WO2015170495A1 - ろ過処理システムおよびろ過処理方法 - Google Patents
ろ過処理システムおよびろ過処理方法 Download PDFInfo
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- WO2015170495A1 WO2015170495A1 PCT/JP2015/054269 JP2015054269W WO2015170495A1 WO 2015170495 A1 WO2015170495 A1 WO 2015170495A1 JP 2015054269 W JP2015054269 W JP 2015054269W WO 2015170495 A1 WO2015170495 A1 WO 2015170495A1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/04—Feed pretreatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/58—Multistep processes
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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
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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
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- 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
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- 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
- C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/12—Addition of chemical agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2649—Filtration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/02—Forward flushing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/04—Backflushing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/162—Use of acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/164—Use of bases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/168—Use of other chemical agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/18—Use of gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
Definitions
- the present invention relates to a filtration treatment system and a filtration treatment method for performing a reverse osmosis membrane treatment with a reverse osmosis membrane after a prefiltration treatment such as membrane filtration or sand filtration.
- the method a method of operating while adding chemicals such as hypochlorous acid and sodium hydroxide in raw water or backwash water, and a chemical cleaning step of periodically immersing a film in a chemical solution containing the chemical are provided.
- the chemical cleaning process is generally composed of a process for dissolving or removing impurities by a chemical and a flushing process for washing away the chemical remaining in the membrane module.
- an oxidizing agent such as hypochlorous acid is usually added to raw water or backwash water, particularly for the purpose of suppressing slime formation.
- an oxidant such as hypochlorous acid is added to the raw water or backwash water by the above method, or if an oxidant washing process is performed, the oxidant remains in the filtered water and reverse osmosis is performed later.
- an oxidant flows into the reverse osmosis membrane treatment apparatus.
- Polyamide reverse osmosis membranes that are generally widely used are vulnerable to oxidizing agents such as hypochlorous acid, and the reverse osmosis membranes deteriorate when exposed to oxidizing agents.
- FIG. 2 shows a schematic configuration of a conventional filtration processing system.
- the water to be treated containing organic matter is stored in the raw water tank 50 and then prefiltered by a separation membrane in the membrane filtration device 52, and the prefiltered water is prefiltered.
- the activated carbon treatment is performed in the activated carbon tower 58, and the activated carbon treated water is stored in the activated carbon treated water tank 60 and then reverse osmosis membrane treated in the reverse osmosis membrane treatment device 56 to obtain concentrated water and permeated water. It is done.
- the membrane filtration device 52 When the membrane filtration device 52 needs to be washed, at least a part of the prefiltered water from the prefiltered water tank 54 is supplied with hypochlorous acid as a cleaning agent, and then membrane filtered as backwash water. It is supplied to the device 52 and backwashing is performed. Hypochlorous acid remaining in the pre-filtered water is removed in the activated carbon tower 58, and then a slime control agent (bactericidal agent) is again applied to the reverse osmosis membrane treatment device in order to suppress slime formation in the reverse osmosis membrane. 56 is added upstream.
- hypochlorous acid as a cleaning agent
- An object of the present invention is to provide a filtration treatment system and a filtration treatment method capable of simplifying the process and reducing the amount of washing wastewater in a filtration treatment in which a water to be treated containing an organic substance is subjected to a prefiltration treatment and then subjected to a reverse osmosis membrane treatment. Is to provide.
- the present invention includes pre-filtration treatment means for removing insoluble components from water to be treated containing organic matter, reverse osmosis membrane treatment means for subjecting pre-filtration treated water from the pre-filtration treatment means to reverse osmosis membrane treatment,
- a chemical supply means for supplying a chemical to the filtration means, and the chemical contains a bromine-based oxidizing agent, a reaction product of a bromine compound and a chlorine-based oxidizing agent, and a sulfamic acid compound, or bromine
- It is a filtration processing system containing the reaction product of a oxidizer or a reaction product of a bromine compound and a chlorine oxidant and a sulfamic acid compound.
- the chemical contains bromine and a sulfamic acid compound, or a reaction product of bromine and sulfamic acid.
- medical agent is a thing obtained by the method including the process of adding bromine to the liquid mixture containing water, an alkali, and a sulfamic acid compound in inert gas atmosphere, and making it react. preferable.
- the pH of the pre-filtered water is 5.5 or more.
- the pH of the water to be treated supplied to the prefiltration means is 5.5 or more.
- the present invention also includes a prefiltration treatment step for removing insoluble components from the water to be treated containing organic matter, a reverse osmosis membrane treatment step for treating the prefiltration treatment water from the prefiltration treatment step with a reverse osmosis membrane,
- the chemical agent contains bromine and a sulfamic acid compound or contains a reaction product of bromine and sulfamic acid.
- the chemical agent may be obtained by a method including a step of adding bromine to a mixed solution containing water, an alkali and a sulfamic acid compound in an inert gas atmosphere and reacting the mixture. preferable.
- the pH of the prefiltration water is 5.5 or more.
- the pH of the to-be-processed water processed at a prefiltration process process is 5.5 or more.
- the present invention provides a filtration treatment system and a filtration treatment method capable of simplifying the process and reducing the amount of washing wastewater in a filtration treatment in which a water to be treated containing an organic substance is subjected to a prefiltration treatment and then subjected to a reverse osmosis membrane treatment. can do.
- the filtration processing system 1 includes a membrane filtration device 12 including a separation membrane as a prefiltration processing unit, and a reverse osmosis membrane processing device 16 as a reverse osmosis membrane processing unit.
- a raw water pipe 24 is connected to the inlet of the raw water tank 10, and the outlet of 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 the prefiltration water tank 14 are connected by a prefiltration water pipe 28, and the outlet of the prefiltration water tank 14 and the inlet of the reverse osmosis membrane treatment device 16 are connected via the pump 20.
- a filtered water supply pipe 30 is connected, a concentrated water pipe 32 is connected to the concentrated water outlet of the reverse osmosis membrane treatment apparatus 16, and a permeated water pipe 34 is connected to the permeated water outlet.
- a lower outlet of the filtration 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 drainage pipe 40 is connected to the primary side of the membrane filtration device 12. ing.
- a medicine supply pipe 38 is connected as a medicine supply means.
- Raw water which is treated water containing organic matter, is stored in the raw water tank 10 through the raw water pipe 24 as necessary, and then supplied to the membrane filtration device 12 through the raw water supply pipe 26 by the pump 18.
- the membrane filtration device 12 insoluble components are removed from the water to be treated by the separation membrane (pre-filtration treatment step).
- the prefiltered water that has been prefiltered is stored in the prefiltered water tank 14 through the prefiltered water pipe 28 as necessary, and then the reverse osmosis membrane treatment device 16 through the prefiltered water supply pipe 30 by the pump 20. To be supplied.
- reverse osmosis membrane treatment device 16 reverse osmosis membrane treatment is performed by the reverse osmosis membrane (reverse osmosis membrane treatment step).
- the concentrated water obtained by the reverse osmosis membrane treatment is discharged through the concentrated water pipe 32, and the permeated water is discharged through the permeated water pipe 34.
- the membrane filtration device 12 When the membrane filtration device 12 needs to be washed, at least a part of the prefiltration water from the prefiltration water tank 14 is backwashed water as a backwash water through the backwash water pipe 36 from the secondary side of the membrane filtration device 12. It is supplied and backwashing is performed (backwashing process).
- the backwash drainage is discharged from the primary side of the membrane filtration device 12 through the backwash drainage pipe 40.
- the cleaning chemical is supplied to the backwash water downstream of the pump 22 of the backwash water pipe 36 through the drug supply pipe 38 (medicine supply process).
- the separation membrane is backwashed.
- FIG. 6 shows a schematic configuration of another example of the filtration processing system according to the embodiment of the present invention.
- the chemical supply pipe 38 is connected to the downstream side of the pump 22 in the backwash water pipe 36, but in the filtration processing system 3 in FIG. 6, the upstream of the pump 18 in the raw water supply pipe 26.
- a drug supply pipe 38 is connected to the side as drug supply means.
- a drug supply pipe 38 may be connected to the raw water tank 10 as a drug supply means.
- Raw water which is treated water containing organic matter, is stored in the raw water tank 10 through the raw water pipe 24 as necessary, and then supplied to the membrane filtration device 12 through the raw water supply pipe 26 by the pump 18.
- the membrane filtration device 12 insoluble components are removed from the water to be treated by the separation membrane (pre-filtration treatment step).
- the cleaning chemical is supplied to the raw water through the chemical supply pipe 38 on the upstream side of the pump 18 of the raw water supply pipe 26 or in the raw water tank 10 (chemical supply step), and membrane filtration is performed with the raw water containing the chemical.
- the separation membrane of the device 12 is washed.
- the prefiltered water that has been prefiltered is subjected to reverse osmosis membrane treatment with a reverse osmosis membrane in the reverse osmosis membrane treatment device 16 (reverse osmosis membrane treatment step) in the same manner as the filtration treatment system 1 of FIG.
- reverse osmosis membrane treatment step at least a part of the prefiltration water is supplied from the prefiltration water tank 14 as backwash water from the secondary side of the membrane filtration device 12, and backwashing is performed. (Back washing process).
- raw water and backwash water are used as chemicals for prevention of clogging of the membrane filtration device 12 as pre-filtration treatment means, slime generation suppression, and cleaning chemicals used in the chemical cleaning process.
- hypobromine oxidant or “reaction product of bromine compound and chlorine oxidant” and “sulfamic acid compound” Use drugs containing.
- a hypobromite stabilization composition produces
- reaction product of bromine-based oxidant and sulfamic acid compound or “reaction product of bromine-based compound and chlorine-based oxidant”
- a hypobromite stabilizing composition which is a "reaction product of a sulfamic acid compound”.
- bromine for example, “bromine”, “chlorination” in at least one of raw water and backwash water, and further in a chemical solution in the chemical washing step.
- bromine and sulfamic acid compound for example, in at least one of raw water and backwash water, and further in the chemical solution of the chemical washing step, “bromine and sulfamic acid compound “Reaction product”, “reaction product of bromine chloride and sulfamic acid compound” or “reaction product of sodium bromide and hypochlorous acid and sulfamic acid compound” is supplied.
- bromine-based oxidant or “reaction product of bromine compound and chlorine-based oxidant” and “sulfamic acid compound” or reaction products thereof are added to the backwash water. What is necessary is just to inject
- brominated oxidant or “reaction product of bromine compound and chlorinated oxidant” and “sulfamic acid compound” may be added separately, or may be added after mixing in stock solutions. Good.
- bromine-based oxidant or “reaction product of bromine compound and chlorine-based oxidant” and “sulfamic acid compound” are added to the raw water, or these reactions. What is necessary is just to inject
- a chemical cleaning step of periodically immersing the separation membrane of the membrane filtration device 12 in a chemical solution containing a chemical may be provided.
- the chemical cleaning step includes a removal step of immersing the separation membrane in a chemical solution containing the chemical to dissolve or remove impurities adhering to the separation membrane, and washing away the chemical remaining in the membrane filtration device 12 with a flushing liquid such as water.
- a flushing step is provided.
- bromine-based oxidant or “reaction product of bromine compound and chlorine-based oxidant” and “sulfamic acid compound” or reaction products thereof are added to the backwash water. What is injected with a chemical injection pump or the like may be used as a chemical solution.
- a “bromine-based oxidant” or “bromine compound” is contained in at least one of raw water and backwash water, and further in a chemical solution in the chemical washing step.
- the presence of the “reactant with the chlorine-based oxidant” and the “sulfamic acid compound” or the presence of these reaction products can prevent the membrane filtration device 12 from being clogged and suppress slime formation. Since the hypobromite stabilizing composition hardly deteriorates the reverse osmosis membrane, it is not necessary to add a reducing agent or install an activated carbon tower or the like before the reverse osmosis membrane treatment. It is not necessary to re-add the slime control agent before the membrane treatment, and the system is simplified.
- the ratio of the equivalent of “sulfamic acid compound” to the equivalent of “bromine-based oxidizing agent” or “reaction product of bromine compound and chlorine-based oxidizing agent” is preferably 1 or more, and is in the range of 1 or more and 2 or less. It is more preferable. If the ratio of the equivalent of “sulfamic acid compound” to the equivalent of “bromine-based oxidizing agent” or “reaction product of bromine compound and chlorine-based oxidizing agent” is less than 1, the active ingredient may not be sufficiently stabilized. If it exceeds 2, the production 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 the amount is less than 0.01 mg / L, a sufficient slime suppressing effect may not be obtained. If the amount is more than 100 mg / L, corrosion of metal materials such as piping may be caused.
- bromine-based oxidizing agents examples include bromine (liquid bromine), bromine chloride, hypobromous acid, bromic acid, bromate and the like.
- the preparations of “bromine and sulfamic acid compound” or “reaction product of bromine and sulfamic acid compound” using bromine are the preparations of “hypochlorous acid, bromine compound and sulfamic acid” and “bromine chloride”. It is more preferable because it has less chloride ions and is less likely to cause corrosion of metal materials such as pipes, compared to the formulation of “and sulfamic acid”.
- bromine and a sulfamic acid compound are present in at least one of raw water and backwash water, and further in a chemical solution in the chemical washing step. Or a reaction product of bromine and a sulfamic acid compound is preferably present.
- bromine compounds examples include sodium bromide, potassium bromide, lithium 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.
- 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.
- Examples of the separation membrane of the membrane filtration device 12 include a nanofiltration membrane (NF membrane), a microfiltration membrane (MF membrane), and an ultrafiltration membrane (UF membrane).
- NF membrane nanofiltration membrane
- MF membrane microfiltration membrane
- UF membrane ultrafiltration membrane
- a sand filtration device can be used as the prefiltration means.
- the filtration treatment method and filtration treatment system according to the present embodiment can be suitably applied particularly to a polyamide polymer membrane which is currently mainstream as a reverse osmosis membrane (RO 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 pH of the raw water that is the treated water is preferably 5.5 or more, more preferably 6.0 or more, and 6.5 or more. More preferably. If the pH of the raw water is less than 5.5, the pH of the feed water (pre-filtered water) to the reverse osmosis membrane treatment device 16 becomes less than 5.5, and the amount of permeated water may decrease.
- the upper limit of the pH of the raw water is not particularly limited as long as it is not higher than the normal upper limit pH of the reverse osmosis membrane (for example, pH 10), but considering the scale precipitation of hardness components such as calcium, the pH is, for example, It is preferable to operate at 9.0 or less.
- the reverse osmosis membrane of the reverse osmosis membrane treatment device 16 is deteriorated and the treated water (permeated water) is run by operating the raw water at a pH of 5.5 or higher. It is possible to secure a sufficient amount of permeated water while suppressing deterioration of water quality and exhibiting a sufficient slime suppressing effect.
- the pH of the raw water supplied to the membrane filtration device 12 that is the prefiltration means is less than 5.0
- the residual rate of stabilized hypobromite before and after the membrane filtration device 12 may decrease. This is presumably because when the pH of the raw water is less than 5.0, the stabilized hypobromite reacts with the membrane of the membrane filtration device 12 and is easily consumed. Although the details of this cause are unknown, when the pH of the raw water is less than 5.0, the proportion of molecular hypobromite in the stabilized hypobromite increases relatively, and the oxidizing power is increased. This may be due to the increase.
- the pH of the raw water supplied to the membrane filtration device 12 that is the prefiltration means is 5.0 or more, the residual rate of stabilized hypobromite before and after the membrane filtration device 12 becomes high.
- the pH is preferably 5.0 or more, and more preferably 6.5 or more.
- the pH of the raw water supplied to the membrane filtration device 12 as the prefiltration means is 5.5 or more. It is more preferable that the pH of the raw water is 6.5 or more.
- the dispersant is used as a hypobromite stabilizing composition for the purpose of scale control. You may use together.
- the dispersant include polyacrylic acid, polymaleic acid, and phosphonic acid.
- the amount of the dispersant added to the feed water (pre-filtered water) is, for example, in the range of 0.1 to 1,000 mg / L as the concentration in the concentrated water.
- the operating conditions such as the recovery rate of the processing device 16 may be adjusted.
- the filtration treatment method and filtration treatment system treats water to be treated containing organic substances such as semiconductor factory wastewater and liquid crystal factory wastewater.
- the TOC of the water to be treated is, for example, in the range of 0.1 mg / L to 10 mg / L.
- the turbidity of the water to be treated is, for example, in the range of 0.1 to 10 degrees.
- composition for filtration treatment contains “bromine-based oxidizing agent” or “reaction product of bromine compound and chlorine-based oxidizing agent” and “sulfamic acid compound”, and further contains an alkali. You may contain.
- composition for filtration treatment is a “reaction product of a bromine-based oxidant and a sulfamic acid compound”, or “a reaction product of a bromine compound and a chlorinated oxidant, a sulfamic acid compound, Of the reaction product ", and may further contain an alkali.
- the bromine-based oxidizing agent, bromine compound, chlorine-based oxidizing agent, and sulfamic acid compound are as described above.
- composition for filtration treatment one containing bromine and a sulfamic acid compound from the viewpoint of low corrosiveness to a metal material such as piping and less by-product of bromic acid, or Those containing a reaction product of bromine and a sulfamic acid compound are preferred.
- composition for filtration according to the present embodiment has higher oxidizing power and significantly higher slime suppressing power and slime peeling power than a combined chlorine-based slime inhibitor such as chlorosulfamic acid.
- the filtration composition according to the present embodiment hardly deteriorates the reverse osmosis membrane, unlike an oxidizing agent such as hypochlorous acid. Further, since the concentration can be measured on site in the same manner as hypochlorous acid or the like, more accurate concentration management is possible.
- the pH of the composition is, for example, more than 13.0, more preferably more than 13.2.
- the pH of the composition is 13.0 or less, the effective halogen in the composition may become unstable.
- the bromic acid concentration in the composition for filtration treatment is less than 5 mg / kg.
- the bromic acid concentration in the composition for filtration treatment is 5 mg / kg or more, the quality of the treated water may deteriorate.
- composition for filtration treatment is obtained by mixing a bromine-based oxidant and a sulfamic acid compound, or by mixing a reaction product of a bromine compound and a chlorine-based oxidant and a sulfamic acid compound. Further, an alkali may be mixed.
- a method for producing a composition for filtration treatment containing bromine and a sulfamic acid compound or a composition for filtration treatment containing a reaction product of bromine and a sulfamic acid compound water, an alkali and a sulfamic acid compound are used. It is preferable to include a step of adding bromine to the mixed liquid to react under an inert gas atmosphere. By adding and reacting under an inert gas atmosphere, the bromate ion concentration in the composition becomes lower, which is preferable.
- 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.
- 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.
- Example 1 In Example 1, the membrane filtration system shown in FIG. 1 is used, and the filtration treatment process (pre-filtration treatment step ⁇ reverse osmosis membrane treatment step) ⁇ back washing step (air back washing ⁇ chemical back washing) ⁇ continuous flushing step is repeated. Drove. The flushing process was 20 seconds. The above-mentioned stabilized hypobromite composition was added as a chemical for chemical cleaning so that the effective halogen concentration (effective chlorine equivalent concentration) in the backwash water was 5 mg / L.
- Example 2 The operation was performed in the same manner as in Example 1 except that the flushing step was omitted.
- Comparative Example 1 In Comparative Example 1, instead of the stabilized hypobromite composition used in Example 1 as a chemical cleaning agent, an aqueous sodium hypochlorite solution was adjusted to an effective chlorine concentration of 5 mg / L in the backwash water. In addition, a continuous operation in which a filtration treatment process (pre-filtration treatment step ⁇ reverse osmosis membrane treatment step) ⁇ back washing step (air back washing ⁇ chemical agent back washing) ⁇ flushing step was repeated was performed. The flushing process was 110 seconds.
- the UF membrane of the prefiltration treatment was able to operate stably without any sudden increase in the transmembrane pressure under any condition.
- 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 Stabilized hypobromite composition prepared as described above is added to an effective halogen concentration (effective chlorine equivalent concentration) of 1 mg / L (effective halogen concentration measurement method: residual chlorine measuring device (Hach) (Measured by the DPD method using “DR-4000”) RO membrane water supply 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)
- Examples 3-1 to 3-10 no decrease in the rejection rate was observed, and the deterioration of the RO membrane was suppressed (the RO membrane rejection rate after 120 hours was 99% or more).
- the RO membrane rejection rate after 120 hours was 99% or more the RO membrane rejection rate after 120 hours was 99% or more.
- no significant decrease in the amount of permeated water was observed the amount of permeated water in the RO membrane was maintained at 80% or more of the initial value after passing water for 24 hours.
- Examples 3-1 and 3-2 no reduction in the rejection rate was observed, and although the deterioration of the RO membrane was suppressed, the amount of permeated water was reduced. Therefore, in order to suppress the generation of slime in the RO membrane while maintaining the amount of permeated water of the RO membrane, the pH of the RO membrane treated water (that is, prefiltered water) is adjusted to 5.5 or higher. Was found to be preferable.
- Example 4 In Example 4, the membrane filtration system shown in FIG. 6 was used, and a continuous operation of the filtration treatment step (pre-filtration treatment step ⁇ reverse osmosis membrane treatment step) was performed. As a chemical, the stabilized hypobromite composition prepared by the above method was added to the water to be treated (raw water) in the prefiltration treatment step so that the effective halogen concentration (effective chlorine equivalent concentration) was 10 mg / L. .
- RO device reverse osmosis membrane treatment device
- -Prefiltration membrane Ultrafiltration membrane (UF membrane) (polyvinylidene fluoride (PVDF) disk filter (Millipore Corporation, Millex VV), nominal pore size 0.1 ⁇ m) ⁇
- Raw water Pure water (pH is adjusted appropriately by adding hydrochloric acid)
- -Drug Stabilized hypobromite composition prepared by the above method is added to raw water so that the effective halogen concentration (effective chlorine equivalent concentration) is 0 mg / L (measurement method of effective halogen concentration: residual chlorine (Measured by the DPD method using a measuring device (“DR-4000” manufactured by Hach))
- the pH of raw water supplied to the prefiltration apparatus is 5.0 or more
- the residual rate of stabilized hypobromite before and after the prefiltration apparatus increases, so the pH of the raw water is 5.0 or more. It was found that the pH was preferably 6.5 or more.
- the pH of the raw water supplied to the prefiltration treatment device is preferably 5.5 or more. It is more preferable that it is 6.5 or more.
- 1,3 Filtration system 10,50 raw water tank, 12,52 membrane filtration device, 14,54 Prefiltration water tank, 16,56 reverse osmosis membrane treatment device, 18, 20, 22 pump, 24 raw water piping, 26 raw water Supply piping, 28 Pre-filtered water piping, 30 Pre-filtered water supply piping, 32 Concentrated water piping, 34 Permeated water piping, 36 Backwash water piping, 38 Chemical supply piping, 40 Backwash drainage piping, 58 Activated carbon tower, 60 Activated carbon treated water tank.
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Abstract
Description
本発明の実施形態に係るろ過処理システムの一例の概略を図1に示し、その構成について説明する。ろ過処理システム1は、前ろ過処理手段として分離膜を備える膜ろ過装置12と、逆浸透膜処理手段として逆浸透膜処理装置16とを備える。
R2NSO3H (1)
(式中、Rは独立して水素原子または炭素数1~8のアルキル基である。)
本実施形態に係るろ過処理用組成物は、「臭素系酸化剤」または「臭素化合物と塩素系酸化剤との反応物」と、「スルファミン酸化合物」とを含有するものであり、さらにアルカリを含有してもよい。
本実施形態に係るろ過処理用組成物は、臭素系酸化剤とスルファミン酸化合物とを混合する、または臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物とを混合することにより得られ、さらにアルカリを混合してもよい。
窒素雰囲気下で、液体臭素:16.9重量%(wt%)、スルファミン酸:10.7重量%、水酸化ナトリウム:12.9重量%、水酸化カリウム:3.94重量%、水:残分を混合して、組成物を調製した。組成物のpHは14、有効ハロゲン濃度(有効塩素換算濃度)は7.5重量%であった。安定化次亜臭素酸組成物の詳細な調製方法は以下の通りである。
図1に示すフローのろ過処理システム1を用い、下記実施例1→実施例2→比較例1→比較例2の順で試験を行った。
(試験条件)
・被処理水:半導体工場排水
pH 6.9~7.3
導電率 340~510μS/cm
TOC 0.1~0.5mg/L
濁度 1~10度
・膜ろ過装置:限外ろ過膜(UF膜)(ポリフッ化ビニリデン(PVDF)製外圧中空糸膜、有効膜面積4m2、公称孔径0.01μm(旭化成株式会社製、UNA-620A))
・逆洗:30分に1回、以下の逆洗工程を行う。
空気逆洗50秒
薬剤逆洗65秒
(24時間に1回は、上記薬剤逆洗65秒のときの逆洗水のpHを、NaOHで10にして逆洗を行った)
・フラッシング工程:0秒(実施例2),20秒(実施例1、比較例2),110秒(比較例1)
逆洗水流量:6.9L/min
・逆浸透膜:ポリアミド製、有効膜面積6.5m2(オルガノ株式会社製、OFR-620)
実施例1では、図1に示す膜ろ過システムを用い、ろ過処理工程(前ろ過処理工程→逆浸透膜処理工程)→逆洗工程(空気逆洗→薬剤逆洗)→フラッシング工程を繰り返し行う連続運転を行った。フラッシング工程は20秒とした。薬剤洗浄用の薬剤としては上記安定化次亜臭素酸組成物を逆洗水中の有効ハロゲン濃度(有効塩素換算濃度)で5mg/Lとなるように添加した。
フラッシング工程を省略した以外は、実施例1と同様にして運転を行った。
比較例1では、薬剤洗浄用の薬剤として実施例1で用いた上記安定化次亜臭素酸組成物の代わりに次亜塩素酸ナトリウム水溶液を逆洗水中の有効塩素濃度で5mg/Lとなるように添加し、ろ過処理工程(前ろ過処理工程→逆浸透膜処理工程)→逆洗工程(空気逆洗→薬剤逆洗)→フラッシング工程を繰り返し行う連続運転を行った。フラッシング工程は110秒とした。
フラッシング工程の時間を20秒に短縮した以外は、比較例1と同様にして運転を行った。
RO装置への給水のpHによる透過水量、膜排除率への影響を比較した。
・試験装置:平膜試験装置
・分離膜:日東電工(株)製、ポリアミド系高分子逆浸透膜 ES20
・運転圧力:0.75MPa
・原水:相模原井水(pH7.2、導電率240μS/cm)
・薬剤:上記のように調製した安定化次亜臭素酸組成物を、有効ハロゲン濃度(有効塩素換算濃度)として1mg/Lとなるよう添加(有効ハロゲン濃度の測定方法:残留塩素測定装置(Hach社製、「DR-4000」)を使用してDPD法により測定)
・RO膜給水pH:4.0(実施例3-1),5.0(実施例3-2),5.5(実施例3-3),6.0(実施例3-4),6.5(実施例3-5),7.0(実施例3-6),7.5(実施例3-7),8.0(実施例3-8),8.5(実施例3-9),9.0(実施例3-10)
・RO膜の排除率への影響:120時間通水後の導電率排除率(%)
(100-[透過水導電率/給水導電率]×100)
・透過水量への影響:24時間通水後の透過水量の保持率(%,対初期値)
実施例4では、図6に示す膜ろ過システムを用い、ろ過処理工程(前ろ過処理工程→逆浸透膜処理工程)の連続運転を行った。薬剤としては上記の方法で調製した安定化次亜臭素酸組成物を、前ろ過処理工程の被処理水(原水)に有効ハロゲン濃度(有効塩素換算濃度)で10mg/Lとなるように添加した。
・原水:洗浄排水
・pH 6.5
・導電率 240μS/cm
・TOC 0.1mg/L
・濁度 <1度
・前ろ過処理装置(膜ろ過装置):限外ろ過膜(UF膜)(ポリエーテルサルフォン(PES)製外圧中空糸膜(ダイセン・メンブレン・システムズ株式会社製、FS10-FS-FUST653)、有効膜面積7.8m2、公称孔径0.5μm)、供給圧0.2MPa、原水の供給水量15t/h
・逆浸透膜処理装置:逆浸透膜(RO膜)(日東電工(株)製、ポリアミド系高分子逆浸透膜 ES20)、供給圧0.6MPa、回収率75%
・通水時間:30日
安定化次亜臭素酸組成物の濃度は、前ろ過処理装置の前後でほぼ同濃度(有効ハロゲン濃度(有効塩素換算濃度)で10mg/L)であり、前ろ過処理装置の部分でほとんど消費されていないことがわかった。また、前ろ過処理装置において、スライムの発生も認められなかった。
前ろ過処理装置へ供給する原水のpHの違いによって、前ろ過処理装置の前後での安定化次亜臭素酸の残留率に違いが認められるか比較した。結果を表3に示す。
・前ろ過処理膜:限外ろ過膜(UF膜)(ポリフッ化ビニリデン(PVDF)製ディスクフィルター(ミリポア株式会社製、Millex VV)、公称孔径0.1μm)
・原水:純水(塩酸を添加して適宜pHを調整)
・薬剤:上記の方法で調製した安定化次亜臭素酸組成物を、有効ハロゲン濃度(有効塩素換算濃度)として○〇mg/Lとなるよう原水に添加(有効ハロゲン濃度の測定方法:残留塩素測定装置(Hach社製、「DR-4000」)を使用してDPD法により測定)
Claims (10)
- 有機物を含む被処理水から不溶解性成分を除去する前ろ過処理手段と、
前記前ろ過処理手段からの前ろ過処理水を逆浸透膜処理する逆浸透膜処理手段と、
前記前ろ過処理手段に薬剤を供給する薬剤供給手段と、
を備え、
前記薬剤が、臭素系酸化剤、または臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物と、を含む、もしくは、臭素系酸化剤、または臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物との反応生成物を含むことを特徴とするろ過処理システム。 - 請求項1に記載のろ過処理システムであって、
前記薬剤が、臭素とスルファミン酸化合物とを含む、もしくは、臭素とスルファミン酸との反応生成物を含むことを特徴とするろ過処理システム。 - 請求項2に記載のろ過処理システムであって、
前記薬剤が、水、アルカリおよびスルファミン酸化合物を含む混合液に臭素を不活性ガス雰囲気下で添加して反応させる工程を含む方法により得られたものであることを特徴とするろ過処理システム。 - 請求項1~3のいずれか1項に記載のろ過処理システムであって、
前記前ろ過処理水のpHが5.5以上であることを特徴とするろ過処理システム。 - 請求項1~3のいずれか1項に記載のろ過処理システムであって、
前記前ろ過処理手段へ供給される被処理水のpHが5.5以上であることを特徴とするろ過処理システム。 - 有機物を含む被処理水から不溶解性成分を除去する前ろ過処理工程と、
前記前ろ過処理工程からの前ろ過処理水を逆浸透膜処理する逆浸透膜処理工程と、
前ろ過処理手段に薬剤を供給する薬剤供給工程と、
を含み、
前記薬剤が、臭素系酸化剤、または臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物と、を含む、もしくは、臭素系酸化剤、または臭素化合物と塩素系酸化剤との反応物と、スルファミン酸化合物との反応生成物を含むことを特徴とするろ過処理方法。 - 請求項6に記載のろ過処理方法であって、
前記薬剤が、臭素とスルファミン酸化合物とを含む、もしくは、臭素とスルファミン酸との反応生成物を含むことを特徴とするろ過処理方法。 - 請求項7に記載のろ過処理方法であって、
前記薬剤が、水、アルカリおよびスルファミン酸化合物を含む混合液に臭素を不活性ガス雰囲気下で添加して反応させる工程を含む方法により得られたものであることを特徴とするろ過処理方法。 - 請求項6~8のいずれか1項に記載のろ過処理方法であって、
前記前ろ過処理水のpHが5.5以上であることを特徴とするろ過処理方法。 - 請求項6~8のいずれか1項に記載のろ過処理方法であって、
前記前ろ過処理工程で処理される被処理水のpHが5.5以上であることを特徴とするろ過処理方法。
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CN106457150B (zh) | 2019-11-05 |
CN106457150A (zh) | 2017-02-22 |
JPWO2015170495A1 (ja) | 2017-04-20 |
SA516380243B1 (ar) | 2020-07-13 |
KR20160143768A (ko) | 2016-12-14 |
US20170044029A1 (en) | 2017-02-16 |
SG11201609169UA (en) | 2016-12-29 |
JP2018079471A (ja) | 2018-05-24 |
US10351444B2 (en) | 2019-07-16 |
KR20180116470A (ko) | 2018-10-24 |
MY176582A (en) | 2020-08-17 |
TW201603876A (zh) | 2016-02-01 |
TWI633928B (zh) | 2018-09-01 |
JP6616855B2 (ja) | 2019-12-04 |
JP6325658B2 (ja) | 2018-05-16 |
KR101990262B1 (ko) | 2019-06-17 |
KR102046581B1 (ko) | 2019-11-19 |
KR20190051084A (ko) | 2019-05-14 |
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