CN109224865A - A kind of preparation method of high selection separation property nanofiltration membrane - Google Patents
A kind of preparation method of high selection separation property nanofiltration membrane Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
Abstract
The invention discloses a kind of preparation methods of high selection separation property nanofiltration membrane, include the following steps: the separating layer of high-throughput, the low inorganic salts removal efficiency of (1) preparation；(2) separating layer of high negative charge density is prepared.It is an advantage of the invention that suitable dendroid polyfunctional group membrane material is added in aqueous phase solution, the lesser polypiperazine-amide separating layer of osmotic resistance is formed；Then, the remaining acid chloride groups of polypiperazine-amide film surface at initial stage are completed using interface polymerization reaction, it is reacted with the strong electronegativity compound containing hydroxyl or amino, persistence enhances film surface electronegativity in a manner of chemical bond, obtains the nanofiltration membrane of high selection separation property；Further, since the strong electronegativity compound introduced contains sulfonic acid group or phosphate group, isoelectric point can keep at lower ph values the electronegativity of film surface, to obtain broader pH value application range lower than conventional polypiperazine-amide nanofiltration membrane.
Description
Technical field
The present invention relates to water-treatment technology fields, and in particular to a kind of preparation method of high selection separation property nanofiltration membrane.
Background technique
Nanofiltration Membrane Separation Technology is a kind of novel membrane separation technique that 1980s Later development gets up, and anti-
Permeable membrane is compared, and nanofiltration membrane has the characteristics that operating pressure is low, permeation flux is big, operating cost is low, selection separation property is high, can be used
In the preparation of drinking water, the recycling of small organic molecule or removal, the concentration of bio-pharmaceutical industry biotic component and purification, Gao Han
The fields such as the processing of salt waste water and the reuse of municipal sewage.
As the core of Nanofiltration Membrane Separation Technology, the nanofiltration membrane with excellent separating property and chemical stability is key,
The preparation method of nanofiltration membrane mainly has phase inversion, lotus electrochemical process, composite algorithm etc. at present.
(1) phase inversion
Phase inversion film starts from nineteen sixties, is proposed earliest by Loeb and Sourirajan, therefore also referred to as
For L-S phase inversion, common membrane material has cellulose and its derivates, hydrophobic polymer, polyimides etc..It had been film-made
Cheng Zhong, more will crucially obtain that aperture is uniform and the lesser dense separation layers of thickness, while ensure separating property and infiltration
Performance, but traditional macromolecule member material is difficult to realize the target simultaneously during inversion of phases.Therefore it is being commercialized at present
Nanofiltration membrane preparation process in, using phase inversion preparation nanofiltration membrane it is less, it will usually prepare the base of microporous barrier in phase separation method
It is aided with other technologies means, such as interfacial polymerization on plinth.
(2) lotus electrochemical process
Lotus electrochemical process is that the group with positive and negative charge is fixed on to the surface of seperation film using different technological means, with
Phase by Electrostatic Absorption and repulsive interaction, realizes the separation of solute.The lotus electrochemical method of film has very much, as L-S phase inversion is straight
It is connected into film, impregnated with method, polymerization, chemical surface treatment etc., but currently without the fixed hand of simple, reproducible film surface charge
Section, therefore this method not yet heavy industrialization application.
(3) composite algorithm
Composite algorithm is the compound one layer ultra-thin surface layer with nanoscale aperture on micropore basal membrane, to realize the mesh of separation
's.Micropore basal membrane only plays a supportive role, and shared osmotic resistance is smaller；And really determine nanofiltration membrane feature and separating property is super
Thin composite layer.
For composite membrane, basement membrane plays supporting role, it is desirable that its with appropriate hole density, aperture and pore-size distribution, and
There are good pressure tightness and physicochemical stability.The preparation of basement membrane uses L-S phase inversion more, and common material has polysulfones, gathers
Ether sulfone, Kynoar etc., while inoranic membrane also can be as the basement membrane of nanofiltration membrane.
When carrying out lock out operation using composite membrane, resistance is concentrated mainly on ultra-thin surface layer, in order to reduce the mass transfer resistance of film
Power should reduce as far as possible the thickness of separating layer under the premise of guaranteeing separation requirement.Currently, the preparation method of separating layer mainly has
Coating, LBL self-assembly, interfacial polymerization etc..Wherein, cladding process and LBL self-assembly method are on the one hand due to the separating layer of its formation
Thickness still in 500nm or so, limits the further promotion of permeation flux；On the other hand stablize to improve the longtime running of separating layer
Property, it is chemically crosslinked, increases operational sequence, be not easy to large-scale industrial production.And interfacial polymerization preparation is received
Filter membrane is then the film-forming method being most widely used at present.It is existing more deep to interfacial polymerization preparation nanofiltration membrane both at home and abroad
Research is concentrated mainly on the influence to nano filter membrane separating property such as research monomeric species, reaction condition, preparation parameter, and is made
The nanofiltration membrane of many superior performances, so that the film is all widely used in many fields.Cadotte first in 1970
Secondary that polymeric membrane for separation is prepared using interfacial polymerization, hereafter interfacial polymerization is just easy to operate and easily controllable etc. with its
Advantage is increasingly by the concern of researcher.Interfacial polymerization has become the most effective nanofiltration membrane produced in the world at present
Method, and industrialization nanofiltration membrane produce used classical way, and the nanofiltration membrane having been commercialized mainly has NF series, NTR system
Column, UTC series, ATF series, MPT series, MPF series and A-15 series etc..
It is raw in conjunction with mainstream by carrying out access analysis to the relevant documents and materials of domestic and international nanofiltration film preparation and Patent data
The nanofiltration membrane particular product performance parameters of business men, it can be found that the performance of nanofiltration membrane is broadly divided into three classes at present: high inorganic salts removal efficiency,
Such as the NF90 that Dow company produces, the removal efficiency to NaCl is more than 90%；High divalent ion removal efficiency, medium monovalention
Removal efficiency, as Dow company produce NF270, to 500ppm MgSO4And the removal efficiency of NaCl is respectively 98%, 40-
60%；Low inorganic salts removal efficiency, high organic molecule removal efficiency, such as Japan day east electrician (Nitto Denko) NTR7410, to chlorine
The removal efficiency for changing sodium and molecular weight 300Da dyestuff is respectively 10-15% and 98%.
It is possible thereby to find to lack high divalent ion removal efficiency at present, the high selection separation property of low monovalention removal efficiency is received
Filter membrane, although the NF270 of Dow company production can efficiently separate monovalention and divalent ion in high saline solns,
It only has 40-60% to the removal efficiency of monovalention such as NaCl at low concentrations, is still not enough to be effectively separated.In addition, mesh
Preceding commercialized nanofiltration membrane isoelectric point is generally all higher than 3.5, i.e., when feeding liquid pH value is lower than 3.5, electricity is presented in film surface substantially
Neutrality, it is relatively low to the removal efficiency of inorganic salts, it is unable to reach application requirement.Therefore, exploitation is a efficiently separates list at low concentrations
Valence inorganic salts are with high price inorganic salts and the lower high selection separation property nanofiltration membrane of isoelectric point has highly important economic benefit, society
It can benefit.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of preparation method of high selection separation property nanofiltration membrane, by this
The nanofiltration membrane that preparation method is prepared can efficiently separate monovalent inorganic salt and high price inorganic salts at low concentrations, while low
Also there is preferable separating effect in pH environment.
In order to achieve the above objectives, the technical scheme adopted by the invention is that: a kind of preparation of high selection separation property nanofiltration membrane
Method, its step are as follows:
(1) separating layer of high-throughput, the low inorganic salts removal efficiency of preparation:
As aqueous phase solution and suitable dendroid membrane material is added using piperazine, is carried out with pyromellitic trimethylsilyl chloride organic phase solution
Interfacial polymerization prepares the polypiperazine-amide separating layer that permeation flux is high, inorganic salts removal efficiency is low；
(2) separating layer of high negative charge density is prepared:
It selects strong electronegativity compound to be dissolved in pure water, and it is separated with the polypiperazine-amide that step (1) preparation is completed
Layer contact, carries out secondary response, forms the separating layer of high negative charge density.
Preferably, the preparation method of above-mentioned high selection separation property nanofiltration membrane, in which: the dendroid membrane material contains
Two and two or more hydroxyls or amido functional group, be specifically as follows polyvinyl alcohol, chitosan, polyethyleneimine, tea polyphenols,
One of the polyalcohols such as tannic acid, gossypose, polyamine high molecular material or compound are a variety of.
Preferably, the preparation method of above-mentioned high selection separation property nanofiltration membrane, in which: the dendroid membrane material it is dense
Degree is 0.01wt%~5.0wt%.
Preferably, the preparation method of above-mentioned high selection separation property nanofiltration membrane, in which: the strong electronegativity compound is extremely
Contain a hydroxyl or amino less, is specifically as follows taurine, sulfamic acid, p-hydroxybenzenyl sulfonate, 1-hydroxy ethylidene-1,1-diphosphonic acid, 2-
One of di guanidine-acetic acid etc. is a variety of.
Preferably, the preparation method of above-mentioned high selection separation property nanofiltration membrane, in which: the strong electronegativity compound
Concentration is 0.01wt%~5.0wt%.
The present invention also provides a kind of high selection separation property nanofiltration membranes as made from above-mentioned preparation method.
Compared with prior art, the invention has the following beneficial effects:
The present invention is added appropriate from the basic principle of interface polymerization reaction in piperazine/pyromellitic trimethylsilyl chloride system
Dendroid polyfunctional group membrane material, reduce aqueous phase solution in migration rate from active reaction object to organic phase, formed infiltration resistance
The lesser polypiperazine-amide separating layer of power；Then, it is remained using the polypiperazine-amide film surface that interface polymerization reaction completes initial stage
Acid chloride groups, reacted with the strong electronegativity compound containing hydroxyl or amino, in a manner of chemical bond persistence enhance
Film surface electronegativity, acquisition have the high selection separation property for having high removal efficiency to divalent ion, having low removal efficiency to monovalention
Nanofiltration membrane；Further, since the strong electronegativity compound introduced contains sulfonic acid group or phosphate group, isoelectric point is lower than routine
Polypiperazine-amide nanofiltration membrane can keep the charge of film surface in lower pH value, to obtain broader pH value application
Range.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Comparative example 1:
The P-3500 polysulfones that U.S. Su Wei is produced is dissolved in n,N-dimethylacetamide first, being configured to mass fraction is
Polysulfones microporous barrier is prepared using phase separation method after vacuum defoamation in 20% casting solution；
Then polysulfones microporous barrier is immersed in the aqueous phase solution of the piperazine containing 2wt%, removes the molten of excess surface with rubber rollers
The polysulfones microporous barrier is contacted 1 minute with the organic phase solution of the pyromellitic trimethylsilyl chloride containing 1wt% after liquid, and in 80 DEG C of baking oven
Heat treatment 5 minutes obtains polypiperazine-amide nanofiltration membrane.
Under conditions of pressure is 0.5MPa, temperature is 25 DEG C, pH value is 7.0 ± 0.2 and pH value is 3.0 ± 0.2, point
Not Ce Shi polypiperazine-amide nanofiltration membrane pure water permeation flux and to 500mg/l NaCl, MgSO4Removal efficiency, acquired results are shown in
Table 1, table 2.
Embodiment 1:
The P-3500 polysulfones that U.S. Su Wei is produced is dissolved in n,N-dimethylacetamide first, being configured to mass fraction is
Polysulfones microporous barrier is prepared using phase separation method after vacuum defoamation in 20% casting solution；
Secondly polysulfones microporous barrier is immersed in the aqueous phase solution of piperazine containing 2wt%, 0.5wt% polyvinyl alcohol, uses rubber rollers
The polysulfones microporous barrier is contacted 1 minute with the organic phase solution of the pyromellitic trimethylsilyl chloride containing 1wt% after removing the solution of excess surface,
And be heat-treated 5 minutes in 80 DEG C of baking oven, obtain polypiperazine-amide nanofiltration membrane.
Then nascent state polypiperazine-amide nanofiltration membrane and the taurine aqueous solution containing 0.5wt% (are selected into pH=7.5 phosphoric acid
Potassium dihydrogen/sodium hydroxide buffer solution) contact 1 minute, secondary response is carried out, strong electronegative group is introduced into nanofiltration film surface,
Prepare high selection separation property nanofiltration membrane.
Under conditions of pressure is 0.5MPa, temperature is 25 DEG C, pH value is 7.0 ± 0.2 and pH value is 3.0 ± 0.2, point
Not Ce Shi polypiperazine-amide nanofiltration membrane pure water permeation flux and to 500mg/l NaCl, MgSO4Removal efficiency, acquired results are shown in
Table 1, table 2.
Embodiment 2:
The P-3500 polysulfones that U.S. Su Wei is produced is dissolved in n,N-dimethylacetamide first, being configured to mass fraction is
Polysulfones microporous barrier is prepared using phase separation method after vacuum defoamation in 20% casting solution；
Secondly polysulfones microporous barrier is immersed in the aqueous phase solution of piperazine containing 2wt%, 0.5wt% polyvinyl alcohol, uses rubber rollers
The polysulfones microporous barrier is contacted 1 minute with the organic phase solution of the pyromellitic trimethylsilyl chloride containing 1wt% after removing the solution of excess surface,
And be heat-treated 5 minutes in 80 DEG C of baking oven, obtain polypiperazine-amide nanofiltration membrane.
Then nascent state polypiperazine-amide nanofiltration membrane and the aqueous sulfamic acid containing 0.5wt% (are selected into pH=7.5
Potassium dihydrogen phosphate/sodium hydroxide buffer solution) contact 1 minute, secondary response is carried out, strong electronegative group is introduced into nanofiltration membrane table
Face prepares high selection separation property nanofiltration membrane.
Under conditions of pressure is 0.5MPa, temperature is 25 DEG C, pH value is 7.0 ± 0.2 and pH value is 3.0 ± 0.2, point
Not Ce Shi polypiperazine-amide nanofiltration membrane pure water permeation flux and to 500mg/l NaCl, MgSO4Removal efficiency, acquired results are shown in
Table 1, table 2.
Embodiment 3:
The P-3500 polysulfones that U.S. Su Wei is produced is dissolved in n,N-dimethylacetamide first, being configured to mass fraction is
Polysulfones microporous barrier is prepared using phase separation method after vacuum defoamation in 20% casting solution；
Secondly polysulfones microporous barrier is immersed in the aqueous phase solution of piperazine containing 2wt%, 0.5wt% tannic acid, is gone with rubber rollers
Except the polysulfones microporous barrier is contacted 1 minute with the organic phase solution of the pyromellitic trimethylsilyl chloride containing 1wt% after the solution of excess surface, and
It is heat-treated 5 minutes in 80 DEG C of baking oven, obtains polypiperazine-amide nanofiltration membrane.
Then nascent state polypiperazine-amide nanofiltration membrane and the 1-hydroxy ethylidene-1,1-diphosphonic acid aqueous solution containing 0.5wt% (are selected into pH
=7.5 potassium dihydrogen phosphates/sodium hydroxide buffer solution) contact 1 minute, secondary response is carried out, the introducing of strong electronegative group is received
Filter membrane surface prepares high selection separation property nanofiltration membrane.
Under conditions of pressure is 0.5MPa, temperature is 25 DEG C, pH value is 7.0 ± 0.2 and pH value is 3.0 ± 0.2, point
Not Ce Shi polypiperazine-amide nanofiltration membrane pure water permeation flux and to 500mg/l NaCl, MgSO4Removal efficiency, acquired results are shown in
Table 1, table 2.
Embodiment 4:
The P-3500 polysulfones that U.S. Su Wei is produced is dissolved in n,N-dimethylacetamide first, being configured to mass fraction is
Polysulfones microporous barrier is prepared using phase separation method after vacuum defoamation in 20% casting solution；
Secondly polysulfones microporous barrier is immersed in the aqueous phase solution of piperazine containing 2wt%, 0.5wt% polyethyleneimine, uses rubber
The polysulfones microporous barrier is contacted 1 point with the organic phase solution of the pyromellitic trimethylsilyl chloride containing 1wt% after the solution of roller removal excess surface
Clock, and be heat-treated 5 minutes in 80 DEG C of baking oven, obtain polypiperazine-amide nanofiltration membrane.
Then nascent state polypiperazine-amide nanofiltration membrane and the taurine aqueous solution containing 0.5wt% (are selected into pH=7.5 phosphoric acid
Potassium dihydrogen/sodium hydroxide buffer solution) contact 1 minute, secondary response is carried out, strong electronegative group is introduced into nanofiltration film surface,
Prepare high selection separation property nanofiltration membrane.
Under conditions of pressure is 0.5MPa, temperature is 25 DEG C, pH value is 7.0 ± 0.2 and pH value is 3.0 ± 0.2, point
Not Ce Shi polypiperazine-amide nanofiltration membrane pure water permeation flux and to 500mg/l NaCl, MgSO4Removal efficiency, acquired results are shown in
Table 1, table 2.
Embodiment 5:
The P-3500 polysulfones that U.S. Su Wei is produced is dissolved in n,N-dimethylacetamide first, being configured to mass fraction is
Polysulfones microporous barrier is prepared using phase separation method after vacuum defoamation in 20% casting solution；
Secondly polysulfones microporous barrier is immersed in the aqueous phase solution of piperazine containing 2wt%, 0.5wt% polyethyleneimine, uses rubber
The polysulfones microporous barrier is contacted 1 point with the organic phase solution of the pyromellitic trimethylsilyl chloride containing 1wt% after the solution of roller removal excess surface
Clock, and be heat-treated 5 minutes in 80 DEG C of baking oven, obtain polypiperazine-amide nanofiltration membrane.
Then nascent state polypiperazine-amide nanofiltration membrane and the aqueous sulfamic acid containing 0.5wt% (are selected into pH=7.5
Potassium dihydrogen phosphate/sodium hydroxide buffer solution) contact 1 minute, secondary response is carried out, strong electronegative group is introduced into nanofiltration membrane table
Face prepares high selection separation property nanofiltration membrane.
Under conditions of pressure is 0.5MPa, temperature is 25 DEG C, pH value is 7.0 ± 0.2 and pH value is 3.0 ± 0.2, point
Not Ce Shi polypiperazine-amide nanofiltration membrane pure water permeation flux and to 500mg/l NaCl, MgSO4Removal efficiency, acquired results are shown in
Table 1, table 2.
Embodiment 6:
The P-3500 polysulfones that U.S. Su Wei is produced is dissolved in n,N-dimethylacetamide first, being configured to mass fraction is
Polysulfones microporous barrier is prepared using phase separation method after vacuum defoamation in 20% casting solution；
Secondly polysulfones microporous barrier is immersed in the aqueous phase solution of piperazine containing 2wt%, 0.5wt% tea polyphenols, is gone with rubber rollers
Except the polysulfones microporous barrier is contacted 1 minute with the organic phase solution of the pyromellitic trimethylsilyl chloride containing 1wt% after the solution of excess surface, and
It is heat-treated 5 minutes in 80 DEG C of baking oven, obtains polypiperazine-amide nanofiltration membrane.
Then nascent state polypiperazine-amide nanofiltration membrane and the 2- di guanidine-acetic acid aqueous solution containing 0.5wt% (are selected
PH=7.5 potassium dihydrogen phosphate/sodium hydroxide buffer solution) contact 1 minute, secondary response is carried out, strong electronegative group is introduced
Nanofiltration film surface prepares high selection separation property nanofiltration membrane.
Under conditions of pressure is 0.5MPa, temperature is 25 DEG C, pH value is 7.0 ± 0.2 and pH value is 3.0 ± 0.2, point
Not Ce Shi polypiperazine-amide nanofiltration membrane pure water permeation flux and to 500mg/l NaCl, MgSO4Removal efficiency, acquired results are shown in
Table 1, table 2.
Embodiment 7:
The P-3500 polysulfones that U.S. Su Wei is produced is dissolved in n,N-dimethylacetamide first, being configured to mass fraction is
Polysulfones microporous barrier is prepared using phase separation method after vacuum defoamation in 20% casting solution；
Secondly polysulfones microporous barrier is immersed in the aqueous phase solution of piperazine containing 2wt%, 0.5wt% chitosan, is gone with rubber rollers
Except the polysulfones microporous barrier is contacted 1 minute with the organic phase solution of the pyromellitic trimethylsilyl chloride containing 1wt% after the solution of excess surface, and
It is heat-treated 5 minutes in 80 DEG C of baking oven, obtains polypiperazine-amide nanofiltration membrane.
Then nascent state polypiperazine-amide nanofiltration membrane and the p-hydroxybenzenyl sulfonate aqueous solution containing 0.5wt% (are selected into pH=
7.5 potassium dihydrogen phosphates/sodium hydroxide buffer solution) contact 1 minute, secondary response is carried out, strong electronegative group is introduced into nanofiltration
Film surface prepares high selection separation property nanofiltration membrane.
Under conditions of pressure is 0.5MPa, temperature is 25 DEG C, pH value is 7.0 ± 0.2 and pH value is 3.0 ± 0.2, point
Not Ce Shi polypiperazine-amide nanofiltration membrane pure water permeation flux and to 500mg/l NaCl, MgSO4Removal efficiency, acquired results are shown in
Table 1, table 2.
Embodiment 8:
The P-3500 polysulfones that U.S. Su Wei is produced is dissolved in n,N-dimethylacetamide first, being configured to mass fraction is
Polysulfones microporous barrier is prepared using phase separation method after vacuum defoamation in 20% casting solution；
Secondly polysulfones microporous barrier is immersed in the aqueous phase solution of piperazine containing 2wt%, 0.5wt% gossypose, is gone with rubber rollers
Except the polysulfones microporous barrier is contacted 1 minute with the organic phase solution of the pyromellitic trimethylsilyl chloride containing 1wt% after the solution of excess surface, and
It is heat-treated 5 minutes in 80 DEG C of baking oven, obtains polypiperazine-amide nanofiltration membrane.
Then nascent state polypiperazine-amide nanofiltration membrane and the p-hydroxybenzenyl sulfonate aqueous solution containing 0.5wt% (are selected into pH=
7.5 potassium dihydrogen phosphates/sodium hydroxide buffer solution) contact 1 minute, secondary response is carried out, strong electronegative group is introduced into nanofiltration
Film surface prepares high selection separation property nanofiltration membrane.
Under conditions of pressure is 0.5MPa, temperature is 25 DEG C, pH value is 7.0 ± 0.2 and pH value is 3.0 ± 0.2, point
Not Ce Shi polypiperazine-amide nanofiltration membrane pure water permeation flux and to 500mg/l NaCl, MgSO4Removal efficiency, acquired results are shown in
Table 1, table 2.
The separating property of each nanofiltration membrane when 1 pH=7.0 of table
The separating property of each nanofiltration membrane when 2 pH=3.0 of table
When table 1 is pH=7.0, the pure water flux and NaCl, MgSO of each nanofiltration membrane4Removal efficiency data, by analysis can be with
It was found that adding dendrimer membrane material in aqueous phase solution and after film surface introduces high elecrtonegativity compound, nanofiltration membrane
Permeation flux increase by 20% or so on year-on-year basis, this is mainly due in aqueous phase solution add dendrimer membrane material after,
Form the lower polypiperazine-amide separating layer of osmotic resistance；It is shown as in terms of cutoff performance left from 45% to the removal efficiency of NaCl
Bottom right drops to 10%~20%, but simultaneously because high electronegative group introducing, dianion by stronger repulsive interaction,
Thus to MgSO4Removal efficiency can maintain the level similar with conventional nanofiltration membrane.
When table 2 is pH=3.0, the pure water flux and NaCl, MgSO of each nanofiltration membrane4Removal efficiency data, with 1 data comparison of table
It can be found that the variation of the pure water flux of each nanofiltration membrane substantially not by a relatively large margin, NaCl, MgSO of conventional nanofiltration membrane4Removing
Rate drops to 22.3%, 95.3% from 43.5% respectively and drops to 83.1%.This is primarily due to the negative of conventional nanofiltration membrane surface
Caused by electrically being ionized as carboxyl, when feeding liquid pH is 3.0, the carboxyl of film surface fails to ionize, and film surface charge is in
Property, it is only capable of being sieved by aperture effect, therefore a sharp decline occurs in removal efficiency.And sulfonic acid group is introduced in film surface
Or after phosphate group, isoelectric point is deviated to low ph value, even if remaining to maintain electronegativity in pH=3.0, so to inorganic salts
Removal efficiency decline is relatively small, expands the pH scope of application of nanofiltration membrane to a certain extent.
The above, preferable specific embodiment only of the invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Design is subject to equivalent substitution or change, should be covered by the scope of protection of the present invention.
Claims (9)
1. a kind of preparation method of high selection separation property nanofiltration membrane, which comprises the steps of:
(1) separating layer of high-throughput, the low inorganic salts removal efficiency of preparation:
As aqueous phase solution and dendroid membrane material is added using piperazine, carries out interfacial polymerization with pyromellitic trimethylsilyl chloride organic phase solution,
Prepare the polypiperazine-amide separating layer that permeation flux is high, inorganic salts removal efficiency is low；
(2) separating layer of high negative charge density is prepared:
It selects strong electronegativity compound to be dissolved in pure water, and its polypiperazine-amide separating layer completed with step (1) preparation is connect
Touching carries out secondary response, forms the separating layer of high negative charge density.
2. the preparation method of high selection separation property nanofiltration membrane according to claim 1, which is characterized in that the dendroid film
Material contains two and two or more hydroxyls or amido functional group.
3. the preparation method of high selection separation property nanofiltration membrane according to claim 1, which is characterized in that the dendroid film
Material is one of polyalcohol, polyamine high molecular material or compound or a variety of.
4. the preparation method of high selection separation property nanofiltration membrane according to claim 1,2 or 3, which is characterized in that the tree
Dendritic membrane material is one of polyvinyl alcohol, chitosan, polyethyleneimine, tea polyphenols, tannic acid, gossypose or a variety of.
5. the preparation method of high selection separation property nanofiltration membrane according to claim 1, which is characterized in that the dendroid film
The concentration of material is 0.01wt%~5.0wt%.
6. the preparation method of high selection separation property nanofiltration membrane according to claim 1, which is characterized in that the strong electronegativity
Compound at least contains a hydroxyl or amino.
7. the preparation method of high selection separation property nanofiltration membrane according to claim 1 or 6, which is characterized in that the forceful electric power
Negativity compound is taurine, in sulfamic acid, p-hydroxybenzenyl sulfonate, 1-hydroxy ethylidene-1,1-diphosphonic acid, 2- di guanidine-acetic acid
It is one or more.
8. the preparation method of high selection separation property nanofiltration membrane according to claim 1, which is characterized in that the strong electronegativity
The concentration of compound is 0.01wt%~5.0wt%.
9. a kind of high selection separation property nanofiltration membrane as made from preparation method according to any one of claims 1 to 8.
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Cited By (5)
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| CN110917906A (en) * | 2019-12-11 | 2020-03-27 | 南京大学 | Ferroelectric nanofiltration membrane material, preparation method and application |
| CN111001317A (en) * | 2019-12-05 | 2020-04-14 | 浙江工业大学 | Novel high-flux high-selectivity composite nanofiltration membrane and preparation method thereof |
| CN111068526A (en) * | 2019-12-19 | 2020-04-28 | 中化(宁波)润沃膜科技有限公司 | Desalination composite membrane and preparation method thereof |
| CN112973467A (en) * | 2019-12-02 | 2021-06-18 | 欧美新材料(浙江)有限公司 | Preparation method of composite nanofiltration membrane and composite nanofiltration membrane |
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| CN110917906A (en) * | 2019-12-11 | 2020-03-27 | 南京大学 | Ferroelectric nanofiltration membrane material, preparation method and application |
| CN111068526A (en) * | 2019-12-19 | 2020-04-28 | 中化(宁波)润沃膜科技有限公司 | Desalination composite membrane and preparation method thereof |
| CN111068526B (en) * | 2019-12-19 | 2022-06-14 | 中化(宁波)润沃膜科技有限公司 | Desalination composite membrane and preparation method thereof |
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