CN109692585A - Nanofiltration membrane and its preparation method and application - Google Patents
Nanofiltration membrane and its preparation method and application Download PDFInfo
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- CN109692585A CN109692585A CN201710982057.XA CN201710982057A CN109692585A CN 109692585 A CN109692585 A CN 109692585A CN 201710982057 A CN201710982057 A CN 201710982057A CN 109692585 A CN109692585 A CN 109692585A
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- nanofiltration membrane
- ammonium
- epoxy group
- polypiperazine
- amide
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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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- 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
- B01D71/48—Polyesters
-
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/16—Membrane materials having positively charged functional groups
-
- 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
Abstract
The present invention relates to seperation film field, a kind of nanofiltration membrane, the application of the preparation method of the nanofiltration membrane and the nanofiltration membrane in water treatment procedure are disclosed.The nanofiltration membrane includes supporting layer and polypiperazine-amide separating layer, one surface of the polypiperazine-amide separating layer is bonded with the supporting layer, another surface is modified by the ammonium salt surface containing epoxy group, so that the epoxy group in the ammonium salt containing epoxy group is attached with polypiperazine-amide.Nanofiltration membrane provided by the invention improves the hydrophily of film, and film surface is made to improve film to the rejection of bivalent cation according to road Nan Zuoyong with positive charge by being connected with the ammonium salt containing epoxy group in polypiperazine-amide film surface.
Description
Technical field
The present invention relates to seperation film fields, and in particular to a kind of nanofiltration membrane, the preparation method of the nanofiltration membrane and the nanofiltration
Application of the film in water treatment procedure.
Background technique
Nanofiltration is a kind of pressure-driven membrane separating process between reverse osmosis between ultrafiltration.The pore diameter range of nanofiltration membrane exists
Several rans, the organic matter removal performance to monovalention and molecular weight less than 200 is poor, and to divalent or multivalent ion and
Organic matter of the molecular weight between 200-500 removal efficiency with higher, can be widely used in water softening, drink water purifying,
Improve water quality, water-oil separating, wastewater treatment and reuse, seawater softening, point of the heavy chemicals such as dyestuff, antibiotic, polypeptide, polysaccharide
The fields such as grade, purifying and concentration.
Currently, commercial nanofiltration membrane mostly using polysulfone ultrafiltration membrane as supporting layer, carries out polynary in situ in ultrafiltration membrane upper surface
The interfacial polymerization of aqueous amine phase and polynary acyl chlorides organic phase, final products are composite nanometer filtering film.The aqueous phase monomers generallyd use are piperazine
Piperazine or piperazine replace amine, and organic phase is pyromellitic trimethylsilyl chloride or the carboxylic acid halides with a kind of multifunctional group, wherein a large amount of unreacteds
Acyl halide group be hydrolyzed into carboxylic acid so that nanofiltration film surface is negatively charged, utilize charge effect, polypiperazine-amide composite nanometer filtering film pair
High-valence anion rejection with higher, also has adjustable rejection to monovalent anion.But in certain specific necks
Domain, bear electrolemma can not work normally because seriously polluted；Further, since road Nan Xiaoying, the nanofiltration membrane of surface bear electricity is to two
The rejection of valence cation is poor, and therefore, more and more attention has been paid to develop to bivalent cation for the research of positively charged nanofiltration membranes
Rejection is high, and the nanofiltration membrane of the surface lotus positive electricity of good water permeability seems increasingly important.
Summary of the invention
The purpose of the present invention is overcoming existing nanofiltration membrane poor to bivalent cation cutoff performance, and provide a kind of pair of divalent
Cationic cutoff performance is excellent, good water permeability nanofiltration membrane and preparation method thereof and the nanofiltration membrane answering in water treatment procedure
With.
Ammonium salt containing epoxy group is connected to polypiperazine-amide film by further investigation discovery by the present inventor
Surface, improves the hydrophily of film, and film surface is made to improve film to bivalent cation according to road Nan Zuoyong with positive charge
Rejection, have thus completed the present invention.
The present invention provides a kind of nanofiltration membranes, wherein the nanofiltration membrane includes supporting layer and polypiperazine-amide separating layer, described
One surface of polypiperazine-amide separating layer is bonded with the supporting layer, and the ammonium salt surface containing epoxy group is passed through on another surface
It is modified, so that the epoxy group in the ammonium salt containing epoxy group is attached with polypiperazine-amide.
The present invention also provides a kind of preparation methods of nanofiltration membrane, method includes the following steps:
(1) polypiperazine-amide separating layer is formed on a surface of supporting layer, obtains composite membrane；
(2) composite membrane that step (1) obtains is contacted with the ammonium salt containing epoxy group, makes the ammonium salt containing epoxy group
In epoxy group and polypiperazine-amide connection occur react.
The present invention also provides nanofiltration membranes prepared by the above method.
In addition, the application the present invention also provides the nanofiltration membrane in water treatment procedure.
Nanofiltration membrane according to the present invention, due to being connected with the ammonium salt containing epoxy group in polypiperazine-amide separation layer surface,
The hydrophily of film is improved, and film surface is made to improve retention of the film to bivalent cation according to road Nan Zuoyong with positive charge
Rate.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the connection reaction mechanism schematic diagram of polypiperazine-amide separating layer and the ammonium chloride containing epoxy group；
Fig. 2 is the infrared spectrogram of nanofiltration membrane made from preparation example 1 and embodiment 1.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of nanofiltration membranes, wherein the nanofiltration membrane includes supporting layer and polypiperazine-amide separating layer, described
One surface of polypiperazine-amide separating layer is bonded with the supporting layer, and the ammonium salt surface containing epoxy group is passed through on another surface
It is modified, so that the epoxy group in the ammonium salt containing epoxy group is attached with polypiperazine-amide.
In the present invention, by being connected with the ammonium salt containing epoxy group in polypiperazine-amide film surface, the parent of film is improved
It is aqueous, and film surface is made to improve film to the rejection of bivalent cation according to road Nan Zuoyong with positive charge.
In the present invention, as nanofiltration membrane of the invention to magnesium sulfate salt rejection rate be 98% or more, preferably 98.5% with
On.
In addition, the water flux of the nanofiltration membrane is preferably 75L/m in the case where meeting above-mentioned salt rejection rate2H or more, more
Preferably 78L/m2H or more, preferably 90L/m2H is hereinafter, more preferably 85L/m2H or less.Water flux as nanofiltration membrane is specific
It can enumerate: 75L/m2h、76L/m2h、77L/m2h、78L/m2h、79L/m2h、80L/m2h、81L/m2h、82L/m2h、83L/
m2h、84L/m2h、85L/m2H or 90L/m2H etc..
According to the present invention, for the supporting layer, there is no particular limitation, can be by existing various with centainly strong
Spend and can be used in nanofiltration, the material of nanofiltration membrane is made, by one of polysulfones, polyether sulfone and polyacrylonitrile or a variety of be made.
In addition, the supporting layer can be single hole or porous structure.
A kind of specific embodiment according to the present invention, the supporting layer include non-woven polyester layer of cloth and are attached to described
In polyester non-woven fabric layer surface one of polysulfones, polyether sulfone and polyacrylonitrile or it is a variety of made of polymeric layer.
In addition, in the present invention, the thickness of the supporting layer can change in a big way, in order to enable supporting layer with
Reach better coordinated purpose between the polypiperazine-amide separating layer, the nanofiltration membrane made has bivalent cation
Preferably cutoff performance and higher water flux, 90-150 μm of thickness of the preferably described supporting layer, more preferably 100-120 μm.
Thickness as supporting layer can specifically be enumerated: 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm,
130 μm, 135 μm, 140 μm, 145 μm or 150 μm etc..
In the present invention, in order to enable the nanofiltration membrane arrived can preferably have to bivalent cation cutoff performance and higher
Water flux, it is preferable that the polypiperazine-amide separating layer is by being formed with 0.002-0.05 μ m-thick in the modified rear surface in surface
Surface modified membrane, be preferably formed with the surface modified membrane of 0.005-0.03 μ m-thick.Thickness as surface modified membrane specifically may be used
To enumerate: 0.002 μm, 0.005 μm, 0.0075 μm, 0.01 μm, 0.012 μm, 0.0125 μm, 0.015 μm, 0.0175 μm, 0.02
μm, 0.022 μm, 0.0225 μm, 0.025 μm, 0.0275 μm, 0.03 μm, 0.04 μm or 0.05 μm etc..
In addition, in order to enable reach better coordinated purpose between supporting layer and the polypiperazine-amide separating layer,
The polypiperazine-amide separating layer with a thickness of 0.05-0.5 μm, it is more excellent be 0.01-0.4 μm, further preferably 0.1-0.3 μ
m.Thickness as polypiperazine-amide separating layer can specifically be enumerated: 0.05 μm, 0.06 μm, 0.07 μm, 0.08 μm, 0.09 μm,
0.1 μm, 0.15 μm, 0.18 μm, 0.2 μm, 0.25 μm, 0.3 μm, 0.4 μm or 0.5 μm etc..
In the present invention, a surface of the polypiperazine-amide separating layer is bonded with the supporting layer, another surface
It is modified by the ammonium salt surface containing epoxy group, so that epoxy group and polypiperazine-amide in the ammonium salt containing epoxy group
It is attached.As long as can be modified to the surface of polypiperazine-amide separating layer as the ammonium salt containing epoxy group, make
The epoxy group and polypiperazine-amide obtained in the ammonium salt containing epoxy group is attached.The ammonium containing epoxy group
Epoxy group in salt can be 1 or 2 or more, preferably 1 or 2, more preferably 1.
The above-mentioned ammonium salt containing epoxy group is preferably ammonium halide salt, more preferably chlorination ammonium salt, bromination ammonium salt or ammonium iodide
Salt, further preferably chlorination ammonium salt.2,3- glycidyl three can be for example selected from as such ammonium salt containing epoxy group
Ammonio methacrylate, 2,3- Epoxypropyl triethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides, diethyl-
2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium chloride, 3- epoxy ammonium bromide, 2,3- epoxy third
Base triethylammonium bromide, 1,2- glycidyl dimethyl dodecyl base ammonium bromide, diethyl -2,3- glycidyl-[3- (methyl
Dimethoxy)] silicon propyl ammonium bromide, 3- epoxy ammonium iodide, 2,3- glycidyl triethyl group ammonium iodide, 1,2- ring
Oxygen propyl group dimethyl dodecyl base ammonium iodide and diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl iodate
One of ammonium is a variety of.Preferably, the ammonium salt containing epoxy group is selected from 2,3- epoxypropyltrimethylchloride chloride, 2,3-
Epoxypropyl triethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides, diethyl -2,3- glycidyl-[3-
(methyl dimethoxy oxygroup)] silicon propyl ammonium chloride, 3- epoxy ammonium bromide, 2,3- glycidyl triethylammonium bromide,
1,2- glycidyl dimethyl dodecyl base ammonium bromide, diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl
One of ammonium bromide is a variety of；It is highly preferred that the ammonium salt containing epoxy group is selected from 2,3- epoxypropyl trimethylammonium chloride
Ammonium, 2,3- Epoxypropyl triethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides and diethyl -2,3- epoxy
One of propyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium chloride is a variety of.
As above-mentioned polypiperazine-amide separating layer, preferably gathered by the way that the polyamine is carried out interface with the polynary acyl chlorides
Conjunction obtains.
In the present invention, term " interfacial polymerization " refers to: it is immiscible at two kinds, the solution there are two types of monomer is dissolved respectively
Interface on (or interface organic phase side) polymerization reaction for carrying out.
In the present invention, for the type of the polyamine, there is no particular limitation, can be for commonly used in the art for systems
Amine compounds used in standby polypiperazine-amide.Preferably, the polyamine is piperazine or is piperazine and selected from polyethyleneimine
The combination of one or both of amine and polyetheramine；More preferably piperazine.In addition, when carrying out interfacial polymerization, it is preferably described more
First amine uses in the form of a solution, can be for the solvent with the aftermentioned polynary acyl chlorides of dissolution not as the solvent for dissolving the polyamine
It is compatible and to the inert solvent of the polyamine.As such solvent for example can for one of water, methanol and acetonitrile or
It is a variety of；Preferably water.
In addition, for the concentration of polyamine in the polynary amine aqueous solution, there is no particular limitation, can be the normal of this field
Rule selection.For example, the concentration of polyamine can be 0.01-10 weight %, preferably 0.1-5 weight in the polynary amine aqueous solution
Measure %, more preferably 0.1-2 weight %.In the polynary amine aqueous solution concentration of polyamine be specifically as follows 0.01 weight %,
0.05 weight %, 0.1 weight %, 0.2 weight %, 0.5 weight %, 1 weight %, 1.5 weight %, 2 weight %, 3 weight %, 4
Weight %, 5 weight %, 6 weight %, 7 weight %, 8 weight %, 9 weight % or 10 weight % etc..
In the present invention, for the type of the polynary acyl chlorides, also there is no particular limitation, can usually use for this field
In preparing chloride compounds used in polypiperazine-amide.Preferably, the polynary acyl chlorides is pyromellitic trimethylsilyl chloride, isophthalic diformazan
One of acyl chlorides and paraphthaloyl chloride are a variety of；More preferably pyromellitic trimethylsilyl chloride.
In addition, the preferably described polynary acyl chlorides uses in the form of a solution when carrying out interfacial polymerization, it is described polynary as dissolving
The solvent of acyl chlorides can be incompatible with the solvent of above-mentioned dissolution polyamine and to the polynary inert solvent of acyl chlorides.As
Such solvent for example can be organic solvent, as the organic solvent be preferably n-hexane, dodecane, normal heptane,
One of Isopar E, Isopar G, Isopar H, Isopar L and Isopar M or a variety of.
In addition, for the concentration of polynary acyl chlorides in the polynary solution of acid chloride, there is no particular limitation, can be this field
Conventional selection.For example, the concentration of polynary acyl chlorides can be 0.025-1 weight % in the polynary solution of acid chloride, preferably
0.05-0.5 weight %.The concentration of polynary acyl chlorides is specifically as follows 0.025 weight %, 0.05 weight in the polynary solution of acid chloride
Measure %, 0.10 weight %, 0.20 weight %, 0.30 weight %, 0.40 weight %, 0.50 weight %, 0.60 weight %, 0.70 weight
Measure %, 0.80 weight %, 0.90 weight % or 1 weight % etc..
Dosage as the polyamine and the polynary acyl chlorides can change in a larger range, it is preferable that
The mass concentration ratio of the polyamine and the polynary acyl chlorides is 1-100:1, more preferably 5-50:1.As the polyamine with
The mass concentration ratio of the polynary acyl chlorides can specifically be enumerated: 1:1,5:1,10:1,15:1,20:1,25:1,30:1,35:1,
40:1,45:1,50:1 or 100:1 etc..
It is separated as the polyamine is obtained polypiperazine-amide of the invention with the polynary acyl chlorides progress interfacial polymerization
There is no particular limitation for the mode of layer, polyamine can be made to carry out interfacial polymerization with polynary acyl chlorides and use various for this field
The conventional way of contact.In the present invention, it is preferred to by supporting layer successively with the solution containing polyamine and contain polynary acyl chlorides
Solution contact, is then heat-treated.
According to the present invention, to the condition of the interface polymerization reaction, there is no particular limitation, can be conventional for this field
Selection, for example, the case where successively being contacted supporting layer with the solution containing polyamine and the solution containing polynary acyl chlorides
Under, time that supporting layer is contacted with the solution containing polyamine is 5-100s, preferably 10-60s (such as can for 10s, 20s,
30s, 40s, 50s or 60s)；The time that supporting layer is contacted with the solution containing polynary acyl chlorides is 5-100s, preferably 10-60s
(such as can be 10s, 20s, 30s, 40s, 50s or 60s).Temperature when above-mentioned contact, which can be 10-40 DEG C, (such as can be
25℃)。
In addition, the condition of the heat treatment includes: that temperature is 40-150 DEG C, time 0.5- when carrying out above-mentioned heat treatment
20min；Preferably, it is 50-120 DEG C that the condition of the heat treatment, which includes: temperature, time 1-10min.Here, heat treatment temperature
Degree for example can be 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C or 120 DEG C.The time of heat treatment for example can be with
For 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min.
The present invention also provides the preparation methods of above-mentioned nanofiltration membrane, method includes the following steps:
(1) polypiperazine-amide separating layer is formed on a surface of supporting layer, obtains composite membrane；
(2) composite membrane that step (1) obtains is contacted with the ammonium salt containing epoxy group, makes the ammonium salt containing epoxy group
In epoxy group and polypiperazine-amide connection occur react.
In the method for the invention, for the supporting layer, there is no particular limitation, various can have one by existing
Fixed intensity and can be used in nanofiltration, the material of nanofiltration membrane is made, by one of polysulfones, polyether sulfone and polyacrylonitrile or more
Kind is made.In addition, the supporting layer can be single hole or porous structure.
A kind of specific embodiment according to the present invention, the supporting layer include non-woven polyester layer of cloth and are attached to described
In polyester non-woven fabric layer surface one of polysulfones, polyether sulfone and polyacrylonitrile or it is a variety of made of polymeric layer.
In addition, in the method for the invention, the thickness of the supporting layer can change in a big way, in order to enable branch
There can be better coordinated between support layer and the polypiperazine-amide separating layer, the nanofiltration membrane enable is preferably
With to bivalent cation cutoff performance, higher water flux, 90-150 μm of thickness of the preferably described supporting layer, more preferably
100-120μm.Thickness as supporting layer can specifically be enumerated: 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μ
M, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm or 150 μm etc..
In the method for the invention, in order to enable the nanofiltration membrane arrived can preferably have to bivalent cation cutoff performance
With higher water flux, it is preferable that the polypiperazine-amide separating layer is by being formed with 0.002- in the modified rear surface in surface
The surface modified membrane of 0.05 μ m-thick is preferably formed with the surface modified membrane of 0.005-0.03 μ m-thick.Thickness as surface modified membrane
Degree can specifically enumerate: 0.002 μm, 0.005 μm, 0.0075 μm, 0.01 μm, 0.012 μm, 0.0125 μm, 0.015 μm,
0.0175 μm, 0.02 μm, 0.022 μm, 0.0225 μm, 0.025 μm, 0.0275 μm, 0.03 μm, 0.04 μm or 0.05 μm etc..
In addition, in order to enable reach better coordinated purpose between supporting layer and the polypiperazine-amide separating layer,
The polypiperazine-amide separating layer with a thickness of 0.005-0.5 μm, it is more excellent be 0.01-0.4 μm, further preferably 0.1-0.3 μ
m.Thickness as polypiperazine-amide separating layer can specifically be enumerated: 0.005 μm, 0.01 μm, 0.02 μm, 0.03 μm, 0.04 μm,
0.05μm、0.06μm、0.07μm、0.08μm、0.09μm、0.1μm、0.15μm、0.18μm、0.2μm、0.25μm、0.3μm、0.4
μm or 0.5 μm etc..
According to the method for the present invention, by forming polypiperazine-amide separation on a surface of supporting layer in step (1)
Layer, to obtain composite membrane.As the method for forming polypiperazine-amide separating layer on a surface of supporting layer, it is preferable that logical
It crosses and polyamine is subjected to interfacial polymerization with polynary acyl chlorides to obtain.Interface is carried out as by the polyamine and the polynary acyl chlorides
Polymerize that there is no particular limitation come the mode that obtains the polypiperazine-amide separating layer, can make for this field polyamine with it is polynary
Acyl chlorides carries out interfacial polymerization and the various conventional ways of contact that use.In the method for the invention, it is preferable that by supporting layer according to
It is secondary to be contacted with the solution containing polyamine and the solution containing polynary acyl chlorides, then it is heat-treated.
In the method for the invention, for the type of the polyamine, there is no particular limitation, can be usual for this field
It is used to prepare amine compounds used in polypiperazine-amide.Preferably, the polyamine is piperazine or is piperazine and selected from poly-
The combination of one or both of aziridine and polyetheramine；More preferably piperazine.In addition, when carrying out interfacial polymerization, preferably
The polyamine uses in the form of a solution, as the solvent for dissolving the polyamine, can be and the aftermentioned polynary acyl chlorides of dissolution
Solvent is incompatible and to the inert solvent of the polyamine.It for example can be in water, methanol and acetonitrile as such solvent
It is one or more；Preferably water.
In addition, for the concentration of polyamine in the polynary amine aqueous solution, there is no particular limitation, can be the normal of this field
Rule selection.For example, the concentration of polyamine can be 0.01-10 weight %, preferably 0.1-5 weight in the polynary amine aqueous solution
Measure %, more preferably 0.1-2 weight %.In the polynary amine aqueous solution concentration of polyamine be specifically as follows 0.01 weight %,
0.05 weight %, 0.1 weight %, 0.2 weight %, 0.5 weight %, 1 weight %, 1.5 weight %, 2 weight %, 3 weight %, 4
Weight %, 5 weight %, 6 weight %, 7 weight %, 8 weight %, 9 weight % or 10 weight % etc..
In the method for the invention, for the type of the polynary acyl chlorides, also there is no particular limitation, can be this field
It is commonly used for preparing chloride compounds used in polypiperazine-amide.Preferably, the polynary acyl chlorides be pyromellitic trimethylsilyl chloride,
One of phthalyl chloride and paraphthaloyl chloride are a variety of；More preferable pyromellitic trimethylsilyl chloride.
In addition, the preferably described polynary acyl chlorides uses in the form of a solution when carrying out interfacial polymerization, it is described polynary as dissolving
The solvent of acyl chlorides can be incompatible with the solvent of above-mentioned dissolution polyamine and to the polynary inert solvent of acyl chlorides.As
Such solvent for example can be organic solvent, as the organic solvent be preferably n-hexane, dodecane, normal heptane,
One of Isopar E, Isopar G, Isopar H, Isopar L and Isopar M or a variety of.
In addition, for the concentration of polynary acyl chlorides in the polynary solution of acid chloride, there is no particular limitation, can be this field
Conventional selection.For example, the concentration of polynary acyl chlorides can be 0.025-1 weight % in the polynary solution of acid chloride, preferably
0.05-0.5 weight %.The concentration of polynary acyl chlorides is specifically as follows 0.025 weight %, 0.05 weight in the polynary solution of acid chloride
Measure %, 0.10 weight %, 0.20 weight %, 0.30 weight %, 0.40 weight %, 0.50 weight %, 0.60 weight %, 0.70 weight
Measure %, 0.80 weight %, 0.90 weight % or 1 weight % etc..
In the method for the invention, the dosage as the polyamine and the polynary acyl chlorides can be in a biggish model
Enclose interior variation, it is preferable that the mass concentration ratio of the polyamine and the polynary acyl chlorides is 1-100:1, more preferably 5-50:1.
Mass concentration ratio as the polyamine and the polynary acyl chlorides can specifically be enumerated: 1:1,5:1,10:1,15:1,20:1,
25:1,30:1,35:1,40:1,45:1,50:1 or 100:1 etc..
According to the method for the present invention, to the condition of the interface polymerization reaction, there is no particular limitation, can be this field
Conventional selection, for example, successively contacting supporting layer with the solution containing polyamine and the solution containing polynary acyl chlorides
In the case where, time that supporting layer is contacted with the solution containing polyamine is 5-100s, preferably 10-60s (such as can be
10s, 20s, 30s, 40s, 50s or 60s)；The time that supporting layer is contacted with the solution containing polynary acyl chlorides is 5-100s, preferably
10-60s (such as can be 10s, 20s, 30s, 40s, 50s or 60s).Temperature when above-mentioned contact can for 10-40 DEG C (such as
It can be 25 DEG C).
In addition, after supporting layer is successively contacted with the solution containing polyamine and the solution containing polynary acyl chlorides, then carry out
When heat treatment, the condition of the heat treatment includes: that temperature is 40-150 DEG C, time 0.5-20min；Preferably, at the heat
The condition of reason includes: that temperature is 50-120 DEG C, time 1-10min.Here, heat treatment temperature for example can for 50 DEG C, 60 DEG C,
70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C or 120 DEG C.The time of heat treatment for example can for 1min, 2min, 3min, 4min,
5min, 6min, 7min, 8min, 9min or 10min.
In steps of a method in accordance with the invention (2), composite membrane and the ammonium salt containing epoxy group that step (1) obtains are connect
Touching makes epoxy group and polypiperazine-amide in the ammonium salt containing epoxy group that connection occur and reacts, thus to described compound
The surface of the polypiperazine-amide separating layer of film is modified.
The mode contacted as the composite membrane for obtaining step (1) with the ammonium salt containing epoxy group does not limit particularly
It is fixed, it can be the various ways of contact commonly used in the art.It include: by step preferably as step (2) implementation process
(1) composite membrane obtained is impregnated in the solution containing the ammonium salt containing epoxy group, is dried after taking-up.
Being impregnated in the time in the solution containing the ammonium salt containing epoxy group for composite membrane, there is no particular limitation,
Preferably, the dip time is 5-120s, it is highly preferred that the dip time is 10-60s.Dip time for example can be
5s, 7s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, 70s, 80s, 90s, 100s, 110s or
120s。
In addition, for the condition of the drying, there is no particular limitation, it is preferable that the condition of the drying includes: temperature
It is 10-40 DEG C, time 1-240h；It is highly preferred that it is 20-30 DEG C that the condition of the drying, which includes: temperature, time 6-
144h。
It according to the method for the present invention, as long as can be to polypiperazine-amide separating layer as the ammonium salt containing epoxy group
Surface is modified, so that the epoxy group in the ammonium salt containing epoxy group and polypiperazine-amide are attached.Institute
The epoxy group stated in the ammonium salt containing epoxy group can be 1 or 2 or more, preferably 1 or 2, more preferably 1.
The above-mentioned ammonium salt containing epoxy group is preferably ammonium halide salt, more preferably chlorination ammonium salt, bromination ammonium salt or ammonium iodide
Salt, further preferably chlorination ammonium salt.2,3- glycidyl three can be for example selected from as such ammonium salt containing epoxy group
Ammonio methacrylate, 2,3- Epoxypropyl triethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides, diethyl-
2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium chloride, 3- epoxy ammonium bromide, 2,3- epoxy third
Base triethylammonium bromide, 1,2- glycidyl dimethyl dodecyl base ammonium bromide, diethyl -2,3- glycidyl-[3- (methyl
Dimethoxy)] silicon propyl ammonium bromide, 3- epoxy ammonium iodide, 2,3- glycidyl triethyl group ammonium iodide, 1,2- ring
Oxygen propyl group dimethyl dodecyl base ammonium iodide and diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl iodate
One of ammonium is a variety of.Preferably, the ammonium salt containing epoxy group is selected from 2,3- epoxypropyltrimethylchloride chloride, 2,3-
Epoxypropyl triethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides, diethyl -2,3- glycidyl-[3-
(methyl dimethoxy oxygroup)] silicon propyl ammonium chloride, 3- epoxy ammonium bromide, 2,3- glycidyl triethylammonium bromide,
1,2- glycidyl dimethyl dodecyl base ammonium bromide and diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon third
One of base ammonium bromide is a variety of；It is highly preferred that the ammonium salt containing epoxy group is selected from 2,3- epoxy chlorine
Change ammonium, 2,3- Epoxypropyl triethyl ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides and diethyl -2,3- ring
One of oxygen propyl group-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium chloride is a variety of.
According to the method for the present invention, molten relative to 100 parts by weight in the solution containing the ammonium salt containing epoxy group
Agent, the content of the ammonium salt containing epoxy group are 0.1-50 parts by weight, preferably 0.25-25 parts by weight, more preferably 0.5-
10 parts by weight.
It is described to contain epoxy group relative to 100 parts by weight solvent in the solution containing the ammonium salt containing epoxy group
The content of ammonium salt can specifically enumerate: 0.1 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 1
Parts by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16
Parts by weight, 18 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 40 parts by weight or 50 parts by weight etc..
The present invention also provides nanofiltration membranes prepared by the above method.
In addition, the application the present invention also provides above-mentioned nanofiltration membrane in water treatment procedure.
The present invention will be described in detail by way of examples below, but the present invention is not limited in following embodiments.
In following embodiments and preparation example, tested using water flux and salt rejection rate of the following methods to nanofiltration membrane.
(1) the initial water flux of nanofiltration membrane:
Nanofiltration membrane is fitted into membrane cisterna, at 0.2 mpa after precompressed 0.5h, in the case where pressure is 0.5MPa, temperature be 25 DEG C of items
The water transit dose of the nanofiltration membrane in 1h is measured under part, and is calculated by the following formula to obtain:
J=Q/ (A=Q), wherein J is water flux (L/m2H), Q is water transit dose (L), and A is effective film surface of nanofiltration membrane
Product (m2), t is the time (h)；
(2) salt rejection rate of nanofiltration membrane:
Nanofiltration membrane is fitted into membrane cisterna, at 0.2 mpa after precompressed 0.5h, in the case where pressure is 0.5MPa, temperature be 25 DEG C of items
The concentration that initial concentration in 1h is salt in the salt raw water solution and permeate of 2000ppm is measured under part to change, and passes through following public affairs
Formula is calculated:
R=(CP-Cf)/CP× C raw water is molten, wherein R is salt rejection rate, CPFor the concentration of salt in stoste, CfFor salt in permeate
Concentration；The salt is MgSO4, MgCl2And CaCl2。
In addition, in following embodiment and preparation example, 2,3- epoxypropyltrimethylchloride chlorides, 2,3- glycidyl, three second
Ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides, diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygen
Base)] silicon propyl ammonium chloride and pyromellitic trimethylsilyl chloride be purchased from lark prestige Science and Technology Ltd.；Isopar E is purchased from western Gansu Province chemical industry
Co., Ltd；Other chemical reagent are purchased from Sinopharm Chemical Reagent Co., Ltd..
(3) film thickness is observed the cross-section morphology of diaphragm by Hitachi S-4800 type high-resolution field emission scanning electron microscope (FESEM),
And then obtain the thickness of film.
(4) infrared spectroscopy is tested to obtain by Nicolet 6700spectrophotometer.
Supporting layer is made using phase inversion, the specific steps are as follows:
A certain amount of polyether sulfone (number-average molecular weight 80000) is dissolved in n,N-Dimethylformamide, it is 18 that concentration, which is made,
The polyethers sulfolane solution of weight %, the deaeration 120min at 25 DEG C；Then, using scraper by polyethers sulfolane solution be coated in (with a thickness of
75 μm) obtain initial film on polyester non-woven fabric, with it is impregnated 60min in the water that temperature is 25 DEG C so that polyester without
The polyethersulfon layer on woven fabric surface, at perforated membrane, most obtains the supporting layer that overall thickness is 115 μm through 3 washings afterwards through inversion of phases.
Preparation example 1
Aqueous solution by the contact of above-mentioned polyether sulfone supporting layer upper surface containing the piperazine that concentration is 0.5 weight %, at 25 DEG C
Drain after contact 10s；Then, supporting layer upper surface is contacted to the Isopar E of the pyromellitic trimethylsilyl chloride containing 0.1 weight % again
Solution contacts drain after 10s at 25 DEG C；Then, film is put into baking oven, heats 3min at 70 DEG C, obtain complex film M 1,
Including supporting layer and separating layer, wherein separating layer with a thickness of 180nm.
After obtained complex film M 1 is impregnated for 24 hours in water, water is measured under the conditions of pressure is 0.5MPa, temperature is 25 DEG C
Flux J and salt rejection rate R to divalent salts, the results are shown in Table 1.
Embodiment 1
At 25 DEG C, the complex film M 1 being prepared according to the method for preparation example 1 is immersed in 2,3- containing 3 weight %
In the aqueous solution of epoxypropyltrimethylchloride chloride, dip time 30s.After taking-up, after drying for 24 hours, obtain in poly- piperazine acyl
Amine separation layer surface is formed with the nanofiltration membrane N1 of surface modified membrane, wherein surface modified membrane with a thickness of 0.015 μm.
After obtained nanofiltration membrane N1 is impregnated for 24 hours in water, water is measured under the conditions of pressure is 0.5MPa, temperature is 25 DEG C
Flux J and salt rejection rate R to divalent salts, the results are shown in Table 1.
Fig. 1 is the reaction mechanism of polypiperazine-amide separating layer and 2,3- epoxypropyltrimethylchloride chloride, passes through film surface
Amino and epoxy group between ring-opening reaction quaternary amines are connected to composite film surface.
Fig. 2 is the infrared spectrogram of nanofiltration membrane made from preparation example 1 and embodiment 1.It can be seen by the infrared spectroscopy of Fig. 2
Out, lower curve is the infrared spectrogram of 1 complex film M 1 of preparation example, and upper curve is the infrared spectroscopy of 1 nanofiltration membrane N1 of embodiment
Figure, relative to complex film M 1, nanofiltration membrane N1 is in 968cm-1There is a new characteristic absorption peak in place, which corresponds to quaternary ammonium salt group
Characteristic absorption.It follows that quaternary ammonium salt group has been successfully attached poly- piperazine by reacting between epoxy and amino
Amide separates layer surface.
Embodiment 2
At 25 DEG C, the complex film M 1 being prepared according to the method for preparation example 1 is immersed in 2,3- containing 5 weight %
In the aqueous solution of Epoxypropyl triethyl ammonium chloride, dip time 10s.After taking-up, after drying for 24 hours, obtain in poly- piperazine acyl
Amine separation layer surface is formed with the nanofiltration membrane N2 of surface modified membrane, wherein surface modified membrane with a thickness of 0.022 μm.
After obtained nanofiltration membrane N2 is impregnated for 24 hours in water, water is measured under the conditions of pressure is 0.5MPa, temperature is 25 DEG C
Flux J and salt rejection rate R to divalent salts, the results are shown in Table 1.
Through infrared spectrum nanofiltration membrane N2 in 968cm-1There is a characteristic absorption peak in place, it follows that quaternary ammonium salt
Group has been successfully attached polypiperazine-amide by the reaction between epoxy and amino and has separated layer surface.
Embodiment 3
At 25 DEG C, the complex film M 1 being prepared according to the method for preparation example 1 is immersed in 1 containing 7.5 weight %,
In the aqueous solution of 2- glycidyl dimethyl dodecyl ammonium chlorides, dip time 60s.After taking-up, after drying for 24 hours, obtain
Be formed with the nanofiltration membrane N3 of surface modified membrane in polypiperazine-amide separation layer surface, wherein surface modified membrane with a thickness of 0.025
μm。
After obtained nanofiltration membrane N3 is impregnated for 24 hours in water, water is measured under the conditions of pressure is 0.5MPa, temperature is 25 DEG C
Flux J and salt rejection rate R to divalent salts, the results are shown in Table 1.
Through infrared spectrum nanofiltration membrane N3 in 968cm-1There is a characteristic absorption peak in place, it follows that quaternary ammonium salt
Group has been successfully attached polypiperazine-amide by the reaction between epoxy and amino and has separated layer surface.
Embodiment 4
According to embodiment 1 prepare nanofiltration membrane method carry out, institute the difference is that, with diethyl -2,3- glycidyl -
[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium chloride replaces 2,3- epoxypropyltrimethylchloride chloride, obtains in polypiperazine-amide point
Absciss layer surface is formed with the nanofiltration membrane N4 of surface modified membrane, wherein surface modified membrane with a thickness of 0.018 μm.
After obtained nanofiltration membrane N4 is impregnated for 24 hours in water, water is measured under the conditions of pressure is 0.5MPa, temperature is 25 DEG C
Flux J and salt rejection rate R to divalent salts, the results are shown in Table 1.
Through infrared spectrum nanofiltration membrane N4 in 968cm-1There is a characteristic absorption peak in place, it follows that quaternary ammonium salt
Group has been successfully attached polypiperazine-amide by the reaction between epoxy and amino and has separated layer surface.
Embodiment 5
According to embodiment 1 prepare nanofiltration membrane method carry out, unlike, 2,3- epoxypropyltrimethylchloride chlorides it is dense
Degree is 1%, obtains separating the nanofiltration membrane N5 that layer surface is formed with surface modified membrane in polypiperazine-amide, wherein surface modified membrane
With a thickness of 0.012 μm.
After obtained nanofiltration membrane N5 is impregnated for 24 hours in water, water is measured under the conditions of pressure is 0.5MPa, temperature is 25 DEG C
Flux J and salt rejection rate R to divalent salts, the results are shown in Table 1.
Through infrared spectrum nanofiltration membrane N5 in 968cm-1There is a characteristic absorption peak in place, it follows that quaternary ammonium salt
Group has been successfully attached polypiperazine-amide by the reaction between epoxy and amino and has separated layer surface.
Embodiment 6
According to embodiment 1 prepare nanofiltration membrane method carry out, unlike, 2,3- epoxypropyltrimethylchloride chlorides it is dense
Degree is 10%, obtains separating the nanofiltration membrane N6 that layer surface is formed with surface modified membrane in polypiperazine-amide, wherein surface modified membrane
With a thickness of 0.020 μm.
After obtained nanofiltration membrane N6 is impregnated for 24 hours in water, water is measured under the conditions of pressure is 0.5MPa, temperature is 25 DEG C
Flux J and salt rejection rate R to divalent salts, the results are shown in Table 1.
Through infrared spectrum nanofiltration membrane N6 in 968cm-1There is a characteristic absorption peak in place, it follows that quaternary ammonium salt
Group has been successfully attached polypiperazine-amide by the reaction between epoxy and amino and has separated layer surface.
Embodiment 7
It is carried out according to the method that embodiment 1 prepares nanofiltration membrane, unlike, composite membrane is impregnating 2,3- glycidyl three
After methyl chloride aqueous ammonium, after taking-up, dry 6h obtains being formed with surface modified membrane in polypiperazine-amide separation layer surface
Nanofiltration membrane N7, wherein surface modified membrane with a thickness of 0.015 μm.
After obtained nanofiltration membrane N7 is impregnated for 24 hours in water, water is measured under the conditions of pressure is 0.5MPa, temperature is 25 DEG C
Flux J and salt rejection rate R to divalent salts, the results are shown in Table 1.
Through infrared spectrum nanofiltration membrane N7 in 968cm-1There is a characteristic absorption peak in place, it follows that quaternary ammonium salt
Group has been successfully attached polypiperazine-amide by the reaction between epoxy and amino and has separated layer surface.
Embodiment 8
It is carried out according to the method that embodiment 1 prepares nanofiltration membrane, unlike, composite membrane is impregnating 2,3- glycidyl three
After methyl chloride aqueous ammonium, after taking-up, dry 72h obtains being formed with surface modified membrane in polypiperazine-amide separation layer surface
Nanofiltration membrane N8, wherein surface modified membrane with a thickness of 0.015 μm.
After obtained nanofiltration membrane N8 is impregnated for 24 hours in water, water is measured under the conditions of pressure is 0.5MPa, temperature is 25 DEG C
Flux J and salt rejection rate R to divalent salts, the results are shown in Table 1.
Through infrared spectrum nanofiltration membrane N8 in 968cm-1There is a characteristic absorption peak in place, it follows that quaternary ammonium salt
Group has been successfully attached polypiperazine-amide by the reaction between epoxy and amino and has separated layer surface.
Embodiment 9
It is carried out according to the method that embodiment 1 prepares nanofiltration membrane, unlike, composite membrane is impregnating 2,3- glycidyl three
After methyl chloride aqueous ammonium, after taking-up, dry 72h obtains being formed with surface modified membrane in polypiperazine-amide separation layer surface
Nanofiltration membrane N9, wherein surface modified membrane with a thickness of 0.015 μm.
After obtained nanofiltration membrane N9 is impregnated for 24 hours in water, water is measured under the conditions of pressure is 0.5MPa, temperature is 25 DEG C
Flux J and salt rejection rate R to divalent salts, the results are shown in Table 1.
Through infrared spectrum nanofiltration membrane N9 in 968cm-1There is a characteristic absorption peak in place, it follows that quaternary ammonium salt
Group has been successfully attached polypiperazine-amide by the reaction between epoxy and amino and has separated layer surface.
Table 1
| Film | MgSO4Salt-stopping rate % | MgCl2Salt-stopping rate % | CaCl2Salt-stopping rate % | Pure water flux L/m2h |
| N1 | 98.77 | 97.92 | 96.81 | 80.7 |
| N2 | 98.52 | 97.22 | 96.38 | 80.5 |
| N3 | 98.65 | 97.41 | 96.56 | 79.8 |
| N4 | 97.92 | 97.02 | 95.83 | 79.0 |
| N5 | 97.88 | 90.52 | 88.57 | 78.5 |
| N6 | 98.70 | 97.85 | 96.67 | 81.2 |
| N7 | 98.35 | 88.62 | 85.91 | 82.4 |
| N8 | 98.81 | 97.98 | 96.89 | 78.6 |
| N9 | 98.89 | 98.01 | 96.94 | 75.2 |
| M1 | 97.85 | 83.5 | 81.2 | 78.3 |
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (16)
1. a kind of nanofiltration membrane, which is characterized in that the nanofiltration membrane includes supporting layer and polypiperazine-amide separating layer, the poly- piperazine acyl
One surface of amine separating layer is bonded with the supporting layer, another surface is modified by the ammonium salt surface containing epoxy group, is made
The epoxy group obtained in the ammonium salt containing epoxy group is attached with polypiperazine-amide.
2. nanofiltration membrane according to claim 1, wherein the nanofiltration membrane is 98% or more to the salt rejection rate of magnesium sulfate.
3. nanofiltration membrane according to claim 1 or 2, wherein the polypiperazine-amide separating layer is by the modified table in surface
It is formed with the surface modified membrane of 0.002-0.05 μ m-thick on face, is preferably formed with the surface modified membrane of 0.005-0.03 μ m-thick.
4. nanofiltration membrane according to claim 1 or 2, wherein the ammonium salt containing epoxy group is ammonium halide salt；
Preferably, the ammonium salt containing epoxy group is selected from 2,3- epoxypropyltrimethylchloride chloride, 2,3- glycidyl, three second
Ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides, diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygen
Base)] silicon propyl ammonium chloride, 2,3- epoxy ammonium bromide, 2,3- glycidyl triethylammonium bromide, 1,2- epoxy third
In base dimethyl dodecyl base ammonium bromide and diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium bromide
It is one or more.
5. nanofiltration membrane according to claim 1 or 2, wherein the polypiperazine-amide separating layer is by by polyamine and more
First acyl chlorides carries out interfacial polymerization and obtains；
The mass concentration ratio of the polyamine and the polynary acyl chlorides is 1-100:1, preferably 5-50:1；
Preferably, the polyamine is piperazine or is piperazine and selected from one or both of polyethyleneimine and polyetheramine
Combination；More preferably piperazine；
Preferably, the polynary acyl chlorides is one of pyromellitic trimethylsilyl chloride, m-phthaloyl chloride and paraphthaloyl chloride or more
Kind.
6. nanofiltration membrane described in any one of -5 according to claim 1, wherein the supporting layer is by polysulfones, polyether sulfone and gathers
One of acrylonitrile a variety of is made.
7. nanofiltration membrane described in any one of -6 according to claim 1, wherein the supporting layer with a thickness of 90-150 μm,
Preferably 100-120 μm；The polypiperazine-amide separating layer with a thickness of 0.05-0.5 μm, preferably 0.1-0.3 μm.
8. a kind of preparation method of nanofiltration membrane, method includes the following steps:
(1) polypiperazine-amide separating layer is formed on a surface of supporting layer, obtains composite membrane；
(2) composite membrane that step (1) obtains is contacted with the ammonium salt containing epoxy group, is made in the ammonium salt containing epoxy group
Epoxy group occurs connection with polypiperazine-amide and reacts.
9. according to the method described in claim 8, wherein, the implementation process of step (2) include: step (1) is obtained it is compound
Film immersion is dried after taking-up in the solution containing the ammonium salt containing epoxy group.
10. according to the method described in claim 9, wherein, in the solution containing the ammonium salt containing epoxy group, relative to
100 parts by weight solvent, the content of the ammonium salt containing epoxy group are 0.1-50 parts by weight, preferably 0.25-25 parts by weight, more
Preferably 0.5-10 parts by weight.
11. the method according to any one of claim 8-10, wherein the ammonium salt containing epoxy group is ammonium halide
Salt；
Preferably, the ammonium salt containing epoxy group is selected from 2,3- epoxypropyltrimethylchloride chloride, 2,3- glycidyl, three second
Ammonium chloride, 1,2- glycidyl dimethyl dodecyl ammonium chlorides, diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygen
Base)] silicon propyl ammonium chloride, 2,3- epoxy ammonium bromide, 2,3- glycidyl triethylammonium bromide, 1,2- epoxy third
In base dimethyl dodecyl base ammonium bromide and diethyl -2,3- glycidyl-[3- (methyl dimethoxy oxygroup)] silicon propyl ammonium bromide
It is one or more.
12. according to the method described in claim 8, wherein, the process for forming polypiperazine-amide separating layer in step (1) includes:
Supporting layer is successively contacted with the solution containing polyamine and the solution containing polynary acyl chlorides, is then heat-treated.
13. according to the method for claim 12, wherein the mass concentration ratio of the polyamine and the polynary acyl chlorides is 1-
100:1, preferably 5-50:1；
Preferably, the polyamine is piperazine or is piperazine and selected from one or both of polyethyleneimine and polyetheramine
Combination；More preferably piperazine；
The polynary acyl chlorides is one of pyromellitic trimethylsilyl chloride, m-phthaloyl chloride and paraphthaloyl chloride or a variety of.
14. the method according to any one of claim 8-13, wherein the supporting layer is by polysulfones, polyether sulfone and gathers
One of acrylonitrile a variety of is made.
15. the nanofiltration membrane that the method as described in any one of claim 8-14 is prepared.
16. application of the nanofiltration membrane in water treatment procedure described in any one of claim 1-7 and 15.
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| CN112023727A (en) * | 2020-08-14 | 2020-12-04 | 万华化学集团股份有限公司 | Anti-pollution antibacterial reverse osmosis membrane, preparation method and application thereof |
| CN112755812A (en) * | 2020-12-18 | 2021-05-07 | 中化(宁波)润沃膜科技有限公司 | High-flux cross-linked composite nanofiltration membrane with intermediate layer and preparation method thereof |
| CN115445458A (en) * | 2022-09-16 | 2022-12-09 | 北京碧水源膜科技有限公司 | Nanofiltration membrane for magnesium-lithium separation and preparation method thereof |
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| CN115445458A (en) * | 2022-09-16 | 2022-12-09 | 北京碧水源膜科技有限公司 | Nanofiltration membrane for magnesium-lithium separation and preparation method thereof |
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Application publication date: 20190430 |