WO2015136992A1 - Procédé de recyclage d'effluent eau de refroidissement et appareil de recyclage - Google Patents

Procédé de recyclage d'effluent eau de refroidissement et appareil de recyclage Download PDF

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Publication number
WO2015136992A1
WO2015136992A1 PCT/JP2015/051685 JP2015051685W WO2015136992A1 WO 2015136992 A1 WO2015136992 A1 WO 2015136992A1 JP 2015051685 W JP2015051685 W JP 2015051685W WO 2015136992 A1 WO2015136992 A1 WO 2015136992A1
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Prior art keywords
water
membrane
dispersant
cooling
reverse osmosis
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PCT/JP2015/051685
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English (en)
Japanese (ja)
Inventor
邦洋 早川
隆彦 内田
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栗田工業株式会社
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Priority to CN201580009395.4A priority Critical patent/CN106029580B/zh
Priority to SG11201607245XA priority patent/SG11201607245XA/en
Publication of WO2015136992A1 publication Critical patent/WO2015136992A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/58—Multistep processes
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/147—Microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/023—Water in cooling circuits
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/05—Conductivity or salinity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • 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
    • C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances

Definitions

  • the present invention relates to a method and an apparatus for recovering cooling effluent in a cooling facility used in industrial processes such as building air conditioning, chemical industry, paper industry, steel industry, and electric power industry.
  • Scale failure occurs on heat transfer surfaces and piping that come into contact with water such as cooling water and boiler water.
  • water such as cooling water and boiler water.
  • salts dissolved in water are concentrated and the heat transfer surface is corroded.
  • scales as a sparingly soluble salt. If the scale adheres to the wall surface of the apparatus, a serious obstacle occurs in the operation of the boiler and heat exchanger, such as a decrease in thermal efficiency and blockage of piping.
  • System 5 is a simple system using only the RO membrane device, but the turbidity contained in the blow water clogs the RO membrane, so that stable treatment is difficult.
  • the RO membrane treatment can be stabilized by agglomeration treatment before the RO membrane or removing turbidity in the blown water with the pretreatment membrane.
  • the blow water contains a dispersant added in the circulating cooling water system, and this dispersant inhibits the aggregation treatment. For this reason, in the agglomeration treatment of the systems 1 to 3, the amount of the flocculant added for the treatment is very large.
  • a dispersing agent is required to disperse the scale components and stabilize the treatment with a high water recovery rate.
  • the dispersing agent in the blown water is removed by the aggregation treatment, It is necessary to add a dispersant to the RO membrane water supply in order to stabilize the scale dispersion and treatment in the membrane.
  • the dispersant in the blown water is removed by the pretreatment membrane. It is necessary to add a dispersant to the RO membrane water supply.
  • the present invention relates to a cooling drainage recovery method that reduces the water treatment cost and improves and stabilizes the water recovery rate when recovering the cooling drainage water such as blow water of the circulating cooling water system by performing RO membrane treatment. It is another object of the present invention to provide a recovery device.
  • the present inventors obtained the following knowledge as a result of intensive studies to solve the above problems.
  • cooling discharge water such as blow water of the circulating cooling water system
  • the pretreatment membrane of the RO membrane is a permeating dispersant added in the circulating cooling water system
  • the circulating cooling water system The dispersant added in the cooling discharge water can be effectively used as a dispersant for the RO membrane by permeating the pretreatment membrane, so that the addition of the dispersant in the water recovery system is not required or dispersed.
  • the additive amount can be reduced. Thereby, while reducing water treatment cost, the improvement and stabilization of a water recovery rate can be aimed at.
  • the present invention has been achieved on the basis of such findings, and the gist thereof is as follows.
  • Discharge water from the circulating cooling water system to which a dispersant for dispersing scale components is added is treated with a water recovery system including a pretreatment membrane and a reverse osmosis membrane, and the treated water is returned to the circulating cooling water system.
  • the dispersant is methacrylic acid and / or acrylic acid, 3-allyloxy-2-hydroxy-1-propanesulfonic acid and / or 2-acrylamido-2-methylpropanesulfonic acid.
  • a method for recovering cooling effluent which is a copolymer obtained by copolymerization of
  • the concentration of the dispersant in the reverse osmosis membrane feed water is measured, and the dispersion is added to the reverse osmosis membrane feed water so that the dispersant concentration becomes a predetermined concentration.
  • a method for recovering cooling effluent comprising adding an agent.
  • the conductivity of one or more of the discharged water, the reverse osmosis membrane water supply and the reverse osmosis membrane concentrated water is measured, and the measured value of the conductivity is obtained. Accordingly, the method for recovering the cooling effluent is characterized by adjusting the water recovery rate of the reverse osmosis membrane.
  • the dispersant concentration of the discharged water and / or reverse osmosis membrane water supply is measured, and the water of the reverse osmosis membrane is measured according to the measured value of the dispersant concentration.
  • [12] A method for recovering cooling discharged water according to any one of [1] to [11], wherein a polymer compound having a phenolic hydroxyl group is added to the discharged water.
  • a pretreatment membrane device through which drained water from the circulating cooling water system is passed, a reverse osmosis membrane device through which the permeated water of the pretreatment membrane device is passed, and a permeated water of the reverse osmosis membrane device
  • the circulating cooling water system has a dispersing agent adding means for adding a dispersing agent for dispersing the scale component to the aqueous system, and the dispersing agent is An apparatus for recovering cooling effluent, which passes through a pretreatment membrane.
  • the dispersant is methacrylic acid and / or acrylic acid, 3-allyloxy-2-hydroxy-1-propanesulfonic acid and / or 2-acrylamido-2-methylpropanesulfonic acid.
  • An apparatus for recovering cooling effluent which is a copolymer obtained by copolymerization of
  • a cooling drainage recovery apparatus characterized by having pH adjusting means for adjusting the pH of the reverse osmosis membrane feed water to 4.0 to 7.5 .
  • the dispersant concentration measuring means for measuring the dispersant concentration of the water supplied to the reverse osmosis membrane, and the dispersant concentration measured by the dispersant concentration measuring means
  • a cooling agent recovery means for adding the dispersing agent to the reverse osmosis membrane water supply so that the concentration of water becomes a predetermined concentration.
  • conductivity measuring means for measuring one or more of the discharged water, reverse osmosis membrane water supply, and reverse osmosis membrane concentrated water, and the conductivity measurement
  • a water recovery rate adjusting means for adjusting the water recovery rate of the reverse osmosis membrane according to the measured value of the means.
  • the dispersant concentration measuring means for measuring the dispersant concentration of the discharged water and / or the reverse osmosis membrane water supply, and the measured value of the dispersant concentration measuring means
  • a water recovery rate adjusting means for adjusting the water recovery rate of the reverse osmosis membrane.
  • the reverse osmosis membrane device is a permeated water circulating means for circulating the reverse osmosis membrane permeated water upstream of the reverse osmosis membrane device, or pure water or deionized water.
  • the cooling discharge water is treated with the pretreatment membrane before the RO membrane, so that the turbidity in the cooling drainage water can be removed and the subsequent RO membrane treatment can be stabilized.
  • the dispersing agent added in the circulating cooling water system and contained in the cooling discharge water permeates through the pretreatment membrane, so that the dispersing agent is effectively used as a dispersing agent for the RO membrane. can do.
  • membrane can be aimed at stabilization of RO membrane process and the improvement of a water recovery rate.
  • cooling drain water recovery method and recovery device of the present invention it is possible to prevent the scale failure of the RO membrane device with a simpler system and perform stable water recovery over a long period of time. .
  • cooling discharge water used for water recovery treatment typically includes blow water from a cooling tower, but is not limited to blow water, and the present invention includes all discharges discharged from a circulating cooling water system. Can be applied to water. For example, part or all of the circulating cooling water may be extracted from the circulating piping of the circulating cooling water system and treated according to the present invention, and then returned to the circulating cooling water system. In addition, it is possible to collect water from the discharged water branched and discharged from the side filter and light filter pipes.
  • cooling discharge water is treated as water to be treated and sequentially treated by the pretreatment membrane device and the RO device, and the treated water is returned to the circulating cooling water system.
  • the cooling discharge water can be treated as it is in the pretreatment membrane device, but since the cooling discharge water may contain coarse turbidity and foreign matter, a strainer is provided in the front stage of the pretreatment membrane device. It is preferable to perform turbidity treatment in the pretreatment membrane device after removing these in advance with a strainer. Operation is possible even if the strainer is omitted, but in this case, the pretreatment film may be damaged by coarse turbidity or foreign matter in the cooling discharge water.
  • an automatic strainer that performs a cleaning process automatically is particularly preferably used.
  • the shape of the strainer is not particularly limited, and any shape such as a Y shape or a bucket shape can be used.
  • the pore size of the strainer is preferably 100 to 500 ⁇ m.
  • the pore size of the strainer is smaller than 100 ⁇ m, the strainer is severely blocked.
  • the pore diameter of the strainer exceeds 500 ⁇ m, there is a high possibility that coarse turbidity or foreign matter that has passed through the strainer will damage the pretreatment film.
  • a filter such as a spool filter or a pleated filter may be used instead of the strainer.
  • a strainer is preferable in terms of replacement frequency and cleaning efficiency.
  • Pretreatment membrane device The cooled discharged water or the cooled discharged water after the turbidity treatment by the strainer is then processed by the pretreatment membrane device.
  • the pretreatment membrane device is for removing turbidity and colloidal components in the cooling discharge water that cause membrane contamination of the RO membrane device. It is a microfiltration membrane (MF membrane) and ultrafiltration membrane (UF membrane). Can be used.
  • the membrane type of the pretreatment membrane device is not particularly limited, and a hollow fiber type or spiral type membrane filtration device can be employed. There is no restriction
  • the molecular weight cutoff of the UF membrane which is a pretreatment membrane, is preferably 30,000 or more. If the molecular weight cut off of the UF membrane is smaller than 30,000, the dispersant in the cooling discharge water cannot be permeated, and it may be necessary to add the dispersant again before the RO membrane device. Although there is no restriction
  • the pore size of the MF membrane as the pretreatment membrane is preferably about 0.1 to 0.01 ⁇ m for the same reason as the molecular weight cut off of the UF membrane.
  • the transmittance of the below-described dispersant calculated by the following formula is preferably 80% or more, particularly 85% or more.
  • the upper limit of the transmittance of the dispersant in the pretreatment film is usually 100%.
  • the pH of the feed water of the pretreatment membrane is 5 or more.
  • the pH of the feed water of the pretreatment membrane is lower than 5, even if a polymer having a sulfonic acid group and a carboxyl group, which will be described later, is used as a dispersant, the transmittance of the pretreatment membrane is lowered, and the effect of the present invention is obtained. It may not be possible.
  • the pH of the feed water for the pretreatment membrane may be 5 or more, and the upper limit is not particularly limited.
  • cooling discharge water such as cooling tower blow water has a pH of 8 to 10, usually about 8 to 9, and it is preferably treated as it is with a pretreatment membrane device.
  • the dispersant added to the circulating cooling water system permeates the pretreatment membrane.
  • a polymer having a sulfonic acid group and a carboxyl group is preferably used. Dispersant dissociates and the function as a dispersant becomes higher as the pH is higher, but in the RO membrane device at the rear stage of the pretreatment membrane device, it is concentrated in the RO membrane device when the pH is high. Since calcium and the like are easily deposited as scales, the treatment is performed under low pH conditions as described later. In the RO membrane apparatus under such a low pH condition, if the dispersant has only a carboxyl group and does not have a sulfonic acid group, it becomes insoluble and cannot function as a dispersant. For this reason, it is preferable to use a polymer having a sulfonic acid group and a carboxyl group as the dispersant.
  • a polymer having a sulfonic acid group and a carboxyl group suitable as a dispersant a copolymer of a monomer having a sulfonic acid group and a monomer having a carboxyl group, or, further, these monomers And terpolymers with other monomers copolymerizable therewith.
  • Examples of the monomer having a sulfonic acid group include conjugated diene sulfonic acids such as 2-methyl-1,3-butadiene-1-sulfonic acid, and sulfonic acid groups such as 3- (meth) allyloxy-2-hydroxypropanesulfonic acid.
  • Unsaturated (meth) allyl ether monomer 2- (meth) acrylamide-2-methylpropanesulfonic acid, 2-hydroxy-3-acrylamidepropanesulfonic acid, styrenesulfonic acid, methallylsulfonic acid, vinylsulfone Acid, allyl sulfonic acid, isoamylene sulfonic acid, or salts thereof, preferably 3-allyloxy-2-hydroxy-1-propanesulfonic acid (HAPS), 2-acrylamido-2-methylpropanesulfonic acid (AMPS) ).
  • HAPS 3-allyloxy-2-hydroxy-1-propanesulfonic acid
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • the monomer having a sulfonic acid group one type may be used alone, or two or more types may be mixed and used.
  • the monomer having a carboxyl group acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, atropic acid, maleic acid, fumaric acid, itaconic acid, hydroxyethylacrylic acid or a salt thereof, preferably examples include acrylic acid and methacrylic acid.
  • the monomer which has a carboxyl group may be used individually by 1 type, and 2 or more types may be mixed and used for it.
  • Examples of monomers copolymerizable with these monomers include amides such as N-tert-butylacrylamide (N-tBAA) and N-vinylformamide.
  • Copolymerized copolymer, amides such as AA, AMPS, N-tert-butylacrylamide (N-tBAA), AA: AMPS: amides 40 to 90: 5 to 30: 5 to 30 (molar ratio) )
  • Copolymerized at a ratio of AA and 3-allyloxy-2-hydroxypropanesulfonic acid (HAPS) at a ratio of AA: HAPS 70 to 90:10 to 30 (molar ratio).
  • the present invention is not limited to these.
  • the polymer having a sulfonic acid group and a carboxyl group preferably has a weight average molecular weight of 1,000 to 30,000. If the weight average molecular weight of the polymer is less than 1,000, the dispersion effect is insufficient. When the weight average molecular weight of the polymer exceeds 30,000, it is difficult to permeate the pretreatment membrane, and the polymer itself is adsorbed on the pretreatment membrane or the RO membrane, which may cause membrane clogging.
  • the amount of the dispersant added in the circulating cooling water system is 3 to 30 mg / concentration as the concentration of the active ingredient (that is, the above polymer) from the viewpoints of the dispersion effect and economy in the cooling tower, and further the dispersion effect in the RO membrane water supply.
  • L particularly 5 to 20 mg / L is preferred. There are no particular restrictions on the method of adding the dispersant and the location of addition.
  • the dispersant in addition to the above-described polymer having a sulfonic acid group and a carboxyl group, other polymer or a phosphoric acid compound such as phosphonic acid may be used as long as a sufficient dispersion effect can be obtained. it can.
  • a scale component that can be generated from the quality of the raw water of the circulating cooling water system is identified, and a type of dispersant that can prevent the generation of the dispersant may be added so as to obtain a concentration at which an effect can be obtained.
  • the type of RO membrane of the RO membrane device is not particularly limited, and is appropriately determined depending on the quality of the cooling discharge water to be treated (the quality of raw water supplied to the circulating cooling water system or the concentration rate in the circulating cooling water system).
  • the RO membrane has a desalination rate of 80% or more, particularly 85% or more. When the desalting rate of the RO membrane is lower than this, desalting efficiency is poor, and treated water (permeated water) with good water quality cannot be obtained.
  • the material of the RO membrane any material such as a polyamide composite membrane or a cellulose acetate membrane can be used. There is no restriction
  • the RO membrane water supply (water that is passed through the RO membrane device as treated water) has a suitable pH as follows.
  • a pH adjusting means for adjusting the pH by adding an acid between the pretreatment membrane device and the RO membrane device.
  • the pH adjusting means include means for adding an acid directly to the RO membrane water supply introduction line and the line mixer provided in the line or to a pH adjusting tank provided separately by a chemical injection pump or the like.
  • the acid used here is not particularly limited, and inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid can be suitably used.
  • the pH of the circulating cooling water has increased to about 8-9 due to the concentration circulation operation.
  • Such a high pH is suitable for the permeation of the dispersant in the pretreatment membrane device.
  • the RO membrane device since the cooling discharge water is further concentrated, there is a concern about generation of scale. In terms of scale suppression, it is preferable that the RO membrane device is operated at a reduced pH.
  • the pH range of the RO membrane water supply is preferably 4.0 to 7.5. When the pH of the RO membrane water supply exceeds 7.5, scales such as calcium carbonate, calcium phosphate, calcium sulfate, and barium sulfate may be deposited depending on the water quality.
  • the silica concentration in the cooling discharge water exceeds 30 mg / L, it is preferable to lower the pH of the RO membrane water supply to 4.0 to 5.5 in order to suppress the precipitation.
  • the lower the pH of the RO membrane feed water the better in terms of preventing scale precipitation.
  • the amount of acid required becomes large, which is economically undesirable.
  • the RO membrane may be blocked.
  • the pH of the cooling discharge water is preferably 5.5 to 7.0, particularly preferably 5.5 to 6.5.
  • humic acid and fulvic acid are dissociated and the RO membrane is blocked, and Ca in the cooling water is effectively dispersed by the dispersant to form a complex with fulvic acid. It becomes difficult.
  • the dispersant added to the circulating cooling water system is one that permeates the pretreatment membrane, so that the dispersant contained in the cooling discharge water and brought into the water recovery system is treated with the treated water (
  • the scale dispersion treatment in the RO membrane device is performed with the dispersant that has been permeated into the permeated water and permeated through the pretreatment membrane. Therefore, the RO membrane water supply needs to contain a dispersant at a concentration effective for the scale dispersion treatment.
  • the concentration of the dispersant in the RO membrane water supply required for the scale dispersion treatment of the RO membrane device differs depending on the quality of the cooling discharge water, the treatment conditions (water recovery rate) of the pretreatment membrane and the RO membrane, and cannot be generally specified.
  • the dispersant concentration of the RO membrane water supply is preferably 3 mg / L or more, particularly about 5 to 30 mg / L.
  • the dispersant is added on the inlet side of the RO membrane device (between the pretreatment membrane device and the RO membrane device). Additional addition is preferred.
  • the dispersant added here those suitable as the dispersant used in the circulating cooling water system described above can be used, but it is not necessarily the same as the dispersant added in the circulating cooling water system, and is different. A dispersant may be used.
  • the dispersant concentration of the RO membrane water supply may be measured, and the amount of dispersant added may be controlled so that the dispersant concentration becomes a predetermined concentration.
  • a method for measuring the dispersant concentration a method using a turbidimetric method (for example, a method described in JP-A-2006-64498) can be employed.
  • the dispersant can be additionally added to the RO membrane water supply by, for example, a dispersant addition unit that is linked to the dispersant concentration measurement unit of the RO membrane water supply.
  • the dispersant dispersed in the cooling discharge water after being added to the circulating cooling water system is used as the RO membrane device.
  • the residence time of the cooling water in the cooling tower of the circulating cooling water system affects the activity of the dispersing agent, the residence time of the cooling tower of the circulating cooling water system so that the dispersant exhibits sufficient activity in the RO membrane device. It may be preferable to adjust the value.
  • the water recovery rate in the RO membrane device is preferably determined in consideration of the scale precipitation tendency in the RO membrane device. Since the conductivity of the cooling effluent treated in the present invention and the concentration of Ca, Mg, etc. in the cooling effluent as a scale factor may vary, the conductivity, Ca concentration, Mg concentration, etc. The RO membrane water recovery rate may be adjusted accordingly. The water recovery rate may be set by determining the presence or absence of scale from pH, dispersant concentration, water quality, and the like.
  • a conductivity meter that measures the conductivity of one or more of the cooling discharge water, RO membrane water supply, and RO membrane concentrated water is provided, and the scale deposition tendency in the RO membrane device is evaluated based on the measured values. And controlling the water recovery rate of the RO membrane device.
  • the measured value of the conductivity meter is high, it is determined that the tendency of scale deposition is high, and the valve opening on the permeate water extraction side of the RO membrane is made small so that the water recovery rate becomes low.
  • the measured value of the conductivity meter is low, it is determined that the tendency of scale deposition is low, and the opening degree of the valve on the permeate extraction side of the RO membrane device is increased so that the water recovery rate is high.
  • the dispersion concentration of the cooling discharge water and / or the RO membrane feed water is measured, and when the measured value of the dispersion concentration is high, it is judged that the tendency of scale precipitation is low, and the RO membrane device is set so that the water recovery rate becomes high. If the measured value of the dispersant concentration is low, it is judged that the tendency of scale precipitation is high, and the RO membrane device has a low water recovery rate. Reduce the valve opening on the permeate extraction side.
  • the cooling exhaust water that is not concentrated inside the device RO membrane permeated water, pure water, or deionized Flushing with water is preferred. This is because when the RO membrane device is stopped while the concentrated water remains in the RO membrane device, silica scale and other scales may be generated depending on the stop time, and the RO membrane device cannot be stably operated when the operation is resumed. Because there is.
  • the RO membrane permeate is circulated to the inlet side of the RO membrane device, the RO membrane concentrated water is discharged out of the system, and the inside of the RO membrane device is moved to the primary side of the RO membrane (for example, the water supply side) and the secondary side (concentrated water side) may be replaced with RO membrane permeate.
  • hypochlorites such as sodium hypochlorite (NaClO), chlorine agents such as chlorine gas, chloramine, chlorinated isocyanurate, monochlorosulfamic acid, etc.
  • the slime control treatment may be performed using these slime control agents added in the circulating cooling water system.
  • a slime control treatment may be performed by adding an additional slime control agent before the RO membrane device.
  • a slime control agent may be added separately after reducing and removing the chlorine agent in the cooling discharge water.
  • One type of these slime control agents may be added, or two or more types may be added simultaneously or alternately. Further, it may be added continuously or intermittently.
  • the RO membrane When cooling discharge water contains heavy metal ions such as copper and iron derived from heat exchangers, the RO membrane is promoted in the presence of redox agents such as thorium hypochlorite and hydrazine and heavy metal ions. May be deteriorated. In that case, by adding a substance having a chelating action of heavy metal (for example, EDTA), contact between the membrane and heavy metal can be prevented, and accelerated deterioration can be prevented.
  • heavy metal for example, EDTA
  • phenolic polymer a polymer compound having a phenolic hydroxyl group (hereinafter referred to as “phenolic polymer”) as a coagulation aid in the cooling discharge water that is the treated water. ) May be added.
  • phenolic polymers examples include vinylphenol homopolymers, modified vinylphenol homopolymers, copolymers of vinylphenol and modified vinylphenol, vinylphenol and / or copolymers of modified vinylphenol and hydrophobic vinyl monomers.
  • polyvinylphenol polymers such as polymers; phenol resins such as polycondensates of phenol and formaldehyde, polycondensates of cresol and formaldehyde, and polycondensates of xylenol and formaldehyde.
  • a resol type secondary reaction is performed on a novolac type phenol resin described in JP2010-131469A, JP2013-255922A, JP2013-255923A, and the like. It is preferable to use the obtained reaction product.
  • the melting point of the phenolic polymer obtained by subjecting the novolac type phenol resin to the resol type secondary reaction is preferably 130 to 220 ° C., particularly 150 to 200 ° C.
  • the phenolic polymer has a weight average molecular weight of preferably 5,000 to 50,000, and more preferably 10,000 to 30,000.
  • the amount of the phenolic polymer added varies depending on the quality of the cooling effluent, and is not particularly limited, but is preferably about 0.01 to 10 mg / L as the active ingredient concentration.
  • the amount of treated water (permeated water) obtained decreases (that is, the water recovery rate decreases) In such a case, these membrane devices are washed to remove clogs and recover the amount of treated water.
  • the chemicals used for the cleaning treatment can be appropriately selected according to the occluding substance and membrane material. For example, hydrochloric acid, sulfuric acid, nitric acid, sodium hypochlorite, sodium hydroxide, citric acid, oxalic acid, etc. are selected. be able to.
  • the cooling discharge water used for water recovery treatment in the following examples and reference examples is a cooling tower blow water (hereinafter, simply referred to as a circulating cooling water system) operating at a concentration factor of 3.5 times using Chiba industrial water as raw water. "Blow water”).
  • a circulating cooling water system the dispersants described in the respective examples and comparative examples are added so that the dispersant concentration in the system becomes a predetermined retention concentration, and sodium hypochlorite (NaClO) is added in the system.
  • the slime control treatment is performed by adding the residual chlorine concentration of 0.5 mg / L.
  • the pH of the blow water is 8.5 to 8.9 (about 8.8).
  • MF membrane was used as a pretreatment membrane, and water was collected by treating blow water in the order of strainer, MF membrane device, and RO membrane device.
  • the mesh pore diameter of the strainer is 400 ⁇ m.
  • MF membrane “Pureia GS (hydrophilic PVDF, pore size 0.02 ⁇ m, external pressure type)” manufactured by Kuraray Co., Ltd. was used.
  • RO membrane “KROA-2032-SN (polyamide ultra-low pressure RO membrane)” manufactured by Kurita Kogyo Co., Ltd. was used.
  • the cleaning frequency of the MF membrane device was 1 time / 30 minutes.
  • the blow water was sequentially passed through the strainer and the MF membrane device without adjusting the pH, and then sulfuric acid was added at the inlet side of the RO membrane device to adjust to pH 5.0.
  • sulfuric acid was added at the inlet side of the RO membrane device to adjust to pH 5.0.
  • sodium bisulfite is added at the inlet side of the RO membrane device to reduce the residual chlorine concentration to 0.05 mg / L or less, and “Kuriverter (registered trademark) IK-110” (bonded chlorine) manufactured by Kurita Kogyo Co., Ltd.
  • the system slime control agent was added at 10 mg / L, and the slime control treatment of the RO membrane device was performed.
  • the water recovery rates of the MF membrane device and RO membrane device started from 90% and 80%, respectively, and the total water recovery rate was 72%. Since the blow water has a high organic substance concentration, the water recovery rate of the MF membrane device and the RO membrane device gradually decreases with time. When the water recovery rate of the MF membrane device or the RO membrane device fell below 50%, the device was once stopped and washed, and water flow was resumed under the condition that the total water recovery rate was 72%. Under this condition, the water flow and recovery process were continued for one month.
  • the dispersant concentration of the pretreatment membrane (MF membrane) feed water is 10.5 mg / L
  • the dispersant concentration of the RO membrane feed water is 10.3 mg / L.
  • the recovery rate was 70%.
  • Example 2 Blow water was collected in the same manner as in Example 1 except that AA / HAPS was used instead of AA / AMPS as the dispersant. Table 1 shows the dispersant concentration of the pretreatment membrane and RO membrane and the average water recovery rate.
  • Example 3 Blow water was recovered in the same manner as in Example 1 except that AA / AMPS / N-tBAA was used in place of AA / AMPS as the dispersant.
  • Table 1 shows the dispersant concentration of the pretreatment membrane and RO membrane and the average water recovery rate.
  • Example 4 Blow water was collected in the same manner as in Example 1 except that the pH of the MF membrane feed water was adjusted to 5.5. Table 1 shows the dispersant concentration of the pretreatment membrane and RO membrane and the average water recovery rate.
  • Example 5 Blow water was collected in the same manner as in Example 1 except that the retention concentration of the dispersant in the circulating cooling water system was 3 mg / L and that 7 mg / L of dispersant was added to the RO membrane water supply. Table 1 shows the dispersant concentration of the pretreatment membrane and RO membrane and the average water recovery rate.
  • Example 6 An alkaline solution of a phenolic polymer (active ingredient concentration 16% by weight, pH 12) having a weight average molecular weight of 12000 and a melting point of 170 ° C. produced according to the method of Example I-1 of JP2013-255923A is used as blow water.
  • the blow water was recovered in the same manner as in Example 1 except that 1 mg / L was added as the active ingredient concentration.
  • Table 1 shows the dispersant concentration of the pretreatment membrane and RO membrane and the average water recovery rate.
  • Example 1 Blow water was collected in the same manner as in Example 1 except that the pH of the MF membrane feed water was adjusted to 4.5. Table 1 shows the dispersant concentration of the pretreatment membrane and RO membrane and the average water recovery rate.
  • Example 2 Blow water was collected in the same manner as in Example 1 except that a UF membrane (“PW2540C30” manufactured by GE) having a molecular weight cut-off of 10,000 was used as the pretreatment membrane.
  • Table 1 shows the dispersant concentration of the pretreatment membrane and RO membrane and the average water recovery rate.
  • Example 5 Blow water was collected in the same manner as in Example 1 except that the concentration of the dispersant retained in the circulating cooling water system was 1 mg / L. Table 1 shows the dispersant concentration of the pretreatment membrane and RO membrane and the average water recovery rate.
  • Table 1 shows the following. According to the present invention, by performing the treatment so that an effective amount of the dispersant remains in the RO membrane water supply, a stable treatment can be continued with a high water recovery rate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

Lors du recyclage d'un effluent eau de refroidissement par le biais d'un traitement par membrane d'OI, la présente invention réduit le coût du traitement de l'eau, améliore le taux de récupération d'eau, et stabilise le traitement de l'eau, ledit effluent eau de refroidissement comprenant de l'eau nébulisée dans un système d'eau de refroidissement en circulation. La présente invention concerne ainsi un procédé de recyclage de l'eau qui consiste à soumettre un effluent eau de refroidissement évacué à partir d'un système d'eau de refroidissement en circulation à un traitement dans un système de récupération d'eau comprenant à la fois une membrane de prétraitement et une membrane d'OI et à renvoyer l'eau traitée vers le système d'eau de refroidissement en circulation, un dispersant qui peut passer à travers la membrane de prétraitement étant ajouté dans le système d'eau de refroidissement en circulation comme dispersant destiné à disperser les constituants du calcaire. En d'autres termes, ce procédé consiste à utiliser une membrane perméable à un dispersant comme membrane de prétraitement située en amont de la membrane d'OI et permet ainsi à un dispersant ajouté dans le système d'eau de refroidissement en circulation d'être également efficacement utilisé dans le système de récupération d'eau. Ainsi, la présente invention permet de réduire le coût de traitement de l'eau, d'améliorer le taux de récupération de l'eau, et de stabiliser le traitement de l'eau.
PCT/JP2015/051685 2014-03-14 2015-01-22 Procédé de recyclage d'effluent eau de refroidissement et appareil de recyclage WO2015136992A1 (fr)

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SG11201607245XA SG11201607245XA (en) 2014-03-14 2015-01-22 Method for recycling cooling water effluent and recycling apparatus

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JP2019202246A (ja) * 2018-05-21 2019-11-28 王子ホールディングス株式会社 水処理装置および水処理方法
EP4122894A1 (fr) * 2021-07-22 2023-01-25 Newtec Water Systems NV Procédé et système de purification d'eau

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JP6128171B2 (ja) * 2015-07-09 2017-05-17 栗田工業株式会社 冷却排出水の回収方法及び回収装置
JP6682401B2 (ja) * 2016-08-18 2020-04-15 オルガノ株式会社 逆浸透膜を用いる水処理方法
JP2019122943A (ja) * 2018-01-19 2019-07-25 オルガノ株式会社 水処理方法および水処理装置
JP6777130B2 (ja) * 2018-10-05 2020-10-28 栗田工業株式会社 膜用水処理薬品及び膜処理方法
JP6801731B2 (ja) * 2019-03-28 2020-12-16 栗田工業株式会社 純水製造装置及び純水製造方法
WO2020203527A1 (fr) * 2019-03-29 2020-10-08 栗田工業株式会社 Inhibiteur de tartre pour membranes à osmose inverse et procédé de traitement par membrane à osmose inverse
JP7173220B1 (ja) * 2021-06-03 2022-11-16 栗田工業株式会社 逆浸透膜装置の運転方法

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EP4122894A1 (fr) * 2021-07-22 2023-01-25 Newtec Water Systems NV Procédé et système de purification d'eau

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