CN106621841A - Preparation method of positively charged nanofiltration membrane - Google Patents
Preparation method of positively charged nanofiltration membrane Download PDFInfo
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- CN106621841A CN106621841A CN201611269832.9A CN201611269832A CN106621841A CN 106621841 A CN106621841 A CN 106621841A CN 201611269832 A CN201611269832 A CN 201611269832A CN 106621841 A CN106621841 A CN 106621841A
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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
- B01D69/02—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/16—Membrane materials having positively charged functional groups
Abstract
The invention relates to a preparation method of a positively charged nanofiltration membrane. The preparation method comprises the steps of preparation of a pretreatment base membrane, preparation of a coating solution, coating and solidifying. The positively charged nanofiltration membrane has good stability and leaching resistance. According to the preparation method, the charge performance and the hydrophilic-hydrophobic property of the positively charged nanofiltration membrane can be improved through adjusting components and proportions of a copolymer monomer and the water flux of the positively charged nanofiltration membrane can be effectively improved. The preparation method of the positively charged nanofiltration membrane is simple, the production cost is low, the used functional polymer material is simple and available and has a good industrial application prospect.
Description
【Technical field】
The invention belongs to technical field of membrane separation.More particularly it relates to a kind of preparation side of positively charged nanofiltration membranes
Method.
【Background technology】
Membrane separation technique due to investment it is little, take up an area less, pollution-free, efficient, energy-conservation the features such as be developing progressively as one
Plant new material isolation and purification method.Wherein, nanofiltration drives membrane separating process as a kind of novel pressure, it has also become membrance separation
Focus in technical research.Nanofiltration is a kind of film between reverse osmosiss and ultrafiltration point grown up after the eighties in 20th century
From technology, early stage is referred to as " low pressure reverse osmosis " or " loose reverse osmosiss " isolation technics.The molecular cut off of NF membrane is 200~
2000Da, suitably separates the low relative molecular mass Organic substance such as nanoscale dissolved constituent and retention saccharide, therefore is referred to as " to receive
Filter ".Nanofiltration membrane separation material relies primarily on two kinds of effects of aperture screening and Coulomb repulsion, therefore material can be selected whereby
Selecting property is separated.Because NF membrane has the separating effect of this uniqueness, water softening, wastewater treatment, biology are widely used in
Separation and purification of materials process in the fields such as pharmacy, petrochemical industry.
Most of commercialization NF membrane is composite membrane and for bear electrolemma.NF membrane is mainly by porous support layer and surface
Functional layer is constituted.At present, mainly using polyamide-based PA films obtained in interfacial polymerization, and using vinegar obtained in phase inversion
The films such as poly- (ether) sulfone of acid cellulose CA, sulfonation, sulfonated polyether-ether-ketone.The former salt rejection rate is high, flux is big, operating pressure requirement is low,
But intolerant to free chlorine, ant-scaling and pollution capacity are poor.The latter's making is easier to, low price, and resistance to free chlorine, face are smooth to be difficult
Fouling and pollution, but poor heat resistance, easily generation chemistry and biodegradation.Generally require in actual applications to use Positively charged membrane,
For example high volence metal ion recovery, electroplating wastewater processing, containing radioactive metal ion process etc. be required for using Positively charged membrane.It is existing
The functional polymer material and preparation method that exploitation prepares positively charged nanofiltration membranes is also little.
Surface-coated method is a kind of simple film-forming method, and this method is simply directly coated on functional polymer solution
In membrane surface, then immobilization is processed.Structure of composite membrane and performance obtained in this method are easy to regulation and control, can be after adopting
Crosslinking Treatment mode and control crosslinked fluid crosslinking degree come improve and regulate and control made Positively charged composite nanofiltration membrane stability and
Leachability.Simultaneously surface-coated method filming technology is simple, it is easy to accomplish industrialization production.CN 02103752 discloses one kind will
Polyacrylate and amino esters polymer is coated in membrane surface the method for preparing positively charged nanofiltration membranes by cross-linking method.But should
Crosslinking time needed for method is 5h, and long-time crosslinking causes made composite nanometer filtering film industrialization continuous prodution difficult to realize,
Also exist using problem of environmental pollution caused by organic solvent simultaneously.
For the deficiencies in the prior art, the present inventor on the basis for summarizing prior art, by lot of experiments
With analysis, a kind of preparation method of Positively charged composite nanofiltration membrane is developed.
【The content of the invention】
[technical problem to be solved]
It is an object of the invention to provide a kind of preparation method of positively charged nanofiltration membranes.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of preparation method of positively charged nanofiltration membranes.
The step of preparation method, is as follows:
A. pretreatment basement membrane is prepared
Compound concentration be by weight 0.1~0.3% polyvinyl alcohol water solution and concentration for by weight 0.1~
0.3% Tween solution;Polyvinyl alcohol water solution is with Tween solution according to volume ratio 1:0.8~1.2 mix homogeneously, obtains
Mid-coating liquid;Then, described mid-coating liquid is coated uniformly on porous support layer, is dried, obtain described
Pretreatment basement membrane;
B. coating liquid is prepared
2~5 weight account polyethylene alcohol and 3.6~4.4 weight portion cationic polyelectrolytes are added in 100 weight portion water,
Mixing, the solution mineral acid or inorganic base aqueous solution that dissolving is obtained adjusts its pH value to 2, then the solution is heated to into temperature
75~80 DEG C of degree, obtains a kind of mixed copolymer;Then
Add 0.5~3.0 weight portion glutaraldehyde toward described mixed copolymer, dissolving, mix homogeneously enters at room temperature
Row 7.2~8.2min of precrosslink, is then used by originally being water-cooled to room temperature, obtains described coating liquid;
C. coating and solidification
The coating liquid that step B is obtained is coated uniformly on the pretreatment basement membrane that step A is obtained, then in 70~75 DEG C of temperature
Down plus heat extraction water, baking and curing, described positively charged nanofiltration membranes are obtained.
A preferred embodiment of the invention, in step, described porous support layer selected from polysulfones, poly- third
Alkene nitrile or vinylidene difluoride planar ultrafiltration membrane.
Another kind of preferred implementation of the invention, in step, described mid-coating liquid temperature 20~
It is coated under conditions of 30 DEG C and relative air humidity 55~65%, the coated weight of the mid-coating liquid is 28~43g/
m2。
Another kind of preferred implementation of the invention, in step, the mid-coating liquid is in temperature 60~80
10~25min is dried under conditions of DEG C.
Another kind of preferred implementation of the invention, in stepb, described mineral acid is hydrochloric acid, sulphuric acid, nitric acid
Or phosphoric acid;The concentration of the inorganic acid aqueous solution is 1~4M.
Another kind of preferred implementation of the invention, in stepb, described inorganic base is sodium hydroxide, hydrogen-oxygen
Change potassium, sodium carbonate or potassium carbonate;The concentration of the inorganic base aqueous solution is 1~5M.
Another kind of preferred implementation of the invention, in stepb, described cationic polyelectrolyte selected from sun from
Subbundle element, polyethyleneimine, poly diallyldimethylammonium chloride, polyvinyl chlorimide or diallyl dimethyl ammoniumchloride.
Another kind of preferred implementation of the invention, in step C, the coating liquid is in the epilamellar painting of pretreatment
The amount of covering is 40~55g/m2。
Another kind of preferred implementation of the invention, in step C, described coating liquid 20~30 DEG C of temperature with
It is coated under conditions of relative air humidity 55~65%.
Another kind of preferred implementation of the invention, in step C, described baking and curing is in temperature 60~80
10~25min of baking and curing under conditions of DEG C.
The present invention is described in more detail below.
The present invention relates to a kind of preparation method of positively charged nanofiltration membranes.
The step of preparation method, is as follows:
A. pretreatment basement membrane is prepared
Compound concentration be by weight 0.1~0.3% polyvinyl alcohol water solution and concentration for by weight 0.1~
0.3% Tween solution;Polyvinyl alcohol water solution is with Tween solution according to volume ratio 1:0.8~1.2 mix homogeneously, obtains
Mid-coating liquid;Then, described mid-coating liquid is coated uniformly on porous support layer, is dried, obtain described
Pretreatment basement membrane;
In the present invention, the Main Function of polyvinyl alcohol is the adhesion for strengthening positive electrocoat and porous support layer, is solved
Coating is lost in sex chromosome mosaicism.The Main Function of tween is the effect of surfactant, improves polyvinylalcohol coats uniformity.
In the present invention, if the concentration of polyvinyl alcohol water solution is more than 0.1~0.3% scope, intervening layers
The larger film that is easily caused of the viscosity of liquid is not respectively formed defect;
If the concentration of Tween solution is more than 0.1~0.3% scope, easily formation coat is thicker causes to apply break
Fall into;
Inter-coat is easily caused if when the volume ratio of polyvinyl alcohol water solution and Tween solution exceedes the scope
Liquid adhesion is weaker, it is impossible to solve the loss sex chromosome mosaicism of coating.
According to the present invention, described porous support layer is selected from polysulfones, polyacrylonitrile or vinylidene difluoride planar ultrafiltration membrane.This
The flat plate ultrafiltration membrane that invention is used is the product sold in the market, such as by auspicious anode membrane technology (Beijing) company limited of middle section
With trade name polysulfones PS ultrafilter membranes sell polysulphone flat ultrafiltration membrane, by Sepro companies of the U.S. with trade name PAN50 sell gather
Acrylonitrile flat plate ultrafiltration membrane, Chemical Industry Science Co., Ltd is ranked by Shanghai with trade name ML_DF series of micropores film sell it is poly- partially
Fluoride flat ultrafilter membrane.
In the present invention, described mid-coating liquid is in 20~30 DEG C of temperature and the bar of relative air humidity 55~65%
It is coated under part, the coated weight of the mid-coating liquid is 28~43g/m2。
In the present invention, the coating equipment for using during coating is the coating equipment being usually used in the art, for example
The extrusion coated machine of slit or roll coater.
In coating, if the coated weight of the mid-coating liquid exceedes described scope, mid-coat layer is blocked up
The positive electrocoat of lotus is caused to be easy to run off.
According to the present invention, the mid-coating liquid is dried 10~25min in temperature under conditions of 60~80 DEG C of temperature,
Obtain described pretreatment basement membrane.
B. coating liquid is prepared
2~5 weight account polyethylene alcohol and 3.6~4.4 weight portion cationic polyelectrolytes are added in 100 weight portion water,
Mixing, the solution mineral acid or inorganic base aqueous solution that dissolving is obtained adjusts its pH value to 2, then the solution is heated to into temperature
75~80 DEG C of degree, obtains a kind of mixed copolymer;Then
Add 0.5~3.0 weight portion glutaraldehyde toward described mixed copolymer, dissolving, mix homogeneously enters at room temperature
Row 7.2~8.2min of precrosslink, is then used by originally being water-cooled to room temperature, obtains described coating liquid;
In this step, the mixed copolymer that polyvinyl alcohol is obtained with cationic polyelectrolyte is the lotus through precrosslink
Positive electricity coating liquid.
Described cationic polyelectrolyte is selected from cationic cellulose, polyethyleneimine, poly diallyldimethylammonium chloride, polyethylene
Base chlorimide or diallyl dimethyl ammoniumchloride.The cationic polyelectrolyte that the present invention is used is to sell in the market
Product, the cation for example sold with trade name cationic cellulose JR400 by Guangzhou Nan Jia Chemical Industry Science Co., Ltd is fine
Dimension element, the poly diallyldimethylammonium chloride sold with trade name poly diallyldimethylammonium chloride by lark prestige company, by lark prestige company with business
The name of an article polyvinyl chlorimide sale polyvinyl chlorimide, by lark prestige company with trade name polydiene dimethylamine
The diallyl dimethyl ammoniumchloride of ammonium chloride sale.
In the present invention, when such as the amount of pectin/polyvinyl alcohol is more than 2~5 weight portion, then polyethylene is remained after precrosslink reaction
Alcohol is larger compared with most lotus positive electricity coating fluid viscosity to cause film uneven;If the amount of cationic polyelectrolyte is more than 3.6~4.4 weights
During amount part, then the finer and close impact membrane flux of the positive electrocoat of lotus;
In this step, described mineral acid is hydrochloric acid, sulphuric acid, nitric acid or phosphoric acid;The inorganic acid aqueous solution it is dense
Degree is 1~4M.
Described inorganic base is sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate;The concentration of the inorganic base aqueous solution
It is 1~5M.
In the present invention, the dominant response of described mixed copolymer and glutaraldehyde is the hydroxyl and penta in mixed copolymer
Aldehyde radical condensation reaction in dialdehyde forms stable ehter bond.
In the present invention, if glutaraldehyde addition exceedes described scope, it is easily caused crosslinking and excessively causes to apply
Cover.
C. coating and solidification
The coating liquid that step B is obtained is coated uniformly on the pretreatment basement membrane that step A is obtained, then in 70~75 DEG C of temperature
Down plus heat extraction water, baking and curing, described positively charged nanofiltration membranes are obtained.
According to the present invention, the coating liquid is 40~55g/m in the epilamellar coated weight of pretreatment2.If coated weight surpasses
Described scope is crossed, then membrane coat is thicker causes membrane flux to reduce.
In this step, described coating liquid is under conditions of 20~30 DEG C of temperature and relative air humidity 55~65%
It is coated.
Described baking and curing is 10~25min of baking and curing under conditions of 60~80 DEG C of temperature.
The step is coated the equipment for using as described in the foregoing, and the step carries out baking and curing process to be made
Equipment is all the coating equipment being usually used in the art, the extrusion coated machine of such as slit or roll coater.
Positively charged nanofiltration membranes of the present invention are to divalent salts CaCl2Have a higher salt rejection rate, and the salt rejection rate of monovalent salt NaCl compared with
It is low.Determined according to reverse osmosis membrane method of testing national standard analysis method, such as under 25 DEG C, 0.41MPa pressure,
250ppmCaCl2Solution salt rejection rate commonly reaches 80~95%, and the salt rejection rate of monovalent salt NaCl is generally 27~31%, water flux
For 35~56L/ (m2·h).Additionally, PEG600 (500ppm) molecular cut off of positively charged nanofiltration membranes of the present invention is up to 90%
(25 DEG C, 0.41MPa).Therefore, positively charged nanofiltration membranes of the present invention can be used for the differences such as the recovery of water softening, wastewater treatment and metal
Field, has broad application prospects.
The present invention can have positively charged nanofiltration membranes different by adjusting monomeric species and its ratio in coating liquid
Performance.Preparation method of the present invention can effectively shorten crosslinking time, improve speed of production, improve positively charged nanofiltration membrane flux, carry
High positively charged nanofiltration membranes resistance leachability and stability, it is easy to continuous prodution, and non-environmental-pollution.
[beneficial effect]
The invention has the beneficial effects as follows:
(1) present invention by adjustment polymer monomers composition and proportioning just can improve the charge of positively charged nanofiltration membranes with
Hydrophilic and hydrophobic, referring specifically to the Zeta potential in embodiment and contact angle characterize data.Additionally, being made by precrosslink and rear crosslinking
The water flux of positively charged nanofiltration membranes of the present invention can be effectively improved with coat thickness is adjusted.
(2) positively charged nanofiltration membranes of the invention have good stability and resistance leachability, referring specifically to embodiment part
Membrane component calcium chloride longtime running flux and salt rejection rate finally stablize data.Therefore, positively charged nanofiltration membranes of the invention can be with
It is advantageously used in water softening, wastewater treatment and other purposes, separating property is stable, applied widely.
(3) the preparation method process of positively charged nanofiltration membranes of the present invention is simple, and coating, filming technology are simple, aqueous solvent cleaning
Environmental protection, low production cost, the functional polymer material that uses of the present invention is simple and easy to get, thus preparation method of the present invention have it is good
Good prospects for commercial application.
【Specific embodiment】
The present invention is will be better understood that by following embodiments.
Embodiment 1:The preparation of positively charged nanofiltration membranes
The implementation steps of the embodiment are as follows:
A. pretreatment basement membrane is prepared
Compound concentration is the tween water that by weight 0.1% polyvinyl alcohol water solution and concentration are by weight 0.1%
Solution;Polyvinyl alcohol water solution is with Tween solution according to volume ratio 1:0.8 mix homogeneously, obtains mid-coating liquid;Then,
According to the coated weight 34g/m of the mid-coating liquid2, described mid-coating liquid is relatively wet in 20 DEG C of temperature and air
It is coated uniformly on polysulphone flat ultrafiltration membrane porous support layer under conditions of degree 58%, is dried under conditions of 80 DEG C of temperature
10min obtains described pretreatment basement membrane;
B. coating liquid is prepared
2 weight account polyethylene alcohol and 3.6 weight portion cationic cellulose cationic polyelectrolytes are added to into 100 weight portion water
In, mixing, dissolving, the solution for obtaining the hydrochloric acid mineral acid or concentration 3M sodium hydroxide inorganic base aqueous solution of concentration 1M are by its pH
Value is adjusted to 2, then the solution is heated to into 75 DEG C of temperature, obtains a kind of mixed copolymer;Then
Add 2.0 weight portion glutaraldehydes toward described mixed copolymer, dissolve, mix homogeneously is carried out at room temperature pre-
Crosslinking 7.2min, is then used by originally being water-cooled to room temperature, obtains described coating liquid;
C. coating and solidification
According to coated weight 50g/m2, the painting for obtaining step B under conditions of 20 DEG C of temperature with relative air humidity 55%
Covering liquid is coated uniformly on the pretreatment basement membrane that step A is obtained, then at 74 DEG C of temperature plus heat extraction water, in the bar of temperature 60 C
Baking and curing 25min under part, obtains described positively charged nanofiltration membranes.
Determined according to reverse osmosis membrane method of testing national standard analytical, positively charged nanofiltration manufactured in the present embodiment
Film under conditions of 25 DEG C of temperature with pressure 0.41MPa, 250ppmCaCl2The rejection of solution separating is 84.4%, water flux
It is 53.32L/ (m2H), 250ppmCaCl2It is finally steady that the rejection of solution longtime running finally stabilizes to 85.3%, water flux
It is set to for 52.25L/ (m2H), without substantially decay, this shows positive electrocoat base for calcium chloride longtime running flux and salt rejection rate
This is not lost in;Under conditions of 25 DEG C and pressure 0.48MPa of temperature, 2000ppmMgSO4The rejection of solution separating is
28.4%th, water flux is 56.34L/ (m2·h);Under conditions of 25 DEG C and pressure 0.41MPa of temperature, 250ppmPEG600 is molten
It is 56.24L/ (m that the detached rejection of liquid is 82.2%, water flux2·h).Additionally, the Ztea potential values of made diaphragm are
26mv;Contact angle is 60 °.
Embodiment 2:The preparation of positively charged nanofiltration membranes
The implementation steps of the embodiment are as follows:
A. pretreatment basement membrane is prepared
Compound concentration is the tween water that by weight 0.2% polyvinyl alcohol water solution and concentration are by weight 0.2%
Solution;Polyvinyl alcohol water solution is with Tween solution according to volume ratio 1:1.0 mix homogeneously, obtain mid-coating liquid;Then,
According to the coated weight 40g/m of the mid-coating liquid2, described mid-coating liquid is relatively wet in 22 DEG C of temperature and air
It is coated uniformly on polyacrylonitrile flat ultrafilter membrane porous support layer under conditions of degree 55%, is dried under conditions of 80 DEG C of temperature
20min, obtains described pretreatment basement membrane;
B. coating liquid is prepared
4 weight account polyethylene alcohol and 3.8 weight account polyethylene iminium cations polyelectrolyte are added to into 100 weight portion water
In, mixing, dissolving, the solution for obtaining the sulphuric acid mineral acid of concentration 2M or concentration 2M potassium hydroxide inorganic base aqueous solution its pH value
Adjust to 2, then the solution is heated to into 77 DEG C of temperature, obtain a kind of mixed copolymer;Then
Add 0.5 weight portion glutaraldehyde toward described mixed copolymer, dissolve, mix homogeneously is carried out at room temperature pre-
Crosslinking 8.2min, is then used by originally being water-cooled to room temperature, obtains described coating liquid;
C. coating and solidification
According to coated weight 45g/m2, the painting for obtaining step B under conditions of 28 DEG C of temperature with relative air humidity 60%
Covering liquid is coated uniformly on the pretreatment basement membrane that step A is obtained, then adds heat extraction water under temperature 70 C, in the bar of temperature 60 C
Baking and curing 25min under part, obtains described positively charged nanofiltration membranes.
Determined according to reverse osmosis membrane method of testing national standard analytical, positively charged nanofiltration manufactured in the present embodiment
Film under conditions of 25 DEG C of temperature with pressure 0.41MPa, 250ppmCaCl2The rejection of solution separating is 87.2%, water flux
It is 45.45L/ (m2H), 250ppmCaCl2It is finally steady that the rejection of solution longtime running finally stabilizes to 87.8%, water flux
It is set to 52.5L/ (m2H), without substantially decay, this shows positive electrocoat substantially not for calcium chloride longtime running flux and salt rejection rate
It is lost in;Under conditions of 25 DEG C and pressure 0.48MPa of temperature, 2000ppmMgSO4The rejection of solution separating is 40.7%, water
Flux is 44.93L/ (m2·h);Under conditions of 25 DEG C of temperature with pressure 0.41MPa, 250ppmPEG600 solution separating is cut
Stay rate be 84.5%, water flux be 53.2L/ (m2·h).Additionally, the Ztea potential values of made diaphragm are 28mv;Contact angle is
55°。
Embodiment 3:The preparation of positively charged nanofiltration membranes
The implementation steps of the embodiment are as follows:
A. pretreatment basement membrane is prepared
Compound concentration is the tween water that by weight 0.3% polyvinyl alcohol water solution and concentration are by weight 0.3%
Solution;Polyvinyl alcohol water solution is with Tween solution according to volume ratio 1:1.2 mix homogeneously, obtain mid-coating liquid;Then,
According to the coated weight 43g/m of the mid-coating liquid2, described mid-coating liquid is relatively wet in 30 DEG C of temperature and air
It is coated uniformly on vinylidene difluoride planar ultrafiltration membrane porous support layer under conditions of degree 65%, does under conditions of temperature 70 C
Dry 20min, obtains described pretreatment basement membrane;
B. coating liquid is prepared
3 weight account polyethylene alcohol and 4.4 weight portion poly diallyldimethylammonium chloride cationic polyelectrolytes are added to into 100 weight portions
In water, mixing, dissolving, the solution for obtaining the nitric acid mineral acid or concentration 1M sodium carbonate inorganic base aqueous solution of concentration 3M are by its pH
Value is adjusted to 2, then the solution is heated to into 80 DEG C of temperature, obtains a kind of mixed copolymer;Then toward described mixing copolymerization
Add 3.0 weight portion glutaraldehydes in thing, dissolve, mix homogeneously carries out at room temperature precrosslink 7.6min, is then used by tap water
Room temperature is cooled to, described coating liquid is obtained;
C. coating and solidification
According to coated weight 55g/m2, the painting for obtaining step B under conditions of 30 DEG C of temperature with relative air humidity 65%
Covering liquid is coated uniformly on the pretreatment basement membrane that step A is obtained, then at 75 DEG C of temperature plus heat extraction water, in 80 DEG C of bar of temperature
Baking and curing 20min under part, obtains described positively charged nanofiltration membranes.
Determined according to reverse osmosis membrane method of testing national standard analytical, positively charged nanofiltration manufactured in the present embodiment
Film under conditions of 25 DEG C of temperature with pressure 0.41MPa, 250ppmCaCl2The rejection of solution separating is 90.3%, water flux
It is 35.2L/ (m2·h);Under conditions of 25 DEG C and pressure 0.48MPa of temperature, 2000ppmMgSO4The rejection of solution separating is
53.1%th, water flux is 32.2L/ (m2H), 250ppmCaCl2The rejection of solution longtime running finally stabilizes to 55.3%,
Water flux finally stabilizes to 35.7L/ (m2H), without substantially decay, this shows just for calcium chloride longtime running flux and salt rejection rate
Electrocoat is not lost in substantially;Under conditions of 25 DEG C and pressure 0.41MPa of temperature, the rejection of 250ppmPEG600 solution separating
Be 90%, water flux be 35.5L/ (m2·h).Additionally, the Ztea potential values of made diaphragm are 30mv;Contact angle is 48 °.
Embodiment 4:The preparation of positively charged nanofiltration membranes
The implementation steps of the embodiment are as follows:
A. pretreatment basement membrane is prepared
Compound concentration is the tween water that by weight 0.1% polyvinyl alcohol water solution and concentration are by weight 0.3%
Solution;Polyvinyl alcohol water solution is with Tween solution according to volume ratio 1:0.9 mix homogeneously, obtains mid-coating liquid;Then,
According to the coated weight 36g/m of the mid-coating liquid2, described mid-coating liquid is relatively wet in 28 DEG C of temperature and air
It is coated uniformly on polysulphone flat ultrafiltration membrane porous support layer under conditions of degree 62%, is dried under conditions of 80 DEG C of temperature
20min, obtains described pretreatment basement membrane;
B. coating liquid is prepared
5 weight account polyethylene alcohol and 4.0 weight account polyethylene base chlorimide cationic polyelectrolytes are added to into 100 weight
In part water, mixing, dissolving, the solution for obtaining with the phosphoric acid mineral acid or concentration 5M potassium carbonate inorganic base aqueous solution of concentration 4M by its
PH value is adjusted to 2, then the solution is heated to into 78 DEG C of temperature, obtains a kind of mixed copolymer;Then
Add 1.0 weight portion glutaraldehydes toward described mixed copolymer, dissolve, mix homogeneously is carried out at room temperature pre-
Crosslinking 7.4min, is then used by originally being water-cooled to room temperature, obtains described coating liquid;
C. coating and solidification
According to coated weight 40g/m2, the painting for obtaining step B under conditions of 24 DEG C of temperature with relative air humidity 58%
Covering liquid is coated uniformly on the pretreatment basement membrane that step A is obtained, then at 72 DEG C of temperature plus heat extraction water, in 80 DEG C of bar of temperature
Baking and curing 10min under part, obtains described positively charged nanofiltration membranes.
Determined according to reverse osmosis membrane method of testing national standard analytical, positively charged nanofiltration manufactured in the present embodiment
Film under conditions of 25 DEG C of temperature with pressure 0.41MPa, 250ppmCaCl2The rejection of solution separating is 92.4%, water flux
It is 34.2L/ (m2·h);Under conditions of 25 DEG C and pressure 0.48MPa of temperature, 2000ppmMgSO4The rejection of solution separating is
55%th, water flux is 33.6L/ (m2H), 250ppmCaCl2The rejection of solution longtime running finally stabilizes to 55.2%, water
Flux finally stabilizes to 35.6L/ (m2H), without substantially decay, this shows positive electricity for calcium chloride longtime running flux and salt rejection rate
Coating is not lost in substantially;Under conditions of 25 DEG C and pressure 0.41MPa of temperature, the rejection of 250ppmPEG600 solution separating is
87%th, water flux is 38.4L/ (m2·h).Additionally, the Ztea potential values of made diaphragm are 31mv;Contact angle is 45 °.
Embodiment 5:The preparation of positively charged nanofiltration membranes
The implementation steps of the embodiment are as follows:
A. pretreatment basement membrane is prepared
Compound concentration is the tween water that by weight 0.3% polyvinyl alcohol water solution and concentration are by weight 0.2%
Solution;Polyvinyl alcohol water solution is with Tween solution according to volume ratio 1:1.1 mix homogeneously, obtain mid-coating liquid;Then,
According to the coated weight 28g/m of the mid-coating liquid2, described mid-coating liquid is relatively wet in 26 DEG C of temperature and air
It is coated uniformly on vinylidene difluoride planar ultrafiltration membrane porous support layer under conditions of degree 60%, does under conditions of temperature 60 C
Dry 25min, obtains described pretreatment basement membrane;
B. coating liquid is prepared
4 weight account polyethylene alcohol are added to 4.2 weight portion diallyl dimethyl ammoniumchloride cationic polyelectrolytes
In 100 weight portion water, mixing, dissolving, the solution for obtaining the hydrochloric acid mineral acid or concentration 4M sodium hydroxide inorganic base of concentration 2M
Aqueous solution adjusts its pH value to 2, then the solution is heated to into 78 DEG C of temperature, obtains a kind of mixed copolymer;Then
Add 2.5 weight portion glutaraldehydes toward described mixed copolymer, dissolve, mix homogeneously is carried out at room temperature pre-
Crosslinking 7.8min, is then used by originally being water-cooled to room temperature, obtains described coating liquid;
C. coating and solidification
According to coated weight 54g/m2, the painting for obtaining step B under conditions of 25 DEG C of temperature with relative air humidity 62%
Covering liquid is coated uniformly on the pretreatment basement membrane that step A is obtained, then at 73 DEG C of temperature plus heat extraction water, in the bar of temperature 60 C
Baking and curing 25min under part, obtains described positively charged nanofiltration membranes.
Determined according to reverse osmosis membrane method of testing national standard analytical, positively charged nanofiltration manufactured in the present embodiment
Film under conditions of 25 DEG C of temperature with pressure 0.41MPa, 250ppmCaCl2The rejection of solution separating is that 95%, water flux is
32.4L/(m2H), 250ppmCaCl2The rejection of solution longtime running finally stabilizes to 95.3%, water flux and finally stabilizes to
32.7L/(m2H), without substantially decay, this shows that positive electrocoat does not flow substantially for calcium chloride longtime running flux and salt rejection rate
Lose;Under conditions of 25 DEG C and pressure 0.48MPa of temperature, 2000ppmMgSO4The rejection of solution separating is 58%, water flux
It is 32.5L/ (m2·h);Under conditions of 25 DEG C and pressure 0.41MPa of temperature, the rejection of 250ppmPEG600 solution separating
Be 90%, water flux be 35.2L/ (m2·h).Additionally, the Ztea potential values of made diaphragm are 32mv;Contact angle is 49 °.
Claims (10)
1. a kind of preparation method of positively charged nanofiltration membranes, it is characterised in that as follows the step of the preparation method:
A. pretreatment basement membrane is prepared
Compound concentration is that by weight 0.1~0.3% polyvinyl alcohol water solution and concentration are by weight 0.1~0.3%
Tween solution;Polyvinyl alcohol water solution is with Tween solution according to volume ratio 1:0.8~1.2 mix homogeneously, obtains intermediate layer
Coating liquid;Then, described mid-coating liquid is coated uniformly on porous support layer, is dried, obtain described pretreatment
Basement membrane;
B. coating liquid is prepared
2~5 weight account polyethylene alcohol and 3.6~4.4 weight portion cationic polyelectrolytes are added in 100 weight portion water, are mixed,
The solution mineral acid or inorganic base aqueous solution that dissolving is obtained adjusts its pH value to 2, then the solution is heated to into temperature 75
~80 DEG C, obtain a kind of mixed copolymer;Then 0.5~3.0 weight portion glutaraldehyde is added toward described mixed copolymer, it is molten
Solution, mix homogeneously carries out at room temperature 7.2~8.2min of precrosslink, is then used by originally being water-cooled to room temperature, obtains described
Coating liquid;
C. coating and solidification
The coating liquid that step B is obtained is coated uniformly on the pretreatment basement membrane that step A is obtained, then at 70~75 DEG C of temperature plus
Heat extraction water, baking and curing obtains described positively charged nanofiltration membranes.
2. preparation method according to claim 1, it is characterised in that in step, described porous support layer is selected from poly-
Sulfone, polyacrylonitrile or vinylidene difluoride planar ultrafiltration membrane.
3. preparation method according to claim 1, it is characterised in that in step, described mid-coating liquid is in temperature
It is coated under conditions of 20~30 DEG C of degree and relative air humidity 55~65%, the coated weight of the mid-coating liquid is 28
~43g/m2。
4. preparation method according to claim 1, it is characterised in that in step, the mid-coating liquid is in temperature
10~25min is dried under conditions of 60~80 DEG C.
5. preparation method according to claim 1, it is characterised in that in stepb, described mineral acid is hydrochloric acid, sulfur
Acid, nitric acid or phosphoric acid;The concentration of the inorganic acid aqueous solution is 1~4M.
6. preparation method according to claim 1, it is characterised in that in stepb, described inorganic base be sodium hydroxide,
Potassium hydroxide, sodium carbonate or potassium carbonate;The concentration of the inorganic base aqueous solution is 1~5M.
7. preparation method according to claim 1, it is characterised in that in stepb, described cationic polyelectrolyte choosing
From cationic cellulose, polyethyleneimine, poly diallyldimethylammonium chloride, polyvinyl chlorimide or diallyl dimethyl chlorine
Change ammonium.
8. preparation method according to claim 1, it is characterised in that in step C, the coating liquid is in pretreatment basement membrane
On coated weight be 40~55g/m2。
9. preparation method according to claim 1, it is characterised in that in step C, described coating liquid temperature 20~
30 DEG C with relative air humidity 55~65% under conditions of be coated.
10. preparation method according to claim 1, it is characterised in that in step C, described baking and curing is in temperature
10~25min is dried under conditions of 60~80 DEG C.
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CN110860214A (en) * | 2019-12-19 | 2020-03-06 | 上海洁晟环保科技有限公司 | Base film layer, preparation method thereof and composite nanofiltration membrane containing base film layer |
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