CN106693706B - A kind of nanofiltration membrane, preparation method and application - Google Patents
A kind of nanofiltration membrane, preparation method and application Download PDFInfo
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- CN106693706B CN106693706B CN201710034544.3A CN201710034544A CN106693706B CN 106693706 B CN106693706 B CN 106693706B CN 201710034544 A CN201710034544 A CN 201710034544A CN 106693706 B CN106693706 B CN 106693706B
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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
- B01D61/027—Nanofiltration
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
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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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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Abstract
The present invention provides a kind of preparation methods of nanofiltration membrane comprising following steps: A) polymer is mixed with solvent, cosolvent, obtain polymer solution；B the polymer solution) is poured into supporting body surface, then knifing, obtained primary membrane is subjected to inversion of phases in solidification bath, obtains nanofiltration membrane；The polymer is reacted to obtain by organohalogen compounds with phenolphthalin；The organohalogen compounds are selected from dichloro diphenyl sulfone and difluoro benzophenone one or two or tetrafluoro diphenyl sulphone (DPS).The polyether sulphone or poly(aryl ether ketone) that this patent contains carboxyl using side chain are prepared for novel hydrophilic nanofiltration membrane using the phase inversion that non-solvent induces as raw material, which can be used for the water treatment procedures such as the decoloration of waste water containing dye, dyestuff recycling and purifying.The results show that such nanofiltration membrane is to the lotus negative electricity dye separative efficiency with higher and antifouling property dissolved in water body.
Description
Technical field
The present invention relates to composite membrane technology field more particularly to a kind of nanofiltration membranes, preparation method and application.
Background technique
With increasingly deficient and environmental problem the continuous aggravation of water resource, need of the people for efficient water treatment technology
Ask more more and more intense.Water treatment technology based on porous isolation technics is widely used, and has passed through purifying surface
Water, the processing modes such as industrial wastewater and seawater desalination provide fresh water for our daily lifes and industrial and agricultural production.Nanofiltration membrane is
Separating property is in the pressure-actuated isolation technics of one kind between ultrafiltration membrane and reverse osmosis membrane, be mainly characterized by can compared with
(0.1~0.6MPa) retains the organic molecule or polyvalent mineral salt ion that relative molecular weight is greater than 300 under low operating pressure, and
Monovalention selectively passes through, and main separating mechanism is aperture screening and Donnan effect；It can select according to actual needs
The nanofiltration membrane material of different charges and different pore size achievees the purpose that separation.It is simultaneous just because of its flexible and changeable adjustable denaturation
Has energy-saving and environment-friendly treatment process, so that it is widely used in the necks such as wastewater treatment, decoloration, dyestuff purifying and the softening of water
Domain.
According to the charge difference of film surface, nanofiltration membrane can be divided into positively charged nanofiltration membranes and nanofiltration membrane with negative electric charge.For making
The polymer of standby nanofiltration membrane mainly has cellulose acetate (CA), sulfonated polysulfone (SPS), sulfonated polyether sulfone (SPES), fragrant adoption
Amide (PA), polypiperazine-amide and polyvinyl alcohol (PVA) etc..Currently, being specifically included that there are many kinds of the preparation methods of nanofiltration membrane
1) composite algorithm；2) phase inversion；3) blending method；4) ontology or surface-modification method etc.；Wherein, composite algorithm is current nanofiltration film preparation
It is middle to use most and more effective method, and the main preparation methods of commercialization nanofiltration membrane；Its main means is using boundary
Face polymerization micropore support basement membrane on construct the ultra-thin active separating layer with nanoscale aperture, with reach separation, purifying
Purpose；The basement membrane of composite membrane can be inoranic membrane, be also possible to microporous polymer film, it is most common be use polysulfone ultrafiltration membrane as
The basement membrane of composite membrane.Polymer material for constructing surface-active separating layer mainly has poly- (ether) sulfone of polypiperazine-amide, sulfonation
Class, aromatic polyamide etc..Phase inversion is the composition by controlling casting solution, and through the exchange between solvent, keeps polymer molten
Liquid is by liquid-phase conversion at the process of solid phase；Using the easy to operate of phase inversion preparation nanofiltration membrane, can also adjust as needed
The composition of casting solution, realization regulate and control nanofiltration membrane pattern, aperture and its distribution.Blending method is to make two or more polymer
Multicomponent system is formed in certain solvent, and regulates and controls the compatibility between different component, to overcome single material defects, is realized
The raising of nanofiltration membrane comprehensive performance.Membrane material ontology or surface-modification method, with the continuous expansion of nanofiltration membrane application range, membrane material
The modifies surface modification with film of the sheet of material is the new method developed in recent years.It mainly include chemic modified method, low-temperature plasma
Body technique and photochemical modification method etc..Due to the denaturation versatile and flexible and adjustable of method, develops adapt to different need at present
It will be with the nanofiltration membrane material of a variety of different use.But for industrial wastewaters systems such as some salts containing high concentration, dyestuffs
Or high temperature fluid, however it remains some urgent problems, such as: a) contamination resistance of film is poor；B) heat resistance of film
Difference.
Printing and dyeing industry can generate the more waste water containing aromatic azo dyestuff in links such as dyeing, rinsings, therein
Dyestuff is not easy to be degraded under field conditions (factors), thus waste water decoloration and recovery processing difficulty it is larger.Meanwhile in order to dye, it is solid
Color or dyestuff purifying, can be added the inorganic salts of high concentration in dye solution.High concentration salinity contained in waste water is into one
Step increases the difficulty of wastewater treatment.Traditional treatment method of printing and dying wastewater includes chemical precipitation method, biological degradation method, electrochemistry
Oxidizing process, Ozonation, activated carbon adsorption and membrane separation process etc..Compared with other processing methods, membrane separation process has not
Be related to chemically reacting, operate it is relatively easy, cost is relatively low, and it is gradable processing and be used in combination with other processing methods to mention
The advantages that high water treatment effect.But it is presently available for high temperature fluid, such as weaving and dyestuff industrial waste water treatment film material
And the type and quantity of finished film are all very limited.
In document " water treatment technology ", 19 (1993) 138, describe to have the sulfonated polyether sulfone of phenolphthalein base side chain
(SPES-C) it is membrane material, has good retention with the elecrtonegativity dyestuff that phase inversion has been made to relative molecular mass greater than 360
The nanofiltration membrane of rate.But nanofiltration membrane skin thickness obtained is larger, and the flux of film is relatively low.In document Journal of
It is described in Membrane Science161 (1999) 185 and is prepared for having using poly- (2,3- benzodiazine ether sulfone ketone) (PPESK)
There is the heat-resistance type nanofiltration membrane of heat, chemistry and mechanical stability, which can carry out the separation of dyestuff (relative molecular weight 600-900),
And for high temperature fluid such as the processing of weaving and dying industrial wastewater.But due to the hydrophobic property of material itself, antipollution energy
Power needs further increase.In document Journal of Membrane Science, 477 (2015) 183-193, by polyamides
Amine composite membrane is used for treatment of dyeing wastewater, and maximum operation (service) temperature is 50 DEG C, and the pH range used is 3~10, and PA membrane
Chemically and physically stability it is also poor.In view of the temperature of actual dying is higher, soda acid range is wider, needs to be added
The adjustment equipments such as condensing plant and soda acid detection, this adds increased the costs of wastewater treatment, limit polyamide composite nanofiltration membrane
For actual dye separation process.Therefore exploitation can be used in treatment of dyeing wastewater, with resistance to mild contamination resistance
Nanofiltration membrane material is of great significance.
Summary of the invention
Present invention solves the technical problem that being to provide a kind of preparation method of nanofiltration membrane, nanofiltration membrane provided by the present application is simultaneous
Have heatproof and contamination resistance.
In view of this, this application provides a kind of preparation methods of nanofiltration membrane, comprising the following steps:
A), polymer, solvent are mixed with cosolvent, obtains polymer solution；
B), the polymer solution is poured into supporting body surface, then knifing, obtained primary membrane is water-soluble in coagulating bath
Inversion of phases is carried out in liquid, obtains nanofiltration membrane；
The polymer is reacted to obtain by organohalogen compounds with phenolphthalin；The organohalogen compounds be selected from dichloro diphenyl sulfone with
Difluoro benzophenone one or two or tetrafluoro diphenyl sulphone (DPS).
Preferably, the solvent be one of dimethylformamide, dimethyl acetamide and N-Methyl pyrrolidone or
A variety of, the cosolvent is one of ethylene glycol monomethyl ether, glycol dimethyl ether and Isosorbide-5-Nitrae-dioxane or a variety of；The solvent
Mass ratio with cosolvent is (2~5): 1.
Preferably, the solvent is N-Methyl pyrrolidone, and the cosolvent is Isosorbide-5-Nitrae-dioxane.
Preferably, the solid content of polymer is 15~25wt% in the polymer solution.
Preferably, step A) in, the mixed temperature is 50~70 DEG C；Step B) in, the polymer solution is toppled over
It is 20~30 DEG C in the temperature of supporting body surface, relative humidity is 30%~40%.
Preferably, the molar ratio of the organohalogen compounds and phenolphthalin is 1:1.
Preferably, the reaction carries out under the catalytic condition and protective atmosphere of alkali compounds, the temperature of the reaction
Degree is 150~200 DEG C, time of the reaction is 12~for 24 hours.
Present invention also provides a kind of nanofiltration membranes, including supporter and the polymeric layer for being compounded in supporting body surface；It is described
Polymeric layer is reacted to obtain by organohalogen compounds with phenolphthalin；The organohalogen compounds are selected from dichloro diphenyl sulfone and difluoro benzophenone
One or two or tetrafluoro diphenyl sulphone (DPS).
Present invention also provides prepared by the preparation method described in above scheme or nanofiltration membrane described in above scheme exists
Application on isolation and purification dyeing waste water fluid.
Preferably, the temperature of the dyeing waste water fluid is 20~95 DEG C, and pH is 1~10.
This application provides a kind of preparation methods of nanofiltration membrane to contain carboxyl for side chain during preparing nanofiltration membrane
Polyether sulphone or poly(aryl ether ketone) as preparation nanofiltration membrane raw material, by non-solvent induce phase inversion, obtained nanofiltration
Film；Above-mentioned polyether sulphone or poly(aryl ether ketone) have+have heat resistance, while the carboxyl on its side chain can improve the dissolution of polymer
Performance can also improve the hydrophily of nanofiltration membrane, and therefore, the nanofiltration membrane of the application preparation has both heatproof and antifouling property；Into one
Step, nanofiltration membrane provided by the present application is a kind of polyether sulphone or poly(aryl ether ketone) for containing carboxyl (negatively charged), to lotus negative electricity dye
Separative efficiency with higher.
Detailed description of the invention
Fig. 1 is the flow diagram of present invention preparation nanofiltration membrane；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram for the poly(aryl ether ketone) (PAEK-COOH) that the present invention synthesizes；
Fig. 3 is that the section structure scanning electron microscope for the nanofiltration membrane containing poly(aryl ether ketone) (PAEK-COOH) that the present invention synthesizes is shone
Piece；
Fig. 4 is the dynamic contamination resistance for the nanofiltration membrane that the present invention synthesizes and the antipollution exponent data figure of film.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of preparation methods of nanofiltration membrane, comprising the following steps:
A), polymer is mixed with solvent, cosolvent, obtains polymer solution；
B), the polymer solution is poured into supporting body surface, then knifing, obtained primary membrane is water-soluble in coagulating bath
Inversion of phases is carried out in liquid, obtains nanofiltration membrane；
The polymer is reacted to obtain by organohalogen compounds with phenolphthalin；The organohalogen compounds be selected from dichloro diphenyl sulfone with
Difluoro benzophenone one or two or tetrafluoro diphenyl sulphone (DPS).
The application contains the polyether sulphone (PAES-COOH, FPAES-COOH) or poly(aryl ether ketone) (PAEK- of carboxyl with side chain
COOH) be used as raw material, using non-solvent induce phase inversion be prepared for nanofiltration membrane, the nanofiltration membrane have preferable hydrophily with
Temperature tolerance makes it can be used for the decoloration of waste water containing dye, the water treatment procedures such as dyestuff recycling and purifying.
According to the present invention, the preparation raw polymer first for nanofiltration membrane is the polyether sulphone that side chain contains carboxyl
(PAES-COOH, FPAES-COOH) or poly(aryl ether ketone) (PAEK-COOH)；The polymer is by organohalogen compounds and phenolphthalin
Reaction obtains；The organohalogen compounds are selected from dichloro diphenyl sulfone and difluoro benzophenone one or two or tetrafluoro diphenyl sulphone (DPS).Specifically
, the side chain is the polyether sulphone of carboxyl or poly(aryl ether ketone) is the warp with organohalogen compounds and phenolphthalin under the conditions of base catalysis
Polycondensation reaction is prepared；It is more specific:
By organohalogen compounds, phenolphthalin, K2CO3It is added to dimethyl sulfoxide (DMS O) dry full of nitrogen atmosphere
It is reacted in 2.0L there-necked flask, is divided to water and polycondensation two processes；Then after above-mentioned reaction system being cooled to room temperature, by mixture
System pours into the 10%HCl aqueous solution of 4.5L, obtains the polymer of threadiness；Collect obtained polymer, and with water and ether
It successively washs, is then dried in vacuo, obtain the polymer of target；The organohalogen compounds are selected from dichloro diphenyl sulfone and difluorodiphenyl
Ketone one or two or tetrafluoro diphenyl sulphone (DPS).
It is above-mentioned prepare polymer during, the molar ratio of the organohalogen compounds and phenolphthalin is 1:1；The K2CO3
As catalyst, the DMSO is as solvent；The temperature of the reaction is 150~200 DEG C, in a particular embodiment, described anti-
The temperature answered is 180 DEG C, time of the reaction is 12~for 24 hours；The vacuum drying temperature is 100~150 DEG C, and the time is
12~for 24 hours；In a particular embodiment, the vacuum drying temperature is 120 DEG C, time 12h.
The experimental results showed that above-mentioned polymer provided by the invention has good dissolubility, common polarity is dissolved in
In aprotic solvent dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone and dimethyl sulfoxide；In addition, this is birdsed of the same feather flock together
Closing object also has preferable mechanical performance and a thermal stability, and 200 DEG C of glass transition temperature >, 320 DEG C of thermal decomposition temperature >.
After the primary raw material of nanofiltration membrane determines, the application has then carried out the preparation of nanofiltration membrane, prepares the temperature of nanofiltration membrane
Preferably 20~30 DEG C of degree, relative humidity is 30%~40%.The application is prepared for receiving using the phase inversion that non-solvent induces
Filter membrane, wherein the solid content of solvent, cosolvent, cosolvent and polymer has the aperture of nanofiltration membrane and surface topography and determines to make
With.Herein described solvent is selected from one of dimethylformamide, dimethyl acetamide and N-Methyl pyrrolidone or a variety of；
The cosolvent is selected from one of ethylene glycol monomethyl ether, glycol dimethyl ether and 1,4- dioxane or a variety of.In embodiment,
The solvent is N-Methyl pyrrolidone, and the cosolvent is Isosorbide-5-Nitrae-dioxane.The mass ratio of the solvent and cosolvent is
(2~5): 1, in a particular embodiment, the mass ratio of the solvent and the cosolvent is 4:1.The application is first by polymer
It being mixed with solvent, cosolvent, obtains polymer solution, the solid content of polymer is 15~25% in the polymer solution,
In embodiment, the solid content of the polymer is 18%.
After obtaining polymer solution, in order to avoid the gas in polymer solution impacts nanofiltration membrane, the application
It is preferred that by being poured upon again in supporting body surface after polymer solution degassing, and knifing is carried out, to guarantee the equal of nanofiltration membrane
Even property.The knifing is carried out according to technological means well known to those skilled in the art, is not limited particularly this application
System；Exemplary, the application carries out knifing with scraper, and the knife gap of scraper is 150 μm.The application preferably places the film after knifing
Obtained primary membrane is put into solidification bath again after so that solvent is volatilized and carries out inversion of phases to get nanofiltration membrane is arrived by 5~10s.
Standing time in above-mentioned solidification bath is 20~30min.The solidification bath is preferably deionized water.In order to go
Except the organic solvent in the film obtained after inversion of phases in coagulating bath, film is preferably removed and placed in 50 DEG C by the application from coagulating bath
Hot water in sufficiently wash away remaining organic solvent.The flow chart that the application prepares nanofiltration membrane is specific as shown in Figure 1, nanofiltration membrane
Preparation process specifically includes: on polymer solution (preparation of casting solution)-supporter in knifing-coagulating bath inversion of phases-film in water
Middle immersion-finished film.Herein described supporter be supporter well known to those skilled in the art, but for nanofiltration membrane and
Speech, the embodiment of the present application preferably use polyester non-woven fabric.
Present invention also provides a kind of nanofiltration membranes comprising supporter and the polymeric layer for being compounded in supporting body surface；Institute
It states polymeric layer and reacts to obtain with phenolphthalin by organohalogen compounds；The organohalogen compounds are selected from dichloro diphenyl sulfone and difluorodiphenyl
Ketone one or two or tetrafluoro diphenyl sulphone (DPS).
Present invention also provides application of the above-mentioned nanofiltration membrane on isolation and purification dyeing waste water fluid.It is herein described to receive
The temperature range of filter membrane used is 20~95 DEG C, and pH range is 1~10.
Poor for heat resistance existing for current nanofiltration membrane, contamination resistance difference common problem, with heat resistance
Polyarylethersulfone polymer or poly aryl ether ketone polymer side group introduce carboxyl to form hydrophilic film material.This nanofiltration membrane is being protected
While holding original polymer thermostable, but also the hydrophily of nanofiltration membrane material itself is improved, antifouling property
It is improved.Meanwhile it accurately controlling, avoiding conducive to the carboxyl-content to polymer as comonomer using phenolphthalin
Functional group content caused by functionizing method is unstable afterwards and the unstable problem of polymer batch.In addition, due to carboxyl be with
The mode of covalent bond is connected with main polymer chain, will not due to water body dissolution and souring and lead to polymer carboxyl-content
It reduces, to ensure that the performances such as dyestuff retention and the flux of nanofiltration membrane are stable, lasting.
Experimental result shows that nanofiltration membrane provided by the present application has higher permeation flux to bear electricity dye solution and cuts
It stays, flux can be stablized in 94.8L m-2h-1~115.0L m-2h-1Between, retention reaches 99.2% or more.Polymer is good
Thermal stability also gives the preferable high temperature resistance of the nanofiltration membrane, the dye that film changes temperature range between 20 DEG C~95 DEG C
Expect that the strainability of solution is stablized, there is preferable separating effect, can be used for separating dyestuff in dyeing waste water or dyestuff
Concentration and recovery.In addition, such nanofiltration membrane material shows good anti-dye pollution capacity, the four kinds of bear electricity tested are contaminated
The adsorbance of material is respectively less than 5%.
For a further understanding of the present invention, below with reference to embodiment to the preparation method of nanofiltration membrane provided by the invention with answer
With being described in detail, protection scope of the present invention is not limited by the following examples.
Embodiment 1
By phenolphthalin (0.50mol), dichloro diphenyl sulfone or tetrafluoro diphenyl sulphone (DPS) or difluoro benzophenone or dichloro diphenyl sulfone+difluoro
Benzophenone (0.50mol), K2CO3(0.85mol), DMSO (1.5L) are added to the dry 2.0L there-necked flask full of nitrogen atmosphere
In；Under nitrogen protection, 140 DEG C of condition Toluenes divide water to react 4~6h；It steams toluene and is warming up to 180 DEG C, reaction 12~for 24 hours；
After reaction system is cooled to room temperature, mixed system is poured into the 10%HCl aqueous solution of 4.5L, obtains the polymer of threadiness；
Obtained polymer is collected, and is successively washed with water and ether, then 120 DEG C of vacuum drying for 24 hours, obtain the polymer of target,
Yield is greater than 95.0%.The following are the reaction equations of the polymer of preparation:
According to above-mentioned reaction equation it is found that obtaining polyether sulphone (PAES- when reaction raw materials are phenolphthalin and dichloro diphenyl sulfone
COOH)；
When reaction raw materials are phenolphthalin and difluoro benzophenone, poly(aryl ether ketone) (PAEK-COOH) is obtained；
When reaction raw materials are phenolphthalin, dichloro diphenyl sulfone and difluoro benzophenone, mPAEK-co-nPAES-COOH is obtained；Work as m
When=n=0.5,0.5PAEK-co-0.5PAES-COOH is obtained；
When reaction raw materials are phenolphthalin and tetrafluoro diphenyl sulphone (DPS), polyether sulphone (FPAES-COOH) is obtained.
The hydrogen nuclear magnetic resonance spectrogram of PAEK-COOH is as shown in Figure 2.
Under 60 DEG C of heating conditions, the polymer P AEK-COOH mixed solvent for being dissolved in NMP and DO is formed homogeneous and transparent
Polymer solution, the solid content control of polymer are 4:1 in the mass ratio of 18wt%, NMP and DO；Above-mentioned polymer solution is taken off
After gas, maturation process, under conditions of 25 DEG C of environment temperature, relative humidity 30~40%, it is poured on non-woven fabrics, and with 150 μ
The scraper knifing of m knife gap；After solvent volatilizees 5s, primary membrane is put into solidification bath at once and keeps 20min；By film from solidifying
Remaining organic solvent is sufficiently washed away in 50 DEG C of hot water Gu being removed and placed in bath.Fig. 3 is nanofiltration membrane manufactured in the present embodiment
Section structure photo.
The detection of nanofiltration film properties: it is 23.75cm that film, which is cut into circular mounting in validity test area,2Cross-flow test pond
On, test temperature is 25 DEG C and operation test pressure is 4bar.Film needs pre- under the above pressure before carrying out official testing
Press 2h.Mainly investigate following both sides performance: pure water (dye solution) flux, dyestuff rejection.
Dye solution flux: the water volume by penetrating nanofiltration membrane effective area in the unit of account time can measure film
Dye solution permeation flux (Flux, F), unit Lm-2·h-1, formula is as follows:
Wherein V is the water volume in the unit time through film effective area, and A is the effective area of film, and t is the time.
Dyestuff rejection: under the conditions of operating pressure is 0.4MPa, concentration 100mgL-1Dyestuff for testing nanofiltration
The retention of film dyestuff, rejection (Rejection, R) are calculated by following equation:
Wherein CfAnd CpThe concentration of dyestuff respectively in mother liquor and permeate, every group of separation performance data are based on three
The average data of membrane sample is tested simultaneously.The concentration of dyestuff is measured with ultraviolet specrophotometer -1800 (SHIMADZU).It investigates
Dyestuff mainly Congo red (CR), Coomassie brilliant blue (BBR), Evans blue (EB) and Direct Red 23 (DR23).
The pH range that dye solution is adjusted using 1M HCl is 2.0~4.0；Such as emphasized without special, what this patent used
Dyes is Congo red (CR).Then, the dye solution of film is penetrated by collecting, and the dye of film is calculated separately according to formula
Expect flux, rejection, test data the results are shown in Table 1.
Embodiment 2
Nanofiltration membrane is prepared according to the method for embodiment 1, the difference is that it is molten to carry out corresponding flux, the dyestuff of retention test
Liquid, pH range are 5.0~7.0, and test data the results are shown in Table 1.
Embodiment 3
Nanofiltration membrane is prepared according to the method for embodiment 1, the difference is that it is molten to carry out corresponding flux, the dyestuff of retention test
Liquid, pH range are 8.0~10.0 (being adjusted using 1M NaOH), and test data the results are shown in Table 1.
Embodiment 4
Nanofiltration membrane is prepared according to the method for embodiment 1, the difference is that it is molten to carry out corresponding flux, the dyestuff of retention test
Liquid, pH range are > 11.0 (being adjusted using 1M NaOH), and test data the results are shown in Table 1.
Embodiment 5
Nanofiltration membrane is prepared according to the method for embodiment 1, the difference is that carrying out the dyes of corresponding flux, retention test
Direct Red 23 (DR23) is changed into, test data the results are shown in Table 1.
Embodiment 6
Nanofiltration membrane is prepared according to the method for embodiment 1, the difference is that carrying out the dyes of corresponding flux, retention test
Coomassie brilliant blue (BBR) is changed into, test data the results are shown in Table 1.
Embodiment 7
Nanofiltration membrane is prepared according to the method for embodiment 1, the difference is that carrying out the dyes of corresponding flux, retention test
Evans blue (EB) is changed into, test data the results are shown in Table 1.
Embodiment 8
Nanofiltration membrane is prepared according to the method for embodiment 1, the difference is that carrying out corresponding flux, the temperature of retention test is 40
DEG C, the dye solution pH range for retaining test is 5.0~7.0, and test data the results are shown in Table 1.
Embodiment 9
Nanofiltration membrane is prepared according to the method for embodiment 1, the difference is that carrying out corresponding flux, the temperature of retention test is 60
DEG C, the dye solution pH range for retaining test is 5.0~7.0, and test data the results are shown in Table 1.
Embodiment 10
Nanofiltration membrane is prepared according to the method for embodiment 1, the difference is that carrying out corresponding flux, the temperature of retention test is 80
DEG C, the dye solution pH range for retaining test is 5.0~7.0, and test data the results are shown in Table 1.
Embodiment 11
Nanofiltration membrane is prepared according to the method for embodiment 1, the difference is that carrying out corresponding flux, the temperature of retention test is 95
DEG C, the dye solution pH range for retaining test is 5.0~7.0, and test data the results are shown in Table 1.
Embodiment 12
Nanofiltration membrane is prepared according to the method for embodiment 1, and carries out corresponding flux, retention test, retains the dyestuff of test
PH value of solution range is 5.0~7.0.The difference is that polymer is changed to PAES-COOH, test data the results are shown in Table 1.
Embodiment 13
Nanofiltration membrane is prepared according to the method for embodiment 1, and carries out corresponding flux, retention test, retains the temperature of test
It is 60 DEG C, the dye solution pH range for retaining test is 5.0~7.0.The difference is that polymer is changed to PAES-COOH, test
Data result is shown in Table 1.
Embodiment 14
Nanofiltration membrane is prepared according to the method for embodiment 1, and carries out corresponding flux, retention test, retains the temperature of test
It is 95 DEG C, the dye solution pH range for retaining test is 5.0~7.0.The difference is that polymer is changed to PAES-COOH, test
Data result is shown in Table 1.
Embodiment 15
Nanofiltration membrane is prepared according to the method for embodiment 1, and carries out corresponding flux, retention test, retains the dyestuff of test
PH value of solution range is 5.0~7.0.The difference is that polymer is changed to PAEK0.5-co-PAES0.5-COOH, test data result
It is shown in Table 1.
Embodiment 16
Nanofiltration membrane is prepared according to the method for embodiment 1, and carries out corresponding flux, retention test, retains the temperature of test
It is 60 DEG C, the dye solution pH range for retaining test is 5.0~7.0.The difference is that polymer is changed to PAEK0.5-co-
PAES0.5-COOH, test data the results are shown in Table 1.
Embodiment 17
Nanofiltration membrane is prepared according to the method for embodiment 1, and carries out corresponding flux, retention test, retains the temperature of test
It is 95 DEG C, the dye solution pH range for retaining test is 5.0~7.0.The difference is that polymer is changed to PAEK0.5-co-
PAES0.5-COOH, test data the results are shown in Table 1.
Embodiment 18
Nanofiltration membrane is prepared according to the method for embodiment 1, and carries out corresponding flux, retention test, retains the dyestuff of test
PH value of solution range is 5.0~7.0.The difference is that polymer is changed to FPAES-COOH, test data the results are shown in Table 1.
Embodiment 19
Nanofiltration membrane is prepared according to the method for embodiment 1, and carries out corresponding flux, retention test, retains the temperature of test
It is 60 DEG C, the dye solution pH range for retaining test is 5.0~7.0.The difference is that polymer is changed to FPAES-COOH, test
Data result is shown in Table 1.
Embodiment 20
Nanofiltration membrane is prepared according to the method for embodiment 1 and carries out corresponding flux, retention test, and the temperature for retaining test is
95 DEG C, the dye solution pH range for retaining test is 5.0~7.0.The difference is that polymer is changed to FPAES-COOH, number is tested
According to the results are shown in Table 1.
1 the application nanofiltration film properties of table compare tables of data
The contamination resistance of nanofiltration membrane is mainly the anti-dye pollution capacity and anti-protein-contamination ability for passing through test film
Two aspects are illustrated by taking PAEK-COOH film as an example come what is evaluated, as a result as shown in table 2 and Fig. 4:
Table 2PAEK-COOH film surface Dye Adsorption rate tables of data
Table 2 is institute's test dye in the absorption result of film surface, and the anti-dye absorption property of film is by the way that film to be soaked in
5h in the dye solution of 100ppm is removed with water ultrasonic cleaning after taking-up and is deposited rather than the dyestuff for being adsorbed on film surface, re-test
The film of dyestuff and the absorbance of dye solution were adsorbed, is compared and is obtained by the two.It can be seen that from the absorption result of table 2, dyestuff
5% is respectively less than in the adsorbance of film surface, it is seen that film has preferable contamination resistance to dyestuff.
As shown in Fig. 4 (a), the anti-protein-contamination experiment of film passes through the protein solution (ox blood of dynamic filtration 1000ppm
Albumin, BSA) measurement；Two cycle periods are tested, the anti-pollution staining index of film can be calculated.The water flux response rate of film
FRR, gross contamination index Rt, reversible membrane fouling index RrWith irreversible membrane fouling index RirAs shown in Fig. 4 (b), the water flux of film is replied
Rate is 91.5% (FRR=91.5%), and gross contamination rate is 28.5%, and wherein reversible membrane fouling and irreversible membrane fouling are respectively 20.0%
With 8.5%.In the antipollution experiment of film, the pollution of film is mainly shown as the reversible membrane fouling as caused by concentration polarization, and by film
Irreversible membrane fouling caused by adsorbed proteins is relatively small, therefore gained nanofiltration membrane also shows good anti-protein-contamination
Energy.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of preparation method of nanofiltration membrane, comprising the following steps:
A), polymer, solvent are mixed with cosolvent, obtains polymer solution；
B), the polymer solution is poured into supporting body surface, then knifing, by obtained primary membrane in solidification bath
Inversion of phases is carried out, nanofiltration membrane is obtained；
The polymer is reacted to obtain by organohalogen compounds with phenolphthalin；The organohalogen compounds are selected from dichloro diphenyl sulfone and difluoro
Benzophenone one or two or tetrafluoro diphenyl sulphone (DPS).
2. preparation method according to claim 1, which is characterized in that the solvent is dimethylformamide, dimethyl second
One of amide and N-Methyl pyrrolidone are a variety of, and the cosolvent is ethylene glycol monomethyl ether, glycol dimethyl ether and Isosorbide-5-Nitrae-
One of dioxane is a variety of；The mass ratio of the solvent and cosolvent is (2~5): 1.
3. preparation method according to claim 1, which is characterized in that the solvent is N-Methyl pyrrolidone, described total
Solvent is 1,4- dioxane.
4. preparation method according to claim 1, which is characterized in that the solid content of polymer is in the polymer solution
15~25wt%.
5. preparation method according to claim 1, which is characterized in that step A) in, the mixed temperature is 50~70
℃；Step B) in, the polymer solution be poured into supporting body surface temperature be 20~30 DEG C, relative humidity be 30%~
40%.
6. preparation method according to claim 1, which is characterized in that the molar ratio of the organohalogen compounds and phenolphthalin is
1:1。
7. preparation method according to claim 1, which is characterized in that it is described reaction alkali compounds catalytic condition with
It being carried out under protective atmosphere, the temperature of the reaction is 150~200 DEG C, the time of the reaction is 12~for 24 hours.
8. a kind of nanofiltration membrane, including supporter and the polymeric layer for being compounded in supporting body surface；The polymeric layer is by organic halogen
Compound reacts to obtain with phenolphthalin；The organohalogen compounds are selected from dichloro diphenyl sulfone and difluoro benzophenone one or two or four
Fluorine diphenyl sulphone (DPS).
9. prepared by the described in any item preparation methods of claim 1~7 or nanofiltration membrane according to any one of claims 8 separation with
Purify the application on dyeing waste water fluid.
10. application according to claim 9, which is characterized in that the temperature of the dyeing waste water fluid is 20~95 DEG C, pH
It is 1~10.
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| CN111992043B (en) * | 2020-09-11 | 2022-06-28 | 长春工业大学 | Preparation method of carboxyl-containing polyaryletherketone ultrafiltration membrane |
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| CN106008978A (en) * | 2016-06-30 | 2016-10-12 | 吉林大学 | Carboxyl-side-group-containing polyarylether copolymers and preparation method thereof, and application of copolymers in aspect of ultrafiltration membrane hydrophilic modification |
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| WO2007006300A1 (en) * | 2005-07-09 | 2007-01-18 | Universität Stuttgart | Production of monomer, oligomer and polymer phosphonic acid esters and phosphonic and sulphonic acids by a nucleophile aromatic substitution |
| CN106008978A (en) * | 2016-06-30 | 2016-10-12 | 吉林大学 | Carboxyl-side-group-containing polyarylether copolymers and preparation method thereof, and application of copolymers in aspect of ultrafiltration membrane hydrophilic modification |
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