WO2022209461A1 - 逆浸透膜装置の運転方法 - Google Patents
逆浸透膜装置の運転方法 Download PDFInfo
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- WO2022209461A1 WO2022209461A1 PCT/JP2022/007588 JP2022007588W WO2022209461A1 WO 2022209461 A1 WO2022209461 A1 WO 2022209461A1 JP 2022007588 W JP2022007588 W JP 2022007588W WO 2022209461 A1 WO2022209461 A1 WO 2022209461A1
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- Prior art keywords
- period
- water
- addition
- reverse osmosis
- osmosis membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 257
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 215
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- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- WOHVONCNVLIHKY-UHFFFAOYSA-L [Ba+2].[O-]Cl=O.[O-]Cl=O Chemical compound [Ba+2].[O-]Cl=O.[O-]Cl=O WOHVONCNVLIHKY-UHFFFAOYSA-L 0.000 description 1
- KQOZWBOJTDCKSJ-UHFFFAOYSA-M [K+].[O-]S(=O)(=O)NCl Chemical compound [K+].[O-]S(=O)(=O)NCl KQOZWBOJTDCKSJ-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 230000002353 algacidal effect Effects 0.000 description 1
- 239000003619 algicide Substances 0.000 description 1
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 description 1
- HPEWZLCIOKVLBZ-UHFFFAOYSA-N barium hypochlorite Chemical compound [Ba+2].Cl[O-].Cl[O-] HPEWZLCIOKVLBZ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BEHLMOQXOSLGHN-UHFFFAOYSA-N benzenamine sulfate Chemical compound OS(=O)(=O)NC1=CC=CC=C1 BEHLMOQXOSLGHN-UHFFFAOYSA-N 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- FNXLCIKXHOPCKH-UHFFFAOYSA-N bromamine Chemical compound BrN FNXLCIKXHOPCKH-UHFFFAOYSA-N 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- JXHKAMUFJPEGFF-UHFFFAOYSA-N bromo sulfamate Chemical compound NS(=O)(=O)OBr JXHKAMUFJPEGFF-UHFFFAOYSA-N 0.000 description 1
- VWPXUKSDWYXLKV-UHFFFAOYSA-N bromosulfamic acid Chemical compound OS(=O)(=O)NBr VWPXUKSDWYXLKV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FECFIIXKXJBOSU-UHFFFAOYSA-N butylsulfamic acid Chemical compound CCCCNS(O)(=O)=O FECFIIXKXJBOSU-UHFFFAOYSA-N 0.000 description 1
- YALMXYPQBUJUME-UHFFFAOYSA-L calcium chlorate Chemical compound [Ca+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O YALMXYPQBUJUME-UHFFFAOYSA-L 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
- MAYPHUUCLRDEAZ-UHFFFAOYSA-N chlorine peroxide Chemical compound ClOOCl MAYPHUUCLRDEAZ-UHFFFAOYSA-N 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- VRLDVERQJMEPIF-UHFFFAOYSA-N dbdmh Chemical compound CC1(C)N(Br)C(=O)N(Br)C1=O VRLDVERQJMEPIF-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- BAQKWXACUNEBOT-UHFFFAOYSA-N dibutylsulfamic acid Chemical compound CCCCN(S(O)(=O)=O)CCCC BAQKWXACUNEBOT-UHFFFAOYSA-N 0.000 description 1
- SDUXGMLGPOQMKO-UHFFFAOYSA-N dichlorosulfamic acid Chemical compound OS(=O)(=O)N(Cl)Cl SDUXGMLGPOQMKO-UHFFFAOYSA-N 0.000 description 1
- NXFNZLHFBJYCPG-UHFFFAOYSA-N diethylsulfamic acid Chemical compound CCN(CC)S(O)(=O)=O NXFNZLHFBJYCPG-UHFFFAOYSA-N 0.000 description 1
- YGNOYUCUPMACDT-UHFFFAOYSA-N dimethylsulfamic acid Chemical compound CN(C)S(O)(=O)=O YGNOYUCUPMACDT-UHFFFAOYSA-N 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- XRVWREPFYXZOPK-UHFFFAOYSA-N dipropylsulfamic acid Chemical compound CCCN(S(O)(=O)=O)CCC XRVWREPFYXZOPK-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- IOISAJSHULNACL-UHFFFAOYSA-N ethyl(methyl)sulfamic acid Chemical compound CCN(C)S(O)(=O)=O IOISAJSHULNACL-UHFFFAOYSA-N 0.000 description 1
- SIVVHUQWDOGLJN-UHFFFAOYSA-N ethylsulfamic acid Chemical compound CCNS(O)(=O)=O SIVVHUQWDOGLJN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000035611 feeding Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- OQNCJVQRNFJNJI-UHFFFAOYSA-M lithium N-chlorosulfamate Chemical compound ClNS([O-])(=O)=O.[Li+] OQNCJVQRNFJNJI-UHFFFAOYSA-M 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- YZVQGLCYZLGIAM-UHFFFAOYSA-N methyl(propyl)sulfamic acid Chemical compound CCCN(C)S(O)(=O)=O YZVQGLCYZLGIAM-UHFFFAOYSA-N 0.000 description 1
- 230000007269 microbial metabolism Effects 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- JWQSOOZHYMZRBT-UHFFFAOYSA-N propan-2-ylsulfamic acid Chemical compound CC(C)NS(O)(=O)=O JWQSOOZHYMZRBT-UHFFFAOYSA-N 0.000 description 1
- HLIBNTOXKQCYMV-UHFFFAOYSA-N propylsulfamic acid Chemical compound CCCNS(O)(=O)=O HLIBNTOXKQCYMV-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- QHFDHWJHIAVELW-UHFFFAOYSA-M sodium;4,6-dioxo-1h-1,3,5-triazin-2-olate Chemical class [Na+].[O-]C1=NC(=O)NC(=O)N1 QHFDHWJHIAVELW-UHFFFAOYSA-M 0.000 description 1
- XZPVPNZTYPUODG-UHFFFAOYSA-M sodium;chloride;dihydrate Chemical compound O.O.[Na+].[Cl-] XZPVPNZTYPUODG-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- VYECFMCAAHMRNW-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O.NS(O)(=O)=O VYECFMCAAHMRNW-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- 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
-
- 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
- B01D2321/167—Use of scale inhibitors
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/20—Prevention of biofouling
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Definitions
- the present invention relates to a method of operating a reverse osmosis membrane device, a slime control method applied to the reverse osmosis membrane device, and a water treatment device that implements the method.
- RO membranes Reverse osmosis membranes installed in reverse osmosis membrane equipment have been used in seawater desalination, ultrapure water production, industrial water treatment, wastewater recovery processing, and reuse of wastewater. It is used to remove etc.
- RO membranes Reverse osmosis membranes
- microorganisms such as bacteria and microalgae contained in the water to be treated secrete extracellular substances (e.g., extracellular polysaccharides) to form slime (biofilm).
- Biofouling (membrane clogging due to slime, etc.) is caused by the accumulation of slime that adheres to the reverse osmosis membrane, and the increase of slime due to the microorganisms contained in the slime that adheres to the reverse osmosis membrane. had become
- a slime control agent addition step of adding a slime control agent to raw water a membrane treatment step of adding the slime control agent and treating the raw water containing the slime control agent with a membrane, and membrane-treated membrane-treated water.
- a pure water production method includes an ultraviolet irradiation treatment step of performing an ultraviolet irradiation treatment and an ion exchange treatment step of performing an ion exchange treatment on the ultraviolet irradiation treatment liquid that has been subjected to the ultraviolet irradiation treatment.
- a method for suppressing slime in a membrane reverse osmosis membrane apparatus is a method for suppressing slime applied to a process of passing water to be treated.
- a slime inhibitor X containing dibromo-3-nitrilopropionamide (DBNPA) and a slime inhibitor Y containing at least one selected from the group consisting of the following components (A) to (D) are added.
- the main object of the present invention is to provide a technology that allows a water system having a reverse osmosis membrane device to be operated for a longer period of time.
- the present inventors have found that in a water system having a reverse osmosis membrane device, the first step of intermittently adding an oxidative slime inhibitor to the water to be treated and the addition of an organic slime inhibitor to the water to be treated. It was found that by controlling and operating these processes in combination with the second process, the water system having the reverse osmosis membrane device can be operated for a longer period of time. At this time, the present inventors also found that the slime present in the reverse osmosis membrane of the reverse osmosis membrane device can be better reduced or the increase of slime can be better suppressed, thereby better suppressing biofouling. The inventors have completed the present invention as follows.
- the present invention comprises a first step of intermittently adding an oxidative slime inhibitor and intermittently supplying water to be treated containing the oxidative slime inhibitor to a reverse osmosis membrane device; a second step of adding the organic slime inhibitor at least during "a period other than the addition period of the first step” and supplying the water to be treated containing the organic slime inhibitor to a reverse osmosis membrane device;
- “at least" in “at least the period other than the addition period of the first step” means that the organic slime inhibitor is added to the "addition period of the first step (first intermittent addition period)" and “the first It is added during at least "the whole period or part of the period other than the addition period of the first step” in the period other than the addition period of the step (first non-addition period), for example, the first It may be added during both the no-addition period and the first intermittent addition period, or may be added only during the first no-ad
- the present invention comprises a first step of intermittently adding an oxidative slime inhibitor and intermittently supplying water to be treated containing the oxidative slime inhibitor to a reverse osmosis membrane device; a second step of adding an organic slime inhibitor at least during a period other than the addition period of the first step, and supplying the water to be treated containing the organic slime inhibitor to a reverse osmosis membrane device; A slime control method applied to a reverse osmosis membrane device is provided.
- the present invention provides a water treatment apparatus that implements the operation method of the reverse osmosis membrane device or the slime control method applied to the reverse osmosis membrane device.
- the addition concentration of the oxidative slime inhibitor may be adjusted to be higher than the addition concentration of the organic slime inhibitor.
- the oxidative slime inhibitor may be added once or more during the three days of operation.
- the oxidative slime inhibitor may be added for 10 minutes or more per time.
- the oxidative slime inhibitor may be added at a total chlorine concentration of 0.1 mg/L or more. 0.01 mg/L or more of the organic slime inhibitor may be added.
- the present invention it is possible to provide a technology that enables long-term operation of a water system having a reverse osmosis membrane device.
- the effects of the present invention are not necessarily limited to the effects described herein, and may be any of the effects described herein.
- FIG. 4 is a schematic diagram showing an example of control of the first addition step and the second addition step according to the embodiment of the present invention
- a1 In the first addition step, the oxidative slime inhibitor is intermittently added at regular intervals.
- b1 In the second addition step, an organic slime inhibitor is always added. At this time, the organic slime inhibitor is added at least during a period other than the addition period of the first addition step.
- the horizontal axis is the operating period (hours), and the vertical axis is the amount added.
- FIG. 4 is a schematic diagram showing an example of control of the first addition step and the second step according to the embodiment of the present invention; a2: In the first addition step, the oxidative slime inhibitor is intermittently added at regular intervals.
- a method of operating a reverse osmosis membrane apparatus is a method of intermittently adding an oxidative slime inhibitor to intermittently feed water to be treated containing the oxidative slime inhibitor to a reverse osmosis membrane apparatus. a first step of supplying; a second step of adding an organic slime inhibitor at least during a period other than the addition period of the first step, and supplying the water to be treated containing the organic slime inhibitor to a reverse osmosis membrane device; A method of operating a reverse osmosis membrane device can be provided.
- the slime inhibitor is an agent that can suppress the increase of slime, an agent that can reduce or remove slime present in the membrane, an agent that can kill microorganisms (bactericides, algicides, etc.). , may contain agents (such as antibacterial agents) that can inhibit the growth of microorganisms.
- the numbers of "first" and "second" such as the first step and the second step are attached for convenience of explanation, and by attaching the first and second, the present implementation The form is not narrowly defined and is not particularly limited.
- the oxidative slime inhibitor used in the present embodiment is a component or drug capable of at least suppressing slime derived from microorganisms (e.g., bacteria, fungi, microalgae, etc.) in an oxidation-reduction reaction, or a drug containing these as active ingredients. and can be detected by the DPD method.
- microorganisms e.g., bacteria, fungi, microalgae, etc.
- the halocyanoacetamide compound preferably DBNPA
- the organic slime inhibitor used in the present embodiment inhibits biological functions by reacting with microbial metabolic functions (enzymes, etc.) and microbial cells (e.g., SH groups) to inhibit microorganisms (e.g., , bacteria, fungi, microalgae, etc.) can at least suppress slime, or a drug containing these as active ingredients.
- microbial metabolic functions enzymes, etc.
- microbial cells e.g., SH groups
- microorganisms e.g., bacteria, fungi, microalgae, etc.
- First step using oxidative slime inhibitor In the first step, the oxidative slime inhibitor is intermittently added, and the water to be treated containing the oxidative slime inhibitor is intermittently fed to the reverse osmosis membrane device.
- the step of supplying is preferred.
- the first step includes a first addition step of intermittently adding the oxidative slime inhibitor to the water to be treated, and intermittently supplying the water to be treated containing the oxidative slime inhibitor after addition to the reverse osmosis membrane device. It is preferable to have a first supply step for performing.
- the first step is a step of intermittently adding the oxidative slime inhibitor to the water to be treated.
- the water to be treated containing the oxidative slime inhibitor can be obtained, and the water to be treated containing the oxidative slime inhibitor after addition can be intermittently supplied to the reverse osmosis membrane device ( For example, see FIGS. 1 and 2).
- the first addition step it is preferable to intermittently add the oxidative slime inhibitor.
- the frequency of addition of the oxidative slime inhibitor is preferably one or more additions within a predetermined period. Preferably 2 days, more preferably 1 day.
- the oxidative slime inhibitor may be added by setting "within a predetermined period" to "every predetermined interval", for example, adding once every 3 days or adding once every 1 day. may be Moreover, it may be added once a day or more every 1 to 2 days (more preferably every other day).
- the number of additions of the oxidative slime inhibitor is not particularly limited. It is preferably once. The number of additions may be "within a predetermined period" or "at predetermined intervals".
- the frequency of addition of the oxidative slime inhibitor as a more preferred embodiment, it is preferably added once or more in 3 days, more preferably added once or more in 2 days, and even more preferably. One or more additions per day.
- the period of addition of the oxidative slime inhibitor is not particularly limited, but it is preferably 0.1 minute or more, more preferably 1 minute or more, and still more preferably 10 minutes or more as a suitable lower limit per time (one period). , Still more preferably 30 minutes or more, and a suitable upper limit is preferably 1000 minutes or less, more preferably 500 minutes or less, even more preferably 300 minutes or less, still more preferably 120 minutes or less. The preferred numerical range is preferably 10 minutes or more and 300 minutes or less, more preferably 30 minutes or more and 120 minutes or less.
- the "addition period of the oxidative slime inhibitor" is also referred to as the "first step addition period" or "first intermittent addition period".
- addition period of the oxidative slime inhibitor refers to the “addition period from the start of addition of the oxidative slime inhibitor to the end of addition of the oxidative slime inhibitor", more preferably “oxidation The period during which the system slime inhibitor is continuously added within a range that does not impair the effects of the present invention. period of time”.
- “1 period (specifically, the addition period from the start of addition of the agent to the end of addition of the agent)" of the “addition period of the oxidative slime inhibitor” may be referred to as "1 unit”. good.
- the "period during which the oxidative slime inhibitor is not added” means “a period other than the addition period of the oxidative slime inhibitor", “a period other than the addition period of the first step", or “the first This period is also referred to as “a period other than the intermittent addition period", and this period is also referred to as a “first non-addition period”.
- the period during which no oxidative slime inhibitor is added means “the period from the end of addition of the oxidative slime inhibitor to the start of addition of the oxidative slime inhibitor (i.e., non-addition period)".
- oxidative slime inhibitor refers to a period in which the oxidative slime inhibitor is not continuously added within a range that does not impair the effects of the present invention. period during which the system slime inhibitor is not continuously added”.
- “1 period (specifically, the non-addition period from the end of addition of the drug to the start of addition of the drug)" of the above “period in which no oxidative slime inhibitor is added” is changed to "1 unit".
- the addition concentration of the oxidative slime inhibitor to the aqueous system is not particularly limited, but the total chlorine concentration is preferably 0.1 mg/L or more (more than preferably 0.5 mg/L or more), more preferably 1 mg/L or more, still more preferably 2 mg/L or more, even more preferably 5 mg/L or more, more preferably 10 mg/L or more, still more preferably 25 or It is 30 mg/L or more, and a suitable upper limit is preferably 600 mg/L or less, more preferably 60 mg/L or less.
- the preferred numerical range is preferably 0.1 to 600 mg/L, more preferably 2 to 60 mg/L.
- the addition concentration of the oxidative slime inhibitor it is preferable to adjust the addition concentration of the oxidative slime inhibitor to be higher than the addition concentration of the organic slime inhibitor described later.
- the additive concentration of the organic slime inhibitor is 1 mg/L (as drug mass concentration)
- the additive concentration of the oxidative slime inhibitor is a suitable lower limit value, It is preferably 1 or more, more preferably 1.5 or more, still more preferably 2 or more, and still more preferably 3 or more. 40 or 30 or less.
- the addition concentration of the organic slime inhibitor is 1 mg/L (as drug mass)
- the addition concentration of the oxidative slime inhibitor is It is preferably 2-50, more preferably 3-40.
- the absolute amount (mg/(L/h)) of the oxidative slime inhibitor to be added to the water system per one addition period is not particularly limited, but can be calculated as follows: "addition period of oxidative slime inhibitor per unit x time It can be calculated from the added concentration of the oxidative slime inhibitor (mg/L (as total chlorine concentration))", and the total chlorine concentration is preferably 0.05 mg/(L/h) or more as a suitable lower limit.
- a suitable upper limit is preferably 10000 mg/(L/h) or less, more preferably 10000 mg/(L/h) or less, and further It is preferably 5000 mg/(L/h) or less, still more preferably 1000 mg/(L/h) or less, and more preferably 500 mg/(L/h) or less.
- the preferred numerical range is preferably 0.05 to 10000 mg/(L/h), more preferably 2.5 to 5000 mg/(L/h), more
- the first addition step includes a period during which the oxidative slime inhibitor is added to the water system by intermittently adding the oxidative slime inhibitor (hereinafter also referred to as "first intermittent addition period"), There is also a period during which no oxidative slime inhibitor is added (hereinafter referred to as a “first non-addition period”), and these periods are preferably carried out sequentially or in random order. It is preferable to carry out sequentially. In this case, either the first intermittent addition period or the first no addition period may come first, the first intermittent addition period followed by the first no addition period, or the first no addition period followed by Any of the first intermittent addition periods may be used. Moreover, the number of times of each of the first intermittent addition period and the first non-addition period during the entire operation period of the water system may be singular or plural.
- One unit of the first intermittent addition period is not particularly limited, but the configuration described in the above "Addition period of oxidative slime inhibitor" can be adopted, and a suitable numerical range is preferably 1 to 1000 minutes. , more preferably 10 to 300 minutes.
- One unit of the first non-addition period is not particularly limited, but a suitable lower limit is preferably 1 hour or longer, more preferably 3 hours or longer, still more preferably 5 hours or longer, and still more preferably 10 hours or longer. Also, a suitable upper limit is preferably 200 hours or less, more preferably 150 hours or less, even more preferably 100 hours or less, and even more preferably 50 hours or less. The preferred numerical range is preferably 5 to 100 hours, more preferably 10 to 50 hours.
- Period ratio of the first intermittent addition period per unit and the first non-addition period per unit in the total period of "the first intermittent addition period per unit and the first non-addition period per unit" is not particularly limited, but the fact that the first intermittent addition period per unit is shorter than the first non-addition period per unit reduces the amount of additive chemical used in the water system and allows the water system to be used for a long time. It is suitable from the viewpoint of stable operation.
- the period ratio between the first intermittent addition period per unit and the first non-addition period per unit is preferably 1:2 to 500, more preferably 1:3 to 200, further preferably 1:5 to 100, even more preferably 1:7-50.
- the first intermittent addition period per unit is the average obtained by dividing the total period (days, hours, etc.) of the first intermittent addition periods during a certain operation period by the number of first intermittent addition periods during this operation period. can be a value.
- the first additive-free period per unit is the average obtained by dividing the total period (days, hours, etc.) of the first additive-free periods during a certain operation period by the number of first additive-free periods during this operation period. can be a value.
- the operation period of the first addition step in the present embodiment may be a single period of "the first intermittent addition period per unit and the first non-addition period per unit", or may be the same or different
- the period may be configured by combining a plurality of "first intermittent addition periods per unit and first non-addition periods per unit”.
- the oxidative slime inhibitor or its components are not particularly limited, but examples thereof include combined halogen compounds. , bromine, and the like.
- Examples of the combined halogen compound include combined chlorine-based compounds and combined bromine-based compounds, and one or more selected from these can be used.
- Examples of the combined chlorine compounds include stabilized chlorine compounds and chloramine compounds represented by halogenated hydantoin compounds, and examples of combined bromine compounds include stabilized bromides and halogenated hydantoin compounds. However, it is not limited to these, and one or more selected from these can be used.
- a commercially available product may be used, or one obtained by a known production method may be used.
- the salts of combined halogen compounds such as salts of chloramine compounds and salts of stabilized bromides are not particularly limited, but examples include alkali metal salts such as sodium salts and potassium salts; metal salts; manganese salts, copper salts, zinc salts, iron salts, cobalt salts, other metal salts such as nickel salts; ammonium salts, organic ammonium salts, etc.; amino acid salts such as guanidine salts; 1 type or 2 or more types selected can be used.
- alkali metal salts such as sodium salts and potassium salts
- metal salts such as manganese salts, copper salts, zinc salts, iron salts, cobalt salts, other metal salts such as nickel salts; ammonium salts, organic ammonium salts, etc.
- amino acid salts such as guanidine salts; 1 type or 2 or more types selected can be used.
- a chloramine compound refers to a compound having at least one bond (N—Cl bond) between a nitrogen atom and a chlorine atom.
- chloramine compounds include chloramine, chlorosulfamic acid compounds, and other chloramine compounds, and one or more selected from these can be used.
- Chloramine compounds include, for example, stabilized chlorine compounds produced from those containing stabilizers and chlorine-based oxides; and chlorosulfamic acid compounds produced from those containing sulfamic acid compounds and chlorine-based oxides. and the like, and one or more selected from these can be used.
- the stabilizing agent is not particularly limited as long as it can form a bonded halogen (preferably a stabilizing bonded halogen), and preferably includes compounds having an amino group such as ammonium salts and sulfamic acid compounds. One or more selected from these can be used.
- monovalent functional groups -NH2, -NHR, -NRR'
- amino groups obtained by removing hydrogen from ammonia, primary amines or secondary amines
- ammonium salts include ammonium sulfate, ammonium nitrate, and ammonium chloride, and one or more selected from these can be used. Among these, ammonium sulfate is preferred.
- the sulfamic acid compound constituting the chlorosulfamic acid compound is preferably a compound represented by R 1 R 2 NSO 3 H...[1].
- R 1 and R 2 in the general formula [1] are each independently H or a functional group containing an alkyl group having 1 to 8 carbon atoms or a benzene ring.
- sulfamic acid compounds include sulfamic acid (amidosulfuric acid) in which both R 1 and R 2 groups are hydrogen atoms or salts thereof; N-methylsulfamic acid, N-ethylsulfamic acid, N-propylsulfamic acid, Sulfamic acid or a salt thereof, wherein one of the two groups R 1 and R 2 is a hydrogen atom and the other is an alkyl group having 1 to 8 carbon atoms, such as N-isopropylsulfamic acid and N-butylsulfamic acid; -dimethylsulfamic acid, N,N-diethylsulfamic acid, N,N-dipropylsulfamic acid, N,N-dibutylsulfamic acid, N-methyl-N-ethylsulfamic acid, N-methyl-N-propylsulfamic acid, etc. and two R 1 groups
- the chlorine oxide is not particularly limited, but for example, chlorine gas, chlorine dioxide, hypochlorous acid or its salts, chlorous acid or its salts, chloric acid or its salts, perchloric acid or its salts, chlorine isocyanuric acid or a salt thereof, and one or more selected from these can be used.
- hypochlorites include alkali metal hypochlorites such as sodium hypochlorite and potassium hypochlorite; alkaline hypochlorites such as calcium hypochlorite and barium hypochlorite; metal salts; and the like, and one or more selected from these can be used.
- chlorites include alkali metal chlorites such as sodium chlorite and potassium chlorite; alkaline earth metal chlorites such as barium chlorite; chlorite metal salts; and the like, and one or more selected from these can be used.
- chlorates include ammonium chlorate; alkali metal chlorates such as sodium chlorate and potassium chlorate; alkaline earth metal chlorates such as calcium chlorate and barium chlorate; One or two or more selected from can be used.
- perchlorates include sodium perchlorate and potassium perchlorate, and one or more selected from these can be used.
- chlorinated isocyanurate include chlorinated sodium isocyanurate, and one or more selected from these can be used.
- an aqueous solution of a stabilizer e.g., an aqueous solution of a sulfamic acid compound, etc.
- an aqueous solution of a chlorine-based oxide e.g., an aqueous solution of sodium hypochlorite, etc.
- the pH of the medicament containing the manufactured chloramine compound is preferably 12 or higher, more preferably 13 or higher.
- the ratio of the chlorine - based oxide and the stabilizer (e.g., ammonium salt, sulfamic acid compound, etc.) to be used is not particularly limited.
- agent preferably sulfamic acid compound
- the usage ratio may be the content ratio in the drug.
- the usage ratio of the alkali and the chlorine-based oxide is Cl/alkali metal (molar ratio), preferably 0.3 to 0.4, more preferably 0.30 to 0.36, and the usage ratio is It may be the content ratio in the drug.
- sulfamic acid compound narrowly defined sulfamic acid in which R 1 and R 2 are each H is more preferable, but N-methylsulfamic acid, N,N-dimethylsulfamic acid, N-phenylsulfamic acid, chloramine T, etc. can also be used.
- these sulfamic acids may be used in the form of a free (powder) acid, or may be a salt such as an alkali metal salt such as a sodium salt, a potassium salt, or a lithium salt. One or more selected from these can be used.
- Chlorosulfamic acid refers to sulfamic acid (H 2 NSO 2 OH) in which at least one hydrogen atom in the NH 2 group is replaced with a chlorine atom.
- Chlorosulfamic acid includes, for example, monochlorosulfamic acid, dichlorosulfamic acid and the like.
- Chlorosulfamate is sulfamic acid (H 2 NSO 2 OH) in which at least one hydrogen atom in the OH group is replaced with a metal ion (for example, an alkali metal ion such as lithium ion, sodium ion, potassium ion).
- a metal ion for example, an alkali metal ion such as lithium ion, sodium ion, potassium ion.
- chlorosulfamate include lithium chlorosulfamate, sodium chlorosulfamate, and potassium chlorosulfamate, and one or more selected from these can be used.
- sodium chlorosulfamate is preferred.
- chloramine T etc. can be used as another chloramine compound.
- 1 type(s) or 2 or more types selected from these can be used.
- a stabilized bromide refers to a compound having at least one nitrogen atom (N--Cl bond) or a bond between a carbon atom and a bromine atom (C--Br bond).
- the stabilized bromide is preferably a bromide that is less likely to change due to decomposition in water and that can stably exist in water.
- stabilized bromides include, but are not limited to, reaction products of "a reaction product of a bromine-based oxidizing agent or a bromine compound and a chlorine-based oxide” and a "sulfamic acid compound.”
- the pH of the reaction product is preferably alkaline, more preferably 11 or higher, still more preferably 12 or higher, and even more preferably 13 or higher. These may be commercially available products, or those obtained by known production methods may be used.
- the bromine-based oxidizing agent is not particularly limited, but includes, for example, bromine (liquid bromine), bromine chloride, bromic acid, bromate, and hypobromous acid, and one or more selected from these. can be used.
- bromine compound examples include, but are not limited to, alkali metal bromides such as sodium bromide, potassium bromide and lithium bromide; bromide salts such as ammonium bromide; and hydrobromic acid. One or two or more selected from can be used.
- Chlorine-based oxides e.g., hypochlorites, chlorites, chlorates, perchlorates, chlorinated isocyanurates, etc.
- Chlorine-based oxides e.g., hypochlorites, chlorites, chlorates, perchlorates, chlorinated isocyanurates, etc.
- Descriptions such as “chlorine-based oxides” apply to these, and the configurations and the like described in the descriptions can be adopted as appropriate.
- hypochlorite for example, sodium hypochlorite is preferred.
- the "sulfamic acid compound” is the same as the “sulfamic acid compound” in the “sulfamic acid compound constituting the chlorosulfamic acid compound is a compound represented by R 1 R 2 NSO 3 H ... [1]" in ⁇ chloramine compound> above. ” applies to these, and the configuration and the like of the description can be adopted as appropriate.
- sulfamic acid compounds sulfamic acid or salts thereof are preferred.
- aqueous sodium bromide solution and sodium hypochlorite are mixed to form a mixed solution 1, while an aqueous sulfamic acid solution and an aqueous sodium hydroxide solution are mixed to form a mixed solution 2.
- a method of mixing the mixed solution 1 and the mixed solution 2 in the presence of an alkali for example, bromamine, bromosulfamic acid, and bromosulfamate, which are composed of an ammonium salt and bromine, and other compounds such as DBNPA can be used.
- halogenated hydantoin compounds include 1-bromo-3-chloro-5,5-dimethylhydantoin (also referred to as "BCDMH"), 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5 ,5-dimethylhydantoin, 1-bromo-3-chloro-5,5-diethylhydantoin, 1,3-dichloro-5,5-diethylhydantoin, and 1-bromo-3-chloro-5-methyl-5-ethyl Hydantoin and the like can be mentioned, and one or more selected from these can be used.
- BCDMH and 1,3-dichloro-5,5-dimethylhydantoin are preferred from the viewpoints of the balance of the dissolution rate with the solid agent (B) when in contact with water, availability, and the like.
- the halogenated hydantoin compound may be a commercial product or can be obtained by a known production method.
- the agent can be obtained by reacting the stabilizer with the chlorine-based oxide and/or the bromine-based oxidizing agent.
- the hydantoin compound include compounds having a hydantoin skeleton.
- the hydantoin compound include hydantoin, 5,5-dialkylhydantoin (e.g., 5,5-dimethylhydantoin, 5-methylethylhydantoin, 5-methylhydantoin, butylhydantoin, 5-ethylbutylhydantoin, etc.), and one or more selected from these can be used.
- dialkyl may be the same or different alkyl groups, and examples of the alkyl group include those having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms), and may be linear or branched. Examples include a methyl group, an ethyl group, and a butyl group, and one or more selected from these can be used.
- the oxidative slime inhibitor may appropriately contain an optional component or an optional chemical within a range that does not impair the effects of the present invention.
- optional ingredients or agents include anticorrosive agents (corrosion inhibitors), scale inhibitors, slime control agents, solvents or dispersion media such as water, dispersant enzymes, bactericides and antifoaming agents.
- corrosion inhibitors corrosion inhibitors
- scale inhibitors slime control agents
- solvents or dispersion media such as water, dispersant enzymes, bactericides and antifoaming agents.
- solvents or dispersion media such as water, dispersant enzymes, bactericides and antifoaming agents.
- the agent is not limited to this, and various agents generally used for water treatment may be used.
- one or more of these optional ingredients or agents can be appropriately selected.
- optional components or optional chemicals may be added or used as appropriate.
- the first supply step is preferably a step of intermittently supplying the water to be treated containing the oxidative slime inhibitor to the reverse osmosis membrane device.
- the water system can be operated for a longer period of time.
- biofouling occurring in a reverse osmosis membrane provided in a reverse osmosis membrane device can be suppressed, and by suppressing the biofouling, the water system can be stably operated for a long period of time. can do.
- the first supply step when the water to be treated containing the oxidative slime inhibitor is intermittently supplied to the reverse osmosis membrane device, the period during which the water to be treated containing the oxidative slime inhibitor is supplied ("second and a period during which the water to be treated containing the oxidative slime inhibitor is not supplied (also referred to as a "first non-supply period").
- First addition step For the various conditions in the first supply step, the configurations described in the above "1-1-1. First addition step” can be appropriately adopted.
- the supply frequency in the first supply step and its predetermined period, the number of times of supply, the supply frequency, the supply period, the supply concentration of the oxidative slime inhibitor to the water system, the amount of the oxidative slime inhibitor supplied to the water system per one supply period The absolute amount, one unit of the first supply period, the period ratio between the first intermittent supply period per unit and the first non-supply period per unit, etc. are described in the above "1-1-1. First addition step".
- addition frequency and its predetermined period the number of additions, the addition frequency, the addition period, the concentration of the oxidative slime inhibitor added to the water system, the absolute amount of the oxidative slime inhibitor added to the water system per one addition period, the first addition One unit of the period, the period ratio between the first intermittent addition period per unit and the first non-addition period per unit, and the like can be appropriately adopted.
- the supply frequency of the water to be treated containing the oxidative slime inhibitor is not particularly limited, but is preferably supplied once or more during a predetermined period, and more preferably once during the predetermined period. This supply frequency may be "within a predetermined period" or "at predetermined intervals".
- the number of times the oxidative slime inhibitor is supplied is not particularly limited, but the preferred upper limit is more preferably 2 times or less, and still more preferably 1 time.
- the frequency of supplying the water to be treated containing the oxidative slime inhibitor is preferably once or more in three days, more preferably once in two days (more preferably every other day). More preferably, one or more feedings per day.
- the number of times of supply may be "within a predetermined period" or "at predetermined intervals".
- the supply frequency of the oxidative slime inhibitor it is preferably supplied once or more in three days, more preferably once or more in one day, as a more suitable embodiment.
- the supply period of the water to be treated containing the oxidative slime inhibitor is not particularly limited. minutes or less.
- the "supply period of the water to be treated containing the oxidative slime inhibitor” refers to the “supply period from the start of the supply of the oxidative slime inhibitor to the end of the supply of the oxidative slime inhibitor". In a narrower sense, it means “a period during which the supply of the oxidative slime inhibitor is continuously supplied without being stopped”. Further, in the present specification, the "supply period of the water to be treated containing the oxidative slime inhibitor” is also referred to as the “first step supply period” or the “first intermittent supply period”. Further, in this specification, “1 period (specifically, the supply period from the start of supply of the chemical to the end of supply of the chemical)" of "the supply period of the water to be treated containing the oxidative slime inhibitor” is , "one unit".
- the period during which the water to be treated containing the oxidative slime inhibitor is not supplied means “the period other than the period for which the water to be treated containing the oxidative slime inhibitor is supplied", "the supply of the first step This period may also be referred to as “a period other than the period” or “a period other than the first intermittent supply period", and this period may also be referred to as a “first non-supply period”.
- the period during which the water to be treated containing the oxidative slime inhibitor is not supplied means “the non-supply period from the end of supply of the oxidative slime inhibitor to the start of supply of the oxidative slime inhibitor.
- the above-mentioned “period in which the water to be treated containing the oxidative slime inhibitor is not supplied” is defined as “one period (specifically, a non-supply period from the end of supply of the chemical to the start of supply of the chemical )” may be set as “one unit”.
- the supply concentration of the oxidative slime inhibitor to the aqueous system is not particularly limited, but the total chlorine concentration is preferably 0.1 mg / L or more (more preferably 0.5 mg /L or more), more preferably 1 mg/L or more, still more preferably 2 mg/L or more, even more preferably 5 mg/L or more, more preferably 10 mg/L or more, still more preferably 25 mg/L or more, and A suitable numerical range is preferably 5 to 500 mg/L, more preferably 25 to 300 mg/L.
- the absolute amount (mg ⁇ time) of the oxidative slime inhibitor supplied to the reverse osmosis membrane device per supply period is not particularly limited, the amount of the oxidative slime inhibitor per unit supply It can be calculated from "period ⁇ supply concentration of oxidative slime inhibitor at that time", and the total chlorine concentration is preferably 0.05 mg / (L / h) or more, more preferably 0.05 mg / (L / h) or more as a suitable lower limit.
- 1 mg/(L/h) or more more preferably 0.5 mg/(L/h) or more, still more preferably 1 mg/(L/h) or more, more preferably 2.5 mg/(L/h) or more, More preferably 10 mg/(L/h) or more, still more preferably 25 mg/(L/h) or more, and a suitable numerical range is preferably 0.05 to 10000 mg/(L/h), more preferably is 2.5 to 5000 mg/(L/h), more preferably 10 to 1000 mg/(L/h).
- the water to be treated containing the oxidative slime inhibitor is supplied to the reverse osmosis membrane device, thereby supplying the water to be treated containing the oxidative slime inhibitor to the reverse osmosis membrane device (hereinafter referred to as , also referred to as "first intermittent supply period") and a period in which the water to be treated containing the oxidative slime inhibitor is not supplied to the reverse osmosis membrane device (hereinafter also referred to as "first non-supply period”), These periods are preferably performed sequentially or out of order. It is preferable to carry out sequentially.
- first intermittent supply period and first additive-free supply period is preferably based on the order of the first intermittent addition period and first additive-free period described above.
- the number of times of each of the first intermittent supply period and the first non-supply period during the entire operation period of the water system may be singular or plural.
- One unit of the first intermittent supply period is not particularly limited, but a suitable numerical range is preferably 1 to 1000 minutes, more preferably 10 to 300 minutes.
- One unit of the first non-supply period is not particularly limited, but a preferable numerical range is preferably 5 to 100 hours, more preferably 10 to 50 hours.
- the period ratio of the first intermittent supply period per unit and the first non-supply period per unit in the total period of "the first intermittent supply period per unit and the first non-supply period per unit" is although not particularly limited, the first intermittent supply period per unit is preferably shorter than the first non-supply period per unit, and more preferably 1:7-50.
- the first intermittent supply period per unit is the average value obtained by dividing the total period (days, etc.) of the first intermittent supply periods during a certain operation period by the number of first intermittent supply periods during this operation period. There may be.
- the first no-supply period per unit is the average value obtained by dividing the total period (days, etc.) of the first no-supply periods during a certain operation period by the number of first no-supply periods during this operation period.
- the operation period of the first supply step in the present embodiment may be a single period of "the first intermittent supply period per unit and the first non-supply period per unit", or may be the same or different The period may be configured by combining a plurality of "first intermittent supply periods per unit and first supply periods per unit". This single period or a plurality of combined periods is preferably based on a single period or a plurality of combined periods of the "first intermittent addition period per unit and first non-addition period per unit" described above. is.
- Second step using organic slime inhibitor In the second step, the organic slime inhibitor is added at least during a period other than the addition period of the first step, and the water to be treated contains the organic slime inhibitor. is preferably supplied to the reverse osmosis membrane device. Furthermore, the second step includes a second addition step of adding the organic slime inhibitor, and a second supply step of supplying the water to be treated containing the organic slime inhibitor after the addition to the reverse osmosis membrane device. is preferred.
- the second step is a step of adding the organic slime inhibitor at least during a period other than the addition period of the first step. Thereby, the water to be treated containing the organic slime inhibitor can be obtained, and the water to be treated containing the organic slime inhibitor after addition can be supplied to the reverse osmosis membrane device (for example, 1 and Figure 2).
- the organic slime inhibitor at least during "a period other than the addition period of the first step".
- the organic slime inhibitor may be added during both the one-addition-free period and the first intermittent-addition period, or the organic slime inhibitor may be added only during the first additive-free period (for example, , see FIGS. 1 and 2).
- the addition of the organic slime inhibitor during the first non-addition period may be the addition of the organic slime inhibitor during the entire period or part of the first non-addition period.
- the addition of the organic slime inhibitor during the first intermittent addition period may be the addition of the organic slime inhibitor during the entire period or part of the first intermittent addition period.
- the organic slime inhibitor in the second step, it is preferable to add the organic slime inhibitor during the entire period of the first additive-free period, out of the entire period or part of the first additive-free period.
- the partial period of the first additive-free period is preferably 50% or more, more preferably 70% or more, still more preferably 90% or more, and even more preferably 95% of the entire first additive-free period. % or more, more preferably 98% or more, still more preferably 99% or more, and even more preferably 100% (also referred to as the entire period).
- the organic slime inhibitor is more preferable to add the organic slime inhibitor continuously or discontinuously during "at least the period other than the addition period of the first step", but it is preferable to add it continuously. is more preferred, and constant addition is even more preferred.
- the organic slime inhibitor is preferably added continuously or discontinuously at least during the "first non-addition period per unit", but it is added continuously. is more preferred.
- the term “discontinuous” means that there may exist a period during which the organic slime inhibitor is added and a period during which the organic slime inhibitor is stopped, as long as the effects of the present invention are not impaired.
- the period of addition is preferably longer than the period of suspension, and the period of suspension is preferably within 1/10 of the period of addition, more preferably within 5/100, more preferably 2.5 /100 or less, more preferably 1/500 or less.
- the period during which the organic slime inhibitor is added “continuously” means “the period of addition from the start of addition of the organic slime inhibitor to the end of addition of the organic slime inhibitor". , More preferably, it refers to “a period in which the organic slime inhibitor is continuously added within a range that does not impair the effects of the present invention", and in a narrower sense, "without stopping the addition of the organic slime inhibitor
- the term “continuous addition period” is also referred to as “constant addition period”. For example, an operation period of 60 minutes and a “non-addition period of 0 minutes and an addition period of 60 minutes” may be mentioned as the "constant addition period”.
- “continuously” may have a period during which the drug is stopped as long as it is within the same effect as the constant addition of the present invention.
- the period during which the drug is stopped during the day is preferably within 60 minutes, more preferably within 30 minutes, still more preferably within 15 minutes, even more preferably within 5 minutes, more preferably 0 minutes ("always (also referred to as “addition period”).
- the period during which the drug is stopped during one hour of operation is preferably within 5 minutes, more preferably within 1 minute, still more preferably within 5 minutes, and more preferably 0 minutes (also referred to as "continuous addition period"). be.
- the period of addition of the organic slime inhibitor is not particularly limited.
- the entire period of operation of the reverse osmosis membrane device or the entire period of the first step may be set as the period of addition of the organic slime inhibitor, but it is more specific.
- the preferred lower limit per time (one period) is preferably 0.1 days or more, more preferably 0.3 days or more, still more preferably 0.5 days or more, and even more preferably 1 day
- the upper limit is preferably 30 days or less, more preferably 10 days or less, still more preferably 7 days or less, and even more preferably 3 days or less.
- the preferred numerical range is preferably 0.5 days or more and 7 days or less, more preferably 1 day or more and 3 days or less.
- the addition concentration of the organic slime inhibitor to the aqueous system is not particularly limited, but as a drug mass, a suitable lower limit is preferably 0.001 mg / L or more, more preferably 0.01 mg/L or more, more preferably 0.05 mg/L or more, and even more preferably 0.1 mg/L or more, and a suitable upper limit is preferably 10000 mg/L or less, more preferably 1000 mg/L. L or less, more preferably 100 mg/L or less, and even more preferably 50 mg/L or less. The preferred numerical range is preferably 0.01 to 100 mg/L, more preferably 0.1 to 50 mg/L.
- the absolute amount (mg (as drug mass)) of the organic slime inhibitor added to the water system per one addition period is not particularly limited, but "addition period of organic slime inhibitor x organic slime inhibitor at that time can be calculated from the "addition concentration", and a suitable lower limit is preferably 0.002 mg / (L / h) or more, more preferably 0.02 mg / (L / h) or more, still more preferably 0.2 mg / (L / h) or more, still more preferably 2 mg / (L / h) or more, and a suitable upper limit is preferably 6000000 mg / (L / h) or less, more preferably 300000 mg / (L / h) 30000 mg/(L/h) or less, more preferably 3000 mg/(L/h) or less.
- the preferred numerical range is preferably 0.2 to 30000 mg/(L/h), more preferably 2 to 3000 mg/(L/h).
- Organic slime inhibitors or their components are not particularly limited, but include, for example, isothiazoline compounds, halocyanoacetamide compounds, aldehyde compounds, and oxime compounds represented by tetrazolyloxime and dichloroglyoxime. 1 type, or 2 or more types can be used. Further, the organic slime inhibitor may be a drug containing one or two or more compounds selected from these. As the organic slime inhibitor or the compound used for the organic slime inhibitor, a commercially available product may be used, or one obtained by a known production method may be used.
- isothiazoline compounds include, but are not limited to, 5-chloro-2-methyl-4-isothiazolin-3-one (Cl-MIT), 2-methyl-4-isothiazolin-3-one (MIT), 2-ethyl -4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-ethyl-4-isothiazolin-3-one, 5-chloro-2-t-octyl-4 -isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-cyclohexyl-4-isothiazolin-3-one and the like.
- the isothiazoline compound a complex compound of the isothiazoline compound described above and magnesium chloride, magnesium nitrate, copper chloride, copper nitrate, calcium chloride, or the like may be used. One or more selected from these can be used.
- the isothiazolin compounds 5-chloro-2-methyl-4-isothiazolin-3-one (Cl-MIT) and 2-methyl-4-isothiazolin-3-one (MIT) or mixtures thereof are preferred.
- halocyanoacetamide compounds include, but are not limited to, 2-halo-3-nitrilopropionamides such as 2-chloro-3-nitrilopropionamide and 2-bromo-3-nitrilopropionamide; 2,2-dihalo-3-nitrilopropionamides such as 3-nitrilopropionamide, 2,2-dibromo-3-nitrilopropionamide (DBNPA), 2-chloro-2-bromo-3-nitrilopropionamide; N- N—C1-3 alkyl-2-halo-3-nitrilopropionamides such as methyl-2-chloro-3-nitrilopropionamide, N-methyl-2-bromo-3-nitrilopropionamide; N-methyl-2, 2-dichloro-3-nitrilopropionamide, N-C1-3 alkyl-2,2-dihalo-3-nitrilopropionamide
- X 1 and X 2 each independently represent a halogen atom or a hydrogen atom, and at least one of X 1 and X 2 is a halogen atom.
- R 3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- Halogen atoms include chlorine atoms and bromine atoms, with bromine atoms being preferred.
- C1-3 alkyl may be linear or branched and includes, for example, methyl group, ethyl group, n-propyl group, iso-propyl group and the like. One or more selected from these can be used.
- dihalonitrilopropionamides are preferred, and among these, 2,2-dibromo-3-nitrilopropionamide (DBNPA) is more preferred.
- DBNPA 2,2-dibromo-3-nitrilopropionamide
- the aldehyde compound is not particularly limited, and examples thereof include monoaldehyde compounds such as acetaldehyde; dialdehyde compounds such as glyoxal and orthophthalaldehyde; and one or more selected from these can be used. .
- dialdehyde compounds are preferred, and among dialdehyde compounds, glutaraldehyde is preferred from the viewpoint of high safety.
- the oxime compound is not particularly limited, but includes oxime compounds having a tetrazole ring (CH 2 N 4 ) (e.g., tetrazolyl oxime, etc.), halogenated oxime compounds, (e.g., dichloroglyoxime, etc.), and the like. One or more selected from these can be used.
- Halogenated oxime compounds include, for example, dichloroglyoxime, ⁇ -chlorobenzaldoxime, ⁇ -chlorobenzaldoxime acetate, 4-hydroxyphenyl- ⁇ -ketoacetohydroxymic acid chloride (also known as Paracrox), One or more selected from these can be used.
- DBNPA 2,2-dibromo-3-nitrilopropionamide
- Cl-MIT 5-chloro-2-methyl-4-isothiazolin-3-one
- MIT 2-methyl- One or more selected from 4-isothiazolin-3-one
- glutaraldehyde and the like are preferred.
- the organic slime inhibitor may contain optional ingredients or optional chemicals as appropriate within a range that does not impair the effects of the present invention.
- an optional component or an optional chemical may be added or used as appropriate, apart from the addition or use of the organic slime inhibitor.
- various chemical agents that can be generally used for water treatment may be used, and the configuration described in the above ⁇ Oxidative slime inhibitor> "Optional component or optional chemical" can be adopted as appropriate.
- the second supplying step is preferably a step of supplying the water to be treated containing the organic slime inhibitor to the reverse osmosis membrane device.
- the water system can be operated for a longer period of time.
- biofouling occurring in a reverse osmosis membrane provided in a reverse osmosis membrane device can be suppressed, and by suppressing the biofouling, the water system can be stably operated for a long period of time. can do.
- Second addition step For the various conditions in the second supply step, the configurations described in the above “1-2-1. Second addition step” can be appropriately adopted.
- the supply period in the second supply step the supply concentration of the organic slime inhibitor to the water system, the absolute amount of the organic slime inhibitor supplied to the water system per one supply period, etc.
- the addition period of the second addition step, the addition concentration of the organic slime inhibitor to the water system, the absolute amount of the organic slime inhibitor added to the water system per one addition period, etc. can be appropriately adopted.
- the water to be treated containing the organic slime inhibitor is preferably supplied to the reverse osmosis membrane device during "at least a period other than the supply period of the first step.”
- the water to be treated containing the organic slime inhibitor is preferably supplied to the reverse osmosis membrane device continuously or discontinuously, more preferably continuously, and is constantly supplied during the operating period. is more preferable.
- the term "continuously" supplied period of the organic slime inhibitor means “supply period from the start of supply of the organic slime inhibitor to the end of supply of the organic slime inhibitor". In a narrower sense, it means “a period in which the supply of the organic slime inhibitor is continuously supplied without stopping", and this narrow sense is referred to as "a period of constant supply".
- the supply period of the organic slime inhibitor is not particularly limited, and the entire period of operation of the reverse osmosis membrane device or the entire period of the first step may be set as the supply period of the organic slime inhibitor, but it is a more specific embodiment. , preferably 0.5 days or more and 7 days or less, more preferably 1 day or more and 3 days or less, per one time (one period).
- the supply concentration of the organic slime inhibitor to the reverse osmosis membrane device is not particularly limited, but a suitable numerical range is preferably 0.01 to 100 mg/L, more preferably is 0.1 to 50 mg/L.
- the absolute amount (mg) of the organic slime inhibitor to be supplied to the reverse osmosis membrane device per supply period is not particularly limited, but a suitable numerical range is preferably 0.2 to 30000 mg/(L/h), More preferably 2 to 3000 mg/(L/h).
- control of the first step and the second step in the present embodiment In the method of the present embodiment, it is preferable to control the first step and the second step, so that the water system having the reverse osmosis membrane device can be maintained for a longer period of time. can drive In the method of the present embodiment, a more preferred aspect is to control the first addition step and the second addition step, whereby the water to be treated containing the oxidative slime inhibitor and/or the organic slime inhibitor can be better supplied to the reverse osmosis membrane device, thereby allowing the water system having the reverse osmosis membrane device to operate stably for a longer period of time.
- the slime present in the reverse osmosis membrane of the reverse osmosis membrane device can be reduced or the increase of slime can be suppressed, thereby improving biofouling. can also be suppressed to
- the first step and the second step can be performed at the same time or at different times, and are more preferably performed at the same time. Moreover, in the method of the present embodiment, the first step and the second step may be performed in parallel or in series, but are preferably performed in parallel. In the method of the present embodiment, as a more preferred aspect, it is more preferred to perform the first step and the second step simultaneously and in parallel. Further, in the method of the present embodiment, during the addition of the oxidative slime inhibitor in the first step (preferably, during the continuous addition), the organic slime inhibitor in the second step may be added. Alternatively, the addition may be stopped, and it is preferable to continuously add the organic slime inhibitor in the second step while the oxidative slime inhibitor in the first step is not being added.
- the first step and/or the second step based on the operation starting point of the first step and/or the second step.
- the operational origins may be the same or different.
- the operation starting point is not particularly limited and may be set arbitrarily. At the time of resuming operation, at the time of adding chemicals, setting an arbitrary period, etc.), and one or a combination of two or more selected from these can be used.
- the operation start point may be the start of the first intermittent addition or the start of the first non-addition of the first step, or any point within the second addition period of the second step.
- the start of the first intermittent addition or the start of the first non-addition of the first step within the second addition period of the second step may be set as the start of operation.
- both the first and second processes are additive-free periods (for example, maintenance, adjustment of addition timing of both processes, both stop, etc.)
- at least one of the first and second processes may be the starting point of operation, or the simultaneous addition of the chemicals of both the first step and the second step may be the starting point of operation.
- FIG. 1 is a schematic diagram showing Example 1 of control of the first addition step and the second addition step according to the embodiment of the present invention.
- the first addition step the oxidative slime inhibitor is intermittently added at regular intervals.
- Example 1 b1 In the second addition step, an organic slime inhibitor is always added. At this time, the organic slime inhibitor is added at least during a period other than the addition period of the first addition step.
- the horizontal axis is the operating period (hours), and the vertical axis is the amount added. Further, the operating period 0h of the first addition step and the operating period 0h of the second addition step may be used as starting points of operation.
- the intermittent addition periods in the first addition step may be the same or different periods, and the intermittent addition amounts may be the same or different amounts. Also, each interval of intermittent addition may be the same or different intervals.
- the water to be treated can contain the oxidative slime inhibitor and/or the organic slime inhibitor. Then, according to Control Example 1 of the present embodiment, the water to be treated containing the oxidative slime inhibitor and/or the organic slime inhibitor is supplied to the reverse osmosis membrane device as the first supply step and the second supply step. be. At this time, the water to be treated containing the oxidative slime inhibitor and/or the organic slime inhibitor can be supplied to the reverse osmosis membrane device in a pattern similar to the addition pattern of a1 and b1 as shown in FIG. can.
- the water to be treated containing only the organic slime inhibitor, the water to be treated containing the oxidative slime inhibitor and the organic slime inhibitor, and so on are supplied to the reverse osmosis membrane apparatus in this order.
- a water system having a reverse osmosis membrane device can be stably operated for a longer period of time. It is possible to better reduce slime present in the reverse osmosis membrane of the reverse osmosis membrane device or to suppress the increase of slime, thereby better suppressing biofouling.
- FIG. 2 is an example of a schematic diagram showing Example 2 of control of the first addition step and the second step according to the embodiment of the present invention.
- a2 of Example 2 the first addition step
- the oxidative slime inhibitor is intermittently added at regular intervals.
- b2 of Example 2 In the second addition step, the organic slime inhibitor is continuously added during "a period other than the addition period of the first addition step.”
- the horizontal axis is the operating period (hours), and the vertical axis is the amount added.
- the operating period 0h of the first addition step and the operating period 0h of the second addition step may be used as starting points of operation.
- the parts that overlap with the description of FIG. 1 are omitted as appropriate.
- the intermittent addition periods in the first addition step may be the same or different periods, and the intermittent addition amounts may be the same or different amounts. Also, each interval of intermittent addition may be the same or different intervals.
- the organic slime inhibitor in the second addition step, may be added continuously during the entire period or part of the "period other than the period of addition in the first addition step.” Moreover, in the second addition step, the organic slime inhibitor may be added discontinuously.
- control example 3 of the first addition step and the second addition step may be combined.
- Example 2 may be repeated or performed in any order.
- the control example 1 may be followed by the control example 2, or the control example 2 may be followed by the control example 1.
- the control example 1, the control example 2, The control may be performed in the order of example 2 of the above control.
- the water to be treated can contain the oxidative slime inhibitor and/or the organic slime inhibitor. Then, according to Control Example 2 of the present embodiment, the water to be treated containing the oxidative slime inhibitor and/or the organic slime inhibitor is supplied to the reverse osmosis membrane device as the first supply step and the second supply step. be. At this time, the water to be treated containing the oxidative slime inhibitor and/or the organic slime inhibitor can be supplied to the reverse osmosis membrane device in a pattern similar to the addition pattern of a2 and b2 as shown in FIG. can.
- the water to be treated containing only the organic slime inhibitor, the water to be treated containing only the oxidative slime inhibitor, and so on are supplied to the reverse osmosis membrane apparatus in this order.
- a water system having a reverse osmosis membrane device can be stably operated for a longer period of time. It is possible to better reduce slime present in the reverse osmosis membrane of the reverse osmosis membrane device or to suppress the increase of slime, thereby better suppressing biofouling.
- the place of addition of the oxidative slime inhibitor and/or the organic slime inhibitor may be the same or different (see, for example, FIG. 3).
- the place of addition is preferably upstream of the reverse osmosis membrane device that performs the reverse osmosis membrane treatment and before that.
- an oxidative slime inhibitor and/or an organic slime inhibitor is added.
- the location is preferably at or before or after the safety filter device, more preferably at the safety filter device and upstream thereof, more specifically, at the safety filter device and the processing device upstream thereof.
- the security filter device can perform a turbidity removing film treatment step, which will be described later, and may be a turbidity removing film device.
- the safety filter device can appropriately employ a membrane (for example, MF membrane, etc.) that can be used for the turbidity removal membrane device as a safety filter.
- a membrane for example, MF membrane, etc.
- Biofouling of these membrane devices can also be suppressed, and biofouling of the reverse osmosis membrane device can be further suppressed. Therefore, the water system can be stably operated for a longer period of time.
- the operating method in this embodiment can be applied to a reverse osmosis membrane device.
- the method of this embodiment can be applied to slime control methods, biofouling control methods, water systems, devices, or systems.
- the process according to this embodiment can be applied to any device or system.
- the first step and the second step may be the first method and the second method, the first apparatus and the second apparatus, the first system and the second system, respectively.
- the operating method in this embodiment can be applied to a water system having at least a reverse osmosis membrane device.
- a water system equipped with a reverse osmosis membrane device is not particularly limited, but includes, for example, a water treatment water system; a circulating water system such as a cooling tower; a process water system such as paper pulp manufacturing;
- a coagulation treatment process in which raw water flows in and a coagulant is injected into the raw water to form coagulation or flocculation of turbidity, sediment and supernatant from the water to be treated containing coagulation
- a solid-liquid separation step for separating into and a turbidity removal membrane treatment step for further removing turbidity and the like from the inflowing supernatant before the reverse osmosis membrane treatment may be arranged sequentially or in random order. Further, these processing steps may be performed using a processing apparatus or a processing unit configured to perform each processing step.
- a flocculation process performed by a flocculation treatment device 5 configured to flow in raw water and inject a flocculant into the raw water to form flocculation or flocculation of turbidity or the like;
- a solid-liquid separation step performed by a solid-liquid separation device 4 configured to separate sediment and supernatant from the water to be treated containing aggregates, and turbidity and the like from the inflowing supernatant before reverse osmosis membrane treatment
- a pretreatment process is performed by the safety filter 3 configured to perform a turbidity removal film treatment, and the water to be treated containing the pretreated oxidative slime inhibitor and/or organic slime inhibitor is supplied. It includes a reverse osmosis membrane treatment step performed by
- a raw water supply channel configured to supply raw water
- a raw water supply channel configured to separate the raw water supplied from the raw water supply channel into permeated water and concentrated water
- a water treatment device preferably an ultrapure water device
- a reverse osmosis membrane device configured as follows.
- a raw water supply channel configured to supply raw water
- a filtration device configured to filter the raw water supplied from the raw water supply channel
- Examples include a filtered water tank, a security filter device configured to pretreat the filtered water to be treated with a reverse osmosis membrane, and a water treatment device provided with a reverse osmosis membrane device.
- the above-described turbidity removal film treatment may be performed in a safety filter device.
- Raw water used in the present embodiment is not particularly limited, and examples include industrial wastewater containing organic matter, seawater/brine water, freshwater (river water, lake water, etc.), industrial water/city water etc.
- the pH of raw water or water to be treated is not particularly limited, but is preferably 3-9, more preferably 4-8, and still more preferably 5-8.
- the pH may be adjusted with a pH adjuster.
- the temperature of raw water or water to be treated is not particularly limited, but is preferably 4 to 50°C, more preferably 10 to 40°C.
- the TOC of raw water or water to be treated is not particularly limited, but is preferably 1 to 100 mg/L, more preferably 1 to 50 mg/L, still more preferably 1 to 10 mg/L.
- the ORP of raw water or water to be treated is preferably 200-600 mV, more preferably 200-400 mV.
- the reverse osmosis membrane apparatus used in the present embodiment is not particularly limited, and is preferably configured so as to be able to remove ions, organic matter, and the like in raw water using a reverse osmosis membrane. It is preferable that the reverse osmosis membrane device is configured so as to be capable of desalinating seawater, producing ultrapure water, treating industrial water, recovering wastewater, and reusing wastewater. Moreover, the reverse osmosis membrane device may include a single unit or a plurality of units having reverse osmosis membranes. The water system may also have one or more reverse osmosis membrane devices.
- the membrane used in this embodiment is a reverse osmosis membrane (hereinafter also referred to as "RO membrane”), a nanofiltration membrane (hereinafter also referred to as "NF membrane”), or the like.
- the RO membrane is not particularly limited, and examples thereof include polyamide-based, polyethersulfone-based, polysulfone-based, polyimide-based, polyethyleneimine-based, polyethylene oxide-based, and cellulose acetate-based materials.
- the polyamide-based RO membrane has the advantage that it can be preferably used because it has a high rejection rate of ionic substances and a large flux.
- the conditions of the water to be treated (hereinafter also referred to as "supply water") to be supplied to the reverse osmosis membrane device in the present embodiment can be appropriately set according to the treatment capacity or purpose of the reverse osmosis membrane device or the reverse osmosis membrane process. It is possible, but not particularly limited.
- water to be treated supplied to the reverse osmosis membrane device
- the pH of the supplied water for example, the pH of the supplied water, the amount of supplied water, the supplied water temperature, the water pressure (MPa) of the supplied water, the TOC (Total Organic Carbon) of the supplied water, Oxidation-reduction potential (ORP) of feed water and the like can be mentioned, and one or more of these conditions can be selected.
- TOC Total Organic Carbon
- ORP Oxidation-reduction potential
- TOC be the organic matter in the feed water.
- water to be treated to be supplied to the reverse osmosis membrane device is also referred to as "water supply”, but the water supply refers to water introduced into the reverse osmosis membrane device and subjected to reverse osmosis membrane treatment.
- the inlet water of a reverse osmosis membrane device corresponds.
- the pH of the feed water is not particularly limited, but is preferably 3-9, more preferably 4-8, and still more preferably 5-8.
- the pH may be adjusted with a pH adjuster.
- the amount of supplied water is not particularly limited, but is preferably 5 to 200 mL/min.
- the water pressure of the feed water is not particularly limited, but is preferably 0.1 to 10 MPa.
- the temperature of the supplied water is not particularly limited, but is preferably 4 to 50°C, more preferably 10 to 40°C.
- the TOC of the feed water is not particularly limited, but is preferably 1 to 100 mg/L, more preferably 1 to 50 mg/L, still more preferably 1 to 10 mg/L.
- the ORP of the feed water is preferably 200-600 mV, more preferably 200-400 mV.
- the flow rate of the supplied water is preferably 3 to 10 m 3 /h per 8-inch spiral module.
- a pretreatment step may be included in which organic substances, turbidity, and the like are removed from the water to be treated in the pretreatment section before the water to be treated is supplied to the reverse osmosis membrane device.
- the water to be treated to be supplied to the reverse osmosis membrane device is preferably pretreated with a security filter device.
- a security filter device For example, as a pretreatment process, raw water (water to be treated) is filtered with a filtration device, and the filtered water is passed through a filtered water tank and a security filter. Thereby, it is possible to obtain the water to be treated to be supplied to the pretreated reverse osmosis membrane device or the reverse osmosis membrane process.
- the safety filter is not particularly limited. can be used, and these may be combined as appropriate. As a result, impurities such as turbidity in the water to be treated supplied to the reverse osmosis membrane device can be reduced.
- the water to be treated that is supplied to the reverse osmosis membrane device contains the oxidative slime inhibitor and/or the organic slime inhibitor, so that the biofouling that occurs in the reverse osmosis membrane device is properly controlled.
- the effects caused by the oxidative slime inhibitor and / or the organic slime inhibitor for example, antibacterial, bactericidal, algicidal, microbial growth inhibition, microbial metabolism inhibition, etc.
- the effect of suppressing biofouling that occurs in the reverse osmosis membrane device and the effect of the chemicals used can be expected.
- Total residual chlorine concentration free chlorine concentration + activated combined chlorine concentration + stabilized combined chlorine concentration.
- Free chlorine concentration free chlorine concentration by DPD method (pocket residual chlorine meter, manufactured by HACH) Chlorine concentration measurement result (mg-Cl 2 /L)].
- Activated binding chlorine concentration From the chlorine concentration measurement result (mg-Cl 2 /L) after 300 seconds with the DPD (Free) reagent, which is a reagent for measuring free chlorine, the free chlorine concentration (mg-Cl 2 /L) Value after subtracting the measurement result.
- the pH (25°C) of the water to be treated can be measured with a handy pH meter manufactured by HRIBA. Moreover, the TOC of the water to be treated can be measured with a TOC meter. The ORP of the water to be treated can be measured with an ORP meter.
- the method for operating the reverse osmosis membrane apparatus according to the present embodiment may be a method for treating a reverse osmosis membrane.
- the operating method according to the present embodiment can be applied to an apparatus or system.
- the operation method of the reverse osmosis membrane apparatus according to the present invention includes the first step, the second step, the oxidative slime inhibitor, and the organic slime inhibitor, which overlap with the following "2.” and "3.” , etc., are omitted as appropriate, but the descriptions such as "2.”
- the slime control method applied to the reverse osmosis membrane device according to the present embodiment is the first, which overlaps with the above “1.", the following "3.”, etc.
- the description of each configuration such as the step, the second step, the oxidative slime inhibitor, the organic slime inhibitor, etc. will be omitted as appropriate, but the explanations of "1.” It applies, and the configuration and the like of the description can be adopted as appropriate.
- the slime control method according to the present embodiment can be applied to a device or system.
- an oxidative slime inhibitor is intermittently added, and water to be treated containing the oxidative slime inhibitor is intermittently fed to the reverse osmosis membrane device.
- a first step of supplying to and a second step of adding the organic slime inhibitor at least during a period other than the addition period of the first step, and supplying the water to be treated containing the organic slime inhibitor to a reverse osmosis membrane device. is preferred.
- the addition concentration of the oxidative slime inhibitor during one addition period is higher than the addition concentration of the organic slime inhibitor during one addition period. It is preferable to add the oxidative slime inhibitor once or more during the three days of operation. It is preferable to add the oxidative slime inhibitor for 10 minutes or more per time. It is preferable to add the oxidative slime inhibitor to a total chlorine concentration of 0.1 mg/L or more. It is preferable to add 0.01 mg/L or more of the organic slime inhibitor.
- Water treatment equipment according to the present embodiment includes the first step, the second step, the oxidative slime inhibitor, and the organic slime, which overlap with the above “1.”, “2.”, etc. Although the description of each configuration such as the inhibitor is omitted as appropriate, the descriptions of "1.”
- the water treatment apparatus according to the present embodiment may be a water treatment apparatus or a water system having at least a reverse osmosis membrane device.
- the water treatment device may be a treated water system or a water treatment system.
- the water treatment device is a first step of intermittently adding an oxidative slime inhibitor and intermittently supplying water to be treated containing the oxidative slime inhibitor to a reverse osmosis membrane device; a second step of adding an organic slime inhibitor at least during a period other than the addition period of the first step, and supplying the water to be treated containing the organic slime inhibitor to a reverse osmosis membrane device; It is preferable that it is a water treatment apparatus that implements the method of the present embodiment.
- the water treatment apparatus according to the present embodiment preferably implements the operation method of the reverse osmosis membrane apparatus of the present embodiment or the slime control method applied to the reverse osmosis membrane apparatus of the present embodiment.
- the water treatment apparatus includes a first chemical addition unit, a second chemical addition unit, and a reverse osmosis membrane unit, and preferably includes a control unit that controls these units. It is preferable to further include a security filter section as a pretreatment section.
- the first drug addition section and the second drug addition section are preferably connected to a flow path upstream or downstream of the safety filter section and a flow path upstream of the reverse osmosis membrane section.
- the water to be treated containing each chemical added to the water to be treated can be supplied to the reverse osmosis membrane device. Also, each of these units may be singular or plural, and these units may be devices.
- the present embodiment may be implemented by a control unit, or may be implemented by a device such as a control device for water treatment, a water treatment device, a water treatment system, or a water system.
- a control unit configured to perform the first step and the second step or an apparatus including such a control unit is preferable. This allows the method of the present embodiment to be better implemented.
- the control unit supplies the first chemical addition unit and the second chemical addition unit with chemical addition conditions (addition timing (for example, intermittent, continuous target), addition amount, etc.), the first step and the second step can be controlled and carried out.
- additional timing for example, intermittent, continuous target
- addition amount etc.
- the control unit may monitor the supply state of the water to be treated containing the drug to the reverse osmosis membrane device using various measuring devices, and if necessary, the measurement result can be fed back to the first addition step and the second addition step to control them.
- the control unit controls the first chemical addition unit and the second chemical addition unit based on the supply state, respectively, the more preferable chemical addition situation (addition timing (for example, intermittent, continuous), addition concentration, etc. ), the first step and the second step can be controlled and carried out.
- additional timing for example, intermittent, continuous
- addition concentration etc.
- control unit preferably executes steps 11 and 21 below in parallel at the same time, and more preferably executes steps 12 and 22 at the same time in parallel. preferred.
- control unit adjusts the addition amount of the oxidative slime inhibitor and the oxidative slime inhibitor to the water to be treated in the first addition step and the second addition step, and the timing and period of addition of these, while oxidizing. It is possible to prepare water to be treated that contains an organic slime inhibitor and/or an organic slime inhibitor. In the first supply step and the second supply step, the control unit reverse osmosis the water to be treated containing the oxidative slime inhibitor and/or the organic slime inhibitor prepared in the first addition step and the second addition step.
- the controller can stably operate the water system having the reverse osmosis membrane device for a longer period of time. As a result, biofouling and the like that occur in the reverse osmosis membrane device can also be suppressed.
- the control unit controls the first chemical addition unit so as to intermittently add the oxidative slime inhibitor to the water-based water to be treated.
- the first chemical addition unit intermittently adds the oxidative slime inhibitor to the water-based water to be treated.
- the control unit controls to intermittently supply the water to be treated containing the oxidative slime inhibitor to the reverse osmosis membrane device after the addition.
- the control unit controls the second chemical addition unit so as to add the organic slime inhibitor at least during a period other than the addition period of the first step.
- the second chemical addition section adds the organic slime inhibitor at least during a period other than the addition period of the first step.
- the control unit controls to supply the water to be treated containing the post-addition organic slime inhibitor to the reverse osmosis membrane device.
- the control unit controls the addition concentration of the oxidative slime inhibitor (as total chlorine concentration) to the first chemical addition unit and the second chemical addition unit to be higher than the addition concentration of the organic slime inhibitor (as chemical mass concentration). is preferably instructed to be adjusted to be higher so that each desired drug loading can be achieved.
- the control unit instructs the first agent addition unit to add the oxidative slime inhibitor once or more during the operation period of 3 days, so that the desired addition period can be
- the control unit preferably instructs the first agent addition unit to add the oxidative slime inhibitor for 0.1 minutes or more per time, thereby setting the desired addition period. be able to.
- a control unit (not shown) can control a first chemical addition device 10 and a second chemical addition device 20 provided in a water system having a reverse osmosis membrane device.
- the control section can instruct the first chemical addition device 10 to add the oxidative slime inhibitor upstream of the safety filter 3 or the reverse osmosis membrane device 2 along the first step.
- the control section can instruct the second chemical addition device 20 to add the organic slime inhibitor upstream of the security filter 3 or the reverse osmosis membrane device 2 along the second step.
- the controller can supply the water to be treated containing the oxidative slime inhibitor and/or the organic slime inhibitor to the reverse osmosis membrane device 2 .
- the control unit controls and executes the first addition step and the second addition step, so that the water system having the reverse osmosis membrane device can be stably operated for a longer period of time.
- the method of the present embodiment is used for implementing or managing methods such as the method for operating the reverse osmosis membrane apparatus and the method for controlling slime (for example, the methods described in "1.” and “2.” above). It can also be realized by a device or a control unit provided in the device (the control unit includes a CPU, a processor, or the like), and the device or the control unit can be provided. Examples of devices for implementing or managing include computers, notebook computers, desktop computers, tablet PCs, PLCs, servers, cloud services, and the like.
- the device for implementing or managing the above includes an input unit such as a touch panel and a keyboard, a communication unit such as a transmission/reception unit between each unit, a network, a network access unit, and a display unit such as a touch panel and a display. good too. Thereby, the method of this embodiment can be implemented.
- the device for implementing or managing can appropriately include, for example, a CPU, a RAM, a storage unit, a display unit, a communication unit, and the like as a configuration, and the configuration can be configured as necessary, for example, for data transmission It may be connected by a bus as a road.
- the method of the present embodiment can be programmed into hardware resources including storage media (nonvolatile memory (USB memory, etc.), SSD (Solid State Drive), HDD (Hard Disk Drive), CD, DVD, Blu-ray, etc.). , and implemented by the control unit.
- storage media nonvolatile memory (USB memory, etc.), SSD (Solid State Drive), HDD (Hard Disk Drive), CD, DVD, Blu-ray, etc.
- the method of this embodiment can be provided as a program.
- a storage medium storing the method of the present embodiment can be provided. Thereby, the method of this embodiment can be implemented.
- a reverse osmosis membrane device or slime configured to be able to operate a reverse osmosis membrane device or control slime of a reverse osmosis membrane device, including the control unit, the storage medium, the program, etc.
- a device, water treatment device, system or water-based system or the like can be provided to implement controls or the like. Thereby, the method of this embodiment can be implemented.
- These devices, water treatment devices, systems, water systems, etc. may be configured so as to be able to respond appropriately according to the purpose.
- an oxidative slime inhibitor is intermittently added to the computer, and water to be treated containing the oxidative slime inhibitor is intermittently supplied to the reverse osmosis membrane device. and the organic slime inhibitor is added at least during a period other than the addition period of the first step, and the water to be treated containing the organic slime inhibitor is fed to the reverse osmosis membrane device.
- a second function configured to supply a reverse osmosis membrane device, including, but not limited to, operation or slime control.
- each configuration such as the first step, the second step, the oxidative slime inhibitor, the organic slime inhibitor, etc., which overlaps the configurations such as “1.” and “2.” Although descriptions are omitted as appropriate, the descriptions such as "1.”
- the present technology can employ the following configurations. [1] a first step of intermittently adding an oxidative slime inhibitor and intermittently supplying water to be treated containing the oxidative slime inhibitor to a reverse osmosis membrane device; a second step of adding an organic slime inhibitor at least during a period other than the addition period of the first step, and supplying the water to be treated containing the organic slime inhibitor to a reverse osmosis membrane device; A method of operating a reverse osmosis membrane device.
- the oxidative slime inhibitor is a combined halogen agent, preferably one or more selected from chloramine compounds, stabilized bromides and halogenated hydantoin compounds, more preferably chloramine compounds. and/or a stabilized bromide, the method according to any one of the above [1] to [7].
- the organic slime inhibitor is one or more selected from isothiazoline compounds, halocyanoacetamide compounds, aldehyde compounds, and oxime compounds, preferably 2,2-dibromo-3 - selected from nitrilopropionamide (DBNPA), 5-chloro-2-methyl-4-isothiazolin-3-one (Cl-MIT) and 2-methyl-4-isothiazolin-3-one (MIT), and glutaraldehyde
- DBNPA nitrilopropionamide
- Cl-MIT 5-chloro-2-methyl-4-isothiazolin-3-one
- MIT 2-methyl-4-isothiazolin-3-one
- glutaraldehyde glutaraldehyde
- a water treatment device or water treatment system, or a control unit or control device configured to carry out the method according to any one of [1] to [9] above may be provided.
- the control unit may comprise a CPU
- the control device is preferably a computer device. It may be a water treatment apparatus or a water treatment system having the controller or the controller.
- a controller, water treatment device, control system or water treatment system configured to execute the program.
- the water to be treated is raw water to which ethanol 50 mg/L as C, ammonium chloride 10 mg/L as N, and sodium dihydrogen phosphate 0.5 mg/L as P are added as substrates. did.
- the raw water (water to be treated) had a pH of 6 to 8, a TOC of 1 mg/L, an ORP of 300 mV, and a water temperature of 25°C.
- This water to be treated is pressurized to 1.5 MPa by a pump, and supplied as feed water (water volume: 100 mL/min, water pressure: 0.2 MPa, water temperature: 25 ° C.) to the concentrated liquid chamber of the RO membrane device and RO Membrane treatment was performed.
- feed water water volume: 100 mL/min, water pressure: 0.2 MPa, water temperature: 25 ° C.
- a 4-inch spiral type RO membrane element manufactured by Nitto Denko Co., Ltd., ES20
- the feed water flow rate was 3-10 m 3 /h per 8-inch spiral module.
- the change in differential pressure means the change in the difference between the pressure at the start of measurement set at 0 kPa and the pressure for each water passage time after the start.
- aqueous sodium hydroxide solution was prepared using pure water so that sodium hydroxide (manufactured by Kishida Chemical Co., Ltd.) was 48% by mass. After mixing 19.5 g of the sodium hydroxide aqueous solution prepared in advance and 7.5 g of pure water, 15.0 g of amidosulfuric acid (sulfamic acid) (manufactured by Kishida Chemical Co., Ltd.) was added and mixed.
- ⁇ Test Example 2> To the raw water, as a substrate, IPA 1.4 mg / L as C, sodium dihydrogen phosphate 0.02 mg / L as P was added to the water to be treated, and the temperature of the water to be treated was 30 ° C. The test was carried out under the same conditions as in ⁇ Test Example 1> above, except that the setting was adjusted to , and the following conditions were adopted as the fungicide addition conditions.
- Example 2-1 The organic slime inhibitor in the second step is continuously added for a "fixed period of time", and then, during the period when the addition of the organic slime inhibitor in the second step is stopped, the oxidative slime inhibitor in the first step is added for a fixed period of time. The sequential additions were repeated in this order. As a result, the oxidative slime inhibitor is intermittently added, and the water to be treated containing the oxidative slime inhibitor is continuously passed through the reverse osmosis membrane device for a "fixed period of time".
- the organic slime inhibitor is continuously added in “a period other than the addition period of the first step", and the water to be treated containing the organic slime inhibitor is fed to the reverse osmosis membrane device "the second Water is passed continuously for a period other than the addition period of one step.
- Cl-MIT which is an organic slime inhibitor used in the second step
- Cl-MIT drug mass
- Fig. 4 shows the results of changes in differential pressure (kpa) up to 6 days in Example 2-1 and Comparative Example 2-1. Since Example 2-1 clearly slowed down the increase in differential pressure, a result was obtained that suggested that the method of Example 2-1 had a very excellent slime suppressing function. Furthermore, in Example 2-1, both the organic slime inhibitor and the oxidative slime inhibitor were carried out at low concentrations. Very good slime suppression was obtained, and it was confirmed that even if both the organic slime inhibitor and the oxidative slime inhibitor are at low concentrations, the slime inhibitory function can be exhibited satisfactorily.
- ⁇ Test Example 3> To the raw water, ethanol 50 mg / L as C, ammonium chloride 20 mg / L as N, sodium dihydrogen phosphate 1.0 mg / L as P as a substrate was added to the water to be treated, and a disinfectant The test was carried out under the same conditions as in ⁇ Test Example 1> above, except that the following conditions were adopted as the addition conditions.
- the water to be treated containing the organic slime inhibitor As a result, the water to be treated containing the organic slime inhibitor, the water to be treated containing both the oxidative slime inhibitor and the organic slime inhibitor, the water to be treated containing the organic slime inhibitor, and so on, in that order. , is supplied to the reverse osmosis membrane device.
- Cl-MIT which is an organic slime inhibitor used in the second step
- Cl-MIT is constantly passed continuously at 0.5 mg/L as chemical mass (Cl-MIT)
- the water to be treated containing the chemical is always continuously fed to the downstream RO membrane device.
- monochlorosulfamic acid an oxidative slime inhibitor
- Example 3-1 clearly slowed down the increase in differential pressure, a result was obtained that suggested that the method of Example 3-1 had a very excellent slime suppressing function. Furthermore, in Example 3-1, the oxidative slime inhibitor was used at a high concentration, but the change in this differential pressure was 10 KPa or less even after 16 days, so very good slime inhibition was achieved. As a result, it was confirmed that the slime-suppressing function could be exhibited satisfactorily.
- ⁇ Test Example 4> To the raw water, as a substrate, ethanol 30 mg / L as C, ammonium chloride 10 mg / L as N, sodium dihydrogen phosphate 0.5 mg / L as P was added to the water to be treated, water to be treated The test was conducted under the same conditions as in ⁇ Test Example 1> above, except that the water temperature was adjusted to 20°C and the slime inhibitor addition period and addition concentration shown in Table 2 were set.
- Comparative Example 4-6 Comparative Example 4-7, and Example 4-1, as shown in Table 2, the first step and the second step were performed in parallel.
- Table 2 below shows the chemical addition conditions and the number of days required for the differential pressure to reach 100 kPa. As shown in Table 2, the treatment in which the first addition step of intermittently adding the oxidative slime inhibitor and the second addition step of constantly adding the organic slime inhibitor are performed in parallel has the longest blockage days. The results suggest that the slime-suppressing action was the most excellent.
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Abstract
Description
有機系スライム抑制剤を少なくとも「前記第一工程の添加期間以外の期間」に添加して、当該有機系スライム抑制剤を含有する被処理水を逆浸透膜装置に供給する第二工程と、を有する、逆浸透膜装置の運転方法を提供するものである。なお、「少なくとも前記第一工程の添加期間以外の期間」の「少なくとも」とは、有機系スライム抑制剤を、「前記第一工程の添加期間(第一間欠添加期間)」及び「前記第一工程の添加期間以外の期間(第一無添加期間)」のうちの少なくとも「前記第一工程の添加期間以外の期間の全期間又は一部期間」において、添加することであり、例えば、第一無添加期間と第一間欠添加期間の両方の期間において添加してもよいし、第一無添加期間のみの期間において添加してもよい(一例として、図1及び図2参照)。
本発明は、酸化系スライム抑制剤を間欠的に添加して、当該酸化系スライム抑制剤を含有する被処理水を逆浸透膜装置に間欠的に供給する第一工程と、
有機系スライム抑制剤を少なくとも前記第一工程の添加期間以外の期間に添加して、当該有機系スライム抑制剤を含有する被処理水を逆浸透膜装置に供給する第二工程と、を有する、逆浸透膜装置に適用するスライム制御方法を提供するものである。
本発明は、前記逆浸透膜装置の運転方法、又は、前記逆浸透膜装置に適用するスライム制御方法を実施する、水処理装置を提供するものである。
前記酸化系スライム抑制剤を、運転期間3日間のうちで1回以上添加してもよい。
前記酸化系スライム抑制剤を、1回当たり10分以上添加してもよい。
前記酸化系スライム抑制剤を、全塩素濃度として0.1mg/L以上添加してもよい。
前記有機系スライム抑制剤を、0.01mg/L以上添加してもよい。
本発明は、酸化系スライム抑制剤を間欠的に添加して、当該酸化系スライム抑制剤を含有する被処理水を逆浸透膜装置に間欠的に供給する第一工程と、
有機系スライム抑制剤を少なくとも前記第一工程の添加期間以外の期間に添加して、当該有機系スライム抑制剤を含有する被処理水を逆浸透膜装置に供給する第二工程と、を有する、逆浸透膜装置の運転方法を提供することができる。
本明細書において用いられるスライム抑制剤とは、スライムの増加を抑制できる薬剤であり、膜に存在するスライムを低減又は除去できる薬剤、微生物を殺すことができる薬剤(殺菌剤、殺藻剤など)、微生物の増殖を抑制できる薬剤(抗菌剤など)を含みうる。また、本明細書における、第一工程、第二工程などの「第一」及び「第二」の番号は、説明の便宜上付したものであり、第一及び第二を付すことにより、本実施形態が、狭義に限定されず、特に限定されるものではない。
第一工程は、酸化系スライム抑制剤を間欠的に添加して、当該酸化系スライム抑制剤を含有する被処理水を逆浸透膜装置に間欠的に供給する工程であることが好適である。
さらに、第一工程は、酸化系スライム抑制剤を被処理水に間欠添加する第一添加工程と、添加後の酸化系スライム抑制剤を含有する被処理水を逆浸透膜装置に間欠的に供給する第一供給工程とを有することが好適である。
第一工程は、酸化系スライム抑制剤を被処理水に間欠的に添加する工程である。これにより、当該酸化系スライム抑制剤を含有する被処理水を得ることができ、添加後の酸化系スライム抑制剤を含有する被処理水を逆浸透膜装置に間欠的に供給することができる(例えば、図1及び図2参照)。
酸化系スライム抑制剤の添加回数は、特に限定されないが、好適な上限値として、好ましくは10回以下、より好ましくは5回以下、さらに好ましくは3回以下、さらにより好ましくは2回以下、より好ましくは1回である。この添加回数は、「所定期間のうち」であってもよく、「所定間隔ごと」であってもよい。
酸化系スライム抑制剤の添加頻度において、より好適な態様として、好ましくは3日のうちで1回以上の添加であり、より好ましくは2日のうちで1回以上の添加であり、さらに好ましくは1日のうちで1回以上の添加である。
本明細書において、「酸化系スライム抑制剤の添加期間」を、「第一工程の添加期間」又は「第一間欠添加期間」ともいう。
本明細書において、「酸化系スライム抑制剤の添加期間」の「1期間(具体的には、薬剤の添加開始時から薬剤の添加終了時までの添加期間)」を、「1単位」としてもよい。
本明細書において、「酸化系スライム抑制剤を添加していない期間」は、「酸化系スライム抑制剤の添加終了時から酸化系スライム抑制剤の添加開始時までの期間(すなわち無添加期間)」をいい、より好ましくは酸化系スライム抑制剤が本発明の効果を損なわない範囲内で連続的に添加されていない期間をいい、より狭義では、「酸化系スライム抑制剤の添加が行われずに酸化系スライム抑制剤が連続的に添加されていない期間」をいう。
本明細書において、上記「酸化系スライム抑制剤を添加していない期間」の「1期間(具体的には、薬剤の添加終了時から薬剤の添加開始時までの無添加期間)」を「1単位」としてもよい。
また、本実施形態における第一添加工程の運転期間は、「1単位当たりの第一間欠添加期間及び1単位当たりの第一無添加期間」の単数の期間であってもよいし、同一又は異なる「1単位当たりの第一間欠添加期間及び1単位当たりの第一無添加期間」を複数組み合わせて構成された期間であってもよい。
酸化系スライム抑制剤又はこの成分として、特に限定されないが、例えば、結合ハロゲン化合物などが挙げられ、当該酸化系スライム抑制剤は、結合ハロゲン化合物を含む薬剤であってもよく、ハロゲンとして例えば、塩素、臭素などが挙げられる。
当該結合ハロゲン化合物として、結合塩素系化合物、結合臭素系化合物などが挙げられ、これらから選択される1種又は2種以上を使用することができる。
当該結合塩素系化合物として、例えば、ハロゲン化ヒダントイン化合物などに代表される安定化塩素化合物、クロラミン化合物などが挙げられ、結合臭素系化合物として、例えば、安定化臭化物、ハロゲン化ヒダントイン化合物などが挙げられるが、これらに限定されず、これらから選択される1種又は2種以上を使用することができる。酸化系スライム抑制剤又は酸化系スライム抑制剤に使用する化合物は、市販品を用いてもよいし、公知の製造方法にて得たものを用いてもよい。
クロラミン化合物とは、窒素原子と塩素原子との結合(N-Cl結合)を少なくとも1つ有する化合物を指していう。
クロラミン化合物として、例えば、クロラミン、クロロスルファミン酸化合物、これら以外のクロラミン化合物などが挙げられ、これらから選択される1種又は2種以上を使用することができる。
クロラミン化合物としては、例えば、安定化剤と塩素系酸化物とを含むものから生成される安定化塩素化合物など;スルファミン酸化合物と塩素系酸化物とを含むものから生成されるクロロスルファミン酸化合物など;などが挙げられ、これらから選択される1種又は2種以上を使用することができる。
スルファミン酸化合物として、例えば、2つのR1基及びR2基が共に水素原子であるスルファミン酸(アミド硫酸)又はその塩;N-メチルスルファミン酸、N-エチルスルファミン酸、N-プロピルスルファミン酸、N-イソプロピルスルファミン酸、N-ブチルスルファミン酸などの2つのR1基及びR2基のうち一方が水素原子で他方が炭素数1~8のアルキル基であるスルファミン酸又はその塩;N,N-ジメチルスルファミン酸、N,N-ジエチルスルファミン酸、N,N-ジプロピルスルファミン酸、N,N-ジブチルスルファミン酸、N-メチル-N-エチルスルファミン酸、N-メチル-N-プロピルスルファミン酸などの2つのR1基及びR2基が共に炭素数1~8のアルキル基であるスルファミン酸又はその塩;などが挙げられるが、これらに限定されない。これらから選択される1種又は2種以上を使用することができる。
次亜塩素酸塩としては、例えば、次亜塩素酸ナトリウム、次亜塩素酸カリウムなどの次亜塩素酸アルカリ金属塩;次亜塩素酸カルシウム、次亜塩素酸バリウムなどの次亜塩素酸アルカリ土類金属塩;などが挙げられ、これらから選択される1種又は2種以上を使用することができる。
亜塩素酸塩としては、例えば、亜塩素酸ナトリウム、亜塩素酸カリウムなどの亜塩素酸アルカリ金属塩;亜塩素酸バリウムなどの亜塩素酸アルカリ土類金属塩;亜塩素酸ニッケルなどの他の亜塩素酸金属塩;などが挙げられ、これらから選択される1種又は2種以上を使用することができる。
塩素酸塩としては、例えば、塩素酸アンモニウム;塩素酸ナトリウム、塩素酸カリウムなどの塩素酸アルカリ金属塩;塩素酸カルシウム、塩素酸バリウムなどの塩素酸アルカリ土類金属塩;などが挙げられ、これらから選択される1種又は2種以上を使用することができる。
過塩素酸塩としては、例えば、過塩素酸ナトリウム、過塩素酸カリウムなどが挙げられ、これらから選択される1種又は2種以上を使用することができる。
塩素化イソシアヌル酸塩としては、例えば、塩素化イソシアヌル酸ナトリウムなどが挙げられ、これらから選択される1種又は2種以上を使用することができる。
例えば、クロロスルファミン酸ナトリウムの製造例としては、特許文献3(WO2011/125762;特許5720964公報)の〔実施例〕に記載の方法を参照することができる。
塩素系酸化物と安定化剤(例えば、アンモニア塩、スルファミン酸化合物等)との使用割合は、特に限定されないが、塩素系酸化剤の全塩素濃度(Cl2)1モルに対して、塩素安定化剤(好適にはスルファミン酸化合物)を0.5~5.0モルにすることが好ましく、より好ましくは0.5~2.0モル、さらに1.0~1.5モルとすることがより好ましい。当該使用割合は、薬剤中の含有割合であってもよい。
アルカリと塩素系酸化物との使用割合が、Cl/アルカリ金属(モル比)で、好ましくは0.3~0.4、より好ましくは0.30~0.36であり、当該使用割合は、薬剤中の含有割合であってもよい。
クロロスルファミン酸塩としては、例えば、クロロスルファミン酸リチウム、クロロスルファミン酸ナトリウム、及びクロロスルファミン酸カリウムなどが挙げられ、これらから選択される1種又は2種以上を使用することができる。これらの中でも、クロロスルファミン酸ナトリウムが好ましい。
また、その他のクロラミン化合物としては、クロラミンTなどを用いることができる。また、これらから選択される1種又は2種以上を使用することができる。
安定化臭化物とは、窒素原子(N-Cl結合)ないしは炭素原子と臭素原子との結合(C-Br結合)を少なくとも1つ有する化合物を指していう。安定化臭化物とは、水中において分解などによる変化が生じ難く、生成した臭化物が水中で安定して存在することが可能な臭化物が好適である。
安定化臭化物としては、例えば、「臭素系酸化剤又は臭素化合物と、塩素系酸化物との反応物」と「スルファミン酸化合物」との反応生成物などが挙げられるが、これらに限定されない。当該反応生成物のpHは、アルカリであることが好ましく、より好ましくは11以上、さらに好ましくは12以上、さらにより好ましくは13以上である。これらは市販品を用いてもよいし、公知の製造方法にて得たものを用いてもよい。
例えばアンモニウム塩と臭素からなるブロマミンかブロモスルファミン酸、及びブロモスルファミン酸塩、その他の化合物としてはDBNPAなどを用いることができる。
ハロゲン化ヒダントイン化合物として、例えば、1-ブロモ-3-クロロ-5,5-ジメチルヒダントイン(「BCDMH」ともいう)、1,3-ジクロロ-5,5-ジメチルヒダントイン、1,3-ジブロモ-5,5-ジメチルヒダントイン、1-ブロモ-3-クロロ-5,5-ジエチルヒダントイン、1,3-ジクロロ-5,5-ジエチルヒダントイン、及び1-ブロモ-3-クロロ-5-メチル-5-エチルヒダントインなどが挙げられ、これらから選択される1種又は2種以上を使用することができる。これらのうち、水と接触した場合の溶出速度の固形剤(B)とのバランスや入手容易性などの観点から、BCDMH、及び1,3-ジクロロ-5,5-ジメチルヒダントインが好ましい。
また、本実施形態の第一工程において、前記酸化系スライム抑制剤の添加又は使用とは、別に、さらに任意成分又は任意薬剤を、適宜添加又は使用してもよい。
第一供給工程は、酸化系スライム抑制剤を含有する被処理水を逆浸透膜装置に間欠的に供給する工程であることが好適であり、この第一供給工程と、下記第二工程における第二供給工程とが組み合わさることで、水系をより長期的に運転することができる。より好適な態様として、逆浸透膜装置に備えられている逆浸透膜で発生するバイオファウリングを抑制することができ、当該バイオファウリングを抑制することで、水系を長期的に安定して運転することができる。
例えば、第一供給工程における供給頻度及びその所定期間、供給回数、供給頻度、供給期間、水系に対する酸化系スライム抑制剤の供給濃度、1供給期間当たりの水系に供給される酸化系スライム抑制剤の絶対量、第一供給期間の1単位、1単位当たりの第一間欠供給期間と1単位当たりの第一無供給期間との期間比率などは、上記「1-1-1.第一添加工程」の添加頻度及びその所定期間、添加回数、添加頻度、添加期間、水系に対する酸化系スライム抑制剤の添加濃度、1添加期間当たりの水系に添加される酸化系スライム抑制剤の絶対量、第一添加期間の1単位、1単位当たりの第一間欠添加期間と1単位当たりの第一無添加期間との期間比率などを、適宜採用することができる。
酸化系スライム抑制剤の供給回数は、特に限定されないが、好適な上限値として、より好ましくは2回以下、さらに好ましくは1回である。酸化系スライム抑制剤を含む被処理水の供給頻度は、好ましくは3日のうちで1回以上の供給であり、より好ましくは2日のうちで(より好適には1日置きに)1回以上、さらに好ましくは1日のうちで1回又はそれ以上の供給である。また、この供給回数は、「所定期間のうち」であってもよく、「所定間隔ごと」であってもよい。
酸化系スライム抑制剤の供給頻度において、より好適な態様として、好ましくは3日のうちで1回以上の供給であり、より好ましくは1日のうちで1回以上の供給である。
また、本明細書において、「酸化系スライム抑制剤を含む被処理水の供給期間」を、「第一工程の供給期間」又は「第一間欠供給期間」ともいう。
また、本明細書において、「酸化系スライム抑制剤を含む被処理水の供給期間」の「1期間(具体的には、薬剤の供給開始時から薬剤の供給終了時までの供給期間)」を、「1単位」としてもよい。
本明細書において、「酸化系スライム抑制剤を含む被処理水を供給していない期間」は、「酸化系スライム抑制剤の供給終了時から酸化系スライム抑制剤の供給開始時までの無供給期間」をいい、より狭義では、「酸化系スライム抑制剤の逆浸透膜装置への供給が行われずに連続的に供給されていない期間」をいう。
本明細書において、上記「酸化系スライム抑制剤を含む被処理水を供給していない期間」の「1期間(具体的には、薬剤の供給終了時から薬剤の供給開始時までの無供給期間)」を「1単位」としてもよい。
第一無供給期間の1単位は、特に限定されないが、好適な数値範囲として、好ましくは5~100時間、より好ましくは10~50時間である。
なお、1単位当たりの第一間欠供給期間は、ある運転期間中の第一間欠供給期間の合計期間(日など)を、この運転期間中の第一間欠供給期間の数で割った平均値であってもよい。また、1単位当たりの第一無供給期間は、ある運転期間中の第一無供給期間の合計期間(日など)を、この運転期間中の第一無供給期間の数で割った平均値であってもよい。
また、本実施形態における第一供給工程の運転期間は、「1単位当たりの第一間欠供給期間及び1単位当たりの第一無供給期間」の単数の期間であってもよいし、同一又は異なる「1単位当たりの第一間欠供給期間及び1単位当たりの第一供給期間」を複数組み合わせて構成された期間であってもよい。この単数の期間又は複数の組み合わせの期間は、上述した「1単位当たりの第一間欠添加期間及び1単位当たりの第一無添加期間」の単数の期間又は複数の組み合わせの期間に基づくことが好適である。
第二工程は、有機系スライム抑制剤を少なくとも前記第一工程の添加期間以外の期間に添加して、当該有機系スライム抑制剤を含有する被処理水を逆浸透膜装置に供給することが好適である。
さらに、第二工程は、有機系スライム抑制剤を添加する第二添加工程と、添加後の有機系スライム抑制剤を含有する被処理水を逆浸透膜装置に供給する第二供給工程とを有することが好適である。
第二工程は、有機系スライム抑制剤を、少なくとも「前記第一工程の添加期間以外の期間」に添加する工程である。これにより、当該有機系スライム抑制剤を含有する被処理水を得ることができ、添加後の有機系スライム抑制剤を含有する被処理水を逆浸透膜装置に供給することができる(例えば、図1及び図2参照)。
第二工程において、第一無添加期間での有機系スライム抑制剤の添加は、第一無添加期間の全期間又は一部期間での有機系スライム抑制剤の添加であってもよい。
また、第二工程において、第一間欠添加期間での有機系スライム抑制剤の添加は、第一間欠添加期間の全期間又は一部期間での有機系スライム抑制剤の添加であってもよい。
また、第二工程において、有機系スライム抑制剤を、少なくとも「1単位当たりの第一無添加期間」において、連続的に又は不連続的に添加することが、より好ましいが、連続的に添加することがさらに好ましい。
有機系スライム抑制剤又はこの成分として、特に限定されないが、例えば、イソチアゾリン化合物、ハロシアノアセトアミド化合物、アルデヒド化合物、及びテトラゾリルオキシムやジクロログリオキシムに代表されるオキシム化合物などが挙げられ、これらから1種又は2種以上を使用することができる。また、当該有機系スライム抑制剤は、これらから選択される1種又は2種以上の化合物を含む薬剤であってもよい。有機系スライム抑制剤又は有機系スライム抑制剤に使用する化合物は、市販品を用いてもよいし、公知の製造方法にて得てたものを用いてもよい。
イソチアゾリン化合物として、特に限定されないが、例えば、5-クロロ-2-メチル-4-イソチアゾリン-3-オン(Cl-MIT)、2-メチル-4-イソチアゾリン-3-オン(MIT)、2-エチル-4-イソチアゾリン-3-オン、2-n-オクチル-4-イソチアゾリン-3-オン、5-クロロ-2-エチル-4-イソチアゾリン-3-オン、5-クロロ-2-t-オクチル-4-イソチアゾリン-3-オン、4,5-ジクロロ-2-n-オクチル-4-イソチアゾリン-3-オン、4,5-ジクロロ-2-シクロヘキシル-4-イソチアゾリン-3-オンなどを挙げることができ、これらから1種又は2種以上を使用することができる。また、イソチアゾリン化合物としては、上述のイソチアゾリン化合物と塩化マグネシウム、硝酸マグネシウム、塩化銅、硝酸銅、塩化カルシウムなどとの錯化合物を用いてもよい。これらから選択される1種又は2種以上を使用することができる。
イソチアゾリン化合物の中でも、5-クロロ-2-メチル-4-イソチアゾリン-3-オン(Cl-MIT)、及び2-メチル-4-イソチアゾリン-3-オン(MIT)又はこれらの混合物が好ましい。
ハロシアノアセトアミド化合物として、特に限定されないが、例えば、2-クロロ-3-ニトリロプロピオンアミド、2-ブロモ-3-ニトリロプロピオンアミドなどの2-ハロ-3-ニトリロプロピオンアミド;2,2-ジクロロ-3-ニトリロプロピオンアミド、2,2-ジブロモ-3-ニトリロプロピオンアミド(DBNPA)、2-クロロ-2-ブロモ-3-ニトリロプロピオンアミドなどの2,2-ジハロ-3-ニトリロプロピオンアミド;N-メチル-2-クロロ-3-ニトリロプロピオンアミド、N-メチル-2-ブロモ-3-ニトリロプロピオンアミドなどのN-C1-3アルキル-2-ハロ-3-ニトリロプロピオンアミド;N-メチル-2,2-ジクロロ-3-ニトリロプロピオンアミド、N-メチル-2,2-ジブロモ-3-ニトリロプロピオンアミドなどのN-C1-3アルキル-2,2-ジハロ-3-ニトリロプロピオンアミドなどが挙げられ、これらから選択される1種又は2種以上を使用することができる。
なお、ハロシアノアセトアミド化合物は、NC-CX1X2-(C=O)-NHR3・・・〔2〕で表される化合物であってもよい。当該一般式〔2〕中、X1,X2は各々独立にハロゲン原子又は水素原子を表し、X1,X2のうち少なくとも一方はハロゲン原子である。R3は水素原子又は炭素数1~3のアルキル基を表す。ハロゲン原子として、塩素原子、臭素原子が挙げられ、臭素原子が好ましい。C1-3アルキルとして、直鎖状又は分枝鎖状のいずれでもよいが、例えば、メチル基、エチル基、n-プロピル基、iso-プロピル基などが挙げられる。これらから選択される1種又は2種以上を使用することができる。
アルデヒド化合物として、特に限定されないが、例えば、アセトアルデヒドなどのモノアルデヒド化合物;グリオキザール、オルトフタルアルデヒドなどのジアルデヒド化合物などが挙げられ、これらから選択される1種又は2種以上を使用することができる。
アルデヒド化合物の中でも、ジアルデヒド化合物が好ましく、ジアルデヒド化合物の中でも、安全性が高い観点から、グルタルアルデヒドが好ましい。
オキシム化合物として、特に限定されないが、テトラゾール環(CH2N4)を有するオキシム化合物(例えば、テトラゾリルオキシムなど)、及びハロゲン化オキシム化合物、(例えば、ジクロログリオキシムなど)などが挙げられ、これらから選択される1種又は2種以上を使用することができる。当該オキシム化合物は、分子内に>C=N-OHで表される構造を有する化合物である。
テトラゾール環を有するオキシム化合物として、例えば、ピカルブトラゾクス(分子式 :C20H23N7O3、分子量:409.44、CASNo.500207-04-5)などが挙げられる。
ハロゲン化オキシム化合物として、例えば、ジクロログリオキシム、α-クロロベンズアルドキシム、α-クロロベンズアルドキシムアセテート、4-ヒドロキシフェニル-α-ケトアセトヒドロキシム酸クロライド(別名パラクロックス)などが挙げられ、これらから選択される1種又は2種以上を使用することができる。
第二供給工程は、有機系スライム抑制剤を含有する被処理水を逆浸透膜装置に供給する工程であることが好適である。この第二供給工程と、上記第一工程における第一供給工程とが組み合わさることで、水系をより長期的に運転することができる。より好適な態様として、逆浸透膜装置に備えられている逆浸透膜で発生するバイオファウリングを抑制することができ、当該バイオファウリングを抑制することで、水系を長期的に安定して運転することができる。
例えば、第二供給工程における供給期間、水系に対する有機系スライム抑制剤の供給濃度、1供給期間当たりの水系に供給される有機系抑制剤の絶対量などは、上記「1-2-1.第二添加工程」の添加期間、水系に対する有機系スライム抑制剤の添加濃度、1添加期間当たりの水系に添加される有機系スライム抑制剤の絶対量などを、適宜採用することができる。
本明細書において、有機系スライム抑制剤の「連続的に」供給される期間とは、「有機系スライム抑制剤の供給開始時から有機系スライム抑制剤の供給終了時までの供給期間」をいい、より狭義では、「有機系スライム抑制剤の供給が停止されずに連続的に供給されている期間」をいい、この狭義を「常時供給の期間」とする。
本実施形態の方法において、第一工程及び第二工程を制御することが好適であり、これにより逆浸透膜装置を有する水系をより長期的に運転できる。
本実施形態の方法において、より好適な態様として、第一添加工程及び第二添加工程を制御することであり、これにより、酸化系スライム抑制剤及び/又は有機系スライム抑制剤を含む被処理水を逆浸透膜装置により良好に供給することができ、これにより逆浸透膜装置を有する水系をより長期的に安定して運転できる。さらに、第一添加工程及び第二添加工程を制御することにより、逆浸透膜装置の逆浸透膜に存在するスライムの低減又はスライムの増加抑制をより良好にでき、これによりバイオファウリングをより良好に抑制することもできる。
また、本実施形態の方法において、第一工程及び第二工程は、並列的に又は直列的に行ってもよいが、並列的に行うことが好適である。
本実施形態の方法において、より好適な態様として、第一工程及び第二工程を同時期にかつ並列的に行うことがより好適である。
また、本実施形態の方法において、第一工程の酸化系スライム抑制剤を添加する間(好適には、連続的に添加する間)は、第二工程の有機系スライム抑制剤を添加してもよいし添加停止としてもよく、さらに第一工程の酸化系スライム抑制剤を添加しない間は、第二工程の有機系スライム抑制剤を連続的に添加することが好適である。
運転起点として、特に限定されず、任意に設定してもよいが、例えば、日付(年月日時分秒)、並びに、第一工程及び/又は第二工程の運転状況(例えば、運転開始時、運転再開時、薬剤添加時、任意の期間設定など)などが挙げられ、これらから選択される1種又は2種以上の組み合わせを用いることができる。
これにより、逆浸透膜装置を有する水系をより長期的に安定して運転できる。逆浸透膜装置の逆浸透膜に存在するスライムの低減又はスライムの増加抑制をより良好にでき、これによりバイオファウリングをより良好に抑制することもできる。
なお、第一添加工程の各間欠添加期間は、同じ又は異なる期間であってもよく、各間欠添加量は、同じ又は異なる量であってもよい。また、間欠添加の各間隔は、同じ又は異なる間隔であってもよい。
また、第二添加工程において、有機系スライム抑制剤を、「第一添加工程の添加期間以外の期間」の全期間又は一部期間で連続的に添加してもよい。また、第二添加工程において、有機系スライム抑制剤を不連続的に添加してもよい。
これにより、逆浸透膜装置を有する水系をより長期的に安定して運転できる。逆浸透膜装置の逆浸透膜に存在するスライムの低減又はスライムの増加抑制をより良好にでき、これによりバイオファウリングをより良好に抑制することもできる。
さらに逆浸透膜装置に供給する被処理水を保安フィルター処理するために、逆浸透膜装置の前に保安フィルター装置を設ける場合には、酸化系スライム抑制剤及び/又は有機系スライム抑制剤の添加場所は、保安フィルター装置又はその前後であることが好適であり、さらに、保安フィルター装置及びその上流に設けることが好適であり、より具体的には、保安フィルター装置とその上流にある処理装置との間の添加用の流路に設けることがより好適である。
保安フィルター装置は、後述する除濁膜処理工程を行うことができ、除濁膜装置であってもよい。保安フィルター装置は、除濁膜装置に使用可能な膜(例えばMF膜など)を、保安フィルターとして、適宜採用することができる。
これにより、保安フィルター処理装置内のスライムも抑制し、これの下流となる逆浸透膜装置のスライムも抑制することができる。また、これら膜装置のバイオファウリングも抑制することができ、より逆浸透膜装置のバイオファウリングを抑制することができる。このため、水系をより長期的に安定して運転できる。
本実施形態に係る工程は、装置又はシステムに適用することができる。例えば第一工程及び第二工程を、それぞれ、第一方法及び第二方法、第一装置及び第二装置、第一システム及び第二システムとしてもよい。
本実施形態における運転方法は、少なくとも逆浸透膜装置を有する水系に適用することができる。
本実施形態で用いられる原水(例えば、被処理水)は、特に限定されず、例えば、有機物を含んだ産業用排水、海水・かん水、淡水(河川水、湖水など)、工業用水・市水などが挙げられる。
原水又は被処理水の水温は、特に限定されないが、好ましくは4~50℃、さらに好ましくは10~40℃である。
原水又は被処理水のTOCは、特に限定されないが、好ましくは1~100mg/L、より好ましくは1~50mg/L、さらに好ましくは1~10mg/Lである。
原水又は被処理水のORPは、好ましくは200~600mV、より好ましくは200~400mVである。
本実施形態に用いられる逆浸透膜装置は、特に限定されず、逆浸透膜を用いて原水中のイオン類や有機物などを除去できるように構成されていることが好適である。逆浸透膜装置は、海水淡水化、超純水製造、工業用水処理、排水回収処理及び排水の再利用などを行いうるように構成されていることが好適である。また、逆浸透膜装置は、逆浸透膜を有するユニットを単数又は複数備えていてもよい。また、水系は、単数又は複数の逆浸透膜装置を有していてもよい。
本実施形態に用いる膜は逆浸透膜(以下、「RO膜」ともいう)やナノろ過膜(以下、「NF膜」ともいう)などである。RO膜は、特に限定されず、例えば、ポリアミド系、ポリエーテルスルホン系、ポリスルホン系、ポリイミド系、ポリエチレンイミン系、ポリエチレンオキシド系、酢酸セルロース系などが挙げられる。この中でも、ポリアミド系RO膜は、イオン性物質の阻止率が高く、流束が大きいので好適に用いることができる利点を有する。
なお、本発明において、「逆浸透膜装置に供給する被処理水」を「給水」ともいうが、当該給水は、逆浸透膜装置に導入されて逆浸透膜処理される水をさし、通常逆浸透膜装置の入口水が該当する。
供給水量は、特に限定されないが、好ましくは5~200mL/minである。
供給水の水圧は、特に限定されないが、好ましくは0.1~10MPaである。
供給の水温は、特に限定されないが、好ましくは4~50℃、さらに好ましくは10~40℃である。
供給水のTOCは、特に限定されないが、好ましくは1~100mg/L、より好ましくは1~50mg/L、さらに好ましくは1~10mg/Lである。
供給水のORPは、好ましくは200~600mV、より好ましくは200~400mVである。
また、供給水の流速は、8インチスパイラルモジュール1本あたり3~10m3/hが好ましい。
逆浸透膜装置に供給する被処理水は、保安フィルター装置にて前処理することが好適である。例えば、前処理工程として、原水(被処理水)を、濾過装置で濾過し、濾過処理水は濾過処理水槽、及び保安フィルターを経る工程などが挙げられる。
これにより、前処理した逆浸透膜装置又は逆浸透膜工程に供給するための被処理水を得ることができる。
保安フィルターとして、特に限定されないが、例えば、単数又は複数の精密濾過膜(MF膜)処理、単数又は複数の限外濾過膜(UF)処理などが挙げられ、これらから1種又は2種以上を使用することができ、これらを適宜組み合わせてもよい。これにより、逆浸透膜装置に供給する被処理水の濁質などの不純物を低減することができる。
<全残留塩素濃度の算出方法>
なお、全残留塩素濃度は以下の方法をもとに算出する。なお、JIS K 0400-33-10:1999を参照することができる。
全残留塩素濃度=遊離塩素濃度+活性化結合塩素濃度+安定化結合塩素濃度。
遊離塩素濃度:DPD法(ポケット残留塩素計、HACH社製)による遊離塩素濃度[ここで、DPD法による遊離塩素濃度は、遊離塩素測定用試薬であるDPD(Free)試薬による5~30秒後の塩素濃度測定結果(mg-Cl2/L)]。
活性化結合塩素濃度:遊離塩素測定用試薬であるDPD(Free)試薬による300秒後の塩素濃度測定結果(mg-Cl2/L)から、上記遊離塩素濃度(mg-Cl2/L)の測定結果を差し引いた値。
安定化結合塩素濃度:全塩素測定用試薬であるDPD(Total)試薬による180秒後の塩素濃度測定結果(mg-Cl2/L)から、遊離塩素測定用試薬であるDPD(Free)試薬による300秒後の塩素濃度測定結果(mg-Cl2/L)を差し引いた値。
遊離塩素比率(%)=(遊離塩素濃度/全残留塩素濃度)×100
安定化結合塩素比率(%)=(安定化結合塩素濃度/全残留塩素濃度)×100
なお、試験環境の温度は25℃とする。
また、本発明に係る逆浸透膜装置の運転方法は、下記「2.」「3.」などの構成と重複する、第一工程、第二工程、酸化系スライム抑制剤、有機系スライム抑制剤などの各構成などの説明については適宜省略するが、当該「2.」「3.」などの説明が、本実施形態にも当てはまり、当該説明の構成等を適宜採用することができる。
本発明に係る逆浸透膜装置に適用するスライム制御方法は、上記「1.」下記「3.」などの構成と重複する、第一工程、第二工程、酸化系スライム抑制剤、有機系スライム抑制剤などの各構成などの説明については適宜省略するが、当該「1.」「3.」などの説明が、本実施形態にも当てはまり、当該説明の構成等を適宜採用することができる。また、本実施形態に係るスライム制御方法は、装置又はシステムに適用することができる。
有機系スライム抑制剤を少なくとも前記第一工程の添加期間以外の期間に添加して、当該有機系スライム抑制剤を含有する被処理水を逆浸透膜装置に供給する第二工程と、を有することが好適である。
前記酸化系スライム抑制剤を、運転期間3日間のうちで1回以上添加することが好適である。
前記酸化系スライム抑制剤を、1回当たり10分以上添加することが好適である。
前記酸化系スライム抑制剤を、全塩素濃度として0.1mg/L以上添加することが好適である。
前記有機系スライム抑制剤を、0.01mg/L以上添加することが好適である。
本発明に係る水処理装置は、上記「1.」「2.」などの構成と重複する、第一工程、第二工程、酸化系スライム抑制剤、有機系スライム抑制剤などの各構成などの説明については適宜省略するが、当該「1.」「2.」などの説明が、本実施形態にも当てはまり、当該説明の構成等を適宜採用することができる。
また、本実施形態に係る水処理装置は、逆浸透膜装置を少なくとも有する水処理装置又は水系であってもよい。当該水処理装置は、水処理水系、又は水処理システムであってもよい。
酸化系スライム抑制剤を間欠的に添加して、当該酸化系スライム抑制剤を含有する被処理水を逆浸透膜装置に間欠的に供給する第一工程と、
有機系スライム抑制剤を少なくとも前記第一工程の添加期間以外の期間に添加して、当該有機系スライム抑制剤を含有する被処理水を逆浸透膜装置に供給する第二工程と、を有する、本実施形態の方法を実施する水処理装置であることが好適である。
本実施形態に係る水処理装置は、本実施形態の逆浸透膜装置の運転方法、又は、本実施形態の逆浸透膜装置に適用するスライム制御方法を実施することが好適である。
制御部は、第一薬剤添加部及び第二薬剤添加部に対して、被処理水に添加される酸化系スライム抑制剤及び有機系スライム抑制剤の薬剤添加条件(添加タイミング(例えば間欠的、連続的)、添加量など)を指示することで、第一工程及び第二工程を制御し実施することができる。
また、制御部は、第一工程及び第二工程において、逆浸透膜装置への薬剤を含む被処理水の供給状態を各種測定装置を用いて監視してもよく、必要に応じてこの測定結果を第一添加工程及び第二添加工程にフィードバックし、これらを制御することもできる。
第一工程のステップ12として、制御部は、添加後、酸化系スライム抑制剤を含有する被処理水を逆浸透膜装置に間欠的に供給するように制御する。
第二工程のステップ21として、制御部は、有機系スライム抑制剤を少なくとも前記第一工程の添加期間以外の期間に添加するように、第二薬剤添加部を制御する。制御部の指示により、第二薬剤添加部は、有機系スライム抑制剤を少なくとも前記第一工程の添加期間以外の期間に添加する。
第二工程のステップ22として、制御部が、添加後有機系スライム抑制剤を含有する被処理水を逆浸透膜装置に供給するように制御する。
また、制御部は、第一薬剤添加部に対して、酸化系スライム抑制剤を、運転期間3日間のうちで1回以上添加するように指示することが好適であり、これにより所望の添加期間にすることができる。
また、制御部は、酸化系スライム抑制剤を、第一薬剤添加部に対して、1回当たり0.1分以上添加するように指示することが好適であり、これにより所望の添加期間にすることができる。
・〔1〕 酸化系スライム抑制剤を間欠的に添加して、当該酸化系スライム抑制剤を含有する被処理水を逆浸透膜装置に間欠的に供給する第一工程と、
有機系スライム抑制剤を少なくとも前記第一工程の添加期間以外の期間に添加して、当該有機系スライム抑制剤を含有する被処理水を逆浸透膜装置に供給する第二工程と、を有する、逆浸透膜装置の運転方法。
・〔2〕 酸化系スライム抑制剤を間欠的に添加して、当該酸化系スライム抑制剤を含有する被処理水を逆浸透膜装置に間欠的に供給する第一工程と、
有機系スライム抑制剤を少なくとも前記第一工程の添加期間以外の期間に添加して、当該有機系スライム抑制剤を含有する被処理水を逆浸透膜装置に供給する第二工程と、を有する、逆浸透膜装置に適用するスライム制御方法。
・〔4〕 前記酸化系スライム抑制剤を、運転期間3日間のうちで1回以上添加する、前記〔1〕~〔3〕のいずれか一つに記載の方法。
・〔5〕 前記酸化系スライム抑制剤を、1回当たり10分以上添加する、前記〔1〕~〔4〕のいずれか一つに記載の方法。
・〔6〕 前記酸化系スライム抑制剤を、全塩素濃度として0.1mg/L以上添加する、前記〔1〕~〔5〕のいずれか一つに記載の方法。
・〔7〕 前記有機系スライム抑制剤を、0.01mg/L以上添加する、前記〔1〕~〔6〕のいずれか一つに記載の方法。
・〔8〕 前記酸化系スライム抑制剤が、結合ハロゲン剤であり、好適にはクロラミン化合物、安定化臭化物及びハロゲン化ヒダントイン化合物から選択される1種又は2種以上、より好適には、クロラミン化合物及び/又は安定化臭化物である、前記〔1〕~〔7〕のいずれか一つに記載の方法。
・〔9〕 前記有機系スライム抑制剤が、イソチアゾリン化合物、ハロシアノアセトアミド化合物、アルデヒド化合物、及びオキシム化合物から選択される1種又は2種以上であり、好適には、2,2-ジブロモ-3-ニトリロプロピオンアミド(DBNPA)、5-クロロ-2-メチル-4-イソチアゾリン-3-オン(Cl-MIT)、及び2-メチル-4-イソチアゾリン-3-オン(MIT)、及びグルタルアルデヒドから選択される1種又は2種以上である、前記〔1〕~〔8〕のいずれか一つに記載の方法。
・〔11〕 前記〔1〕~〔9〕のいずれか一つに記載の方法を実施するように構成されている、水処理装置若しくは水処理水系、又は制御部若しくは制御装置を備えてもよく、当該制御部にはCPUを備えてもよく、当該制御装置は、好適には、コンピュータ装置である。当該制御部又は当該制御装置を有する水処理装置又は水処理水系であってもよい。
・〔13〕 コンピュータに、前記〔1〕~〔9〕のいずれか一つに記載の方法を実施させる、プログラム。
・〔14〕 コンピュータに、 酸化系スライム抑制剤を間欠的に添加して、当該酸化系スライム抑制剤を含有する被処理水を逆浸透膜装置に間欠的に供給する第一工程を実行する第一機能と、
有機系スライム抑制剤を少なくとも前記第一工程の添加期間以外の期間に添加して、当該有機系スライム抑制剤を含有する被処理水を逆浸透膜装置に供給する第二工程を実行する第二機能と、を含む、逆浸透膜装置の運転を実現させるプログラム又は当該プログラムを格納したコンピュータ可読媒体、若しくは当該プログラム或いは当該媒体を含む装置。当該プログラムを実施するように構成されている、制御部、水処理装置、制御システム又は水処理水系。
原水に、基質を添加し、微生物によるバイオファウリング効果を促進させた。具体的には、原水に、基質として、エタノール 50mg/L as C、塩化アンモニウム 10mg/L as N、リン酸二水素ナトリウム 0.5mg/L as Pになるように添加したものを被処理水とした。原水(被処理水)のpHは6~8、TOCは1 mg/L、ORPは300mV、水温は25℃であった。
この被処理水を、ポンプで1.5MPaに加圧し、供給水(水量は100mL/min、水圧は0.2 MPa、水温は25℃)として、RO膜装置の濃縮液室に供給してRO膜処理を行った。RO膜装置は芳香族ポリアミド系RO膜の4インチスパイラル型RO膜エレメント(日東電工(株)製、ES20)を1本ベッセルに充填したものを用いた。供給水の流速は、8インチスパイラルモジュール1本あたり3~10m3/hであった。差圧の変化とは、測定開始時の圧を0kPaと設定し、開始後の通水時間ごとの圧との差の変化を意味する。
逆浸透膜に対するスライム抑制の評価に際しては、非特許文献1(J. S. Vrouwenvelder et. al.)にある膜ファウリングシミュレータを用いて、表1にある条件で差圧が100kPa増加するまでにかかる日数を測定し、この差圧に達した日をバイオファウリングが発生した日、すなわち閉塞日とした。この閉塞になる日数が長いほど、スライム抑制できていると評価する。
〔比較例1-2〕:モノクロロスルファミン酸ナトリウム 1.5mg/L as全塩素濃度(T-Cl)にて、この単独の薬剤を開始0日から閉塞になるまで、常時添加を行った。
比較例3:Cl-MIT 0.15 mg/L as Cl-MITにて、この単独の薬剤を開始0日から閉塞になるまで、常時添加を行った。
〔実施例1-1〕:<J1-1>の第一工程と<J2-2>の第二工程とを、並列的に一緒に行った。
<J1-1>において、開始0日から、毎日、午前8時から2時間、酸化系スライム抑制剤であるモノクロロスルファミン酸ナトリウムを6mg/L as T-Clにて、被処理水に添加し、当該薬剤を含む被処理水がRO膜装置に供給された。
<J2-2>において、開始0日から、有機系スライム抑制剤であるCl-MIT(5-クロロ-2-メチル-4-イソチアゾリン-3-オン)を0.15mg/L as薬剤質量(Cl‐MIT)にて常時添加し、当該薬剤を含む被処理水がRO膜装置に供給された。常時添加の場合、薬剤を被処理水に0日から添加開始後、閉塞になるまで、その薬剤の添加を停止させずに、その薬剤を連続的に被処理水に添加し、当該薬剤を含む被処理水が逆浸透膜に供給された。<J1-1>及び<J2-2>の添加時期が重複する期間については、これらを含む被処理水がRO膜装置に供給された。
水酸化ナトリウム(キシダ化学株式会社製)が48質量%となるように、純水を用いて水酸化ナトリウム水溶液を調製した。この予め調製した水酸化ナトリウム水溶液19.5gと純水7.5gとを混合した後、アミド硫酸(スルファミン酸)(キシダ化学株式会社製)15.0gを添加混合した。その後、さらに、有効塩素濃度12質量%の次亜塩素酸ソーダ(旭硝子株式会社製)58.0gを添加混合し、モノクロロスルファミン酸試薬を調製した。なお、本薬剤の全塩素濃度は7質量% as Cl2である。
単一のスライム抑制剤をそれぞれ常時添加するよりも、異なる系統のスライム抑制剤を数日ごとに交互に添加する方がよいことが確認できた。
酸化系スライム抑制剤を、一日一回、2時間、間欠添加する第一添加工程、及び有機系スライム抑制剤を常時添加する第二添加工程を、並列的に、行うことにより、閉塞日数が長くなり、スライム抑制作用がより優れていたことが確認できた。
原水に、基質として、IPA 1.4 mg/L as C、リン酸二水素ナトリウム 0.02mg/L as Pになるように添加した被処理水を用いたこと、被処理水の水温を30℃に設定調整したこと、そして殺菌剤添加条件として以下の条件を採用したこと以外は、上記<試験例1>と同じ条件で試験を実施した。
有機系スライム抑制剤であるCl-MITを、0.1 mg/L as薬剤質量(Cl‐MIT)にて連続添加し、RO膜装置に連続通水した。これにより、薬剤を含む被処理水は、その下流のRO膜装置に連続通水されている。
第二工程の有機系スライム抑制剤を「一定時間」連続添加し、次いで、第二工程の有機系スライム抑制剤の添加停止の期間に、第一工程の酸化系スライム抑制剤を「一定時間」連続添加することを、この順序で繰り返し行った。
これにより、酸化系スライム抑制剤を間欠的に添加して、当該酸化系スライム抑制剤を含有する被処理水を逆浸透膜装置に、「一定時間」連続通水している。一方で、有機系スライム抑制剤を、「前記第一工程の添加期間以外の期間」に連続添加して、当該有機系スライム抑制剤を含有する被処理水を、逆浸透膜装置に「前記第一工程の添加期間以外の期間」で連続通水している。
原水に、基質として、エタノール 50mg/L as C、塩化アンモニウム 20mg/L as N、リン酸二水素ナトリウム 1.0mg/L as Pになるように添加した被処理水を用いたこと、そして殺菌剤添加条件として以下の条件を採用したこと以外は、上記<試験例1>と同じ条件で試験を実施した。
有機系スライム抑制剤であるCl-MITを、0.5 mg/L as 薬剤質量(Cl‐MIT)にて連続添加し、RO膜装置に常時連続通水した。これにより、薬剤を含む被処理水は、その下流のRO膜装置に連続通水されている。
第二工程の有機系スライム抑制剤を「常時」連続添加すること、及び、第一工程の酸化系スライム抑制剤を「一定間隔にて一定時間」連続添加することを、並列的に行った。
これにより、酸化系スライム抑制剤を間欠的に添加して、当該酸化系スライム抑制剤を含有する被処理水を逆浸透膜装置に、「一定時間」連続通水している。一方で、有機系スライム抑制剤を、少なくとも「前記第一工程の添加期間以外の期間」に「常時」連続添加して、当該有機系スライム抑制剤を含有する被処理水を、逆浸透膜装置に「常時」連続通水している。これにより、有機系スライム抑制剤を含む被処理水、酸化系スライム抑制剤及び有機系スライム抑制剤を併用して含む被処理水、有機系スライム抑制剤を含む被処理水・・・の順で、逆浸透膜装置に供給されている。
原水に、基質として、エタノール 30mg/L as C、塩化アンモニウム 10mg/L as N、リン酸二水素ナトリウム 0.5mg/L as Pになるように添加した被処理水を用いたこと、被処理水の水温を20℃に設定調整したこと、そして、表2に示す、スライム抑制剤の添加期間及び添加濃度に設定した以外は、上記<試験例1>と同じ条件で試験を実施した。
Claims (8)
- 酸化系スライム抑制剤を間欠的に添加して、当該酸化系スライム抑制剤を含有する被処理水を逆浸透膜装置に間欠的に供給する第一工程と、
有機系スライム抑制剤を少なくとも前記第一工程の添加期間以外の期間に添加して、当該有機系スライム抑制剤を含有する被処理水を逆浸透膜装置に供給する第二工程と、を有する、逆浸透膜装置の運転方法。 - 前記酸化系スライム抑制剤の添加濃度が、前記有機系スライム抑制剤の添加濃度よりも高くなるように調整する、請求項1に記載の逆浸透膜装置の運転方法。
- 前記酸化系スライム抑制剤を、運転期間3日間のうちで1回以上添加する、請求項1又は2に記載の逆浸透膜装置の運転方法。
- 前記酸化系スライム抑制剤を、1回当たり10分以上添加する、請求項1~3のいずれか一項に記載の逆浸透膜装置の運転方法。
- 前記酸化系スライム抑制剤を、全塩素濃度として0.1mg/L以上添加する、請求項1~4のいずれか一項に記載の逆浸透膜装置の運転方法。
- 前記有機系スライム抑制剤を、0.01mg/L以上添加する、請求項1~5のいずれか一項に記載の逆浸透膜装置の運転方法。
- 酸化系スライム抑制剤を間欠的に添加して、当該酸化系スライム抑制剤を含有する被処理水を逆浸透膜装置に間欠的に供給する第一工程と、
有機系スライム抑制剤を少なくとも前記第一工程の添加期間以外の期間に添加して、当該有機系スライム抑制剤を含有する被処理水を逆浸透膜装置に供給する第二工程と、を有する、逆浸透膜装置に適用するスライム制御方法。 - 請求項1~6のいずれか一項に記載の逆浸透膜装置の運転方法、又は、請求項7に記載の逆浸透膜装置に適用するスライム制御方法を実施する、水処理装置。
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