CN107635652A - The method of modifying of reverse osmosis membrane, reverse osmosis membrane, the operation method of the processing method of boron water and seperation film - Google Patents

The method of modifying of reverse osmosis membrane, reverse osmosis membrane, the operation method of the processing method of boron water and seperation film Download PDF

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Publication number
CN107635652A
CN107635652A CN201680011498.9A CN201680011498A CN107635652A CN 107635652 A CN107635652 A CN 107635652A CN 201680011498 A CN201680011498 A CN 201680011498A CN 107635652 A CN107635652 A CN 107635652A
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China
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reverse osmosis
osmosis membrane
bromine
chlorine
sulfamic acid
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CN107635652B (en
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吉川浩
中村勇规
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PRGANO CORP
Organo Corp
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PRGANO CORP
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Priority claimed from JP2015034342A external-priority patent/JP6484460B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

Deterioration for suppressing reverse osmosis membrane is provided and improves the method for modifying of the reverse osmosis membrane through water quality of reverse osmosis membrane.A kind of method of modifying of reverse osmosis membrane, makes polyamide-based reverse osmosis membrane be contacted with following substances, and the material is：The reactant and sulfamic acid compound of bromine system oxidant or bromine compounds and chlorine system oxidant；Or the reactant of bromine system oxidant or bromine compounds with chlorine system oxidant, the reaction product with sulfamic acid compound.

Description

Method of modifying, reverse osmosis membrane, the processing method of boron water and the separation of reverse osmosis membrane The operation method of film
Technical field
The present invention relates to the method for modifying of polyamide-based reverse osmosis membrane；By the method for modifying and the reverse osmosis membrane of modification； Use the processing method of the boron water of the reverse osmosis membrane；And the operation method of seperation film.
Background technology
In the presence of the method for modifying through water quality etc. for being relatively used for improving reverse osmosis membrane (RO films).Wherein, have defined The free chlorine comprising bromine is set to be contacted with reverse osmosis membrane and improve the method for performance in time.
For example, the processing method of following reverse-osmosis membrane element is recorded in patent document 1：It has polyamide table in carrying In the membrane separation device of the reverse-osmosis membrane element of layer, after reverse-osmosis membrane element to be filled to the pressure vessel to membrane separation device, The free chlorine aqueous solution comprising bromine is set to be contacted with foregoing reverse-osmosis membrane element.
However, in the method for patent document 1, although can temporarily improve water quality, if long-term make dissociating comprising bromine Chlorine water solution water flowing, then reverse osmosis membrane deterioration, water quality reduce.
In addition, in the operation of polyamide-based seperation film such as reverse osmosis membrane (RO films), nano-filtration membrane (NF films), such as in order to When suppressing clayey and using various bromine system oxidants, bromine system oxidant can be flowed into seperation film sometimes.As bromine system oxidant, It can enumerate：The reactant of the oxidants such as hypochlorous acid and bromide ion, hypobromous acid etc..However, have known to these bromine system oxidants Following problem：The pH of processed water is more low, and the transmission water for more easily making seperation film reduces (with reference to non-patent literature 1).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2003-088730 publications
Non-patent literature
Non-patent literature 1：Desalination 280(2011)80-86
The content of the invention
Problems to be solved by the invention
It is an object of the present invention to provide for suppressing the deterioration of reverse osmosis membrane and improving the transmission water quality of reverse osmosis membrane Reverse osmosis membrane method of modifying；By the method for modifying and the reverse osmosis membrane of modification；And the boracic using the reverse osmosis membrane The processing method of water.
In addition, it is an object of the present invention to provide can also suppress to pass through even if making bromine system oxidant contact with seperation film The reduction of water, the operation method for making the seperation film that separation membrane device stably runs.
The solution used to solve the problem
The present invention is a kind of method of modifying of reverse osmosis membrane, and it makes polyamide-based reverse osmosis membrane be contacted with following substances, institute Stating material is：The reactant and sulfamic acid compound of bromine system oxidant or bromine compounds and chlorine system oxidant；Or bromine system The reactant of oxidant or bromine compounds with chlorine system oxidant, the reaction product with sulfamic acid compound.
The present invention is a kind of method of modifying of reverse osmosis membrane, and it makes the mixture and polyamides of bromine and sulfamic acid compound Amine system reverse osmosis membrane contacts；Or make the reaction product of bromine and sulfamic acid compound, contacted with polyamide-based reverse osmosis membrane.
In the method for modifying of foregoing reverse osmosis membrane, the reaction product of foregoing bromine and sulfamic acid compound is preferably through bag Include the method for following process and obtain：Bromine is added to comprising water, alkali and sulfamic acid chemical combination under non-active gas atmosphere In the mixed liquor of thing and reacted.
In the method for modifying of foregoing reverse osmosis membrane, aforementioned contact is carried out preferably in the range of pH4~6.5.
In the method for modifying of foregoing reverse osmosis membrane, foregoing polyamides system reverse osmosis membrane is carried out preferably by chlorine system oxidant Chlorine processing.
In the method for modifying of foregoing reverse osmosis membrane, aforementioned contact is preferably carried out in more than pH5.5.
The present invention is a kind of reverse osmosis membrane, and it is the method for modifying by foregoing reverse osmosis membrane and modification.
The present invention is a kind of processing method of boron water, and it is modified using the method for modifying by foregoing reverse osmosis membrane Reverse osmosis membrane to boron water carry out reverse osmosis membrane processing.
In addition, the present invention is a kind of operation method of seperation film, it makes bromine system oxidant, with being carried out using chlorine system oxidant The polyamide-based seperation film contact of chlorine processing.
In the operation method of aforementioned separation membrane, the pH of processed water when making the bromine system oxidant be contacted with aforementioned separation membrane is excellent Elect more than 5.5 as.
In the operation method of aforementioned separation membrane, it is preferred that foregoing bromine system oxidant contains bromine system oxidant or bromination is closed The reactant and sulfamic acid compound of thing and chlorine system oxidant；Or bromine system oxidant or bromine compounds aoxidize with chlorine system The reactant of agent, the reaction product with sulfamic acid compound.
In the operation method of aforementioned separation membrane, foregoing bromine system oxidant preferably comprises the mixing of bromine and sulfamic acid compound Thing or the reaction product for preferably comprising bromine and sulfamic acid compound.
In the operation method of aforementioned separation membrane, the reaction product of foregoing bromine and sulfamic acid compound preferably through including The method of following process and obtain：Bromine is added to comprising water, alkali and sulfamic acid compound under non-active gas atmosphere Mixed liquor in and reacted.
The effect of invention
In the present invention, can provide deterioration for suppressing reverse osmosis membrane and improve reverse osmosis membrane through the anti-of water quality The method of modifying of permeable membrane；By the method for modifying and the reverse osmosis membrane of modification；And the boron water using the reverse osmosis membrane Processing method.
In addition, in the operation method of the seperation film of the present invention, by implementing chlorine processing to seperation film in advance, even if making afterwards Bromine system oxidant contacts with seperation film, can also suppress the reduction through water, separation membrane device is stably run.
Embodiment
Hereinafter, illustrated for embodiments of the present invention.Present embodiment is only to implement of the invention one, this hair It is bright to be not limited to present embodiment.
<The method of modifying and reverse osmosis membrane of reverse osmosis membrane>
The method of modifying of the reverse osmosis membrane of embodiments of the present invention is following method：Make polyamide-based reverse osmosis membrane with Material contact is stated, the material is：The reactant and sulfamic acid of bromine system oxidant or bromine compounds and chlorine system oxidant Compound；Or the reactant of bromine system oxidant or bromine compounds with chlorine system oxidant, the reaction production with sulfamic acid compound Thing.In addition, the reverse osmosis membrane of embodiments of the present invention is and the reverse osmosis membrane of modification by the method for modifying of the reverse osmosis membrane. Wherein, " modification " of the reverse osmosis membrane in this specification is sometimes referred to as the improvement through water quality and the improvement through water quality (hinders The raising of gear rate), suppression (the i.e. drop of stop rate of the suppression for also sometimes referred to as passing through the reduction of water and the reduction for passing through water quality Low suppression).
The method of modifying of the reverse osmosis membrane of embodiments of the present invention is to make " bromine system oxidant " and " sulfamic acid chemical combination Thing " is present in water supply to polyamide-based reverse osmosis membrane etc. as modifying agent and makes what it was contacted with polyamide-based reverse osmosis membrane Method；Or " reactant of bromine compounds and chlorine system oxidant " and " sulfamic acid compound " is set to be present in polyamide-based As modifying agent and the method that makes it be contacted with polyamide-based reverse osmosis membrane in water supply of reverse osmosis membrane etc..Thus, in water supply etc. In, it is believed that generation hypobromous acid stabilized composition.
In addition, the method for modifying of the reverse osmosis membrane of embodiments of the present invention is made as " bromine system oxidant and amino sulphur The hypobromous acid stabilized composition of the reaction product of acid compound " is present in conduct in water supply to polyamide-based reverse osmosis membrane etc. Modifying agent and the method for making it be contacted with polyamide-based reverse osmosis membrane；Or make as " bromine compounds is anti-with chlorine system oxidant Answer thing, with the reaction product of sulfamic acid compound " hypobromous acid stabilized composition be present in polyamide-based reverse osmosis membrane Water supply etc. in as modifying agent and the method that makes it be contacted with polyamide-based reverse osmosis membrane.
Specifically, the method for modifying of the reverse osmosis membrane of embodiments of the present invention be make for example " bromine ", " bromine chloride ", " hypobromous acid " or " sodium bromide and hypochlorous reactant " and " sulfamic acid compound " are present in polyamide-based reverse osmosis membrane Water supply etc. in and the method that makes it be contacted with polyamide-based reverse osmosis membrane.
In addition, the method for modifying of the reverse osmosis membrane of embodiments of the present invention is made for example as " bromine and sulfamic acid The reaction product of compound ", " bromine chloride and the reaction product of sulfamic acid compound " or " sodium bromide and hypochlorous reactant, With the reaction product of sulfamic acid compound " hypobromous acid stabilized composition be present in water supply to polyamide-based reverse osmosis membrane In and the method that makes it be contacted with polyamide-based reverse osmosis membrane.It should be noted that as " bromine and sulfamic acid compound What kind of reaction product ", although not knowing compound generated, think to generate as hypobromous acid stabilisation compound " bromine Sulfamic acid (bromosulfamic acid) ".
By these methods, the deterioration of reverse osmosis membrane can be suppressed, improve the stop rate of reverse osmosis membrane, improvement passes through water Matter.Because hypobromous acid stabilized composition hardly deteriorates polyamide-based reverse osmosis membrane, therefore, even if temporarily not improving water Matter, but make the water comprising above-mentioned modifying agent that with polyamide-based reverse osmosis membrane water flowing and contacting, counter-infiltration can also be suppressed for a long time The deterioration of film, the reduction of the stop rate of reverse osmosis membrane can be suppressed, suppress the reduction of water quality.
In the method for modifying of the reverse osmosis membrane of present embodiment, for example, can be with the anti-of polyamide-based reverse osmosis membrane When permeable membrane device is run, by killer injecting pump etc. will " bromine system oxidant " or the reactant of chlorine system oxidant " bromine compounds and " and " sulfamic acid compound " is injected into the water supply to reverse osmosis membrane.Can also in water supply respectively add " bromine system oxidant " or " reactant of bromine compounds and chlorine system oxidant " and " sulfamic acid compound " or it can also add after stoste is mixed with each other Add in water supply.In addition, for example, it is also possible in addition " bromine system oxidant " or " reactant of bromine compounds and chlorine system oxidant " In the water of " sulfamic acid compound ", impregnate polyamide-based reverse osmosis membrane and make the time as defined in its contact.
In addition, for example, can by killer injecting pump etc. by " reaction product of bromine system oxidant and sulfamic acid compound " or " reactant of the bromine compounds with chlorine system oxidant, the reaction product with sulfamic acid compound " is injected into polyamide-based reverse osmosis In the water supply of permeable membrane.In addition, for example, it is also possible to addition " reaction product of bromine system oxidant and sulfamic acid compound " or In the water of " reactant of the bromine compounds with chlorine system oxidant, the reaction product with sulfamic acid compound ", dipping is polyamide-based Reverse osmosis membrane simultaneously makes the time as defined in its contact.
For the modification based on modifying agent, for example, can be transported in the reverse osmosis membrane apparatus with polyamide-based reverse osmosis membrane During row, above-mentioned modifying agent is continually or intermittently added in the water supply to reverse osmosis membrane, can also be in the resistance of reverse osmosis membrane When gear rate reduces, above-mentioned modifying agent is continually or intermittently added in the water supply to reverse osmosis membrane or by reverse osmosis membrane It is impregnated into the water comprising modifying agent.
Contact of the modifying agent to reverse osmosis membrane can be carried out in atmospheric conditions, under pressurized conditions or under reduced pressure, from It can also be modified even if reverse osmosis membrane apparatus is not stopped, the viewpoint that can reliably carry out the modification of reverse osmosis membrane etc. goes out Hair, is preferably carried out under an increased pressure.Contact of the modifying agent to reverse osmosis membrane is for example preferably in 0.1MPa~8.0MPa scope Pressurized conditions under carry out.
Contact of the modifying agent to reverse osmosis membrane can for example be carried out under the temperature conditionss of 5 DEG C~35 DEG C of scope.
The equivalent of " sulfamic acid compound " is relative to " bromine system oxidant " or " reaction of bromine compounds and chlorine system oxidant The ratio between equivalent of thing " is preferably more than 1, more preferably more than 1 and less than 2 scope.The equivalent phase of " sulfamic acid compound " When being less than 1 for the ratio between equivalent of " bromine system oxidant " or " reactant of bromine compounds and chlorine system oxidant ", it is possible to make anti- Permeable membrane deteriorates, during more than 2, manufacturing cost increase sometimes.
The effective halogen concentration contacted with reverse osmosis membrane is in terms of effective chlorine density conversion, preferably 0.01~100mg/L.It is low When 0.01mg/L, sufficient modified effect can not be obtained sometimes, during higher than 100mg/L, it is possible to cause the bad of reverse osmosis membrane The corrosion of change, pipe arrangement etc..
As bromine system oxidant, can enumerate：Bromine (liquid bromine), bromine chloride, bromic acid, bromate, hypobromous acid etc..
Among these, using bromine " bromine and sulfamic acid compound (mixture of bromine and sulfamic acid compound) " or The preparation of the preparation of " reaction product of bromine and sulfamic acid compound " and " hypochlorous acid with bromine compounds and sulfamic acid " and Compared with the preparation of " bromine chloride is with sulfamic acid " etc., chloride ion is few, and polyamide-based reverse osmosis membrane will not be made further to deteriorate, And cause the possibility of the corrosion of the metal material of pipe arrangement etc. low, therefore it is preferred that.
That is, the method for modifying of the reverse osmosis membrane of embodiments of the present invention preferably makes bromine and sulfamic acid compound, with gathering Acid amides system reverse osmosis membrane contacts (mixture of bromine and sulfamic acid compound is contacted with polyamide-based reverse osmosis membrane) or made The reaction product of bromine and sulfamic acid compound, contact with polyamide-based reverse osmosis membrane.
As bromine compounds, can enumerate：Sodium bromide, KBr, lithium bromide, ammonium bromide and hydrobromic acid etc..Among these, from From the viewpoint of preparation cost etc., preferred sodium bromide.
As chlorine system oxidant, such as can enumerate：Chlorine, chlorine dioxide, hypochlorous acid or its salt, chlorous acid or its salt, chlorine Acid or its salt, perchloric acid or its salt, chlorinated isocyanuric acid or its salt etc..Among these, as salt, such as it can enumerate：Hypochlorous acid The hypochlorous acid such as the alkali metal hypochlorites such as sodium, postassium hypochlorite, calcium hypochlorite, barium hypochlorite alkali salt, sodium chlorite, sub- chlorine Other metal chlorites, the chlorine such as the chlorous acid such as the alkali metal chlorites such as sour potassium, barium chlorite alkali salt, chlorous acid nickel Chloric acid alkali salts such as the chloric acid such as sour ammonium, sodium chlorate, potassium chlorate alkali metal salt, calcium chlorate, barium chlorate etc..These chlorine systems aoxidize Agent can be used alone, and can also combine two or more use.As chlorine system oxidant, from the viewpoint of treatability etc., It is preferred that use sodium hypochlorite.
Sulfamic acid compound is the compound shown in below general formula (1).
R2NSO3H (1)
(in formula, R independently is the alkyl of hydrogen atom or carbon number 1~8.)
As sulfamic acid compound, such as except 2 R bases are the sulfamic acid (amidosulfuric of hydrogen atom Acid beyond), can also enumerate：N- methylsulfamic acids, N- ethylaminos sulfonic acid, N- propylcarbamics sulfonic acid, N- isopropylaminos One of 2 R bases such as sulfonic acid, N- butylamino sulfonic acid are hydrogen atom, the amino sulphur for the alkyl that another one is carbon number 1~8 Acid compound, N, N- dimethylaminos sulfonic acid, N, N- diethylaminos sulfonic acid, N, N- dipropylaminos sulfonic acid, N, N- dibutyl 2 R bases such as sulfamic acid, N- methyl-N-ethylaminos sulfonic acid, N- methyl-N-propylamino sulfonic acid are carbon number 1~8 The sulfamic acid compound of alkyl, one of 2 R bases such as N- benzenesulfamics be hydrogen atom, another one be carbon number 6 The sulfamic acid compound of~10 aryl or their salt etc..As sulfamate, such as can enumerate：Sodium salt, sylvite etc. Other metals such as the alkali salts such as alkali metal salt, calcium salt, strontium salt, barium salt, manganese salt, mantoquita, zinc salt, molysite, cobalt salt, nickel salt Salt, ammonium salt and guanidinesalt etc..Sulfamic acid compound and these salt can be used alone, and can also combine two or more use. As sulfamic acid compound, from the viewpoint of carrying capacity of environment etc., preferably using sulfamic acid (amidosulfuric acid)。
In the method for modifying of the reverse osmosis membrane of present embodiment, there can also be alkali.As alkali, can enumerate：Sodium hydroxide, Alkali hydroxides such as potassium hydroxide etc..From low temperature when product stability etc. from the viewpoint of, can be applied in combination sodium hydroxide and Potassium hydroxide.In addition, alkali can not be solid-state, but use in form of an aqueous solutions.
What the method for modifying of the reverse osmosis membrane of present embodiment was used as reverse osmosis membrane is the polyamides of main flow at present Amine system polymeric membrane.Polyamide-based polymeric membrane is relatively low for the patience of oxidant, if making free chlorine etc. and polyamide-based high score Sub- film continuously contacts, then can cause significantly reducing for film properties.However, the method for modifying of the reverse osmosis membrane in present embodiment In, so significant film properties are hardly produced in polyamide polymeric membrane to be reduced.
In the method for modifying of the reverse osmosis membrane of present embodiment, contact of the above-mentioned modifying agent to polyamide-based reverse osmosis membrane is excellent PH is selected in more than 3 and less than 8 in the range of carry out, carried out more preferably in the range of pH4~6.5.If above-mentioned modifying agent is to poly- The contact of acid amides system reverse osmosis membrane is carried out in below pH3, then long-term in contact of the above-mentioned modifying agent to polyamide-based reverse osmosis membrane During progress, the deterioration of reverse osmosis membrane, stop rate is caused to reduce sometimes, if being carried out more than 8, modified effect does not fill sometimes Point.Particularly, if being contacted in the range of pH4~6.5, the deterioration of reverse osmosis membrane can be suppressed and fully improved anti- The transmission water quality of permeable membrane.In order that the contact of modifying agent is carried out in the range of above-mentioned pH, such as can be by reverse osmosis membrane The pH of water supply is maintained within the above range or can be maintained the pH of the maceration extract of reverse osmosis membrane within the above range.
In the reverse osmosis membrane apparatus with polyamide-based reverse osmosis membrane, in more than the pH5.5 of the water supply to reverse osmosis membrane When producing incrustation scale, can also combine dispersant with bromine system oxidant or hypobromous acid stabilized composition to suppress incrustation scale makes With.As dispersant, such as can enumerate：Polyacrylic acid, poly, phosphonic acids etc..Dispersant to the addition of water supply for example with Concentration in RO condensed waters is calculated as 0.1~1000mg/L scope.
In addition, in order to suppress the generation of incrustation scale without using dispersant, such as can enumerate：Reverse osmosis membrane apparatus can be adjusted The service condition such as the rate of recovery so that the silica concentration in RO condensed waters is below solubility, and make as calcium incrustation scale The bright lattice rel index (Langelier's index) of index is less than 0.
It is preferably to be carried out using chlorine system oxidant as reverse osmosis membrane in the method for modifying of the reverse osmosis membrane of present embodiment Chlorine processing.That is, by bromine system oxidant and sulfamic acid compound or by the reactant of bromine compounds and chlorine system oxidant, With sulfamic acid compound as modifying agent, make it with having carried out the polyamide-based reverse osmosis membrane of chlorine processing using chlorine system oxidant Contact；Or by the reaction product of bromine system oxidant and sulfamic acid compound or by the anti-of bromine compounds and chlorine system oxidant The reaction product of thing and sulfamic acid compound is answered to make it with having carried out chlorine processing using chlorine system oxidant as modifying agent Polyamide-based reverse osmosis membrane contact.
The method of modifying of the reverse osmosis membrane of embodiments of the present invention is chlorine system oxidant is present in polyamide-based anti- In the water supply of permeable membrane or rinse water etc. and after contacting it, make modifying agent be present in water supply to polyamide-based reverse osmosis membrane or In rinse water etc. and make its contact method.It can be present in modifying agent to having carried out chlorine processing using chlorine system oxidant to gather In water supply of acid amides system reverse osmosis membrane etc. and make its contact.
By these methods, chlorine system oxidant is set fully to be contacted in advance with polyamide-based seperation film to carry out chlorine processing, And then modifying agent is contacted with polyamide-based seperation film, it is possible thereby to suppress the deterioration of seperation film, and improvement is through water and thoroughly Cross water quality.
The contact of chlorine system oxidant and modifying agent to reverse osmosis membrane can in atmospheric conditions, under pressurized conditions or depressurize Under the conditions of carry out, from the viewpoint of modification that can reliably carry out reverse osmosis membrane etc., preferably carry out under an increased pressure.Chlorine It is that the contact of oxidant and modifying agent to reverse osmosis membrane is for example preferably entered under the pressurized conditions of 0.1MPa~10MPa scope OK.
The contact of chlorine system oxidant and modifying agent to reverse osmosis membrane for example can be in the temperature of 0 DEG C~100 DEG C of scope Under the conditions of carry out.
Contact of the chlorine system oxidant to reverse osmosis membrane is excellent in terms of the value of effective chlorine density [mg-Cl/L] × time [hour] Elect 0.1~1000mg-Cl/L hours as.If being less than 0.1mg-Cl/L hours, can not obtain at the sufficient chlorine to film Effect is managed, if more than 1000mg-Cl/L hours, deteriorates film sometimes.
The pH of processed water during the contact of chlorine system oxidant is preferably 4~13 scope, more preferably 6~12 scope. When pH is less than 4, reduced sometimes through water, when pH is more than 13, reverse osmosis membrane deteriorates sometimes.
Modifying agent and the pH that the processed water when reverse osmosis membrane of chlorine processing contacts has been carried out using chlorine system oxidant are preferred For the scope of more than 5.5, more preferably more than 6.0, more preferably pH6.5~10.If modifying agent using chlorine system with being aoxidized The contact that agent has carried out the polyamide-based reverse osmosis membrane of chlorine processing is carried out in pH less than 5.5 times, then when pH is less than 5.5, even if in advance Chlorine processing first is implemented to reverse osmosis membrane, can also be influenceed sometimes by passing through water as caused by modifying agent and reducing.PH is more than 10 When, excessively increase through water sometimes.
In the method for modifying of the seperation film of present embodiment, modifying agent is " hypobromous acid stabilized composition "." hypobromous acid is steady Surely composition is changed " harmful effect that brings of the stop rate to reverse osmosis membrane is small, even if continuous make an addition to the counter-infiltration handled through chlorine In film, modified effect is also high.
The method of modifying of the reverse osmosis membrane of embodiments of the present invention is chlorine system oxidant is present in polyamide Be in water supply of reverse osmosis membrane etc. and make its contact after, " bromine system oxidant " and " sulfamic acid compound " is present in polyamides As modifying agent and the method that makes it be contacted with polyamide-based reverse osmosis membrane in water supply of amine system reverse osmosis membrane etc.；Or make " bromine Compound and the reactant of chlorine system oxidant " and " sulfamic acid compound " are present in water supply to polyamide-based reverse osmosis membrane etc. It is middle as modifying agent and the method that makes it be contacted with polyamide-based reverse osmosis membrane.Thus, in water supply etc., it is believed that generation time bromine Sour stabilized composition.
In addition, the method for modifying of the reverse osmosis membrane of embodiments of the present invention is chlorine system oxidant is present in poly- In water supply of acid amides system reverse osmosis membrane etc. and make its contact after, make as " the reaction of bromine system oxidant and sulfamic acid compound The hypobromous acid stabilized composition of product " be present in water supply to polyamide-based reverse osmosis membrane etc. as modifying agent and make its with The method or make as " the reactant and sulfamic acid of bromine compounds and chlorine system oxidant that polyamide-based reverse osmosis membrane contacts The hypobromous acid stabilized composition of the reaction product of compound ", which is present in be used as in water supply to polyamide-based reverse osmosis membrane etc., to be changed Property agent and the method for making it be contacted with polyamide-based reverse osmosis membrane.
Specifically, the method for modifying of the reverse osmosis membrane of embodiments of the present invention is for example to be present in chlorine system oxidant In water supply to polyamide-based reverse osmosis membrane etc. and after contacting it, make " bromine ", " bromine chloride " or " sodium bromide with it is hypochlorous anti- Answer thing " and " sulfamic acid compound " be present in water supply to polyamide-based reverse osmosis membrane etc. as modifying agent and make its with it is poly- The method of acid amides system reverse osmosis membrane contact.
In addition, the method for modifying of the reverse osmosis membrane of embodiments of the present invention is chlorine system oxidant is present in poly- In water supply of acid amides system reverse osmosis membrane etc. and make its contact after, make as " reaction product of bromine and sulfamic acid compound ", " chlorine Change the reaction product of bromine and sulfamic acid compound " or it is " sodium bromide and hypochlorous reactant, anti-with sulfamic acid compound Answer product " hypobromous acid stabilized composition be present in water supply to polyamide-based reverse osmosis membrane etc. as modifying agent and making it The method contacted with polyamide-based reverse osmosis membrane.
In the method for modifying of the reverse osmosis membrane of present embodiment, for example, it is also possible to polyamide-based reverse osmosis membrane During the operation of reverse osmosis membrane apparatus, chlorine system oxidant is injected into water supply to polyamide-based reverse osmosis membrane etc. by killer injecting pump etc. In after, by killer injecting pump etc. by " bromine system oxidant " or the reactant of chlorine system oxidant " bromine compounds with " and " sulfamic acid Compound " injects as modifying agent." bromine system oxidant " or " bromine compounds and chlorine system oxidant can be added respectively in water supply etc. Reactant " and " sulfamic acid compound "；Or it can also be added to after stoste is mixed with each other in water supply etc..In addition, example Such as, it can also impregnate polyamide-based reverse osmosis membrane in the water added with chlorine system oxidant or modifying agent and make its contact regulation Time.
In addition, for example, it is also possible to chlorine system oxidant is injected into the confession to polyamide-based reverse osmosis membrane by killer injecting pump etc. After in water etc., by killer injecting pump etc. by " reaction product of bromine system oxidant and sulfamic acid compound " or " bromine compounds and chlorine It is the reactant of oxidant, the reaction product with sulfamic acid compound " injected as modifying agent.In addition, for example, it is also possible to In water added with chlorine system oxidant or modifying agent, impregnate polyamide-based reverse osmosis membrane and make the time as defined in contact.
Modification based on chlorine system oxidant or modifying agent for example can be in the reverse osmosis membrane with polyamide-based reverse osmosis membrane During plant running, chlorine system oxidant or above-mentioned modifying agent are continually or intermittently added in water supply to reverse osmosis membrane etc..
It is as described above for bromine system oxidant, bromine compounds, chlorine system oxidant and sulfamic acid compound.
In bromine system oxidant, " bromine and the sulfamic acid compound " of bromine or the " reaction of bromine and sulfamic acid compound are used Preparation of preparation and " bromine chloride and sulfamic acid " of the preparation of product " and " hypochlorous acid and bromine compounds and sulfamic acid " etc. Compare, chloride ion is few, and polyamide-based reverse osmosis membrane will not be made further to deteriorate, and it has to RO through films such as water through water Imitate halogen amount of leakage it is less, therefore, as reverse osmosis membrane with clayey inhibitor more preferably.In addition, cause the metal of pipe arrangement etc. The possibility of the corrosion of material is low, therefore more preferably.
That is, the method for modifying of the reverse osmosis membrane of embodiments of the present invention preferably exists chlorine system oxidant and makes it with gathering After the reverse osmosis membrane contact of acid amides system, make bromine and sulfamic acid compound as modifying agent and it is connect with polyamide-based reverse osmosis membrane Touch or make the reaction product of bromine and sulfamic acid compound as modifying agent and it is contacted with polyamide-based reverse osmosis membrane.
As the method for modifying with the reverse osmosis membrane by present embodiment and the polyamide-based reverse osmosis membrane of modification The purposes of reverse osmosis membrane apparatus, such as can enumerate：Desalinization, Sewage treatment etc..Particularly preferred use passes through present embodiment The method of modifying of reverse osmosis membrane and the polyamide-based reverse osmosis membrane of modification to boron water carry out reverse osmosis membrane processing.By using The method of modifying of the reverse osmosis membrane of present embodiment is modified to polyamide-based reverse osmosis membrane, and the stop rate of boron significantly improves.
<The operation method of seperation film>
The operation method of the seperation film of embodiments of the present invention is bromine system oxidant, with being carried out using chlorine system oxidant The method of the polyamide-based seperation film contact of chlorine processing.
The operation method of the seperation film of embodiments of the present invention is chlorine system oxidant is present in polyamide-based separation In the water supply of film or rinse water etc. and after contacting it, bromine system oxidant is set to be present in water supply to polyamide-based seperation film or clear In wash water etc. and make its contact method.Bromine system oxidant can also be made to be present in having carried out chlorine processing using chlorine system oxidant The water supply of polyamide-based seperation film etc. in and make its contact.In addition, the operation method on the seperation film of present embodiment can With using the seperation film for contacting chlorine system oxidant in advance, and make the oxidant contact of bromine system at the scene, chlorine can also be made at the scene It is to be contacted with bromine system oxidant after oxidant contacts with seperation film.
By these methods, polyamide-based seperation film is fully contacted with chlorine system oxidant in advance and carry out chlorine processing, by This contacts the reduction that can also suppress through water even if bromine system oxidant with seperation film, separation membrane device is stably run. By making chlorine system oxidant be contacted in advance with seperation film, chlorine can be imported in separation membrane material.In the film of chlorine is imported with, by In being not easy to import bromine, thus it is speculated that：It is not easily susceptible to the influence for generally causing the bromine system oxidant reduced through water.
The contact of chlorine system oxidant and bromine system oxidant to seperation film can in atmospheric conditions, under pressurized conditions or subtract Carried out under the conditions of pressure, from can reliably carry out seperation film chlorine handle, manufacture handle water while carrying out contact processing Deng from the viewpoint of, preferably carry out under an increased pressure.The contact of chlorine system oxidant and bromine system oxidant to seperation film is for example It is preferred that carried out under the pressurized conditions of 0.1MPa~10MPa scope.
The contact of chlorine system oxidant and bromine system oxidant to seperation film for example can be in the temperature of 0 DEG C~100 DEG C of scope Carried out under the conditions of degree.
Contact of the chlorine system oxidant to seperation film is in terms of the value of effective chlorine density [mg-Cl/L] × time [hour], preferably For 0.1~1000mg-Cl/L hours.If being less than 0.1mg-Cl/L hours, it can not obtain and effect is handled to the abundant chlorine of film Fruit, if more than 1000mg-Cl/L hours, deteriorate film sometimes.
Effective halogen concentration based on the bromine system oxidant contacted with seperation film is in terms of effective chlorine density conversion, preferably 0.01~100mg/L.If being less than 0.01mg/L, sufficient clayey inhibition etc. can not be obtained sometimes, if being more than 100mg/ L, it is likely that cause the corrosion of deterioration, the pipe arrangement of seperation film etc..
The pH of processed water during the contact of chlorine system oxidant is preferably 4~13 scope, more preferably 6~12 scope. When pH is less than 4, reduced sometimes through water, when pH is more than 13, seperation film deteriorates sometimes.
The pH of processed water during the oxidant contact of bromine system is preferably more than 5.5, and more preferably more than 6.0, it is further excellent Elect the scope of pH6.5~10 as.When pH is less than 5.5, even if implementing chlorine processing to seperation film in advance, also sometimes by by bromine It is the influence that oxidant causes to reduce through water.When pH is more than 10, can excessively increase through water sometimes.
In the operation method of the seperation film of present embodiment, as bromine system oxidant, have no particular limits.As bromine system Oxidant, it can enumerate：" hypobromite " etc., " reaction product of chlorine system oxidant and bromide ion ", " hypobromous acid stabilisation group Compound " etc., but be preferably " hypobromous acid stabilized composition ".The stop rate of " hypobromous acid stabilized composition " to seperation film is brought Harmful effect it is small, and even if continuous be added in the seperation film handled through chlorine, can also run steadily in the long term.
For example, after making chlorine system oxidant be present in water supply to polyamide-based seperation film etc. and contacting it, make " bromine system Oxidant " and " sulfamic acid compound " exist and it is contacted with polyamide-based seperation film；Or make " bromine compounds and chlorine Be the reactant of oxidant " and " sulfamic acid compound " exist and it is contacted with polyamide-based seperation film.Thus, supplying water In, it is believed that generation hypobromous acid stabilized composition.
In addition, for example, chlorine system oxidant can be made to be present in water supply to polyamide-based seperation film etc. and make its contact Afterwards, make to exist as the hypobromous acid stabilized composition of " reaction product of bromine system oxidant and sulfamic acid compound " and make it Contacted with polyamide-based seperation film；Or make as " the reactant and sulfamic acid chemical combination of bromine compounds and chlorine system oxidant The hypobromous acid stabilized composition of the reaction product of thing " exists and it is contacted with polyamide-based seperation film.
Specifically, the operation method of the seperation film of embodiments of the present invention is chlorine system oxidant is present in pair In water supply of polyamide-based seperation film etc. and after contacting it, make " bromine ", " bromine chloride " or " sodium bromide and hypochlorous reaction There is and make the method that it is contacted with polyamide-based seperation film in thing " and " sulfamic acid compound ".
In addition, the operation method of the seperation film of embodiments of the present invention is chlorine system oxidant is present in polyamides In water supply of amine system seperation film etc. and make its contact after, make as " reaction product of bromine and sulfamic acid compound ", " bromine chloride With the reaction product of sulfamic acid compound " or " reaction production of the sodium bromide with hypochlorous reactant, with sulfamic acid compound There is and make the method that it is contacted with polyamide-based seperation film in the hypobromous acid stabilized composition of thing ".
In the operation method of the seperation film of present embodiment, for example, can be in the seperation film with polyamide-based seperation film During plant running, after by killer injecting pump etc., chlorine system oxidant is injected into water supply to seperation film etc., noted by killer injecting pump etc. Enter " bromine system oxidant " or " reactant of bromine compounds and chlorine system oxidant " and " sulfamic acid compound ".It can also supply water It is middle add respectively " bromine system oxidant " or the reactant of chlorine system oxidant " bromine compounds with " and " sulfamic acid compound " or It can also be added to after stoste is mixed with each other in water supply.
In addition, for example, it is also possible to chlorine system oxidant is injected into the water supply to polyamide-based seperation film by killer injecting pump etc. After in, " reaction product of bromine system oxidant and sulfamic acid compound " or " bromine compounds and chlorine are injected by killer injecting pump etc. It is the reactant of oxidant, the reaction product with sulfamic acid compound ".
The equivalent of " sulfamic acid compound " is relative to " bromine system oxidant " or " reaction of bromine compounds and chlorine system oxidant The ratio between equivalent of thing " is preferably more than 1, more preferably more than 1 and less than 2 scope.The equivalent phase of " sulfamic acid compound " When the ratio between equivalent for " bromine system oxidant " or the reactant of chlorine system oxidant " bromine compounds with " is less than 1, it is possible to make point Deteriorated from film, during more than 2, manufacturing cost increase sometimes.
It is as described above for bromine system oxidant, bromine compounds, chlorine system oxidant and sulfamic acid compound.
In bromine system oxidant, " bromine and the sulfamic acid compound " of bromine or the " reaction of bromine and sulfamic acid compound are used Preparation of preparation and " bromine chloride and sulfamic acid " of the preparation of product " and " hypochlorous acid and bromine compounds and sulfamic acid " etc. Compare, chloride ion is few, and polyamide-based seperation film will not be made further to deteriorate, and it is to RO through films such as water through the effective of water The amount of leakage of halogen is less, therefore, as seperation film with clayey inhibitor more preferably.In addition, cause the metal material of pipe arrangement etc. Corrosion possibility it is low, therefore more preferably.
That is, the operation method of the seperation film of embodiments of the present invention preferably makes chlorine system oxidant be present in polyamide-based In water supply of seperation film etc. and make its contact after, bromine and sulfamic acid compound is contacted or is made with polyamide-based seperation film The reaction product of bromine and sulfamic acid compound contacts with polyamide-based seperation film.
In the operation method of the seperation film of present embodiment, bromine system oxidant can be further set to exist together with alkali.Make For alkali, can enumerate：Alkali hydroxides such as sodium hydroxide, potassium hydroxide etc..From low temperature when product stability etc. from the viewpoint of, can So that sodium hydroxide and potassium hydroxide is applied in combination.In addition, alkali can not be solid-state, but use in form of an aqueous solutions.
As seperation film, can enumerate：It is reverse osmosis membrane (RO films), nano-filtration membrane (NF films), secondary filter film (MF films), super Filter membrane (UF films) etc..Among these, particularly reverse osmosis membrane (RO films) goes for the seperation film of embodiments of the present invention Operation method.Furthermore it is possible to the operation method of the seperation film of embodiments of the present invention is suitable for as reverse osmosis membrane At present be main flow polyamide-based polymeric membrane.If polyamide-based polymeric membrane contacts with bromine system oxidant, easily cause Through the reduction of water, such as in the presence of bromide ion, if addition free chlorine etc., can generate hypobromite in water, If it is temporarily contacted with polyamide-based polymeric membrane, cause significantly reducing through water.However, point of present embodiment From in the operation method of film, polyamide-based polymeric membrane hardly produces so significant film properties and reduced.
In reverse osmosis membrane apparatus with polyamide-based reverse osmosis membrane, the water supply to reverse osmosis membrane is produced with more than pH5.5 During incrustation scale, dispersant and bromine system oxidant or hypobromous acid stabilized composition can also be applied in combination to suppress incrustation scale.Make For dispersant, such as can enumerate：Polyacrylic acid, poly, phosphonic acids etc..Dispersant is for example concentrated to the addition of water supply with RO Concentration in water is calculated as 0.1~1000mg/L scope.
In addition, in order to suppress the generation of incrustation scale without using dispersant, such as can enumerate：Reverse osmosis membrane apparatus can be adjusted The service condition such as the rate of recovery so that the silica concentration in RO condensed waters is below solubility, and make as calcium incrustation scale The bright lattice rel index of index is less than 0.
<Modifier composite>
The modifier combination used in the method for modifying of the reverse osmosis membrane of present embodiment and the operation method of seperation film Thing contains " bromine system oxidant " or " reactant of bromine compounds and chlorine system oxidant " and " sulfamic acid compound ", can also enter One step contains alkali.
In addition, the modifier composite of present embodiment contains " the reaction production of bromine system oxidant and sulfamic acid compound Thing " or " reactant of the bromine compounds with chlorine system oxidant, the reaction product with sulfamic acid compound ", can also further contain There is alkali.
It is as described above for bromine system oxidant, bromine compounds, chlorine system oxidant and sulfamic acid compound.
As the modifier composite of present embodiment, in order to which polyamide-based reverse osmosis membrane etc. will not be made more to deteriorate, and it is right RO is less through the amount of leakage of effective halogen of water, preferably comprises bromine and sulfamic acid compound (containing bromine and sulfamic acid The mixture of compound), such as the mixture containing bromine, sulfamic acid compound, alkali and water or bromine and sulfamic acid compound Reaction product, such as the mixture of the reaction product of bromine, sulfamic acid compound, alkali and water.
The modifier composite of present embodiment has polyamides compared with the modifying agent such as hypochlorous acid, free chlorine comprising bromine The modified effect of amine system reverse osmosis membrane etc., and hardly cause such as hypochlorous acid, notable film comprising the free chlorine of bromine Deterioration.The influence that common concentration deteriorates to film can substantially be ignored.Therefore, most suitable as polyamide-based counter-infiltration The modifying agent of film etc..
The differences such as the modifier composite of present embodiment is with hypochlorous acid, the free chlorine comprising bromine, hardly through anti- Permeable membrane etc., therefore influence hardly is brought on processing water water quality.Furthermore it is possible to determined at the scene in the same manner as hypochlorous acid etc. Concentration, therefore can be with more accurate management concentration.
The pH of composition is for example more than 13.0, and more preferably more than 13.2.If the pH of composition is less than 13.0, sometimes Effective halogen in composition becomes unstable.
Bromic acid concentration in modifier composite is preferably less than 5mg/kg.If the bromic acid concentration in modifier composite is More than 5mg/kg, then RO uprises through the concentration of the bromic acid ion of water etc. sometimes.
<The manufacture method of modifier composite>
The modifier composite of present embodiment can by the way that bromine system oxidant is mixed with sulfamic acid compound or Bromine compounds is mixed with the reactant and sulfamic acid compound of chlorine system oxidant and obtained, can also further mixed base.
As the modifier composite containing bromine and sulfamic acid compound or containing bromine and sulfamic acid compound The manufacture method of the modifier composite of reaction product, preferably include following process：Bromine is added under non-active gas atmosphere The process reacted into the mixed liquor comprising water, alkali and sulfamic acid compound or under non-active gas atmosphere Process bromine being added in the mixed liquor comprising water, alkali and sulfamic acid compound.By adding under non-active gas atmosphere Calais is reacted or added under non-active gas atmosphere, can make the bromic acid ion concentration step-down in composition, or make RO is through the bromic acid ion concentration step-down in water etc..
Do not limited as the non-active gas used, but from manufacture etc. aspect, preferably in nitrogen and argon gas It is at least one kind of, the aspect particularly from manufacturing cost etc., preferably nitrogen.
The oxygen concentration in reactor when adding bromine is preferably less than 6%, and more preferably less than 4%, more preferably Less than 2%, particularly preferably less than 1%.If the oxygen concentration in reactor during bromine reaction is more than 6%, reaction system sometimes The growing amount increase of interior bromic acid.
The adding rate of bromine is relative to the overall amount of composition, preferably below 25 weight %, more preferably more than 1 weight % And 20 below weight %.The adding rate of bromine is relative to the overall amount of composition, if more than 25 weight %, sometimes in reaction system Bromic acid growing amount increase.If being less than 1 weight %, modified effect is deteriorated sometimes.
Reaction temperature when adding bromine is preferably controlled in more than 0 DEG C and less than 25 DEG C of scope, but from manufacturing cost etc. Aspect set out, more preferably control more than 0 DEG C and in less than 15 DEG C of scope.If reaction temperature when adding bromine is more than 25 DEG C, then the growing amount increase of the bromic acid in reaction system sometimes, if less than 0 DEG C, freezes sometimes.
Embodiment
Hereinafter, enumerating embodiment and comparative example, more specifically the present invention is described in detail, but the present invention does not limit In following examples.
[preparation of hypobromous acid stabilized composition 1]
In a nitrogen atmosphere by liquid bromine：16.9 weight % (wt%), sulfamic acid：10.7 weight %, sodium hydroxide： 12.9 weight %, potassium hydroxide：3.94 weight %, water：Surplus is mixed, and prepares hypobromous acid stabilized composition 1.Hypobromous acid The pH of stabilized composition 1 is 14, and effective halogen concentration (effective chlorine converted score) is 7.5 weight %.Hypobromous acid stabilisation group The detailed preparation method of compound 1 is as described below.
It is continuously injected into use and controls the flow of nitrogen make it that the oxygen in reaction vessel is dense with mass flow controller Spend in the 4 mouthfuls of flasks for the 2L for enclosing nitrogen for maintaining 1%, add 1436g water, 361g sodium hydroxide is mixed, Be subsequently added into 300g sulfamic acid mixed after, while maintain cooling cause reaction solution temperature be 0~15 DEG C, on one side plus Enter 473g liquid bromine, and then add 48% potassium hydroxide solution 230g, obtain relative to the overall amount of composition with weight ratio The ratio for being calculated as the equivalent of sulfamic acid 10.7%, the equivalent of bromine 16.9% and sulfamic acid and bromine is 1.04 objective composition. The pH of the solution of generation is determined by glass electrode method, is as a result 14.The bromine containing ratio of the solution of generation is by using KI Bromine is converted into after iodine and determined using the method for sodium thiosulfate progress redox titration, is as a result 16.9%, is theoretical The 100.0% of containing ratio (16.9%).In addition, the oxygen concentration in reaction vessel during bromine reaction uses JIKCO Ltd.'s " Oxygen Monitor JKO-02LJDII " are determined.It should be noted that bromic acid concentration is less than 5mg/kg.
<Embodiment 1, comparative example 1,2>
Hypobromous acid stabilized composition 1 (embodiment 1), hypochlorous acid (comparative example 1), the hypobromous acid of above-mentioned preparation are used respectively (sodium bromide and hypochlorous mixture) (comparative example 2) is used as modifying agent, and carrying out polyamide-based macromolecule reverse osmosis membrane, (day is eastern electric Work Co. Ltd. system " ES20 ", φ 75mm Flat Membrane, be reduced to NaCl stops rate=95%) modification.Modification be with In the reverse osmosis membrane apparatus of the reverse osmosis membrane, with operating pressure 0.75MPa, the water for the above-mentioned modifying agent for making to the addition of 1ppm is in pH Water flowing 24 hours is implemented at=5,25 ± 1 DEG C.Then, with operating pressure 0.75MPa, the sodium chloride that with the addition of 500ppm is made (NaCl) and 1ppm above-mentioned modifying agent water at pH=7,25 ± 1 DEG C continuous water flowing until turn into CT (concentration times (Concentration Time)) untill value=1000 [ppmh].Raw water and the electrical conductivity through water are determined, is calculated following NaCl stop rates.CT values are as follows to be calculated.Show the result in table 1.It should be noted that in comparative example 2, add respectively in water Add sodium bromide：15 weight %, 12% aqueous sodium hypochlorite solution：42.4 weight % are as modifying agent.
NaCl stops rate [%]=(100- [passing through water conductivity/water supply electrical conductivity] × 100)
CT values [ppmh]=(free chloro concentration) × (time of contact)
[table 1]
In this way, being used as modifying agent by using the hypobromous acid stabilized composition 1 of embodiment 1, reverse osmosis membrane can be suppressed Deterioration, and improve reverse osmosis membrane transmission water quality.Use the hypochlorous acid of comparative example 1, the free chlorine for including bromine of comparative example 2 When, although can temporarily improve water quality, if long-term water flowing, reverse osmosis membrane deterioration, NaCl stops rate reduces.
<Embodiment 2>
Using above-mentioned preparation hypobromous acid stabilized composition 1 as modifying agent and under the same conditions as example 1 It is modified the influence supplied water with continuous water flowing, investigation pH to reverse osmosis membrane.Show the result in table 2.
[table 2]
In this way, in pH=3, NaCl stops rate is improved by modified, if but continuous water flowing until turning into modified CT values Untill=1000 [ppmh], NaCl stop rates somewhat reduce.In pH=8.0, NaCl stops rate is small by modified raising, But the reduction based on NaCl stops rate caused by continuous water flowing is not caused.In the range of pH4~6.5, NaCl stops Rate is improved by modified, even if continuous water flowing will not also cause untill as modified CT value=1000 [ppmh] The reduction of NaCl stop rates.Thus, it is known that：Contact of the modifying agent to polyamide-based reverse osmosis membrane is preferably in pH more than 3 and less than 8 In the range of carry out, carried out more preferably in the range of pH4~6.5.
<Embodiment 3>
After the reverse osmosis membrane processing for carrying out boron water under the following conditions, carried out by method same as Example 1 anti- Film process is permeated, then carries out the reverse osmosis membrane processing of boron water.Show the result in table 3.
(experiment condition)
Using the hypobromous acid stabilized composition 1 of above-mentioned preparation as modifying agent, polyamide-based macromolecule counter-infiltration is carried out The modification of film (8 inches of elements of Nitto Denko Corp's system " SWC5 ", being reduced to boron stop rate=78%).Modification be with In the reverse osmosis membrane apparatus of the reverse osmosis membrane, with operating pressure 6.0MPa, the water for the above-mentioned modifying agent for making to the addition of 4ppm is in pH Water flowing 300 hours is implemented at=6.5,24 ± 1 DEG C.Then, with operating pressure 6.0MPa, the boron that makes to the addition of 4ppm and The water flowing at pH=7,24 ± 1 DEG C of the water of 4ppm above-mentioned modifying agent.Utilize ICP emission spectrophotometers (SII NanoTechnology Inc. systems, SPS3100), raw water, condensed water are determined and through water by ICP ICP Atomic Emission Spectrophotometers method Boron concentration, calculate following boron stop rates.Show the result in table 3.
Boron stop rate [%]=100- [passes through water boron concentration ÷ { (water supply boron concentration+condensed water boron concentration) ÷ 2 } × 100]
[table 3]
In this way, being modified reverse osmosis membrane using hypobromous acid stabilized composition 1, as a result the stop rate of boron improves.
<Embodiment 4>
Using the hypobromous acid stabilized composition 1 of above-mentioned preparation as modifying agent, polyamide-based macromolecule counter-infiltration is carried out The modification of film (" ES15 " of Nitto Denko Corp, being reduced to NaCl stops rate=98.5%).Reverse osmosis membrane is impregnated 1ppm above-mentioned modifying agent is added in ultra-pure water and adjusts pH into 7 water, is implemented 72 hours at 25 ± 1 DEG C.Then, With operating pressure 0.75MPa, make 500ppm sodium chloride (NaCl) solution water flowing at pH=7,25 ± 1 DEG C.Determine raw water and Through the electrical conductivity of water, following NaCl stop rates are calculated.Show the result in table 4.
NaCl stops rate [%]=(100- [passing through water conductivity/water supply electrical conductivity] × 100)
[table 4]
In this way, confirm：Under immersion condition, by hypobromous acid stabilized composition, reverse osmosis membrane can be also produced Modification.
[the presence or absence of chlorine processing and the relation reduced through water during modifying agent water flowing]
For contacting the seperation film of chlorine system oxidant in advance and leading to not in contact with the seperation film of chlorine system oxidant in modifying agent The behavior through water during water compares.
(chlorine treatment conditions)
RO films：Polyamide-based macromolecule reverse osmosis membrane is (in water temperature：25 DEG C, operating pressure：Under conditions of 0.75MPa, The electrical conductivity stop rate of 2000mg/L NaCl solution is more than 95%)
Chlorine treatment conditions：Addition is calculated as 10mg-CL/L sodium hypochlorite with effective chlorine in pure water, and by pH adjust to 10, the water flowing 1 hour at pressure 0.75MPa, 25 DEG C of water temperature
(modifying agent water flowing condition)
Experimental rig：Flat board membrane pilot unit contained
Seperation film：Polyamide-based macromolecule reverse osmosis membrane is (in water temperature：25 DEG C, operating pressure：Under conditions of 0.75MPa, The electrical conductivity stop rate of 2000mg/L NaCl solution is more than 95%) or it is implemented anti-obtained from above-mentioned chlorine is handled Permeable membrane
Operating pressure：0.75MPa
Raw water：Xiang Moyuan cities well water (the μ S/cm of electrical conductivity 240)
Test water pH：6.5
Medicament：The hypobromous acid stabilized composition 1 of above-mentioned preparation is added, so that effectively (effective chlorine converts halogen concentration Concentration) turn into 1mg/L
(evaluation method)
Seperation film is to the influence through water：After water flowing 120 hours through water quantity holding rate (%)
([modifying agent water flowing 120 hours after through the transmission water before water/modifying agent water flowing] × 100)
<Embodiment 5>
Hypobromous acid stabilisation as modifying agent is made under these conditions to the seperation film for implementing above-mentioned chlorine processing in advance The water flowing of composition 1.Show the result in table 5.
<Embodiment 6>
In addition to using the above-mentioned seperation film that chlorine is handled is not carried out in advance, carried out under conditions of same as Example 5 Water flowing.Show the result in table 5.
[table 5]
Prior chlorine processing is for by the produced influence that through water reduces of the modifying agent to RO films
In embodiment 6, after making modifying agent water flowing, the 70% of initial value is decreased below through water, but in embodiment 5 The transmission water of middle holding more than 80%.
[influence of pH during modifying agent water flowing]
(modifying agent water flowing condition)
Experimental rig：Flat board membrane pilot unit contained
Seperation film：Polyamide-based macromolecule reverse osmosis membrane is (in water temperature：25 DEG C, operating pressure：Under conditions of 0.75MPa, The electrical conductivity stop rate of 2000mg/L NaCl solution is more than 95%)
Operating pressure：0.75MPa
Raw water：Xiang Moyuan cities well water (the μ S/cm of electrical conductivity 240)
Test water pH：5.0~8.0
Medicament：The hypobromous acid stabilized composition 1 of above-mentioned preparation is added, making effective halogen concentration, (effective chlorine conversion is dense Degree) turn into 1mg/L
(evaluation method)
Seperation film is to the influence through water：After water flowing 120 hours through water quantity holding rate (%)
([modifying agent water flowing 120 hours after through the transmission water before water/modifying agent water flowing] × 100)
<Embodiment 7~10>
Hypobromous acid is set to stabilize combination under conditions of pH5.0~8.0 the above-mentioned seperation film for implementing chlorine processing in advance The water flowing of thing 1.Show the result in table 6.
<Embodiment 11~14>
Hypobromous acid is set to stabilize combination under conditions of pH5.0~8.0 the above-mentioned seperation film that chlorine processing is not carried out in advance The water flowing of thing 1.Show the result in table 6.
[table 6]
The influence of pH when modifying agent contacts with RO films
Understand：The pH of processed water when making the modifying agent be contacted with seperation film is preferably more than 5.5, more preferably 6.0 with On.
[influence of the species of modifying agent]
(experimental condition)
Experimental rig：Flat board membrane pilot unit contained
Seperation film：To polyamide-based macromolecule reverse osmosis membrane, (electrical conductivity in 2000mg/L NaCl solution hinders in advance Gear rate is more than 95%) implement chlorine processing
Operating pressure：0.75MPa
Raw water：Xiang Moyuan cities well water (the μ S/cm of electrical conductivity 240)
Test water pH：7.0
Medicament：The hypobromous acid stabilized composition 1 of above-mentioned preparation or following hypobromous acid stabilized compositions 2 are added, is made Effective halogen concentration (effective chlorine converted score) is 10mg/L
Test period：64 days
(evaluation method)
The electrical conductivity stop rate (%) of the front and rear RO films of experiment
(hypobromous acid stabilized composition 2)
By sodium bromide：11 weight %, 12% aqueous sodium hypochlorite solution：50 weight %, sulfamic acid sodium：14 weight %, hydrogen Sodium oxide molybdena：8 weight %, water：Surplus is mixed, and prepares hypobromous acid stabilized composition 2.Hypobromous acid stabilized composition 2 PH is 14, and effective halogen concentration (effective chlorine converted score) is 6 weight %.The composition of hypobromous acid stabilized composition 2 it is detailed Thin preparation method is as described below.
In reaction vessel add 17g water, add 11g sodium bromide and stir and make its dissolve after, add 50g's 12% aqueous sodium hypochlorite solution simultaneously mixes, and then, after adding 14g sulfamic acid sodium and stirring and dissolve it, adds 8g hydrogen Sodium oxide molybdena and stir make its dissolving, so as to obtain objective composition.
<Embodiment 15>
Make the water flowing of hypobromous acid stabilized composition 1, the electrical conductivity stop rate of the seperation film before and after determination test.Result is shown In table 7.
<Embodiment 16>
Make the water flowing of hypobromous acid stabilized composition 2, the electrical conductivity stop rate of the seperation film before and after determination test.Result is shown In table 7.
[table 7]
The influence of the species of modifying agent
Embodiment 15,16 keeps more than 90% electrical conductivity stop rate, but embodiment 15 shows higher stop rate.
[influence of the chlorine system oxidant to the order of contact of seperation film in chlorine processing]
(experimental condition)
Experimental rig：Flat board membrane pilot unit contained
Seperation film：Polyamide-based macromolecule reverse osmosis membrane is (in water temperature：25 DEG C, operating pressure：Under conditions of 0.75MPa, The electrical conductivity stop rate of 2000mg/L NaCl solution is more than 95%)
Operating pressure：0.75MPa
Raw water：Ultra-pure water
Chlorine system oxidant：Sodium hypochlorite
(evaluation method)
The electrical conductivity stop rate (%) of the front and rear seperation film of experiment
<Embodiment 17>
Chlorine system oxidant is set to 10mg-CL/L × hour to the order of contact of seperation film.Show the result in table 8.
<Embodiment 18>
Chlorine system oxidant is set to 1034mg-CL/L × hour to the order of contact of seperation film.Show the result in table 8.
[table 8]
Influence of the chlorine system oxidant to the order of contact of dispersion membrane in chlorine processing
It is more than 90% in embodiment 17, but 90% is decreased below in embodiment 18 for electrical conductivity stop rate.
As indicated above, it is known that：By implementing chlorine processing to seperation film is advance, even if making modifying agent be contacted with seperation film afterwards The reduction through water can also be suppressed, separation membrane device is stably run.In addition, understand：By to the advance reality of seperation film After applying chlorine processing, make itself and modifying agent, the deterioration of seperation film can be suppressed, and improve through water and through water quality.

Claims (13)

  1. A kind of 1. method of modifying of reverse osmosis membrane, it is characterised in that
    Polyamide-based reverse osmosis membrane is set to be contacted with following substances, the material is：
    The reactant of bromine system oxidant or bromine compounds and chlorine system oxidant and
    Sulfamic acid compound；
    Or
    The reactant of bromine system oxidant or bromine compounds and chlorine system oxidant, with
    Sulfamic acid compound
    Reaction product.
  2. A kind of 2. method of modifying of reverse osmosis membrane, it is characterised in that
    Make the mixture of bromine and sulfamic acid compound, contacted with polyamide-based reverse osmosis membrane；
    Or make the reaction product of bromine and sulfamic acid compound, contacted with polyamide-based reverse osmosis membrane.
  3. 3. the method for modifying of reverse osmosis membrane according to claim 2, it is characterised in that
    The reaction product of the bromine and sulfamic acid compound is obtained by the method including following process：Nonactive Bromine is added in the mixed liquor comprising water, alkali and sulfamic acid compound and reacted under gas atmosphere.
  4. 4. according to the method for modifying of reverse osmosis membrane according to any one of claims 1 to 3, it is characterised in that
    The contact is carried out in the range of pH4~6.5.
  5. 5. according to the method for modifying of reverse osmosis membrane according to any one of claims 1 to 3, it is characterised in that
    The polyamide-based reverse osmosis membrane has carried out chlorine processing using chlorine system oxidant.
  6. 6. the method for modifying of reverse osmosis membrane according to claim 5, it is characterised in that
    The contact is carried out in more than pH5.5.
  7. 7. a kind of reverse osmosis membrane, it is characterised in that it is changing by reverse osmosis membrane according to any one of claims 1 to 6 Property method and modification.
  8. 8. a kind of processing method of boron water, it is characterised in that use and pass through reverse osmosis according to any one of claims 1 to 6 The method of modifying of permeable membrane and the reverse osmosis membrane of modification carry out reverse osmosis membrane processing to boron water.
  9. 9. a kind of operation method of seperation film, it is characterised in that make bromine system oxidant, with having been carried out using chlorine system oxidant at chlorine The polyamide-based seperation film contact of reason.
  10. 10. the operation method of seperation film according to claim 9, it is characterised in that
    The pH of processed water when making the bromine system oxidant be contacted with the seperation film is more than 5.5.
  11. 11. the operation method of the seperation film according to claim 9 or 10, it is characterised in that
    Bromine system oxidant contains the reactant and sulfamic acid of bromine system oxidant or bromine compounds and chlorine system oxidant Compound；
    Or the reactant of bromine system oxidant or bromine compounds with chlorine system oxidant, the reaction production with sulfamic acid compound Thing.
  12. 12. the operation method of seperation film according to claim 11, it is characterised in that
    Bromine system oxidant contains bromine and sulfamic acid compound or the reaction production containing bromine and sulfamic acid compound Thing.
  13. 13. the operation method of seperation film according to claim 12, it is characterised in that
    The reaction product of the bromine and sulfamic acid compound is obtained by the method including following process：Nonactive Bromine is added in the mixed liquor comprising water, alkali and sulfamic acid compound and reacted under gas atmosphere.
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