CN106029580A - Method for recycling cooling water effluent and recycling apparatus - Google Patents
Method for recycling cooling water effluent and recycling apparatus Download PDFInfo
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- CN106029580A CN106029580A CN201580009395.4A CN201580009395A CN106029580A CN 106029580 A CN106029580 A CN 106029580A CN 201580009395 A CN201580009395 A CN 201580009395A CN 106029580 A CN106029580 A CN 106029580A
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- water
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- cooling
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- reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/58—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
Abstract
In recycling a cooling water effluent through RO membrane treatment, the present invention reduces the cost of water treatment, enhances the recovery ratio of water, and stabilizes the treatment of water, said cooling water effluent including blow water in a circulating cooling water system. The present invention is a water recycling method which comprises subjecting a cooling water effluent discharged from a circulating cooling water system to treatment in a water reclamation system including both a pretreatment membrane and an RO membrane and returning the treated water to the circulating cooling water system, wherein a dispersant that can permeate the pretreatment membrane is added in the circulating cooling water system as a dispersant for dispersing scale components. In other words, this method comprises using a dispersant-permeable membrane as the pretreatment membrane precedent to the RO membrane and thereby enabling a dispersant added in the circulating cooling water system to be effectively utilized also in the water reclamation system. Thus, the present invention can reduce the cost of water treatment, enhance the recovery ratio of water, and stabilize the treatment of water.
Description
Technical field
The present invention relates to a kind of in building air-conditioning, chemical industry, paper processed industry, ironworker's industry processed, electric power work
Recovery method and the retracting device of water is discharged in cooling in the cooling device used in the industrial processes of industry etc..
Background technology
In the thermal conductive surface contacted with aqueous phase or pipe arrangement of cooling water system, boiler water system etc., it may occur that dirt
Obstacle.Particularly, from resource-saving, save energy position for, when by cooling water for system outside
When (discharge) amount of discharging reduces and carries out the situation of highly enriched operating, the salt being dissolved in the water can be dense
Contracting, makes thermal conductive surface become easily and is corroded, and also can form the salt of slightly solubility and dirtization.If dirt is attached
The wall etc. in device, can cause the reduction of the thermal efficiency, pipe arrangement obturation etc. for boiler or heat hand over
It it is great obstacle for the operating of parallel operation.
In recent years, in order to economize on water and save the purpose of the energy, it is desirable to be able to carry out effectively for water as much as possible
The trend utilized becomes notable.When carrying out the situation of highly enriched operating, press down in the precipitation for dirt
Make in a thing, the limit.
By recovery system, the draining of cooling water is reclaimed and returned by this process water carrying out being built with
Framework to cooling tower.As this recovery system, it is however generally that, by reverse osmosis membrane (RO film)
Salt (ion) is removed, and makes process water return in cooling tower.Such as, for as described below
System has carried out studying (patent documentation 1～3).
System 1: coagulation → sand filtration → safe filter screen (safety filter) → RO film
System 2: coagulation → sand filtration → pre-treatment film → RO film
System 3: on coagulation → Pressurized flotation → sand filtration → safe filter screen (safety filter) → RO film
System 4: carbon elimination acid tower → pre-treatment film → RO film
System 5:RO film
Although system 5 is the easy system only with RO film device, but, owing to wrapping in draining
The turbidity contained can cause RO film to block, accordingly, it is difficult to carry out stable process.
As shown in system 1～4, by the prime at RO film, processed by coagulation or pre-treatment film by
Turbidity in draining removes, it is possible to make RO film process stabilisation.But, in draining, include by
Making an addition to the dispersant in circulating cooling water system, this dispersant can process for coagulation and cause obstruction.Therefore,
In the coagulation of system 1～3 processes, the addition of agglutinant required in processes can become the most.
In RO film device, in order to make dirt composition dispersion and with high Water Sproading rate to make process stabilisation,
Need dispersant, but, by comprehending at coagulation, the dispersant in draining is removed, therefore, in order to reach
Become the dirt at RO film to disperse and the stabilisation of process, need to add dispersant in RO film supplies water.
In the system 4 not carrying out coagulation process and the turbidity in draining removed by pre-treatment film,
Similarly, the dispersant in draining can be removed, therefore, in order to reach RO film by pre-treatment film
The stabilisation of the process of device, needs to add dispersant in RO film supplies water.
Patent documentation 1: Japanese Unexamined Patent Publication 2003-1256 publication；
Patent documentation 2: Japanese Unexamined Patent Publication 2002-18437 publication；
Patent documentation 3: Japanese Unexamined Patent Publication 2009-297600 publication.
Summary of the invention
In the water reclamation system of prior art, in order to make the steady running of RO film device, need to carry out
For the interpolation of the dispersant that RO film supplies water, thus can produce cost and operation, processing cost can be caused
Lifting.
The problem of the present invention is to provide a kind of recovery method and retracting device cooling down and discharging water, its
Be the draining etc. for circulating cooling water system cooling discharge water carry out RO film process and carry out Water Sproading
Time, the cost processed by water reduces, and seeks lifting and the stabilisation of Water Sproading rate.
The present inventor etc., are repeated effort research, as a result of which it is, obtain to solve above-mentioned problem
Following understanding.The draining etc. of cooling in to(for) circulating cooling water system is discharged water and is carried out RO film process
And when carrying out Water Sproading, as the pre-treatment film of RO film, use can be through being added in recirculated cooling water
The pre-treatment film of the dispersant in system, is added in circulating cooling water system and is contained in cooling by making
The dispersant discharged in water effectively utilizes through pre-treatment film the dispersant as RO film, it is not necessary to
Carry out the interpolation of dispersant in water reclamation system, or the addition of dispersant can be reduced.By
This, it is possible to the cost processed by water reduces, and can seek lifting and the stabilisation of Water Sproading rate.
The present invention reaches based on above-mentioned knowledge, and its main idea is as follows.
[1] a kind of recovery method cooling down discharge water, it is by including the water of pre-treatment film and reverse osmosis membrane
Recovery system is carried out from the discharge water being added with the circulating cooling water system making the dirt scattered dispersant of composition
Process and make process water return in this circulating cooling water system, it is characterised in that
In this circulating cooling water system, foregoing dispersant passes through this pre-treatment film.
[2] as described in [1] cooling discharge water recovery method, wherein, aforementioned pre-treatment film by following
The transmitance of the foregoing dispersant that numerical expression calculates is more than 80%,
Transmitance=(pre-treatment film is through the dispersant concentration of dispersant concentration/pre-treatment film water supply of water)
×100。
[3] recovery method of water is discharged in the cooling as described in [1] or [2], and wherein, aforementioned pre-treatment film is accurate
Filter membrane or ultrafilter membrane.
[4] recovery method of water is discharged in the cooling as according to any one of [1]～[3], wherein, locates before aforementioned
The pH of the water supply of reason film is set to more than 5.
[5] recovery method of water, wherein, aforementioned pre-treatment are discharged in the cooling as according to any one of [1]～[4]
The molecular cut off of film is more than 30000.
[6] recovery method of water, wherein, foregoing dispersant are discharged in the cooling as according to any one of [1]～[5]
It it is the polymer with sulfonic group and carboxyl.
[7] recovery method of water is discharged in the cooling as described in [6], and wherein, foregoing dispersant is by metering system
Acid and/or acrylic acid and 3-pi-allyl epoxide-2-hydroxyl-1-propane sulfonic acid and/or 2-acrylamide-2-methyl-prop sulphur
The copolymer of acid copolymerization.
[8] cooling as according to any one of [1]～[7] discharges the recovery method of water, wherein, by aforementioned against oozing
The pH of the water supply of permeable membrane is adjusted to 4.0～7.5.
[9] recovery method of water is discharged in the cooling as according to any one of [1]～[8], wherein, measures aforementioned inverse
The concentration of the foregoing dispersant of the water supply of permeable membrane, and this reverse osmosis membrane supply water in add this dispersant with
This dispersant concentration is made to become the concentration of regulation.
[10] recovery method of water is discharged in the cooling as according to any one of [1]～[9], wherein, measures aforementioned
The conductivity of the one or more of water in discharge water, reverse osmosis membrane water supply and reverse osmosis membrane condensed water, and
Measured value according to this conductivity adjusts the Water Sproading rate of this reverse osmosis membrane.
[11] recovery method of water is discharged in the cooling as according to any one of [1]～[10], wherein, measures aforementioned
Discharge the concentration of the foregoing dispersant of water and/or reverse osmosis membrane water supply, and the survey of the concentration according to this dispersant
Definite value adjusts the Water Sproading rate of this reverse osmosis membrane.
[12] recovery method of water is discharged in the cooling as according to any one of [1]～[11], wherein, will have phenol
It is in the macromolecular compound interpolation extremely aforementioned discharge water of hydroxyl.
[13] cooling as according to any one of [1]～[12] discharges the recovery method of water, wherein, at aforementioned water
During the stopping of recovery system, aforementioned reverse osmosis membrane is made to circulate through water, or by pure water or deionized water
Carry out water flowing, and after having carried out the operating this reverse osmosis membrane condensed water being expelled to outside system, make this
Water reclamation system stops.
[14] a kind of retracting device cooling down discharge water, it possesses makes the discharge water from circulating cooling water system
The pre-treatment film device of water flowing, make this pre-treatment film device the reverse osmosis membrane device through water water flowing, with
And make this reverse osmosis membrane device return to the loop back device in this circulating cooling water system through water, its feature exists
In,
Aforementioned recirculated cooling water cording is standby will make the dirt scattered dispersant of composition add the dispersion to this water system
Agent adding set, this dispersant is can be through the dispersant of aforementioned pre-treatment film.
[15] cooling as described in [14] discharges the retracting device of water, wherein, under the passing through of aforementioned pre-treatment film
The transmitance stating the foregoing dispersant that numerical expression calculates is more than 80%,
Transmitance=(pre-treatment film is through the dispersant concentration of dispersant concentration/pre-treatment film water supply of water)
×100。
[16] retracting device of water is discharged in the cooling as described in [14] or [15], and wherein, aforementioned pre-treatment film is
Secondary filter film or ultrafilter membrane.
[17] cooling as according to any one of [14]～[16] discharges the retracting device of water, wherein, by aforementioned
The pH of the water supply of pre-treatment film is set to more than 5.
[18] as according to any one of [14]～[17] cooling discharge water retracting device, wherein, aforementioned before
The molecular cut off processing film is more than 30000.
[19] retracting device of water, wherein, aforementioned point are discharged in the cooling as according to any one of [14]～[18]
Powder is the polymer with sulfonic group and carboxyl.
[20] retracting device of water is discharged in the cooling as described in [19], and wherein, foregoing dispersant is by methyl-prop
Olefin(e) acid and/or acrylic acid and 3-pi-allyl epoxide-2-hydroxyl-1-propane sulfonic acid and/or 2-acrylamide-2-methyl-prop
The copolymer of sulfonic acid copolymerization.
[21] retracting device of water is discharged in the cooling as according to any one of [14]～[20], and wherein, it possesses:
The pH of the water supply of aforementioned reverse osmosis membrane is adjusted to the pH adjusting apparatus of 4.0～7.5.
[22] retracting device of water is discharged in the cooling as according to any one of [14]～[21], and wherein, it possesses:
Measure the dispersant concentration determinator of the concentration of the foregoing dispersant of the water supply of aforementioned reverse osmosis membrane, at this
Reverse osmosis membrane adds this dispersant in supplying water so that this point of being determined by this dispersant concentration determinator
The concentration of powder becomes the dispersant adjusting apparatus of normal concentration.
[23] retracting device of water is discharged in the cooling as according to any one of [14]～[22], and wherein, it possesses:
Measure leading of the one or more of water in aforementioned discharge water, reverse osmosis membrane water supply and reverse osmosis membrane condensed water
The electricity electric conductivity measuring apparatus of rate and adjust this reverse osmosis according to the measured value of this electric conductivity measuring apparatus
The Water Sproading rate adjusting apparatus of the Water Sproading rate of film.
[24] retracting device of water is discharged in the cooling as according to any one of [14]～[23], and wherein, it possesses:
The dispersant concentration of the concentration measuring the foregoing dispersant of aforementioned discharge water and/or reverse osmosis membrane water supply measures
Device and the measured value according to this dispersant concentration determinator adjust the Water Sproading rate of this reverse osmosis membrane
Water Sproading rate adjusting apparatus.
[25] retracting device of water is discharged in the cooling as according to any one of [14]～[24], and wherein, it possesses:
The coagulation assistant feeding device of phenol system hydroxyl is added in aforementioned discharge water.
[26] retracting device of water is discharged in the cooling as according to any one of [14]～[25], wherein, aforementioned inverse
Permeable membrane device possesses: make this reverse osmosis membrane through water this reverse osmosis membrane device prime circulate pass through
Water circle device or make pure water or deionized water at the device of this reverse osmosis membrane device water flowing and should
Reverse osmosis membrane condensed water draining to the condensed water discharger outside system,
Further, this cooling is discharged the retracting device of water and is possessed: control device, this control device is in this cooling
When discharging the stopping of retracting device of water, make aforementioned reverse osmosis membrane through water in prime circulation or by pure
Water or deionized water water flowing, and carrying out the operating that this reverse osmosis membrane condensed water is expelled to outside system
After, the retracting device making this cooling discharge water stops.
[effect of invention]
According to the present invention, process by water being discharged in cooling at the pre-treatment film of the prime of RO film,
Thus, cooling is discharged the turbidity in water to remove, it is possible to make the RO film of rear class process stabilisation.
Further, in the present invention, make add in circulating cooling water system and be contained in cold by being configured to
But the dispersant in water is discharged through this pre-treatment film, it is possible to using this dispersant as the dispersant of RO film
Effectively utilize.Therefore, it is not required to as the system of prior art carry out before RO film
Adding again of the dispersant that level has been removed, the most economically all can be more in operation or process
Efficient activity, it is possible to processing cost is greatly reduced.And, utilize the dispersant having passed through pre-treatment film,
Stabilisation and the lifting of Water Sproading rate that RO film processes can be sought.
For these reasons, if discharging recovery method and the retracting device of water according to the cooling of the present invention, then
The dirty obstacle of RO film device with the simplest system, can be prevented, and can contain in long period
Carry out stable Water Sproading.
Detailed description of the invention
Hereinafter, it is described in detail for embodiments of the present invention.
Water ＞ is discharged in ＜ cooling
In the present invention, discharge water as the cooling being provided with carrying out Water Sproading process, typically, can arrange
Enumerate the draining of cooling tower, but, it is not limited to draining, present invention can be suitably applied to from circulating cooling
The all of discharge water that water system is discharged.Such as, it is possible to be configured to from the circulation pipe arrangement of circulating cooling water system
After part or all of recirculated cooling water being taken out and carried out processing according to the present invention, then make it
Return in this circulating cooling water system.Again, it is possible to will be from side filter (サ イ De Off ィ Le タ), light
The pipe arrangement branch of mass filter (ラ イ ト Off ィ Le タ) the discharge water discharged as processing object,
And carry out Water Sproading.
In the present invention, using this cooling discharge water as processing object water, and by pre-treatment film device
And RO film device sequentially processes, then process water is recycled in circulating cooling water system.
＜ water strainer (strainer) ＞
Water is discharged in above-mentioned cooling, although also can directly be processed by pre-treatment film device, but,
In water is discharged in cooling, owing to having the situation including thick turbidity or foreign body, it is therefore preferable that
The prime of pre-treatment film device arranges water strainer, and these is removed in advance by water strainer, then,
Turbidity removal process is carried out in pre-treatment film device.Although also being able to operate with regard to being omitted by water strainer at last,
But, in this situation, have and discharge the thick turbidity in water or foreign body due to cooling and cause pre-treatment
The probability that film is damaged.
As water strainer, it is particularly suitable for using the automatic water filter automatically carrying out cleaning process.
The shape of water strainer, and not particularly restricted, the drainage of the arbitrary shape of Y type, barrel shape etc. can be used
Device.
The aperture of water strainer, preferably 100～500 μm.If the aperture of water strainer relatively 100 μm are more
Little, then the situation of the blocking of water strainer can become serious.If the aperture of water strainer is more than 500 μm,
The probability then causing pre-treatment film damaged owing to having passed through the thick turbidity of water strainer or foreign body can become
High.
It is used as bobbin filter (yarn I Off ィ Le タ), pleated filter (プ リ Star Off
ィ Le タ) etc. filter replace water strainer.From the viewpoint of exchange frequency, clean efficiency,
Preferably water strainer.
＜ pre-treatment film device ＞
Cooling is discharged water or has been carried out the cooling discharge water after turbidity removal processes by water strainer, then
It is subsequently processed by pre-treatment film device.
Pre-treatment film device, is that the cooling of the reason of fouling membrane in order to will become RO film device is discharged
Turbidity in water or the device of colloidal state composition removing, can use secondary filter film (MF film) or ultrafilter membrane
(UF film).The membranous type formula of pre-treatment film device, and not particularly restricted, hollow wire type, spiral shell can be used
The film filter of rotation type etc..The filter type of pre-treatment film device, also and not particularly restricted, applicable
The mode of any one that interior press filtration, outer press filtration, cross-flow filtration, full dose filter.
As the molecular cut off of the UF film of pre-treatment film, preferably more than 30000.If UF film
Molecular cut off be less compared with 30000, then the dispersant that cooling cannot be made to discharge in water passes through, and has
It may happen that need additionally to add necessity of dispersant in the prime of RO film device.Retaining point of UF film
The upper limit of son amount, and not particularly restricted, but, if below 1000000, then can be by cooling row
The macromolecule Polysaccharides of the plugging reason that may become RO film in water outlet etc. remove.As pre-treatment
The aperture of the MF film of film, based on the reason as the molecular cut off of UF film, preferably 0.1～0.01
μm degree.
In pre-treatment film, the transmitance of the aftermentioned dispersant preferably calculated by following numerical expression is 80%
Above, particularly preferably more than 85%.If the transmitance of the dispersant of pre-treatment film is more above-mentioned lower limit
Lower, then cannot effectively obtain the effect of the present invention.The upper limit of the transmitance of the dispersant of pre-treatment film,
It is typically 100%.
Transmitance=(pre-treatment film is through the dispersant concentration of dispersant concentration/pre-treatment film water supply of water)
×100
In order to obtain above-mentioned dispersant transmitance, use suitable point described later preferably as dispersant
Powder, and, in pre-treatment film device, the pH of the water supply of pre-treatment film is set to more than 5.If
Be the pH of water supply of pre-treatment film for lower compared with 5, use tool described later the most at last as dispersant
Have the polymer of sulfonic group and carboxyl, the transmitance of pre-treatment film also can step-down, and have and cannot obtain this
The situation of the effect of invention.The pH of the water supply of pre-treatment film, as long as being more than 5, for its upper limit,
And it is not particularly restricted.Generally, water is discharged in the cooling of cooling tower draining etc., is pH8～10, it is common that 8～
9 degree, it is therefore preferable that directly process it by pre-treatment film device.
＜ dispersant ＞
In the present invention, it is added in the dispersant in circulating cooling water system, is can be through above-mentioned front place
The dispersant of reason film.
As this dispersant, the polymer that there is sulfonic group with carboxyl is preferably used.
Dispersant, more can dissociate and improve the function as dispersant under conditions of the highest pH, but
It is, in the RO film device of the rear class of pre-treatment film device, if high pH condition, then to fill at RO film
The calcium being concentrated in putting etc. can easily separate out, therefore, as aftermentioned, in low ph condition as dirt
Under process.In RO film device under this low ph condition, if dispersant is only to have carboxyl
And do not have sulfonic dispersant, then can become insoluble, and become cannot obtain as dispersant
Function.Accordingly, as dispersant, the polymer that there is sulfonic group with carboxyl is preferably used.
As being adapted as the polymer with sulfonic group and carboxyl of dispersant, can list and there is sulfonic acid
The monomer of base and there is carboxyl monomer between copolymer, or more and then and can be with these monomer
Carry out the terpolymer between the monomer of copolymerization.
As having sulfonic monomer, can list: 2-methyl isophthalic acid, being total to of 3-butadiene-1-sulfonic acid etc.
Yoke diene sulfonic acid, 3-(methyl) allyloxy-2-hydroxypropanesulfonic acid etc. there is sulfonic unsaturation
(methyl) allyl ether system monomer, 2-(methyl) acrylamide-2-methyl propane sulfonic acid, 2-hydroxyl-3-
Acrylamide propane sulfonic, styrene sulfonic acid, methallylsulfonic acid (Methallyl sulfonic acid),
Vinyl sulfonic acid, allyl sulphonic acid, iso-amylene sulfonic acid (Isoamylene sulfonic acid) or these
Salt etc., preferably 3-allyloxy-2-hydroxyl-1-propane sulfonic acid (HAPS), 2-acrylamide-2-first
Base propane sulfonic acid (AMPS).There is sulfonic monomer, a kind can be used alone, it is possible to by 2
It is used in mixed way more than kind.
As having the monomer of carboxyl, can enumerate: acrylic acid, methacrylic acid .beta.-methylacrylic acid, different Fructus Crotonis
Acid, vinyl acetate, atropic acid (Atropic acid), maleic acid, fumaric acid, itaconic acid, ethoxy
Acrylic acid or these salt etc., preferably acrylic acid, methacrylic acid.There is the monomer of carboxyl, can
1 kind is used alone, it is possible to two or more is used in mixed way.
As can listing N tert butyl acrylamide with the monomer of these monomer copolymerizable
(N-tBAA), the amide-type such as N-ethylene carboxamide.
As being suitable to the dispersant of the present invention, particularly can enumerate: by acrylic acid (AA) and 2-propylene
Amide-2-methyl propane sulfonic acid (AMPS) is with AA:AMPS=70～90:10～30 (mol ratio)
Ratio combined polymerization copolymer, by AA Yu AMPS and N tert butyl acrylamide (N-tBAA)
Deng amide-type with AA:AMPS: amide-type=40～90:5～30:5～the ratio of 30 (mol ratios)
The copolymer of combined polymerization, by AA Yu 3-allyloxy-2-hydroxypropanesulfonic acid (HAPS) with AA:
The copolymer etc. of the ratio combined polymerization of HAPS=70～90:10～30 (mol ratio), but,
It is not limited to these.
There are the weight average molecular weight of sulfonic group and the polymer of carboxyl, preferably 1000～30000.If
The weight average molecular weight of polymer is less than 1000, then dispersion effect insufficient.If the weight average of polymer
Molecular weight for more than 30000, then becomes to be difficult to through pre-treatment film, also, polymer self has absorption
On pre-treatment film or RO film and become the possibility of reason of film blocking.
The addition in circulating cooling water system of dispersant, from the dispersion effect cooling tower and economy
Property and RO film supply water in dispersion effect from the viewpoint of, as effective ingredient (that is to say, on
The polymer stated) concentration, be preferred to be set to 3～30mg/L, particularly to be set to 5～20mg/L
For more preferably.For adding method and the interpolation place of dispersant and not particularly restricted.
As dispersant, in addition to the above-mentioned polymer with sulfonic group and carboxyl, as long as can
Obtain the material of sufficient dispersion effect, be then used as the phosphoric acid of other polymer or phosphonic acids etc.
Compound etc..Dispersant, if for may from produced by the raw water quality of circulating cooling water system dirt
Become to be allocated as correctly grasping, and the dispersant of its kind occurred will be prevented from so that the dense of effect can be obtained
The mode of degree is added.
＜ RO film device ＞
Water is discharged in cooling and has carried out process water (the front place after processing by aforesaid pre-treatment film device
Reason film is through water), then, carried out desalting processing by RO film device.
As the kind of the RO film of RO film device and not particularly restricted, can be according to handled cooling
The water quality discharging water (is supplied to the raw water quality of circulating cooling water system, in the concentration of circulating cooling water system
Multiplying power) suitably determine.The salt rejection rate of RO film is preferably more than 80%, and particularly preferably more than 85%.
If the salt rejection rate of RO film is lower compared with this, then desalting efficiency is poor, it is impossible to obtain the process of good water quality
Water (through water).As the material of RO film, polyamide composite film, cellulose acetate membrane etc. can be used
The film of arbitrary material.For the shape of RO film, also and not particularly restricted, can use hollow wire type,
Any one of spiral type etc..
Supply water in (at the water of RO film device water flowing as processed water) at RO film, as following
There are suitable pH.Adjust to carry out the pH of RO film water supply, be preferably provided at pre-treatment film
Acid the pH adjusting apparatus that pH is adjusted is added between device and RO film device.As pH
Adjusting apparatus, can list and to import pipeline or setting for the water supply of RO film by killer injecting pump etc.
Add acid or for the pH adjustment tank additionally arranged to line mixer in pipeline and substantivity
And add the device etc. of acid.Acid as used herein, and be not particularly limited, can suitably use hydrochloric acid, sulfur
The mineral acid of acid, nitric acid etc..
Generally, in circulating cooling water system, owing to concentration cycles operates, the pH of recirculated cooling water can go up
Rise to 8～9 degree.For the passing through of the dispersant of pre-treatment film device, with this kind high pH it is
Preferable.In RO film device, owing to cooling discharge water is further concentrated, therefore, it is possible to
Produce dirt.From the viewpoint of dirt is suppressed, preferably in RO film device, make pH reduce and
Operate.The pH scope supplied water as RO film, preferably 4.0～7.5.If the pH that RO film supplies water
More than 7.5, then depend on water quality, have the dirt separating out calcium carbonate, calcium phosphate, calcium sulfate, barium sulfate etc.
The situation of class.
When cooling down the silica concentration discharged in the water situation more than 30mg/L, in order to suppress it to analyse
Go out, preferably the pH that RO film supplies water is reduced to 4.0～5.5.From the viewpoint of the precipitation preventing dirt,
The pH that RO film supplies water is the lowest more preferred.In order to the pH that RO film supplies water is reduced to lower compared with 4.0,
The amount of required acid can increase, unsatisfactory on economic face.
If the humic acids containing volume or fulvic acid in water is discharged in cooling, then have and RO film occurs
The situation of blocking.In this situation, the pH that cooling is preferably discharged water is set to 5.5～7.0, particularly preferably sets
It is 5.5～6.5.If the scope of this kind of pH, then acid dissociation is produced for humic acids or fulvic acid and caused
The blocking of RO film be suppressed, and the Ca cooled down in water is effectively dispersed by dispersant,
It is difficult to the complex being formed between fulvic acid.
In the present invention, as the dispersant made an addition in circulating cooling water system, can be through front by using
Process the dispersant of film, and make the dispersant discharged contained by water in cooling and bring into water reclamation system
The process water (through water) of pre-treatment film passes through, and by having passed through the dispersant of pre-treatment film
Carry out the dirty dispersion in RO film device to process.Therefore, in RO film supplies water, it is necessary to make it
Dispersant is comprised for effective concentration for dirt dispersion is processed.
The dispersant concentration that RO required in the dirty dispersion of RO film device processes supplies water, depends on
Cooling discharge the treatment conditions (Water Sproading rate) of the water quality of water, pre-treatment film and RO film etc. and
Different, and cannot make to specify in property ground without exception.It is said that in general, the dispersant concentration that RO film supplies water, it is 3mg/L
Above, particularly preferably 5～30mg/L degree.
Dispersant concentration in supplying water at RO film is not sufficient to obtain sufficient dirt in RO film device
During the situation of dispersion effect, preferably at entrance side (pre-treatment film device and the RO film dress of RO film device
Between putting) and add and add dispersant.As the dispersant added at this, can use and be suitable as
The dispersant of the dispersant used in aforesaid circulating cooling water system, but, and not strictly necessary be with
The dispersant that the dispersant that added in circulating cooling water system is identical, it is possible to use different dispersant.
Also the dispersant concentration that RO film supplies water can be measured, and so that this dispersant concentration becomes rule
The mode of fixed concentration is made to control for dispersant addition.As the assay method of dispersant concentration,
Can use by turbidimetry (such as, described in Japanese Unexamined Patent Publication 2006-64498 publication method) caused
Method.Dispersant, such as, can be interconnected by the dispersant concentration determinator supplied water with RO film mutually
Dynamic dispersant adding set adds and adds to the water supply of RO film.
According to the present invention, in order to the dispersant that will make an addition in circulating cooling water system is as RO film device
Dispersant utilizes, and after making an addition in circulating cooling water system, discharges included in water in cooling and is arranged
The dispersant gone out, when arriving RO film device, it is necessary to remain to be only capable of and act as dispersant
Activity.The holdup time of the cooling water in the cooling tower of circulating cooling water system, owing to meeting is for this
The activity of dispersant impacts, and therefore, also has preferably to make dispersant play in RO film device
When sufficiently the mode of activity was adjusted for holdup time of the cooling tower of circulating cooling water system.
Water Sproading rate in RO film device, it is considered preferred to the precipitation tendency of the dirt in RO film device
Determine.Cooling handled in the present invention discharge water conductivity and become dirt will because of cooling row
The concentration of Ca, Mg etc. in water outlet, has the probability changed, therefore, it is possible to according to RO
The conductivity of condensed water and Ca concentration, Mg concentration etc. are adjusted for the Water Sproading rate of RO film.
Also dependent on pH or dispersant concentration, water quality etc., judge the presence or absence of dirt generation, and to Water Sproading rate
It is set.
Specifically, can list: arrange and discharge water for cooling, RO film supplies water and RO film is dense
The conductivity meter that the conductivity of the one or more of water in shrink is measured, and according to its measured value, come
Tendency is separated out for the dirt in RO film device be evaluated, and for the Water Sproading rate of RO film device
It is controlled.In this situation, when the measured value of conductivity meter is high situation, it is judged that dirt separates out tendency
For height, and in the way of making Water Sproading rate step-down, by the valve opening contracting taking out side through water of RO film
Little.Contrary, when the measured value of conductivity meter is low situation, it is judged that it is low that dirt separates out tendency, and
In the way of making Water Sproading rate uprise, by the valve opening increase taking out side through water of RO film device.
Or, dispersant concentration cooling being discharged to water and/or the water supply of RO film is measured, and works as
When the measured value of dispersant concentration is high situation, it is judged that it is low that dirt separates out tendency, and so that Water Sproading rate
The mode uprised, by the valve opening increase taking out side through water of RO film device and contrary, when
When the measured value of dispersant concentration is low situation, it is judged that it is height that dirt separates out tendency, and so that Water Sproading rate
The mode of step-down, reduces the valve opening through water taking-up side of RO film device.
In RO film device, during situation about having worried especially for the generation of silicon dioxide dirt, excellent
It is selected in when making RO film device stop, discharging water by the internal and unconcentrated cooling of device or RO film is saturating
Cross water, pure water or deionized water to carry out spontaneous evaporation (flashing).It reason for this is that: when
When the most directly making, under the state still remaining condensed water in RO film device, the situation that RO film device stops,
Depend on dwell time, have generation silicon dioxide dirt or other dirt and cause when starting running once again
And become cannot be carried out the situation of the steady running of RO film device.In this situation, can list: such as
When the operating of RO film device stops, carrying out making RO film pass through the water entrance side for RO film device
Circulation, and RO membrance concentration water is expelled to outside system, and by the RO film in RO film device once
Side (water supply side) and secondary side (condensed water side) all carry out the operation replaced with RO film through water.
＜ other process ＞
In the circulating cooling water system of the present invention, as slime control agent (Slime control agent),
Also can add: the hypochlorite of sodium hypochlorite (NaClO) etc., chlorine, chloramines, chlorination trimerization isocyanide
The chlorine agent of hydrochlorate etc., monochloro are for the chlorine of sulfamic acid (モ ノ Network ロ Le ス Le Off ァ ミ Application acid) etc. and acyl
Amine sulphuric acid, there is the secondary bromine of the reacted combined chloride agent of the compound of amido sulfuric acid base, sodium hypobromite etc.
The bromide of hydrochlorate, dibromo hydantoin (dibromohydantoin) etc., bromine and amine or ammonia, there is amide
The reacted combination bromide of the compound of sulfate, DBNPA (di-bromonitrilopropiona,ide), MIT
The organic agent of (Methylisothiazolinone) etc., hydrazine, hydantoin (5,5-dimethyl hydantoin) etc..
These, it is possible to only a kind independent interpolation, it is possible to plurality of combinations is added.
In RO film device, it is possible to utilize these the slime control agent being added in circulating cooling water system
And carry out mucus control process.Also can at the prime of RO film device more so that add add mucus control
Agent also carries out mucus control process.Ask when the oxidative degradation of the RO film caused due to chlorine agent etc. can cause
During situation about inscribing, it is possible to cooling is discharged the chlorine agent in water and first makees reduction removing, then, still further add
Slime control agent.
These slime control agent, can add a kind, it is possible to will more than 2 kinds or add alternately simultaneously.
Also, can add on seriality ground, it is possible to intermittently add.
The feelings of the heavy metal ion coming from the copper of heat exchanger, ferrum etc. are included in discharging water in cooling
During condition, there is the medicament (such as sodium hypochlorite, hydrazine) of redox and depositing of heavy metal ion
Under, RO film has by promoting the probability deteriorated.In this situation, by interpolation, there is heavy metal
The material (such as EDTA) of chelation, it is possible to prevent contacting and preventing from promoting of film and heavy metal
Deterioration.
Polyamide-based RO film, independent of the presence or absence of heavy metal, all can due to contacting between hypochlorite
And deteriorate.Owing to the probability of the reason becoming film deterioration of hypochlorite is high, therefore, should be as much as possible
Avoid using, when applicable situation, preferably after being removed by the chlorine of residual, then for RO film device
Carry out water flowing.
In order to make pre-treatment film device, RO film device stabilisation, it is possible in the cooling as processed water
Discharge in water, add as coagulation auxiliary agent and there is the macromolecular compound of phenol system hydroxyl (below, sometimes
It is referred to as the situation of " phenol macromolecule ").
As phenol macromolecule, can enumerate: vinylphenol be polymerized alone thing, ethene improved phenol individually poly-
Compound, vinylphenol and the copolymer of ethene improved phenol, vinylphenol and/or ethene improved phenol and hydrophobic vinyl
The polyethylene phenol based polymer of the copolymer of monomer；Phenol and the polycondensation of the condensation polymer of formaldehyde, cresol and formaldehyde
The phenol resin of the condensation polymer of thing, xylenol and formaldehyde.As phenol macromolecule, particularly it is preferably used
At Japanese Unexamined Patent Publication 2010-131469 publication, Japanese Unexamined Patent Publication 2013-255922 publication, Japanese Unexamined Patent Publication
Described in 2013-255923 publication etc. first rank phenolic aldehyde tree is carried out for novolak phenolics
Reactant obtained by 2 secondary responses of epoxy-type.
Novolak phenolics is carried out to the phenol obtained by 2 secondary responses of resol type
High molecular fusing point, is 130～220 DEG C, particularly preferably 150～200 DEG C.The high molecular weight average of phenol
Molecular weight, preferably 5000～50000, more preferably 10000～30000.
The high molecular addition of phenol, depends on cooling and discharges the water quality of water and the most different, and special
Do not limit, but, as effective ingredient concentration, it is preferably set to 0.01～10mg/L degree.
When causing the pre-treatment film of MF film device etc. to fill owing to carrying out cooling to discharge the process of water for a long time
Put or time RO film device blocks and cause the situation that obtained process water (through water) amount reduces (also
That is, during the situation that Water Sproading rate reduces), by carrying out cleaning process by stifled for these film device
Plug thing removes, and makes the process water yield recover.As the medicine used in clean process, can be according to stifled
Plug material, film raw material suitably elect, such as, and optional hydrochloric acid, sulphuric acid, nitric acid, hypochlorous acid
Sodium, sodium hydroxide, citric acid, oxalic acid etc..
[embodiment]
Hereinafter, list embodiment and the present invention made to the explanation of more specifically property, but, without departing from
On the premise of idea of the invention, the present invention is not limited to below example.
[dispersant]
The specification of the dispersant used in below example and reference example, as following.
AA/AMPS: acrylic acid and the copolymer of AMPM, acrylic acid: AMPM (mol ratio)=
70:30, weight average molecular weight 10000；
AA/HAPS: acrylic acid and the copolymer of HAPS, acrylic acid: HAPS (mol ratio)=70:
30, weight average molecular weight 8000；
AA/AMPS/N-tBAA: acrylic acid and AMPS and the ternary polymerization of N tert butyl acrylamide
Thing, acrylic acid: AMPM:N-tBAA (mol ratio)=70:20:10, weight average molecular weight 12000；
AA/MA: acrylic acid and the copolymer of maleic acid, acrylic acid: maleic acid (mol ratio)=70:
30, weight average molecular weight 25000.
[water is discharged in cooling]
For carrying out the cooling discharge water of Water Sproading process in below example and reference example, it is
The circulating cooling water system that Chiba water for industrial use is operated as former water carrying out again with concentration rate 3.5
Cooling tower draining (following, to be referred to as " draining " merely).
In this circulating cooling water system, by dispersant described in each embodiment and comparative example with
The mode of the holding concentration that intrasystem dispersant concentration can become regulation is added, and by secondary chlorine
Acid sodium (NaClO) is added in the way of intrasystem concentration of residual chlorine can be made to become 0.5mg/L,
Thus, mucus control process is carried out.
The pH of draining, is 8.5～8.9 (about 8.8).
[embodiment 1]
As pre-treatment film, use MF film, and by with water strainer, MF film device, RO film device
Order draining is processed, thus, carried out Water Sproading.
The grid aperture of water strainer, is 400 μm.MF film, is to use Kuraray company (Network ラ レ society)
" ピ ュ リ ア GS (name of product) (hydrophiling PVDF, aperture 0.02 μm, the external-compression type) " of system.
RO film, is to use chestnut field industry (Co., Ltd.) system " KROA-2032-SN (polyamide ultralow pressure
RO film) ".The clean frequency of MF film device, is set to 1 time/30 minutes.
Draining is after sequentially having carried out water flowing for water strainer, MF film device with not carrying out pH adjustment,
Entrance side at RO film device adds sulphuric acid and is adjusted to pH5.0.Similarly, entering at RO film device
Mouth side is added sodium bisulfite and is made concentration of residual chlorine become below 0.05mg/L, and by the industry of chestnut field
" Network リ バ タ (registered trade mark) IK-110 " (combined chloride system mucus control that (Co., Ltd.) makes
Preparation) add 10mg/L, and the mucus control having carried out RO film device processes.
The Water Sproading rate of MF film device and RO film device, respectively from 90%, 80% from the beginning of, amount to
Water Sproading rate be 72%.Draining, owing to organic concentration is high, therefore, MF film device and RO film
The Water Sproading rate of device can be gradually lowered to diachronism.At MF film device or the Water Sproading of RO film device
When rate becomes the situation less than 50%, device is temporarily ceased and carries out cleaning process, and once again to amount to
Water Sproading rate can become the condition of 72% and start water flowing once again.To continue 1 middle of the month with this condition
Water flowing, recycling are carried out.
In above-mentioned Water Sproading processes, the dispersant concentration of the water supply of pre-treatment film (MF film) is
The dispersant concentration of the water supply of 10.5mg/L, RO film is 10.3mg/L, and the average water in a middle of the month reclaims
Rate is 70%.
[embodiment 2]
As dispersant, replace AA/AMPS to employ AA/HAPS, in addition, by with reality
Execute the identical method of example 1 and carry out the recovery of draining.The dispersion of the water supply of pre-treatment film and RO film
Agent concentration and average Water Sproading rate, as shown in table 1.
[embodiment 3]
As dispersant, AA/AMPS is replaced to employ AA/AMPS/N-tBAA, in addition,
The recovery of draining has been carried out by method same as in Example 1.Pre-treatment film and the confession of RO film
The dispersant concentration of water and average Water Sproading rate, as shown in table 1.
[embodiment 4]
In addition to the pH of the water supply of MF film is adjusted to 5.5, by method same as in Example 1
Carry out the recovery of draining.Dispersant concentration and the average water of the water supply of pre-treatment film and RO film are returned
Yield, as shown in table 1.
[embodiment 5]
The holding concentration of the dispersant in circulating cooling water system is set to 3mg/L, and supplies water at RO film
In add add dispersant 7mg/L, in addition, carried out by method same as in Example 1
The recovery of draining.The dispersant concentration of the water supply of pre-treatment film and RO film and average Water Sproading rate, as
Shown in table 1.
[embodiment 6]
Weight average manufactured by method according to embodiment I-1 of Japanese Unexamined Patent Publication 2013-255923 publication is divided
Son amount 12000, the high molecular alkaline solution of phenol of fusing point 170 DEG C (effective ingredient concentration 16 weight %,
PH12), in draining, with the addition of 1mg/L as effective ingredient concentration, in addition, by with reality
Execute the identical method of example 1 and carry out the recovery of draining.The dispersion of the water supply of pre-treatment film and RO film
Agent concentration and average Water Sproading rate, as shown in table 1.
[reference example 1]
In addition to the pH that MF film supplies water is adjusted to 4.5, come by method same as in Example 1
Carry out the recovery of draining.The dispersant concentration of the water supply of pre-treatment film and RO film and average Water Sproading
Rate, as shown in table 1.
[reference example 2]
As pre-treatment film, employ UF film that molecular cut off is 10000 (GE company
" PW2540C30 "), in addition, carry out draining by method same as in Example 1
Reclaim.The dispersant concentration of the water supply of pre-treatment film and RO film and average Water Sproading rate, such as table 1
Shown in.
[reference example 3]
In addition to the pH that RO film supplies water is adjusted to 7.0, come by method same as in Example 1
Carry out the recovery of draining.The dispersant concentration of the water supply of pre-treatment film and RO film and average Water Sproading
Rate, as shown in table 1.
[reference example 4]
As dispersant, replace AA/AMPS to employ AA/MA, in addition, by with reality
Execute the identical method of example 1 and carry out the recovery of draining.The dispersion of the water supply of pre-treatment film and RO film
Agent concentration and average Water Sproading rate, as shown in table 1.
[reference example 5]
The holding concentration of the dispersant in circulating cooling water system is set to 1mg/L, in addition, passes through
Method same as in Example 1 and carried out the recovery of draining.The water supply of pre-treatment film and RO film
Dispersant concentration and average Water Sproading rate, as shown in table 1.
* 1: the entrance side at RO film adds and adds dispersant.
* 2: in draining, add the high molecular coagulation of phenol system help.
* 3: use the UF film of molecular cut off 10000.
According to table 1, the fact that can learn following.
According to the present invention, by can enter by the way of the dispersant of remaining effective dose in RO film supplies water
Row processes, it is possible to persistently carry out stable process with high Water Sproading rate.
Reference example 1, owing to the water supply pH of film is set to low value, therefore, the dispersant transmitance of pre-treatment film
Low, the dispersant concentration that RO film supplies water is low, and therefore, the average water response rate decreases.
Reference example 2, owing to using the UF film that molecular cut off is little, therefore, front place as pre-treatment film
The dispersant transmitance of reason film is low, and the dispersant concentration that RO film supplies water is low, therefore, and the average water response rate
Decrease.
Reference example 3, the pH supplied water due to RO film is high, there are the precipitation of calcium dirt, film at RO film
The problem of blocking, therefore, the average water response rate decreases.
Reference example 4, only possesses carboxyl owing to using as dispersant and does not have sulfonic polymer,
Therefore, if the pH that RO film supplies water is set to low value, then can occur insoluble, and can't conduct
Dispersant and work, therefore, RO film process can't stablize, the average water response rate decreases.
Reference example 5, owing to the dispersant in circulating cooling water system keeps concentration low, before having passed through the most at last
Processing film, the dispersant concentration that RO film supplies water is the lowest, and therefore, RO film processes can't be stablized, averagely
Water Sproading rate decreases.
Although using specific scheme to be described in detail for the present invention, but, for this area
For technical staff, it will be apparent that on the premise of in without departing from the intent of the present invention and scope, can carry out
Various changes.
The application is based on the Japanese Patent Application 2014-052048 proposed on March 14th, 2014 and carries out
Application, entire contents is quoted by way of reference herein.
Claims (26)
1. cooling down the recovery method discharging water, it is by including the water of pre-treatment film and reverse osmosis membrane
Recovery system is carried out from the discharge water being added with the circulating cooling water system making the dirt scattered dispersant of composition
Process and make process water return in this circulating cooling water system, it is characterised in that
In this circulating cooling water system, foregoing dispersant passes through this pre-treatment film.
2. the recovery method of water, wherein, aforementioned pre-treatment film are discharged in cooling as claimed in claim 1
The transmitance of the foregoing dispersant calculated by following numerical expression is more than 80%,
Transmitance=(pre-treatment film is through the dispersant concentration of dispersant concentration/pre-treatment film water supply of water)
×100。
3. the recovery method of water, wherein, aforementioned pre-treatment are discharged in cooling as claimed in claim 1 or 2
Film is secondary filter film or ultrafilter membrane.
4. the recovery method of the cooling discharge water as according to any one of claims 1 to 3, wherein, will
The pH of the water supply of aforementioned pre-treatment film is set to more than 5.
5. the recovery method of water is discharged in the cooling as according to any one of Claims 1 to 4, wherein, front
The molecular cut off stating pre-treatment film is more than 30000.
6. the recovery method of water is discharged in the cooling as according to any one of Claims 1 to 5, wherein, front
Stating dispersant is the polymer with sulfonic group and carboxyl.
7. the recovery method of water is discharged in cooling as claimed in claim 6, wherein, foregoing dispersant be by
Methacrylic acid and/or acrylic acid and 3-pi-allyl epoxide-2-hydroxyl-1-propane sulfonic acid and/or 2-acrylamide-2-
The copolymer of methyl propane sulfonic acid copolymerization.
8. the recovery method of the cooling discharge water as according to any one of claim 1～7, wherein, will
The pH of the water supply of aforementioned reverse osmosis membrane is adjusted to 4.0～7.5.
9. the recovery method of water is discharged in the cooling as according to any one of claim 1～8, wherein, surveys
The concentration of the foregoing dispersant of the water supply of fixed aforementioned reverse osmosis membrane, and interpolation should in this reverse osmosis membrane supplies water
Dispersant is so that this dispersant concentration becomes the concentration of regulation.
10. the recovery method of water is discharged in the cooling as according to any one of claim 1～9, wherein, surveys
The conduction of the one or more of water in fixed aforementioned discharge water, reverse osmosis membrane water supply and reverse osmosis membrane condensed water
Rate, and the Water Sproading rate of this reverse osmosis membrane is adjusted according to the measured value of this conductivity.
The recovery method of the 11. cooling discharge water as according to any one of claim 1～10, wherein,
Measure the concentration of the foregoing dispersant of aforementioned discharge water and/or reverse osmosis membrane water supply, and according to this dispersant
The measured value of concentration adjusts the Water Sproading rate of this reverse osmosis membrane.
The recovery method of the 12. cooling discharge water as according to any one of claim 1～11, wherein,
The macromolecular compound with phenol system hydroxyl is added to aforementioned discharge water.
The recovery method of the 13. cooling discharge water as according to any one of claim 1～12, wherein,
When the stopping of aforementioned water reclamation system, make aforementioned reverse osmosis membrane circulate through water, or by pure water or
Deionized water carries out water flowing, and is carrying out the operating that this reverse osmosis membrane condensed water is expelled to outside system
After, make this water reclamation system stop.
14. 1 kinds cool down the retracting device discharging water, and it possesses makes the discharge water from circulating cooling water system
The pre-treatment film device of water flowing, make this pre-treatment film device the reverse osmosis membrane device through water water flowing, with
And make this reverse osmosis membrane device return to the loop back device in this circulating cooling water system through water, its feature exists
In,
Aforementioned recirculated cooling water cording is standby will make the dirt scattered dispersant of composition add the dispersion to this water system
Agent adding set, this dispersant is can be through the dispersant of aforementioned pre-treatment film.
15. cool down the retracting device discharging water, wherein, aforementioned pre-treatment film as claimed in claim 14
The transmitance of the foregoing dispersant calculated by following numerical expression be more than 80%,
Transmitance=(pre-treatment film is through the dispersant concentration of dispersant concentration/pre-treatment film water supply of water)
×100。
16. as described in claims 14 or 15 cooling discharge water retracting devices, wherein, aforementioned before
Processing film is secondary filter film or ultrafilter membrane.
The retracting device of the 17. cooling discharge water as according to any one of claim 14～16, wherein,
The pH of the water supply of aforementioned pre-treatment film is set to more than 5.
The retracting device of the 18. cooling discharge water as according to any one of claim 14～17, wherein,
The molecular cut off of aforementioned pre-treatment film is more than 30000.
The retracting device of the 19. cooling discharge water as according to any one of claim 14～18, wherein,
Foregoing dispersant is the polymer with sulfonic group and carboxyl.
20. cool down the retracting device discharging water as claimed in claim 19, and wherein, foregoing dispersant is
By methacrylic acid and/or acrylic acid and 3-pi-allyl epoxide-2-hydroxyl-1-propane sulfonic acid and/or 2-acrylamide
The copolymer of-2-methyl propane sulfonic acid copolymerization.
The retracting device of the 21. cooling discharge water as according to any one of claim 14～20, wherein,
It possesses: the pH of the water supply of aforementioned reverse osmosis membrane is adjusted to the pH adjusting apparatus of 4.0～7.5.
The retracting device of the 22. cooling discharge water as according to any one of claim 14～21, wherein,
It possesses: the dispersant concentration of the concentration measuring the foregoing dispersant of the water supply of aforementioned reverse osmosis membrane measures dress
Putting, in this reverse osmosis membrane supplies water, adding this dispersant so that being measured by this dispersant concentration determinator
The concentration of this dispersant gone out becomes the dispersant adjusting apparatus of normal concentration.
The retracting device of the 23. cooling discharge water as according to any one of claim 14～22, wherein,
It possesses: measure aforementioned discharge water, reverse osmosis membrane supply water and reverse osmosis membrane condensed water in one or more of
The electric conductivity measuring apparatus of conductivity of water and adjust according to the measured value of this electric conductivity measuring apparatus
The Water Sproading rate adjusting apparatus of the Water Sproading rate of this reverse osmosis membrane.
The retracting device of the 24. cooling discharge water as according to any one of claim 14～23, wherein,
It possesses: the dispersant of the concentration measuring the foregoing dispersant of aforementioned discharge water and/or reverse osmosis membrane water supply is dense
Degree determinator and the measured value according to this dispersant concentration determinator adjust the water of this reverse osmosis membrane
The Water Sproading rate adjusting apparatus of the response rate.
The retracting device of the 25. cooling discharge water as according to any one of claim 14～24, wherein,
It possesses: add the coagulation assistant feeding device of phenol system hydroxyl in aforementioned discharge water.
The retracting device of the 26. cooling discharge water as according to any one of claim 14～25, wherein,
Aforementioned reverse osmosis membrane device possesses: make this reverse osmosis membrane circulate in the prime of this reverse osmosis membrane device through water
Through water circle device or make pure water or deionized water this reverse osmosis membrane device water flowing device,
With by the condensed water discharger outside this reverse osmosis membrane condensed water draining to system,
Further, this cooling is discharged the retracting device of water and is possessed: control device, this control device is in this cooling
When discharging the stopping of retracting device of water, make aforementioned reverse osmosis membrane through water in prime circulation or by pure
Water or deionized water water flowing, and carrying out the operating that this reverse osmosis membrane condensed water is expelled to outside system
After, the retracting device making this cooling discharge water stops.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-052048 | 2014-03-14 | ||
| JP2014052048A JP5773013B1 (en) | 2014-03-14 | 2014-03-14 | Cooling discharge water recovery method and recovery device |
| PCT/JP2015/051685 WO2015136992A1 (en) | 2014-03-14 | 2015-01-22 | Method for recycling cooling water effluent and recycling apparatus |
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| CN106029580A true CN106029580A (en) | 2016-10-12 |
| CN106029580B CN106029580B (en) | 2020-06-16 |
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| JP (1) | JP5773013B1 (en) |
| CN (1) | CN106029580B (en) |
| MY (1) | MY175667A (en) |
| SG (1) | SG11201607245XA (en) |
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| WO (1) | WO2015136992A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112739448A (en) * | 2018-10-05 | 2021-04-30 | 栗田工业株式会社 | Water treatment chemical for membrane and membrane treatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6128171B2 (en) | 2015-07-09 | 2017-05-17 | 栗田工業株式会社 | Cooling discharge water recovery method and recovery device |
| JP6682401B2 (en) * | 2016-08-18 | 2020-04-15 | オルガノ株式会社 | Water treatment method using reverse osmosis membrane |
| JP2019122943A (en) * | 2018-01-19 | 2019-07-25 | オルガノ株式会社 | Water treatment method and water treatment equipment |
| JP2019202246A (en) * | 2018-05-21 | 2019-11-28 | 王子ホールディングス株式会社 | Water treatment equipment and water treatment method |
| JPWO2020203527A1 (en) * | 2019-03-29 | 2021-12-02 | 栗田工業株式会社 | Antiscale agent for reverse osmosis membrane and reverse osmosis membrane treatment method |
| JP7173220B1 (en) | 2021-06-03 | 2022-11-16 | 栗田工業株式会社 | Method of operating a reverse osmosis membrane device |
| EP4122894A1 (en) * | 2021-07-22 | 2023-01-25 | Newtec Water Systems NV | A method and system for purifying water |
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| CN112739448A (en) * | 2018-10-05 | 2021-04-30 | 栗田工业株式会社 | Water treatment chemical for membrane and membrane treatment method |
| CN112739448B (en) * | 2018-10-05 | 2022-10-25 | 栗田工业株式会社 | Water treatment chemical for membrane and membrane treatment method |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5773013B1 (en) | 2015-09-02 |
| TW201600468A (en) | 2016-01-01 |
| TWI642635B (en) | 2018-12-01 |
| WO2015136992A1 (en) | 2015-09-17 |
| MY175667A (en) | 2020-07-03 |
| JP2015174030A (en) | 2015-10-05 |
| SG11201607245XA (en) | 2016-10-28 |
| CN106029580B (en) | 2020-06-16 |
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