CN107899432B - A kind of plate compounding nanofiltration membrane and preparation method thereof for water filter purification - Google Patents
A kind of plate compounding nanofiltration membrane and preparation method thereof for water filter purification Download PDFInfo
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Abstract
The present invention relates to water process environmental technology fields, disclose a kind of plate compounding nanofiltration membrane and preparation method thereof for water filter purification.The present invention first uses carboxymethyl cellulose and hyperbranched polyethyleneimine to carry out hydrophilic modifying to polytetrafluoroethylene (PTFE) ultrafiltration membranes, and layer of polyethylene imines-four formyl chloride separating layer of benzene is then prepared on polytetrafluoroethylene (PTFE) ultrafiltration membranes by interfacial polymerization.Plate compounding nanofiltration membrane separating layer of the present invention is not readily separated with base, higher to small organic molecule and ion rejection rate, and performance is stablized, and preparation method saves raw material, reduces production cost, 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 fields, receive more particularly, to a kind of plate compounding that separating layer is not easily to fall off
Filter membrane and preparation method thereof.
Background technique
Nanofiltration starts from the 1970s, membrane aperture retains characteristic between ultrafiltration membrane and reverse osmosis membrane in 1~5nm
Between.It has operating pressure low, to small organic molecule rejection with higher, has to one, divalent ion different
Selectivity is widely used in the fields such as sewage treatment, drink water purifying and drug concentration.Composite nanometer filtering film is mainly by separating
Layer and basement membrane composition, separating property are mainly determined by separating layer structure.Currently, the method for preparative separation layer mainly has interface
Polymerization, ultraviolet radiation graft method and chemical crosslink technique, wherein interfacial polymerization is the common method of industrial production, and this method is benefit
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 of separating layer
What is leaned on is the surface that weaker physical action is covered on basement membrane, in actual application, in the presence of hydraulic pressure, separating layer compared with
It is easy to fall off from basement membrane, causes the breakage of nanofiltration 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 will cause water flux and 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 will cause to ion
It is reduced with the rejection of small molecule, water flux and rejection is more difficult optimizes simultaneously.
China Patent Publication No. is that CN103933881 discloses a kind of side that composite nanometer filtering film is prepared using interfacial polymerization
Method, this method use Cyanuric Chloride or hexachlorocyclotriph,sphazene as organic phase monomer and water phase using ultrafiltration membrane as porous support layer
In two-phase interface interfacial polymerization occurs for monomer, although being capable of separation retention with higher to low molecule organic matter and ion
Rate, but higher rejection is to realize that compactness is higher, the water of composite nanometer filtering film by increasing the compactness of its separating layer
Flux is lower, influences composite nanometer filtering film filter efficiency；China Patent Publication No. is that CN103007791 discloses a kind of lotus positive electricity
The preparation method of composite nanometer filtering film is aqueous phase monomers, equal benzene using polyethyleneimine, chitosan quaternary ammonium salt, nano-titanium dioxide
Three formyl chlorides are organic phase monomer, form polymer separating layer in membrane surface by interfacial polymerization, separating layer is by simple
Physical action is covered on branch basement membrane, and the active force between polymer separating layer and supporting layer is weaker, is easy to separate with supporting layer,
Film service life is shorter.China Patent Publication No. is that CN104324622 discloses a kind of system of polytetrafluoroethylene (PTFE) composite nanometer filtering film
Preparation Method, after hydrophobic microporous teflon membran is activated hydrophilic modifying using sodium dodecyl benzene sulfonate aqueous solution, then benefit
With aqueous phase monomers and oil phase monomer, polymerization reaction generates separating layer on hydrophilic polytetrafluoroethylmicroporous basement membrane, which needs more
Chemical raw material, higher cost.
Summary of the invention
The present invention is to overcome prior art plate compounding nanofiltration membrane separating layer in sewage water filtration to connect not with basement membrane
Securely, it is easy to fall off from basement membrane, the problem of cutoff performance and water flux of nanofiltration membrane cannot optimize simultaneously provides a kind of point
Absciss layer is not easy to fall off from basement membrane, has the plate compounding of preferable cutoff performance and water flux simultaneously to small molecule and ion
Nanofiltration membrane.The present invention also provides a kind of preparation methods of plate compounding nanofiltration membrane for water filter purification.
To achieve the goals above, the invention adopts the following technical scheme: a kind of plate for water filter purification is multiple
Nanofiltration membrane is closed, including hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes and the filtering for being covered in hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes top
Layer, the preparation methods of the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes the following steps are included:
(1) 1~3g hyperbranched polyethyleneimine and 0.01~0.05mol hydrogen bromide are added to 180~200mL deionization
In water, it is then placed in supersonic wave cleaning machine and carries out 3~5h of ultrasonic dissolution in the absence of air conditions, obtain solution A；
(2) 2~4g modified carboxy methyl cellulose is added in 160~180mL deionized water solution, concussion dissolution, shake
Swinging makes it 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 anti-in solution A
1~2h is answered, is then taken out, divided in rectangle aluminum frame and fixes it, is placed in oven and dried 20~60min, is obtained
The hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes of nascent state.
Hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes have to pass through the filtering that hydrophilic modifying could be used for 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 fall off from polytetrafluoroethylene (PTFE) basement membrane.There is a large amount of amino, amino on hyperbranched polyethyleneimine
With preferable hydrophilicity, hyperbranched polyethyleneimine is grafted on carboxymethyl cellulose molecule, PTFE base is made
Film has preferable hydrophilicity, to improve the water flux of polytetrafluoroethylene (PTFE) basement membrane, grafting polyethylene imine is in carboxymethyl fibre
On dimension element, so it is not easy to fall off from polytetrafluoroethylene (PTFE) basement membrane, keep 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 composite nanometer filtering film to the rejection of 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, and 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 sufficiently cover carboxymethyl fibre that the present invention, which carries out secondary immersion reaction,
Dimension element, prevents membrane surface partial region from not penetrating carboxymethyl cellulose molecule, and carboxymethyl cellulose is made to cover polytetrafluoroethyl-ne
Alkene ultrafiltration membranes surface is more uniform and increases the planarization of hydrophilic membrane surface.
Preferably, in the step (1) hyperbranched polyethyleneimine molecular weight be 10000Da, 20000Da or
70000Da。
The polyethyleneimine of macromolecule has more amino, and amino is hydrophilic radical, and quantity is more, basement membrane
Hydrophily is stronger.
Preferably, oven temperature control is at 60~80 DEG C in the step (3).
Preferably, in the step (2) modified carboxy methyl cellulose preparation method the following steps are included:
(a) 10~20g flax and 4~8g sodium hydroxide are added in 30~40mL dimethylformamide, are then added again
Enter 0.03~0.08mol triethyl phosphate, be 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, be cooled to after heating often
Temperature obtains etherification process liquid；
(c) hydrochloric acid that 0.2~0.3mol/L is added into etherification process liquid is neutralized, and pH 7~8 is made, by filtering,
Alcohol is put into vacuum oven dry 2~4h after washing, 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
It seeks filtration membrane and there is certain heat resistance in epilamellar substance, the present invention prepares alkalization step in carboxymethyl cellulose
Triethyl phosphate is added in rapid, crosslinks it with carboxymethyl cellulose, forms the inside of carboxymethyl cellulose certain
Reticular structure, the energy needed for carboxymethyl cellulose decomposes increase, and substantially increase the heat resistance of carboxymethyl cellulose molecule, protect
Hold the stabilization of the hydrophilicity of composite nanometer filtering film.
Preferably, heating process is first to be warming up to 40~50 DEG C in the step (b), 30~40min is handled, is then risen
Temperature handles 40~60min to 60~70 DEG C.
A kind of preparation method of the plate compounding nanofiltration membrane for water filter purification, comprising the following steps:
(A) the equal four formyl chloride solid particle of benzene of 0.8~2g and 120~160mL n-hexane are added in conical flask, are put into
3~6h of magnetic agitation in water-bath, temperature control at 50~60 DEG C, then are cooled to room temperature to obtain organic phase solution A；
Selecting equal four formyl chloride of benzene is the organic phase monomer of interfacial polymerization, and there are four acid chloride groups for tool, anti-with amino
Should be able to power it is stronger, the polyamide degree of cross linking reacted is also higher, be conducive to improve composite nanometer filtering film filter layer heat resistance and
Compactness improves its cutoff performance to organic molecule.
(B) that 1~3g sodium hydroxide and 0.1~0.4g lauryl sodium sulfate are added to 200~220mL deionization is water-soluble
In liquid, aqueous phase solution B is obtained after mixing evenly；
Since acyl chlorides reacts meeting hydrochloric acid with amine, make the pH of reaction solution in acidity, acid condition can prevent acyl chlorides and amine from continuing
Reaction, so carrying out the hydrochloric acid of neutralization reaction generation using sodium hydroxide；It the use of lauryl sodium sulfate is surfactant；Due to
During basement membrane hydrophilic modifying, it is grafted on carboxymethyl cellulose using hyperbranched polyethyleneimine, so in aqueous phase solution,
It does not need that amine monomers are added, saves raw material.
(C) hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes are submerged initially in 10~40min in aqueous phase solution B, rapidly with examination after taking-up
Paper wipes the extra 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 can be modified
Polytetrafluoroethylene (PTFE) basement membrane, makes it have hydrophily；On the other hand, a part of amino on hyperbranched polyethyleneimine and equal benzene four
The acid chloride groups of formyl chloride crosslink reaction, form the separating layer (shown in Fig. 3) with compact texture, have in separating layer and receive
The other aperture of meter level, to enable composite nanometer filtering film to retain small molecule organic pollutant and ion, so invention uses over-expense
Change the substance that polyethyleneimine had both been used as basement membrane hydrophilic modifying, have as the reaction raw materials for generating separating layer, saved raw material, drops
Low cost.Some acid chloride groups does not participate in reaction on four formyl chloride of equal benzene, and hydrolysis generates carboxyl, can be improved separating layer
Hydrophilicity, although generate separating layer it is comparatively dense, have an adverse effect to water flux, pass through the hydrophilic basement membrane of basement membrane
There is preferable hydrophilic effect with separating layer, separating layer densification can be offset to water flux bring negative effect, make nanofiltration membrane
Rejection with higher simultaneously, water flux still with higher, rejection to small molecule and ion and water flux can be same
When optimized.
(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 solidification friendship
Connection immerses in deionized water after taking-up and washes away the complete monomer of unreacted, is then stored in sodium bicarbonate aqueous solution and obtains plate
Composite nanometer filtering film.
On the composite nanometer filtering film of nascent state, there is no adequately handed over for hyperbranched polyethyleneimine and four formyl chloride of equal benzene
Connection, is put into baking oven and carries out curing process, can be further improved the degree of cross linking of equal benzene four formyl chlorides and hyperbranched polyethyleneimine,
The compactness for improving separating layer, to improve its rejection to small molecule organic pollutant.
Preferably, reacting 10~60min in the step (C).
Preferably, at 55~70 DEG C, curing time is 15~30min for solidification temperature control in the step (D).
Therefore, it the invention has the following beneficial effects: the separating layer of (1) composite nanometer filtering film is secured, is not easy to take off from basement membrane
It falls；(2) composite nanometer filtering film is higher to small molecule organic pollutant and ion rejection rate；(3) composite nanometer filtering film has preferable parent
Aqueous energy, water flux are big；(4) raw material is saved, cost is reduced.
Detailed description of the invention
Fig. 1 is the structural schematic 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.
Appended drawing reference
Hydrophilic polytetrafluoroethylmicroporous flat plate ultrafiltration basement membrane 1, filter layer 2.
Specific 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 unless otherwise instructed the conventional method of this field.
Embodiment 1
The invention adopts the following technical scheme: Fig. 1 is the structural schematic diagram of polytetrafluoroethylene (PTFE) composite nanometer filtering film, one kind is used for
The plate compounding nanofiltration 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 methods of the hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes the following steps are included:
(1) hyperbranched polyethyleneimine and 0.01mol hydrogen bromide that 1g molecular weight is 10000Da are added to 180mL and gone
In ionized water, it is then placed in supersonic wave cleaning machine and carries out ultrasonic dissolution 3h in the absence of air conditions, obtain solution A；
(2) 2g modified carboxy methyl cellulose is added in 160mL deionized water solution, concussion dissolution, concussion makes its point
It dissipates and uniformly obtains solution B；
(3) hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes are immersed in 4h in solution B, place into solution A and reacts after taking-up
1h then takes out, and is divided in rectangle aluminum frame and fixes it, is put into baking oven, and 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, place into solution after taking-up
20min is reacted in A, then divide basement membrane in rectangle aluminum frame and fixes it, is then placed in baking oven in 50 DEG C of condition
Lower dry 15min, obtains hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes.
Wherein, modified carboxy methyl cellulose preparation method the following steps are included:
(a) 10g flax and 4g sodium hydroxide are added in 30mL dimethylformamide, then add 0.03mol phosphorus
Triethylenetetraminehexaacetic acid ester is heated to 40 DEG C, and 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, processing
Then 30min is 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 pH 7 is made, and is put after suction filtration, alcohol are washed
Enter dry 2h, crushing in vacuum oven and obtains modified carboxy methyl cellulose.
A kind of preparation method of the plate compounding nanofiltration membrane for water filter purification, comprising the following steps:
(A) the equal four formyl chloride solid particle of benzene of 0.8g and 120mL n-hexane are added in conical flask, are put into water-bath
Magnetic agitation 3h, temperature control at 50 DEG C, then are cooled to room temperature to obtain organic phase solution A；
(B) 1g sodium hydroxide and 0.1g lauryl sodium sulfate are added in 200mL deionized water solution, are stirred evenly
After obtain aqueous phase solution B；
(C) hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes are submerged initially in 10min in aqueous phase solution B, are wiped with test paper rapidly after taking-up
The solution that membrane surface is extra is removed, then basement membrane is immersed in organic phase solution A, reaction 10min is carried out, is come into being after taking-up
The composite nanometer filtering film of state；
(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 solidification friendship
Connection, solidification temperature control at 55 DEG C, curing time 15min, immerse in deionized water after taking-up and wash away the complete monomer of unreacted,
Then it is stored in sodium bicarbonate aqueous solution and obtains plate compounding nanofiltration membrane.
Embodiment 2
The invention adopts the following technical scheme: a kind of plate compounding nanofiltration 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 methods of ethylene ultrafiltration membranes the following steps are included:
(1) hyperbranched polyethyleneimine and 0.02mol hydrogen bromide that 1.5g molecular weight is 20000Da are added to 190mL
In deionized water, it is then placed in supersonic wave cleaning machine and carries out ultrasonic dissolution 3.5h in the absence of air conditions, obtain solution
A；
(2) 2.5g modified carboxy methyl cellulose is added in 165mL deionized water solution, concussion dissolution, concussion makes it
It is uniformly dispersed to obtain solution B；
(3) hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes are immersed in 5h in solution B, place into solution A and reacts after taking-up
1.2h then takes out, and is divided in rectangle aluminum frame and fixes it, is put into baking oven, controls oven temperature at 65 DEG C, does
Dry 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, place into solution after taking-up
25min is reacted in A, then divide basement membrane in rectangle aluminum frame and fixes it, is then placed in baking oven in 55 DEG C of condition
Lower dry 20min, obtains hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes.
Wherein, modified carboxy methyl cellulose preparation method the following steps are included:
(a) 12g flax and 5g sodium hydroxide are added in 32mL dimethylformamide, then add 0.04mol phosphorus
Triethylenetetraminehexaacetic acid ester is heated to 45 DEG C, and 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, processing
Then 32min is 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 pH 7.2 is made, and by filtering, alcohol is washed
After be put into vacuum oven dry 2.5h, crushing obtains modified carboxy methyl cellulose.
A kind of preparation method of the plate compounding nanofiltration membrane for water filter purification, comprising the following steps:
(A) the equal four formyl chloride solid particle of benzene of 1g and 130mL n-hexane are added in conical flask, are put into magnetic in water-bath
Power stirs 4h, and temperature controls at 53 DEG C, then is cooled to room temperature to obtain organic phase solution A；
(B) 1.5g sodium hydroxide and 0.2g lauryl sodium sulfate are added in 210mL deionized water solution, stirring is equal
Aqueous phase solution B is obtained after even；
(C) hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes are submerged initially in 20min in aqueous phase solution B, are wiped with test paper rapidly after taking-up
The solution that membrane surface is extra is removed, then basement membrane is immersed in organic phase solution A, reaction 20min is carried out, is come into being after taking-up
The composite nanometer filtering film of state；
(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 solidification friendship
Connection, solidification temperature control at 60 DEG C, curing time 17min, immerse in deionized water after taking-up and wash away the complete monomer of unreacted,
Then it is stored in sodium bicarbonate aqueous solution and obtains plate compounding nanofiltration membrane.
Embodiment 3
The invention adopts the following technical scheme: a kind of plate compounding nanofiltration 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 methods of ethylene ultrafiltration membranes the following steps are included:
(1) hyperbranched polyethyleneimine and 0.03mol hydrogen bromide that 2g molecular weight is 70000Da are added to 195mL and gone
In ionized water, it is then placed in supersonic wave cleaning machine and carries out ultrasonic dissolution 4h in the absence of air conditions, obtain solution A；
(2) 3g modified carboxy methyl cellulose is added in 170mL deionized water solution, concussion dissolution, concussion makes its point
It dissipates and uniformly obtains solution B；
(3) hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes are immersed in 6h in solution B, place into solution A and reacts after taking-up
1.5h 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, does
Dry 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, are placed into after taking-up molten
30min is reacted in liquid A, then divide basement membrane in rectangle aluminum frame and fixes it, is then placed in baking oven in 60 DEG C of item
Dry 25min, obtains hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes under part.
Wherein, modified carboxy methyl cellulose preparation method the following steps are included:
(a) 15g flax and 6g sodium hydroxide are added in 35mL dimethylformamide, then add 0.05mol phosphorus
Triethylenetetraminehexaacetic acid ester is heated to 50 DEG C, and 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, processing
Then 35min is 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 pH 7.5 is made, and by filtering, alcohol is washed
After be put into vacuum oven dry 3h, crushing obtains modified carboxy methyl cellulose.
A kind of preparation method of the plate compounding nanofiltration membrane for water filter purification, comprising the following steps:
(A) the equal four formyl chloride solid particle of benzene of 1.5g and 140mL n-hexane are added in conical flask, are put into water-bath
Magnetic agitation 4.5h, temperature control at 55 DEG C, then are cooled to room temperature to obtain organic phase solution A；
(B) 2g sodium hydroxide and 0.25g lauryl sodium sulfate are added in 215mL deionized water solution, stirring is equal
Aqueous phase solution B is obtained after even；
(C) hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes are submerged initially in 25min in aqueous phase solution B, are wiped with test paper rapidly after taking-up
The solution that membrane surface is extra is removed, then basement membrane is immersed in organic phase solution A, reaction 30min is carried out, is come into being after taking-up
The composite nanometer filtering film of state；
(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 solidification friendship
Connection, solidification temperature control at 65 DEG C, curing time 20min, immerse in deionized water after taking-up and wash away the complete monomer of unreacted,
Then it is stored in sodium bicarbonate aqueous solution and obtains plate compounding nanofiltration membrane.
Embodiment 4
The invention adopts the following technical scheme: a kind of plate compounding nanofiltration 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 methods of ethylene ultrafiltration membranes the following steps are included:
(1) hyperbranched polyethyleneimine and 0.04mol hydrogen bromide that 2.5g molecular weight is 10000Da are added to 198mL
In deionized water, it is then placed in supersonic wave cleaning machine and carries out ultrasonic dissolution 4.5h in the absence of air conditions, obtain solution
A；
(2) 3.5g modified carboxy methyl cellulose is added in 175mL deionized water solution, concussion dissolution, concussion makes it
It is uniformly dispersed to obtain solution B；
(3) hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes are immersed in 7h in solution B, place into solution A and reacts after taking-up
1.8h then takes out, and is divided in rectangle aluminum frame and fixes it, is put into baking oven, controls oven temperature at 75 DEG C, does
Dry 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, place into solution after taking-up
35min is reacted in A, then divide basement membrane in rectangle aluminum frame and fixes it, is then placed in baking oven in 65 DEG C of condition
Lower dry 30min, obtains hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes.
Wherein, modified carboxy methyl cellulose preparation method the following steps are included:
(a) 18g flax and 7g sodium hydroxide are added in 38mL dimethylformamide, then add 0.06mol phosphorus
Triethylenetetraminehexaacetic acid ester is heated to 53 DEG C, and 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, processing
Then 38min is 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 pH 7.7 is made, and by filtering, alcohol is washed
After be put into vacuum oven dry 3.5h, crushing obtains modified carboxy methyl cellulose.
A kind of preparation method of the plate compounding nanofiltration membrane for water filter purification, comprising the following steps:
(A) the equal four formyl chloride solid particle of benzene of 1.8g and 150mL n-hexane are added in conical flask, are put into water-bath
Magnetic agitation 5h, temperature control at 58 DEG C, then are cooled to room temperature to obtain organic phase solution A；
(B) 2.5g sodium hydroxide and 0.3g lauryl sodium sulfate are added in 218mL deionized water solution, stirring is equal
Aqueous phase solution B is obtained after even；
(C) hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes are submerged initially in 30min in aqueous phase solution B, are wiped with test paper rapidly after taking-up
The solution that membrane surface is extra is removed, then basement membrane is immersed in organic phase solution A, reaction 40min is carried out, is come into being after taking-up
The composite nanometer filtering film of state；
(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 solidification friendship
Connection, solidification temperature control at 67 DEG C, curing time 25min, immerse in deionized water after taking-up and wash away the complete monomer of unreacted,
Then it is stored in sodium bicarbonate aqueous solution and obtains plate compounding nanofiltration membrane.
Embodiment 5
The invention adopts the following technical scheme: a kind of plate compounding nanofiltration 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 methods of ethylene ultrafiltration membranes the following steps are included:
(1) hyperbranched polyethyleneimine and 0.05mol hydrogen bromide that 3g molecular weight is 70000Da are added to 200mL and gone
In ionized water, it is then placed in supersonic wave cleaning machine and carries out ultrasonic dissolution 5h in the absence of air conditions, obtain solution A；
(2) 4g modified carboxy methyl cellulose is added in 180mL deionized water solution, concussion dissolution, concussion makes its point
It dissipates and uniformly obtains solution B；
(3) hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes are immersed in 8h in solution B, place into solution A and reacts after taking-up
2h then takes out, and is divided in rectangle aluminum frame and fixes it, is put into baking oven, and 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, place into solution after taking-up
40min is reacted in A, then divide basement membrane in rectangle aluminum frame and fixes it, is then placed in baking oven in 70 DEG C of condition
Lower dry 40min, obtains hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes.
Wherein, modified carboxy methyl cellulose preparation method the following steps are included:
(a) 20g flax and 8g sodium hydroxide are added in 40mL dimethylformamide, then add 0.08mol phosphorus
Triethylenetetraminehexaacetic acid ester is heated to 55 DEG C, and 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, processing
Then 40min is 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 pH 8 is made, and is put after suction filtration, alcohol are washed
Enter dry 4h, crushing in vacuum oven and obtains modified carboxy methyl cellulose.
A kind of preparation method of the plate compounding nanofiltration membrane for water filter purification, comprising the following steps:
(A) the equal four formyl chloride solid particle of benzene of 2g and 160mL n-hexane are added in conical flask, are put into magnetic in water-bath
Power stirs 6h, and temperature controls at 60 DEG C, then is cooled to room temperature to obtain organic phase solution A；
(B) 3g sodium hydroxide and 0.4g lauryl sodium sulfate are added in 220mL deionized water solution, are stirred evenly
After obtain aqueous phase solution B；
(C) hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes are submerged initially in 40min in aqueous phase solution B, are wiped with test paper rapidly after taking-up
The solution that membrane surface is extra is removed, then basement membrane is immersed in organic phase solution A, reaction 60min is carried out, is come into being after taking-up
The composite nanometer filtering film of state；
(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 solidification friendship
Connection, solidification temperature control at 70 DEG C, curing time 30min, immerse in deionized water after taking-up and wash away the complete monomer of unreacted,
Then it is stored in sodium bicarbonate aqueous solution and obtains plate compounding nanofiltration membrane.
Comparative example 1
The invention adopts the following technical scheme: a kind of plate compounding nanofiltration 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 methods of ethylene ultrafiltration membranes the following steps are included:
(1) hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration membranes are immersed in the dodecyl sodium sulfate water that mass fraction is 1.5%
7.5h in solution, then takes out, and is divided in rectangle aluminum frame and fixes it, is put into baking oven, and control oven temperature exists
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 that mass fraction is 1.5%
Then basement membrane is divided in rectangle aluminum frame and fixes it by 3.5h in sulfonic acid sodium water solution, place into baking oven at 60 DEG C
Under the conditions of dry 25min, obtain hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes.
A kind of preparation method of the plate compounding nanofiltration membrane for water filter purification, comprising the following steps:
(A) the equal four formyl chloride solid particle of benzene of 1.5g and 140mL n-hexane are added in conical flask, are put into water-bath
Magnetic agitation 4.5h, temperature control at 55 DEG C, then are cooled to room temperature to obtain organic phase solution A；
(B) 4g hyperbranched polyethyleneimine, 2g sodium hydroxide and 0.25g lauryl sodium sulfate are added to 215mL
In deionized water solution, aqueous phase solution B is obtained after mixing evenly；
(C) hydrophilic polytetrafluoroethylmicroporous ultrafiltration membranes are submerged initially in 25min in aqueous phase solution B, are wiped with test paper rapidly after taking-up
The solution that membrane surface is extra is removed, then basement membrane is immersed in organic phase solution A, reaction 30min is carried out, is come into being after taking-up
The composite nanometer filtering film of state；
(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 solidification friendship
Connection, solidification temperature control at 65 DEG C, curing time 20min, immerse in deionized water after taking-up and wash away the complete monomer of unreacted,
Then it is stored in sodium bicarbonate aqueous solution and obtains plate compounding nanofiltration membrane.
Examples 1 to 5 and comparative example 1 (do not carry out parent to it using carboxymethyl cellulose and hyperbranched polyethyleneimine
Water is modified) sample nanofiltration membrane to 100mg/LPEG600 (molecular weight polyethylene glycol 600), 100mg/L PEG800 (polyethylene glycol
Molecular weight 800), 1000mg/L sodium sulphate and the rejection of 1000mg/L sodium chloride solution, water flux tested, test result
It is as follows:
Test condition: test hydraulic pressure 0.2Mpa, 25 DEG C of test temperature, run 5h after, rejection, water flux to nanofiltration membrane
It is tested.
Test condition: test hydraulic pressure 0.5Mpa, after running 48h, leads to the rejection of nanofiltration membrane, water by 25 DEG C of test temperature
Amount is tested.
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, to small organic molecule and ion have higher rejection when, water flux also with higher；In high pressure 0.5Mpa
It under test condition, is tested by long-time, the rejection of nanofiltration membrane is basically unchanged.Composite nanometer filter membrane sample in comparative example 1 exists
Under normal pressure 0.2Mpa test condition, although there is the retention with higher of higher rejection to small organic molecule and ion
Rate, but its water flux is lower, influences filter efficiency；Under high pressure 0.5Mpa test condition, tested by long-time, nanofiltration membrane
Rejection decline it is more, this is because under conditions of higher operating pressure, nanofiltration membrane operates for a long time, separating layer part
It falls off, leads to the reduction of separating layer cutoff performance.
The sample nanofiltration membrane of Examples 1 to 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 the composite nanometer filtering film of Examples 1 to 5 preparation is significantly less than connecing for the composite nanometer filtering film of the preparation of comparative example 1
Feeler, it was demonstrated that Examples 1 to 5 nanofiltration membrane has better hydrophilicity, and the water that hydrophily is conducive to improve composite nanometer filtering film is logical
Amount.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this profession
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
It is right according to the technical essence of the invention for the equivalent embodiment of equivalent variations, but without departing from the technical solutions of the present invention
Any simple modification, equivalent change and modification made by above embodiments, all of which are still within the scope of the technical scheme of the invention.
Claims (8)
1. a kind of plate compounding nanofiltration membrane for water filter purification, which is characterized 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 the following steps are included:
(1) 1 ~ 3g hyperbranched polyethyleneimine and 0.01 ~ 0.05mol hydrogen bromide are added in 180 ~ 200mL deionized water, so
After be put into supersonic wave cleaning machine and carry out 3 ~ 5h of ultrasonic dissolution in the absence of air conditions, obtain solution A；
(2) 2 ~ 4g modified carboxy methyl cellulose is added in 160 ~ 180mL deionized water solution, concussion dissolution, concussion makes it
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, be placed in oven and dried 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, place into solution A 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 nanofiltration membrane for water filter purification according to claim 1, which is characterized in that described
The molecular weight of hyperbranched polyethyleneimine is 10000 Da, 20000 Da or 70000Da in step (1).
3. a kind of plate compounding nanofiltration membrane for water filter purification according to claim 1, which is characterized in that described
Oven temperature control is at 60 ~ 80 DEG C in step (3).
4. a kind of plate compounding nanofiltration membrane for water filter purification according to claim 1, which is characterized in that described
In step (2) modified carboxy methyl cellulose preparation method the following steps are included:
(a) 10 ~ 20g flax and 4 ~ 8g sodium hydroxide are added in 30 ~ 40mL dimethylformamide, then add 0.03 ~
0.08mol triethyl phosphate is heated to 40 ~ 55 DEG C, and 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, be cooled to room temperature, obtain after heating
Etherification process liquid；
(c) hydrochloric acid that 0.2 ~ 0.3mol/L is added into etherification process liquid is neutralized, and pH 7 ~ 8 is made, after suction filtration, alcohol are washed
Dry 2 ~ 4h is put into vacuum oven, and crushing obtains modified carboxy methyl cellulose.
5. a kind of plate compounding nanofiltration membrane for water filter purification according to claim 4, which is characterized in that described
Heating process is first to be warming up to 40 ~ 50 DEG C in step (b), handles 30 ~ 40min, is then warming up to 60 ~ 70 DEG C, processing 40 ~
60min。
6. a kind of system of the plate compounding nanofiltration membrane for water filter purification as described in claim 1 ~ 5 any claim
Preparation Method, which comprises the following steps:
(A) the equal four formyl chloride solid particle of benzene of 0.8 ~ 2g and 120 ~ 160mL n-hexane are added in conical flask, are put into water-bath
Middle 3 ~ 6h of magnetic agitation, temperature control at 50 ~ 60 DEG C, then are cooled to room temperature to obtain organic phase solution A；
(B) 1 ~ 3g sodium hydroxide and 0.1 ~ 0.4g lauryl sodium sulfate are added in 200 ~ 220mL deionized water solution, are 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 with test paper rapidly after taking-up
Then basement membrane is immersed in organic phase solution A, is reacted, answering for nascent state is obtained after taking-up by the extra solution of membrane surface
Close nanofiltration membrane；
(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 solidification crosslinking, take
It is immersed in deionized water after out and washes 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 nanofiltration membrane for water filter purification according to claim 6, special
Sign is, 10 ~ 60min is reacted in the step (C).
8. a kind of preparation method of plate compounding nanofiltration membrane for water filter purification according to claim 6, special
Sign is that at 55 ~ 70 DEG C, curing time is 15 ~ 30min for solidification temperature control in the step (D).
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| CN109553184B (en) * | 2018-12-29 | 2024-04-02 | 殷伟卿 | MBR (Membrane biological reactor) flat plate separation membrane, MBR flat plate membrane module and application thereof |
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| CN115105973B (en) * | 2022-06-28 | 2023-04-21 | 哈尔滨工业大学（深圳） | Nanofiltration membrane preparation method for efficient magnesium-lithium separation and application |
| CN116531961B (en) * | 2023-07-04 | 2023-09-19 | 中国农业大学 | Positively charged nanofiltration membrane for removing uranium and cesium in nuclear radioactive wastewater and preparation method thereof |
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