CN107899432A - A kind of plate compounding NF membrane for water filter purification and preparation method thereof - Google Patents
A kind of plate compounding NF membrane for water filter purification and preparation method thereof Download PDFInfo
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- CN107899432A CN107899432A CN201711397348.9A CN201711397348A CN107899432A CN 107899432 A CN107899432 A CN 107899432A CN 201711397348 A CN201711397348 A CN 201711397348A CN 107899432 A CN107899432 A CN 107899432A
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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
- B01D69/06—Flat membranes
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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
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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
-
- 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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
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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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The present invention relates to water process environmental technology field, discloses a kind of plate compounding NF membrane for water filter purification and preparation method thereof.The present invention first carries out hydrophilic modifying using carboxymethyl cellulose and hyperbranched polyethyleneimine to polytetrafluoroethylene (PTFE) ultrafiltration membranes, then prepares the equal four formyl chloride separating layer of benzene of layer of polyethylene imines on polytetrafluoroethylene (PTFE) ultrafiltration membranes by interfacial polymerization.Plate compounding NF membrane separating layer of the present invention is not readily separated with basic unit, higher to organic molecule and ion rejection rate, and performance is stablized, and preparation method saves raw material, reduces production cost, is suitable for plant chimney stalk, municipal wastewater processing and the softening of drinking water pretreatment.
Description
Technical field
The present invention relates to water process environmental technology field, is received more particularly, to a kind of separating layer plate compounding not easily to fall off
Filter membrane and preparation method thereof.
Background technology
Nanofiltration starts from the 1970s, membrane aperture is in 1~5nm, and retention characteristic is between ultrafiltration membrane and reverse osmosis membrane
Between.It has operating pressure low, has higher rejection to small organic molecule, has to one, divalent ion different
Selectivity, it is widely used in the fields such as sewage disposal, drink water purifying and medicine concentration.Composite nanometer filtering film is mainly by separating
Layer and basement membrane composition, its separating property are mainly determined by separating layer structure.At present, the method for preparative separation layer mainly has interface
Polymerization, ultraviolet radiation graft method and chemical crosslink technique, wherein interfacial polymerization are the common methods of industrial production, and this method is profit
One layer of separating layer is generated in membrane surface cross-linking reaction by interfacial polymerization with aqueous phase monomers and organic phase monomer.Because separating layer
What is leaned on is the surface that weaker physical action is covered in basement membrane, in actual application, under the action of hydraulic pressure, separating layer compared with
Easily come off from basement membrane, cause the breakage of NF membrane, lose the cutoff performance to small molecule and ion.The separating layer of preparation is got over
Densification, the nano aperture in separating layer is higher to the rejection of small molecule or ion with regard to smaller, but water flux can be caused to subtract
It is small；Otherwise separating layer compactness is poorer, and the nano aperture in separating layer is bigger, and water flux is bigger, but can cause to ion
Reduced with the rejection of small molecule, water flux and rejection is more difficult optimizes at the same time.
China Patent Publication No. discloses a kind of method that composite nanometer filtering film is prepared using interfacial polymerization for CN103933881,
This method is used as organic phase monomer and aqueous phase monomers using ultrafiltration membrane as porous support layer, using Cyanuric Chloride or hexachlorocyclotriph,sphazene
Interfacial polymerization occurs in two-phase interface, although can have higher rejection to the separation of low molecule organic matter and ion,
It is that higher rejection is to realize that compactness is higher, the water flux of composite nanometer filtering film by increasing the compactness of its separating layer
It is lower, influence composite nanometer filtering film filter efficiency；To disclose a kind of lotus positive electricity compound for CN103007791 for China Patent Publication No.
The preparation method of NF membrane, is aqueous phase monomers using polyethyleneimine, chitosan quaternary ammonium salt, nano-titanium dioxide, equal benzene front three
Acyl chlorides is organic phase monomer, forms polymer separating layer in membrane surface by interfacial polymerization, separating layer relies on simple physics
Effect is covered on branch basement membrane, and the active force between polymer separating layer and supporting layer is weaker, is easily separated with supporting layer, and film makes
It is shorter with the service life.China Patent Publication No. discloses a kind of preparation side of polytetrafluoroethylene (PTFE) composite nanometer filtering film for CN104324622
Method, after hydrophobic microporous teflon membran is activated hydrophilic modifying using sodium dodecyl benzene sulfonate aqueous solution, recycles water
Phase monomer and the oil phase monomer polymerisation on hydrophilic polytetrafluoroethylmicroporous basement membrane generate separating layer, which needs more chemistry
Raw material, cost are higher.
The content of the invention
The present invention is to overcome prior art plate compounding NF membrane separating layer in sewage water filtration to be connected not with basement membrane
Firmly, easily come off from basement membrane, the problem of cutoff performance and water flux of NF membrane cannot optimize at the same time, there is provided Yi Zhongfen
Absciss layer is not easy to come off from basement membrane, has the plate compounding of preferable cutoff performance and water flux at the same time to small molecule and ion
NF membrane.Present invention also offers a kind of preparation method of the plate compounding NF membrane for water filter purification.
To achieve these goals, the present invention uses following technical scheme：A kind of tablet for water filter purification is answered
Close NF membrane, including hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes and the filtering for being covered in hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes top
Layer, the preparation method of the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes comprise the following steps：
(1) 1~3g hyperbranched polyethyleneimines and 0.01~0.05mol hydrogen bromides are added to 180~200mL deionized waters
In, progress 3~5h of ultrasonic dissolution under conditions of air is completely cut off is then placed in supersonic wave cleaning machine, obtains solution A；
(2) 2~4g modified carboxy methyl celluloses and will be added in 160~180mL deionized water solutions, concussion dissolving, concussion
It is set to be uniformly dispersed to obtain solution B；
(3) hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes are immersed in 4~8h in solution B, are placed into after taking-up and 1 is reacted in solution A
~2h, then takes out, and is divided in rectangle aluminum frame and fixes it, is put into baking oven dry 20~60min, is come into being
The hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of state.
Hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes, which have to pass through hydrophilic modifying, could be used for the filtering of sewage, polytetrafluoroethylene (PTFE)
The hydrophily of ultrafiltration membranes is better, and water flux is bigger, is conducive to improve sewage water filtration efficiency.Polytetrafluoroethylene (PTFE) ultrafiltration membranes table
Face is in fiber-node structure (shown in Fig. 2), after carboxymethyl cellulose molecule is contacted with polytetrafluoroethylene (PTFE) ultrafiltration membranes, carboxymethyl
Cellulosic molecule enters between the fibre bundle crack of polytetrafluoroethylene (PTFE) ultrafiltration membranes, and is wrapped on fibre bundle, the present invention
Using the stickiness of carboxymethyl cellulose, the carboxymethyl cellulose being wrapped on fibre bundle is adhered to polytetrafluoroethylene (PTFE) basement membrane
On fibre bundle, it is not easy to come off from polytetrafluoroethylene (PTFE) basement membrane.There is substantial amounts of amino, amino on hyperbranched polyethyleneimine
With preferable hydrophilicity, hyperbranched polyethyleneimine is grafted on carboxymethyl cellulose molecule, makes PTFE base
Film has preferable hydrophilicity, so as to improve the water flux of polytetrafluoroethylene (PTFE) basement membrane, grafting polyethylene imine is fine in carboxymethyl
On dimension element, so it is not easy to come off from polytetrafluoroethylene (PTFE) basement membrane, make the hydrophilicity of polytetrafluoroethylene (PTFE) basement membrane relatively stable；
In addition the hydrophilic layer that carboxymethyl cellulose and polyethyleneimine are formed is covered in membrane surface, can greatly reduce the seam of basement membrane
Gap size, is conducive to improve rejection of the composite nanometer filtering film to organic molecule pollutant.
(4) the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of nascent state are again dipped into 2~5h in solution B, are placed into after taking-up
20~40min is reacted in solution A, then basement membrane is divided in rectangle aluminum frame and fixes it, is then placed in baking oven 50
Dry 15~40min, obtains hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes under conditions of~70 DEG C.
It is to make polytetrafluoroethylene (PTFE) ultrafiltration membranes surface fully cover carboxymethyl fibre that the present invention, which carries out secondary immersion reaction,
Dimension element, prevents membrane surface subregion from not penetrating carboxymethyl cellulose molecule, carboxymethyl cellulose is covered polytetrafluoroethyl-ne
The planarization of the more uniform hydrophilic membrane surface of increase in alkene ultrafiltration membranes surface.
Preferably, in the step (1) molecular weight of hyperbranched polyethyleneimine for 10000Da, 20000Da or
70000Da。
The polyethyleneimine of macromolecule has more amino, and amino is hydrophilic radical, its quantity is more, basement membrane
Hydrophily is stronger.
Preferably, oven temperature control is at 60~80 DEG C in the step (3).
Preferably, the preparation method of modified carboxy methyl cellulose comprises the following steps in the step (2)：
(a) 10~20g flax and 4~8g sodium hydroxides are added in 30~40mL dimethylformamides, then added
0.03~0.08mol triethyl phosphates, are heated to 40~55 DEG C, stirring carries out 2~3h of basification, obtains basification liquid；
(b) 0.04~0.08mol acetic acid is added in basification liquid and carries out etherification process, heating postcooling is obtained to room temperature
To etherification process liquid；
(c) hydrochloric acid that 0.2~0.3mol/L is added into etherification process liquid is neutralized, and it is 7~8 to make pH, and by filtering, alcohol is washed
After be put into vacuum drying chamber dry 2~4h, crushing obtains modified carboxy methyl cellulose.
Heating process condition is often used in factory's manufacture production, the waste water of discharge is accompanied with certain temperature, this will
Seek filtration membrane and there is certain heat resistance in epilamellar material, the present invention prepares alkalization step in carboxymethyl cellulose
Triethyl phosphate is added in rapid, it is crosslinked with carboxymethyl cellulose, makes being internally formed for carboxymethyl cellulose certain
Net structure, carboxymethyl cellulose, which decomposes required energy, to be increased, and is substantially increased the heat resistance of carboxymethyl cellulose molecule, is protected
Hold the stabilization of the hydrophilicity of composite nanometer filtering film.
Preferably, heating process handles 30~40min, Ran Housheng to be first warming up to 40~50 DEG C in the step (b)
Temperature handles 40~60min to 60~70 DEG C.
A kind of preparation method of plate compounding NF membrane for water filter purification, comprises the following steps：
(A) the equal four formyl chloride solid particles of benzene of 0.8~2g and 120~160mL n-hexanes are added in conical flask, are put into water-bath
3~6h of magnetic agitation in pot, temperature control are subsequently cooled to room temperature and obtain organic phase solution A at 50~60 DEG C；
The organic phase monomer that equal four formyl chloride of benzene is interfacial polymerization is selected, it has four acid chloride groups, the reaction energy with amino
Power is stronger, and the polyamide degree of cross linking reacted is also higher, is conducive to improve heat resistance and the densification of composite nanometer filtering film filter layer
Property, improve its cutoff performance to organic molecule.
(B) that 1~3g sodium hydroxides and 0.1~0.4g lauryl sodium sulfate are added to 200~220mL deionizations is water-soluble
In liquid, aqueous phase solution B is obtained after stirring evenly；
Due to acyl chlorides and amine reaction meeting hydrochloric acid, the pH for making reaction solution is in acidity, and acid condition can prevent acyl chlorides, and the reaction was continued with amine,
So carry out the hydrochloric acid of neutralization reaction generation using sodium hydroxide；The use of lauryl sodium sulfate is surfactant；Due in base
During film hydrophilically modified, it is grafted on carboxymethyl cellulose using hyperbranched polyethyleneimine, so in aqueous phase solution, is not required to
Amine monomers are added, save raw material.
(C) hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes are submerged initially in 10~40min in aqueous phase solution B, rapid examination after taking-up
Paper wipes the unnecessary solution of membrane surface away, then immerses in organic phase solution A basement membrane, is reacted, come into being after taking-up
The composite nanometer filtering film of state；
During basement membrane hydrophilic modifying, there is double action using hyperbranched polyethyleneimine：On the one hand poly- four can be modified
Vinyl fluoride basement membrane, makes it have hydrophily；On the other hand, a part of amino on hyperbranched polyethyleneimine and equal four formyl of benzene
The acid chloride groups of chlorine crosslink reaction, form the separating layer (shown in Fig. 3) with compact texture, have nanoscale in separating layer
Other aperture, so that composite nanometer filtering film can retain small molecule organic pollution and ion, so invention uses hyperbranched poly
Aziridine both material as basement membrane hydrophilic modifying, has the reaction raw materials as generation separating layer, has saved raw material, reduced into
This.Some acid chloride groups does not participate in reaction, hydrolysis generation carboxyl, it is possible to increase the parent of separating layer on four formyl chloride of equal benzene
Water-based energy, although the separating layer of generation is comparatively dense, has a negative impact water flux, by the hydrophilic basement membrane of basement membrane and divides
Absciss layer has preferable hydrophilic effect, can offset the negative effect that separating layer densification brings water flux, have NF membrane
There is higher rejection at the same time, still there is higher water flux, the rejection and water flux to small molecule and ion can obtain at the same time
To optimization.
(D) composite nanometer filtering film of nascent state is divided and is fixed in rectangle aluminum frame, be then placed in baking oven and carry out curing friendship
Connection, immerses in deionized water after taking-up and washes away the complete monomer of unreacted, be then stored in sodium bicarbonate aqueous solution and obtain tablet
Composite nanometer filtering film.
On the composite nanometer filtering film of nascent state, hyperbranched polyethyleneimine and four formyl chloride of equal benzene are not handed over sufficiently
Connection, is put into baking oven and carries out curing process, can further improve the degree of cross linking of equal four formyl chloride of benzene and hyperbranched polyethyleneimine,
The compactness of separating layer is improved, so as to improve its rejection to small molecule organic pollution.
Preferably, 10~60min of reaction in the step (C).
Preferably, at 55~70 DEG C, hardening time is 15~30min for solidification temperature control in the step (D).
Therefore, the present invention has the advantages that：(1) separating layer of composite nanometer filtering film is firm, is not easy to take off from basement membrane
Fall；(2) composite nanometer filtering film is higher to small molecule organic pollution and ion rejection rate；(3) composite nanometer filtering film has preferable parent
Water-based energy, water flux are big；(4) raw material is saved, reduces cost.
Brief description of the drawings
Fig. 1 is the structure diagram of polytetrafluoroethylene composite nanometer filtering film.
Fig. 2 is surface microscopic fiber-node structure schematic diagram of polytetrafluoroethylene ultrafiltration membranes.
Fig. 3 is polytetrafluoroethylene composite nanometer filtering film surface microscopic compact texture schematic diagram.
Reference numeral
Hydrophilic polytetrafluoroethylmicroporous flat plate ultrafiltration basement membrane 1, filter layer 2.
Embodiment
Below by specific embodiment, technical scheme is described further.
In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art,
Method in embodiment, is the conventional method of this area unless otherwise instructed.
Embodiment 1
The present invention uses following technical scheme：Fig. 1 is the structure diagram of polytetrafluoroethylene (PTFE) composite nanometer filtering film, and one kind is used for
The plate compounding NF membrane of water filter purification, including hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes 1 and it is covered in hydrophilic polytetrafluoroethyl-ne
The filter layer 2 on alkene ultrafiltration membranes top, the preparation method of the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes comprise the following steps：
(1) hyperbranched polyethyleneimine and 0.01mol hydrogen bromides that 1g molecular weight is 10000Da are added to 180mL deionizations
In water, the progress ultrasonic dissolution 3h under conditions of air is completely cut off is then placed in supersonic wave cleaning machine, obtains solution A；
(2) 2g modified carboxy methyl celluloses and will be added in 160mL deionized water solutions, concussion dissolving, concussion makes it scattered
Uniformly obtain solution B；
(3) hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes are immersed in 4h in solution B, are placed into after taking-up and 1h is reacted in solution A, so
After take out, divided in rectangle aluminum frame and fix it, be put into baking oven, control oven temperature is dry at 60 DEG C
20min, obtains the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of nascent state；
(4) the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of nascent state are again dipped into 2h in solution B, are placed into after taking-up in solution A
20min is reacted, then basement membrane is divided in rectangle aluminum frame and fixes it, is then placed in baking oven and is done under conditions of 50 DEG C
Dry 15min, obtains hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes.
Wherein, the preparation method of modified carboxy methyl cellulose comprises the following steps：
(a) 10g flax and 4g sodium hydroxides are added in 30mL dimethylformamides, then add 0.03mol tricresyl phosphates
Ethyl ester, is heated to 40 DEG C, stirring carries out basification 2h, obtains basification liquid；
(b) 0.04mol acetic acid is added in basification liquid and carries out etherification process, be first warming up to 40 DEG C, handle 30min, so
After be warming up to 60 DEG C, handle 40min, be cooled to room temperature, obtain etherification process liquid；
(c) hydrochloric acid that 0.2mol/L is added into etherification process liquid is neutralized, and it is 7 to make pH, is put into after suction filtration, alcohol are washed true
Dry 2h, crushing obtain modified carboxy methyl cellulose in empty drying box.
A kind of preparation method of plate compounding NF membrane for water filter purification, comprises the following steps：
(A) the equal four formyl chloride solid particles of benzene of 0.8g and 120mL n-hexanes are added in conical flask, are put into magnetic force in water-bath
3h is stirred, temperature control is subsequently cooled to room temperature and obtains organic phase solution A at 50 DEG C；
(B) 1g sodium hydroxides and 0.1g lauryl sodium sulfate are added in 200mL deionized water solutions, after stirring evenly
To aqueous phase solution B；
(C) hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes are submerged initially in 10min in aqueous phase solution B, base is wiped away with test paper rapidly after taking-up
The unnecessary solution of film surface, then basement membrane is immersed in organic phase solution A, carry out reaction 10min, nascent state is obtained after taking-up
Composite nanometer filtering film；
(D) composite nanometer filtering film of nascent state is divided and is fixed in rectangle aluminum frame, be then placed in baking oven and carry out curing crosslinking, Gu
Change temperature control at 55 DEG C, hardening time 15min, immersed after taking-up in deionized water and wash away the complete monomer of unreacted, then
It is stored in sodium bicarbonate aqueous solution and obtains plate compounding NF membrane.
Embodiment 2
The present invention uses following technical scheme：A kind of plate compounding NF membrane for water filter purification, including it is hydrophilic
Polytetrafluoroethylene (PTFE) ultrafiltration membranes 1 and the filter layer 2 for being covered in hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes top, the hydrophilic polytetrafluoro
The preparation method of ethene ultrafiltration membranes comprises the following steps：
(1) by 1.5g molecular weight be 20000Da hyperbranched polyethyleneimine and 0.02mol hydrogen bromides be added to 190mL go from
In sub- water, the progress ultrasonic dissolution 3.5h under conditions of air is completely cut off is then placed in supersonic wave cleaning machine, obtains solution A；
(2) 2.5g modified carboxy methyl celluloses and will be added in 165mL deionized water solutions, concussion dissolving, concussion makes its point
Dissipate and uniformly obtain solution B；
(3) hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes are immersed in 5h in solution B, are placed into after taking-up and 1.2h is reacted in solution A,
Then take out, divided in rectangle aluminum frame and fix it, be put into baking oven, control oven temperature is dry at 65 DEG C
30min, obtains the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of nascent state；
(4) the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of nascent state are again dipped into 3h in solution B, are placed into after taking-up in solution A
25min is reacted, then basement membrane is divided in rectangle aluminum frame and fixes it, is then placed in baking oven and is done under conditions of 55 DEG C
Dry 20min, obtains hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes.
Wherein, the preparation method of modified carboxy methyl cellulose comprises the following steps：
(a) 12g flax and 5g sodium hydroxides are added in 32mL dimethylformamides, then add 0.04mol tricresyl phosphates
Ethyl ester, is heated to 45 DEG C, stirring carries out basification 2.2h, obtains basification liquid；
(b) 0.05mol acetic acid is added in basification liquid and carries out etherification process, be first warming up to 42 DEG C, handle 32min, so
After be warming up to 62 DEG C, handle 45min, be cooled to room temperature, obtain etherification process liquid；
(c) hydrochloric acid that 0.22mol/L is added into etherification process liquid is neutralized, and it is 7.2 to make pH, is put after suction filtration, alcohol are washed
Enter dry 2.5h, crushing in vacuum drying chamber and obtain modified carboxy methyl cellulose.
A kind of preparation method of plate compounding NF membrane for water filter purification, comprises the following steps：
(A) the equal four formyl chloride solid particles of benzene of 1g and 130mL n-hexanes are added in conical flask, are put into magnetic force in water-bath and stir
4h is mixed, temperature control is subsequently cooled to room temperature and obtains organic phase solution A at 53 DEG C；
(B) 1.5g sodium hydroxides and 0.2g lauryl sodium sulfate are added in 210mL deionized water solutions, after stirring evenly
Obtain aqueous phase solution B；
(C) hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes are submerged initially in 20min in aqueous phase solution B, base is wiped away with test paper rapidly after taking-up
The unnecessary solution of film surface, then basement membrane is immersed in organic phase solution A, carry out reaction 20min, nascent state is obtained after taking-up
Composite nanometer filtering film；
(D) composite nanometer filtering film of nascent state is divided and is fixed in rectangle aluminum frame, be then placed in baking oven and carry out curing crosslinking, Gu
Change temperature control at 60 DEG C, hardening time 17min, immersed after taking-up in deionized water and wash away the complete monomer of unreacted, then
It is stored in sodium bicarbonate aqueous solution and obtains plate compounding NF membrane.
Embodiment 3
The present invention uses following technical scheme：A kind of plate compounding NF membrane for water filter purification, including it is hydrophilic
Polytetrafluoroethylene (PTFE) ultrafiltration membranes 1 and the filter layer 2 for being covered in hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes top, the hydrophilic polytetrafluoro
The preparation method of ethene ultrafiltration membranes comprises the following steps：
(1) hyperbranched polyethyleneimine and 0.03mol hydrogen bromides that 2g molecular weight is 70000Da are added to 195mL deionizations
In water, the progress ultrasonic dissolution 4h under conditions of air is completely cut off is then placed in supersonic wave cleaning machine, obtains solution A；
(2) 3g modified carboxy methyl celluloses and will be added in 170mL deionized water solutions, concussion dissolving, concussion makes it scattered
Uniformly obtain solution B；
(3) hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes are immersed in 6h in solution B, are placed into after taking-up and 1.5h is reacted in solution A,
Then take out, divided in rectangle aluminum frame and fix it, be put into baking oven, control oven temperature is dry at 70 DEG C
40min, obtains the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of nascent state；
(4) the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of nascent state are again dipped into 3.5h in solution B, solution A is placed into after taking-up
Middle reaction 30min, then basement membrane is divided in rectangle aluminum frame and fix it, is then placed in baking oven under conditions of 60 DEG C
Dry 25min, obtains hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes.
Wherein, the preparation method of modified carboxy methyl cellulose comprises the following steps：
(a) 15g flax and 6g sodium hydroxides are added in 35mL dimethylformamides, then add 0.05mol tricresyl phosphates
Ethyl ester, is heated to 50 DEG C, stirring carries out basification 2.5h, obtains basification liquid；
(b) 0.06mol acetic acid is added in basification liquid and carries out etherification process, be first warming up to 45 DEG C, handle 35min, so
After be warming up to 65 DEG C, handle 50min, be cooled to room temperature, obtain etherification process liquid；
(c) hydrochloric acid that 0.25mol/L is added into etherification process liquid is neutralized, and it is 7.5 to make pH, is put after suction filtration, alcohol are washed
Enter dry 3h, crushing in vacuum drying chamber and obtain modified carboxy methyl cellulose.
A kind of preparation method of plate compounding NF membrane for water filter purification, comprises the following steps：
(A) the equal four formyl chloride solid particles of benzene of 1.5g and 140mL n-hexanes are added in conical flask, are put into magnetic force in water-bath
4.5h is stirred, temperature control is subsequently cooled to room temperature and obtains organic phase solution A at 55 DEG C；
(B) 2g sodium hydroxides and 0.25g lauryl sodium sulfate are added in 215mL deionized water solutions, after stirring evenly
Obtain aqueous phase solution B；
(C) hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes are submerged initially in 25min in aqueous phase solution B, base is wiped away with test paper rapidly after taking-up
The unnecessary solution of film surface, then basement membrane is immersed in organic phase solution A, carry out reaction 30min, nascent state is obtained after taking-up
Composite nanometer filtering film；
(D) composite nanometer filtering film of nascent state is divided and is fixed in rectangle aluminum frame, be then placed in baking oven and carry out curing crosslinking, Gu
Change temperature control at 65 DEG C, hardening time 20min, immersed after taking-up in deionized water and wash away the complete monomer of unreacted, then
It is stored in sodium bicarbonate aqueous solution and obtains plate compounding NF membrane.
Embodiment 4
The present invention uses following technical scheme：A kind of plate compounding NF membrane for water filter purification, including it is hydrophilic
Polytetrafluoroethylene (PTFE) ultrafiltration membranes 1 and the filter layer 2 for being covered in hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes top, the hydrophilic polytetrafluoro
The preparation method of ethene ultrafiltration membranes comprises the following steps：
(1) by 2.5g molecular weight be 10000Da hyperbranched polyethyleneimine and 0.04mol hydrogen bromides be added to 198mL go from
In sub- water, the progress ultrasonic dissolution 4.5h under conditions of air is completely cut off is then placed in supersonic wave cleaning machine, obtains solution A；
(2) 3.5g modified carboxy methyl celluloses and will be added in 175mL deionized water solutions, concussion dissolving, concussion makes its point
Dissipate and uniformly obtain solution B；
(3) hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes are immersed in 7h in solution B, are placed into after taking-up and 1.8h is reacted in solution A,
Then take out, divided in rectangle aluminum frame and fix it, be put into baking oven, control oven temperature is dry at 75 DEG C
50min, obtains the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of nascent state；
(4) the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of nascent state are again dipped into 4h in solution B, are placed into after taking-up in solution A
35min is reacted, then basement membrane is divided in rectangle aluminum frame and fixes it, is then placed in baking oven and is done under conditions of 65 DEG C
Dry 30min, obtains hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes.
Wherein, the preparation method of modified carboxy methyl cellulose comprises the following steps：
(a) 18g flax and 7g sodium hydroxides are added in 38mL dimethylformamides, then add 0.06mol tricresyl phosphates
Ethyl ester, is heated to 53 DEG C, stirring carries out basification 2.8h, obtains basification liquid；
(b) 0.07mol acetic acid is added in basification liquid and carries out etherification process, be first warming up to 48 DEG C, handle 38min, so
After be warming up to 68 DEG C, handle 55min, be cooled to room temperature, obtain etherification process liquid；
(c) hydrochloric acid that 0.28mol/L is added into etherification process liquid is neutralized, and it is 7.7 to make pH, is put after suction filtration, alcohol are washed
Enter dry 3.5h, crushing in vacuum drying chamber and obtain modified carboxy methyl cellulose.
A kind of preparation method of plate compounding NF membrane for water filter purification, comprises the following steps：
(A) the equal four formyl chloride solid particles of benzene of 1.8g and 150mL n-hexanes are added in conical flask, are put into magnetic force in water-bath
5h is stirred, temperature control is subsequently cooled to room temperature and obtains organic phase solution A at 58 DEG C；
(B) 2.5g sodium hydroxides and 0.3g lauryl sodium sulfate are added in 218mL deionized water solutions, after stirring evenly
Obtain aqueous phase solution B；
(C) hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes are submerged initially in 30min in aqueous phase solution B, base is wiped away with test paper rapidly after taking-up
The unnecessary solution of film surface, then basement membrane is immersed in organic phase solution A, carry out reaction 40min, nascent state is obtained after taking-up
Composite nanometer filtering film；
(D) composite nanometer filtering film of nascent state is divided and is fixed in rectangle aluminum frame, be then placed in baking oven and carry out curing crosslinking, Gu
Change temperature control at 67 DEG C, hardening time 25min, immersed after taking-up in deionized water and wash away the complete monomer of unreacted, then
It is stored in sodium bicarbonate aqueous solution and obtains plate compounding NF membrane.
Embodiment 5
The present invention uses following technical scheme：A kind of plate compounding NF membrane for water filter purification, including it is hydrophilic
Polytetrafluoroethylene (PTFE) ultrafiltration membranes 1 and the filter layer 2 for being covered in hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes top, the hydrophilic polytetrafluoro
The preparation method of ethene ultrafiltration membranes comprises the following steps：
(1) hyperbranched polyethyleneimine and 0.05mol hydrogen bromides that 3g molecular weight is 70000Da are added to 200mL deionizations
In water, the progress ultrasonic dissolution 5h under conditions of air is completely cut off is then placed in supersonic wave cleaning machine, obtains solution A；
(2) 4g modified carboxy methyl celluloses and will be added in 180mL deionized water solutions, concussion dissolving, concussion makes it scattered
Uniformly obtain solution B；
(3) hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes are immersed in 8h in solution B, are placed into after taking-up and 2h is reacted in solution A, so
After take out, divided in rectangle aluminum frame and fix it, be put into baking oven, control oven temperature is dry at 80 DEG C
60min, obtains the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of nascent state；
(4) the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of nascent state are again dipped into 5h in solution B, are placed into after taking-up in solution A
40min is reacted, then basement membrane is divided in rectangle aluminum frame and fixes it, is then placed in baking oven and is done under conditions of 70 DEG C
Dry 40min, obtains hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes.
Wherein, the preparation method of modified carboxy methyl cellulose comprises the following steps：
(a) 20g flax and 8g sodium hydroxides are added in 40mL dimethylformamides, then add 0.08mol tricresyl phosphates
Ethyl ester, is heated to 55 DEG C, stirring carries out basification 3h, obtains basification liquid；
(b) 0.08mol acetic acid is added in basification liquid and carries out etherification process, be first warming up to 50 DEG C, handle 40min, so
After be warming up to 70 DEG C, handle 60min, be cooled to room temperature, obtain etherification process liquid；
(c) hydrochloric acid that 0.3mol/L is added into etherification process liquid is neutralized, and it is 8 to make pH, is put into after suction filtration, alcohol are washed true
Dry 4h, crushing obtain modified carboxy methyl cellulose in empty drying box.
A kind of preparation method of plate compounding NF membrane for water filter purification, comprises the following steps：
(A) the equal four formyl chloride solid particles of benzene of 2g and 160mL n-hexanes are added in conical flask, are put into magnetic force in water-bath and stir
6h is mixed, temperature control is subsequently cooled to room temperature and obtains organic phase solution A at 60 DEG C；
(B) 3g sodium hydroxides and 0.4g lauryl sodium sulfate are added in 220mL deionized water solutions, after stirring evenly
To aqueous phase solution B；
(C) hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes are submerged initially in 40min in aqueous phase solution B, base is wiped away with test paper rapidly after taking-up
The unnecessary solution of film surface, then basement membrane is immersed in organic phase solution A, carry out reaction 60min, nascent state is obtained after taking-up
Composite nanometer filtering film；
(D) composite nanometer filtering film of nascent state is divided and is fixed in rectangle aluminum frame, be then placed in baking oven and carry out curing crosslinking, Gu
Change temperature control at 70 DEG C, hardening time 30min, immersed after taking-up in deionized water and wash away the complete monomer of unreacted, then
It is stored in sodium bicarbonate aqueous solution and obtains plate compounding NF membrane.
Comparative example 1
The present invention uses following technical scheme：A kind of plate compounding NF membrane for water filter purification, including hydrophilic poly- four
Vinyl fluoride ultrafiltration membranes 1 and the filter layer 2 for being covered in hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes top, it is described hydrophilic polytetrafluoroethylmicroporous
The preparation method of ultrafiltration membranes comprises the following steps：
(1) hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes are immersed in the sodium dodecyl sulfate aqueous solution that mass fraction is 1.5%
Middle 7.5h, then takes out, and is divided in rectangle aluminum frame and fixes it, is put into baking oven, controls oven temperature at 70 DEG C,
Dry 40min, obtains the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of nascent state；
(2) the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of nascent state are again dipped into the dodecyl sodium sulfonate that mass fraction is 1.5%
3.5h in sodium water solution, then basement membrane is divided in rectangle aluminum frame and fix it, places into the condition at 60 DEG C in baking oven
Lower dry 25min, obtains hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes.
A kind of preparation method of plate compounding NF membrane for water filter purification, comprises the following steps：
(A) the equal four formyl chloride solid particles of benzene of 1.5g and 140mL n-hexanes are added in conical flask, are put into magnetic force in water-bath
4.5h is stirred, temperature control is subsequently cooled to room temperature and obtains organic phase solution A at 55 DEG C；
(B) 4g hyperbranched polyethyleneimines, 2g sodium hydroxides and 0.25g lauryl sodium sulfate are added to 215mL deionizations
In aqueous solution, aqueous phase solution B is obtained after stirring evenly；
(C) hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes are submerged initially in 25min in aqueous phase solution B, base is wiped away with test paper rapidly after taking-up
The unnecessary solution of film surface, then basement membrane is immersed in organic phase solution A, carry out reaction 30min, nascent state is obtained after taking-up
Composite nanometer filtering film；
(D) composite nanometer filtering film of nascent state is divided and is fixed in rectangle aluminum frame, be then placed in baking oven and carry out curing crosslinking, Gu
Change temperature control at 65 DEG C, hardening time 20min, immersed after taking-up in deionized water and wash away the complete monomer of unreacted, then
It is stored in sodium bicarbonate aqueous solution and obtains plate compounding NF membrane.
Embodiment 1~5 and comparative example 1 (do not carry out parent using carboxymethyl cellulose and hyperbranched polyethyleneimine to it
Water be modified) sample NF membrane to 100mg/LPEG600 (molecular weight polyethylene glycol 600), 100mg/L PEG800 (polyethylene glycol
Molecular weight 800), the rejection of 1000mg/L sodium sulphate and 1000mg/L sodium chloride solutions, water flux tested, test result
It is as follows：
Test condition：Hydraulic pressure 0.2Mpa is tested, 25 DEG C of test temperature, after running 5h, rejection, water flux to NF membrane carry out
Test.
Test condition：Hydraulic pressure 0.5Mpa is tested, 25 DEG C of test temperature, after running 48h, rejection, water to NF membrane are led to
Amount is tested.
It can be obtained by test result：Composite nanometer filter membrane sample prepared by the embodiment of the present invention 1~5 is surveyed in normal pressure 0.2Mpa
Under the conditions of examination, have to organic molecule and ion higher rejection when, also there is higher water flux；In high pressure 0.5Mpa
Under test condition, tested by long-time, the rejection of NF membrane is basically unchanged.Composite nanometer filter membrane sample in comparative example 1 exists
Under normal pressure 0.2Mpa test conditions, although to organic molecule and ion with higher rejection with higher retention
Rate, but its water flux is relatively low, influences filter efficiency；Under high pressure 0.5Mpa test conditions, tested by long-time, NF membrane
Rejection decline more, this is because under conditions of higher operating pressure, NF membrane operates for a long time, it separates layer segment
Come off, cause the reduction of separating layer cutoff performance.
The sample NF membrane of embodiment 1~5 and comparative example 1 (hydrophilic modifying is not carried out to it using carboxymethyl cellulose)
Contact angle test result it is as follows：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | |
| Contact angle (°) | 45.24 | 48.37 | 50.63 | 48.65 | 49.75 | 87.86 |
The contact angle of composite nanometer filtering film prepared by embodiment 1~5 is significantly less than the contact of the composite nanometer filtering film of the preparation of comparative example 1
Angle, it was demonstrated that 1~5 NF membrane of embodiment has more preferable hydrophilicity, and hydrophily is conducive to improve the water flux of composite nanometer filtering film.
The above described is only a preferred embodiment of the present invention, not make limitation in any form to the present invention, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any to be familiar with this professional technology people
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
For the equivalent embodiment of equivalent variations, as long as being the technical spirit pair according to the present invention without departing from technical solution of the present invention content
Any simple modification, equivalent change and modification that above example is made, in the range of still falling within technical solution of the present invention.
Claims (8)
1. a kind of plate compounding NF membrane for water filter purification, it is characterised in that including hydrophilic polytetrafluoroethylmicroporous ultrafiltration
Basement membrane and the filter layer for being covered in hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes top, the system of the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes
Preparation Method comprises the following steps：
（1）1 ~ 3g hyperbranched polyethyleneimines and 0.01 ~ 0.05mol hydrogen bromides are added in 180 ~ 200mL deionized waters, so
After be put into supersonic wave cleaning machine under conditions of air is completely cut off progress 3 ~ 5h of ultrasonic dissolution, obtain solution A；
（2）By 2 ~ 4g modified carboxy methyl celluloses and it is added in 160 ~ 180mL deionized water solutions, concussion dissolving, concussion makes
It is uniformly dispersed to obtain solution B；
（3）Hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes are immersed in 4 ~ 8h in solution B, placed into after taking-up in solution A reaction 1 ~
2h, then takes out, and is divided in rectangle aluminum frame and fixes it, is put into baking oven dry 20 ~ 60min, obtains nascent state
Hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes；
（4）The hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of nascent state are again dipped into 2 ~ 5h in solution B, solution A is placed into after taking-up
20 ~ 40min of middle reaction, then basement membrane is divided in rectangle aluminum frame and fix it, is then placed in baking oven at 50 ~ 70 DEG C
Under the conditions of dry 15 ~ 40min, obtain hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes.
2. a kind of plate compounding NF membrane for water filter purification according to claim 1, it is characterised in that described
Step（1）The molecular weight of middle hyperbranched polyethyleneimine is 10000 Da, 20000 Da or 70000Da.
3. a kind of plate compounding NF membrane for water filter purification according to claim 1, it is characterised in that described
Step（3）Middle oven temperature control is at 60 ~ 80 DEG C.
4. a kind of plate compounding NF membrane for water filter purification according to claim 1, it is characterised in that described
Step（2）The preparation method of middle modified carboxy methyl cellulose comprises the following steps：
（a）10 ~ 20g flax and 4 ~ 8g sodium hydroxides are added in 30 ~ 40mL dimethylformamides, then add 0.03 ~
0.08mol triethyl phosphates, are heated to 40 ~ 55 DEG C, stirring carries out 2 ~ 3h of basification, obtains basification liquid；
（b）0.04 ~ 0.08mol acetic acid is added in basification liquid and carries out etherification process, heating postcooling is obtained to room temperature
Etherification process liquid；
（c）The hydrochloric acid that 0.2 ~ 0.3mol/L is added into etherification process liquid is neutralized, and it is 7 ~ 8 to make pH, after suction filtration, alcohol are washed
Dry 2 ~ 4h is put into vacuum drying chamber, and crushing obtains modified carboxy methyl cellulose.
5. a kind of plate compounding NF membrane for water filter purification according to claim 4, it is characterised in that described
Step（b）Middle heating process handles 30 ~ 40min to be first warming up to 40 ~ 50 DEG C, is then warming up to 60 ~ 70 DEG C, and processing 40 ~
60min。
A kind of 6. system of plate compounding NF membrane for water filter purification as described in claim 1 ~ 5 any claim
Preparation Method, it is characterised in that comprise the following steps：
（A）The equal four formyl chloride solid particles of benzene of 0.8 ~ 2g and 120 ~ 160mL n-hexanes are added in conical flask, are put into water-bath
Middle 3 ~ 6h of magnetic agitation, temperature control are subsequently cooled to room temperature and obtain organic phase solution A at 50 ~ 60 DEG C；
（B）1 ~ 3g sodium hydroxides and 0.1 ~ 0.4g lauryl sodium sulfate are added in 200 ~ 220mL deionized water solutions, stirred
Aqueous phase solution B is obtained after mixing uniformly；
（C）Hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes are submerged initially in 10 ~ 40min in aqueous phase solution B, are wiped away after taking-up with test paper rapidly
The unnecessary solution of membrane surface, then basement membrane is immersed in organic phase solution A, reacted, answering for nascent state is obtained after taking-up
Close NF membrane；
（D）The composite nanometer filtering film of nascent state is divided and is fixed in rectangle aluminum frame, is then placed in baking oven and carries out curing crosslinking, take
Immersed after going out in deionized water and wash away the complete monomer of unreacted, be then stored in sodium bicarbonate aqueous solution and obtain plate compounding and receive
Filter membrane.
7. a kind of preparation method of plate compounding NF membrane for water filter purification according to claim 6, it is special
Sign is, the step（C）10 ~ 60min of middle reaction.
8. a kind of preparation method of plate compounding NF membrane for water filter purification according to claim 6, it is special
Sign is, the step（D）At 55 ~ 70 DEG C, hardening time is 15 ~ 30min for middle solidification temperature control.
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