CN102272052A - Water-treating method and water-treating member - Google Patents
Water-treating method and water-treating member Download PDFInfo
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- CN102272052A CN102272052A CN2010800041533A CN201080004153A CN102272052A CN 102272052 A CN102272052 A CN 102272052A CN 2010800041533 A CN2010800041533 A CN 2010800041533A CN 201080004153 A CN201080004153 A CN 201080004153A CN 102272052 A CN102272052 A CN 102272052A
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- water treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/04—Feed pretreatment
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
Abstract
A problem occurring in a water-treating plant is that the adsorption of organic matters dissolved in water by the surface of a reverse osmotic membrane, which is used in a high-performance treatment, causes deterioration in the membrane performance and, therefore, a reverse osmotic membrane module should be replaced at a high frequency. To solve this problem, the organic matters causing the deterioration in the membrane performance are preliminarily removed prior to the adsorption thereof by a reverse osmotic membrane by using a hydrophobic pretreating adsorbent, which is capable of selectively adsorbing the causative organic matters, to thereby lower the replacement frequency of reverse osmotic membrane, since these causative organic matters have carbonyl group and are adsorbed by a surface having a contact angle of greater than or equal to 40 DEG C. A material of the pretreating adsorbent can selectively adsorb the causative organic matters because of having a carbonyl group at the binding site of a polymer.
Description
Technical field
The present invention relates to the preconditioning technique of reverse osmosis membrane, this reverse osmosis membrane separation is removed water dissolved organism and the ionogen that is used for advanced treatment of wastewater.
Background technology
In the advanced treatment that water purifies, use reverse osmosis membrane.Semi-permeable membranes is used on the reverse osmosis membrane surface, and the material of semi-permeable membranes roughly is divided into cellulose acetate class and aromatic polyamide class.Wherein, the reverse osmosis membrane of aromatic polyamide class is owing to water permeability and go the ionogen performance higher, is widely used in industry.Its structure adopts the composite semipermeable membrane structure that forms the aromatic polyamide film on micropore porous matter supporter more, and the thickness of aromatic polyamide part is below the 1 μ m.
Reverse osmosis membrane is used to remove organism, the ionogen that is dissolved in the water in final processing of the advanced treatment of seawater fresh waterization, the pure water preparation that is used for precise electronic apparatus manufacturings such as semi-conductor, tap water, sewage, waste water etc.
In such use, under the situation of the final processing that is used for sewage, through following treating processes water is offered reverse osmosis membrane usually.At first, by the sieve that is called screen cloth thick inclusion contained in the sewage, rubbish etc. are removed.Then, adding flocculation agent as required waits and makes the sedimentation and separating in settling bowl of tiny outstanding absurd creature such as sand.In supernatant water, also contain seston and dissolved organic matter etc., utilize microorganism to decompose.The metabolite that produces microorganism is as mud, and mud separates by the sedimentation in settling bowl or by fine filtration membrane with water.Through containing seston hardly in the sewage primary treatment water of above-mentioned processing, carry out disinfection in this stage and to wait the water quality that extremely can banish in the rivers and creeks to purify.In Japan, banish to the rivers and creeks to utilize natural purification in this stage, carry out water cycle.Yet, in the Middle East, the hinterland, continent, do not have the island etc. in rivers and creeks, wish sewage primary treatment water further purified and be used as tap water or process water utilizes again owing to do not have needed competent rivers and creeks of natural purification and lake.Reverse osmosis membrane is used for removing the dissolved organic matter and the ionogen of decontaminated water primary treatment water in this final processing.
In the sewage primary treatment water, though change according to the difference until the processing of being carried out on last stage, organism is scaled TOC (total organic carbon amount) and then contains 5～20mg/L.This is separated by reverse osmosis membrane, organism can be reduced to below the 1mg/L.
Be used for the final reverse osmosis membrane of handling of sewage,, be folded into the shape that is called spiral more in order to increase the film surface-area in the module (module).At the fixing reverse osmosis membrane of marsupial shape of the core of central authorities, be rolled into umbrella and form right cylinder.It is that 4 inches, 8 inches equal lengths are the round shape of 1m that module mainly adopts diameter.
Reverse osmosis membrane is a kind of of separatory membrane, uses the filter type of the water of separatory membrane that dual mode is arranged.A kind of is the full dose filtering type, and it is to make the mode of the full dose of the water of being supplied with by film, can not be deposited in the surface of film by the composition of film.Another kind is the cross flow filter mode, and water and face flow abreast, and a part of water penetrates film and becomes infiltration water, and the remaining state that increases with solute concentration is used as condensed water and takes out in module.In the filtration of reverse osmosis membrane, use the latter's cross flow filter mode.In this mode, reduced owing to separate out solute or concentration to the film surface and increased caused load increase.But, even also exist solute to be adsorbed on face in the cross flow filter mode, amount of seepage through the time deterioration problem.
Absorption is in the adsorptive of face, and the scale of separating out except existing near ionogen concentration face to increase (ス ケ one Le), the microorganism in the water also exist organism to carry out the adsorbed organic matter dirt the biological pollution that face is bred.Though termly face is washed with clean water, remove adsorptive by shearing force, be adsorbed with under the organic situation and can't fully remove by shearing force, cause needs to change the reverse osmosis membrane module owing to accumulate at leisure.Need be out of service for a long time when changing the reverse osmosis membrane module, in addition because the reverse osmosis membrane module can not be carried out regeneration, the reverse osmosis membrane module that need more renew becomes the reason that causes running cost to increase.
For this reason, existence has increased organism has been prolonged the method for life of reverse osmosis membrane when changing in the pre-treatment of removing in advance before the reverse osmosis membrane.As pretreatment process, the method that organism is decomposed in existence, by absorption or the flocculation organism method of removing etc., as the method for the latter's adsorb organic compound, the method for the sorbent material that use and reverse osmosis membrane identical materials constitute is disclosed in patent documentation 1.In addition, the method that the hydroaropic substance in the dissolved organic matter is removed in absorption is disclosed in patent documentation 2.
As organic activated carbon of sorbent is famous.Yet in using process of active carbon, because absorption sewage primary treatment water is contained organic almost whole, the replacing frequency of gac is higher, can not the acquisition cost advantage even therefore reduced the replacing frequency of reverse osmosis membrane.
The prior art document
Patent documentation
Patent documentation 1: No. the 3864817th, Japan's special permission
Patent documentation 2: TOHKEMY 2007-244979 number
Summary of the invention
Invent problem to be solved
In the regeneration process of sewage and waste water, under the situation of using reverse osmosis membrane to handle after the biological activity sludge treatment, the existed in the reverse osmosis membrane surface adsorption difficult decomposing organic matter that is dissolved in the water and make discharge through the time deterioration problem.Though cleaning the reverse osmosis membrane surface of deterioration with clean water can restorability, owing to be difficult to complete restore funcitons, needs to change reverse osmosis membrane.Running cost increase when the water treatment more in short-term of the life-span of reverse osmosis membrane.Remove organic method though exist by pre-treatment, be difficult to the effect that obtains to reduce cost.
The objective of the invention is to solve above-mentioned problem, by increasing the life-span that pre-treatment cheaply prolongs reverse osmosis membrane, thereby reduce the running cost that manipulation of regeneration spent of sewage and waste water.
Solve the means of problem
The sewage primary treatment water that is supplied to reverse osmosis membrane is that it is 5～20mg/L that the hard-decomposed organic that contains is converted into TOC (total organic carbon amount) via the water after the organism disaggregating treatment of microorganism.The kind of hard-decomposed organic be can not determine to a kind of.In the cross flow filter mode, be discharged from condensed water by the isolating composition of reverse osmosis membrane, the organism that can discharge can not become the worsening reason of reverse osmosis membrane, need not remove energetically.By water treatment process shown in Figure 1, by only will the organism of reverse osmosis membrane surface adsorption optionally efficient adsorb the pre-treatment sorbent material of removing well, solve this problem.
At first, analyze the adsorb organic compound on the surface that is adsorbed in reverse osmosis membrane.Owing to contain multicomponent, can not determine its composition, but the organism that contains carbonyl as can be known is easy to absorption.Other, also contain in the adsorption component Si type siloxane, contain amino component etc.
In addition, the result who studies with the adsorptive capacity of the hard-decomposed organic that is adsorbed in reverse osmosis membrane is determined, in the water in the contained hard-decomposed organic, it is about 5% that the organism that is adsorbed in reverse osmosis membrane is converted into TOC, even in water, exist organism in addition also can not be adsorbed in reverse osmosis membrane, can not become water flowing rate worsening reason.
Then, for the condition of surface of studying reverse osmosis membrane and the relation of organic adsorptive capacity, prepare wetting ability and be the reverse osmosis membrane that the contact angle of water changes, research is adsorbed in the result of the organism adsorptive capacity of film, as shown in Figure 2, determined to reduce in the hydrophilic surface adsorptive capacity.Hence one can see that, and the pre-treatment sorbent material becomes the higher above surface of contact angle 40 degree of hydrophobicity comparatively speaking by making, can optionally adsorb the organic components that is easy to be adsorbed in reverse osmosis membrane.
On the other hand, the pre-treatment sorbent material uses in water, the organism by contacting in the planar water with water, therefore in liquid, be easy to produce bubble, contact angle is on the above surface of 90 degree, thereby organism is difficult to the adsorptive power reduction of contact membranes surface.Therefore, contact angle must be in the scope of 40～90 degree.
The mechanism of reverse osmosis membrane adsorb organic compound roughly has two kinds.A kind of by molecular interaction, between the similar material of molecular structure, produce avidity.Can think that from the analysis of adsorptive the avidity between the worsening reason material of the material that contains carbonyl, amino etc. and reverse osmosis membrane is higher, it is better therefore to contain carbonyl or amino polymer in repeating unit.As an example, comprise polymeric amide, polyimide, polyester, polycarbonate, urethane, acrylic resin, urea resin, polyethylene terephthalate etc.In order to make contact angle is more than 40 degree, preferably contains carbonatoms and be hydrocarbon or aromatic nucleus more than 4 in main chain and side chain.In addition, for and type siloxane between avidity, also can preferably in main chain or side chain, contain siloxane structure.And the structure that is comprised in main chain or the side chain is not limited only to a kind, can improve adsorption efficiency by containing multiple structure.
Hold with the reverse osmosis membrane surface and have under the situation of pre-treatment sorbent material of adsorption surface of identical adsorptive power, thereby before supplying with reverse osmosis membrane with have reverse osmosis membrane identical table area more than the pre-treatment sorbent material contact and remove the organism that becomes worsening reason, can make the life-span of reverse osmosis membrane become 2 times.For the surface-area that makes sorbent material increases, can consider particle, netted, fiber, filter sieve etc. as the shape of sorbent material, but be not limited thereto.
The pre-treatment sorbent material is that surface-area is especially big under the situation of porous plastids such as filter sieve.When the surface-area of sorbent material increases, can control the volume of the equipment that increases in the pre-treatment, or can in existing equipment jar, sorbent material be set.Herein, so-called porous plastid is meant that thickness is the tabular material of 10 μ m～5mm, or has the shape of packing material in the certain space and have communicating aperture in inside so that the material that water can pass through, and this porous plastid can be used as the purposes of sorbent material.
The mode chart of the communicating aperture of the porous plastid that uses as sorbent material is shown in Fig. 6.As shown in Figure 6, when the hole that exists from certain one side of porous plastid to opposite face, the diameter that will be the direction of approximate vertical with the direction of passage of water is defined as the aperture, and the mean pore size in the face is that the material of 5～200 μ m is suitable for as sorbent material.Thereby mean pore size when 5 μ m are following then water increase at saturating out of date resistance and can not obtain to handle the water yield, or since the composition beyond the adsorption component be easy to stop up.On the other hand, when mean pore size is 200 μ m when above, the effect of making porous plastid and increase surface-area reduces, and is unhelpful for the volume that suppresses pre-processing device.
Porous plastid is owing to exist the space, has the insufficient and situation about not being able to support oneself of physical strength for the seeing through of water.In addition, even thereby under the situation of supporting oneself, also exist be accompanied by seeing through of water and be compressed, situation that transit dose that communicating aperture deforms water reduces.Therefore, preferably with porous plastid and supporter and usefulness.Especially under the situation of flat porous plastid, make the thickness direction of water by porous plastid, and with the plane parallel of porous plastid supporter is set.
Supporter, so long as have following intensity material, thickness, maintenance method, the material that does not produce leachable in the water is got final product, described intensity is meant and does not obstruct water and water is passed through, when water is seen through with 0.1Mpa with respect to the length of the length direction of inboardend, the change in location of the centre of length direction is in 5%, for example resene can use the spacer web of polyethylene, polypropylene, polyethylene terephthalate, polystyrene etc., and metal species can be used screen cloth, punch metal of stainless steel, titanium etc. etc.
The formation method of porous plastid, for example under the situation of polymeric amide, comprise that damp process or liberation method etc. modulate polyamide solution by the good solvent of consistency, and with solution coat on base material with in the water vapour that is placed on high humidity after the film forming, when polymeric amide being separated out by adding the bad solvent of consistency at water or the bad good solvent of the mid-commutation capacitive of solvent of consistency.In the case, form the following less aperture of 10 μ m.In addition, also have following method, promptly when being shaped, add whipping agent and after this add microparticals such as soluble polymkeric substance or metal oxide, can form the above bigger aperture of 10 μ m in the case.Yet the preparation method of porous-film is not limited thereto.
In addition, there is following method, promptly modifies the method for material in advance at the substrate surface of porous matter with adsorption function.Sorbent material only helps to adsorb the organism that becomes worsening reason on the surface.When sorbent material integral body is formed by the material with adsorption function, because the cost of sorbent material parts increases, therefore adopt following structure, promptly form the shape of sorbent material, and coat by material with adsorption function in outmost surface by base material such as glass, general synthetic resin cheaply.At this moment, combine firmly between base material and the material, can and have between the material of adsorption function at base material and form tack coat or reaction beginning layer with adsorption function in order to make.
Carry out the reverse osmosis membrane pre-treatment by above-mentioned sorbent material, can be in advance only the organism of the performance degradation reason of reverse osmosis membrane be optionally adsorbed and it is removed from water, in addition, because it is less for the organism accumulation of sorbent material, the replacing frequency of sorbent material is lower, obtains pretreatment process cheaply by only making outmost surface have adsorption function.
The invention effect
According to the present invention,, can reduce the running cost of the manipulation of regeneration that is used for sewage and waste water by increasing the life-span that pre-treatment cheaply prolongs reverse osmosis membrane.
Description of drawings
Fig. 1 is water treatment process figure according to an embodiment of the invention.
Fig. 2 is the contact angle on surface and the organism adsorptive capacity of worsening reason.
Fig. 3 is the relation of the number of the particle diameter of spherical adsorbent and accessible reverse osmosis membrane module.
Fig. 4 is the checking result of polymeric amide sorbing material according to an embodiment of the invention.
Fig. 5 is the checking result of polyimide sorbing material according to an embodiment of the invention.
Fig. 6 is the diagrammatic sketch of the definition in the mode chart of communicating aperture of expression porous insert and aperture.
Embodiment
Below, utilize embodiment to describe.
Fig. 1 is the sketch chart according to water treatment method of the present invention.Sewage primary treatment water is by screen cloth rubbish etc. to be removed, and makes tiny outstanding absurd creature sedimentations such as sand by adding flocculation agent etc., and then the water that utilizes Institute of Micro-biology to decompose, and it contains seston and dissolved organic matter etc.Through the sewage primary treatment water of as above handling, it is 5～20mg/L that dissolved organic matter that contains and ionogen are scaled TOC (total organic carbon amount).
In water treatment of the present invention, utilize the pre-treatment sorbent material that this sewage primary treatment water is handled, absorption removes the organism in anhydrating.
Further, make carried out pretreated treating water when exerting pressure by reverse osmosis membrane, remove the ionogen in the treating water thus, and end treatment.The ionogen of being removed is removed as condensed water.
In each embodiment, the pre-treatment sorbent material as the life-span that is used to prolong reverse osmosis membrane carries out the checking of following material, and its result is summarized among Fig. 4 and Fig. 5.Each embodiment and comparative example are following to carry out.
About the adsorptive power of material, verify by following method.As the Facing material of sorbent material, use the polymeric amide (being shown in Chemical formula 2) that obtains by mphenylenediamine and terephthalic acid (being shown in Chemical formula 1) polymerization.
This polymeric amide is representative materials a kind of of the surfacing of reverse osmosis membrane.
Thin film dipped in 0.5% aqueous solution of mphenylenediamine with the poly(vinylidene fluoride) of hydrophilization, take out and the control dry liquids after, impregnated in benzophenone-4, in the hexane solution of 4 '-dicarboxylic acid 0.1%, take out also control dry liquids.Repeat aforesaid operations 5 times, form polymeric membrane on the surface of film.This polymeric membrane is made of the polymeric amide that mphenylenediamine and terephthalic acid polymerization obtain.The film of the subsidiary polymeric membrane that obtains is cleaned drying with pure water.
On the other hand, as the organic model substance of the worsening reason of reverse osmosis membrane, prepare 0.05% aqueous solution (being shown in chemical formula 3) as amino acid whose a kind of phenylalanine.
Phenylalanine contains carbonyl, the amino as the organic feature functionality group of worsening reason, in addition since its with the skeleton of reverse osmosis membrane in contained aromatic nucleus have stronger avidity, therefore select it as model substance.
To be formed with by mphenylenediamine, benzophenone-4, the film cut-off of the polymeric membrane that 4 '-dicarboxylic acid constitutes directly is fixed on the bottom surface of stainless steel pressurizing vessel for the circle of 45mm, add phenylalanine 0.5% solution 50ml, to make itself and atmospheric pressure reduction be 0.1Mpa and pressurizeed 3 minutes by nitrogen gas pressure, so that phenylalanine is adsorbed in film surface.Concentration to the phenylalanine solution before and after the absorption is measured with the TOC meter, calculates adsorptive capacity by concentration difference, and the result is 1.9mg.
In addition, resulting high molecular water contact angle is 52 degree, is the scope of organic absorption that is suitable for the worsening reason of reverse osmosis membrane.
About the preventing polluting effect of reverse osmosis membrane, followingly confirm.With sorbent material film forming on sheet glass.Sorbent material was put into the stirring of sewage primary treatment water after 2 hours, this water conservancy is carried out pressure filtration with reverse osmosis membrane, organic concentration in the water is measured by TOC meter, when relatively having sorbent material and the adsorptive capacity when not having sorbent material reverse osmosis membrane.Its result and compares under the situation that does not have sorbent material, and the adsorptive capacity to reverse osmosis membrane reduces 60% under the situation of sorbent material existing, and has confirmed the organic effect that the worsening reason of reverse osmosis membrane is removed in absorption.At this moment, make adsorbent surface long-pending with the reverse osmosis membrane surface-area be equal area.
As the adsorbent surface material, embodiment 2 adopts mphenylenediamine and benzophenone-4, and the combination of 4 '-dicarboxylic acid (being shown in chemical formula 4) prepares polymeric amide (being shown in chemical formula 5), mensuration adsorptive capacity and contact angle with the method identical with embodiment 1.
As the adsorbent surface material, embodiment 3 adopts mphenylenediamines and hexanedioyl chlorine (being shown in chemical formula 6) to prepare polymeric amide (being shown in chemical formula 7), mensuration adsorptive capacity and contact angle with the method identical with embodiment 1.
As the adsorbent surface material, embodiment 4 adopts 1, and 6-hexanediamine and hexanedioyl chlorine (being shown in chemical formula 8) prepare polymeric amide (being shown in chemical formula 9), mensuration adsorptive capacity and contact angle with the method identical with embodiment 1.
Adsorptive capacity is 1.8mg among the embodiment 2, and contact angle is 49 degree; Adsorptive capacity is 1.4mg among the embodiment 3, and contact angle is 54 degree; Adsorptive capacity is 1.5mg among the embodiment 4, and contact angle is 63 degree.
Comparative example 1
For the organism of the worsening reason of estimating reverse osmosis membrane adsorptive capacity to the hydrophilization surface, use the hydrophilization PVDF membrane, measure adsorptive capacity similarly to Example 1.Its result, adsorptive capacity are 0.9mg, and contact angle is 14 degree.As shown in Figure 4, comparing adsorptive capacity with embodiment 1 is below 50%, uses as sorbent material for the surface that wetting ability is higher, and adsorptive capacity is also not enough.
Embodiment 5～7
As sorbing material polyimide is studied.This be because, each imide bond contains two carboxyls, can expect that its adsorptive capacity of separating organic matter for indissoluble is higher.The material of research is the polyimide precursor solution of market sale, changes into system PIX (registered trademark) L110SX (embodiment 5) and daily output chemistry system サ Application エ バ one (registered trademark) 9441 (embodiment 6) by Hitachi.In addition, in embodiment 7, studied the polymeric amide identical as a comparison with embodiment 1.
The solution dilution that will contain sorbing material, on the glass substrate by after the spin-coating method coating, 70 ℃ with solvent seasoning, under 200 ℃, be cured the sorbent material for preparing on flat board.The contact angle of the sorbent material that makes is 69 degree among the embodiment 5, is 53 degree among the embodiment 6.
On the other hand, the polymeric amide of embodiment 7, to be immersed in benzophenone-4 by the handled glass substrate of the silane coupling agent with amino end group, in the hexane solution of 4 '-dicarboxylic acid 0.1%, after taking-up and control are done, be immersed in 0.5% aqueous solution of mphenylenediamine, take out and control dried, repeat 5 times aforesaid operations, form polymeric membrane on the surface.Contact angle is 52 degree.
On these surfaces, flow through the sewage primary treatment water that is supplied to reverse osmosis membrane, and measure its adsorptive capacity.Its result, the adsorptive capacity when supplying with 0.2ml/ minute after 5 minutes are, are 0.52 μ g/cm among the embodiment 5
2, be 0.15 μ g/cm among the embodiment 6
2, be 0.08 μ g/cm among the embodiment 7
2, embodiment 5,6 is than embodiment 7 (being same material with embodiment 1) as can be known, adsorptive capacity is higher.
For embodiment 5,6, study preventing polluting effect similarly to Example 1 for reverse osmosis membrane, its result, 80% the effect that obtains among the embodiment 5 demoting, 70% effect is reduced among the embodiment 6.
Comparative example 2
As other the comparative example on hydrophilization surface, measure adsorptive capacity similarly to Example 7 for glass surface.Its result, adsorptive capacity are 0.03 μ g/cm
2, contact angle is 7 degree.
As shown in Figure 5, compare with embodiment 7, adsorptive capacity is below 40%, and the higher surface of wetting ability uses its adsorptive capacity also not enough as sorbent material.
Embodiment 8
Studied sorbent material and be the long-pending and cost of adsorbent surface under the emboliform situation.Under the adsorptive power of the adsorbent surface situation identical, can be used for the pre-treatment of the reverse osmosis membrane of identical table area with reverse osmosis membrane.When the spherical particle of non-porous plastid be that is to say that with 50% of the closeest filling space occupancy 37% is filled to module with reverse osmosis membrane and is same size, the relation of particle diameter and surface-area as shown in Figure 3.The ordinate zou of Fig. 3 is standardized with the reverse osmosis membrane surface-area of each module to the surface-area of gained, is scaled number of modules.That is to say, expression be filled with 1 module of the pre-treatment sorbent material of reverse osmosis membrane module same size the reverse osmosis membrane number of modules that can handle.
For the processing of sorbent material, big more being easy to more in the footpath of sorbent material handled.On the other hand, the number of the reverse osmosis membrane module that each pre-treatment sorbent material module institute can handle when the diameter of sorbent material was big reduces, because the increase of the volume of the caused equipment of increase of pre-treatment sorbent material.When 1 pre-treatment sorbent material module can be handled 10 reverse osmosis membrane modules at least, the sorbent material diameter was below the 250 μ m.
In the diameter range of this sorbent material, as an example with the particle diameter of 100 μ m, to make the situation of ball by sorbent material, come the budget material cost with the situation that on cheap granulated glass sphere base material, forms the sorbing material film, when sorbent material was 100k$, it is high approximately 10 times that the former with the latter is compared material cost.Because particle diameter was big more should difference big more, forming the film with adsorption function for pre-treatment sorbent material cheaply on base material is effective means.
Embodiment 9
With mean pore size is that 5 μ m, thickness are that the polymeric amide porous-film of 40 μ m cuts
Circle, what be provided as supporter in its downstream side has a perforated stainless steel of same diameter, fixes with O type circle, makes the pre-treatment sorbent material thus.To can cycle through the porous-film of this pre-treatment sorbent material through primary treatment water (the total organic carbon amount 3.7mg/L) 300ml of sewage of biological treatment at 10 minutes, measure the total organic carbon amount.In addition, equally with primary treatment water 300ml at 10 minutes internal recycle by behind the porous-film, make by after the square reverse osmosis membrane surface of water contact 100mm, placed 4 hours in the time of stirring.At this moment, to the reverse osmosis membrane pressurization, water does not filter.Measure the total organic carbon amount of the water after handling.Further, as a comparison, the total organic carbon amount that does not contact the primary treatment water of reverse osmosis membrane by the polymeric amide porous-film is measured.
Its result, the total organic carbon amount by the water behind the porous-film is reduced to 3.2mg/L, and an organic as can be known part is adsorbed on the porous-film.In addition, the total organic carbon amount by the water behind contact reverse osmosis membrane surface of the water behind the porous-film is 3.2mg/L, to being adsorbed as below the measuring limit of reverse osmosis membrane.On the other hand, the total organic carbon amount that contacts the water of reverse osmosis membrane by porous-film is not reduced to 3.4mg/L, can distinguish under the situation of not carrying out adsorption treatment, and the reverse osmosis membrane surface has been polluted in organic part absorption.Expression can prevent the pollution of reverse osmosis membrane by polymeric amide porous-film sorbent material thus.
Claims (15)
1. water treatment method, it is characterized in that, processed water is being carried out in the water treatment method of reverse osmosis membrane processing, before described biological decomposition is handled back and described reverse osmosis membrane processing, the processing that the water treatment part that makes the described processed water and the hydrophobicity of Facing material be higher than described reverse osmosis membrane contacts.
2. water treatment method according to claim 1 is characterized in that, described water treatment part is for having the water treatment part of carbonyl in the high molecular joint portion of Facing material.
3. water treatment method according to claim 2 is characterized in that, the surfacing of described water treatment part is the polyimide with imide bond.
4. water treatment method according to claim 2 is characterized in that, the surfacing of described water treatment part is the polymeric amide with amido linkage.
5. water treatment method according to claim 1 is characterized in that, contain amino, aromatic nucleus, carbonatoms in the repeating unit of the material of the Facing material of described water treatment part and be alkyl chain more than 4 any or a plurality of.
6. water treatment method according to claim 1 is characterized in that, when the Facing material of described water treatment part was formed at dull and stereotyped going up, the contact angle of its water was 40 degree～90 degree.
7. water treatment method according to claim 2 is characterized in that, described water treatment part is the porous insert with communicating aperture that water can pass through, and the mean pore size of this communicating aperture is 5～200 μ m.
8. water treatment method according to claim 7 is characterized in that, described water treatment part has described porous insert and supports the supporter of this porous insert.
9. water treatment part, it is for carrying out in the water treatment of reverse osmosis membrane processing after biological decomposition is handled processed water, before described biological decomposition is handled back and described reverse osmosis membrane processing, the water treatment part that contacts with described processed water, it is characterized in that the hydrophobicity of surfacing is higher than reverse osmosis membrane.
10. water treatment part according to claim 9 is characterized in that, has carbonyl at the polymer combining site of surfacing.
11. water treatment part according to claim 9 is characterized in that, surfacing is the polyimide with imide bond.
12. water treatment part according to claim 9 is characterized in that, surfacing is the polymeric amide with amido linkage.
13. water treatment part according to claim 9 is characterized in that, contain amino, aromatic nucleus, carbonatoms in the repeating unit of surfacing and be alkyl chain more than 4 any or a plurality of.
14. water treatment part according to claim 9 is characterized in that, when described surfacing was formed at dull and stereotyped going up, the contact angle of its water was 40 degree～90 degree.
15. water treatment part according to claim 9 is characterized in that, described surfacing is the porous insert with communicating aperture that water can pass through, and the mean pore size of this communicating aperture is 5～200 μ m.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-055886 | 2009-03-10 | ||
| JP2009055886 | 2009-03-10 | ||
| JP2009269434A JP5581669B2 (en) | 2009-03-10 | 2009-11-27 | Water treatment method, water treatment member and water treatment facility |
| JP2009-269434 | 2009-11-27 | ||
| PCT/JP2010/000890 WO2010103731A1 (en) | 2009-03-10 | 2010-02-15 | Water-treating method and water-treating member |
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| CN102272052A true CN102272052A (en) | 2011-12-07 |
| CN102272052B CN102272052B (en) | 2014-11-26 |
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| Country | Link |
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| JP (1) | JP5581669B2 (en) |
| CN (1) | CN102272052B (en) |
| WO (1) | WO2010103731A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111836678A (en) * | 2018-03-15 | 2020-10-27 | 东丽株式会社 | Fluid separation membrane |
| CN112266496A (en) * | 2020-10-29 | 2021-01-26 | 江苏厚生新能源科技有限公司 | Multilayer composite film based on polyimide modification and preparation process thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012196590A (en) * | 2011-03-18 | 2012-10-18 | Asahi Kasei Chemicals Corp | Filtration membrane, cleaning means of filtration membrane, and selection method of pretreat means |
| WO2015199017A1 (en) * | 2014-06-27 | 2015-12-30 | 日立金属株式会社 | Adsorption member |
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| JPS6146203A (en) * | 1984-08-09 | 1986-03-06 | Nitto Electric Ind Co Ltd | Composite semipermeable membrane and its manufacture |
| US5112641A (en) * | 1989-01-28 | 1992-05-12 | Kokusai Electric Co., Ltd. | Wafer transfer method in vertical cvd diffusion apparatus |
| JPH1190500A (en) * | 1997-09-25 | 1999-04-06 | Mitsubishi Rayon Co Ltd | Method for treatment of sludge |
| JPH11333454A (en) * | 1998-01-19 | 1999-12-07 | Nikkiso Co Ltd | Oily solute adsorbent and water purifier |
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| JPH0232950B2 (en) * | 1982-12-28 | 1990-07-24 | Yamamura Kagaku Kenkyusho Kk | MIZUNOSEISEIHOHO |
| JP2855668B2 (en) * | 1989-07-05 | 1999-02-10 | 三菱化学株式会社 | Polyimide separation membrane |
| JPH04305287A (en) * | 1991-04-01 | 1992-10-28 | Kubota Corp | Water treating equipment |
| JPH11314087A (en) * | 1998-05-06 | 1999-11-16 | Nikkiso Co Ltd | Apparatus for producing highly pure water |
| JP5149515B2 (en) * | 2007-02-23 | 2013-02-20 | 日本碍子株式会社 | Ink-containing wastewater treatment method |
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- 2009-11-27 JP JP2009269434A patent/JP5581669B2/en not_active Expired - Fee Related
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2010
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Patent Citations (5)
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| JPS6146203A (en) * | 1984-08-09 | 1986-03-06 | Nitto Electric Ind Co Ltd | Composite semipermeable membrane and its manufacture |
| US5112641A (en) * | 1989-01-28 | 1992-05-12 | Kokusai Electric Co., Ltd. | Wafer transfer method in vertical cvd diffusion apparatus |
| JPH1190500A (en) * | 1997-09-25 | 1999-04-06 | Mitsubishi Rayon Co Ltd | Method for treatment of sludge |
| JPH11333454A (en) * | 1998-01-19 | 1999-12-07 | Nikkiso Co Ltd | Oily solute adsorbent and water purifier |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111836678A (en) * | 2018-03-15 | 2020-10-27 | 东丽株式会社 | Fluid separation membrane |
| CN112266496A (en) * | 2020-10-29 | 2021-01-26 | 江苏厚生新能源科技有限公司 | Multilayer composite film based on polyimide modification and preparation process thereof |
| CN112266496B (en) * | 2020-10-29 | 2023-01-20 | 江苏厚生新能源科技有限公司 | Multilayer composite film based on polyimide modification and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010103731A1 (en) | 2010-09-16 |
| CN102272052B (en) | 2014-11-26 |
| JP5581669B2 (en) | 2014-09-03 |
| JP2010234353A (en) | 2010-10-21 |
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