WO2016104356A1 - 分離膜のスライム抑制方法 - Google Patents

分離膜のスライム抑制方法 Download PDF

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Publication number
WO2016104356A1
WO2016104356A1 PCT/JP2015/085476 JP2015085476W WO2016104356A1 WO 2016104356 A1 WO2016104356 A1 WO 2016104356A1 JP 2015085476 W JP2015085476 W JP 2015085476W WO 2016104356 A1 WO2016104356 A1 WO 2016104356A1
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Prior art keywords
membrane
bromine
separation membrane
water
slime
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PCT/JP2015/085476
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English (en)
French (fr)
Japanese (ja)
Inventor
吉川　浩
染谷　新太郎
雅人 都司
千晴 大森
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オルガノ株式会社
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Priority claimed from JP2015034205A external-priority patent/JP6513424B2/ja
Application filed by オルガノ株式会社 filed Critical オルガノ株式会社
Priority to KR1020177016226A priority Critical patent/KR101966569B1/ko
Priority to CN201580070782.9A priority patent/CN107108277B/zh
Priority to SG11201704614YA priority patent/SG11201704614YA/en
Priority to MYPI2017702134A priority patent/MY188356A/en
Publication of WO2016104356A1 publication Critical patent/WO2016104356A1/ja
Priority to SA517381683A priority patent/SA517381683B1/ar

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
    • B01D65/06—Membrane cleaning or sterilisation ; Membrane regeneration with special washing compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/08—Prevention of membrane fouling or of concentration polarisation
    • 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
    • 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
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens

Definitions

  • the slime suppression method of the separation membrane according to the present embodiment despite exhibiting a slime suppression effect equal to or higher than that of a chlorine-based oxidizing agent such as hypochlorous acid, compared with a chlorine-based oxidizing agent, Since the elimination rate of the brominated trihalomethane produced in the separation membrane is extremely high, the trihalomethane in the permeated water of the separation membrane can be greatly reduced. For this reason, the slime inhibitor used with the slime suppression method of the separation membrane which concerns on this embodiment is suitable as a slime inhibitor for separation membranes.
  • a method in which “bromine-based oxidant” and “sulfamic acid compound” are present, “reaction product of bromine compound and chlorine-based oxidant”, and “sulfamic acid compound” ”, A method in which“ a reaction product of a bromine-based oxidant and a sulfamic acid compound ”is present, or“ a reaction product of a reaction product of a bromine compound and a chlorinated oxidant and a sulfamic acid compound ”
  • the method in which the “product” is present has an extremely low deterioration effect on the separation membrane, and can be directly introduced into the separation membrane to suppress slime. For this reason, the slime inhibitor used by these slime suppression methods is more suitable as a slime inhibitor for separation membranes.
  • the trihalomethane precursor can be measured as a trihalomethane production ability (THMFP) (mg / L) by a measurement method based on “a special method for the maintenance of water quality in a tap water source area for prevention of specific water use damage”. Specifically, the sample was produced under the conditions of pH 7.0, temperature 20 ° C., reaction time 24 hours, and sodium hypochlorite added so that the free residual chlorine concentration after 24 hours was 1 to 2 mg / L. In this method, the amount of trihalomethane produced is determined by simultaneous analysis using a purge / trap / gas chromatograph / mass spectrometer. The trihalomethane precursor can also be measured with a TOC meter or the like.
  • TMMFP trihalomethane production ability
  • the trihalomethane precursor When the trihalomethane precursor is present at 0.001 mg / L or more as the trihalomethane precursor (THMFP) (mg / L), trihalomethane is likely to be generated.
  • the concentration is L or more, preferably 0.01 mg / L or more, and more preferably 0.02 mg / L or more, the method for suppressing slime of the separation membrane according to this embodiment is more effective.
  • the concentration is L or more, preferably 0.01 mg / L or more, and more preferably 0.02 mg / L or more, the method for suppressing slime of the separation membrane according to this embodiment is more effective.
  • limiting in particular in the upper limit of the trihalomethane production ability of the feed water or washing water to a membrane separator For example, it is 1 mg / L or less.
  • Slime inhibitors such as “hypobromite” and “hypobromite stabilizing composition in which bromine-based oxidant and sulfamic acid coexist” used in the method for suppressing slime of a separation membrane according to an embodiment of the present invention are Slime suppression effect (bactericidal effect) equivalent to or better than hypochlorous acid.
  • bromine trihalomethane is mainly produced.
  • these “hypobromite” and “hypobromite stabilization composition” unlike ordinary hypochlorous acid, hardly increases the amount of trihalomethane generated with increasing bromide ion concentration. .
  • the slime suppression method for a separation membrane according to this embodiment is suitable as a slime suppression method for a membrane separation device using feed water or washing water containing a trihalomethane precursor and bromide ions.
  • the slime suppression method for a separation membrane enables a slime suppression treatment that minimizes the trihalomethane concentration in the permeated water of the separation membrane while having a high slime suppression effect.
  • bromine-based oxidant or “bromine compound and chlorine” is fed into the feed water or the wash water to the membrane separator using the feed water or the wash water containing the trihalomethane precursor. What is necessary is just to inject
  • the “bromine compound” and the “chlorine oxidant” may be added separately to the aqueous system, or may be added to the aqueous system after being mixed with the stock solution.
  • a “bromine oxidant” or a “reaction product of a bromine compound and a chlorine oxidizer” and “sulfamic acid” may be injected by a chemical injection pump or the like.
  • the “bromine-based oxidant” or “reaction product of bromine compound and chlorine-based oxidant” and the “sulfamic acid compound” may be added separately to the aqueous system, or they are mixed together in the stock solution and then into the aqueous system. It may be added.
  • the separation membrane slime suppression method according to the present embodiment can suppress the deterioration of the separation membrane and effectively sterilize the separation membrane during the operation suspension even in the membrane separation system that operates and halts the operation. It becomes.
  • a raw water pipe 16 is connected to the inlet of the raw water tank 10.
  • the outlet of the raw water tank 10 and the inlet of the membrane separation device 12 are connected by a raw water supply pipe 18 via a pump 14.
  • a permeated water pipe 20 is connected to the permeated water outlet of the membrane separator 12, and a concentrated water pipe 22 is connected to the concentrated water outlet.
  • a sterilizing agent supply pipe 24 is connected between the pump 14 in the raw water supply pipe 18 and the inlet of the membrane separation device 12.
  • the raw water to be treated is stored in the raw water tank 10 as necessary, and then supplied to the membrane separation device 12 through the raw water supply pipe 18 by the pump 14.
  • membrane separation processing is performed by the separation membrane (membrane separation processing step).
  • the permeated water (treated water) obtained by the membrane separation treatment is discharged through the permeated water pipe 20, and the concentrated water is discharged through the concentrated water pipe 22.
  • the concentrated water may be circulated to the raw water tank 10 or the raw water supply pipe 18.
  • the raw water in the raw water tank 10 is passed through the membrane separator 12 and a predetermined concentration of bactericide is added to the raw water through the bactericide supply pipe 24 from the bactericide supply mechanism, and the operation of the membrane separation system 1 is performed.
  • the pump 14 is stopped and the bactericide is stopped during the operation of the membrane separation system 1. May be present in the membrane separation device 12.
  • operation stop means that the membrane separation system 1 has not obtained treated water (permeated water).
  • a bactericidal agent is added to the backwashing water, and the membrane separation system 1 is not in operation.
  • a disinfectant may be present in the membrane separation device 12.
  • a level switch is installed in the raw water tank 10, the operation is stopped when the water level in the raw water tank 10 detected by the level switch during operation is lower than a predetermined height, and the level switch is detected during the operation stop. Control may be performed so that the operation is resumed when the water level in the raw water tank 10 becomes higher than a predetermined height.
  • bromine-based oxidizing agent and “sulfamic acid compound” are used as disinfectants (slime suppressing agents) during the operation stop of the membrane separation system 1 in which the operation and the operation stop are performed.
  • a hypobromite stabilization composition produces
  • the slime suppression method of the separation membrane which concerns on this embodiment is a "bromine-type oxidizing agent and a sulfamic acid compound as a disinfectant (slime inhibitor) during the operation stop of the membrane separation system 1 in which an operation
  • a reaction product of a reaction product of a bromine compound and a chlorinated oxidant and a sulfamic acid compound is present in the membrane separation device 12.
  • the method for suppressing the slime of the separation membrane includes, for example, “bromine”, “bromine chloride”, “hypobromine” during the operation stop of the membrane separation system 1 in which the operation and the operation stop are performed.
  • the “acid” or “reaction product of sodium bromide and hypochlorous acid” and the “sulfamic acid compound” are present in the membrane separator 12.
  • the method for suppressing slime of the separation membrane according to the present embodiment can be performed during, for example, “reaction product of bromine and sulfamic acid compound”, “salt chloride” during the operation stop of the membrane separation system 1 in which the operation and the operation stop are performed.
  • the reaction product of bromine and sulfamic acid compound ", or the reaction product of sodium bromide and hypochlorous acid and the reaction product of sulfamic acid compound” hypobromite stabilization composition This is a method of existing in the separation device 12.
  • the “reactant” and the “sulfamic acid compound” may be injected into the aqueous system by a chemical injection pump or the like.
  • the “bromine-based oxidant” or “reaction product of bromine compound and chlorine-based oxidant” and the “sulfamic acid compound” may be added separately to the aqueous system, or they are mixed together in the stock solution and then into the aqueous system. It may be added.
  • reaction product of bromine-based oxidant and sulfamic acid compound or “reaction of bromine compound and chlorine-based oxidant”
  • reaction product of the product and the sulfamic acid compound may be injected into the aqueous system by a chemical injection pump or the like.
  • the ratio of the equivalent of “sulfamic acid compound” to the equivalent of “bromine-based oxidant” or “reaction product of bromine compound and chlorine-based oxidant” is 1 or more. It is preferable that it is in the range of 1 or more and 2 or less. If the ratio of the equivalent of “sulfamic acid compound” to the equivalent of “bromine-based oxidant” or “reaction product of bromine compound and chlorine-based oxidant” is less than 1, the film may be deteriorated. When it exceeds, manufacturing cost may increase.
  • the effective halogen concentration in contact with 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, it may cause deterioration of the separation membrane and corrosion of piping.
  • bromine-based oxidizing agents examples include bromine (liquid bromine), bromine chloride, bromic acid, bromate, and hypobromite.
  • the preparation of “bromine and sulfamic acid compound (mixture of bromine and sulfamic acid compound)” or “reaction product of bromine and sulfamic acid compound” using bromine is composed of “hypochlorous acid and bromine compound and Compared to sulfamic acid preparations and bromine chloride and sulfamic acid preparations, the amount of trihalomethane produced is small, and the reverse osmosis membrane (RO membrane) does not deteriorate further, and the reverse osmosis membrane (RO membrane) permeates. Since the amount of effective halogen leaked into membrane permeated water such as water is smaller, it is more preferable as a slime inhibitor for separation membranes such as reverse osmosis membranes (RO membranes).
  • RO membranes reverse osmosis membranes
  • bromine and a sulfamic acid compound are present in feed water or washing water to a membrane separation apparatus including a separation membrane, which contains a trihalomethane precursor (preferably, a mixture of bromine and a sulfamic acid compound is present).
  • a reaction product of bromine and a sulfamic acid compound is present in the feed water or the washing water containing a trihalomethane precursor and supplied to a membrane separation apparatus including a separation membrane.
  • bromine compounds include sodium bromide, potassium bromide, lithium bromide, ammonium bromide and hydrobromic acid. Of these, sodium bromide is preferable from the viewpoint of formulation cost and the like.
  • 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.
  • alkali metal chlorites such as sodium chlorite and potassium chlorite
  • alkaline earth metal chlorites such as barium chlorite
  • other metal chlorites such as nickel chlorite
  • Alkali metal chlorates such as ammonium chlorate, sodium chlorate and potassium chlorate
  • alkaline earth metal chlorates such as calcium chlorate and barium chlorate.
  • chlorine-based oxidants may be used alone or in combination of two or more.
  • sodium hypochlorite is preferably used from the viewpoint of handleability.
  • the sulfamic acid compound is a compound represented by the following general formula (1).
  • R 2 NSO 3 H (1) (In the formula, R is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)
  • 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
  • One of two R groups such as a sulfamic acid compound, N-phenylsulfamic acid and the like, both of which are alkyl groups having 1 to 8 carbon atoms Is a hydrogen atom and the other sulfamic acid compound or a salt thereof, such as an aryl group having 6 to 10 carbon atoms.
  • the sulfamate include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt, strontium salt and barium salt, manganese salt, copper salt, zinc salt, iron salt, cobalt salt, Other metal salts such as nickel salts, ammonium salts, guanidine salts and the like can be mentioned.
  • the sulfamic acid compounds and salts thereof may be used alone or in combination of two or more.
  • sulfamic acid compound sulfamic acid (amidosulfuric acid) is preferably used from the viewpoint of environmental load.
  • an alkali may be further present.
  • 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).
  • RO membrane reverse osmosis membrane
  • NF membrane nanofiltration membrane
  • MF membrane microfiltration membrane
  • UF membrane ultrafiltration membrane
  • the method for suppressing slime of the separation membrane according to the embodiment of the present invention can be suitably applied particularly to a reverse osmosis membrane (RO membrane).
  • the slime suppression 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 have a relatively low resistance to oxidizing agents, and when free chlorine or the like is continuously brought into contact with the polyamide polymer membrane, the membrane performance is significantly reduced.
  • such a remarkable decrease in membrane performance hardly occurs even in the polyamide polymer membrane.
  • the reverse osmosis membrane (RO membrane) is deteriorated and treated water (permeated water) is deteriorated by operating at a pH of 5.5 or higher for the water supplied to the RO device. It is possible to secure a sufficient amount of permeated water while suppressing deterioration of water quality and exhibiting a sufficient slime suppressing effect.
  • a dispersant may be used in combination with a bromine-based oxidizing agent or a hypobromite stabilizing composition for scale control.
  • examples of 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.
  • an RO device is used so that the silica concentration in the RO concentrated water is less than the solubility and the Langeria index, which is a calcium scale index, is less than 0. Adjusting the operating conditions such as the recovery rate.
  • RO device examples include seawater desalination and wastewater recovery.
  • the slime inhibitor composition for separation membrane contains “bromine-based oxidant” or “reaction product of bromine compound and chlorine-based oxidant” and “sulfamic acid compound”, Furthermore, you may contain an alkali.
  • the slime inhibitor composition for separation membrane includes a “reaction product of a bromine-based oxidant and a sulfamic acid compound” or a “reaction product of a bromine compound and a chlorine-based oxidant, and a sulfamic acid. It contains a reaction product of a compound 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 reverse osmosis membrane (RO membrane) or the like is not further deteriorated, and the amount of effective halogen leaked into membrane permeated water such as RO permeated water is smaller.
  • Containing bromine and a sulfamic acid compound containing a mixture of bromine and sulfamic acid compound
  • a sulfamic acid compound for example, a mixture of bromine, sulfamic acid compound, alkali and water, or reaction of bromine with sulfamic acid compound
  • a product containing a product for example, a mixture of a reaction product of bromine and a sulfamic acid compound, an alkali, and water is preferable.
  • the slime inhibitor composition for a separation membrane according to the present embodiment has a high oxidizing power, slime inhibitory power, and slime peeling power, which is remarkably high compared to a combined chlorine-based slime inhibitor such as chlorosulfamic acid. Similarly, it hardly causes significant film deterioration like hypochlorous acid having high oxidizing power. At normal use concentrations, the effect on film degradation can be substantially ignored. Therefore, it is optimal as a slime inhibitor for separation membranes such as reverse osmosis membranes (RO membranes).
  • RO membranes reverse osmosis membranes
  • the slime inhibitor composition for separation membrane according to the present embodiment hardly permeates the reverse osmosis membrane (RO membrane), 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 slime inhibitor composition for separation membrane according to the present embodiment reacts with the trihalomethane precursor to produce bromine-based trihalomethane, but is easily eliminated by the separation membrane, and the trihalomethane in the permeated water of the separation membrane is greatly reduced. It is thought that it is done.
  • 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 bromic acid concentration in the slime inhibitor composition for separation membrane is preferably less than 5 mg / kg. If the bromate concentration in the slime inhibitor composition for separation membrane is 5 mg / kg or more, the concentration of bromate ions in the permeated water may increase.
  • the slime inhibitor composition for a separation membrane is a mixture of a bromine-based oxidant and a sulfamic acid compound, or a reaction product of a bromine compound and a chlorine-based oxidant, and a sulfamic acid compound. And may be further mixed with an alkali.
  • the inert gas to be used is not limited, at least one of nitrogen and argon is preferable from the viewpoint of production and the like, and nitrogen is particularly preferable from the viewpoint of manufacturing cost and the like.
  • the oxygen concentration in the reactor during the addition of bromine is preferably 6% or less, more preferably 4% or less, further preferably 2% or less, and particularly preferably 1% or less. If the oxygen concentration in the reactor during the bromine reaction exceeds 6%, the amount of bromic acid produced in the reaction system may increase.
  • 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 sterilizing power 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.
  • 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 Minutes were mixed to prepare composition 1.
  • the pH of Composition 1 was 14, and the effective halogen concentration (effective chlorine equivalent concentration) was 7.5% by weight.
  • the detailed preparation method of the composition 1 is as follows.
  • the pH of the resulting solution was 14 as measured by the glass electrode method.
  • the bromine content of the resulting solution was 16.9% as measured by a redox titration method using sodium thiosulfate after bromine was converted to iodine with potassium iodide, and the theoretical content (16.9% ) Of 100.0%.
  • the oxygen concentration in the reaction vessel during the bromine reaction was measured using “Oxygen Monitor JKO-02 LJDII” manufactured by Zico Corporation.
  • the bromic acid concentration was less than 5 mg / kg.
  • composition 2 Sodium bromide: 11% by weight, 12% sodium hypochlorite aqueous solution: 50% by weight, sodium sulfamate: 14% by weight, sodium hydroxide: 8% by weight, water: the residue was mixed to prepare composition 2.
  • the pH of Composition 2 was 14, and the effective halogen concentration (effective chlorine equivalent concentration) was 6% by weight.
  • the detailed preparation method of the composition 2 is as follows.
  • composition 2 (1100 mg / kg).
  • composition 1 less than 50 mg / kg).
  • composition 3 A 9% by weight aqueous sodium hypobromite solution (Kanto Chemical Co., Ltd., Deer Grade 1) was used as Composition 3.
  • composition 4 A 12 wt% aqueous sodium hypochlorite solution was used as Composition 4.
  • compositions 1 to 4 were added to the raw water of the reverse osmosis membrane device, respectively, and the total trihalomethane concentration in the separation membrane feed water and the separation membrane permeated water, the total trihalomethane in the reverse osmosis membrane (RO membrane) Exclusion rates were compared.
  • raw water the following simulated water was used in Examples 1 to 3 and Comparative Example 1, and pure water was used in Reference Examples 1 and 2.
  • Test apparatus Flat membrane test apparatus Separation membrane: Polyamide polymer reverse osmosis membrane ES15 manufactured by Nitto Denko Corporation ⁇ Operating pressure: 0.75 MPa ⁇
  • Raw water Simulated water with trihalomethane production ability of 0.01 mg / L (pure water added with 8.9 mg / L humic acid (manufactured by Wako Pure Chemical Industries) as a trihalomethane precursor, TOC: 5 mg / L) or pure Water / drug: Compositions 1 to 4 are added so that the effective halogen concentration (effective chlorine equivalent concentration) is 3 mg / L.
  • Raw water pH The pH of the test water is adjusted to 8 after the drug is added.
  • Total trihalomethane concentration in RO water supply and RO permeated water, removal rate of total trihalomethane in reverse osmosis membrane (RO membrane) Compositions 1 to 4 as shown in Table 1 were added to simulated water or pure water, and the pH was adjusted to 8. The water temperature was adjusted to 25 ° C. and circulated through the RO apparatus. Four hours later, the total trihalomethane concentration (mg / L) in the RO water supply and RO permeated water was measured. From the total trihalomethane concentration in the RO water supply and RO permeated water, the removal rate (%) of the total trihalomethane in the reverse osmosis membrane (RO membrane) was determined. The results are shown in Table 1.
  • the total trihalomethane refers to four substances of chloroform, bromodichloromethane, dibromochloromethane and bromoform.
  • Total trihalomethane concentration was measured by a simultaneous analysis method using a purge / trap / gas chromatograph / mass spectrometer in accordance with the method (Ministry of Health, Labor and Welfare Notification No. 261) established by the Minister of Health, Labor and Welfare based on the provisions of the Ministerial Ordinance on Water Quality Standards. .
  • compositions 1, 2, 4 to 7 are added to the raw water of the reverse osmosis membrane device to influence the exclusion rate of the reverse osmosis membrane (RO membrane), the effect on the permeated water, and the oxidizing power. Compared.
  • composition 6 Composition 6 containing bromine chloride, sodium sulfamate, and sodium hydroxide was used. The pH of the composition 6 was 14, and the effective halogen concentration (effective chlorine equivalent concentration) was 7% by weight.
  • composition 7 Sodium bromide: 15% by weight, 12% sodium hypochlorite aqueous solution: 42.4% by weight were separately added to water.
  • Test apparatus Flat membrane test apparatus Separation membrane: Polyamide polymer reverse osmosis membrane ES20 manufactured by Nitto Denko Corporation ⁇ Operating pressure: 0.75 MPa
  • Raw water Sagamiharai water (pH 7.2, conductivity 240 ⁇ S / cm, bromide ion concentration less than 1.0 mg / L) ⁇
  • Drug Compositions 1, 2, 4 to 7 are added so that the effective halogen concentration (effective chlorine equivalent concentration) is 10 mg / L.
  • compositions 1, 2, 4 to 7 were added to simulated water, and the bactericidal power was compared.
  • compositions 1, 2, 5, and 6 maintained a high reverse osmosis membrane (RO membrane) rejection rate, had low effective halogen concentration (effective chlorine equivalent concentration) of permeated water, and high oxidation power and bactericidal power.
  • compositions 1, 2, 5, and 6 maintained the highest reverse osmosis membrane (RO membrane) rejection rate and had the lowest effective halogen concentration (effective chlorine equivalent concentration) of permeated water. .
  • Composition 4 had high oxidizing power and bactericidal power, but the rejection rate of the reverse osmosis membrane (RO membrane) was reduced, and the effective halogen concentration (effective chlorine equivalent concentration) of the permeated water was also high.
  • the composition 7 had high oxidizing power and bactericidal power, the effective halogen concentration (effective chlorine equivalent concentration) of permeated water was slightly high.
  • composition 1 ′ In the same manner as in Composition 1, in a nitrogen atmosphere, liquid bromine: 17% by weight (wt%), sulfamic acid: 10.7% by weight, sodium hydroxide: 12.9% by weight, potassium hydroxide: 3.95 The composition 1 ′ was prepared by mixing the weight%, water: residue. Composition 1 ′ had a pH of 14, an effective halogen concentration (effective chlorine equivalent concentration) of 7.5% by weight, and a bromic acid concentration of less than 5 mg / kg.
  • composition 8 In the atmosphere without nitrogen purge, liquid bromine: 17% by weight (wt%), sulfamic acid: 10.7% by weight, sodium hydroxide: 12.9% by weight, potassium hydroxide: 3.95% by weight, Water: the residue was mixed to prepare composition 8.
  • Composition 8 had a pH of 14, an effective halogen concentration (effective chlorine equivalent concentration) of 7.4% by weight, and a bromic acid concentration of 63 mg / kg.
  • Test apparatus Flat membrane test apparatus Separation membrane: Polyamide polymer reverse osmosis membrane ES20 manufactured by Nitto Denko Corporation ⁇ Operating pressure: 0.75 MPa
  • Raw water Sagamiharai water (pH 7.2, conductivity 240 ⁇ S / cm)
  • -Drug Compositions 1 'and 8 are added so that the effective halogen concentration (effective chlorine equivalent concentration) is 50 mg / L.
  • composition 1 ' the bromate ion concentration in the feed water and permeate was less than 1 ⁇ g / L.
  • composition 8 the bromate ion concentration in the feed water and permeated water was higher than in composition 1 '.
  • hypobromite stabilizing composition which is a “reaction product of bromine-based oxidant and sulfamic acid compound” is used as a slime inhibitor (Example 4)
  • “bromine-based oxidant” is used.
  • Example 5 when hypochlorous acid, which is a general slime inhibitor, is used (Comparative Example 2), hypochlorous acid is a reaction product of hypochlorous acid and a sulfamic acid compound. It compared about the trihalomethane density
  • composition 9 was prepared by mixing 12% aqueous sodium hypochlorite solution: 50% by weight, sulfamic acid: 10% by weight, sodium hydroxide: 8% by weight, water: residue. The pH of the composition 9 was 14, and the effective halogen concentration (effective chlorine equivalent concentration) was 6% by weight.
  • compositions 1, 3, and 4 were added to the raw water, and the total trihalomethane concentrations in the treated water were compared.
  • the following simulated water was used as raw water.
  • Raw water Simulated water (pure water with humic acid (manufactured by Wako Pure Chemical Industries) 8.9 mg / L as a trihalomethane precursor and sodium bromide (manufactured by Kanto Kagaku, special grade) as a bromide ion source with a concentration of 0.1 to Added to 300mg / L) -Drug: Compositions 1, 3, and 4 are added so that the effective halogen concentration (effective chlorine equivalent concentration) is 3 mg / L.-Raw water pH: adjusted so that the pH of the test water is 8 after the drug is added. Temperature: 25 ° C ⁇ Measurement method of effective halogen concentration: measured by DPD method using residual chlorine measuring device (manufactured by Hach, “DR-4000”)
  • Total trihalomethane concentration in treated water Compositions 1, 3, and 4 were added to the simulated water and the pH was adjusted to 8, and the water temperature was adjusted to 25 ° C. and stirred for 4 hours. After 4 hours of stirring, the total trihalomethane concentration (mg / L) in the treated water was measured. The results are shown in FIG. Here, the total trihalomethane refers to four substances of chloroform, bromodichloromethane, dibromochloromethane and bromoform.
  • Total trihalomethane concentration was measured by a simultaneous analysis method using a purge / trap / gas chromatograph / mass spectrometer in accordance with the method (Ministry of Health, Labor and Welfare Notification No. 261) established by the Minister of Health, Labor and Welfare based on the provisions of the Ministerial Ordinance on Water Quality Standards. .
  • the effective halogen concentration is determined by diluting the sample and using a multi-item water quality analyzer DR / 4000 manufactured by HACH (in the case of the total halogen concentration, the measurement item is “total chlorine”), and the effective chlorine measurement method (DPD (diethyl-p -Phenylenediamine) method) (mg / L asCl 2 ).
  • the effective halogen referred to here is a value measured by an effective chlorine measuring method (DPD method).
  • an effective bromine concentration mg / L asCl 2
  • the measured value by the effective chlorine measurement method (DPD method) is 2.25 (159.8).
  • compositions 1, 2 ′ which are hypobromite stabilizing compositions, have a lower total halogen concentration in simulated seawater than composition 4. Suppressed. This is because the hypobromite stabilization composition is more stable than hypochlorous acid and hypobromite, and a portion of the hypobromite stabilization composition and chlorination in artificial seawater. This is thought to be due to the reaction of the product ions and the production of bound chlorine with extremely high stability.
  • Test conditions -Separation membrane: Nitto Denko Corporation, polyamide polymer reverse osmosis membrane ES15
  • Test water Simulated seawater A or simulated seawater B or simulated water C
  • Chemicals added to a total halogen concentration of 10 mg / L asCl 2
  • Test water pH adjusted to a predetermined pH using sodium hydroxide aqueous solution or sulfuric acid aqueous solution
  • Immersion storage period of separation membrane 30 days
  • Conditions room temperature (25 ° C) under light-shielding conditions
  • composition 4 when the separation membrane is stored for a long period of time, the separation membrane deteriorates and the rejection rate is greatly reduced.
  • compositions 1 and 2 'maintain a high rejection rate even if the separation membrane is stored for a long period of time. Film deterioration was suppressed.
  • the degradation of the separation membrane is suppressed, and the separation membrane is effectively removed during the shutdown. It was found that it can be sterilized.

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JP2020058963A (ja) * 2018-10-05 2020-04-16 オルガノ株式会社 水処理装置および水処理方法
JP2021030189A (ja) * 2019-08-29 2021-03-01 オルガノ株式会社 水処理装置および水処理方法

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JP6819781B2 (ja) * 2018-04-26 2021-01-27 栗田工業株式会社 逆浸透膜処理方法、水系のバイオファウリング抑制方法及びそのための装置
JP6706702B1 (ja) * 2019-03-07 2020-06-10 オルガノ株式会社 逆浸透膜を用いる水処理方法および水処理装置
CN113648836A (zh) * 2021-05-12 2021-11-16 同济大学 一种控制膜源消毒副产物前体物泄露的方法
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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