CN106943891A - Anti-pollution composite membrane and preparation method thereof, oil hydrosol separation method - Google Patents
Anti-pollution composite membrane and preparation method thereof, oil hydrosol separation method Download PDFInfo
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- CN106943891A CN106943891A CN201710169596.1A CN201710169596A CN106943891A CN 106943891 A CN106943891 A CN 106943891A CN 201710169596 A CN201710169596 A CN 201710169596A CN 106943891 A CN106943891 A CN 106943891A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
Abstract
Anti-pollution composite membrane and preparation method thereof, oil hydrosol separation method.The present invention disclose it is a kind of can respectively for different charged oil hydrosols and carry corresponding charging performance anti-pollution composite membrane, and preparation method thereof and for the oil hydrosol separation method of different charging performances, wherein, anti-pollution composite membrane efficiently separates layer including what is scribbled on basement membrane and basement membrane inner surface, efficiently separate layer be for the electric oil hydrosol of bear is sieved and electrical charge rejection sulfonated polymer coating or for lotus positive electricity oil hydrosol is sieved and electrical charge rejection aminated macromolecule coating, there is the charging performance of negative electricity or positive electricity after further composite membrane can also being handled and adsorbed through the surfactant solution containing anion or cation.Composite membrane disclosed in this invention being removed and possess very high antifouling property for different state-of-charge oil emulsions so that the effectively oil emulsion in retention water body, improves effluent quality, and processing cost is relatively low.
Description
Technical field
The invention belongs to water treatment field, and in particular to a kind of towards containing the different resistants that electrically oil is removed of lotus in waste water
Contaminate composite film material and its preparation method and application of the material.
Background technology
Oily waste water pollution is likely to result in destructive destruction to the ecosystem, and potential danger is also resulted in health
Evil.With industrial expansion, the yield of oil product is increasing, but the lagging in development due to various technologies and management are perfect not to the utmost
Make it that a large amount of oil products enter water body etc. reason, form pollution.The pollution of oily waste water be mainly shown as influence drinking water sources and
Groundwater resources, endanger aquatic resources, are detrimental to health, and pollute air, influence production estimation, destroy natural landscape, very
To it is also possible to producing safety problem because of the oil product burning of coalescence.In view of the contaminative of oily waste water, China's regulation oil-containing
Waste water highest allows concentration of emission to be 10mg/L.
Main component in oily waste water is oil emulsion, and the removal of this part is the most key.The particle diameter of oil emulsion be 0.1~
20 microns of superfine oil droplet, due to the presence of surfactant so that it is dispersed in water body in the form of stable.It is most normal at present
The processing mode seen includes the integrated technique of physics, chemistry, biological mode, membrane technology partition method and various ways.
Water-oil separating membrane material in conventional membrane technology partition method is perforated membrane (micro-filtration and ultrafiltration), can remove breast
Carburetion, but it is relatively low to other material clearances.But its membrane material surface is easy to stick oil emulsion formation fouling membrane, causes water outlet product
Matter degradation, and film properties restorability is low, it is difficult to solve the stability of longtime running, adds the application of micro-filtration milipore filter
Cost, reduces treatment effeciency.Also it is unfavorable for the application in the long-time stability operation in the serious area of oily wastewater pollution.Relative to micro-
Filter ultrafiltration, nanofiltration (NF) membrane material is also used for the processing of oil hydrosol, NF membrane has porosity small, surface it is smooth and
The advantages of anti-pollution, it, can also part while water-oil separating is realized also with the centrifugation to multivalent ion in addition
Organics removal and high price salt, energy consumption are relatively low, are the membrane materials more excellent compared to many empty membrane material separating effects.
In various methods, coating is that oil-containing charge Dilute Polymer Solutions are applied directly onto into membrane surface, then is located
Compound one layer of membrane surface after reason plays the superthin layer of anti-pollution, and its superthin layer is most thin up to several nanometers, so that
Transmembrane pressure and operating pressure decline to a great extent；Even curface also improves the anti-fouling performance of filtering so that flux does not wane simultaneously
Subtract or faint decay.
It is general in oily waste water to exist in the way of anions and canons surfactant is stable, so with different charges
The coating composite membrane of energy can realize that oil droplet (is predominantly emulsified due to the effect such as electrical charge rejection, sieving actoion and smooth surface
Oil) effectively catching and obvious antifouling property.But the oil hydrosol point for different charging performances is not yet related at present
From composite membrane research and application, accordingly, in the preparation method and application technology of composite membrane, yet not on containing
The corresponding resistant to pollution separation membrane of the oil hydrosol of different charging performances is removed in oily waste water.
The content of the invention
In view of the problem of above-mentioned prior art is present, it is an object of the invention to propose that one kind can be directed to different lotuses respectively
Electric oil hydrosol and with corresponding charging performance anti-pollution composite membrane, and preparation method thereof and for different charging performances
Oil hydrosol separation method.Composite membrane disclosed in this invention can for different state-of-charge oil emulsions be removed and
Possess very high antifouling property, thus effectively retention water body in oil emulsion, improve effluent quality, and processing cost compared with
It is low.
What is scribbled on anti-pollution composite membrane disclosed in this invention, including basement membrane and basement membrane inner surface efficiently separates layer；Its
In, efficiently separate layer be for the electric oil hydrosol of bear is sieved and electrical charge rejection sulfonated polymer coating or for pair
Lotus positive electricity oil hydrosol carries out the aminated macromolecule coating of screening and electrical charge rejection.
Further, composite membrane has after being handled and adsorbed through the surfactant solution containing anion or cation
The charging performance of negative electricity or positive electricity.
Further, sulfonation or aminated macromolecule coating composite membrane efficiently separate thickness degree for 0.01~20 μm.It is preferred that
, thickness degree is efficiently separated for 1~20 μm.
Further, sulfonated polymer is in sulfonated polyether-ether-ketone, sulfonated polystyrene, sulfonated polyaniline or SPSF
One or more, the aminated macromolecule is the sulfonated polyether-ether-ketone of grafted amino group, amination polyether-ether-ketone, amino polyphenyl
The one or more of ethene, amination modified polyaniline or amination polysulfones.
Further, the material of basement membrane is that the high molecular polymer of suction-operated can occur with surfactant.It is preferred that
, the material of basement membrane can be selected from polyether sulfone, polysulfones, polyacrylonitrile, polyvinyl chloride, polyethylene or Kynoar；It is described molten
Agent is methanol, ethanol, acetone, N, dinethylformamide, N, N- dimethylacetylamide, hexane, one kind of ethyl acetate or several
Kind.
Further, basement membrane can be hollow-fibre membrane, tubular membrane or Flat Membrane.
Invention additionally discloses the method that this anti-pollution composite membrane is prepared by polymeric coating layer method, comprise the following steps,
Sulfonation or aminated macromolecule are dissolved in solvent coating solution is made, then coating solution is coated on basement membrane inner surface
To obtain composite membrane.
Further, obtained composite membrane is immersed and handled in the surfactant solution containing anion or cation
After absorption so that there is the charging performance of negative electricity or positive electricity after composite membrane adsorption activity agent.
Further, sulfonated polymer is in sulfonated polyether-ether-ketone, sulfonated polystyrene, sulfonated polyaniline or SPSF
One or more, the aminated macromolecule is the sulfonated polyether-ether-ketone of grafted amino group, amination polyether-ether-ketone, amino polyphenyl
The one or more of ethene, amination modified polyaniline or amination polysulfones；The solvent be methanol, ethanol, acetone, N,
Dinethylformamide, N, N- dimethylacetylamide, hexane, the one or more of ethyl acetate；Sulfonation in the coating solution
Or the mass percent concentration of aminated macromolecule is 0.01%~10%.It is preferred that, sulfonation or amination are high in coating solution
The mass percent concentration of molecule is 0.5~10%.
Further, coating time is 1~30s.
Further, surfactant is many sodium alkyl sulfonates, Alkylbenzensulfonate and many alkyl quaternary ammonium compounds
It is one or more of.
Invention additionally discloses the oil hydrosol separation method that different charging performances are directed to based on above-mentioned composite membrane, using through table
Anti-pollution composite membrane after face activator solution processing and absorption is handled water body；Or above-mentioned any type anti-pollution is compound
Water body of the film to addition compositions comprising cationic surfactants or containing anion surfactant is handled, wherein, through containing anion
The composite membrane with load electricity is used to handle containing anion surfactant after surfactant solution is handled and adsorbed
Water body, after being handled and adsorbed through compositions comprising cationic surfactants solution with charged composite membrane be used for handle fellatio from
The water body of sub- surfactant.
Further, surfactant is many sodium alkyl sulfonates, Alkylbenzensulfonate and many alkyl quaternary ammonium compounds
It is one or more of.The solvent of surfactant solution is exactly mainly the aqueous solution, towards water treatment system.General surfactant
It can be carried out absorption.
It can continue to reduce compared to film permeation flux in conventional process mode processing procedure, effluent quality declines, institute of the present invention
That brings has the beneficial effect that：
(1) anti-pollution composite membrane disclosed in this invention makes doughnut using sulfonation or aminated macromolecule coating and answered
Close NF membrane and efficiently separate layer as basement membrane inner surface, being removed for different state-of-charge oil emulsions can be directed to, and have
Very high antifouling property, and osmotic water flux is lifted to a certain extent.
(2) mode to composite membrane absorption surface activating agent can improve the flux of this material, and absorption can increase later
The carrying capacity of membrane material, also has to raising antifouling property and has certain effect.
(3) manufacture craft of anti-pollution composite membrane is simple, is prepared using existing polymeric coating layer method, and it is overall into
This is lower compared with counter-infiltration micro-filtration, ultrafiltration or NF membrane.
(4) anti-pollution composite membrane disclosed in this invention, can apply oil removing in oily waste water, in application process, relatively
The charged coating macromolecule used in current commercial nanofiltration membrane, the present invention has higher hydrophily, and operating pressure is low.Pass
The composite membrane of system, such as micro-filtration, ultrafiltration, nanofiltration, by water body is squeezed into composite membrane group under 3~10bar operating pressure
Carried out in part one or more levels infiltration water outlet, and anti-pollution composite membrane disclosed in this invention do not have to operating pressure it is special
It is required that.
(5) penetrating fluid after being combined film process through anti-pollution can reach China《Sewage discharge comprehensive standard》(GB
8978-1996) first discharge standard.
Brief description of the drawings
Fig. 1 is one-level nanofiltration device structural representation of the invention.
In figure, 1：Feed reservoir, 1-1：Penetrating fluid, 2：Primary filter, 3：Compression pump, 4：Nanofiltration component, 5：Regulation
Valve, 6：Draining valve.
Fig. 2 is two grades of nanofiltration device structural representations of the invention.
In figure, 1：Feed reservoir, 1-1：Two grades of nanofiltration liquid pools (one-level penetrating fluid), 1-2：Two grades of nanofiltration penetrating fluids, 2：It is primary
Filter, 3：Compression pump, 4：One-level nanofiltration component, 4-1：Two grades of nanofiltration components.
Embodiment
Illustrate the embodiment of invention below by way of specific instantiation, those skilled in the art can be said institute by this explanation
The content of exposure easily understands other advantages and effect of the present invention.The present invention can also pass through specific implementations different in addition
Mode is embodied or practiced, and the various details in this specification can also be based on different viewpoints and application, without departing from this
Various modifications or alterations are carried out under the spirit of invention.
A kind of anti-pollution composite membrane disclosed in embodiment, the composite membrane is to be made using polymeric coating layer method, including basement membrane
With efficiently separate layer.Basement membrane can be the milipore filter basement membrane and ultrafiltration membranes of hollow-fibre membrane, tubular membrane or Flat Membrane.Basement membrane
Scribbled on inner surface and efficiently separate layer, efficiently separate layer for sulfonated polymer coating or aminated macromolecule coating.Effectively divide
Absciss layer thickness is 0.01~20 μm, preferably 1~20 μm.
Wherein, sulfonated polymer coating membrane material carries out sieving actoion to the electric oil hydrosol of bear and electrical charge rejection is acted on,
Aminated macromolecule coating membrane material carries out sieving actoion to lotus positive electricity oil hydrosol and electrical charge rejection is acted on, to realize to difference
The removal of charging performance oil hydrosol and the raising of antifouling property, can have in the case of the lower pressure of commercial nanofiltration membrane
There is higher water yield, can be resistant to the pollution of different charged oil emulsions.
Further, the osmotic water flux of composite film material can also be improved in the case where adding surfactant, can
Efficient processing oily waste water.Obtained composite membrane can be specifically immersed in the surfactant solution containing anion or cation
After being handled and being adsorbed, the charging performance of negative electricity or positive electricity is made it have.
The preparation method of the anti-pollution composite membrane is also disclosed in embodiment, with doughnut sulfonation or aminated macromolecule
Exemplified by coating composite nanometer filtering film, it is made by following steps：Sulfonation or aminated macromolecule are dissolved in solvent, prepares and applies
Layer solution；Then coating solution is coated on nanofiltration basement membrane inner surface, obtains composite membrane；By obtained composite membrane 50~70
The heat treatment of 5~10 hours is carried out in DEG C environment, sulfonation or aminated macromolecule coating composite nanometer filtering film are obtained after drying.
Wherein, the mass percent concentration of sulfonation or aminated macromolecule is 0.01~10% in coating solution, is preferably
0.5~10%.Sulfonated polymer is selected from sulfonated polyether-ether-ketone, sulfonated polystyrene, sulfonated polyaniline, SPSF；Or amino
Change macromolecule be selected from the sulfonated polyether-ether-ketone of grafted amino group, it is amination polyether-ether-ketone, aminopolystyrene, amination modified poly-
The one or more of aniline or amination polysulfones.The solvent of coating solution is selected from methanol, ethanol, acetone, tetrahydrofuran, N, N-
One or more in dimethylformamide, N, N- dimethylacetylamide, hexane, ethyl acetate.
The thickness degree that efficiently separates of doughnut sulfonation or amination high score coating composite nanometer filtering film is 0.01 in embodiment
~20 μm, preferably 1~20 μm.Its thickness can be controlled by coating solution concentrations, coating time and coating number of times.
When the surface of above-mentioned nanofiltration basement membrane is coated, it is coated or incites somebody to action using single film inner chamber submergence coating solution
In film inner chamber, circulation is repeatedly coated coating solution.Can be multiple when especially to salt or not high dissolved organic matter rejection
Coating, to improve the rejection of dissolved matter.The rejection of material increases to 90% from 70% after repeatedly coating
Coating solution is 1~30s to the coating time of nanofiltration basement membrane.The length of coating time to thickness, osmotic water flux,
Rejection all has a certain impact.Normal conditions, coating time is longer, and thickness is thicker, and osmotic water flux is lower, and rejection is got over
Height, therefore be also required to according to demand be controlled coating time, but these amounts just change less time length to a certain extent.
The material of basement membrane is that the high molecular polymer of suction-operated can occur with surfactant.Basement membrane can be hollow
Tunica fibrosa, tubular membrane or Flat Membrane.The material of Hollow Fiber Ultrafiltration basement membrane employed in embodiment be selected from polyether sulfone, polysulfones,
Polypropylene cyanogen, polyvinyl chloride, the one or more of polyethylene or Kynoar.
The surfactant used is many sodium alkyl sulfonates, Alkylbenzensulfonate and many alkyl quaternary ammonium compound.
The present invention is composite membrane is possessed negative electricity or just using the purpose of sulfonated polymer or aminated macromolecule coating
The charging performance of electricity, improves its processing antifouling property to oil hydrosol.Due to sulfonated polymer or aminated macromolecule pair
Surfactant has certain suction-operated, so as to reach resistant to pollution while improving processing flux.It is worth noting that, absorption
The mode main purpose of surfactant is to increase the charged of membrane material later to improve the flux of this material, but adsorb
Amount, also has to raising antifouling property and has certain effect.
A kind of oil hydrosol separation method for different charging performances is also disclosed in embodiment, i.e., it is public using institute of the invention
Application of the anti-pollution composite membrane opened in oiliness sewage treatment field.The anti-pollution composite membrane be applied to water body be lotus positive electricity or
The oiliness sewage treatment of bear electricity oil emulsion, and applied to the removal of oil emulsion in water body.
Under 3~10bar operating pressure, oily waste water is squeezed into containing doughnut sulfonated polymer by compression pump
One-level or multistage infiltration water outlet are carried out in the composite nanometer filter membrane module of coating or aminated macromolecule coating.During concrete application,
Water process is penetrated using one-level when oil content concentration is less than 10,000ppm in water body, when oil content concentration is higher than in water body
Can be using two grades or more stages infiltration water process during 10,000ppm.
By the composite membrane of the present invention can effectively retain in the oil emulsion in waste water, the water body of processing oil content be 1~
10,000mg/L.In the case where the operating pressure of waste water oil removing is only 3bar~10bar, the rejection to oil is more than 95%,
Water yield is permeated big, from 10L/m2Hbar can be improved more than several times, for traditional micro-filtration milipore filter, to behaviour
Particular/special requirement is had no as pressure, higher osmotic water flux is just obtained with down in relatively low operating pressure, while obtaining pole
High oily rejection and certain salt rejection rate.
The composite membrane of the present invention is removed the charged oil in waste water by one-step method, and increase antifouling property, and necessarily
Degree lifts osmotic water flux, is a kind of simple and efficient water-oil separating material.If necessary to simultaneously remove waste water in just,
Load electricity oil, successively can be handled by the composite membrane of two kinds of charging performances, such as can carry out two steps using the device of accompanying drawing 2
Method processing.
The composite membrane manufacture craft of the present invention is simple, and the penetrating fluid after processing can reach industrial wastewater discharge standard, relatively
In micro-filtration milipore filter, with good antifouling property, during the oil hydrosol of processing surfactant stabilization, osmotic water flux is high
And there can be the lifting of certain amplitude, in addition, the extension of the processing oily waste water of composite membrane need to only increase corresponding membrane module
It can just realize.Use the compound film process oily waste water, energy effectively save cost while improvement water environment, moreover it is possible to enter one
Step removes high price salt and suspended material in oily waste water etc., and treatment effeciency is high, low operation cost, facilitates various occasions special
It is the area that oily waste water discharge capacity is big and emission request is strict.
To be illustrated more clearly that technical scheme, below in conjunction with the accompanying drawings and specific embodiment is combined to the present invention
Film oil removal process is further elaborated：
One-level nanofiltration device shown in Fig. 1, simply mistake is carried out containing the oily waste water in feed reservoir 1 by primary filter 2
Filter, enters the nanofiltration component 4 of composite membrane, forms production water and dense draining, dense draining can flow back, also may be used after being pressurizeed through compression pump 3
Directly to discharge, depending on the degree of scarcity of water resource.
Two grades of nanofiltration devices shown in Fig. 2 can further be located one-level nanofiltration infiltration water outlet by two grades of nanofiltration devices
Reason, connection and processing method are similar with one-level nanofiltration device, no longer go to live in the household of one's in-laws on getting married herein.
Embodiment 1
Sulfonated polyether-ether-ketone is dissolved in methanol solution and prepares the solution that sulfonated polymer concentration is 0.01%.Using single
Coating is coated on PVDF flat board basement membranes (inner and outer diameter is respectively 0.9mm, 1.4mm), by film in 65 degrees Celsius of environment
Reason obtains the composite membrane with effective coating (efficiently separating layer), effective painting of sulfonated polyether-ether-ketone composite nanometer filtering film for 6 hours
Thickness degree is 0.01 μm, and the NF membrane is assembled into hollow fiber film assembly using process progress oil removing as shown in Figure 1.
Material liquid is oily waste water, the oil emulsion that addition dodecyl sodium sulfate is stablized.Here and below several realities
The synthetic emulsified oil that experiment is used in example is applied, the main component of waste water in itself is exactly to emulsify in actual use
Oil.Implementing regulation compression pump and valve in running makes pressure reach 3bar.Oil content can not be detected in infiltration water, be met
《Sewage discharge comprehensive standard》(GB 8978-1996) first discharge standard.Osmotic water flux is undamped during plant running,
And have the rising of certain amplitude.The minimum 34.5LMH of the water yield of membrane module, i.e. 11.5L/m in device2·h·bar。
Embodiment 2
Sulfonated polyether sulfone is dissolved in the coating solution that methanol solution prepares polymer concentration 5.0%, PES is coated to
Film is post-processed 6 hours in (basement membrane MWCO is 100000Da, and boss ratio is 0.9/1.3mm), 65 degree of environment on flat board basement membrane
Composite membrane is obtained, effective coating layer thickness of sulfonated polyether-ether-ketone composite nanometer filtering film is 1 μm, and the NF membrane is assembled into composite membrane group
Part carries out oil removing using the shown process of such as accompanying drawing 1.
Material liquid is oily waste water, the oil emulsion that addition sodium cetanesulfonate is stablized.Implement to adjust in running
Section compression pump and valve make pressure reach 6bar.Oil content can not be detected in infiltration water, be met《Sewage discharge comprehensive standard》(GB
8978-1996) first discharge standard.Osmotic water flux is undamped during plant running, and has the rising of certain amplitude.Device
The minimum 69LMH of water yield of middle membrane module.
Embodiment 3
Sulfonated polyether-ether-ketone is dissolved in the coating solution that methanol solution prepares polymer concentration 10%, using circulation coating
It is coated on polypropylene cyanogen tubular type basement membrane (internal-and external diameter is 0.7/1.1mm), 60 degree or so hot-air blowings are combined for 6 hours
Film, effective coating layer thickness of sulfonated polyether-ether-ketone composite nanometer filtering film is 20 μm, and the NF membrane is assembled into composite membrane component utilizes
Shown process such as accompanying drawing 1 carries out oil removing.
Material liquid is oily waste water, the oil emulsion that addition myristyl sodium sulfonate is stablized.Implement to adjust in running
Section compression pump and valve make pressure reach 8bar.Oil content can not be detected in infiltration water, be met《Sewage discharge comprehensive standard》(GB
8978-1996) first discharge standard.Osmotic water flux is undamped during plant running, and has the rising of certain amplitude.Device
The minimum 80.5LMH of water yield of middle membrane module.
Embodiment 4
Aminopolystyrene is dissolved in the coating solution that methanol solution prepares polymer concentration 1.5%, applied using circulation
Layer is coated on polypropylene cyanogen Hollow Fiber Ultrafiltration basement membrane (internal-and external diameter is 0.7/1.1mm), and 60 degree or so hot-air blowings 6 are small
When obtain composite membrane, effective coating layer thickness of aminopolystyrene composite nanometer filtering film is 5-6 μm, the NF membrane is assembled into compound
Membrane module carries out oil removing using the shown process of such as accompanying drawing 1.
Material liquid is oily waste water, the oil emulsion that addition tetradecane dimethyl benzyl ammonium chloride is stablized.Implement operation
During regulation compression pump and valve pressure is reached 8bar.It is 3mg/L to permeate oil content in water, is met《Sewage discharge is comprehensive
Standard》(GB 8978-1996) first discharge standard.Osmotic water flux is undamped during plant running.Membrane module in device
The minimum 80.5LMH of water yield.
Advantage in embodiment is to use hollow-fibre membrane for basement membrane, is made using sulfonation or aminated macromolecule coating
Hollow fiber compound nanofiltration membrane, by the application of its oil removing in oily waste water.The manufacture craft of NF membrane is simple, is permeated after processing
Liquid can reach China《Sewage discharge comprehensive standard》(GB 8978-1996) first discharge standard, and have in processing procedure
Fabulous antifouling property, while lifting osmotic water flux to a certain extent.Relative to current commercial nanofiltration membrane, operation pressure
Power is low, and water flux is high, can be effectively cost-effective while oil-water separation emulsion improves sewage discharge.
The above, only presently preferred embodiments of the present invention, and any formal and substantial limit value of non-invention should
When pointing out, for those skilled in the art, on the premise of the inventive method is not departed from, if can also make
Dry to improve and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
In the case of not departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are the Equivalent embodiments of the present invention；Meanwhile, all substantial technologicals pair according to the present invention
The variation, modification and evolution for any equivalent variations that above-described embodiment is done, still fall within the scope of technical scheme
It is interior.
Claims (10)
1. a kind of anti-pollution composite membrane, it is characterised in that：Layer is efficiently separated including what is scribbled on basement membrane and basement membrane inner surface；Its
In, efficiently separate layer be for the electric oil hydrosol of bear is sieved and electrical charge rejection sulfonated polymer coating or for pair
Lotus positive electricity oil hydrosol carries out the aminated macromolecule coating of screening and electrical charge rejection.
2. composite membrane as claimed in claim 1, it is characterised in that：The composite membrane is lived through the surface containing anion or cation
Property agent solution handled and adsorbed after there is the charging performance of negative electricity or positive electricity.
3. composite membrane as claimed in claim 1, it is characterised in that：Sulfonation or aminated macromolecule coating composite membrane are efficiently separated
Thickness degree is 0.01~20 μm.
4. the composite membrane stated such as claim 3, it is characterised in that：Thickness degree is efficiently separated for 1~20 μm.
5. composite membrane as claimed in claim 1, it is characterised in that：The sulfonated polymer is sulfonated polyether-ether-ketone, sulfonation gathers
One or more in styrene, sulfonated polyaniline or SPSF, the aminated macromolecule gathers for the sulfonation of grafted amino group
Ether ether ketone, amination polyether-ether-ketone, aminopolystyrene, one kind or several of amination modified polyaniline or amination polysulfones
Kind.
6. composite membrane as claimed in claim 1, it is characterised in that：The material of the basement membrane is that can occur with surfactant
The high molecular polymer of suction-operated.
7. a kind of preparation method of anti-pollution composite membrane, it is characterised in that：By polymeric coating layer method prepare as claim 1 to
Anti-pollution composite membrane described in 6 any one.
8. the preparation method of composite membrane as claimed in claim 7, its feature exists：By the immersion of obtained composite membrane containing anion or
After being handled and adsorbed in the surfactant solution of cation so that there is negative electricity or positive electricity after composite membrane adsorption activity agent
Charging performance.
9. the preparation method of composite membrane as claimed in claim 7 or 8, its feature exists：The sulfonated polymer is sulfonated polyether
One or more in ether ketone, sulfonated polystyrene, sulfonated polyaniline or SPSF, the aminated macromolecule is grafting ammonia
Sulfonated polyether-ether-ketone, amination polyether-ether-ketone, aminopolystyrene, amination modified polyaniline or the amination polysulfones of base
One or more；The solvent be methanol, ethanol, acetone, N, dinethylformamide, N, N- dimethylacetylamide, hexane,
The one or more of ethyl acetate；The mass percent concentration of sulfonation or aminated macromolecule is 0.01% in the coating solution
~10%.
10. a kind of oil hydrosol separation method for different charging performances, it is characterised in that：Using such as claim 1 to 6 times
Anti-pollution composite membrane described in meaning one is handled water body；Or using the resistant as described in claim 1 to 6 any one
Dye composite membrane is handled adding compositions comprising cationic surfactants or water body containing anion surfactant, wherein, through containing
The composite membrane with load electricity is lived for handling containing anionic surface after anionic surfactant solution is handled and adsorbed
Property agent water body, after being handled and adsorbed through compositions comprising cationic surfactants solution with charged composite membrane be used for handle
The water body of compositions comprising cationic surfactants.
Priority Applications (1)
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| CN110980883A (en) * | 2019-12-24 | 2020-04-10 | 天津膜天膜科技股份有限公司 | Method for removing divalent ions in water by whole membrane method |
| CN111072106A (en) * | 2018-10-19 | 2020-04-28 | 日东电工株式会社 | Water treatment system and water treatment method |
| CN111229061A (en) * | 2020-01-17 | 2020-06-05 | 西安交通大学 | Porous graphene separation membrane and preparation method thereof |
| WO2023115735A1 (en) * | 2021-12-24 | 2023-06-29 | 广州兆瑞医学生物科技有限公司 | Surface-modified membrane and application thereof |
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| CN111072106A (en) * | 2018-10-19 | 2020-04-28 | 日东电工株式会社 | Water treatment system and water treatment method |
| CN110980883A (en) * | 2019-12-24 | 2020-04-10 | 天津膜天膜科技股份有限公司 | Method for removing divalent ions in water by whole membrane method |
| CN111229061A (en) * | 2020-01-17 | 2020-06-05 | 西安交通大学 | Porous graphene separation membrane and preparation method thereof |
| CN111229061B (en) * | 2020-01-17 | 2021-11-19 | 西安交通大学 | Porous graphene separation membrane and preparation method thereof |
| WO2023115735A1 (en) * | 2021-12-24 | 2023-06-29 | 广州兆瑞医学生物科技有限公司 | Surface-modified membrane and application thereof |
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