, when reclaiming, preventing flux reduction that RO membrane separation unit internal cause organism causes in face absorption, biological pollution when carrying out stabilizing treatment for a long time, can reduce TOC concentration in the water effectively, obtain the treating water of high water quality, but have following unfavorable condition.
Promptly, open the technology of 2005-169372 communique record according to the spy, for in the RO feedwater, adding the condensed water (following claim sometimes " RO condensed water ") of carrying out the processing of RO membrane sepn after fouling prevents agent and obtaining, because the fouling added prevents that agent is concentrated, prevent agent so become the foulings that contain in a large number as the COD composition.That is,, fouling can not and be concentrated through the RO film in the condensed water side owing to preventing agent.Particularly, open the technology of 2005-169372 communique according to the spy, add a large amount of foulings and prevent agent, its amount is 5 times of calcium ions in the RO feedwater more than the weight, and it is carried out the processing of RO membrane sepn, contains a large amount of foulings and prevent agent in resulting RO condensed water.
Usually, the RO condensed water is delivered to the draining treatment process, handle the back discharging through biological treatment and coagulative precipitation, but in general, fouling prevents that agent is difficult to remove by coagulative precipitation processing and biological treatment, and in addition, fouling prevents that agent from also being the material that hinders aggregation.Therefore, deliver to the draining treatment process, then except the load of draining treatment process increases, COD value in the discharge water is increased wait, make the water quality reduction if will contain the RO condensed water that a large amount of foulings prevent agent like this.
Therefore, the object of the invention is, provides the TOC value that comprises the COD value with this RO condensed water to reduce effectively, prevents the dysgenic treatment process and the treatment unit that contains the organism draining of RO condensed water to draining processing etc.
The present invention's (the 1st of invention 1-) the treatment process that contains the organism draining is characterized in that, comprises following operation: add fouling and prevent that the fouling of agent from preventing agent interpolation operation in containing the organism draining; Prevent that with having added this fouling the organism draining that contains of agent from supplying to the reverse osmosis membrane separation device, is separated into the reverse osmosis membrane separation operation of permeate water and condensed water; The pH that the pH that contains the organism draining that supplies to this reverse osmosis membrane separation device is adjusted to more than 9.5 adjusts operation; Wherein, have in described condensed water and to add the oxide treatment operation that ozone comes this condensed water of oxide treatment.
The 2nd the treatment process that contains the organism draining is characterized in that, in the 1st, described oxide treatment operation is and with the promotes oxidn treatment process of ozone and hydrogen peroxide.
The 3rd the treatment process that contains the organism draining is characterized in that, in the 1st or the 2nd, the pH of the treating water of described oxide treatment operation is 5.6～8.6.
The 4th the treatment process that contains the organism draining is characterized in that, in the 1st or the 2nd, has the pH that adds alkali reagent in described condensed water, make the water in the described oxide treatment operation and reaches 9.8～11 alkali and add operation.
The 5th the treatment process that contains the organism draining is characterized in that, in each of the 1st～4, has the activated carbon treatment operation that the treating water that makes described oxide treatment operation contacts with gac.
The 6th the treatment process that contains the organism draining, it is characterized in that,, prevent that in described fouling agent from adding in the operation in the 1st～5 each, add fouling and prevent agent to described contain in the organism draining, its amount is this 5 times of containing calcium ion in the organism draining more than the weight.
The 7th the treatment process that contains the organism draining is characterized in that, for the 6th, prevents that in described fouling agent from adding in the operation, adds fouling in the organism draining and prevents agent to described containing, and its amount contains 5～50 times of weight of the calcium ion in the organism draining for this.
The 8th the treatment process that contains the organism draining, it is characterized in that, in each of the 1st～7, the reverse osmosis membrane of described reverse osmosis membrane separation device is that to have at 1.47MPa, 25 ℃, pH be that under 7 the condition salt solution of 1500mg/L to be carried out the salt rejection ratio of reverse osmosis membrane separation when handling be the low pollution reverse osmosis membrane of polyethenol series of the desalting performance 95% or more.
The 9th the treatment process that contains the organism draining is characterized in that, in the 1st～8 each, adjusts in the operation at described pH, and the described pH that contains the organism draining is adjusted to 10.5～12.
The 10th the treatment process that contains the organism draining is characterized in that, in the 1st～9 each, is adding before described fouling prevents agent, contains the organism draining and carries out cationic exchange and handle described.
The present invention's (the 11st) the treatment unit that contains the organism draining is characterized in that having: add fouling and prevent that the fouling of agent from preventing the agent adding device in containing the organism draining; The reverse osmosis membrane separation device that the organism draining is separated into permeate water and condensed water that contains that this fouling prevents agent will have been added; The pH that contains the organism draining that supplies to this reverse osmosis membrane separation device is adjusted to pH adjustment unit more than 9.5; Wherein, have in described condensed water the ozone of interpolation and come the oxide treatment unit of this condensed water of oxide treatment.
The 12nd the treatment unit that contains the organism draining is characterized in that, in the 11st, described oxide treatment unit is and with the promotes oxidn processing unit of ozone and hydrogen peroxide.
The 13rd the treatment unit that contains the organism draining is characterized in that, in the 11st or 12, the pH of the unitary treating water of described oxide treatment is 5.6～8.6.
The 14th the treatment unit that contains the organism draining is characterized in that, in the 11st or 12, has and adds alkali reagent in described condensed water, make that the pH of water reaches 9.8～11 alkali adding device in the described oxide treatment unit.
The 15th the treatment unit that contains the organism draining is characterized in that, in each of the 11st～14, has the gac tower that imports the unitary treating water of described oxide treatment.
The 16th the treatment unit that contains the organism draining, it is characterized in that,, prevent in the agent adding device in described fouling in the 11st～15 each, add fouling and prevent agent to described contain in the organism draining, its amount is this 5 times of containing calcium ion in the organism draining more than the weight.
The 17th the treatment unit that contains the organism draining, it is characterized in that,, prevent in the agent adding device in described fouling for the 16th, add fouling and prevent agent to described contain in the organism draining, its amount contains 5～50 times of weight of the calcium ion in the organism draining for this.
The 18th the treatment unit that contains the organism draining, it is characterized in that, in each of the 11st～17, the reverse osmosis membrane of described reverse osmosis membrane separation device is that to have at 1.47MPa, 25 ℃, pH be that under 7 the condition salt solution of 1500mg/L to be carried out the salt rejection ratio of reverse osmosis membrane separation when handling be the low pollution reverse osmosis membrane of polyethenol series of the desalting performance 95% or more.
The 19th the treatment unit that contains the organism draining is characterized in that, in the 11st～18 each, in described pH adjustment unit, the described pH that contains the organism draining is adjusted to 10.5～12.
The 20th the treatment unit that contains the organism draining is characterized in that, in each of the 11st～19, equipment will supply to described fouling and prevent that the organism draining that contains of agent adding device from carrying out the cation exchange tower that cationic exchange is handled.
According to treatment process and the treatment unit that contains the organism draining of the present invention, the draining that containing of will discharging from electronics manufacturing works, other various fields, high density to the draining of low-concentration organic, particularly contained nonionic surfactant with the RO membrane separation unit handle, when reclaiming, prevent flux reduction that RO membrane separation unit internal cause organism caused in face absorption, biological pollution and when carrying out stabilizing treatment for a long time, TOC concentration in the water can be reduced effectively and obtain the treating water of high water quality.And, can also be easily and handle effectively and comprise in the RO condensed water that fouling prevents the organic substance of agent, alleviate load to follow-up draining treatment process.
That is, in the present invention since in RO feedwater, add fouling prevent agent and adjust to pH 9.5 or more after to the water flowing of RO membrane separation unit, as previously mentioned, can suppress in the RO membrane separation unit biological pollution, and suppress the face obstruction that causes because of fouling.
In addition, like this, by preventing that with add fouling in RO feedwater the RO condensed water that agent obtains from carrying out ozonize, oxygenolysis is removed and is comprised and come from the organic substance (TOC) the COD composition, in the condensed water that fouling in the RO condensed water prevents agent effectively.And, with biological treatment relatively, utilize the speed of response of the oxide treatment that ozone carries out fast, so can the space that be provided with of device be reduced equipment miniaturization.
Ozone Oxidation Treatment of the present invention can be and handles (the 2nd, 11) with the promotes oxidn of ozone and hydrogen peroxide.
Ozone Oxidation Treatment or and handle with the promotes oxidn of ozone and hydrogen peroxide, TOC in the condensed water and the hydroxyl free radical reaction that comes from ozone or hydrogen peroxide at first become the such oxygen compound of organic acid.Owing to generating the pH reduction that organic acid causes processed water, so even continue directly to add ozone etc. under the state that this pH reduces, the reactivity of ozone etc. also reduces.Therefore, remove, must add a large amount of ozone in order further TOC to be decomposed.Therefore,, usually, need in the former water of ozone Oxidation Treatment, add alkali reagent, make pH be alkalescence in order to prevent such reducing because of pH reduces the reactivity that causes.
In the present invention, contain that the organism draining is handled with the RO membrane sepn and the RO condensed water of the high pH that obtains for what will adjust to the high pH value of pH more than 9.5, handle owing to use this ozone Oxidation Treatment or promotes oxidn, be used to prevent such reduce the alkali reagent that the reactivity that causes reduces because of generating pH that organic acid caused so can not need to add.
But, the condensed water of this pH alkalescence, in ozone Oxidation Treatment or promotes oxidn processing, cause pH to reduce because of generating organic acid, when pH reaches pH neutral range about 5.6～8.6, because reaction is difficult to carry out, so pH can further not reduce, the result can stably obtain the neutral treating water.This pH neutral treating water can not carry out pH to be adjusted, directly discharging (the 3rd, 13).
But, in the present invention, pH for the water in ozone Oxidation Treatment or the promotes oxidn processing, do not reduce even generate organic acid pH yet, before ozone Oxidation Treatment or promotes oxidn processing, in condensed water, add alkali reagent, make alkaline range about reactive high, pH9.8～11 reach ozone or hydroxyl radical free radical, can react by promotes oxidn thus, use small amount of ozone just can decompose effectively and remove TOC (the 4th, 14).
Such ozone Oxidation Treatment or promotes oxidn by with oxide treatment water activated carbon treatment, can be removed oxygenant residual in the treating water (ozone, hydrogen peroxide) (the 5th, 15) after handling.By this activated carbon treatment, also can remove the TOC that residues in the water.
In the present invention, when in containing the organism draining, adding fouling and preventing that the amount of agent is very few, therefore then can not get sufficient fouling and prevent effect, in containing the organism draining, add fouling and prevent that the amount of agent is preferably 5 times of calcium ion in the RO feedwater more than the weight (the 6th, 16).
In addition, in the present invention, even prevent that in this fouling agent from being under the situation of salt such as sodium salt, fouling prevents that the addition of agent from also being the value that the form with acid converts and obtains.
In addition, in the present invention, particularly as the RO film, preferred use following RO film to carry out the RO membrane sepn to handle: having at 1.47MPa, 25 ℃, pH is that under 7 the condition salt solution of 1500mg/L to be carried out the salt rejection ratio (hereinafter to be referred as " salt rejection ratio ") of RO membrane sepn when handling be that low pollution of polyethenol series of the desalting performance 95% or more used RO film (the 8th, 18).So low pollution the reasons are as follows of preferred use with the RO film.
That is, above-mentioned low pollution is compared with normally used aromatic polyamide film with the RO film, owing to eliminate the charging property on film surface, wetting ability is improved, thereby very excellent aspect stain resistance.But, containing the water of a large amount of nonionic surfactants relatively, its stain resistance effect reduces, and flux reduces as time passes.
On the other hand, in the present invention, adjust to more than 9.5 by the pH with the RO feedwater, the nonionic surfactant that might make the reduction of RO membrane flux is from the face desorb, even so under the situation of using normally used aromatic polyamide film, the extreme that also can suppress flux reduces.But when the nonionic surfactant concentration in the RO feedwater was high, its effect reduced, and life-time service causes flux to reduce.
Therefore, in the present invention, in order to solve such problem, preferably combination is above-mentioned to be had low the pollution with RO film and pH that RO is fed water of the polyethenol series of specific desalting performance and adjusts to the condition of carrying out water flowing more than 9.5, thus, even for the RO feedwater that contains the high density nonionic surfactant, do not cause that flux reduces, and can carry out stable work for a long time yet.
In the present invention, in order to carry out more effective processing, preferably adopt following condition.
(1) pH of RO feedwater preferably adjusts to more than 10.5, particularly adjusts to 10.5～12 (the 9th, 19).
(2) fouling prevents that the addition of agent from being 5～50 times of amounts (the 7th, 17) of calcium ion concn.
When (3) calcium ion concn of RO feedwater is high,, carries out cationic exchange and handle, remove calcium (the 10th, 20) as adding the pre-treatment that fouling prevents agent.
Description of drawings
Fig. 1: the system diagram that is the embodiment of expression treatment process that contains the organism draining of the present invention and treatment unit.
Nomenclature
1 former water pot
2 RO membrane separation units
3 RO concentrate water pot
4 ozone reaction towers
6 ozone generation machines
8 gac towers
9 ion exchange towers
Embodiment
Below the treatment process that contains the organism draining that present invention will be described in detail with reference to the accompanying and the embodiment of treatment unit.
Fig. 1 is the system diagram of the embodiment of expression treatment process that contains the organism draining of the present invention and treatment unit.Among the figure, P
1, P
2, P
3It is pump.
In Fig. 1, after the interpolation fouling prevents agent in the former water (containing the organism draining) that imports through former water pot 1, add alkali reagent pH is adjusted to more than 9.5, then, import to RO membrane separation unit 2 and carry out the processing of RO membrane sepn.
Prevent agent as the fouling of in former water, adding; preferred use ethylenediamine tetraacetic acid (EDTA) (EDTA) or nitrilotriacetic acid(NTA) chelating class foulings such as (NTA) easy and metal ion formation coordination compound after the alkali scope is dissociated prevent agent; but; in addition; can also use (methyl) acrylate copolymer and salt thereof; low-molecular weight polymers such as toxilic acid polymkeric substance and salt thereof; ethylenediamine tetramethylene phosphonic acid and salt thereof; hydroxy ethylene diphosphonic acid and salt thereof; nitrilo trimethylene phosphonic and salt thereof; the phosphonic acids and the phosphonate of phosphinylidyne butane tricarboxylic acid and salt thereof etc., hexa metaphosphoric acid and salt thereof; the inorganic polymer phosphate of tripolyphosphate and salt etc. thereof and inorganic polymeric phosphate etc.These foulings prevent that agent can be used alone or two or more kinds may be used.
In the present invention, fouling prevents that the addition of agent is preferably 5 times of calcium ion concn in the former water (being added with the water that fouling prevents agent) more than the weight.When fouling prevents 5 times of weight of the calcium ion concn in the not enough former water of the addition of agent, can not fully obtain the additive effect that fouling prevents agent.Because it is not preferred from the cost aspect consideration of medicament that excessive interpolation fouling prevents agent, so be preferably 5～50 times of weight of the calcium ion concn in the former water.
Add the former water finish scale preventive agent, then add alkali reagent pH is adjusted to more than 9.5, preferred more than 10, more preferably 10.5～12, for example pH is adjusted to 10.5～11 after, import to RO membrane separation unit 2.As alkali reagent as used herein, be sodium hydroxide, potassium hydroxide etc., be that alkali reagent is just passable so long as the pH of former water can be adjusted to inorganic more than 9.5, there is no particular limitation.
RO film as RO membrane separation unit 2 is to have alkali-proof material, for example, can enumerate polyetheramides composite membrane, composite membrane of polyvinyl alcohol, aromatic polyamide film etc., still, according to aforesaid reason, preferably using salt rejection ratio is that low pollution of polyethenol series more than 95% used the RO film.This RO film can be the film of pattern arbitrarily such as spiral type, macaroni yarn type, tubular-type.
For the permeate water of RO membrane separation unit 2, then add acid pH is adjusted to 4～8, further implement as required to be reused or to discharge after the activated carbon treatment etc.As acid as used herein, special qualification useless can be enumerated mineral acids such as hydrochloric acid, sulfuric acid.
On the other hand, the condensed water of RO membrane separation unit 2 is added hydrogen peroxide (H after being stored in the concentrated water pot 3 of RO as required
2O
2) and/or alkali reagent after, deliver to ozone reaction tower 4 and carry out oxide treatment.
Not necessarily must add hydrogen peroxide to condensed water, but,, can utilize the generation hydroxyl radical free radical stronger to improve oxygenolysis efficient than the oxidizing power of ozone by adding hydrogen peroxide, can realize the further minimizing of ozone addition, so preferably add hydrogen peroxide.
The position that hydrogen peroxide adds can be in condensed water with before ozone contacts, also can be after the interpolation of alkali reagent.The interpolation of hydrogen peroxide is preferably carried out pipeline to the transport pipe of condensed water and is injected as shown in Figure 1, still, in this case, the such agitating unit of line mixer (linemixer) is set preferably.
In addition, having no particular limits about the addition of hydrogen peroxide, suitably determine according to the water quality of condensed water, desired treating water water quality etc., is about 1～10 times of weight with respect to the TOC in the condensed water usually.
As ozone reaction tower 4, as long as can keep the reactive high alkaline range of ozone or hydroxyl radical free radical and make condensed water absorb ozone effectively and make the reaction carry out, just there is no particular limitation, can be as shown in Figure 1, scatter condensed water from the aproll plate 5 that is arranged on reaction tower 4 tops, to pass through the pattern of the diffuser 7 diffusing gas of tower bottom from the ozone that ozone generation machine 6 is carried, in addition, can also be the open tank with mechanical type stirrer.In addition, can also be arranged on the line mixer or the such interior ozone supply unit of stream of turbulence pump of pipeline.But, fully contact with condensed water in order to make ozone, make the TOC oxidizing reaction to heavens in the condensed water, reactive tank preferably is set.
In the present invention, by to the RO condensed water that imports to ozone reaction tower 4 or in ozone reaction tower 4, add alkali reagent, make the pH of outflow water of water in this ozone reaction tower 4 or ozone reaction tower 4 reach 9～12, more preferably reach 9.8～11, can promote the oxidizing reaction of utilizing ozone to carry out thus.During the pH value less than 9 of this adjustment, can not fully obtain because of adding the effect of the raising oxygenolysis efficient due to the alkali reagent.Yet when this pH value was too high, the pH for the treatment of water uprised, and all was not preferred for thereafter biological treatment or discharging.
As the alkali reagent that is used to adjust this pH, can use mineral-type alkali reagents such as sodium hydroxide, potassium hydroxide.
But this alkali reagent not necessarily must add, and as previously mentioned, because RO condensed water of the present invention is generally the high pH value about pH10～12, even it directly is supplied in ozone Oxidation Treatment or promotes oxidn processing, also can obtain sufficient reaction efficiency.So, in this case, obtain pH and be about 5.6～8.6 neutral treating water, this treating water can directly discharge, even the perhaps follow-up situation that biologic treatment process is arranged especially it is not carried out pH yet and adjusts, can be directly in biological treatment.
Also there is no particular limitation as the addition means of ozone, as shown in Figure 1, can carry out according to following method: will from the ozone of ozone generation machine 6 in ozone reaction tower 4 by diffuser 7 the loose method of gas or the common methods of injecting with injector such as method.In addition, also can use RO permeate water etc. with ozone solution in wherein, add as ozone water.
The addition of ozone according to the water quality of condensed water, have or not and different with the difference of hydrogen peroxide and addition thereof, still, with respect to the TOC of condensed water, is about 1～50 times of weight usually.
In Fig. 1, the discharge water that comes from ozone reaction tower 4 is directed to gac tower 8, after residual ozone or hydrogen peroxide are removed, is discharged to outside the system discharging or further carry out a biological disposal upon as treating water.Treatment condition in this gac tower 8 suitably determine according to the outflow ozone in water of ozone reaction tower 4 or the residual quantity of hydrogen peroxide.By this activated carbon treatment, the TOC that remains in the ozonize water further can be removed.
The treating water that so obtains under the situation that TOC concentration is fully reduced, can directly or as required discharge behind the interpolation acid adjustment pH.In addition, under the situation that the TOC for the treatment of water is not fully reduced, can with deliver to the draining treatment process after other draining mixes and handle, perhaps it further can be removed TOC to the deionizer water flowing.
In Fig. 1, ion exchange tower 9 is set as deionizer.As deionizer, can use ion exchange unit, reverse osmosis membrane apparatus, electric regenerative deionizer etc.As ion exchange unit can be the mixed bed formula ion exchange tower that is filled with Zeo-karb and anionite-exchange resin with admixture, also can be 23 tower, 45 tower desalting plants that two kinds of resins are filled in each tower.The gac tower is flowed out water to the deionizer water flowing, and then the ionic TOC in the water is removed, and can be contained the treating water of TOC hardly.Can be with the discharging of this treating water, also can reclaim and re-use.
According to the present invention, as shown in Figure 1, prevent agent by the fouling of in former water, adding specified amount, and carry out the RO membrane sepn after adjusting to pH more than 9.5 and handle, can not cause that the flux in the RO membrane separation unit reduces, can carry out stable treated for a long time, obtain the high water conditioning water that TOC is highly removed.In addition, will handle that the RO condensed water that obtains be carried out ozone Oxidation Treatment or promotes oxidn is handled by this RO membrane sepn, thus can with the organic substance in the condensed water to heavens oxygenolysis remove.
Fig. 1 is an example of expression embodiment of the present invention, as long as be no more than aim of the present invention, is not limited to any illustrated mode.In Fig. 1, add fouling among the Xiang Yuanshui and prevent after the agent, add alkali reagent and carry out the pH adjustment, but, also can after former water interpolation alkali reagent carry out the pH adjustment, add fouling and prevent agent, in addition, can also carry out the interpolation that pH adjustment and fouling prevent agent simultaneously.In addition, being not limited to 1 section processing with the processing of RO membrane separation unit, can be that the multistage more than 2 sections is handled.In addition, for the draining that contains TOC of discharging etc. from electronics manufacturing works, basically the situation that seldom has calcium ion of becoming the fouling reason etc. to sneak into, but when sneaking into calcium ion etc. in the former water, can be before the interpolation fouling prevents agent, the cation exchange tower of calcium ion is removed in setting, removes calcium in advance.And then, can be provided for adjusting pH or add the tempering tank that fouling prevents agent.
In addition, when handling the RO condensed water, under the situation that the multistage that carries out with the RO membrane separation unit more than 2 sections is handled, can carry out so oxide treatment, also can carry out same processing other RO condensed water to the RO condensed water of the 1st section RO membrane separation unit.
In addition, remove in ozone Oxidation Treatment or promotes oxidn are handled residual ozone or hydrogen peroxide and be not limited to the gac tower, can be undertaken by adding reductive agents such as sodium bisulfite.But, can remove aspect the residual TOC preferred activated carbon treatment.
In the present invention, be supplied in the RO condensed water that ozone Oxidation Treatment or promotes oxidn are handled, preferably contain and be difficult to biodegradable fouling and prevent TOC such as agent or tensio-active agent, ozone Oxidation Treatment of the present invention or promotes oxidn are handled and are played a role effectively.But, also can contain easy biodegradable fouling and prevent agent, can also contain fouling and prevent agent organism in addition, any situation no matter, with they oxygenolysis, can alleviate the load of subsequent biological treatment by ozone, the area that is provided with of aerator tank is reduced.Perhaps can obtain the good discharge water of water quality.
[embodiment]
Below enumerate embodiment and be described more specifically the present invention.
Embodiment 1
The TOC concentration based on tensio-active agent be 5mg/L, calcium ion concn be the draining of 10mg/L as former water, handle with device shown in Figure 1.At first, add EDTA among the Xiang Yuanshui and bind scale preventive agent (disodium edta), its amount is 5 times of weight of the calcium ion concn of former water, then, add NaOH and make pH reach 10.5, under the condition of water-flowing amount 80L/h, the rate of recovery 75%, carry out the RO membrane sepn with RO membrane separation unit (the low pressure aromatic polyamide type RO film " ES-10 " of day eastern electrician's system) and handle.
After interpolation was the hydrogen peroxide of 1.2 times of amounts with respect to TOC in the RO condensed water that obtains by this RO membrane sepn processing, adding with respect to TOC was the ozone of 10 times of amounts.Then, under the condition of water flowing SV10/h to the water flowing of gac tower, and then under the condition of water flowing SV20m/h with the outflow water of gac tower to the ion exchange tower water flowing, obtain treating water, described ion exchange tower mixes the DIAION SK1B (Mitsubishi chemical Co., Ltd's goods) be filled with as Zeo-karb with 1: 1 (weight ratio) and as the Lewatit M500 (BAYER company goods) of anionite-exchange resin.
Study the pH and the TOC concentration of RO condensed water in this processing, remove rate with pH, TOC concentration and the TOC of ozonize water (the outflow water of ozone reaction tower), and pH, TOC concentration and the TOC of gac tower outflow water remove rate, and pH, TOC concentration, the TOC for the treatment of water (the outflow water of ion exchange tower) remove rate, and the result is illustrated in the table 1.
Embodiment 2
Except not to the RO condensed water is added hydrogen peroxide, all the other and embodiment 1 handle in the same manner, pH, TOC concentration and the TOC of research ozonize water (the outflow water of ozone reaction tower) remove rate, remove rate with pH, TOC concentration and the TOC of the outflow water of gac tower, and pH, TOC concentration, the TOC for the treatment of water (the outflow water of ion exchange tower) remove rate, and the result is illustrated in the table 1.
Embodiment 3
Except the addition that increases alkali so that the pH of ozonize water reach 10, all the other and embodiment 1 handle in the same manner, pH, TOC concentration and the TOC of research ozonize water (the outflow water of ozone reaction tower) remove rate, remove rate with pH, TOC concentration and the TOC of the outflow water of gac tower, and pH, TOC concentration, the TOC for the treatment of water (the outflow water of ion exchange tower) remove rate, and the result is illustrated in the table 1.
Table 1
| The RO condensed water | Embodiment 1 | Embodiment 2 | Embodiment 3 | |||||||
| Ozonize water | The outflow water of gac tower | Treating water | Ozonize water | The outflow water of gac tower | Treating water | Ozonize water | The outflow water of gac tower | Treating water | ||
| pH | 10.5 | 7.5 | 6.8 | 6.8 | 6.8 | 7.2 | 7.1 | 10 | 8.2 | 7.0 |
| TOC concentration (mg/L) | 20 | 14 | 5 | 0.4 | 18 | 10 | 0.8 | 12 | 5 | 0.2 |
| TOC removes rate (%) | - | 30 | 75 | 98 | 10 | 50 | 96 | 40 | 75 | 99 |
| Appendix | Promotes oxidn is handled | Ozone Oxidation Treatment | High pH promotes oxidn is handled | |||||||
As shown in Table 1, according to the present invention, the TOC in the RO condensed water can be removed to heavens.
The possibility of industrial application
The present invention can be effective to from the electronic equipment manufacturing field, field of semiconductor manufacture, other various industrial fields are discharged contains high concentration to the water treatment of the discharging of the draining of low concentration TOC or recovery, recycling.
Claims (20)
1, a kind of treatment process that contains the organism draining is characterized in that, comprises following operation:
In containing the organism draining, add fouling and prevent that the fouling of agent from preventing agent interpolation operation;
Prevent that with having added this fouling the organism draining that contains of agent from supplying to the reverse osmosis membrane separation device, is separated into the reverse osmosis membrane separation operation of permeate water and condensed water;
The pH that the pH that contains the organism draining that supplies to this reverse osmosis membrane separation device is adjusted to more than 9.5 adjusts operation;
Wherein, have in described condensed water and to add the oxide treatment operation that ozone comes this condensed water of oxide treatment.
2, the treatment process that contains the organism draining according to claim 1 is characterized in that, described oxide treatment operation is and with the promotes oxidn treatment process of ozone and hydrogen peroxide.
3, the treatment process that contains the organism draining according to claim 1 and 2 is characterized in that, the pH of the treating water of described oxide treatment operation is 5.6～8.6.
4, the treatment process that contains the organism draining according to claim 1 and 2 is characterized in that, has the pH that adds alkali reagent in described condensed water, make the water in the described oxide treatment operation and reaches 9.8～11 alkali and add operation.
5, according to each described treatment process that contains the organism draining in the claim 1～4, it is characterized in that having the activated carbon treatment operation that the treating water that makes described oxide treatment operation contacts with gac.
6, according to each described treatment process that contains the organism draining in the claim 1～5, it is characterized in that, prevent that in described fouling agent from adding in the operation, add these 5 times of foulings more than the weight of calcium ion that contain in the organism draining in the organism draining and prevent agent to described containing.
7, the treatment process that contains the organism draining according to claim 6 is characterized in that, prevents that in described fouling agent from adding in the operation, adds this fouling that contains 5～50 times of weight of calcium ion in the organism draining in the organism draining and prevents agent to described containing.
8, according to each described treatment process that contains the organism draining in the claim 1～7, it is characterized in that the reverse osmosis membrane of described reverse osmosis membrane separation device is that to have at 1.47MPa, 25 ℃, pH be that under 7 the condition salt solution of 1500mg/L to be carried out the salt rejection ratio of reverse osmosis membrane separation when handling be the low pollution reverse osmosis membrane of polyethenol series of the desalting performance 95% or more.
9, according to each described treatment process that contains the organism draining in the claim 1～8, it is characterized in that, adjust in the operation, the described pH that contains the organism draining is adjusted to 10.5～12 at described pH.
10, according to each described treatment process that contains the organism draining in the claim 1～9, it is characterized in that,, will describedly contain the organism draining and carry out the cationic exchange processing adding before described fouling prevents agent.
11, a kind of treatment unit that contains the organism draining is characterized in that having:
In containing the organism draining, add fouling and prevent that the fouling of agent from preventing the agent adding device;
The reverse osmosis membrane separation device that the organism draining is separated into permeate water and condensed water that contains that this fouling prevents agent will have been added;
The pH that contains the organism draining that supplies to this reverse osmosis membrane separation device is adjusted to pH adjustment unit more than 9.5;
Wherein, have in described condensed water the ozone of interpolation and come the oxide treatment unit of this condensed water of oxide treatment.
12, the treatment unit that contains the organism draining according to claim 11 is characterized in that, described oxide treatment unit is and with the promotes oxidn processing unit of ozone and hydrogen peroxide.
13, according to claim 11 or the 12 described treatment unit that contain the organism draining, it is characterized in that the pH of the unitary treating water of described oxide treatment is 5.6～8.6.
14, according to claim 11 or the 12 described treatment unit that contain the organism draining, it is characterized in that having and in described condensed water, add alkali reagent, make that the pH of water reaches 9.8～11 alkali adding device in the described oxide treatment unit.
15, according to each described treatment unit that contains the organism draining in the claim 11～14, it is characterized in that having the gac tower that imports the unitary treating water of described oxide treatment.
16, according to each described treatment unit that contains the organism draining in the claim 11～15, it is characterized in that, prevent in the agent adding device in described fouling, add these 5 times of foulings more than the weight of calcium ion that contain in the organism draining and prevent agent to described contain in the organism draining.
17, the treatment unit that contains the organism draining according to claim 16 is characterized in that, prevents in the agent adding device in described fouling, adds this fouling that contains 5～50 times of weight of calcium ion in the organism draining and prevents agent to described contain in the organism draining.
18, according to each described treatment unit that contains the organism draining in the claim 11～17, it is characterized in that the reverse osmosis membrane of described reverse osmosis membrane separation device is that to have at 1.47MPa, 25 ℃, pH be that under 7 the condition salt solution of 1500mg/L to be carried out the salt rejection ratio of reverse osmosis membrane separation when handling be the low pollution reverse osmosis membrane of polyethenol series of the desalting performance 95% or more.
19, according to each described treatment unit that contains the organism draining in the claim 11～18, it is characterized in that, in described pH adjustment unit, the described pH that contains the organism draining is adjusted to 10.5～12.
According to each described treatment unit that contains the organism draining in the claim 11～19, it is characterized in that 20, equipment will be fed into described fouling and prevent that the organism draining that contains in the agent adding device from carrying out the cation exchange tower that cationic exchange is handled.
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| JP2006083282A JP2007253115A (en) | 2006-03-24 | 2006-03-24 | Organic matter-containing wastewater treatment method and apparatus |
| JP2006083282 | 2006-03-24 | ||
| JP2006-083282 | 2006-03-24 |
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| JP (1) | JP2007253115A (en) |
| KR (1) | KR101353002B1 (en) |
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| CN101041522B (en) | 2012-12-05 |
| TW200740704A (en) | 2007-11-01 |
| TWI461372B (en) | 2014-11-21 |
| KR20070096857A (en) | 2007-10-02 |
| KR101353002B1 (en) | 2014-01-22 |
| JP2007253115A (en) | 2007-10-04 |
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