WO2016136304A1 - Procédé pour la modification de membrane d'osmose inverse, membrane d'osmose inverse, procédé de traitement pour de l'eau contenant du bore et procédé pour la mise en œuvre d'une membrane d'osmose inverse - Google Patents

Procédé pour la modification de membrane d'osmose inverse, membrane d'osmose inverse, procédé de traitement pour de l'eau contenant du bore et procédé pour la mise en œuvre d'une membrane d'osmose inverse Download PDF

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Publication number
WO2016136304A1
WO2016136304A1 PCT/JP2016/050710 JP2016050710W WO2016136304A1 WO 2016136304 A1 WO2016136304 A1 WO 2016136304A1 JP 2016050710 W JP2016050710 W JP 2016050710W WO 2016136304 A1 WO2016136304 A1 WO 2016136304A1
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WIPO (PCT)
Prior art keywords
reverse osmosis
bromine
osmosis membrane
sulfamic acid
membrane
Prior art date
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PCT/JP2016/050710
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English (en)
Japanese (ja)
Inventor
吉川　浩
勇規 中村
Original Assignee
オルガノ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2015034342A external-priority patent/JP6484460B2/ja
Priority claimed from JP2015034048A external-priority patent/JP6506987B2/ja
Application filed by オルガノ株式会社 filed Critical オルガノ株式会社
Priority to CN201680011498.9A priority Critical patent/CN107635652B/zh
Priority to SG11201706491XA priority patent/SG11201706491XA/en
Priority to MYPI2017703018A priority patent/MY186884A/en
Priority to KR1020177022296A priority patent/KR101990231B1/ko
Publication of WO2016136304A1 publication Critical patent/WO2016136304A1/fr
Priority to SA517382121A priority patent/SA517382121B1/ar

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Classifications

    • 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

Definitions

  • Patent Document 1 in a membrane separation apparatus equipped with a reverse osmosis membrane element having a polyamide skin layer, after filling the reverse osmosis membrane element into a pressure vessel in the membrane separation apparatus, bromine is added to the reverse osmosis membrane element.
  • a method for treating a reverse osmosis membrane element in which a free chlorine aqueous solution is brought into contact is described.
  • Patent Document 1 can temporarily improve the water quality, but if a free chlorine aqueous solution containing bromine is passed for a long time, the reverse osmosis membrane deteriorates and the water quality decreases.
  • bromine oxidants In the operation of polyamide separation membranes such as reverse osmosis membranes (RO membranes) and nanofiltration membranes (NF membranes), for example, when various bromine oxidants are used for the purpose of slime suppression, bromine oxidants It may flow into the separation membrane.
  • the bromine-based oxidizing agent include a reaction product of an oxidizing agent such as hypochlorous acid and bromide ions, and hypobromite.
  • these brominated oxidants are known to have a problem that the lower the pH of the water to be treated, the easier it is to reduce the amount of permeated water of the separation membrane (see Non-Patent Document 1).
  • An object of the present invention is to provide a reverse osmosis membrane modification method for improving the quality of permeated water of a reverse osmosis membrane while suppressing deterioration of the reverse osmosis membrane, a reverse osmosis membrane modified by the modification method, and
  • the object is to provide a method for treating boron-containing water using the reverse osmosis membrane.
  • a polyamide-based reverse osmosis membrane is brought into contact with a bromine-based oxidant or a reaction product of a bromine compound and a chlorine-based oxidant and a sulfamic acid compound, or a bromine-based oxidant or a bromine compound.
  • This is a method for modifying a reverse osmosis membrane in which a reaction product with a chlorine-based oxidant and a reaction product with a sulfamic acid compound are brought into contact with each other.
  • the reaction product of the bromine and the sulfamic acid compound is a step of reacting the mixed liquid containing water, alkali and sulfamic acid compound by adding bromine in an inert gas atmosphere. It is preferable that it was obtained by the method of including.
  • the contact is performed in a pH range of 4 to 6.5.
  • the contact is preferably performed at a pH of 5.5 or more.
  • the present invention is a reverse osmosis membrane modified by the method for modifying a reverse osmosis membrane.
  • the bromine-based oxidant contains a bromine-based oxidant, a reaction product of a bromine compound and a chlorine-based oxidant, and a sulfamic acid compound, or a bromine-based oxidant, or It is preferable to contain a reaction product of a bromine compound and a chlorine-based oxidant and a reaction product of a sulfamic acid compound.
  • the bromine-based oxidant contains a mixture of bromine and a sulfamic acid compound or a reaction product of bromine and a sulfamic acid compound.
  • a polyamide-based reverse osmosis membrane is contacted with a bromine-based oxidizing agent or a reaction product of a bromine compound and a chlorine-based oxidizing agent, and a sulfamic acid compound.
  • a reaction product of a sulfamic acid compound into contact with a bromine-based oxidant or a reaction product of a bromine compound and a chlorine-based oxidant.
  • a “bromine-based oxidizing agent” and a “sulfamic acid compound” are present as modifiers in water supply to a polyamide-based reverse osmosis membrane.
  • a method of bringing the polyamide-based reverse osmosis membrane into contact with the polyamide-based reverse osmosis membrane, or a method of bringing a “reaction product of a bromine compound and a chlorine-based oxidant” and a “sulfamic acid compound” into contact with the polyamide-based reverse osmosis membrane is thought that a hypobromite stabilization composition produces
  • the method for reforming a reverse osmosis membrane includes a reaction product of a bromine-based oxidant and a sulfamic acid compound as a modifier in water supply to a polyamide-based reverse osmosis membrane.
  • a reaction product of a reaction product of a bromine compound and a chlorine-based oxidant and a sulfamic acid compound in the presence of a hypobromite stabilizing composition, which is in contact with a polyamide-based reverse osmosis membrane.
  • the reverse osmosis membrane modification method includes, for example, “reaction product of bromine and sulfamic acid compound”, “bromine chloride” in water supply to a polyamide-based reverse osmosis membrane.
  • the reaction product of sulfamic acid compound and sulfamic acid compound "or" reaction product of sodium bromide and hypochlorous acid and sulfamic acid compound "is present. This is a method of contacting with a polyamide-based reverse osmosis membrane.
  • it is not clear what kind of compound is generated as “reaction product of bromine and sulfamic acid compound”, but “bromosulfamic acid” which is a hypobromite stabilizing compound is generated. Conceivable.
  • hypobromite stabilizing composition hardly deteriorates the polyamide-based reverse osmosis membrane, it is not a temporary improvement in water quality, but the water containing the above modifier is used as a polyamide-based reverse osmosis membrane for a long time. Even if the water is passed through and contacted, the deterioration of the reverse osmosis membrane is suppressed, and the reduction of the blocking rate of the reverse osmosis membrane, that is, the deterioration of water quality is suppressed.
  • a polyamide-based reverse osmosis membrane is immersed for a predetermined time in water to which “bromine-based oxidant” or “reaction product of bromine compound and chlorine-based oxidant” and “sulfamic acid compound” are added. And may be contacted.
  • the contact of the modifier with the reverse osmosis membrane may be performed under a temperature condition in the range of 5 ° C to 35 ° C, for example.
  • Examples of the chlorine-based oxidizing agent include chlorine gas, chlorine dioxide, hypochlorous acid or a salt thereof, chlorous acid or a salt thereof, chloric acid or a salt thereof, perchloric acid or a salt thereof, chlorinated isocyanuric acid or a salt thereof.
  • examples of the salt include alkali metal hypochlorites such as sodium hypochlorite and potassium hypochlorite, alkaline earth hypochlorite such as calcium hypochlorite and barium hypochlorite.
  • sulfamic acid compound examples include sulfamic acid (amidosulfuric acid) in which both two R groups are hydrogen atoms, N-methylsulfamic acid, N-ethylsulfamic acid, N-propylsulfamic acid, N- A sulfamic acid compound in which one of two R groups such as isopropylsulfamic acid and N-butylsulfamic acid is a hydrogen atom and the other is an alkyl group having 1 to 8 carbon atoms, N, N-dimethylsulfamic acid, N, Two R groups such as N-diethylsulfamic acid, N, N-dipropylsulfamic acid, N, N-dibutylsulfamic acid, N-methyl-N-ethylsulfamic acid, N-methyl-N-propylsulfamic acid, etc.
  • sulfamic acid amidosulfuric
  • a dispersant is used as a bromine-based oxidant or hypobromine to suppress the scale. You may use together with an acid stabilization composition.
  • the dispersant include polyacrylic acid, polymaleic acid, and phosphonic acid.
  • the amount of the dispersant added to the feed water is, for example, in the range of 0.1 to 1,000 mg / L as the concentration in the RO concentrated water.
  • the reverse osmosis membrane is chlorinated with a chlorine-based oxidant. That is, a polyamide-type reverse osmosis membrane chlorinated with a chlorine-based oxidant is brought into contact with a sulfamic acid compound and a bromine-based oxidant or a reaction product of a bromine compound and a chlorine-based oxidant as a modifier. Alternatively, a reaction product of a sulfamic acid compound is brought into contact with a bromine-based oxidizing agent or a reaction product of a bromine compound and a chlorine-based oxidizing agent.
  • the amount of permeated water and the quality of the permeated water can be controlled while sufficiently degrading the separation membrane by bringing the polyamide-based separation membrane into sufficient contact with the chlorinated oxidant in advance and treating with chlorine, and further bringing the modifier into contact. Improved.
  • the contact of the chlorine-based oxidant and the modifier with the reverse osmosis membrane may be performed under a temperature condition in the range of 0 ° C. to 100 ° C., for example.
  • the contact of the chlorine-based oxidizing agent with the reverse osmosis membrane is preferably 0.1 to 1000 mg-Cl / L ⁇ hr as a value of effective chlorine concentration [mg-Cl / L] ⁇ time [hr]. If it is less than 0.1 mg-Cl / L ⁇ hr, a sufficient chlorination effect cannot be obtained for the film, and if it exceeds 1000 mg-Cl / L ⁇ hr, the film may be deteriorated.
  • the method for reforming a reverse osmosis membrane according to an embodiment of the present invention is, for example, in the presence of a chlorine-based oxidant in water supply to a polyamide-based reverse osmosis membrane and the like.
  • a method of contacting a polyamide-based reverse osmosis membrane in the presence of “bromine-based oxidant” and “sulfamic acid compound”, or “reaction product of bromine compound and chlorine-based oxidant” and “sulfamic acid compound” It is a method of making it exist and making it contact with a polyamide-type reverse osmosis membrane. Thereby, it is thought that a hypobromite stabilization composition produces
  • the method for reforming a reverse osmosis membrane includes, for example, supplying a polyamide-based reverse osmosis membrane with water in the presence of a chlorinated oxidant, and then modifying the reverse osmosis membrane.
  • the method for modifying a reverse osmosis membrane is, for example, a method in which a chlorinated oxidant is present in contact with water in a polyamide-based reverse osmosis membrane and the like, and then the modifier is contacted.
  • reaction product of bromine and sulfamic acid compound "reaction product of bromine chloride and sulfamic acid compound”, or "reaction product of sodium bromide and hypochlorous acid, sulfamic acid compound
  • This is a method in which a hypobromite stabilizing composition as a reaction product is present and brought into contact with a polyamide-based reverse osmosis membrane.
  • bromine-based oxidant or “reaction product of bromine compound and chlorine-based oxidant” and the “sulfamic acid compound” may be added separately to the feed water or the like, or mixed with the stock solution. May be added to the water supply. Further, for example, a polyamide-based reverse osmosis membrane may be immersed and contacted in water to which a chlorine-based oxidizing agent or a modifier is added for a predetermined time.
  • reaction product of bromine-based oxidizing agent and sulfamic acid compound Or a reaction product of a reaction product of a bromine compound and a chlorine-based oxidizing agent and a sulfamic acid compound ”may be injected by a chemical injection pump or the like.
  • a polyamide-based reverse osmosis membrane may be immersed and contacted in water to which a chlorine-based oxidizing agent or a modifier is added for a predetermined time.
  • the modification with the chlorinated oxidant or the modifier is performed by, for example, supplying the chlorinated oxidant or the above-mentioned modified water into the reverse osmosis membrane during the operation of the reverse osmosis membrane apparatus including the polyamide-based reverse osmosis membrane. What is necessary is just to add a quality agent continuously or intermittently.
  • the preparation of “bromine and sulfamic acid compound” or “reaction product of bromine and sulfamic acid compound” using bromine is the preparation of “hypochlorous acid, bromine compound and sulfamic acid” and Less chloride ions, less polyamide-based reverse osmosis membranes, and less effective halogen leakage into membrane permeate such as RO permeate compared to “bromine chloride and sulfamic acid” formulations Therefore, it is more preferable as a slime inhibitor for reverse osmosis membranes. Further, it is more preferable because it is less likely to cause corrosion of metal materials such as piping.
  • Examples of the use of the reverse osmosis membrane device including the polyamide-based reverse osmosis membrane modified by the reverse osmosis membrane modification method according to this embodiment include seawater desalination and wastewater recovery.
  • the boron rejection rate is significantly improved.
  • the operation method of the separation membrane according to the embodiment of the present invention is a method in which a bromine-based oxidizing agent is brought into contact with a polyamide-based separation membrane that has been chlorinated with a chlorine-based oxidizing agent.
  • the contact of the chlorine-based oxidant and bromine-based oxidant to the separation membrane may be performed under normal pressure, pressurized or reduced pressure conditions, but the separation membrane can be reliably chlorinated. In view of being able to perform contact treatment while producing water, it is preferable to carry out under pressure.
  • the contact of the chlorine-based oxidant and bromine-based oxidant with the separation membrane is preferably performed under a pressurized condition in the range of 0.1 MPa to 10 MPa, for example.
  • the contact of the chlorine-based oxidizing agent with the separation membrane is preferably 0.1 to 1000 mg-Cl / L ⁇ hr as a value of effective chlorine concentration [mg-Cl / L] ⁇ time [hr]. If it is less than 0.1 mg-Cl / L ⁇ hr, a sufficient chlorination effect cannot be obtained for the film, and if it exceeds 1000 mg-Cl / L ⁇ hr, the film may be deteriorated.
  • the effective halogen concentration by the bromine-based oxidizing agent that contacts the separation membrane is preferably 0.01 to 100 mg / L in terms of effective chlorine concentration. If it is less than 0.01 mg / L, a sufficient slime-inhibiting effect may not be obtained. If it is more than 100 mg / L, there is a possibility of causing deterioration of the separation membrane and corrosion of the piping.
  • the pH of the water to be treated when the chlorinated oxidant comes into contact is preferably in the range of 4 to 13, more preferably in the range of 6 to 12.
  • the pH is less than 4, the amount of permeated water may decrease, and when the pH exceeds 13, the separation membrane may deteriorate.
  • the pH of the water to be treated when the bromine-based oxidant comes into contact is preferably 5.5 or more, more preferably 6.0 or more, and even more preferably in the range of 6.5 to 10.
  • the pH is less than 5.5, even if the separation membrane has been subjected to chlorination in advance, it may be affected by a decrease in the amount of permeated water due to the bromine-based oxidizing agent. If the pH exceeds 10, the amount of permeated water may increase too much.
  • the bromine-based oxidant is not particularly limited.
  • bromine-based oxidizing agents include “hypobromite” and the like, “reaction products of chlorine-based oxidizing agents and bromide ions”, “hypobromite stabilization composition”, etc. It is a “hypobromite stabilization composition”.
  • the “hypobromite stabilizing composition” has little adverse effect on the rejection of the separation membrane, and can be stably operated for a long time even when continuously added to the chlorinated separation membrane.
  • a chlorinated oxidant is present and contacted, and then a “bromine-based oxidant” and a “sulfamic acid compound” are present to form a polyamide-based separation membrane.
  • a hypobromite stabilization composition produces
  • hypobromine which is a “reaction product of a bromine-based oxidizing agent and a sulfamic acid compound” Stabilize hypobromite in the presence of an acid stabilizing composition and contact with a polyamide separation membrane, or “reaction product of a bromine compound and a chlorinated oxidant and a sulfamic acid compound”
  • the composition may be present in contact with the polyamide separation membrane.
  • bromine chloride or “reaction product of sodium bromide and hypochlorous acid” and “sulfamic acid compound” are present and brought into contact with a polyamide separation membrane.
  • the operation method of the separation membrane according to the embodiment of the present invention is, for example, a method in which a bromine and a sulfamic acid compound are contacted in the presence of a chlorine-based oxidizing agent in water supply to a polyamide-based separation membrane.
  • a bromine and a sulfamic acid compound are contacted in the presence of a chlorine-based oxidizing agent in water supply to a polyamide-based separation membrane.
  • reaction product of bromoamine and sulfamic acid compound or "Reaction product of sodium bromide and hypochlorous acid and sulfamic acid compound”
  • a bromite stabilizing composition is present and brought into contact with a polyamide separation membrane.
  • reaction product of a bromine-based oxidant and a sulfamic acid compound or “bromine A reaction product of a reaction product of a compound and a chlorine-based oxidant and a sulfamic acid compound ” may be injected by a chemical injection pump or the like.
  • the ratio of the equivalent of “sulfamic acid compound” to the equivalent of “bromine-based oxidizing agent” or “reaction product of bromine compound and chlorine-based oxidizing agent” is preferably 1 or more, and is in the range of 1 or more and 2 or less. It is more preferable. If the ratio of the equivalent amount of the “sulfamic acid compound” to the equivalent amount of the “bromine-based oxidant” or “reaction product of the bromine compound and the chlorine-based oxidant” is less than 1, the separation membrane may be deteriorated. If it exceeds, the manufacturing cost may increase.
  • the bromine-based oxidizing agent, bromine compound, chlorine-based oxidizing agent, and sulfamic acid compound are as described above.
  • the preparation of “bromine and sulfamic acid compound” or “reaction product of bromine and sulfamic acid compound” using bromine is the preparation of “hypochlorous acid, bromine compound and sulfamic acid” and Compared to “bromine chloride and sulfamic acid” preparations, etc., it has less chloride ions, does not deteriorate the polyamide separation membrane, and has less leakage of effective halogen into membrane permeated water such as RO permeated water. More preferable as a slime inhibitor for separation membranes. Further, it is more preferable because it is less likely to cause corrosion of metal materials such as piping.
  • an alkali may be further present together with the bromine-based oxidizing agent.
  • the alkali include alkali hydroxides such as sodium hydroxide and potassium hydroxide. From the viewpoint of product stability at low temperatures, sodium hydroxide and potassium hydroxide may be used in combination. Further, the alkali is not solid and may be used as an aqueous solution.
  • the separation membrane examples include a reverse osmosis membrane (RO membrane), a nanofiltration membrane (NF membrane), a microfiltration membrane (MF membrane), and an ultrafiltration membrane (UF membrane).
  • the operation method of the separation membrane according to the embodiment of the present invention can be preferably applied to a reverse osmosis membrane (RO membrane).
  • the operation method of the separation membrane which concerns on embodiment of this invention is suitably applicable to the polyamide-type polymer membrane which is mainstream these days as a reverse osmosis membrane.
  • Polyamide polymer membranes tend to decrease the amount of permeated water when they come into contact with bromine-based oxidants. For example, when free chlorine or the like is added in the presence of bromide ions, hypobromite is generated in water. When contacted with the polymer polymer membrane even temporarily, the permeated water amount significantly decreases.
  • such a remarkable decrease in membrane performance hardly occurs even in the polyamide polymer membrane.
  • a dispersant is used as a bromine-based oxidant or hypobromine to suppress the scale. You may use together with an acid stabilization composition.
  • the dispersant include polyacrylic acid, polymaleic acid, and phosphonic acid.
  • the amount of the dispersant added to the feed water is, for example, in the range of 0.1 to 1,000 mg / L as the concentration in the RO concentrated water.
  • the modifier composition used in the reverse osmosis membrane modification method and separation membrane operation method according to the present embodiment is a "bromine-based oxidant" or "a reaction product of a bromine compound and a chlorine-based oxidant” It contains “sulfamic acid compound” and may further contain alkali.
  • the modifier composition according to the present embodiment is a "reaction product of a bromine-based oxidant and a sulfamic acid compound", or "a reaction product of a bromine compound and a chlorinated oxidant, a sulfamic acid compound, Of the reaction product ", and may further contain an alkali.
  • the bromine-based oxidizing agent, bromine compound, chlorine-based oxidizing agent, and sulfamic acid compound are as described above.
  • the modifier composition according to the present embodiment contains bromine and a sulfamic acid compound because the polyamide-based reverse osmosis membrane and the like are not further deteriorated and the amount of effective halogen leaked into the RO permeate is smaller.
  • a mixture of bromine and sulfamic acid compound for example, a mixture of bromine, sulfamic acid compound, alkali and water, or containing a reaction product of bromine and sulfamic acid compound, for example bromine
  • a mixture of a reaction product of a sulfamic acid compound with an alkali, and water is preferable.
  • the modifier composition according to the present embodiment has a modification effect of a polyamide-based reverse osmosis membrane or the like, compared with a modifier such as hypochlorous acid or free chlorine containing bromine, but the following It hardly causes significant film deterioration such as chlorous acid and free chlorine containing bromine. At normal use concentrations, the effect on film degradation can be substantially ignored. Therefore, it is optimal as a modifier for polyamide-based reverse osmosis membranes.
  • the modifier composition according to the present embodiment hardly permeates the reverse osmosis membrane or the like, and therefore has little influence on the quality of treated water. Further, since the concentration can be measured on site in the same manner as hypochlorous acid or the like, more accurate concentration management is possible.
  • the pH of the composition is, for example, more than 13.0, more preferably more than 13.2.
  • the pH of the composition is 13.0 or less, the effective halogen in the composition may become unstable.
  • the bromate concentration in the modifier composition is preferably less than 5 mg / kg. When the bromate concentration in the modifier composition is 5 mg / kg or more, the concentration of bromate ions such as RO permeated water may increase.
  • the modifier composition according to the present embodiment is obtained by mixing a bromine-based oxidant and a sulfamic acid compound, or by mixing a reaction product of a bromine compound and a chlorine-based oxidant and a sulfamic acid compound. Further, an alkali may be mixed.
  • a method for producing a modifier composition containing bromine and a sulfamic acid compound, or a modifier composition containing a reaction product of bromine and a sulfamic acid compound water, an alkali and a sulfamic acid compound are used. It is preferable to include a step of reacting by adding bromine to the mixed solution containing inert gas atmosphere or a step of adding bromine to the mixed solution containing water, alkali and sulfamic acid compound under inert gas atmosphere. By adding and reacting under an inert gas atmosphere, or adding under an inert gas atmosphere, the bromate ion concentration in the composition is lowered, and the bromate ion concentration in RO permeated water and the like is lowered. .
  • the addition ratio of bromine is preferably 25% by weight or less, more preferably 1% by weight or more and 20% by weight or less based on the total amount of the composition. If the bromine addition rate exceeds 25% by weight relative to the total amount of the composition, the amount of bromic acid produced in the reaction system may increase. If it is less than 1% by weight, the reforming effect may be inferior.
  • the reaction temperature at the time of bromine addition is preferably controlled in the range of 0 ° C. to 25 ° C., but more preferably in the range of 0 ° C. to 15 ° C. from the viewpoint of production cost.
  • the reaction temperature at the time of bromine addition exceeds 25 degreeC, the production amount of the bromic acid in a reaction system may increase, and when it is less than 0 degreeC, it may freeze.
  • Hypobromite Stabilizing Composition 1 Under nitrogen atmosphere, liquid bromine: 16.9% by weight (wt%), sulfamic acid: 10.7% by weight, sodium hydroxide: 12.9% by weight, potassium hydroxide: 3.94% by weight, water: remaining The components were mixed to prepare Hypobromite Stabilized Composition 1.
  • the pH of the hypobromite stabilizing composition 1 was 14, and the effective halogen concentration (effective chlorine equivalent concentration) was 7.5% by weight.
  • the detailed preparation method of the hypobromite stabilization composition 1 is as follows.
  • Hypobromite stabilizing composition 1 prepared above (Example 1), hypochlorous acid (Comparative Example 1), hypobromite (mixture of sodium bromide and hypochlorous acid) (Comparative Example 2)
  • ES20 polyamide-based polymer reverse osmosis membranes
  • CT (Concentration Time) value 1000 [ppm ⁇ Continuous water flow until h].
  • the conductivity of raw water and permeated water was measured, and the following NaCl rejection was calculated.
  • the CT value was calculated as follows. The results are shown in Table 1.
  • NaCl rejection [%] (100 ⁇ [permeate conductivity / feed water conductivity] ⁇ 100)
  • CT value [ppm ⁇ h] (Free chlorine concentration) ⁇ (Contact time)
  • Example 2 Using the hypobromite stabilizing composition 1 prepared above as a modifier, reforming and continuous water flow were performed under the same conditions as in Example 1, and the influence of the pH of the feed water to the reverse osmosis membrane was examined. . The results are shown in Table 2.
  • the NaCl rejection rate was improved by the reforming, but when the water was continuously passed until the CT value after modification was 1000 [ppm ⁇ h], the NaCl rejection rate was slightly decreased.
  • the improvement of the NaCl rejection rate due to the reforming was small, but the decrease of the NaCl rejection rate due to continuous water flow did not occur.
  • the NaCl rejection rate was improved by the reforming, and the NaCl rejection rate did not decrease even when water was continuously passed until the CT value after modification was 1000 [ppm ⁇ h]. From this, it was found that the contact of the modifier with the polyamide-based reverse osmosis membrane is preferably performed in the range of more than pH 3 and less than 8, more preferably in the range of pH 4 to 6.5. .
  • Example 3 After performing the reverse osmosis membrane treatment of boron-containing water under the following conditions, the reverse osmosis membrane treatment was performed in the same manner as in Example 1, followed by the reverse osmosis membrane treatment of boron-containing water. The results are shown in Table 3.
  • Chlorine treatment conditions RO membrane: polyamide polymer reverse osmosis membrane (water temperature: 25 ° C., operating pressure: 0.75 MPa, conductivity rejection of 2000 mg / L NaCl solution is 95% or more)
  • Chlorine treatment conditions 10 mg-CL / L of sodium hypochlorite as effective chlorine was added to pure water, adjusted to pH 10, water flow for 1 hr at a pressure of 0.75 MPa and a water temperature of 25 ° C.
  • Test device Flat membrane test device Separation membrane: Polyamide polymer reverse osmosis membrane (water temperature: 25 ° C., operating pressure: 0.75 MPa, conductivity rejection of 2000 mg / L NaCl solution is 95% or more ), Or reverse osmosis membrane with the above chlorination treatment and operating pressure: 0.75 MPa ⁇
  • Raw water Sagamiharai water (conductivity 240 ⁇ S / cm)
  • Drug Hypobromite stabilization composition 1 prepared above is added so that the effective halogen concentration (effective chlorine equivalent concentration) is 1 mg / L.
  • Example 5 Hypobromite stabilizing composition 1 as a modifier was passed through the separation membrane subjected to the chlorination in advance under the above conditions. The results are shown in Table 5.
  • Example 6 Water was passed under the same conditions as in Example 5 except that the above separation membrane not subjected to chlorination was used. The results are shown in Table 5.
  • Example 6 after passing the modifier, the permeated water amount decreased to less than 70% of the initial value, but in Example 5, the permeated water amount was maintained at 80% or more.
  • Test device Flat membrane test device Separation membrane: Polyamide polymer reverse osmosis membrane (water temperature: 25 ° C., operating pressure: 0.75 MPa, conductivity rejection of 2000 mg / L NaCl solution is 95% or more ) ⁇ Operating pressure: 0.75 MPa ⁇
  • Raw water Sagamiharai water (conductivity 240 ⁇ S / cm)
  • Test water pH 5.0 to 8.0 ⁇
  • Drug Hypobromite stabilization composition 1 prepared above is added so that the effective halogen concentration (effective chlorine equivalent concentration) is 1 mg / L.
  • Hypobromite stabilizing composition 1 was passed through the separation membrane that had been previously chlorinated under conditions of pH 5.0 to 8.0. The results are shown in Table 6.
  • Example 15 Hypobromite stabilization composition 1 was passed through, and the conductivity rejection rate in the separation membrane before and after the test was measured. The results are shown in Table 7.
  • Test device Flat membrane test device Separation membrane: Polyamide polymer reverse osmosis membrane (water temperature: 25 ° C., operating pressure: 0.75 MPa, conductivity rejection of 2000 mg / L NaCl solution is 95% or more ) ⁇ Operating pressure: 0.75 MPa ⁇
  • Raw water Ultrapure water ⁇
  • Chlorine oxidizer Sodium hypochlorite
  • Example 18 The degree of contact of the chlorine-based oxidant with the separation membrane was 1034 mg-CL / L ⁇ hr. The results are shown in Table 8.

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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)
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  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne un procédé pour la modification d'une membrane d'osmose inverse dans le but d'améliorer la qualité de l'eau ayant été filtrée à travers la membrane d'osmose inverse, tout en supprimant la détérioration de la membrane d'osmose inverse. Le procédé pour la modification d'une membrane d'osmose inverse consiste : à mettre en contact un oxydant à base de brome ou un produit réactionnel d'un composé du brome et d'un oxydant à base de chlore et un composé de l'acide sulfamique avec une membrane d'osmose inverse à base de polyamide ; ou en variante, à mettre en contact un produit réactionnel d'un composé de l'acide sulfamique et d'un oxydant à base de brome ou un produit réactionnel d'un composé du brome et d'un oxydant à base de chlore avec une membrane d'osmose inverse à base de polyamide.
PCT/JP2016/050710 2015-02-24 2016-01-12 Procédé pour la modification de membrane d'osmose inverse, membrane d'osmose inverse, procédé de traitement pour de l'eau contenant du bore et procédé pour la mise en œuvre d'une membrane d'osmose inverse WO2016136304A1 (fr)

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CN201680011498.9A CN107635652B (zh) 2015-02-24 2016-01-12 反渗透膜的改性方法、反渗透膜、含硼水的处理方法以及分离膜的运行方法
SG11201706491XA SG11201706491XA (en) 2015-02-24 2016-01-12 Method for modifying reverse osmosis membrane, reverse osmosis membrane, treatment method for boron-containing water, and method for operating separation membrane
MYPI2017703018A MY186884A (en) 2015-02-24 2016-01-12 Method for modifying reverse osmosis membrane, reverse osmosis membrane, treatment method for boron-containing water, and method for operating separation membrane
KR1020177022296A KR101990231B1 (ko) 2015-02-24 2016-01-12 역침투막의 개질 방법, 역침투막, 붕소 함유수의 처리 방법, 및 분리막의 운전 방법
SA517382121A SA517382121B1 (ar) 2015-02-24 2017-08-14 طريقة لتعديل غشاء التناضح العكسي، غشاء التناضح العكسي، طريقة معالجة المياه التي تحتوي على البورون، وطريقة لتشغيل غشاء الفصل

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JP2015-034342 2015-02-24
JP2015034048A JP6506987B2 (ja) 2015-02-24 2015-02-24 逆浸透膜の改質方法、およびホウ素含有水の処理方法

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JP2018030074A (ja) * 2016-08-23 2018-03-01 オルガノ株式会社 ポリアミド系逆浸透膜、およびそのポリアミド系逆浸透膜の製造方法
WO2018084061A1 (fr) * 2016-11-07 2018-05-11 オルガノ株式会社 Procédé de traitement par membrane d'osmose inverse et système de traitement par membrane d'osmose inverse
JP2018122267A (ja) * 2017-02-02 2018-08-09 オルガノ株式会社 逆浸透膜の改質方法、逆浸透膜、および、非荷電物質含有水の処理方法
WO2018142904A1 (fr) * 2017-02-02 2018-08-09 オルガノ株式会社 Procédé de modification de membrane d'osmose inverse, membrane d'osmose inverse, procédé de traitement d'eau contenant une substance non chargée, procédé de fonctionnement pour membrane d'osmose inverse et dispositif de membrane d'osmose inverse
US10124297B1 (en) 2018-03-06 2018-11-13 Kuwait Institute For Scientific Research Thin film nanocomposite nanofiltration membrane
JP2018187572A (ja) * 2017-05-09 2018-11-29 オルガノ株式会社 逆浸透膜の運転方法および逆浸透膜装置
CN111201076A (zh) * 2018-01-18 2020-05-26 株式会社Lg化学 用于制备水处理分离膜的方法和由此制备的水处理分离膜

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CN116422152B (zh) * 2023-06-15 2023-09-26 杭州尚善若水环保科技有限公司 反渗透膜处理系统的运行方法

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WO2018084061A1 (fr) * 2016-11-07 2018-05-11 オルガノ株式会社 Procédé de traitement par membrane d'osmose inverse et système de traitement par membrane d'osmose inverse
JPWO2018084061A1 (ja) * 2016-11-07 2019-04-11 オルガノ株式会社 逆浸透膜処理方法および逆浸透膜処理システム
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JP2018122267A (ja) * 2017-02-02 2018-08-09 オルガノ株式会社 逆浸透膜の改質方法、逆浸透膜、および、非荷電物質含有水の処理方法
WO2018142904A1 (fr) * 2017-02-02 2018-08-09 オルガノ株式会社 Procédé de modification de membrane d'osmose inverse, membrane d'osmose inverse, procédé de traitement d'eau contenant une substance non chargée, procédé de fonctionnement pour membrane d'osmose inverse et dispositif de membrane d'osmose inverse
TWI786081B (zh) * 2017-02-02 2022-12-11 日商奧璐佳瑙股份有限公司 逆滲透膜之改質方法、逆滲透膜、含有非荷電物質之水的處理方法
JP2018187572A (ja) * 2017-05-09 2018-11-29 オルガノ株式会社 逆浸透膜の運転方法および逆浸透膜装置
JP7144922B2 (ja) 2017-05-09 2022-09-30 オルガノ株式会社 逆浸透膜の運転方法および逆浸透膜装置
CN111201076A (zh) * 2018-01-18 2020-05-26 株式会社Lg化学 用于制备水处理分离膜的方法和由此制备的水处理分离膜
US10124297B1 (en) 2018-03-06 2018-11-13 Kuwait Institute For Scientific Research Thin film nanocomposite nanofiltration membrane

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