CN109863122A

CN109863122A - Use the method for treating water and water treatment facilities of reverse osmosis membrane

Info

Publication number: CN109863122A
Application number: CN201780065515.1A
Authority: CN
Inventors: 铃木雄大; 都司雅人
Original assignee: PRGANO CORP
Current assignee: PRGANO CORP; Organo Corp
Priority date: 2016-10-25
Filing date: 2017-07-31
Publication date: 2019-06-07
Anticipated expiration: 2037-07-31
Also published as: TWI727106B; CN109863122B; WO2018078988A1; TW201827347A; KR20190057369A; KR102291224B1

Abstract

The present invention provides a kind of method for treating water of water using reverse osmosis membrane processing containing ammonia, wherein the antibacterial agent containing sulfamic acid compound and chlorine system or bromine system oxidant is inhibited to penetrate through reverse osmosis membrane.This method for treating water using reverse osmosis membrane is the water containing ammonia for reverse osmosis membrane processing to be employed, antibacterial agent wherein containing sulfamic acid compound and bromine system or chlorine system oxidant is present in pending water, and reverse osmosis membrane is neutral film or cationically charged film.

Description

Use the method for treating water and water treatment facilities of reverse osmosis membrane

Technical field

The present invention relates to the method for treating water and water treatment facilities that use reverse osmosis membrane (RO film).

Background technique

In the method for treating water using reverse osmosis membrane (RO film), usually using various antibacterial agents (sticky mud inhibitor) conduct The countermeasure of biological pollution.Chlorine system oxidant (such as hypochlorous acid etc.) is representative antibacterial agent, and is usually added to reverse osmosis Stage before permeable membrane is for sterilizing to system.Since chlorine system oxidant is likely to deteriorate reverse osmosis membrane, chlorine It is that oxidant is usually just reduced decomposition before reverse osmosis membrane, or is intermittently introduced reverse osmosis membrane.

In addition, using the compound chlorine agent being made of chlorine system oxidant and sulfamic acid compound as antibacterial agent, (foundry loam inhibits Agent) it is introduced into the method (referring to patent document 1) in the water by reverse osmosis membrane processing, and for by the anti-of bromine system oxidant Answer product or mixture, the reaction product of bromine based compound and chlorine system oxidant and sulfamic acid compound mixture or The method (referring to patent document 2) that reaction product is added in pending water is known.

Antibacterial agent containing chlorine system oxidant or bromine system oxidant and sulfamic acid compound is highly effective, because they Not only there is excellent sterilizing function, but also be unlikely to cause the oxidation deterioration of polyamide-based reverse osmosis membrane, reverse osmosis membrane pair It has little effect with high rejection, and to the quality of the processing water of subsequent workshop section (infiltration water).

Existing technical literature

Patent document

Patent document 1:JP2006-263510A

Patent document 2:JP2015-062889A

Summary of the invention

Technical problem

However it has been found that containing chlorine system oxidant or bromine system oxidant in the case where pending water contains ammonia (ammonium ion) Tend to penetrate through reverse osmosis membrane with a part of the antibacterial agent of sulfamic acid compound.Because antibacterial agent penetrates through reverse osmosis Film will lead to the deterioration of processing water water quality and the equipment of subsequent workshop section deteriorates, it is desirable that inhibiting this infiltration.

The object of the present invention is to provide a kind of method and apparatus, are contained with being used in using reverse osmosis membrane processing when being used for water process When having the pending water of ammonia, inhibit to wear containing the infiltration of the antibacterial agent of chlorine system oxidant or bromine system oxidant and sulfamic acid compound Cross reverse osmosis membrane.

Solution to problem

The present invention provides a kind of method for treating water using reverse osmosis membrane, uses reverse osmosis membrane processing containing the to be processed of ammonia Water, wherein the antibacterial agent containing bromine system oxidant or chlorine system oxidant and sulfamic acid compound is introduced into pending water, instead Permeable membrane is neutral film or cationically charged film.

In addition, using reverse osmosis membrane processing containing ammonia the present invention also provides a kind of method for treating water using reverse osmosis membrane Pending water, wherein the antibacterial agent containing bromine and sulfamic acid compound is introduced into pending water, reverse osmosis membrane is neutral Film or cationically charged film.

In the above-mentioned method for treating water using reverse osmosis membrane, the ammonium concentration in pending water is preferably at least 1mg/ L。

In the above-mentioned method for treating water using reverse osmosis membrane, the amount of the ammonia preferably in pending water of the reduction containing ammonia, so In the water of the reduced ammonia reduction of the amount that antibacterial agent is introduced into ammonia afterwards.

In the above-mentioned method for treating water using reverse osmosis membrane, the ammonia density of the water of ammonia reduction is preferably no greater than 5mg/L.

In the above-mentioned method for treating water using reverse osmosis membrane, preferably handled by ammonia stripping to reduce containing the to be processed of ammonia Ammonia in water.

In the above-mentioned method for treating water using reverse osmosis membrane, preferably reduced by using the ammonolysis craft processing of oxidant Ammonia in pending water containing ammonia.

In addition, using reverse osmosis membrane processing containing ammonia the present invention also provides a kind of water treatment facilities using reverse osmosis membrane Pending water, wherein the antibacterial agent containing bromine system oxidant or chlorine system oxidant and sulfamic acid compound is introduced medicament In pending water, reverse osmosis membrane is neutral film or cationically charged film.

In addition, the present invention also provides a kind of water treatment facilities using reverse osmosis membrane, with reverse osmosis membrane processing containing ammonia Pending water, wherein the antibacterial agent containing bromine and sulfamic acid compound is introduced into pending water, reverse osmosis membrane is neutral film Or cationically charged film.

In the above-mentioned water treatment facilities using reverse osmosis membrane, the ammonium concentration in pending water is preferably at least 1mg/ L。

The above-mentioned water treatment facilities using reverse osmosis membrane preferably includes ammonia and reduces unit, reduces in the pending water containing ammonia Ammonia amount, wherein antibacterial agent is introduced in the amount of ammonia and has been reduced by ammonia in the water of ammonia reduction of unit reduction.

In the above-mentioned water treatment facilities using reverse osmosis membrane, the ammonia density of the water of ammonia reduction is preferably no greater than 5mg/L.

The ammonia stripping processing that the above-mentioned water treatment facilities for using reverse osmosis membrane preferably includes to reduce unit as above-mentioned ammonia is set It is standby.

The above-mentioned water treatment facilities for using reverse osmosis membrane preferably includes the oxidant that uses that unit is reduced as above-mentioned ammonia Ammonolysis craft processing unit.

Advantageous effect of the invention

In the present invention, in method for treating water and water treatment facilities, pending water using reverse osmosis membrane processing containing ammonia, The antibacterial agent containing chlorine system oxidant or bromine system oxidant and sulfamic acid compound can be inhibited to penetrate through reverse osmosis membrane.

Detailed description of the invention

Fig. 1 is the water process for showing the method for treating water using reverse osmosis membrane according to an embodiment of the invention The structural schematic diagram of one example of system.

Fig. 2 is the schematic structure for evaluating the flat membrane experimental rig of the rejection of reverse osmosis membrane in embodiment and comparative example Figure.

Fig. 3 is the figure shown in embodiment 1 and comparative example 1 relative to the antibacterial agent permeability (%) of film surface zeta potential (- mV).

Fig. 4 is the figure shown in embodiment 2 and comparative example 2 relative to the antibacterial agent permeability (%) of ammonium concentration (mg/L).

Fig. 5 is the figure shown in embodiment 3 and comparative example 3 relative to the antibacterial agent permeability (%) of ammonium concentration (mg/L).

Fig. 6 is to show an example of the water treatment facilities using reverse osmosis membrane of an embodiment according to the present invention to show Meaning property structure chart.

Fig. 7 is the water process system for showing the water treatment facilities using reverse osmosis membrane of an embodiment according to the present invention The schematic diagram of one example of system.

Fig. 8 is the figure shown in embodiment 4-1 relative to the antibacterial agent permeability (%) of ammonium concentration (mg/L).

Fig. 9 is the figure shown in embodiment 4-2 relative to the antibacterial agent permeability (%) of ammonium concentration (mg/L).

Figure 10 is the schematic diagram for the guide device for evaluating the permeability of the antibacterial agent in embodiment 5 to 8.

Specific embodiment

Embodiment of the present invention is described below.These embodiments are only to realize example of the invention, and the present invention It is not limited by these embodiments.

Method for treating water according to embodiments of the present invention using reverse osmosis membrane is a kind of use neutral film or cationically charged Method of the film as reverse osmosis membrane, wherein by the antibacterial agent containing bromine system oxidant or chlorine system oxidant and sulfamic acid compound It is introduced into the pending water containing ammonia." antibacterial agent containing bromine system oxidant and sulfamic acid compound " can be containing stabilization Hypobromous acid composition antibacterial agent, which contains the mixing of " bromine system oxidant " and " sulfamic acid compound " Object, or can be the antibacterial agent containing stable hypobromous acid composition, which contains " bromine system oxidant and ammonia The reaction product of base sulfoacid compound "." antibacterial agent containing chlorine system oxidant and sulfamic acid compound " can be containing steady The antibacterial agent of fixed hypochlorous acid composition, the hypochlorous acid composition contain " chlorine system oxidant " and " sulfamic acid class compound " Mixture, or can be the antibacterial agent containing stable hypochlorous acid composition, which contains " chlorine system oxidant With the reaction product of sulfamic acid compound ".

In other words, the method for treating water according to embodiments of the present invention using reverse osmosis membrane is a kind of using reverse osmosis membrane The method for handling the pending water containing ammonia, wherein by the mixture of " bromine system oxidant " and " sulfamic acid compound ", or " chlorine system Oxidant " and the mixture of " sulfamic acid compound " are introduced into pending water, and neutral film or cationically charged film are used as Reverse osmosis membrane.As a result, it is believed that stable hypobromous acid composition or the combination of stable hypochlorous acid can be generated in processed water Object.

In addition, the method for treating water using reverse osmosis membrane according to another embodiment of the invention is a kind of using reverse osmosis The method of pending water of the film process containing ammonia, wherein can will be " reaction product of bromine system oxidant and sulfamic acid compound " Stable hypobromous acid composition or " reaction product of chlorine system oxidant and sulfamic acid compound " stable hypochlorous acid Composition is introduced into pending water, and neutral film or cationically charged film are used as reverse osmosis membrane.

Specifically, the method for treating water using reverse osmosis membrane according to an embodiment of the invention is a kind of using reverse osmosis The method that permeable membrane handles the pending water containing ammonia, wherein " bromine ", " bromine chloride ", " hypobromous acid " or " sodium bromide and hypochlorous anti- Answer product " and " sulfamic acid compound " and mixture be introduced into pending water, and neutral film or cationically charged film are used Make reverse osmosis membrane.Alternatively, method for treating water can be such method, wherein can be by " hypochlorous acid " and " sulfamic acid chemical combination The mixture of object " is introduced into pending water, and neutral film or cationically charged film are used as reverse osmosis membrane.

In addition, the method for treating water using reverse osmosis membrane according to another embodiment of the invention is a kind of using reverse osmosis The method of pending water of the film process containing ammonia, wherein for example, stable hypobromous acid composition is (that is, " bromine and sulfamic acid chemical combination The reaction product of object ", " reaction product of bromine chloride and sulfamic acid compound ", " hypobromous acid and sulfamic acid compound it is anti- Answer product " or " reaction product of sulfamic acid compound and sodium bromide and hypochlorous reaction product ") it is introduced into pending water In, and use neutral film or cationically charged film as reverse osmosis membrane.Alternatively, method for treating water can be such method, In can will be that the stable hypochlorous acid composition of " reaction product of hypochlorous acid and sulfamic acid compound " introduces pending water In, and neutral film or cationically charged film are used as reverse osmosis membrane.

As further investigation as a result, it was found by the inventors of the present invention that when pending water contains ammonia, used reverse osmosis The charge of permeable membrane changes permeability of the antibacterial agent by film.In general, many reverse osmosis membranes are negatively charged, but find the electricity for working as film When lotus is close to neutral charge, the permeability reduction of antibacterial agent.When containing bromine system oxidant or chlorine system oxidant and sulfamic acid The antibacterial agent of object is closed when being introduced into the pending water containing ammonia, by using neutral film or cationically charged film as reverse osmosis membrane, Antibacterial agent can be inhibited to penetrate through reverse osmosis membrane.

In the method for treating water according to embodiments of the present invention using reverse osmosis membrane, stable hypobromous acid composition or Stable hypochlorous acid composition shows similar or excellent foundry loam inhibitory effect, and and chlorine to chlorine system oxidant such as hypochlorous acid It is that oxidant is compared, it is smaller on the deterioration of reverse osmosis membrane influence, therefore the oxidative degradation of reverse osmosis membrane can be inhibited, inhibit simultaneously The fouling of reverse osmosis membrane.As a result, steady used in the method for treating water according to embodiments of the present invention using reverse osmosis membrane Fixed hypobromous acid composition or stable hypochlorous acid composition are advantageously used for the processing using reverse osmosis membrane containing the to be processed of ammonia Sticky mud inhibitor in the method for treating water of water.

In the method for treating water according to embodiments of the present invention using reverse osmosis membrane, " containing bromine system oxidant and In the case where the antibacterial agent of sulfamic acid compound ", because chlorine system oxidant is not present, the deterioration of reverse osmosis membrane is influenced special It is small.When including chlorine system oxidant, it may be necessary to consider the generation of chloric acid.

In the method for treating water according to embodiments of the present invention using reverse osmosis membrane, when " bromine system oxidant " is bromine When, since there is no chlorine system oxidant, therefore influencing on the deterioration of reverse osmosis membrane may be very low.

In the method for treating water according to embodiments of the present invention using reverse osmosis membrane, " bromine system oxidant " or " chlorine system Oxidant " and " sulfamic acid compound " can be injected into the pending water containing ammonia such as using chemical feed pump In.Respectively " bromine system oxidant " or " chlorine system oxidant " and " sulfamic acid compound " can be added in pending water, Or it can be mixed and be then added in pending water with stoste.

Furthermore, it is possible to will " the reaction production of bromine system oxidant and sulfamic acid compound such as using chemical feed pump Object " or " reaction product of chlorine system oxidant and sulfamic acid compound " are injected into the pending water containing ammonia.

In the method for treating water according to embodiments of the present invention using reverse osmosis membrane, " sulfamic acid compound " works as Measuring relative to the ratio of " bromine system oxidant " or the equivalent of " chlorine system oxidant " is preferably 1 or more, and more preferably at least 1 to little In 2.If the equivalent of " sulfamic acid compound " is small relative to the ratio of " bromine system oxidant " or the equivalent of " chlorine system oxidant " In 1, it is likely that the deterioration of film occurs, and if ratio is more than 2, production cost will increase sometimes.

The total cl concn contacted with reverse osmosis membrane is calculated, preferably 0.01 to 100mg/L with equivalence unit cl concn.Such as The fruit concentration is less than 0.01mg/L, then is difficult to obtain satisfactory foundry loam inhibitory effect sometimes, and if concentration is greater than 100mg/L is then likely to occur deterioration or pipeline corrosion of reverse osmosis membrane etc..

In the method for treating water according to embodiments of the present invention using reverse osmosis membrane, the ammonium ion in pending water is dense Degree is preferably at least 1mg/L, more preferably 5mg/L or more.When the ammonium concentration in pending water is at least 1mg/L, by The variation of antibacterial agent permeability caused by membrane charge tends to increase, and when the ammonium concentration in pending water is 5mg/L More than, then the difference of the permeability of the antibacterial agent as caused by membrane charge may be especially big.

((total chlorine is dense for ammonia density (mg/L)/antimicrobial agent concentration relative to the ratio of total cl concn for ammonia density in pending water Degree: mg/L)) it is for example in the range of 0.01 to 50, preferably in the range of 0.01 to 1.0.If ammonia is dense in pending water The ratio relative to total cl concn is spent less than 0.01 or is greater than 1.0, then for anionically charged film, neutral film and cationically charged The difference of the antibacterial agent permeability of film there may come a time when to reduce.

The example of bromine system oxidant includes bromine (bromine), bromine chloride, bromic acid, bromate and hypobromous acid etc..Hypobromous acid can be with It is prepared by reacting bromide (such as sodium bromide) with chlorine system oxidant (such as hypochlorous acid).

Wherein, with the preparation of the preparation of " hypochlorous acid, bromine compounds and sulfamic acid " and " bromine chloride and sulfamic acid " Etc. comparing, using the preparation of bromine, such as use " bromine and sulfamic acid compound (mixture of bromine and sulfamic acid compound) " or The preparation of " reaction product of bromine and sulfamic acid compound ", it is intended to show the less generation of by-product bromic acid, and not It may cause very much the deterioration of reverse osmosis membrane, and be therefore particularly preferably used as the sticky mud inhibitor of reverse osmosis membrane.

In other words, the method for treating water according to embodiments of the present invention using reverse osmosis membrane is preferably included bromine and amino Sulfoacid compound is introduced into and (is introduced into the mixture of bromine and sulfamic acid compound) into the pending water containing ammonia.In addition, also It is preferred that the reaction product of bromine and sulfamic acid compound is introduced into pending water.

The example of bromine compounds includes sodium bromide, potassium bromide, lithium bromide, ammonium bromide and hydrobromic acid.Wherein, with regard to production cost Deng for, sodium bromide is preferred.

The example of chlorine system oxidant include chlorine, chlorine dioxide, hypochlorous acid or its salt, chlorous acid or its salt, chloric acid or its Salt, perchloric acid or its salt and chlorinated isocyanuric acid or its salt.Wherein, the example of salt include hypochlorous alkali metal salt (as follows Sodium chlorate and postassium hypochlorite), hypochlorous alkali salt (such as calcium hypochlorite and barium hypochlorite), chlorous alkali metal salt (such as sodium chlorite and potassium chlorite), chlorous alkali salt (such as barium chlorite), other chlorous metal salts (such as Chlorous acid nickel), the alkali metal salt (such as ammonium chlorate, sodium chlorate, potassium chlorate) of chloric acid, chloric acid alkali salt (such as calcium chlorate and Barium chlorate).It can be used alone any one of these chlorine system oxidants, or two or more oxidants can be used Combination.From be easily handled etc. consideration, it is preferable to use sodium hypochlorite is as chlorine system oxidant.

Sulfamic acid compound is the compound that general formula as follows (1) indicates.

R₂NSO₃H (1)

(in the formula, each R independently indicates hydrogen atom or the alkyl with 1 to 8 carbon atom.)

In addition to two R groups be all hydrogen atom sulfamic acid (sulfamic acid, amidosulfuric acid) it Outside, the example of sulfamic acid compound include two of them R group first is that hydrogen atom and the other is have 1 to 8 carbon original The sulfamic acid compound of sub- alkyl, such as N- methylsulfamic acid, N- ethylamino sulfonic acid, N- propylcarbamic sulfonic acid, N- are different Propylcarbamic sulfonic acid and N- butylamino sulfonic acid；Two of them R group is the amino sulphur of the alkyl with 1 to 8 carbon atom Acid compound, such as N, N- dimethylamino sulfonic acid, N, N- diethylamino sulfonic acid, N, N- dipropylamino sulfonic acid, N, N- bis- Butylamino sulfonic acid, N- methyl-N-ethylamino sulfonic acid and N- methyl-N-propylamino sulfonic acid acid；One of two of them R group Be hydrogen atom and the other is the sulfamic acid compound of the aryl with 6-10 carbon atom, such as N- benzenesulfamic； And the salt of above-mentioned acid.The example of sulfamate includes alkali metal salt such as sodium salt and sylvite, alkali salt such as calcium salt, strontium salt And barium salt, other metal salts such as manganese salt, mantoquita, zinc salt, molysite, cobalt salt and nickel salt and ammonium salt and guanidine salt.These sulfamic acids One of compound or salt can be used alone, or the combination of two or more compounds or salt can be used.With regard to environment , it is preferable to use sulfamic acid is as sulfamic acid compound for influence etc..

In the method for treating water according to embodiments of the present invention using reverse osmosis membrane, alkali is preferably also introduced.The example of alkali Attached bag includes alkali hydroxide, such as sodium hydroxide and potassium hydroxide.For obtaining good product stability etc. at low temperature, The combination of sodium hydroxide and potassium hydroxide can be used.In addition, alkali may not be with solid but make in form of an aqueous solutions With.

Method for treating water according to embodiments of the present invention using reverse osmosis membrane can be advantageously applied for polyamide-based Polymer film is most widely used at present reverse osmosis membrane.Polyamide-based polymer film has relatively low antioxidant, And if free chlorine etc. is continuously contacted with the holding of polyamide-based polymer film, the significant deterioration of film properties may occur.So And in the method for treating water according to embodiments of the present invention using reverse osmosis membrane, even for polyamide-based polymer film, The significant deterioration of such film properties there's almost no.

Reverse osmosis membrane includes neutral film, anionically charged film and cationically charged film.In the present specification, neutral film defines To use zeta potential measurement method described in following example to be at least -10mV in the zeta potential that pH7.0 is measured but being less than 5mV Film；Cationically charged film is defined as the film that zeta potential is 5mV or more, and anionically charged film is defined as zeta potential less than -10mV Film.The zeta potential of neutral film is preferably at least -5mV, more preferably at least -3.9mV, even more preferably -1.3mV or more.Although right The upper limit of the zeta potential of cationically charged film is not particularly limited, but zeta potential is for example no more than 20mV.

In the method for treating water according to embodiments of the present invention using reverse osmosis membrane, by using neutral film or sun from Subband electrolemma is as reverse osmosis membrane, compared with the case where using anionically charged film, can preferably inhibit to aoxidize containing chlorine system The antibacterial agent of agent or bromine system oxidant and sulfamic acid compound penetrates through reverse osmosis membrane.

The example of commercially available neutral film includes BW30XFR (being manufactured by Dow Chemical company), LFC3 (You Dong electrician Company's manufacture), TML20 (being manufactured by Toray) and OFR625 (being manufactured by Ao Lujia Nao company).

The example of commercially available cationically charged film includes ES10C (manufacture of You Dong electrician company) etc..

The example of commercially available anionically charged film includes ES15, ES20, CPA3 and CPA5 (by day east electrician corporation Make) and RE-8040BLN (being manufactured by Woongjin Chemical Co., Ltd).

In the method for treating water according to embodiments of the present invention using reverse osmosis membrane, it is supplied to comprising reverse osmosis membrane The pH of the pending water of reverse osmosis membrane processing equipment is preferably at least 5.5, more preferably at least 6.0, even more preferably 6.5 with On.If the pH of pending water, less than 5.5, the amount for permeating water reduces sometimes.In addition, with regard to the pH of pending water the upper limit and Speech, is not particularly limited, and condition is the generally applicable upper limit pH (for example, pH10) that pH is no more than reverse osmosis membrane, but if In view of the precipitation of scales of the hard component of such as calcium, then the device preferably is operated when such as pH value is 9.0 or less.Work as use When the method for treating water according to embodiments of the present invention using reverse osmosis membrane, pass through the pending water condition in 5.5 or more pH Under operated, the deterioration of the deterioration of reverse osmosis membrane and the water quality of processing water (infiltration water) can be inhibited, and may insure to enable The satisfied amount of seepage of people, while realizing satisfactory foundry loam inhibitory effect.

When the pH of pending water is 5.5 or more, in the case where forming scale in reverse osmosis membrane processing equipment, in order to press down Scale processed can use dispersing agent and above-mentioned antibacterial agent combination.The example of dispersing agent includes polyacrylic acid, poly and phosphine Acid.Be added to the amount of the dispersing agent in pending water, for example, for the concentration in RO condensed water, can 0.1 to In the range of 1000mg/L.

In addition, a kind of method for inhibiting scale to occur in the case where not using dispersing agent includes, for example, adjusting reverse osmosis The operating condition of film process equipment, such as the rate of recovery, so that the silica concentration in RO condensed water is not higher than solubility, and Langelier index (it is the index of calcium fouling) is not more than 0.

The example application of reverse osmosis membrane processing equipment includes pure water production, sea water desalination and Sewage treatment.

It is thought that the method for treating water according to embodiments of the present invention using reverse osmosis membrane is useless especially suitable for being applied to Water recycling, for example, the Sewage treatment in electronics industry.Electronics industry waste water usually contains the organic substance of low molecular weight, waste water A kind of possible process of recycling is flow type shown in FIG. 1, is including biological treating equipment 10 and film process equipment 14 Biological treatment system 16 after the stage, the reverse osmosis membrane treatment system 26 comprising reverse osmosis membrane processing equipment 22, as with In the water treatment facilities for implementing the method for treating water according to embodiments of the present invention using reverse osmosis membrane.

Water treatment system 1 shown in Fig. 1 includes as the biological treating equipment 10 of biological processing unit, biological treatment of water Slot 12, the film process equipment 14 as film process unit, film process sink 18 and as the water treatment facilities for using reverse osmosis membrane Reverse osmosis membrane treatment system 26.Reverse osmosis membrane treatment system 26 includes with neutral film or cationically charged film as reverse osmosis The reverse osmosis membrane processing equipment 22 of film process unit.Reverse osmosis membrane treatment system 26 can also be comprising for storing pending water Handle sink 20, and the second reverse osmosis membrane processing equipment 24 as the second reverse osmosis membrane processing unit.

In water treatment system 1, the raw water of such as electronics industry waste water is supplied in biological treating equipment 10, and Biological treatment (biological treatment step) is carried out in biological treating equipment 10.Biological treatment of water by biological treatment can be according to need It is stored in biological treatment sink 12, is then fed into film process equipment 14, it is (clear to carry out film process using clarification film herein (film process step) clearly).Film process water through film process, which can according to need, to be stored in film process sink 18, then conduct Pending water is supplied and is stored in the processing sink 20 of reverse osmosis membrane treatment system 26.By the pending water from processing sink 20 Supply is carried out instead in reverse osmosis membrane processing equipment 22 using neutral film or cationically charged film to reverse osmosis membrane processing equipment 22 It permeates film process (reverse osmosis membrane processing step).The infiltration water obtained in reverse osmosis membrane processing is discharged from system.Condensed water It can be discharged, or if desired, can be fed into the second reverse osmosis membrane processing equipment 24, then instead second from system Second of reverse osmosis membrane processing (the second reverse osmosis membrane processing step) is carried out in permeable membrane processing equipment 24.In the second reverse osmosis membrane The condensed water obtained in processing is discharged from system.Infiltration water can be discharged from system, or if desired, can be fed into In processing sink 20 and recycle.

Antibacterial agent containing bromine system oxidant or chlorine system oxidant and sulfamic acid compound is introduced into pending water, but Antibacterial agent can be added at least one of biological treatment sink 12, film process sink 18 and processing sink 20.Antibacterial agent It can also be added at the pipeline, connection biological treatment sink 12 and film of connection biological treating equipment 10 and biological treatment sink 12 Manage the pipeline of equipment 14, the pipeline of junctional membrane processing equipment 14 and film process sink 18, connection film process sink 18 and processing water In the pipeline of slot 20 and at least one in connection processing sink 20 and the pipeline of reverse osmosis membrane processing equipment 22.At This etc., best method include being added to processing sink 20, being added to connection film process sink 18 and processing sink 20 Pipeline, or be added to connection processing sink 20 and reverse osmosis membrane processing equipment 22 pipeline.In confirmation film process sink 18 It, can be by antibacterial before being concentrated by the reverse osmosis membrane of reverse osmosis membrane processing equipment 22 in the case where middle generation foundry loam Agent is added in film process sink 18 or pipeline before and after it, still, since the film process water in film process sink 18 is through common In the backwash of film process equipment 14, it is thus possible to the often antibacterial agent of waste a part addition.Antibacterial agent is being added to biology In the case where handling in sink 12 or pipeline before and after it, suspended organic matter matter that antimicrobial moiety is generated after biological treatment The additive amount for meaning to can increase antibacterial agent is consumed, operating cost is caused to increase, therefore is only viscous when existing in whole system Mud can just use this method when generating risk.

The water treatment system 1 of Fig. 1 shows the example of biological treatment system 16 comprising at the biology of specific installation Equipment 10, biological treatment sink 12 and film process equipment 14 are managed, but also can be used and these equipment are combined into individual unit Film separated activated sludge equipment (MBR).

In the water treatment system 1 of Fig. 1, the low-molecular-weight organic matter etc. contained in raw water is decomposed by biological treatment, Microbe metabolite etc. is retained by the film process equipment 14 containing clarification film etc., and various ions and any residual organic matter matter etc. are then It is retained by the neutral film of reverse osmosis membrane processing equipment 22 or cationically charged film, to obtain processing water (infiltration water).This In the Sewage treatment of type, ammonia be may be embodied in waste water itself, and ammonia can also be generated frequently by biological treatment.Example Such as, when the waste water containing the tetramethylammonium hydroxide as organic substance carries out biological treatment, tend to be easy to produce ammonia.

At this point, the clarification film and reverse osmosis membrane of subsequent workshop section exist by the microbe metabolite that biological treatment generates and even Remaining remnants low molecular weight organic matters biological pollution may be a problem after biological treatment.It is powerful by using showing The hypochlorous acid of bactericidal effect is come to solve this problem be a kind of possible countermeasure, but hypochlorous acid causes to have become in recent years sometimes The deterioration of the polyamide-based reverse osmosis membrane of mainstream.Workshop section before reverse osmosis membrane provides activated carbon tower or reducing agent decanting point It is possible, but in any case, initial launch cost is often problematic.Therefore, in water treatment system 1, pass through Antibacterial agent containing bromine system oxidant or chlorine system oxidant and sulfamic acid compound is introduced into the pending water containing ammonia, not only Powerful sterilizing function can be obtained, and the oxidative degradation of polyamide-based reverse osmosis membrane may be less likely, and reverse osmosis The rejection of film may be very high, it means that has little effect to the quality of the processing water (infiltration water) of subsequent workshop section.

When adding antibacterial agent in this way, if antibacterial agent penetrates into processing water side, the deterioration of water water quality is handled It is likely to become a problem.Therefore, in the method for treating water according to embodiments of the present invention using reverse osmosis membrane, by It uses neutral film or cationically charged film as reverse osmosis membrane in reverse osmosis membrane processing equipment 22, the infiltration of antibacterial agent can be inhibited By reverse osmosis membrane, antibacterial agent is nearly no detectable in infiltration water.

In addition, at this point, the pH of the pending water of supply reverse osmosis membrane processing equipment 22, i.e. reverse osmosis membrane processing equipment 22 Operating pH is preferably 9 or less.In the case where being more than the alkaline condition of pH9, the salt rejection rate of reverse osmosis membrane is deteriorated sometimes, and antibacterial The oxidability of agent declines sometimes.If be supplied to the pH of pending water of reverse osmosis membrane processing equipment 22 be 9 hereinafter, if can More advantageously to keep the water quality of RO infiltration water, and it can preferably inhibit the generation of foundry loam.

In the Sewage treatment process of such as water treatment system 1,24 (salt water of the second reverse osmosis membrane processing equipment is usually provided RO) to increase the water rate of recovery.Second reverse osmosis membrane processing equipment 24 receives the condensed water from reverse osmosis membrane processing equipment 22 and makees For raw water, by obtained infiltration water back to processing sink 20, and condensed water is discharged from system.In the second reverse osmosis membrane processing There is also the risks that foundry loam generates in equipment 24, but if antibacterial agent is low by the permeability of reverse osmosis membrane processing equipment 22, Then antimicrobial moiety can be retained in supplied in the raw water of the second reverse osmosis membrane processing equipment 24.By in reverse osmosis membrane processing It uses neutral film or cationically charged film as reverse osmosis membrane in equipment 22, a large amount of antimicrobial moieties can be retained in and be used for In the raw water of two reverse osmosis membrane processing equipment 24, it is meant that the foundry loam in the second reverse osmosis membrane processing equipment 24 can be inhibited to produce It is raw.

In the water treatment system 1 of Fig. 1, carried out biological treatment as the pretreated example before reverse osmosis membrane processing Description, but in the pre-treatment step carried out before reverse osmosis membrane processing, can carry out as needed any Or the pretreatment of chemistry, such as biological treatment, flocculation treatment, flocculating setting processing, pressure flotation processing, filtration treatment, film point From two or more any group in processing, active carbon processing, ozone treatment or ultraviolet treatment with irradiation or these processing It closes.

In reverse osmosis membrane treatment system 26, in addition to reverse osmosis membrane, as needed, which may also include pump, safe mistake Filter, flow measurement equipment, pressure measuring device, temperature measurement equipment, oxidation-reduction potential (ORP) measuring device, residual chlorine Measuring device, conductivity measurement equipment, pH measuring device and/or apparatus for energy recovery etc..

In water treatment system 1, if it is desired, can be to biological treatment sink 12 and its pipeline of front and back, film process water Biological treatment at the pipeline and processing sink 20 of slot 18 and its front and back and its at least one position in the pipeline of front and back Addition is except stable hypobromous acid composition or the combination of stable hypochlorous acid at least one of water, film process water and pending water PH adjusting agent and scale inhibitor except object.

An example of the water treatment facilities using reverse osmosis membrane of embodiment according to the present invention is shown in Fig. 6 It summarizes.The structure of the device is described below.

Water treatment facilities 3 shown in fig. 6 includes that the ammonia for reducing the amount of the ammonia in the pending water containing ammonia reduces equipment 30 and with the neutral film or the cationic reverse osmosis membrane processing equipment 34 with film as reverse osmosis membrane processing unit.At water Reason device 3 can also include the sink 32 of the ammonia reduction for storing the water of ammonia reduction.

In water treatment facilities 3, pending water pipeline 36 is connected to the entrance that ammonia reduces equipment 30.Ammonia reduces equipment 30 The entrance of the sink 32 of outlet and ammonia reduction is connected by the pipeline 38 of the water of ammonia reduction.The outlet of the sink 32 of ammonia reduction and anti- The entrance of permeable membrane processing equipment 34 is connected by the water pipeline 40 containing antibacterial agent.Infiltration water pipeline 42 is connected at reverse osmosis membrane The infiltration water out of equipment 34 is managed, concentration water pipeline 44 is connected to concentration water out.Antibacterial agent addition pipeline 46 is connected to ammonia and subtracts Few sink 32.

The operation of method for treating water and water treatment facilities 3 according to embodiments of the present invention is described below.

In water treatment facilities 3, the pending water containing ammonia (ammonium ion) is supplied to ammonia by pending water pipeline 36 and subtracts Few equipment 30 reduces the amount (ammonia reduction step) that ammonia can be reduced in equipment 30 in ammonia.

Water pipeline 38 of the water of ammonia reduction obtained after ammonia reduction by ammonia reduction is carried out reducing equipment 30 by ammonia, If desired, being fed in the sink 32 of ammonia reduction and storing.Addition contains bromine system oxidant or chlorine system oxidant and ammonia The antibacterial agent of base sulfoacid compound, and (antibacterial agent addition step in the water for the ammonia reduction being introduced into the sink 32 of ammonia reduction Suddenly).Antibacterial agent can also be added in the water pipeline 38 of ammonia reduction or the water pipeline 40 containing antibacterial agent.

The water containing antibacterial agent for introducing antibacterial agent is supplied to reverse osmosis membrane processing by the water pipeline 40 containing antibacterial agent and sets Standby 34, reverse osmosis membrane processing (reverse osmosis membrane processing step) is carried out in reverse osmosis membrane processing equipment 34.From reverse osmosis membrane processing The infiltration water of acquisition is discharged as processing water by infiltration water pipeline 42, and condensed water is discharged by concentration water pipeline 44.

As studying repeatedly as a result, the inventors found that containing bromine system oxidant or chlorine system oxidant and amino The permeability of the antibacterial agent of sulfoacid compound increases with the ammonia density in pending water.Therefore, by reverse osmosis membrane The ammonia density in pending water is reduced before reason as pretreatment, can be inhibited containing bromine system oxidant or chlorine system oxidant and ammonia The antibacterial agent of base sulfoacid compound penetrates through reverse osmosis membrane.When the ammonia density in the water of ammonia reduction is not more than 5mg/L, due to Ammonia reduce and to the reducing effect of antibacterial agent permeability may especially effectively.

Ammonia reduces equipment 30 and is not particularly limited, as long as its amount that can reduce the ammonia (ammonium ion) in pending water is i.e. It can.The example that ammonia reduces equipment 30 includes carrying out the ammonia that ammonia stripping is handled to strip processing equipment, carry out ammonolysis craft using oxidant The ammonolysis craft processing equipment of processing and the pretreatment for using reverse osmosis membrane.Wherein, just hardly increase the risk for generating foundry loam And chemicals identical with the antibacterial agent used in subsequent workshop section is made to can be used as oxidant to not increase and must use Chemicals type for, preferably progress ammonia stripping processing ammonia stripping processing equipment and using oxidant carry out ammonolysis craft at The ammonolysis craft processing equipment of reason.

The processing of ammonia stripping is a kind of processing method, wherein aqueous slkali is added in the water containing ammonia, and after heating, So that water is passed through the stripper filled with filler and contacted with steam and air, to make to move in gas phase containing the ammonia in ammonium hydroxide.

It is, for example, destilling tower that ammonia, which strips processing equipment, inside porous plate or filler etc. be installed, and from destilling tower Top, which introduces, contains ammonium hydroxide, while steam is blown into from the lower part of tower, then by making to contact containing ammonium hydroxide with steam, can will contain ammonium hydroxide In free ammonia forced from water to steam side.The ammonia forced out in this way can also carry out resolution process.The ammonia point The example of solution processing includes making ammonia by the catalytic tower filled with catalyst to convert ammonia to harmless nitrogen Method, and the method for making ammonia and sulfuric acid reaction to produce ammonium sulfate, but ammonia can also be collected and sharp again as ammonium hydroxide With.

PH in the processing of ammonia stripping is preferably 10 or more, and more preferable 10.5 or more, even more preferably 10.5 to 12.If ammonia PH in stripping processing is less than 10, then free ammonia (NH₃) ratio reduce, ammonia removal efficiency is low sometimes.If at ammonia stripping PH in reason is more than 12, then is likely to occur problem, including during the processing of ammonia stripping in destilling tower porous plate or filler deterioration A possibility that and alkali chemicals increased costs.

The efficiency of ammonia stripping processing increases with temperature and is increased, therefore increases to water temperature at 40 DEG C extremely usually using steam Value within the scope of 100 DEG C, the preferably temperature within the scope of 80 DEG C to 100 DEG C.

The example that may be used in the oxidant in the ammonolysis craft processing of oxidant includes chlorine system oxidant, the oxidation of bromine system Agent, brominated system's oxidant and sulfamic acid compound stable hypobromous acid composition and contain chlorine system oxidant and amino The stable hypochlorous acid composition of sulfoacid compound, wherein preferably stable hypobromous acid composition and stable hypochlorous acid combination Object.Chlorine system oxidant, bromine system oxidant, stable hypobromous acid composition and stable hypochlorous acid composition example include with such as Lower chlorine system oxidant, bromine system oxidant, stable hypobromous acid composition and the stable identical object of hypochlorous acid composition Matter.The oxidant used in ammonolysis craft processing is preferably to introduce what ammonia was reduced in subsequent workshop section with after ammonia reduces step The identical substance of antibacterial agent in water.By using oxidant identical with the antibacterial agent in the water for being introduced into ammonia reduction, and with Oxidant is used greater than the desired amount of amount of ammonolysis craft, remaining oxidant may be used as subsequent workshop section's reverse osmosis after ammonolysis craft processing Antibacterial agent in permeable membrane processing equipment.

The amount of oxidant used in ammonolysis craft processing is set, so that the molar concentration of effectively halogen is (with effective chlorine density Calculate) relative to ammoniacal nitrogen (NH in pending water₄- N) molar concentration ratio be preferably at least 1.6, more preferable 2.0 with On.The ratio is bigger, and it is bigger that ammonia reduces effect.Molar concentration (being calculated with effective chlorine density) by ensuring effective halogen is opposite The ratio of the molar concentration of ammoniacal nitrogen is 2.0 or more in pending water, and the remaining oxidizing agent from ammonolysis craft processing can be It is used as antibacterial agent in subsequent workshop section's reverse osmosis membrane processing equipment.The upper limit of the molar concentration ratio is for example no more than 100.

Using the pH in the ammonolysis craft processing of oxidant for example in the range of 3 to 10, and preferably 4 to 9 range It is interior.If the pH in ammonolysis craft processing is less than 3, ammoniacal nitrogen discomposing effect is low sometimes, and if pH is more than 10, subsequent work The increase of the rejection of section reverse osmosis membrane there may come a time when to need to adjust pH to more neutral setting.

Temperature during being handled using the ammonolysis craft of oxidant is for example in the range of 0 DEG C to 100 DEG C, and preferably 0 DEG C in the range of 40 DEG C.If the temperature in ammonolysis craft processing is lower than 0 DEG C, handles water and freeze sometimes, and if temperature More than 100 DEG C, then oxidant or ammonia may volatilize, and lead to the reduction of ammonolysis craft efficiency.

Ammonia reduces the ammonia density in step in pending water for example in the range of 0.1mg/L to 500mg/L, and preferably In the range of 0.1mg/L to 30mg/L.

In the water treatment facilities and method according to embodiments of the present invention using reverse osmosis membrane, it will be aoxidized containing bromine system The antibacterial agent of agent or chlorine system oxidant and sulfamic acid compound, which is introduced, to be reduced the reduction ammonia amount of equipment 30 by using ammonia and obtains Ammonia reduction water in." antibacterial agent containing bromine system oxidant and sulfamic acid compound " can be containing stable hypobromous acid The antibacterial agent of composition, the hypobromous acid composition contain the mixture of " bromine system oxidant " and " sulfamic acid compound ", or It can be the antibacterial agent containing stable hypobromous acid composition, which contains " bromine system oxidant and sulfamic acid The reaction product of compound "." antibacterial agent containing chlorine system oxidant and sulfamic acid class compound " can be containing stable The antibacterial agent of hypochlorous acid composition, the hypochlorous acid composition contain the mixing of " chlorine system oxidant " and " sulfamic acid compound " Object, or can be is the antibacterial agent containing stable hypochlorous acid composition, the hypochlorous acid composition contain " chlorine system oxidant and The reaction product of sulfamic acid compound ".

In other words, it in the water treatment facilities and method according to embodiments of the present invention using reverse osmosis membrane, can incite somebody to action The mixture or " chlorine system oxidant " and " sulfamic acid compound " mixture of " bromine system oxidant " and " sulfamic acid compound " It is introduced into the water of ammonia reduction.As a result, it is believed that stable hypobromous acid composition or stable time can be produced in the water of ammonia reduction Chloric acid composition.

In addition, in the water treatment facilities and method using reverse osmosis membrane according to other embodiments of the present invention, it can With by stable hypobromous acid composition (it is " reaction product of bromine system oxidant and sulfamic acid compound ") or stable time Chloric acid composition (" reaction product of chlorine system oxidant and sulfamic acid compound ") is introduced into the water of ammonia reduction.

Specifically, in the water treatment facilities and method according to embodiments of the present invention using reverse osmosis membrane, by " bromine ", " bromine chloride ", " hypobromous acid " or " sodium bromide and hypochlorous reaction product " and the mixture of " sulfamic acid compound " introduce ammonia In the water of reduction.Alternatively, the mixture of " hypochlorous acid " and " sulfamic acid compound " can be introduced into the water of ammonia reduction.

In addition, in the water treatment facilities and method according to embodiments of the present invention using reverse osmosis membrane, it will be stable (it is " reaction product of bromine and sulfamic acid compound " to hypobromous acid composition, " bromine chloride is reacted with sulfamic acid compound Product ", " reaction product of hypobromous acid and sulfamic acid compound " or " sulfamic acid compound and sodium bromide and hypochlorous anti- Answer the reaction product of product ") it is introduced into the water of ammonia reduction.Alternatively, can (it be " hypochlorous acid by stable hypochlorous acid composition With the reaction product of sulfamic acid compound ") it is introduced into the water of ammonia reduction.

In the water treatment facilities and method according to embodiments of the present invention using reverse osmosis membrane, stable hypobromous acid group Close object or stable hypochlorous acid composition show with such as hypochlorous chlorine system oxidants like or superior foundry loam inhibit Effect, and compared with chlorine system oxidant, it is smaller on the deterioration of reverse osmosis membrane influence, therefore the oxidation of reverse osmosis membrane can be inhibited Deterioration, while inhibiting the pollution of reverse osmosis membrane.As a result, being filled in the water process according to embodiments of the present invention using reverse osmosis membrane It sets and is advantageously used for sticky mud inhibitor with hypobromous acid composition stable used in method or stable hypochlorous acid composition, use In the water treatment facilities and method of the pending water for using reverse osmosis membrane processing to contain ammonia.

In the various water treatment facilities and method according to embodiments of the present invention using reverse osmosis membrane, " containing bromine It is the antibacterial agent of oxidant and sulfamic acid compound " in the case where, because chlorine system oxidant is not present, to the bad of reverse osmosis membrane Changing influence may be especially small.When there are chlorine system oxidant, leading to the problem of for chloric acid may be one.

In the various water treatment facilities and method according to embodiments of the present invention using reverse osmosis membrane, when " bromine system oxygen When agent " is bromine, because chlorine system oxidant is not present, influencing on the deterioration of reverse osmosis membrane may be very low.

It, can be for example using change in the water treatment facilities and method according to embodiments of the present invention using reverse osmosis membrane " bromine system oxidant " or " chlorine system oxidant " and " sulfamic acid compound " is injected into the water of ammonia reduction by product feed pump etc.. " bromine system oxidant " or " chlorine system oxidant " and " sulfamic acid compound " can be added separately in the water of ammonia reduction, or will Stoste, which mixes, to be then added in the water of ammonia reduction.

Furthermore, it is possible to by " bromine system oxidant reacts production with sulfamic acid compound such as using chemical feed pump In object " or the water of " reaction product of chlorine system oxidant and sulfamic acid compound " injection ammonia reduction.

In the water treatment facilities and method according to embodiments of the present invention using reverse osmosis membrane, " sulfamic acid chemical combination The equivalent of object " is preferably 1 or more relative to the ratio of " bromine system oxidant " or the equivalent of " chlorine system oxidant ", more preferably extremely Few 1 in the range of no more than 2.If the equivalent of " sulfamic acid compound " is relative to " bromine system oxidant " or " chlorine system oxidation The ratio of agent " equivalent is less than 1, it is likely that the deterioration of film occurs, and if the ratio is more than 2, production cost increases sometimes Add.

The total cl concn contacted with reverse osmosis membrane is calculated, preferably 0.01 to 100mg/L with equivalence unit cl concn.Such as The fruit concentration is less than 0.01mg/L, then is difficult to obtain satisfactory foundry loam inhibitory effect sometimes, and if concentration is greater than 100mg/L, then a possibility that being likely to occur the deterioration of reverse osmosis membrane or the corrosion of pipeline etc..

In the water treatment facilities and method according to embodiments of the present invention using reverse osmosis membrane, in the water of ammonia reduction Ammonium concentration is preferably no greater than 5mg/L, more preferable 1mg/L or smaller.If the ammonium concentration in the water of ammonia reduction is more than 5mg/L, then antibacterial agent is easier to penetrate through reverse osmosis membrane.

Ratio (ammonia density (mg/L)/antimicrobial agent concentration (total chlorine of the ammonia density relative to total cl concn in the water of ammonia reduction Concentration: mg/L)) for example in following range: 0.01~50.If ammonia reduction water ammonia density relative to total cl concn It when ratio is less than 0.01, is then satisfactorily retained due to antibacterial agent by reverse osmosis membrane, in terms of further reducing ammonia density There may be the effects of very little, and if ammonia density is more than 50, even if ammonia density reduces, the permeability of antibacterial agent can also be protected Hold effect very high, and that reduction permeability may not observed.

In the water treatment facilities and method according to embodiments of the present invention using reverse osmosis membrane, it can also introduce an alkali into In the water of ammonia reduction.

In the water treatment facilities and method according to embodiments of the present invention using reverse osmosis membrane, it is supplied to comprising reverse osmosis The pH of the water of the ammonia reduction of the reverse osmosis membrane processing equipment of permeable membrane is preferably at least 5.5 or more, more preferably at least 6.0, even more It is preferred that 6.5 or more.If the pH of the water of ammonia reduction, less than 5.5, the amount for permeating water reduces sometimes.In addition, ammonia is reduced For the upper limit of the pH of water, be not particularly limited, if pH be no more than reverse osmosis membrane generally applicable upper limit pH (for example, PH10), but if it is considered that the precipitation of scales of the hard component of such as calcium, then operate under being preferably for example 9.0 or less in pH value The equipment.When using the water treatment facilities and method according to embodiments of the present invention using reverse osmosis membrane, by subtracting in ammonia The pH of few water is operated under conditions of being 5.5 or more, can be inhibited the deterioration of reverse osmosis membrane and be handled water (infiltration water) The deterioration of water quality, and can ensure satisfactory amount of seepage while realizing satisfactory foundry loam inhibitory effect.

When the pH of the water of ammonia reduction is 5.5 or more, in the case where scale occurs in reverse osmosis membrane equipment, in order to inhibit Scale can use dispersing agent and antibacterial agent combination.The example of dispersing agent includes polyacrylic acid, poly and phosphonic acids etc.. It is added to the amount of the dispersing agent in the water of ammonia reduction, for example, for the concentration in RO condensed water, 0.1 to 1000mg/L's In range.

In addition, an example of the method for inhibiting scale to generate in the case where not using dispersing agent includes that adjusting is reverse osmosis The operating condition of film device, such as the rate of recovery, so that the silica concentration in RO condensed water is not higher than solubility, and Langelier index (it is the index for being calcium scale) is not more than 0.

Bromine system oxidant, bromine compounds, chlorine system oxidant, sulfamic acid conjunction object, alkali and reverse osmosis membrane are all as described above.

It is thought that according to embodiments of the present invention will be particularly useful for using the water treatment facilities and method of reverse osmosis membrane Water recycling, such as the Sewage treatment in electronics industry.Electronics industry waste water usually contains low molecular weight organic matters, Sewage treatment A kind of possible process be flow type shown in Fig. 7, in the biology comprising biological treating equipment 50 and film process equipment 54 In the subsequent workshop section of processing system 56, setting can be used for executing the water process according to embodiments of the present invention using reverse osmosis membrane Method, comprising ammonia reduce equipment 30 and reverse osmosis membrane processing equipment 34 water treatment facilities 3.

Water treatment system 5 shown in fig. 7 includes as the biological treating equipment 50 of biological processing unit, biological treatment of water Slot 52, the film process equipment 54 as film process unit, film process sink 58 and above-mentioned water treatment facilities 3.Water treatment system 5 is also It may include the second reverse osmosis membrane equipment 60 as the second reverse osmosis membrane processing unit.

In water treatment system 5, the raw water of such as electronics industry waste water is supplied in biological treating equipment 50, and Biological treatment (biological treatment step) is carried out in biological treating equipment 50.Biological treatment of water by biological treatment can be according to need It is stored in biological treatment sink 52, is then fed into film process equipment 54, it is (clear to carry out film process using clarification film herein (film process step) clearly).Film process water through film process, which can according to need, to be stored in film process sink 58, then conduct Pending water reduces equipment 30 for the ammonia of Water feeding treatment device 3, is reduced (ammonia reduction step in the amount that ammonia reduces ammonia in equipment 30 Suddenly).

It is supplied to as needed in the water that ammonia reduces the ammonia reduction in equipment 30 Jing Guo ammonia reduction and is stored in ammonia reduction In sink 32.The antibacterial agent containing bromine system oxidant or chlorine system oxidant and sulfamic acid compound is added, and is introduced into ammonia In the water of ammonia reduction in the sink 32 of reduction (antibacterial agent addition step).Antibacterial agent can also be added to the sink of ammonia reduction In the pipeline of 32 front and backs.

The water containing antibacterial agent for having had been incorporated into antibacterial agent is supplied into reverse osmosis membrane processing equipment 34, in reverse osmosis membrane processing Reverse osmosis membrane processing (reverse osmosis membrane processing step) is carried out in equipment 34.The infiltration water obtained by reverse osmosis membrane processing is as processing Water passes through concentration water pipeline discharge by infiltration water pipeline discharge, condensed water.The infiltration water obtained in reverse osmosis membrane processing from It is discharged in system.Condensed water can be discharged from system, or if desired, can be fed into the second reverse osmosis membrane processing equipment In 60, second of reverse osmosis membrane processing (the second reverse osmosis membrane processing step is then carried out in the second reverse osmosis membrane processing equipment 60 Suddenly).The condensed water obtained in second of reverse osmosis membrane processing is discharged from system.Infiltration water can be discharged from system, or Person reduces in sink 32 and recycles if desired, ammonia can be fed into.

The water treatment system 5 of Fig. 7 shows the example of biological treatment system 56 comprising at the biology of specific installation Equipment 50, biological treatment sink 52 and film process equipment 54 are managed, but also can be used and these equipment are combined into individual unit Film separated activated sludge equipment (MBR).

In the water treatment system 5 of Fig. 7, the low-molecular-weight organic matter etc. contained in raw water is decomposed by biological treatment, Microbe metabolite etc. is retained by the film process equipment 54 containing clarification film etc., is then reduced in ammonia and is reduced ammonia in equipment 30 Amount, various ions and any residual organic matter matter etc. are then retained by reverse osmosis membrane processing equipment 34, to obtain processing water (infiltration Water).In such Sewage treatment, ammonia be may be embodied in waste water itself, and ammonia is also produced frequently by biological treatment It is raw.For example, tending to be easy to produce when the waste water containing the tetramethylammonium hydroxide as organic substance carries out biological treatment Ammonia.

At this point, the reverse osmosis membrane of subsequent workshop section exists by the microbe metabolite biological pollution that biological treatment generates and even Remaining remnants low molecular weight organic matters may be a problem after biological treatment.By using showing powerful bactericidal effect Hypochlorous acid come to solve this problem be a kind of possible countermeasure, but hypochlorous acid causes to have become the poly- of mainstream in recent years sometimes The deterioration of amide system reverse osmosis membrane.Workshop section before reverse osmosis membrane provides activated-charcoal column or reducing agent decanting point is also possible , but in any case, initial launch cost is often problematic.Therefore, in water treatment system 5, by subtracting in ammonia The amount that ammonia is reduced in few equipment, then draws the antibacterial agent containing bromine system oxidant or chlorine system oxidant and sulfamic acid compound In the water for entering ammonia reduction, powerful sterilizing function can be not only obtained, but also the oxidative degradation of polyamide-based reverse osmosis membrane may It is less likely, and the rejection of reverse osmosis membrane may be very high, it means that the matter of the processing water (infiltration water) of subsequent workshop section Amount has little effect.

When adding antibacterial agent in this way, if antibacterial agent penetrates into processing water side, the deterioration of water water quality is handled It is likely to become a problem.Therefore, in the water treatment facilities and method according to embodiments of the present invention using reverse osmosis membrane, By reducing the ammonia density in pending water before reverse osmosis membrane processing as pretreatment, antibacterial agent can be inhibited to penetrate through Reverse osmosis membrane is nearly no detectable antibacterial agent in infiltration water.

In addition, at this point, the pH of the water of the ammonia reduction of supply reverse osmosis membrane processing equipment 34, i.e. reverse osmosis membrane processing equipment 34 Operation pH be preferably 9 or less.Under the conditions of being more than the alkali of pH9, the salt rejection rate of reverse osmosis membrane is deteriorated sometimes, and antibacterial The oxidability of agent reduces sometimes.If be supplied to the water of ammonia reduction of reverse osmosis membrane processing equipment 34 pH be 9 hereinafter, if The water quality of RO infiltration water can be more advantageously kept, and can preferably inhibit the generation of foundry loam.

In the Sewage treatment process of such as water treatment system 5,60 (salt water of the second reverse osmosis membrane processing equipment is usually provided RO) to increase the water rate of recovery.Second reverse osmosis membrane processing equipment 60 receives the condensed water from reverse osmosis membrane processing equipment 34 and makees For raw water, obtained infiltration water is returned into the sink 32 of ammonia reduction, and condensed water is discharged from system.In the second reverse osmosis membrane There is also the risks that foundry loam generates in processing equipment 60, but if antibacterial agent passes through the permeability of reverse osmosis membrane processing equipment 34 Low, then antimicrobial moiety can be retained in supplied in the raw water of the second reverse osmosis membrane processing equipment 60.Due to a large amount of antibacterial agents Component is retained in the raw water for the second reverse osmosis membrane processing equipment 60, can be inhibited in the second reverse osmosis membrane processing equipment 60 Foundry loam generate.

In the water treatment system 5 of Fig. 7, carried out biological treatment as the pretreated example before reverse osmosis membrane processing Description, but in the pre-treatment step carried out before reverse osmosis membrane processing, can carry out as needed any Or the pretreatment of chemistry, such as biological treatment, flocculation treatment, flocculating setting processing, pressure flotation processing, filtration treatment, film point From two or more any group in processing, active carbon processing, ozone treatment or ultraviolet treatment with irradiation or these processing It closes.

In water treatment facilities 3, in addition to reverse osmosis membrane, as needed, which may also include pump, security filter, stream Measurement equipment, pressure measuring device, temperature measurement equipment, oxidation-reduction potential (ORP) measuring device, residual chlorine measurement are set Standby, conductivity measurement equipment, pH measuring device and/or apparatus for energy recovery etc..

In water treatment system 5, if it is desired, can be to biological treatment sink 52 and its pipeline of front and back, film process water Slot 58 and its pipeline and ammonia of front and back reduce the biological treatment at least one position in sink 32 and its pipeline of front and back The addition of at least one of water of water, film process water and ammonia reduction is combined except stable hypobromous acid composition or stable hypochlorous acid PH adjusting agent and scale inhibitor except object.

Antibacterial agent according to embodiments of the present invention contains stable hypobromous acid composition or stable hypochlorous acid composition, contains There is the mixture of " bromine system oxidant or chlorine system oxidant " and " sulfamic acid compound ", and alkali can also be contained.

In addition, antibacterial agent according to another embodiment of the invention contains stable hypobromous acid composition, (it contains " bromine system The reaction product of oxidant and sulfamic acid compound ") or stable hypochlorous acid composition (it contains " chlorine system oxidant and ammonia The reaction product of base sulfoacid compound "), and alkali can also be contained.

Bromine system oxidant, bromine compounds, chlorine system oxidant and sulfamic acid compound are as described above.

The example of the commercially available stable hypochlorous acid composition containing chlorine system oxidant and sulfamic acid compound includes The product " Kuriverter IK-110 " of Kurita Water Industries Co., Ltd production.

In order to realize the less deterioration of reverse osmosis membrane, antibacterial agent according to embodiments of the present invention preferably comprises bromine and amino Sulfoacid compound (mixture of bromine and sulfamic acid compound), for example, bromine, sulfamic acid compound, alkali and water mixture； Or the reaction product containing bromine and sulfamic acid compound, such as reaction product, alkali and the water of bromine and sulfamic acid compound Mixture.

In various antibacterial agents according to embodiments of the present invention, and containing chlorine system oxidant and sulfamic acid compound Antibacterial agent (such as chloro sulfamic acid) is compared, and (contains bromine system oxidant and sulfamic acid containing stable hypobromous acid composition Compound) antibacterial agent, especially contain stable hypobromous acid composition (containing bromine and sulfamic acid compound) antibacterial agent, It can show that higher oxidability, significant higher foundry loam inhibits and foundry loam separating capacity, and almost without causing having There is the significant film deterioration as observed by hypochlorous acid of other compositions of similar high oxidative capacity.In the case where generally using concentration, Influence to film deterioration can substantially be ignored.As a result, these reagents are ideal antibacterial agents.

Different from hypochlorous acid, antibacterial agent according to embodiments of the present invention hardly penetrates through reverse osmosis membrane, therefore right Water quality treatment has little effect.In addition, because concentration can be measured at the scene in the mode similar with hypochlorous acid etc., it can To carry out more accurate concentration control.

The pH value of antibacterial agent is for example higher than 13.0, and preferably higher than 13.2.If the pH of antibacterial agent be 13.0 hereinafter, if antibacterial Effective halogen in agent becomes unstable sometimes.

Bromate concentration in antibacterial agent is preferably smaller than 5mg/kg.If bromate concentration in antibacterial agent be 5mg/kg with On, then the concentration of bromate ion can increase in RO infiltration water.

Antibacterial agent according to embodiments of the present invention is by mixing bromine system oxidant or chlorine system oxidant with sulfamic acid compound It closes and obtains, alkali can also be mixed into the reagent.

Preparation is preferably wrapped containing the antibacterial agent method of stable hypobromous acid composition (containing bromine and sulfamic acid compound) The step of bromine is added and is reacted with the mixed solution containing water, alkali and sulfamic acid under inert gas atmosphere is included, or lazy Under property gas atmosphere, the step that bromine is added in the mixed solution containing water, alkali and sulfamic acid compound.By in inertia It is added under gas atmosphere and induced reaction, or by being added under inert gas atmosphere, antibacterial agent can be reduced In bromate ion concentration, and can reduce RO infiltration water in bromate ion concentration.

Although inert gas used is not particularly limited, consider from production angle etc., preferably in nitrogen and argon gas At least one, and for production cost etc., nitrogen is particularly preferred.

Oxygen concentration in bromine addition present invention container is preferably no greater than 6%, more preferably no more than 4%, even more excellent Choosing is not more than 2%, particularly preferred 1% or smaller.If the oxygen concentration in bromine reaction present invention container is more than 6%, instead Answer the amount of the bromic acid generated in system will increase sometimes.

Relative to the total weight of antibacterial agent, the adding proportion of bromine is preferably more than 25wt%, more preferably at least 1wt% but not More than 20wt%.If the adding proportion of bromine is more than 25wt% relative to the total weight of antibacterial agent, then generated in reaction system The amount of bromic acid will increase sometimes.If the ratio is less than 1wt%, bactericidal effect may be poor.

Reaction temperature during bromine adds is preferably controlled at least 0 DEG C in the range of no more than 25 DEG C, and just production For cost etc., more preferably control is at least 0 DEG C in the range of being no more than 15 DEG C.If the reaction temperature during bromine adds is super Cross 25 DEG C, then the amount of the bromic acid generated in reaction system will increase sometimes, and if temperature is lower than 0 DEG C, reaction system may It can freeze.

Embodiment

The present invention will be described in more detail for a series of embodiment and comparative examples used below, but the present invention is not by following embodiment Limitation.

[preparation of stable hypobromous acid composition (composition 1)]

By bromine: 16.9wt%, sulfamic acid: 10.7wt%, sodium hydroxide: 12.9wt%, potassium hydroxide: 3.94wt% and Water: surplus is mixed in a nitrogen atmosphere to prepare stable hypobromous acid composition (composition 1).Stable hypobromous acid group The pH for closing object is 14, and total cl concn is 7.5wt%.Prepare being described in detail as follows for the method for stable hypobromous acid composition.

Continuously nitrogen is injected in 2L four-neck flask under the flow controlled by mass flow controller, is made in reaction vessel Oxygen concentration be maintained at 1%, 1436g water and 361g sodium is added, after stirring, 300g sulfamic acid is added and simultaneously mixes, then makes Flask is cooling, and reacting liquid temperature is made to be maintained at 0~15 DEG C, and 473g bromine is added, and it is molten that 48% potassium hydroxide of 230g is then added Liquid contains the total weight for being equivalent to composition to obtain the stable hypobromous acid composition (composition 1) of target 10.7% sulfamic acid and 16.9% bromine, the equivalent of sulfamic acid is 1.04 relative to the ratio of the equivalent of bromine.Use glass The pH of the solution of glass electrode method measurement preparation, obtained value are 14.It is thio to replace bromine then to use with iodo with potassium iodide is used The method that sodium sulphate carries out redox titration, measures the bromine content of the solution of preparation, shows 16.9% value, this is theoretical 100.0% (16.9%) of content.In addition, using " the Oxygen Monitor JKO- manufactured by Jikco Co., Ltd 02LJDII " measures the oxygen concentration in bromine reaction present invention container.Bromic acid concentration is less than 5mg/kg.

PH measurement carries out under the following conditions.

Electrode type: glass electrode

PH meter: IOL-30 type is manufactured by DKK-TOA company

Electrode calibration: using the neutral phosphate standard solution (2 type) manufactured by Northeast chemical company pH (6.86) and by The pH (9.18) of the borate standard solution (2 type) of same company's manufacture carries out two o'clock calibration.

Measurement temperature: 25 DEG C

Measured value: electrode is immersed in the liquid in measurement, and the value after record is stablized is used as measured value, and record three times measures Average value.

[preparation of stable hypochlorous acid composition (composition 2)]

By 12% aqueous sodium hypochlorite solution: 50wt%, sulfamic acid: 12wt%, sodium hydroxide: 8wt%, He Shui: surplus mixes Together to prepare stable hypochlorous acid composition (composition 2).The pH of composition 2 is 13.7, and total cl concn is 6.2wt%.

[zeta potential of reverse osmosis membrane measures]

Use the zeta potential of the zeta potential and granulometry system ELSZ measurement series reverse osmosis membrane that are manufactured by great Zhong electronics corporation.Make The zeta potential of reverse osmosis membrane is calculated by the electric osmose figure measured with Sen Gangben equation and Smoluchowski equation as follows.

(Sen Gangben equation)

U_obs(z)=AU₀(z/b)²+ΔU₀(z/b)+(1-A)U₀+U_p

Here,

Z: the distance away from the center slot (cell)

U_obs(z): the apparent mobility of z location in slot

A:1/ [(2/3)-(0.420166/K)]

Wherein K=a/b:2a and 2b indicates the horizontal and vertical length of slot cross section, and a > b

U_p: the true migration rate of particle

U₀: the average mobility of slot upper and lower surfaces

ΔU₀: the difference of the mobility of the upper and lower surfaces of slot

(Smoluchowski equation)

The π η U/ of ζ=4 ε

Here,

U: electromobility

ε: solvent dielectric constant

η: solvent viscosity

Use 10mM NaCl aqueous solution (pH about 5.4) as measurement solution.For each sample, two groups of pairings are prepared, often To including the aqueous solution and sample, a pair is adjusted to acid pH (pH2,3,4,5,6 or 7), another pair is adjusted to alkaline pH (pH8 or 9), measures zeta potential at each pH.Using 25 DEG C of pure water (refractive index: 1.3328, viscosity: 0.8878, dielectric constant: 78.3) physical property values of the value as solvent.

[experimental condition and test method]

Pass through the permeability of planar film test measurement antibacterial agent.The Membrane Master C70- manufactured by Dong electrician company F streaming planar film sample pool for testing slot is for making planar film sample cell slot.By Dong electrician company manufacture reverse osmosis membrane ES15, The reverse osmosis membrane OFR625 of ES10C and LFC3, Ao Lujia Nao company manufacture and the reverse osmosis membrane TML20 use manufactured by Toray Make planar film.It is representative neutral film by the LFC3 that Dong electrician company manufactures.It is by the ES10C that Dong electrician company manufactures The film sold as cationically charged film.By the TML20 of Toray manufacture and by the manufacture of Ao Lujia Nao company OFR625 is neutral film, and is anionically charged film by the ES15 that Dong electrician company manufactures.The flat membrane used be it is circular, directly Diameter is 75mm.The process is shown in FIG. 2.

For the test water (pending water) tested for flat membrane, using by being added to antibacterial agent by the way that sodium chloride is molten Solution in pure water obtained from 500mg/L solution, then pH is adjusted to 7.0 using hydrochloric acid or sodium hydroxide and is prepared Solution.Antibacterial agent is added to reach the antimicrobial agent concentration for being about 3-10mg/L with total chlorine meter.Using condenser by water temperature It is adjusted to 25 ± 1 DEG C.The operating pressure of reverse osmosis membrane is set as 0.75MPa.Water will be supplied, reverse osmosis membrane is supplied to 5L/min. After water is supplied about 3 hours, measures processed water and permeate the antimicrobial agent concentration (total cl concn) of water, acquire the infiltration of antibacterial agent Rate.Total cl concn is measured using the multinomial Water Test Kits DR/4000 manufactured by HACH company, and specified by using total chlorine Value (the mg/L, with Cl that measurement method (DPD (diethyl p-phenylenediamine) method) measurement obtains₂Meter).

Ammonium chloride is added, makes ammonia density 0mg/L, 1mg/L, 5mg/L or 10mg/L, measures pending water (total cl concn) With the concentration of each antibacterial agent in infiltration water (total cl concn), and permeability is calculated.Measurement result is as shown in table 1.

[table 1]

In embodiment 1, use stable hypobromous acid composition (composition 1) as antibacterial agent, and when ammonium concentration is When 10mg/L (embodiment 1-1), 5mg/L (embodiment 1-2) or 1mg/L (embodiment 1-3), surveyed under each zeta potential value (mV) It measures antibacterial agent permeability (%).As a result as shown in Figure 3.

In comparative example 1, use stable hypobromous acid composition (composition 1) as antibacterial agent, and when ammonium concentration is When 0mg/L (comparative example 1-1), antibacterial agent permeability (%) is measured under each zeta potential value (mV).As a result as shown in Figure 3.

In comparative example 1, the permeability of antibacterial agent is low, and observe permeability to zeta potential almost without dependence, and In embodiment 1, the permeability of antibacterial agent is higher, moreover, observing the trend lower in zeta potential value more high permeability.Work as ammonium When ion concentration is 5mg/L or more, this trend is particularly evident.

In example 2, use stable hypobromous acid composition (composition 1) as antibacterial agent, measure neutral film (OFR625 (embodiment 2-1), TML20 (embodiment 2-2) and LFC3 (embodiment 2-4) and cationically charged film (ES10C (embodiment 2- 3) antibacterial agent permeability).Correlation between antibacterial agent permeability (%) and ammonium concentration (mg/L) is shown in Figure 4.

In comparative example 2, use stable hypobromous acid composition (composition 1) as antibacterial agent, and measure anionically charged film The antibacterial agent permeability of (ES15 (comparative example 2-1)).It is related between antibacterial agent permeability (%) and ammonium concentration (mg/L) Property is shown in Figure 4.

The reduction in antibacterial agent permeability ratio comparative example 2 in embodiment 2 is more.In particular, when ammonium concentration is When 5mg/L or more, the difference of permeability is bigger.

In embodiment 3, antibacterial agent becomes stable hypochlorous acid composition (composition 2), for neutral film (LFC3 (embodiment Permeability 3-1)) is used to be measured in such a way that embodiment 2 is identical.Antibacterial agent permeability (%) and ammonium concentration (mg/L) it Between correlation it is as shown in Figure 5.

In comparative example 3, antibacterial agent is changed into stable hypochlorous acid composition (composition 2), and with identical with comparative example 2 Mode measures the permeability of anionically charged film (ES15 (comparative example 3-1)).Antibacterial agent permeability (%) and ammonium concentration (mg/L) correlation between is shown in Figure 5.

Even if when using neutral film or cationically charged film, resisting in the case where chlorine system stable hypochlorous acid composition The permeability of microbial inoculum is relatively low.In addition, the difference of permeability is bigger when ammonium concentration is 5mg/L or more.

As described above, by using the implementation in the method for treating water for the pending water for containing ammonia using reverse osmosis membrane processing Method described in example is able to suppress and permeates containing the antibacterial agent of chlorine system oxidant or bromine system oxidant and sulfamic acid compound Across reverse osmosis membrane.

[experimental condition and test method]

Pass through the permeability of planar film test measurement antibacterial agent.The MembraneMaster C70-F manufactured by Dong electrician company Flow-type planar film test trough is for making planar film slot.Use the reverse osmosis membrane ES15 (comparative example manufactured by Dong electrician company 4) and LFC3 (embodiment 4) is used as planar film.By Dong electrician company manufacture ES15 be anionically charged film (zeta potential :- It 35mV), is neutral film (zeta potential: -1.3mV) by the LFC3 that Dong electrician company manufactures.The flat membrane used be it is circular, directly Diameter is 75mm.Process is shown in FIG. 2.

For the test water (pending water) tested for flat membrane, using by by antibacterial agent ((the embodiment 4-1 of composition 1 With comparative example 4-1) or composition 2 (embodiment 4-2 and comparative example 4-2)) it is added to and is obtained and sodium chloride is dissolved in pure water The solution that in 500mg/L solution and then pH is adjusted to 7.0 using hydrochloric acid or sodium hydroxide and is prepared.Antibacterial agent is added To reach the antimicrobial agent concentration for being about 3~10mg/L with total chlorine meter.Using condenser by lower water temperature to 25 ± 1 DEG C.Instead The operating pressure of permeable membrane is set as 0.75MPa.Water will be supplied, reverse osmosis membrane is supplied to 5L/min.

Ammonium chloride, which is added, makes ammonia density reach 0mg/L, 1mg/L, 5mg/L or 10mg/L, and is feeding water into reverse osmosis After permeable membrane about 3 hours, measures pending water (total cl concn) and permeate the concentration of every kind of antibacterial agent in water (total cl concn), and count Calculate permeability.Measurement result is as shown in table 2, correlation such as Fig. 8 (group of antibacterial agent permeability (%) and ammonium concentration (mg/L) Close object 1 (embodiment 4-1 and comparative example 4-1)) and Fig. 9 (composition 2 (embodiment 4-2 and comparative example 4-2)) it is shown.

[table 2]

The permeability of antibacterial agent increases with the increase of ammonia density.In particular, being seeped when ammonia density is 5mg/L or more The increased trend of saturating rate is relatively large, and it is ideal for thinking to be pre-processed being reduced to ammonia density no more than 5mg/L.

In addition, for the type of the reverse osmosis membrane used in this system, it is clear that generated using neutral film LFC3 than using The anionically charged lower antibacterial agent permeability of film ES15.

It is tested using guide device shown in Fig. 10.For raw water (pending water), using by the way that sodium chloride is dissolved in The solution for obtaining 500mg/L solution in pure water, pH being then adjusted to 7.0 and is prepared.Use hydrochloric acid or sodium hydroxide as pH Regulator.Use by the LFC3 (embodiment 5 to 8) or ES15 (comparative example 5 and 6) of the manufacture of Dong electrician company as reverse osmosis The rates of water treatment of raw water is set as 25m by film³/ d, the temperature of feed water are set as 25 DEG C, and supply pressure is set as 0.75MPa.Stable hypobromous acid composition (composition 1) is used as antibacterial agent, and measures total cl concn as the dense of antibacterial agent Degree.

(embodiment 5 and 6, comparative example 5)

In embodiment 5 and comparative example 5-1, ammonia stripping apparatus is used as ammonia and reduces unit, and in embodiment 6 and comparative example 5-2, Without using ammonia stripping apparatus.Ammonium chloride is added in raw water (pending water), present in an amount at least sufficient to generate 200mg/L, 100mg/L or The ammonia density of 20mg/L.It carries out the steam stripped fluid temperature of ammonia and is set as 80 DEG C, pH is set as 10.At this point, measurement pending water and The antimicrobial agent concentration (total chlorine) of the ammonia density of the water of reverse osmosis membrane inlet and the water of reverse osmosis membrane inlet and processing water, Antibacterial agent permeability under the conditions of calculating every group.The results are shown in Table 3.

[table 3]

Compared with Example 6, in embodiment 5, it can reduce the permeability of antibacterial agent.In addition, working as the ammonia of pending water When concentration is 100mg/L or less, the ammonia density of reverse osmosis membrane inlet is not higher than 5mg/L, and antibacterial agent permeability is embodiment 6 0.069 times hereinafter, show particularly effectively reduce permeability.

(embodiment 7 and 8, comparative example 6)

In embodiment 7 and comparative example 6-1, oxidant is added as the method for reducing ammonia, and in embodiment 8 and comparative example 6-2 In, it is added without oxidant.The stable hypobromous acid composition (composition 1) being added at the reverse osmosis membrane of subsequent workshop section is added to make For oxidant.Ammonium chloride is added in raw water (pending water), the ammonia for generating 20mg/L, 15mg/L or 3mg/L is present in an amount at least sufficient to Concentration.It is indicated with total chlorine, the concentration of the oxidant of addition is set as 10mg/L, and pH is set as 7.2.The oxidative decomposition time sets It is set to 30 minutes.The results are shown in Table 4.

[table 4]

Compared with Example 8, in embodiment 7, it can reduce the permeability of antibacterial agent.In addition, working as the ammonia of pending water When concentration is 15mg/L or less, the ammonia density of reverse osmosis membrane inlet is not higher than 5mg/L, and antibacterial agent permeability is embodiment 8 0.056 times hereinafter, show particularly effectively reduce permeability.

The preparation simulation from the water (wherein removing remaining chlorine with active carbon) in the city phase mould original Sagamihara) is removed with active carbon Waste water, and the Ammonia In Aqueous Solution state nitrogen (NH by the way that chloride leach in water, to be present in an amount at least sufficient to preparation₄- N) concentration be 7.8mg- The amount of the aqueous solution of N/L (0.56mmol/L) by chloride leach in water, to prepare simulated wastewater.The simulation so prepared The pH of waste water is 7.2.By stable hypobromous acid composition (composition 1), (simulation that embodiment 9-1 to 9-5) is added to preparation is useless In water, present in an amount at least sufficient to acquisition with Cl₂Count 15mg/L (0.21mmol/L) (embodiment 9-1), with Cl₂Count 40mg/L (0.56mmol/ L) (embodiment 9-2), with Cl₂Count 61mg/L (0.87mmol/L) (embodiment 9-3), with Cl₂It counts 79mg/L (1.11mmol/L) (embodiment 9-4) or with Cl₂Count effective halogen concentration of 99mg/L (1.40mmol/L) (embodiment 9-5).Measure ammoniacal nitrogen (NH₄- N) concentration changes with time (after ten minutes with 30 minutes after), while being stirred and being tried with 500rpm using digital blender Test liquid.After 30 minutes, total cl concn of measurement test water.The results are shown in Table 5.

Total cl concn is indicated using the entry Water Test Kits manufactured by HACH company

Value (the mg/L, with Cl that DR/4000 is measured by total chlorine measurement method (DPD (diethyl p-phenylenediamine) method)₂Meter).It uses The coloring principle of indophenol blue absorption photometry from JIS K 0,102 42.2, using from Kyoritsu Chemical- PACKTEST (ammonium nitrogen, the model: WAK-NH of Check Lab company₄) measurement ammoniacal nitrogen (NH₄- N) concentration (mg/L, in terms of N).

In table 5, it is clear that the reduction effect of ammoniacal nitrogen with effective halogen molar concentration (stable hypobromous acid of addition The molar concentration of composition) ratio increase and increase, the ratio with total cl concn relative to processing front simulation waste water in Ammoniacal nitrogen (NH₄- N) molar concentration (0.56mmol/L) calculate.Particularly, it is clear that when in simulated wastewater with total cl concn phase For ammoniacal nitrogen (NH₄- N) molar concentration calculate effective halogen molar concentration (the stable hypobromous acid composition of addition Molar concentration) ratio be 1.6 (embodiment 9-3) or more when, ammoniacal nitrogen can be decomposed substantially completely.

[table 5]

Reference signs list

1,5: water treatment system

3: water treatment facilities

10,50: biological treating equipment

12,52: biological treatment sink

14,54: film process equipment

16,56: biological treatment system

18,58: film process sink

20: processing sink

22,34: reverse osmosis membrane processing equipment

24,60: the second reverse osmosis membrane processing equipment

26: reverse osmosis membrane treatment system

30: ammonia reduces equipment

32: the sink of ammonia reduction

36: pending water pipeline

38: the water pipeline of ammonia reduction

40: the hydraulic pipeline containing antibacterial agent

42: infiltration water pipeline

44: concentration water pipeline

46: antibacterial agent adds pipeline

Claims

1. a kind of method for treating water using reverse osmosis membrane, for using pending water of the reverse osmosis membrane processing containing ammonia, wherein

Antibacterial agent comprising bromine system oxidant or chlorine system oxidant and sulfamic acid compound is introduced into the pending water, and

The reverse osmosis membrane is neutral film or cationically charged film.

2. a kind of method for treating water using reverse osmosis membrane, for using pending water of the reverse osmosis membrane processing containing ammonia, wherein

Antibacterial agent comprising bromine and sulfamic acid compound is introduced into the pending water, and

The reverse osmosis membrane is neutral film or cationically charged film.

3. the method for treating water according to claim 1 or 2 using reverse osmosis membrane, wherein

Ammonium concentration in the pending water is at least 1mg/L.

4. the method for treating water according to any one of claim 1 to 3 using reverse osmosis membrane, wherein

The amount of ammonia in the pending water containing ammonia is reduced, the amount that the antibacterial agent is then introduced the ammonia is reduced Ammonia reduction water in.

5. the method for treating water according to claim 4 using reverse osmosis membrane, wherein

The ammonia density of the water of the ammonia reduction is not more than 5mg/L.

6. the method for treating water according to claim 4 or 5 using reverse osmosis membrane, wherein

The ammonia in the processing reduction pending water containing ammonia is stripped by ammonia.

7. the method for treating water according to claim 4 or 5 using reverse osmosis membrane, wherein

The ammonia in the pending water containing ammonia is reduced by using the ammonolysis craft processing of oxidant.

8. a kind of water treatment facilities using reverse osmosis membrane, for using pending water of the reverse osmosis membrane processing containing ammonia, wherein

The reverse osmosis membrane is neutral film or cationically charged film.

9. a kind of water treatment facilities using reverse osmosis membrane, for using pending water of the reverse osmosis membrane processing containing ammonia, wherein

The reverse osmosis membrane is neutral film or cationically charged film.

10. the water treatment facilities using reverse osmosis membrane according to claim 8 or claim 9, wherein

Ammonium concentration in the pending water is at least 1mg/L.

11. using the water treatment facilities of reverse osmosis membrane according to any one of claim 8 to 10,

Unit is reduced including ammonia, the amount of the ammonia in the pending water containing ammonia is reduced, wherein the antibacterial agent is introduced in The amount of the ammonia has been reduced by the ammonia in the water of ammonia reduction of unit reduction.

12. the water treatment facilities according to claim 11 using reverse osmosis membrane, wherein

13. the water treatment facilities according to claim 11 or 12 using reverse osmosis membrane, including list is reduced as the ammonia The ammonia of member strips processing equipment.

14. the water treatment facilities according to claim 11 or 12 using reverse osmosis membrane, including list is reduced as the ammonia The ammonolysis craft processing unit using oxidant of member.