CN101597097B - Method of treating waste water containing organic substance - Google Patents
Method of treating waste water containing organic substance Download PDFInfo
- Publication number
- CN101597097B CN101597097B CN2009101488098A CN200910148809A CN101597097B CN 101597097 B CN101597097 B CN 101597097B CN 2009101488098 A CN2009101488098 A CN 2009101488098A CN 200910148809 A CN200910148809 A CN 200910148809A CN 101597097 B CN101597097 B CN 101597097B
- Authority
- CN
- China
- Prior art keywords
- organism
- scale inhibitors
- draining
- water
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
In the performing of treatment/recovery with the use of RO membrane separator as to waste water containing organic substances in high concentration or low concentration, discharged from electronic device manufacturing plants or other facilities of various fields, not only can stable treatment be conducted for a prolonged period of time while preventing biofouling and flux drop attributed to attachment of organic substances to the membrane surface in the RO membrane separator but also the TOC concentration in water can be efficiently reduced to thereby obtain treated water of high quality. Waste water containing organic substances is loaded with a scale inhibitor amounting to at least 5 times by weight the calcium ion concentration in the water and further loaded with an alkali so as to adjust the pH value to 9.5 or higher, and thereafter passed through RO membrane separator (2). By virtue of the adjustment of the pH value of water fed to the RO to 9.5 or higher, any biofouling of the RO membrane separator can be prevented and also any attachment of nonionic surfactant to membrane surface can be prevented to thereby avoid any flux drop. By virtue of the addition of the scale inhibitor, any membrane surface clogging by calcium carbonate scale under high pH conditions can be inhibited.
Description
The application is application number the dividing an application for the PCT application in entering country's stage of " treatment process and the treatment unit that contain the organism draining " that be CN200480040600.5 (international filing date is on October 22nd, 2004), denomination of invention.
Technical field
The present invention relates to use reverse osmosis (RO) membrane separation unit to the treatment process and the device that contain organism (TOC) draining from discharges such as electronic installation manufacturing works.
Background technology
Environmental standard or water quality standard have more and more stricter trend, hope also to the waste water high purification.In order to solve the water deficiency, utilize again in order to reclaim various drainings, also hope to develop high-caliber water technology.
The RO membrane sepn is handled and can be removed the impurity (ionic species, organism, micropartical etc.) in anhydrating efficiently.Following purifying method is documented in the TOHKEMY 2002-336886 communique; When the draining of promptly reclaiming containing of from semiconductor fabrication, discharging acetone, Virahol etc. containing high density TOC or lower concentration TOC utilizes again; At first it is carried out a biological disposal upon; Remove the TOC composition, then biological treatment of water is carried out the RO film and handle.
When the biological treatment draining is supplied water in the RO membrane separation unit, decompose, generate biological metabolite, so the face of RO film gets clogged the flux reduction because of mikrobe causes organism.
Do not carry out a biological disposal upon, but the draining that directly will contain TOC inputs in the RO membrane separation unit, the TOC concentration that flows into the RO membrane separation unit is high, and therefore mikrobe is prone to breeding in the RO membrane separation unit.From being suppressed at the purpose of the biofouling in the RO membrane separation unit, heavy addition slimicide in the draining that contains TOC usually, but the costing an arm and a leg of slimicide.
The draining of discharging from electronic installation manufacturing works; Sneak into nonionic surfactant on the face that is attached to the RO membrane separation unit, that probably flux is reduced sometimes; Therefore; In this draining that contains nonionic surfactant, can not use the RO membrane sepn and handle in the past.
The draining of discharging, except containing above-mentioned organism, also contain oxygenants such as hydrogen peroxide from electronic installation factory.When in draining, containing oxygenant, from the purpose of the RO film oxidative degradation that prevents to be caused by oxygenant, generally the leading portion at the RO membrane separation unit is provided with the activated carbon tower.Owing in these drainings, also contain organism, so activated carbon Ta Neiyi forms the hotbed of mikrobe.If microbial reproduction in the activated carbon tower, then the differential pressure of activated carbon tower rises, so mikrobe is revealed, the SDI value of activated carbon treatment water rises.
Summary of the invention
The object of the present invention is to provide the treatment process and the treatment unit that contain the organism draining; Wherein, Said drainage processing method can obtain the treating water of high water quality through following mode, is promptly using the RO membrane separation unit to handle to reclaim when containing the organism draining, prevents that organism in the RO membrane separation unit is attached on the face and the flux that causes reduces, biofouling; Carry out stabilizing treatment for a long time, simultaneously TOC concentration in the water is reduced efficiently.
Drainage processing method of the present invention comprises following operation: Scale inhibitors adds operation, promptly in containing the organism draining, adds the above Scale inhibitors of 5 times of weight of calcium ion that is equivalent to contain in this organism draining; PH adjusts operation, promptly before adding this Scale inhibitors, afterwards or containing in the organism draining simultaneously and add alkali, pH is adjusted to more than 9.5; The membrane sepn operation promptly through after this Scale inhibitors interpolation operation and the pH adjustment operation, is carried out the reverse osmosis membrane separating treatment to containing the organism draining.
Drain treatment apparatus of the present invention possesses just like lower device: in containing the organism draining, interpolation is equivalent to this Scale inhibitors adding set that contains the Scale inhibitors more than 5 times of weight of calcium ion in the organism draining; Before this Scale inhibitors adds, contain in the organism draining at this and add alkali afterwards or simultaneously, pH is adjusted to the pH setting device more than 9.5; Import through the reverse osmosis membrane separating and treating apparatus that contains the organism draining after this Scale inhibitors adding set and the pH setting device.
In the present invention, even when this Scale inhibitors is salt such as sodium salt, the addition of Scale inhibitors also is the value that the form by acid converts and obtains.
Description of drawings
Fig. 1 is the related treatment process that contains the organism draining of expression embodiment of the present invention and the schematic diagram of treatment unit.
Fig. 2 be RO membrane separation unit in expression embodiment 1 and the comparative example 1,2 membrane flux through the time figure that changes.
Fig. 3 be RO membrane separation unit in expression embodiment 1 and the comparative example 1,2 viable count through the time figure that changes.
Fig. 4 be RO membrane separation unit in expression embodiment 2 and the comparative example 3～5 membrane flux through the time figure that changes.
Fig. 5 be RO membrane separation unit in expression embodiment 1,3 and the comparative example 6,7 membrane flux through the time figure that changes.
Fig. 6 be RO membrane separation unit in expression embodiment 4,5 and the comparative example 8 membrane flux through the time figure that changes.
Fig. 7 is expression embodiment 6 results' figure.
Fig. 8 is expression embodiment 7 results' figure.
Fig. 9 is the related drainage processing method that contains organism and oxygenant of other embodiments of the present invention and the schematic diagram of treatment unit.
Figure 10 be expression embodiment 8 with comparative example 9 in activated carbon treatment water viable count through the time figure that changes.
Figure 11 be RO membrane separation unit in expression embodiment 8 and the comparative example 9 membrane flux through the time figure that changes.
Figure 12 be RO membrane separation unit in expression embodiment 9 and the comparative example 10～12 membrane flux through the time figure that changes.
Figure 13 be RO membrane separation unit in expression embodiment 8,10 and the comparative example 13,14 membrane flux through the time figure that changes.
Embodiment
A kind of mode of the present invention does, adds the Scale inhibitors of specified amount in the processed water in being directed into the RO membrane separation unit (below be sometimes referred to as " RO water supply "), simultaneously pH adjusted to more than 9.5, supplies water to the RO membrane separation unit.
The pH that RO is supplied water adjusts to the reasons are as follows more than 9.5.
Mikrobe can not survive in alkaline range.Therefore; PH through RO is supplied water adjusts to more than 9.5, then in the RO membrane separation unit, even can create nutritious source but mikrobe can not survival environment; Must not add expensive in the past slimicide, can suppress the biofouling in the RO membrane separation unit.
Known might make nonionic surfactant that flux reduces in alkaline range from the face desorb, adjust to more than 9.5 through the pH that RO is supplied water, can suppress these compositions and be attached on the RO face.
In RO supplies water, add be equivalent to this RO supply water in the reasons are as follows of 5 times of Scale inhibitorss more than the weight of calcium ion.
Under few situation, from the draining that contains TOC of discharges such as electronic installation manufacturing works, can be mixed with the calcium ion that causes incrustation scale etc.In the present invention, if the pH that RO is supplied water is transferred to more than 9.5, then under the RO of so high pH working conditions, even be mixed with the calcium ion of denier, also can generate incrustation scales such as lime carbonate, the RO film directly blocks.In the present invention; From the purpose that the face that suppresses to cause because of this incrustation scale blocks,, RO adds Scale inhibitors in supplying water, but when 5 times of amounts of the not enough calcium ion concn of this Scale inhibitors addition; Therefore its additive effect is insufficient, its addition is made as 5 times of calcium ion concn more than the amount.
In this mode; As the RO film, preferred especially the use at 1.47MPa, 25 ℃, pH is that under 7 the condition salt solution of 1500mg/L to be carried out the salt rejection ratio (be designated hereinafter simply as " salt rejection ratio ") of RO membrane sepn when handling be that the low alluvial of the polyvinyl alcohol with desalting performance 95% or more is carried out the processing of RO membrane sepn with the RO film.Preferred this low alluvial of use the reasons are as follows with the RO film.
Above-mentioned low alluvial is compared with normally used aromatic polyamide film with the RO film, has removed the charge on film surface, and wetting ability is improved, and is therefore very excellent aspect stain resistance.Yet with respect to the water that contains nonionic surfactant in a large number, its stain resistance effect reduces, and flux reduces in time.
PH through RO is supplied water adjusts to more than 9.5, and the nonionic surfactant that might make the reduction of RO membrane flux is from the face desorb, even therefore used normally used aromatic series class PA membrane, the extreme that also can suppress flux reduces.But when the nonionic surfactant concentration during RO supplies water was high, its effect also reduced, and is so long-term, and flux reduces.
Therefore; In order to address this is that; Preferably with the low alluvial of above-mentioned polyvinyl alcohol with specific desalting performance with the RO film and the pH that RO supplies water be transferred to 9.5 with on the condition combination of supplying water; Even supply water for the RO that contains the high density nonionic surfactant thus, do not cause that flux reduces yet, can long-term stable operation.
In order to handle more efficiently, preferably adopt following condition.
The pH that preferably RO is supplied water is transferred to more than 10.5, especially preferably is transferred to 10.5～12.
The addition of Scale inhibitors is made as 5～50 times of amounts of calcium ion concn.
When the calcium ion concn that RO supplies water is high, carries out cationic exchange and handle, remove calcium as the pre-treatment of adding Scale inhibitors.
Drainage processing method in this way and treatment unit; Use of the draining that contain high density or low-concentration organic of RO membrane separation unit to discharging from electronic installation manufacturing works, other various fields; The draining that particularly contains nonionic surfactant is handled when reclaiming; Can prevent that organism in the RO membrane separation unit is attached on the face and the flux that causes reduces, biofouling; Can carry out stable treated for a long time, can reduce TOC concentration in the water efficiently simultaneously, thereby obtain the treating water of high water quality.Treating water through obtaining after the present invention's processing can be as former water, BW or the cooling water of making ultrapure water.
Specify this mode related treatment process that contains the organism draining and treatment unit with reference to the accompanying drawings.
Fig. 1 is the related treatment process that contains the organism draining of expression one mode and the schematic diagram of treatment unit.
In Fig. 1, in through jar former water (containing the organism draining) of 1 importing, after the interpolation Scale inhibitors, add alkali, pH is transferred to more than 9.5, import to then in the RO membrane separation unit, carry out the RO membrane sepn and handle.
As the Scale inhibitors that in former water, adds; Preferred YD 30 (EDTA) or the NTA inner complex class Scale inhibitorss such as (NTA) that in the alkali scope, dissociates, is prone to form metals ion and title complex that use; In addition; Can use low-molecular weight polymers such as (methyl) XPA and salt thereof, toxilic acid polymkeric substance and salt thereof; Phosphonic acids and phosphonates such as ethylenediamine tetramethylene phosphonic acid and salt thereof, hydroxy ethylene diphosphonic acid and salt thereof, nitrilo trimethylene phosphonic and salt thereof, phosphonic acids butane group tricarboxylic acid and salt thereof, inorganic polymer phosphate such as hexa metaphosphoric acid and salt thereof, tripolyphosphate and salt thereof and inorganic polymer phosphate etc.
The addition of Scale inhibitors is made as 5 times of calcium ion concn in the former water (having added the water of Scale inhibitors) more than the weight.During 5 times of weight of the calcium ion concn of the addition of Scale inhibitors in the former water of deficiency, can not fully obtain the additive effect of Scale inhibitors.Even excessively add Scale inhibitors, not preferred aspect the pharmaceutical prepn cost yet, therefore, preferably its addition is made as 5～50 times of weight of calcium ion concn in the former water.
Be added with the former water of Scale inhibitors, then add alkaline agent, 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, import to then in the RO membrane separation unit 2.Alkaline agent in this use can be enumerated sodium hydroxide, Pottasium Hydroxide etc., so long as can the inorganics class alkaline agent that pH adjusts to more than 9.5 be got final product, does not have special qualification.
RO film as the RO membrane separation unit has alkali-proof material; For example; Can enumerate polyetheramides composite package, composite membrane of polyvinyl alcohol, aromatic polyamide film etc., also can use at 1.47MPa, 25 ℃, pH is that under 7 the condition 1500mg/L salt solution to be carried out the salt rejection ratio (be designated hereinafter simply as " salt rejection ratio ") of RO membrane sepn when handling be that the RO film is used in the low alluvial of the polyvinyl alcohol with desalting performance more than 95%.Preferred this low alluvial of use the reasons are as follows with the RO film.
Above-mentioned low alluvial compares with normally used aromatic polyamide film with the RO film and since removed the film surface charge, wetting ability is improved, therefore very excellent aspect stain resistance.Yet for the water that contains nonionic surfactant in a large number, its stain resistance effect reduces, and flux reduces in time.
PH through RO is supplied water adjusts to more than 9.5, and the nonionic surfactant that makes the reduction of RO membrane flux probably is from the face desorb, even therefore used the situation of normally used aromatic series class PA membrane, the extreme that also can suppress flux reduces.Yet when the nonionic surfactant concentration during RO supplies water was high, its effect also reduced, and so flux reduces for a long time.Leading portion through at the RO membrane separation unit carries out activated carbon treatment, and the above-mentioned flux reduction problem that causes because of tensio-active agent is alleviated, but handles for a long time, and flux still reduces.
With the low alluvial of above-mentioned polyvinyl alcohol with desalting performance with RO film and the pH that supplies water RO be transferred to 9.5 with on the condition that supplies water make up; Even supply water for the RO that contains the high density nonionic surfactant thus; Can not cause that also flux reduces, and can carry out stable work for a long time.
The RO film can be a type arbitrarily such as spiral, hollow line style, tubular-type.
The condensed water of RO membrane separation unit 2 is added acid as required, and pH is after neutrality in adjustment, is discharged to outside the system.And the permeate water of RO membrane separation unit 2 is then added acid, and pH is adjusted to 4～8, as required, further carries out after the activated carbon treatment, utilizes or discharges.At this, the acid as using does not have special qualification, can enumerate mineral acids such as hydrochloric acid, sulfuric acid.
As shown in Figure 1, in former water, add the Scale inhibitors of specified amount, adjust to pH more than 9.5 simultaneously after; Carrying out the RO membrane sepn handles; Can not cause that thus the flux in the RO membrane separation unit reduces, can carry out processing steady in a long-term, can highly be removed the high water conditioning water of TOC.
Fig. 1 is the figure of one of expression the present invention example, and the present invention is not limited by any diagram.In Fig. 1, add among the Xiang Yuanshui and add alkali after the Scale inhibitors and carry out the pH adjustment, carry out adding Scale inhibitors after the pH adjustment but also can in former water, add alkali, in addition, also can carry out pH adjustment and interpolation Scale inhibitors simultaneously.The processing of carrying out with the RO membrane separation unit is not limited to the one-level processing, also can carry out the multiple-stage treatment more than 2 grades.The situation of sneaking into the calcium ion that causes incrustation scale etc. is basically seldom arranged the draining that contains TOC of discharging from electronic installation manufacturing works etc.; But when in former water, sneaking into calcium ion etc.; Before adding Scale inhibitors, the cation exchange tower of removing calcium ion is set earlier, also can remove calcium in advance.Can also be provided for the tempering tank of pH adjustment and interpolation Scale inhibitors.
The electronic installation manufacturing works draining that contains nonionic class tensio-active agent (pH 7.2, TOC10mg, calcium ion concn 1mg/L) as former water; In former water, add after the disodium edta 10mg/L as Scale inhibitors; Add NaOH; PH is transferred to 10.5, is to carry out the RO membrane sepn under 90% the condition to handle in the recovery with RO membrane separation unit (the low pressure aromatic polyamide type RO film " NTR-759 " that day eastern electrician makes).
Investigate viable count in membrane flux (25 ℃, 1.47MPa) and the RO condensed water of RO membrane separation unit of this moment through the time variation, the result is shown among Fig. 2,3.
What should explain is that the TOC concentration of RO permeate water is 50 μ g/L, can highly remove TOC.
Comparative example 1
In former water, do not add Scale inhibitors, in addition the pH furnishing 7 that RO is supplied water, is handled under the condition identical with embodiment 1, with viable count in the membrane flux of RO membrane separation unit and the RO condensed water through the time variation be shown in respectively among Fig. 2,3.
Comparative example 2
In former water, do not add Scale inhibitors; PH furnishing 7 with RO water supply;, adds RO 5mg/L isothiazoline class slimicide (chestnut field industry (strain) system " Network リ バ one タ EC-503 ") in supplying water; In addition, under the condition identical, handle with embodiment 1, with the membrane flux of RO membrane separation unit and viable count through the time change and be shown in respectively among Fig. 2,3.
Can obviously find out by Fig. 2, in embodiment 1, not reduce even also observe flux behind the beginning 500hr that supplies water, relative therewith, in comparative example 1, supply water behind the beginning 300hr, reduced about half with respect to initial flux.In addition, even in the comparative example that is added with slimicide 2, in the beginning 300hr that supplies water, be reduced to about 60% of initial flux.
Can find out that by Fig. 3 in embodiment 1 and comparative example 2, not observing viable count increases, relative therewith, in comparative example 1, increase along with water supply time increases viable count.
Can know by above result; In comparative example 1, because the synergistic effect that microbial reproduction in the RO film and nonionic surfactant face adhere to, so flux reduces; And in comparative example 2; Even can suppress microbial reproduction through adding slimicide, but because the face of nonionic surfactant adheres to, flux reduces also; In the related embodiment 1 of the present invention, can suppress the interior microbial reproduction of RO membrane separation unit and the face of nonionic surfactant simultaneously and adhere to this two aspect.
Except the pH that RO is supplied water is adjusted to 9.5 (embodiment 2), 9.2 (comparative examples 3), 9 (comparative examples 4) or 8.5 (comparative examples 5); Under the condition identical, handle with embodiment 1; The membrane flux of investigating the RO membrane separation unit through the time change, the result is shown among Fig. 4.
Can know by Fig. 4, be transferred to more than 9.5 through the pH that RO is supplied water, the biofouling that the face that can suppress nonionic surfactant adheres to and causes because of microbial growth, the membrane flux that can suppress the RO membrane separation unit reduces.
Embodiment 3, comparative example 6,7
Except the addition with Scale inhibitors is made as 5mg/L (embodiment 3), 3mg/L (comparative example 6) or 1mg/L (comparative example 7), under the condition identical, handle with embodiment 1, the membrane flux of investigating the RO membrane separation unit through the time change, the result is shown among Fig. 5.What should explain is in Fig. 5, the result who the Scale inhibitors addition is made as the embodiment 1 of 10mg/L to be shown also.
Can be known by Fig. 5, be made as 5 times of calcium ion concn more than the weight through the addition with Scale inhibitors, the membrane flux that can suppress the RO membrane separation unit reduces.At this moment, investigate the RO face of the RO membrane separation unit after membrane flux reduces, confirm to be attached with lime scale.
The electronic installation manufacturing works draining that contains nonionic class tensio-active agent (pH 7.2, TOC 30mg, calcium ion concn 1mg/L) as former water; In former water, add after the disodium edta 10mg/L as Scale inhibitors; Add NaOH; PH is transferred to 10.5, is to carry out the processing of RO membrane sepn under 90% the condition in the recovery with RO membrane separation unit (the low alluvial of the polyvinyl alcohol that day eastern electrician makes is with RO film " LF-10 " (salt rejection ratio is 99.5%)).
Investigate the membrane flux (25 ℃, 1.47MPa) of the RO membrane separation unit of this moment, the result is shown among Fig. 6.
In addition, the TOC concentration of RO permeate water is 100 μ g/L, can highly remove TOC.
Embodiment 5
Use low pressure aromatic polyamide class RO film " NTR-759 " that day eastern electrician makes as the RO film, in addition, under the condition identical, handle with embodiment 4, with the membrane flux of RO membrane separation unit through the time change and be shown among Fig. 6.
Comparative example 8
Except the pH that RO is supplied water is transferred to 7, under the condition identical, handle with embodiment 4, with the membrane flux of RO membrane separation unit through the time change and be shown among Fig. 6.
Can obviously find out by Fig. 6, in embodiment 4,, also not observe flux and reduce even begin after about 1 year (8000hr) from water supply, relative therewith, think that flux is reduced to about 75% of initial flux in embodiment 5.In addition, in comparative example 8, flux is reduced to about 67% of initial flux.Can know by this result; Through the present invention, when handling the higher RO of nonionic surfactant concentration and supply water, the low alluvial of particularly using specific polyvinyl alcohol is during with the RO film; Even what surpassed 1000 hours and so on is long-time, all effective aspect flux stabilizedization.
Embodiment 6
Use acrylic polymers as Scale inhibitors.
The addition of acrylic polymers is made as 1mg/L, 3mg/L, 5mg/L, 10mg/L.In addition, with embodiment 1 the same terms under handle, the membrane flux of investigating the RO membrane separation unit through the time change, the result is shown among Fig. 7.
Can confirm by Fig. 7,, can suppress flux and reduce through being added to 5 times of acrylic polymerss more than the amount of water supply Ca concentration.Film surface after analysis throughput reduces observes separating out of lime scale.
Embodiment 7
Use NTA (NTA) sodium as Scale inhibitors.
The addition of NTA disodium class Scale inhibitors is made as 1.23mg/L, 3.7mg/L, 6.2mg/L, 12.3mg/L (if being respectively 1mg/L, 3mg/L, 5mg/L, 10mg/L by the form conversion of acid); In addition; With embodiment 1 the same terms under handle; The membrane flux of investigating the RO membrane separation unit through the time change, the result is shown among Fig. 8.
Can confirm by Fig. 8,, can suppress the reduction of flux through being added to 5 times of Scale inhibitorss more than the amount of water supply Ca concentration.Film surface after analysis throughput reduces observes separating out of lime scale.
The described drainage processing method of other modes of the present invention is to possess activated carbon treatment operation and the drainage processing method that contains organism and oxygenant that the membrane sepn operation of carrying out the reverse osmosis membrane separating treatment through this draining of activated carbon treatment operation is formed that contains the draining of organism and oxygenant with activated carbon treatment; In stage before the above-mentioned activated carbon treatment operation, have and in draining, add alkali the pH that pH is transferred to 9.5 or more is adjusted operation; In the stage before the above-mentioned membrane sepn operation, have and in draining, add the Scale inhibitors interpolation operation that is equivalent to 5 times of Scale inhibitorss more than the weight of calcium ion in this draining.
The described drain treatment apparatus of other modes of the present invention is to possess activated carbon treatment device and the drain treatment apparatus that contains organism and oxygenant that the membrane separation unit that carries out the reverse osmosis membrane separating treatment through this draining of activated carbon treatment device is formed that contains the draining of organism and oxygenant with activated carbon treatment; It has be located at above-mentioned activated carbon treatment device upstream, in draining, add alkali and pH be transferred to the pH setting device 9.5 or more, and be located at the above-mentioned membrane separation unit upper reaches, interpolation is equivalent to the Scale inhibitors adding set of 5 times of Scale inhibitorss more than the weight of calcium ion in this draining in draining.
Sometimes will supply below to be called " AC water supply " in the processed water of activated carbon treatment.
In related method of this mode and device, the pH that AC is supplied water is transferred to 9.5 or more and the reasons are as follows of Scale inhibitors of interpolation specified amount in RO supplies water.
Mikrobe can not survive in alkaline range.Therefore, be transferred to more than 9.5 through the pH that AC is supplied water, can not survival environment even can form nutritious source mikrobe, can be suppressed at the microbial reproduction in the activated carbon tower.Because activated carbon treatment can not make the pH of water reduce, therefore the pH from the effusive activated carbon treatment water of this activated carbon tower also is that pH is the alkalescence more than 9.5.Through activated carbon treatment water supply RO device with alkalescence, even in the RO membrane separation unit, can suppress the breeding of mikrobe too, there is no need as in the past, to add expensive slimicide, just can prevent the biofouling in the RO membrane separation unit.
In order to handle more efficiently, the pH that AC supplies water preferably is transferred to more than 10.5, especially preferably is transferred to 10.5～12.
Under few situation, from the draining that contains TOC of discharges such as electronic installation manufacturing works, can sneak into the calcium ion that causes incrustation scale etc.If the pH that RO is supplied water is transferred to more than 9.5, even then the calcium ion of denier also can generate incrustation scales such as lime carbonate, this incrustation scale blocks the RO film.For the face that suppresses to cause because of incrustation scale blocks,, RO adds Scale inhibitors in supplying water.When 5 times of amounts of the not enough calcium ion concn of this Scale inhibitors addition, its additive effect is insufficient, therefore preferably its addition is made as 5 times of calcium ion concn more than the amount, more preferably is made as 5～50 times of amounts.
The treatment process and the treatment unit of the draining that contains organism and oxygenant in this way; With activated carbon tower and RO membrane separation unit handle reclaim discharge from electronic installation manufacturing works, other various fields contain the draining of high density or low-concentration organic and oxygenant the time; Can prevent on organism in the RO membrane separation unit is attached to face and the flux that causes reduces; Can prevent the biofouling in activated carbon tower and the RO membrane separation unit; Can carry out stable treated for a long time, and can reduce TOC concentration in the water efficiently, thereby obtain the treating water of high water quality.
In this mode; When activated carbon treatment is carried out in the draining that contains organism and oxygenant; When then carrying out the processing of RO membrane sepn; In the AC that is conducted to activated carbon treatment supplies water, add alkali, be transferred to pH more than 9.5, and in the RO that has carried out the processing of RO membrane sepn supplies water, add the Scale inhibitors of specified amount.As various processing sequences, can enumerate as follows the mode of (i)～(iv).
I) adding Scale inhibitors → pH adjustment → activated carbon treatment → RO membrane sepn handles
Ii) pH adjustment → interpolation Scale inhibitors → activated carbon treatment → RO membrane sepn is handled
Iii) pH adjustment → activated carbon treatment → interpolation Scale inhibitors → RO membrane sepn is handled
Iv) adding Scale inhibitors and pH adjustment → activated carbon treatment → RO membrane sepn handles
Fig. 9 is the schematic diagram of handling by the mode of above-mentioned (i).But, this mode is not talkative also can adopt (ii) above-mentioned or (iii) or mode (iv).Shown in Fig. 9 as the activated carbon tower of activated carbon treatment device, but the activated carbon treatment device has no qualification to the activated carbon tower, so long as can let draining contact with activated carbon, thereby the oxygenant of removing in the draining gets final product.
In Fig. 9, add among the Xiang Yuanshui (containing the draining of organism and oxygenant) after the Scale inhibitors, add alkali and be transferred to pH more than 9.5; Then; In activated carbon tower 11, supply water, activated carbon treatment water is imported in the RO membrane separation unit 13 after jars 12, carry out the RO membrane sepn and handle.
The example of the Scale inhibitors that adds among the Xiang Yuanshui such as above-mentioned.
The addition of Scale inhibitors preferably is made as 5～50 times of weight of calcium ion concn in the former water.Its reason as stated.
Be added with the former water of Scale inhibitors, then add alkaline agent, pH is adjusted to more than 9.5, preferred more than 10, more preferably 10.5～12, for example be adjusted to pH 10.5～11, import in the activated carbon tower 11.Alkaline agent in this use can be enumerated sodium hydroxide, Pottasium Hydroxide etc., so long as the inorganics class alkaline agent that can the pH of former water be adjusted to more than 9.5 gets final product, does not have special qualification.
Active carbon specy as in activated carbon tower 11, using gets final product so long as can remove the material of oxygenants such as coal class, Exocarpium cocois (Cocos nucifera L) class, does not have special qualification.In addition, water supply method can be a up-flow, also can be to fall stream, and water supply SV does not have special qualification yet, preferably by 1～40hr
-1Supply water.
The activated carbon treatment water of oxygenant being removed with activated carbon tower 11 then is directed to the RO membrane separation unit 13 from pump P through jars 12.The preferred RO film of RO device 13 as stated.
The condensed water of RO membrane separation unit 13 is added acid as required, and pH is after neutrality in adjustment, is discharged to outside the system.The permeate water of RO membrane separation unit 13 is then added acid, and pH is adjusted to 4～8, as required, has further carried out after the activated carbon treatment etc., utilizes or discharges.At this, the acid as using does not have special qualification, can enumerate mineral acids such as hydrochloric acid, sulfuric acid.
As shown in Figure 9; In former water, add the Scale inhibitors of specified amount, adjust to pH 9.5 or more simultaneously after, through carrying out the processing of activated carbon treatment and RO membrane sepn; Can not cause that the flux in the RO membrane separation unit reduces; Can also prevent the biofouling of activated carbon tower and RO membrane separation unit, can carry out stable treated for a long time, thereby obtain the high water conditioning water that TOC is highly removed.
Fig. 9 is the figure of one of expression embodiment of the present invention example as stated, as long as the present invention is no more than its main idea, not limited by any diagram.In Fig. 9, in the former water of supplying with the activated carbon tower, add Scale inhibitors, add alkali afterwards and carry out the pH adjustment, carry out adding Scale inhibitors again after the pH adjustment but also can in former water, add alkali, in addition, also can carry out the pH adjustment simultaneously and add Scale inhibitors.
And can in former water, add alkali and carry out being conducted to the activated carbon tower after the pH adjustment, from the effusive water of activated carbon tower, adding Scale inhibitors.When using inner complex class Scale inhibitors, can add, but when using low-molecular weight polymer,, therefore preferably in from the effusive water of activated carbon tower (RO water supply), add probably by activated carbon adsorption in above-mentioned optional position as Scale inhibitors.
Processing with the RO membrane separation unit is not limited to the one-level processing, also can be the multiple-stage treatment more than 2 grades.
The situation of sneaking into the calcium ion that causes incrustation scale etc. is seldom arranged the draining that contains TOC of discharging from electronic installation manufacturing works etc. basically; When sneaking into calcium ion concn that calcium ion etc., RO supply water in the former water when high; Can carry out cationic exchange with cation exchange tower and handle, remove calcium.In this case, in order to reduce the addition of Scale inhibitors, preferably before adding Scale inhibitors, carry out cationic exchange and handle.Can also be provided for the tempering tank of pH adjustment or interpolation Scale inhibitors.
Embodiment 8
The electronic installation manufacturing works draining (pH is 7.2, TOC be that 10mg, calcium ion concn are 1mg/L, oxygenant (hydrogen peroxide) content 30mg/L) that will contain nonionic class tensio-active agent is as former water; In former water, add after the disodium edta 10mg/L as Scale inhibitors; Adding NaOH and be transferred to 10.5 to pH, is 10hr by SV in activated carbon tower (filling the activated carbon " KW10-32 " that Network ラ レ ケ ミ カ Le is made)
-1Supplying water, is under 90% the condition this activated carbon treatment water to be carried out the processing of RO membrane sepn in the recovery with RO membrane separation unit (day low pressure aromatic polyamide type RO film " NTR-759 " that eastern electrician makes).
Investigate viable count and RO membrane separation unit in the activated carbon treatment water of this moment membrane flux (25 ℃, 1.47MPa) through the time change, the result is shown among Figure 10,11.
The TOC concentration of RO permeate water is 50 μ g/L, can highly remove TOC.
Comparative example 9
In former water, do not add NaOH, the pH that AC is supplied water is transferred to 7.2, in addition, under the condition identical, handle with embodiment 8, with the membrane flux of the viable count in the activated carbon treatment water and RO membrane separation unit through the time variation be shown in respectively among Figure 10,11.
Can obviously see following situation by Figure 10,11.
From the activated carbon treatment water of embodiment 8, do not observe viable bacteria, relative therewith, from the activated carbon treatment water of comparative example 9, just observe 10 after 500 hours in the beginning of supplying water
4The viable bacteria of individual/mL is revealed.
In embodiment 8; From the beginning of supplying water,, relative therewith even after 500 hours, also do not observe the flux reduction; In comparative example 9; From 300 hours of the beginning of supplying water, do not see since activated carbon with the membrane flux that causes of organism adsorption reduce, extremely reduce but will observe flux after surpassing 300 hours.
Embodiment 9, comparative example 10～12
Except the pH that AC is supplied water is transferred to 9.5 (embodiment 9), 9.2 (comparative examples 10), 9 (comparative examples 11) or 8.5 (comparative examples 12); Under the condition identical, handle with embodiment 9; The membrane flux of investigating the RO membrane separation unit through the time change, the result is shown among Figure 12.
Can know by Figure 12; PH through AC is supplied water is transferred to more than 9.5; The pH that RO supplies water also becomes more than 9.5, the biofouling that the face that can suppress nonionic surfactant adheres to and causes because of microbial growth, and the membrane flux that can suppress the RO membrane separation unit reduces.
Except the addition with Scale inhibitors is made as 5mg/L (embodiment 10), 3mg/L (comparative example 13) or 1mg/L (comparative example 14); Under the condition identical, handle with embodiment 10; The membrane flux of investigating the RO membrane separation unit through the time change, the result is shown among Figure 13.In Figure 13, the result who the Scale inhibitors addition is made as the embodiment 1 of 10mg/L is shown also.
Can be known by Figure 13, be made as 5 times of calcium ion concn more than the weight through the addition with Scale inhibitors, the membrane flux that can suppress the RO membrane separation unit reduces.At this moment, investigate the RO face of the RO membrane separation unit after membrane flux reduces, confirm to be attached with lime scale.
Claims (8)
1. contain the organism drainage processing method, it comprises following operation:
Scale inhibitors adds operation, and promptly in containing the organism draining, interpolation is equivalent to this and contains the above Scale inhibitors of 5 times of weight of calcium ion in the organism draining;
PH adjusts operation, promptly before the interpolation of this Scale inhibitors, afterwards or simultaneously, contain in the organism draining at this and to add alkali, pH is adjusted to more than 9.5;
The membrane sepn operation is soon added operation through this Scale inhibitors and pH adjustment operation pH afterwards carries out the reverse osmosis membrane separating treatment containing in the organism draining importing reverse osmosis membrane tripping device more than 9.5.
2. the organism drainage processing method that contains as claimed in claim 1 is characterized by, and adds in the operation at this Scale inhibitors, contains to add in the organism draining at this to be equivalent to the Scale inhibitors that this contains 5～50 times of weight of calcium ion in the organism draining.
3. the organism drainage processing method that contains as claimed in claim 1; It is characterized by; The reverse osmosis membrane that is used for this reverse osmosis membrane separating treatment; Be that the salt rejection ratio when the 1500mg/L salt solution is carried out the reverse osmosis membrane separating treatment is that reverse osmosis membrane is used in the low alluvial of polyvinyl alcohol more than 95%, that have desalting performance under 1.47MPa, 25 ℃, pH are 7 condition.
4. the organism drainage processing method that contains as claimed in claim 1 is characterized by, and in this pH adjustment operation, pH is adjusted to 10.5～12, and the pH that imports the processed water in this reverse osmosis membrane tripping device is 10.5～12.
5. the organism drainage processing method that contains as claimed in claim 1 is characterized by, and before adding this Scale inhibitors, this is contained the organism draining carry out the cationic exchange processing.
6. the drainage processing method that contains organism and oxygenant, it comprises following operation:
Scale inhibitors adds operation, and promptly in containing the organism draining, interpolation is equivalent to this and contains the above Scale inhibitors of 5 times of weight of calcium ion in the organism draining;
PH adjusts operation, promptly before the interpolation of this Scale inhibitors, afterwards or simultaneously, contain in the organism draining at this and to add alkali, pH is adjusted to more than 9.5;
The membrane sepn operation is that the reverse osmosis membrane separating treatment is carried out in the organism draining that contains more than 9.5 to add pH after operation and the pH adjustment operation through this Scale inhibitors promptly,
Being characterized as of said drainage processing method, this drainage processing method also are included in the activated carbon treatment operation of carrying out before the above-mentioned membrane sepn operation, the draining that contains organism and oxygenant is handled with activated carbon.
7. drainage processing method as claimed in claim 6 is characterized by, and adds the order of operation, this pH adjustment operation, this activated carbon treatment operation and this membrane sepn operation by this Scale inhibitors and carries out the draining processing.
8. drainage processing method as claimed in claim 6 is characterized by, and adds the order of operation and this membrane sepn operation by this pH adjustment operation, this activated carbon treatment operation, this Scale inhibitors and carries out the draining processing.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003388183 | 2003-11-18 | ||
| JP2003-388183 | 2003-11-18 | ||
| JP2003388183 | 2003-11-18 | ||
| JP2004-026961 | 2004-02-03 | ||
| JP2004026961A JP4496795B2 (en) | 2003-11-18 | 2004-02-03 | Method and apparatus for treating wastewater containing organic matter |
| JP2004026961 | 2004-02-03 | ||
| JP2004232977A JP3906855B2 (en) | 2004-08-10 | 2004-08-10 | Method and apparatus for treating wastewater containing organic matter and oxidizing agent |
| JP2004232977 | 2004-08-10 | ||
| JP2004-232977 | 2004-08-10 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800406005A Division CN100528765C (en) | 2003-11-18 | 2004-10-22 | Method of treating waste water containing organic substance and treating apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101597097A CN101597097A (en) | 2009-12-09 |
| CN101597097B true CN101597097B (en) | 2012-10-17 |
Family
ID=37674928
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800406005A Active CN100528765C (en) | 2003-11-18 | 2004-10-22 | Method of treating waste water containing organic substance and treating apparatus |
| CN2009101488098A Active CN101597097B (en) | 2003-11-18 | 2004-10-22 | Method of treating waste water containing organic substance |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800406005A Active CN100528765C (en) | 2003-11-18 | 2004-10-22 | Method of treating waste water containing organic substance and treating apparatus |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN100528765C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10023487B2 (en) * | 2006-12-12 | 2018-07-17 | Veolia Water Solutions & Technologies Support | Method of recovering oil or gas and treating the resulting produced water |
| JP5608988B2 (en) * | 2009-02-27 | 2014-10-22 | 栗田工業株式会社 | Slime control agent for activated carbon, method of passing water to activated carbon device, method of treating water containing organic matter, and treatment device |
| CN102471101A (en) * | 2009-08-21 | 2012-05-23 | 东丽株式会社 | Fresh water production method |
| JP5884730B2 (en) * | 2011-02-24 | 2016-03-15 | 栗田工業株式会社 | Reverse osmosis membrane scale inhibitor and scale prevention method |
| PT2609990T (en) * | 2011-12-30 | 2022-08-25 | Kemira Oyj | Method for preventing microbial growth on filtration membrane |
-
2004
- 2004-10-22 CN CNB2004800406005A patent/CN100528765C/en active Active
- 2004-10-22 CN CN2009101488098A patent/CN101597097B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN1906132A (en) | 2007-01-31 |
| CN100528765C (en) | 2009-08-19 |
| CN101597097A (en) | 2009-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101464022B1 (en) | Method and apparatus for treating water containing organic matter | |
| CN101041522B (en) | Treating method and treating apparatus of waste water containing organic material | |
| KR101671168B1 (en) | Slime control agent for activated carbon, method of passing water through activated-carbon device, and method and apparatus for treating organic-containing water | |
| EP2554050B9 (en) | Combined chlorine agent, and manufacturing method and method of use for same | |
| US8206592B2 (en) | Treating acidic water | |
| SA516380243B1 (en) | Filtration Treatment System and Filtration Treatment Method | |
| JP5050605B2 (en) | Organic substance processing method and organic substance processing apparatus | |
| CN101597097B (en) | Method of treating waste water containing organic substance | |
| KR20010089561A (en) | Method and Compositions for Minimizing Biological and Colloidal Fouling | |
| Czuba et al. | Towards the circular economy—Sustainable fouling mitigation strategies in ultrafiltration of secondary effluent | |
| JP2005169372A (en) | Method and apparatus for treating organic material-containing waste water | |
| JP2017006899A (en) | Water treatment system, water treatment method, method for producing sterile water, method for producing antibacterial water, and method for managing water treatment method | |
| TW202204032A (en) | Water recovery system and waterrecovery method | |
| KR100969220B1 (en) | A advanced waste-water treatment system comprising a internal filtering screen device | |
| US20080032905A1 (en) | Disinfecting/mineral treating composition and methods | |
| JP3906855B2 (en) | Method and apparatus for treating wastewater containing organic matter and oxidizing agent | |
| JP7492873B2 (en) | Water recovery method and water recovery device | |
| JP7200552B2 (en) | Anti-fouling agent for separation membrane and anti-fouling method | |
| CN111184023A (en) | Oxidizing slime stripping and bactericide, and preparation method and application thereof | |
| Al Ansari | SHMP as Antiscalant for Treating Brackish Water using Reverse Osmosis | |
| US5302292A (en) | Method for treating ground water contamination | |
| Hafsi et al. | Effects of the chemical injection points in pre-treatment on reverse osmosis (RO) plant performance | |
| WO2005049501A1 (en) | Method of treating waste water containing organic substance and treating apparatus | |
| US11945744B2 (en) | Method and apparatus for reusing wastewater | |
| JP2014180586A (en) | Method for preventing generation of scale in reverse osmosis membrane treatment and scale inhibitor for reverse osmosis membrane treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |