Filtration treatment system and filtration treatment method

Abstract

This filtration treatment system is provided with a membrane filtration device as a prefiltration treatment device for removing insoluble components from the water to be treated containing organic substance, a reverse osmosis membrane treatment device for subjecting the prefiltration-treated water to reverse osmosis membrane treatment, and a chemical agent supply pipe for supplying a chemical agent into the membrane filtration device, wherein the chemical agent contains a sulfamic acid compound, and a bromine-based oxidizing agent or the reaction product of a bromine compound with a chlorine-based oxidizing agent, or, contains the reaction product of a sulfamic acid compound with a bromine-based oxidizing agent or with the reaction product of a bromine compound with a chlorine-based oxidizing agent.

Claims

1. A filtration treatment system comprising: a prefiltration treatment filter comprising a filter media for removing insoluble components from a water to be treated that contains organic substance, a reverse osmosis membrane for subjecting a prefiltration-treated water from the prefiltration treatment filter to a reverse osmosis membrane treatment using a polyamide-based polymer membrane, and a chemical agent supply pipe for supplying a chemical agent to water to be treated by the prefiltration treatment filter, wherein the chemical agent comprises: a) a mixture of a bromine-based oxidizing agent and a sulfamic acid compound, b) a mixture of a sulfamic acid compound and a reaction product of a bromine compound with a chlorine-based oxidizing agent, c) a reaction product of a sulfamic acid compound with a bromine-based oxidizing agent, or d) a reaction product of a sulfamic acid compound with a reaction product of a bromine compound with a chlorine-based oxidizing agent; wherein the prefiltration-treated water from the prefiltration treatment filter comprises the chemical agent; wherein the chemical agent is added at a point upstream of the pretreatment filter; and wherein slime generation in the prefiltration treatment filter is inhibited, and slime generation in or on the reverse osmosis membrane is inhibited.

2. The filtration treatment system according to claim 1, wherein the chemical agent either comprises bromine and a sulfamic acid compound, or comprises a reaction product of bromine and a sulfamic acid compound.

3. The filtration treatment system according to claim 2, wherein the chemical agent is obtained by a method which includes adding and reacting bromine, under an inert gas atmosphere, with a mixed solution comprising water, an alkali and a sulfamic acid compound.

4. The filtration treatment system according to claim 1, wherein a pH of the prefiltration-treated water is 5.5 or higher.

5. The filtration treatment system according to claim 1, wherein a pH of the water to be treated that is supplied to the prefiltration treatment filter is 5.5 or higher.

6. A filtration treatment method comprising: a prefiltration in which insoluble components are removed from a water to be treated that contains organic substance, a reverse osmosis membrane contacting in which a prefiltration-treated water from the prefiltration is subjected to a reverse osmosis membrane contacting using a polyamide-based polymer membrane, and supplying a chemical agent to water to be treated by a prefiltration treatment filter at a point upstream of the pretreatment filter, wherein the chemical agent comprises; a) a mixture of a bromine-based oxidizing agent and a sulfamic acid compound, b) a mixture of a sulfamic acid compound and a reaction product of a bromine compound with a chlorine-based oxidizing agent, c) a reaction product of a sulfamic acid compound with a bromine-based oxidizing agent, or d) a reaction product of a sulfamic acid compound with a reaction product of a bromine compound with a chlorine-based oxidizing agent; wherein the prefiltration-treated water from the prefiltration comprises the chemical agent; and wherein slime generation in the prefiltration is inhibited, and slime generation in the reverse osmosis membrane contacting is inhibited.

7. The filtration treatment method according to claim 6, wherein the chemical agent either comprises bromine and a sulfamic acid compound, or comprises a reaction product of bromine and a sulfamic acid compound.

8. The filtration treatment method according to claim 7, wherein the chemical agent is obtained by a method which includes adding and reacting bromine, under an inert gas atmosphere, with a mixed solution comprising water, an alkali and a sulfamic acid compound.

9. The filtration treatment method according to claim 6, wherein a pH of the prefiltration-treated water is 5.5 or higher.

10. The filtration treatment method according to claim 6, wherein a pH of the water to be treated that is treated in the prefiltration is 5.5 or higher.

11. The filtration treatment system according to claim 2, wherein a pH of the prefiltration-treated water is 5.5 or higher.

12. The filtration treatment system according to claim 3, wherein a pH of the prefiltration-treated water is 5.5 or higher.

13. The filtration treatment system according to claim 2, wherein a pH of the water to be treated that is supplied to the prefiltration treatment filter is 5.5 or higher.

14. The filtration treatment system according to claim 3, wherein a pH of the water to be treated that is supplied to the prefiltration treatment filter is 5.5 or higher.

15. The filtration treatment method according to claim 7, wherein a pH of prefiltration water is 5.5 or higher.

16. The filtration treatment method according to claim 8, wherein a pH of the prefiltration-treated water is 5.5 or higher.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a schematic view illustrating one example of a filtration treatment system according to an embodiment of the present invention.

(2) FIG. 2 is a schematic view illustrating a conventional filtration treatment system.

(3) FIG. 3 is a diagram illustrating the temperature-corrected transmembrane pressure difference (kPa @ 25 C.) for an ultrafiltration membrane relative to the number of days of operation in the Examples and Comparative Examples.

(4) FIG. 4 is a diagram illustrating the pressure difference (MPa) upon water passage through a reverse osmosis membrane relative to the number of days of operation in the Examples and Comparative Examples.

(5) FIG. 5 is a diagram illustrating the conductivity inhibition rate (%) for a reverse osmosis membrane relative to the number of days of operation in the Examples and Comparative Examples.

(6) FIG. 6 is a schematic view illustrating another example of a filtration treatment system according to an embodiment of the present invention.

DESCRIPTION OF EMBODIMENTS

(7) Embodiments of the present invention are described below. These embodiments are merely examples of implementing the present invention, and the present invention is in no way limited by these embodiments.

(8) <Filtration Treatment System and Filtration Treatment Method>

(9) An outline of one example of a filtration treatment system according to an embodiment of the present invention is shown in FIG. 1, and the structure of that system is described below. The filtration treatment system 1 includes a membrane filtration device 12 provided with a separation membrane that functions as a prefiltration treatment means, and a reverse osmosis membrane treatment device 16 as a reverse osmosis membrane treatment means.

(10) In the filtration treatment system 1 of FIG. 1, a raw water pipe 24 is connected to the inlet of a raw water tank 10, the outlet from the raw water tank 10 and the inlet of the membrane filtration device 12 are connected by a raw water supply pipe 26 via a pump 18, the outlet of the membrane filtration device 12 and the inlet of a prefiltration-treated water tank 14 are connected via a prefiltration-treated water pipe 28, an outlet of the prefiltration-treated water tank 14 and the inlet of the reverse osmosis membrane treatment device 16 are connected by a prefiltration-treated water supply pipe 30 via a pump 20, a concentrate pipe 32 is connected to a concentrate outlet, and a permeate pipe 34 is connected to a permeate outlet of the reverse osmosis membrane treatment device 16. A lower outlet of the prefiltration-treated water tank 14 and the secondary side of the membrane filtration device 12 are connected by a backwash water pipe 36 via a pump 22, and a backwash wastewater pipe 40 is connected to the primary side of the membrane filtration device 12. A chemical agent supply pipe 38 that functions as a chemical agent supply means is connected to the backwash water pipe 36 at a position downstream from the pump 22.

(11) A filtration treatment method according to an embodiment of the present invention, and the operation of the filtration treatment system 1 are described below.

(12) The raw water that represents the water to be treated containing organic substance passes through the raw water pipe 24, and following storage in the raw water tank 10 where necessary, is fed through the raw water supply pipe 26 and supplied to the membrane filtration device 12 by the pump 18. In the membrane filtration device 12, insoluble components are removed from the water being treated by a separation membrane (prefiltration treatment step).

(13) Having undergone prefiltration, the prefiltration-treated water passes through the prefiltration-treated water pipe 28, and following storage in the prefiltration-treated water tank 14 where necessary, is fed through the prefiltration-treated water supply pipe 30 and supplied to the reverse osmosis membrane treatment device 16 by the pump 20. In the reverse osmosis membrane treatment device 16, a reverse osmosis membrane treatment is performed using a reverse osmosis membrane (reverse osmosis membrane treatment step).

(14) The concentrate obtained in the reverse osmosis membrane treatment is discharged through the concentrate pipe 32, and the permeate is discharged through the permeate pipe 34.

(15) When cleaning of the membrane filtration device 12 becomes necessary, the pump 22 is used to supply at least a portion of the prefiltration-treated water from the prefiltration-treated water tank 14 as a backwash water through the backwash water pipe 36 to the secondary side of the membrane filtration device 12, and backwashing is performed (backwash step). The backwash wastewater passes through the backwash wastewater pipe 40 and is discharged from the primary side of the membrane filtration device 12. During this time, a cleaning chemical agent passes through the chemical agent supply pipe 38 and is supplied to the backwash water in the backwash water pipe 36 at a position downstream from the pump 22 (chemical agent supply step), and the wash water containing the chemical agent is used to backwash the separation membrane and the like of the membrane filtration device 12.

(16) An outline of another example of a filtration treatment system according to an embodiment of the present invention is shown in FIG. 6. In the filtration treatment system 1 of FIG. 1, the chemical agent supply pipe 38 is connected to the backwash water pipe 36 at a position downstream from the pump 22, but in the filtration treatment system 3 illustrated in FIG. 6, the chemical agent supply pipe 38 is connected as a chemical agent supply means to the raw water supply pipe 26 at a position upstream from the pump 18. The chemical agent supply pipe 38 may also be connected to the raw water tank 10 as a chemical agent supply means.

(17) The raw water that represents the water to be treated containing organic substance passes through the raw water pipe 24, and following storage in the raw water tank 10 where necessary, is fed through the raw water supply pipe 26 by the pump 18 and supplied to the membrane filtration device 12. In the membrane filtration device 12, insoluble components are removed from the water being treated by a separation membrane (prefiltration treatment step). Here, the cleaning chemical agent passes through the chemical agent supply pipe 38 and is supplied to the raw water, in either the raw water supply pipe 26 at a position upstream from the pump 18, or in the raw water tank 10 (chemical agent supply step), and the separation membrane and the like of the membrane filtration device 12 is then cleaned using the raw water containing the chemical agent.

(18) In a similar manner to the filtration treatment system 1 of FIG. 1, the prefiltration-treated water that has undergone prefiltration treatment is subjected to a reverse osmosis membrane treatment using a reverse osmosis membrane in the reverse osmosis membrane treatment device 16 (reverse osmosis membrane treatment step). When cleaning of the membrane filtration device 12 becomes necessary, at least a portion of the prefiltration-treated water from the prefiltration-treated water tank 14 is supplied as a backwash water to the secondary side of the membrane filtration device 12, and backwashing is performed (backwash step).

(19) An embodiment in which a stabilized hypobromous acid composition is added as a chemical agent to the raw water that represents the water being treated by the prefiltration treatment means offers the advantages that slime generation in the prefiltration treatment means is inhibited, slime generation on the polyamide reverse osmosis membrane in a subsequent stage can be inhibited with almost no degradation of the reverse osmosis membrane, and additional facilities such as a reducing agent addition means or an activated carbon device or the like may not be provided in a stage prior to the reverse osmosis membrane treatment means.

(20) In the filtration treatment method and the filtration treatment system according to embodiments of the present invention, a chemical agent including a bromine-based oxidizing agent, or a reaction product of a bromine compound and a chlorine-based oxidizing agent, and a sulfamic acid compound, or alternatively, including a reaction product of a sulfamic acid compound with a bromine-based oxidizing agent, or with a reaction product of a bromine compound and a chlorine-based oxidizing agent is added to at least one of the raw water and the backwash water, and if necessary also to the chemical solution of a chemical agent cleaning step, for the purpose of preventing blockages and inhibiting slime generation in the membrane filtration device 12 that functions as the prefiltration treatment means, or as a chemical agent for cleaning that is used in the chemical agent cleaning step.

(21) In other words, in the filtration treatment method and the filtration treatment system according to embodiments of the present invention, a chemical agent is used that includes a bromine-based oxidizing agent or a reaction product of a bromine compound and a chlorine-based oxidizing agent and a sulfamic acid compound. As a result, it is thought that a stabilized hypobromous acid composition is produced in at least one of the raw water and the backwash water, and also in the chemical solution used in the chemical agent cleaning step.

(22) Furthermore, in the filtration treatment method and the filtration treatment system according to embodiments of the present invention, a stabilized hypobromous acid composition that is a reaction product of a sulfamic acid compound with a bromine-based oxidizing agent or a reaction product of a sulfamic acid compound with a reaction product of a bromine compound and a chlorine-based oxidizing agent may be supplied as the aforementioned chemical agent.

(23) In particular, in the filtration treatment method and the filtration treatment system according to an embodiment of the present invention, bromine, bromine chloride or a reaction product of sodium bromide and hypochlorous acid, and a sulfamic acid compound are supplied to at least one of the raw water and the backwash water, and also to the chemical solution used in the chemical agent cleaning step.

(24) Further, in another example of the filtration treatment method and the filtration treatment system according to an embodiment of the present invention, a reaction product of a sulfamic acid compound with bromine, a reaction product of a sulfamic acid compound with bromine chloride or a reaction product of a sulfamic acid compound with a reaction product of sodium bromide and hypochlorous acid is supplied to at least one of the raw water and the backwash water, and also to the chemical solution used in the chemical agent cleaning step.

(25) For example, a bromine-based oxidizing agent or a reaction product of a bromine compound and a chlorine-based oxidizing agent and a sulfamic acid compound, or alternatively a reaction product of these components, may be injected into the backwash water in the backwash water pipe 36 using a chemical feed pump or the like. The bromine-based oxidizing agent or the reaction product of a bromine compound and a chlorine-based oxidizing agent and the sulfamic acid compound may be added separately, or the neat liquids may be mixed together and then added.

(26) Alternatively, the bromine-based oxidizing agent or the reaction product of a bromine compound and a chlorine-based oxidizing agent and the sulfamic acid compound, or alternatively a reaction product of these components, may be injected into the raw water in the raw water tank 10 or the raw water supply pipe 26 using a chemical feed pump or the like.

(27) A chemical agent cleaning step in which the separation membrane and the like of the membrane filtration device 12 are immersed in a chemical solution containing a chemical agent may also be provided periodically. This chemical agent cleaning step includes a removal step of immersing the separation membrane and the like in a chemical solution containing a chemical agent to dissolve or remove impurities adhered to the separation membrane and the like, and a flushing step of washing away any chemical agent retained inside the membrane filtration device 12 with a flushing liquid such as water.

(28) In this case, the bromine-based oxidizing agent or the reaction product of a bromine compound and a chlorine-based oxidizing agent and the sulfamic acid compound, or the reaction product of these components, which is injected into the backwash water in the backwash water pipe 36 using a chemical feed pump or the like, may be used as the above chemical solution.

(29) In the filtration treatment method and the filtration treatment system according to the present embodiment, by ensuring that the bromine-based oxidizing agent or the reaction product of a bromine compound and a chlorine-based oxidizing agent and the sulfamic acid compound, or the reaction product of these components, exist in at least one of the raw water and the backwash water, and also in the chemical solution used in the chemical agent cleaning step, blockages can be prevented and slime generation can be inhibited in the membrane filtration device 12. Because the stabilized hypobromous acid composition may cause almost no degradation of the reverse osmosis membrane, the addition of a reducing agent or installation of an activated carbon column or the like in a stage prior to the reverse osmosis membrane treatment is unnecessary, and an additional slime control agent may not be added at a stage prior to the reverse osmosis membrane treatment, meaning the system can be simplified.

(30) Further, a flushing step may not be performed in the chemical agent cleaning step for the membrane filtration device 12, and even if the supply of raw water is recommenced after washing with only an extremely small amount of flushing liquid, the reverse osmosis membrane in the subsequent stage suffers almost no degradation, meaning the process can be simplified and the amount of backwash wastewater can be reduced.

(31) The ratio of the equivalent weight of the sulfamic acid compound relative to the equivalent weight of the bromine-based oxidizing agent or the reaction product of a bromine compound and a chlorine-based oxidizing agent is preferably 1 or greater, and is more preferably within a range from at least 1 to not more than 2. If the ratio of the equivalent weight of the sulfamic acid compound relative to the equivalent weight of the bromine-based oxidizing agent or the reaction product of a bromine compound and a chlorine-based oxidizing agent is less than 1, then there is a possibility that the active components may not stabilize satisfactorily, whereas if the ratio exceeds 2, then the production costs may sometimes increase.

(32) The effective halogen concentration contacting the separation membrane, calculated as an effective equivalent chlorine concentration, is preferably from 0.01 to 100 mg/L. If this concentration is less than 0.01 mg/L, then a satisfactory slime inhibitory effect may not be obtainable, whereas if the concentration is greater than 100 mg/L, then there is a possibility that corrosion of metal materials such as the pipes may occur.

(33) Examples of the bromine-based oxidizing agent include bromine (liquid bromine), bromine chloride, hypobromous acid, bromic acid, and bromate salts and the like.

(34) Among these, compared with a formulation of hypochlorous acid, a bromine compound and sulfamic acid or a formulation of bromine chloride and sulfamic acid or the like, formulations that use bromine such as bromine and a sulfamic acid compound or a reaction product of bromine and a sulfamic acid compound are preferred, as they tend to contain less chloride ions, and are less likely to cause corrosion of metal materials such as the pipes.

(35) In other words, the filtration treatment method and the filtration treatment system according to embodiments of the present invention preferably incorporate bromine and a sulfamic acid compound, or incorporate a reaction product of bromine and a sulfamic acid compound, in at least one of the raw water and the backwash water, and also in the chemical solution of the chemical agent cleaning step.

(36) Examples of the bromine compound include sodium bromide, potassium bromide, lithium bromide and hydrobromic acid. Among these, in terms of production costs and the like, sodium bromide is preferred.

(37) Examples of the chlorine-based oxidizing agent include chlorine gas, chlorine dioxide, hypochlorous acid or salts thereof, chlorous acid or salts thereof, chloric acid or salts thereof, perchloric acid or salts thereof, and chlorinated isocyanuric acid or salts thereof. Among these, examples of the salts include alkali metal salts of hypochlorous acid such as sodium hypochlorite and potassium hypochlorite, alkaline earth metal salts of hypochlorous acid such as calcium hypochlorite and barium hypochlorite, alkali metal salts of chlorous acid such as sodium chlorite and potassium chlorite, alkaline earth metal salts of chlorous acid such as barium chlorite, other metal salts of chlorous acid such as nickel chlorite, ammonium chlorate, alkali metal salts of chloric acid such as sodium chlorate and potassium chlorate, and alkaline earth metal salts of chloric acid such as calcium chlorate and barium chlorate. Any one of these chlorine-based oxidizing agents may be used alone, or a combination of two or more oxidizing agents may be used. In terms of ease of handling and the like, the use of sodium hypochlorite as the chlorine-based oxidizing agent is preferred.

(38) The sulfamic acid compound is a compound represented by general formula (1) shown below.
R.sub.2NSO.sub.3H(1)
(In the formula, each R independently represents a hydrogen atom or an alkyl group having a carbon number of 1 to 8.)

(39) Examples of the sulfamic acid compound, in addition to sulfamic acid (amidosulfuric acid) in which the two R groups are both hydrogen atoms, include sulfamic acid compounds in which one of the two R groups is a hydrogen atom and the other is an alkyl group having a carbon number of 1 to 8, such as N-methylsulfamic acid, N-ethylsulfamic acid, N-propylsulfamic acid, N-isopropylsulfamic acid and N-butylsulfamic acid, sulfamic acid compounds in which the two R groups are both alkyl groups having a carbon number of 1 to 8, such as N,N-dimethylsulfamic acid, N,N-diethylsulfamic acid, N,N-dipropylsulfamic acid, N,N-dibutylsulfamic acid, N-methyl-N-ethylsulfamic acid and N-methyl-N-propylsulfamic acid, and sulfamic acid compounds in which one of the two R groups is a hydrogen atom and the other is an aryl group having a carbon number of 6 to 10, such as N-phenylsulfamic acid, as well as salts of the above acids. Examples of the sulfamic acid salts include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts, strontium salts and barium salts, other metal salts such as manganese salts, copper salts, zinc salts, iron salts, cobalt salts and nickel salts, as well as ammonium salts and guanidine salts. One of these sulfamic acid compounds or salts may be used alone, or a combination of two or more compounds or salts may be used. In terms of the environmental burden and the like, the use of sulfamic acid (amidosulfuric acid) as the sulfamic acid compound is preferred.

(40) In the filtration treatment method and the filtration treatment system according to embodiments of the present invention, an alkali is preferably also included. Examples of the alkali include alkali hydroxides such as sodium hydroxide and potassium hydroxide. In terms of achieving good product stability at low temperatures, and the like, a combination of sodium hydroxide and potassium hydroxide may also be used. The alkali is typically used not as a solid, but in the form of an aqueous solution.

(41) Examples of the separation membrane of the membrane filtration device 12 include a nanofiltration membrane (NF membrane), microfiltration membrane (MF membrane), and ultrafiltration membrane (UF membrane).

(42) Further, other examples of the prefiltration treatment means besides membrane filtration devices include sand filtration devices and the like.

(43) The filtration treatment method and the filtration treatment system according to embodiments of the present invention can be applied particularly favorably to polyamide-based polymer membranes, which are currently the most widely used reverse osmosis membranes (RO membranes). Polyamide-based polymer membranes have comparatively low resistance to oxidizing agents, and if free chlorine or the like is kept in continuous contact with a polyamide-based polymer membrane, then a marked deterioration may occur in the performance of the membrane. However, in the filtration treatment method and the filtration treatment system according to embodiments of the present invention, this type of marked deterioration in the membrane performance is almost non-existent, even for polyamide polymer membranes.

(44) In the filtration treatment method and the filtration treatment method according to embodiments of the present invention, the pH of the raw water that represents the water to be treated is preferably 5.5 or higher, more preferably 6.0 or higher, and even more preferably 6.5 or higher. If the pH of the raw water is less than 5.5, then the pH of the feed water (prefiltration-treated water) supplied to the reverse osmosis membrane treatment device 16 may fall to less than 5.5, and the volume of permeate may sometimes decrease. Further, there are no particular limitations on the upper limit for the pH of the raw water, provided that the pH is no higher than the typical upper limit pH for reverse osmosis membrane devices (for example, pH 10), but if scale deposition of hard components such as calcium is also considered, then performing operations at a pH of, for example, 9.0 or lower is preferred. When the filtration treatment method and the filtration treatment system according to embodiments of the present invention are used, by performing operations with the pH of the raw water set to 5.5 or higher, degradation of the reverse osmosis membrane of the reverse osmosis membrane treatment device 16 and deterioration in the quality of the treated water (permeate) can be suppressed, a satisfactory slime inhibitory effect can be achieved, and a satisfactory permeate volume can also be ensured.

(45) Further, if the pH of the raw water supplied to the membrane filtration device 12 that functions as the prefiltration treatment means is less than 5.0, then the retention rate of the stabilized hypobromous acid upon passage through the membrane filtration device 12 may sometimes fall. It is thought that this is because if the pH of the raw water is less than 5.0, then the stabilized hypobromous acid may react with the membrane of the membrane filtration device 12, and is therefore slightly more likely to be consumed. The details behind this reasoning are unclear, but it is thought that there is a possibility that the pH of the raw water falling to less than 5.0 may cause a relative increase in the proportion of molecular hypobromous acid within the stabilized hypobromous acid, resulting in increased oxidizing power.

(46) On the other hand, when the pH of the raw water supplied to the membrane filtration device 12 that functions as the prefiltration treatment means is 5.0 or higher, the retention rate of the stabilized hypobromous acid upon passage through the membrane filtration device 12 may increase, and therefore the pH of the raw water is preferably at least 5.0, and is more preferably 6.5 or higher.

(47) If the effect on the permeate volume from the reverse osmosis membrane treatment device 16 downstream from the membrane filtration device 12 is also considered, then the pH of the raw water supplied to the membrane filtration device 12 that functions as the prefiltration treatment means is preferably 5.5 or higher, and a raw water pH of 6.5 or higher is even more preferred. This enables consumption of the stabilized hypobromous acid in the membrane filtration device 12 to be suppressed, degradation of the reverse osmosis membrane of the downstream reverse osmosis membrane treatment device 16 to also be suppressed, and slime generation to be inhibited, while also suppressing any reduction in the permeate volume from the reverse osmosis membrane treatment device 16.

(48) In the reverse osmosis membrane treatment device 16, in those cases where scale develops when the pH of the prefiltration-treated supplied to the reverse osmosis membrane treatment device 16 is 5.5 or higher, a dispersant may be used in combination with the stabilized hypobromous acid composition for the purpose of scale inhibition. Examples of the dispersant include polyacrylic acid, polymaleic acid and phosphonic acid. The amount of the dispersant added to the feed water (prefiltration-treated water), for example in terms of the concentration within the concentrate, is typically within a range from 0.1 to 1,000 mg/L.

(49) Further, one method for inhibiting the occurrence of scale without using a dispersant involves adjusting the operating conditions for the reverse osmosis membrane treatment device 16 such as the recovery rate so that the silica concentration in the concentrate is no higher than the degree of solubility, and the Langelier index, which is an indicator for calcium scale, is not more than 0.

(50) The filtration treatment method and the filtration treatment system according to embodiments of the present invention are used for treating water containing organic substance, such as wastewater from semiconductor plants or wastewater from liquid crystal plants. The TOC of the water to be treated is typically within a range from 0.1 mg/L to 10 mg/L, for example. Further, the turbidity of the water to be treated is typically within a range from 0.1 to 10 degrees, for example.

(51) <Composition for Filtration Treatment>

(52) A composition for a filtration treatment according to an embodiment of the present invention is a composition including a bromine-based oxidizing agent or a reaction product of a bromine compound and a chlorine-based oxidizing agent and a sulfamic acid compound, and may also include an alkali.

(53) Further, the composition for a filtration treatment according to the present embodiment may also be a composition including a reaction product of a bromine-based oxidizing agent and a sulfamic acid compound or a reaction product of a sulfamic acid compound with a reaction product of a bromine compound and a chlorine-based oxidizing agent, and may also include an alkali.

(54) The bromine-based oxidizing agent, the bromine compound, the chlorine-based oxidizing agent, and the sulfamic acid compound are as described above.

(55) In terms of minimizing corrosion of metal materials such as pipes and minimizing the production of by-products such as bromic acid, the composition for a filtration treatment according to the present embodiment preferably includes bromine and a sulfamic acid compound, or a reaction product of bromine and a sulfamic acid compound.

(56) Compared with combined chlorine-based slime inhibitors such as chlorosulfamic acid, the composition for a filtration treatment according to the present embodiment may have higher oxidizing power, and markedly higher slime inhibition and slime-detaching power.

(57) Unlike other oxidizing agents such as hypochlorous acid, the composition for a filtration treatment according to the present embodiment may cause almost no degradation of the reverse osmosis membrane. Further, because the concentration can be measured on site in a similar manner to hypochlorous acid or the like, more accurate concentration control is possible.

(58) The pH of the composition is, for example, higher than 13.0, and is preferably higher than 13.2. If the pH of the composition is 13.0 or lower, then the effective halogen in the composition may sometimes become unstable.

(59) The bromate concentration in the composition for a filtration treatment is preferably less than 5 mg/kg. If the bromate concentration in the composition for a filtration treatment is 5 mg/kg or greater, then the water quality of the treated water may deteriorate.

(60) <Method for Producing Composition for Filtration Treatment>

(61) The composition for a filtration treatment according to an embodiment of the present invention can be obtained by mixing a bromine-based oxidizing agent and a sulfamic acid compound, or by mixing a reaction product of a bromine compound and a chlorine-based oxidizing agent, and a sulfamic acid compound. An alkali may also be mixed into the composition.

(62) The method for producing a composition for a filtration treatment that includes bromine and a sulfamic acid compound, or a composition for a filtration treatment that includes a reaction product of bromine and a sulfamic acid compound, preferably includes a step of adding and reacting bromine, under an inert gas atmosphere, with a mixed solution including water, an alkali and a sulfamic acid compound. Performing the addition and inducing the reaction under an inert gas atmosphere enables the concentration of bromate ions in the composition to be reduced, which is preferred.

(63) Although there are no particular limitations on the inert gas used, at least one of nitrogen and argon is preferred from a production perspective and the like, and nitrogen is particularly preferred in terms of production costs and the like.

(64) The oxygen concentration inside the reaction vessel during the bromine addition is preferably not more than 6%, more preferably not more than 4%, even more preferably not more than 2%, and most preferably 1% or less. If the oxygen concentration inside the reaction vessel during the bromine reaction exceeds 6%, then the amount of bromic acid produced in the reaction system may sometimes increase.

(65) The proportion of bromine added is preferably not more than 25 wt % relative to the total weight of the composition, and is more preferably at least 1 wt % but not more than 20 wt %. If the proportion of bromine added exceeds 25 wt % relative to the total weight of the composition, then the amount of bromic acid produced in the reaction system may sometimes increase. If the proportion is less than 1 wt %, then the sterilizing power may deteriorate.

(66) The reaction temperature during the bromine addition is preferably controlled within a range from at least 0 C. to not more than 25 C., and in terms of production costs and the like, is more preferably controlled within a range from at least 0 C. to not more than 15 C. If the reaction temperature during the bromine addition exceeds 25 C., then the amount of bromic acid produced in the reaction system may sometimes increase, whereas if the temperature is less than 0 C., then the reaction system may freeze.

EXAMPLES

(67) The present invention is described below in further detail using a series of Examples and Comparative Examples, but the present invention is in no way limited by the following examples.

(68) [Preparation of Stabilized Hypobromous Acid Composition]

(69) Liquid bromine: 16.9 wt %, sulfamic acid: 10.7 wt %, sodium hydroxide: 12.9 wt %, potassium hydroxide: 3.94%, and water: the balance were mixed together under a nitrogen atmosphere to prepare a composition. The pH of the composition was 14, and the effective halogen concentration (effective equivalent chlorine concentration) was 7.5 wt %. A more detailed description of the preparation method for the stabilized hypobromous acid composition is presented below.

(70) A 2 liter four-necked flask into which nitrogen gas was injected continuously at a flow rate controlled by a mass flow controller so that the oxygen concentration inside the reaction vessel was maintained at 1% was charged with 1,436 g of water and 361 g of sodium hydroxide, and following mixing, 300 g of sulfamic acid was added and mixed, and with the flask then cooled to maintain the temperature of the reaction solution at 0 to 15 C., 473 g of liquid bromine was added, and 230 g of a 48% solution of potassium hydroxide was then added, thus obtaining the target composition containing 10.7 wt % of sulfamic acid and 16.9 wt % of bromine relative to the total weight of the composition, and having a ratio for the equivalent weight of sulfamic acid relative to the equivalent weight of bromine of 1.04. Measurement of the pH of the thus prepared solution using the glass electrode method yielded a value of 14. Measurement of the bromine content of the prepared solution using a method in which the bromine was substituted with iodine using potassium iodide, and a redox titration was then performed using sodium thiosulfate revealed a value of 16.9%, which was 100.0% of the theoretical content (16.9%). Further, the oxygen concentration inside the reaction vessel during the bromine reaction was measured using an Oxygen Monitor JKO-02 LJDII manufactured by Jikco Ltd. The bromate concentration was less than 5 mg/kg.

(71) [Filtration Treatment]

(72) Using a filtration treatment system 1 having the flow illustrated in FIG. 1, tests were performed in sequence for the following Example 1.fwdarw.Example 2.fwdarw.Comparative Example 1.fwdarw.Comparative Example 2.

(73) (Test Conditions)

(74) Water to be treated: semiconductor plant wastewater pH: 6.9 to 7.3 Conductivity: 340 to 510 S/cm TOC: 0.1 to 0.5 mg/L Turbidity: 1 to 10 degrees Membrane filtration device: ultrafiltration membrane (UF membrane) (formed from polyvinylidene fluoride (PVDF), an external pressure hollow fiber membrane, effective membrane surface area: 4 m.sup.2, nominal pore size: 0.01 m (UNA-620A, manufactured by Asahi Kasei Corporation)) Backwashing: backwash step described below was performed once every 30 minutes Air backwash: 50 seconds Chemical agent backwash 65 seconds (once every 24 hours, the pH of the backwash water during the 65-second chemical agent backwash was adjusted to 10 with NaOH before performing backwashing) Flushing step: 0 seconds (Example 2), 20 seconds (Example 1, Comparative Example 2), or 110 seconds (Comparative Example 1) Backwash water flow rate: 6.9 L/min Reverse osmosis membrane: formed from polyamide, effective surface area: 6.5 m.sup.2 (OFR-620, manufactured by Organo Corporation)

Example 1

(75) In Example 1, the membrane filtration system illustrated in FIG. 1 was used, and a continuous operation was performed by repeating a filtration treatment step (prefiltration treatment step.fwdarw.reverse osmosis membrane treatment step).fwdarw.a backwash step (air backwash.fwdarw.chemical agent backwash).fwdarw.a flushing step. The flushing step was performed for 20 seconds. The stabilized hypobromous acid composition described above was added as the chemical agent for the chemical agent cleaning, in an amount sufficient to produce an effective halogen concentration (effective equivalent chlorine concentration) within the backwash water of 5 mg/L.

Example 2

(76) With the exception of omitting the flushing step, operations were performed in the same manner as Example 1.

Comparative Example 1

(77) In Comparative Example 1, instead of using the aforementioned stabilized hypobromous acid composition used in Example 1 as the chemical agent for the chemical agent cleaning, a hypochlorous acid aqueous solution was added to the backwash water in an amount sufficient to produce an effective chlorine concentration of 5 mg/L, and then a continuous operation was performed by repeating a filtration treatment step (prefiltration treatment step.fwdarw.reverse osmosis membrane treatment step).fwdarw.a backwash step (air backwash.fwdarw.chemical agent backwash).fwdarw.a flushing step. The flushing step was performed for 110 seconds.

Comparative Example 2

(78) With the exception of shortening the time of the flushing step to 20 seconds, operations were performed in the same manner as Comparative Example 1.

(79) The operational results for the Examples and Comparative Examples are shown in FIG. 3 to FIG. 5 and Table 1.

(80) Based on FIG. 3, it is evident that under each of the conditions, operations were able to be performed with good stability, with no dramatic increase in the transmembrane pressure difference for the UF membrane of the prefiltration treatment.

(81) Based on FIG. 4, it is evident that in both Examples 1 and 2, operations were able to be performed with good stability, with no dramatic increase in the pressure difference upon water passage through the reverse osmosis membrane being observed. Based on FIG. 5, it is evident that in both Examples 1 and 2, the inhibition rate for the reverse osmosis membrane was able to be maintained at a high level. Moreover, based on Table 1, it is clear that the amount of backwash wastewater in Example 2 was minimal compared with the Comparative Examples.

(82) In contrast, based on FIG. 4, it is evident that in Comparative Example 1, because the antibacterial agent concentration at the reverse osmosis membrane was low, slime was generated and the pressure difference upon water passage through the membrane increased. Further, the amount of backwash wastewater was large. As a result, the reverse osmosis membrane was replaced after the test of Comparative Example 1.

(83) Further, based on FIG. 5, it is evident that in Comparative Example 2, the reverse osmosis membrane was degraded by chlorine, with a decreasing trend observed for the inhibition rate for the reverse osmosis membrane.

(84) TABLE-US-00001 TABLE 1 Comparative Comparative Example 1 Example 2 Example 1 Example 2 Backwash Stabilized Stabilized Hypo- Hypo- chemical hypo- hypo- chlorous chlorous agent bromous bromous acid acid acid acid Flushing step 20 0 110 20 time [sec] Washing 0.2 5 <0.1 0.2 wastewater halogen concentration [mg/L] Chemical 2.3 0 12.7 2.3 agent backwash wastewater volume [L/repetition]

(85) In this manner, by supplying a chemical agent containing a stabilized hypobromous acid composition to at least one of the raw water and the backwash water as in the Examples, the steps were able to be simplified and the amount of washing wastewater was able to be reduced in a filtration treatment in which a water to be treated containing organic substance was subjected to a prefiltration treatment followed by a reverse osmosis membrane treatment.

(86) [Comparative Tests on the Effects of pH of Feed Water Supplied to RO Device on Permeate Volume and Membrane Rejection Rate]

(87) The effects of the pH of the feed water supplied to the RO device on the permeate volume and the membrane rejection rate were compared.

(88) (Test Conditions)

(89) Test device: flat membrane test device Separation membrane: polyamide-based polymer reverse osmosis membrane ES20, manufactured by Nitto Denko Corporation Operating pressure: 0.75 MPa Raw water: Sagamihara well water (pH: 7.2, conductivity: 240 S/cm) Chemical agent: the stabilized hypobromous acid composition prepared in the manner described above was added in sufficient amount to produce an effective halogen concentration (effective equivalent chlorine concentration) of 1 mg/L (measurement method for effective halogen concentration: measured by the DPD method using a residual chlorine measuring instrument (DR-4000, manufactured by Hach Company)) RO membrane feed water: pH 4.0 (Example 3-1), 5.0 (Example 3-2), 5.5 (Example 3-3), 6.0 (Example 3-4), 6.5 (Example 3-5), 7.0 (Example 3-6), 7.5 (Example 3-7), 8.0 (Example 3-8), 8.5 (Example 3-9), 9.0 (Example 3-10)
(Evaluation Methods) Effect on RO membrane rejection rate: the conductivity inhibition rate (%) after 120 hours of water passage through the membrane
(100[permeate conductivity/feed water conductivity]100) Effect on permeate volume: the retention rate of the permeate volume (%, relative to initial volume) after 24 hours of water passage through the membrane

(90) The test results are shown in Table 2.

(91) TABLE-US-00002 TABLE 2 RO membrane permeate volume retention rate RO membrane (after 24 hours rejection rate pH of RO water passage) (after 120 hours membrane (%, relative to water passage) feed water initial volume) (%) Example 3-1 4.0 44 99 Example 3-2 5.0 57 99 Example 3-3 5.5 80 99 Example 3-4 6.0 94 99 Example 3-5 6.5 97 99 Example 3-6 7.0 97 99 Example 3-7 7.5 97 99 Example 3-8 8.0 97 99 Example 3-9 8.5 99 99 Example 3-10 9.0 99 99

(92) In Examples 3-1 to 3-10, no deterioration in the rejection rate was observed, indicating good suppression of any degradation of the RO membrane (RO membrane rejection rate after 120 hours of 99% or higher). In particular, in Examples 3-3 to 3-10, no significant reduction in the permeate volume was observed (the RO membrane permeate volume was retained at 80% or more of the original volume after 24 hours water passage). In contrast, in Examples 3-1 and 3-2, although no deterioration in the rejection rate was observed, indicating good suppression of RO membrane degradation, the permeate volume decreased. Based on these results, it was clear that in order to maintain the permeate volume for the RO membrane, while inhibiting slime generation on the RO membrane, the pH of the water to be treated by the RO membrane (namely, the prefiltration-treated water) is preferably adjusted to 5.5 or higher.

Example 4

(93) In Example 4, the membrane filtration system illustrated in FIG. 6 was used, and continuous operation of a filtration treatment step (prefiltration treatment step.fwdarw.reverse osmosis membrane treatment step) was performed. The stabilized hypobromous acid composition prepared using the method described above was added to the water to be treated (the raw water) in the prefiltration treatment step as a chemical agent, in an amount sufficient to produce an effective halogen concentration (effective equivalent chlorine concentration) of 10 mg/L.

(94) (Test Conditions)

(95) Raw water: washing wastewater pH: 6.5 Conductivity: 2400/cm TOC: 0.1 mg/L Turbidity: <1 degree Prefiltration treatment device (membrane filtration device): ultrafiltration membrane (UF membrane) (an external pressure hollow fiber membrane formed from polyether sulfone (PES)(FS10-FS-FUST653, manufactured by Daicen Membrane Systems Ltd.), effective membrane surface area: 7.8 m.sup.2, nominal pore size: 0.5 m), supply pressure: 0.2 MPa, raw water supply rate: 15 t/h Reverse osmosis membrane treatment device: reverse osmosis membrane (RO membrane) (polyamide-based polymer reverse osmosis membrane ES20, manufactured by Nitto Denko Corporation), supply pressure: 0.6 MPa, recovery rate: 75% Water passage time: 30 days
(Test Results)

(96) The concentration of the stabilized hypobromous acid composition was substantially the same before and after passage through the prefiltration treatment device (effective halogen concentration (effective equivalent chlorine concentration) of 10 mg/L), confirming that almost none of the composition was consumed in the prefiltration treatment device portion. Further, no slime generation was observed in the prefiltration treatment device.

(97) Furthermore, in the reverse osmosis membrane device (RO device) positioned downstream from the prefiltration treatment device, no reduction in the permeate volume, degradation of the reverse osmosis membrane, or slime generation was observed, and a favorable treatment was able to be conducted.

(98) [Retention Rate of Stabilized Hypobromous Acid Composition Relative to pH of Raw Water Supplied to Prefiltration Treatment Device]

(99) A comparative test was performed to determine whether differences in the retention rate of the stabilized hypobromous acid composition upon passage through the prefiltration treatment device could be observed upon changing in the pH of the raw water supplied to the prefiltration treatment device. The results are shown in Table 3.

(100) (Test Conditions)

(101) Prefiltration treatment device: ultrafiltration membrane (UF membrane) (a disc filter formed from polyvinylidene fluoride (PVDF) (Millex VV, manufactured by Millipore Corporation), nominal pore size: 0.1 m) Raw water: pure water (adjusted to the appropriate pH by adding hydrochloric acid) Chemical agent: the stabilized hypobromous acid composition prepared using the method described above was added to the raw water in sufficient amount to produce an effective halogen concentration (effective equivalent chlorine concentration) of 00 mg/L (measurement method for effective halogen concentration: measured by the DPD method using a residual chlorine measuring instrument (DR-4000, manufactured by Hach Company))

(102) TABLE-US-00003 TABLE 3 Stabilized hypobromous acid composition retention rate upon passage through ultrafiltration membrane Raw water pH (%) 4.0 89.1 5.0 94.2 5.5 94.2 6.5 96.4

(103) Based on Table 3, it was evident that when the pH of the raw water supplied to the prefiltration treatment device fell to less than 5.0, the retention rate of the stabilized hypobromous acid composition upon passage through the prefiltration treatment device decreased slightly. It is thought that this is because as the pH of the raw water falls to less than 5.0, the stabilized hypobromous acid may react with the ultrafiltration membrane, and is therefore slightly more likely to be consumed. The details behind this reasoning are unclear, but it is thought that there is a possibility that the pH of the raw water falling to less than 5.0 may cause a relative increase in the proportion of molecular hypobromous acid within the stabilized hypobromous acid, resulting in increased oxidizing power.

(104) On the other hand, based on the fact that the retention rate of the stabilized hypobromous acid composition upon passage through the prefiltration treatment device increased when the pH of the raw water supplied to the prefiltration treatment device was 5.0 or higher, it was clear that the pH of the raw water is preferably 5.0 or higher, and more preferably 6.5 or higher.

(105) If the effect on the permeate volume from the reverse osmosis membrane treatment device downstream from the prefiltration treatment device is also considered, then the pH of the raw water supplied to the prefiltration treatment device is preferably 5.5 or higher, and a raw water pH of 6.5 or higher is even more preferred. This enables consumption of the stabilized hypobromous acid in the pretreatment filtration device to be suppressed, degradation of the reverse osmosis membrane of the downstream reverse osmosis membrane treatment device to also be suppressed, and slime generation to be inhibited, while also suppressing any reduction in the permeate volume from the reverse osmosis membrane treatment device.

REFERENCE SIGNS LIST

(106) 1, 3: Filtration treatment system 10, 50: Raw water tank 12, 52: Membrane filtration device 14, 54: Prefiltration-treated water tank 16, 56: Reverse osmosis membrane treatment device 18, 20, 22: Pump 24: Raw water pipe 26: Raw water supply pipe 28: Prefiltration-treated water pipe 30: Prefiltration-treated water supply pipe 32: Concentrate pipe 34: Permeate pipe 36: Backwash water pipe 38: Chemical agent supply pipe 40: Backwash wastewater pipe 58: Activated carbon column 60: Activated carbon-treated water tank