CN101940883A - Preparation method of reverse osmosis composite membrane containing nano zeolite molecular sieves - Google Patents
Preparation method of reverse osmosis composite membrane containing nano zeolite molecular sieves Download PDFInfo
- Publication number
- CN101940883A CN101940883A CN201010243109XA CN201010243109A CN101940883A CN 101940883 A CN101940883 A CN 101940883A CN 201010243109X A CN201010243109X A CN 201010243109XA CN 201010243109 A CN201010243109 A CN 201010243109A CN 101940883 A CN101940883 A CN 101940883A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- reverse osmosis
- nano zeolite
- composite membrane
- osmosis composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a preparation method of a reverse osmosis composite membrane containing nano zeolite molecular sieves. The method comprises the following steps: dispersing the nano zeolite molecular sieves into polyamine aqueous solution to obtain a mixture A; dipping a polysulfone supporting membrane into the mixture A, taking out the membrane and then removing a solvent for the memebrane, carrying out interfacial polymerization on the membrane without the solvent in poly-acyl chloride solution, and after-treating the membrane after interfacial polymerization finishes to obtain the reverse osmosis composite membrane containing the nano zeolite molecular sieves; or dispersing the nano zeolite molecular sieves into the poly-acyl chloride solution to obtain a mixture B; and dipping the polysulfone supporting membrane into the polyamine aqueous solution, taking out the membrane and then removing the solvent for the membrane, carrying out interfacial polymerization on the membrane without the solvent in the mixture B, and after-treating the membrane after interfacial polymerization finishes to obtain the reverse osmosis composite membrane containing the nano zeolite molecular sieves. The reverse osmosis composite membrane containing the nano zeolite molecular sieves obtained by the preparation method of the invention has higher desalination rate, higher water flux and higher mechanical strength.
Description
Technical field
The present invention relates to the reverse osmosis membrane preparation field, relate in particular to a kind of preparation method who contains the molecular sieve of Nano zeolite reverse osmosis composite membrane.
Background technology
Reverse osmosis composite membrane has obtained in the desalinization field using widely as realizing one of industrialized membrane technology the earliest.Reverse osmosis composite membrane generally is that one deck ultrathin functional layer is deposited to the film that suitable micropore support membrane surface, aperture forms by interface polymerization reaction, and the functional film material of industrial applications is generally polyamide.Along with water resources problems is on the rise, reverse osmosis technology is extended to fields such as wastewater treatment just gradually from the desalinization field, therefore reverse osmosis membrane has also been proposed new requirement, and high flux, antipollution, resistance to oxidation and high-intensity film are the need of commercial Application.
Traditional organic film has that pliability is good, gas permeability is high, low density advantage, but its anti-solvent, corrosion-resistant, the heatproof degree is all relatively poor; Though and simple inoranic membrane intensity height, corrosion-resistant, anti-solvent, high temperature resistant are more crisp, be difficult for processing.Thereby the focus that to prepare a kind of film that has both advantages concurrently be current research.Hybrid organic-inorganic film is introduced inorganic particle in organic network, improved organic network structure, strengthened the mechanical performance of film, improved the heat endurance of film, the pore structure and the distribution that improve and modified film, regulate the porosity and the hydrophilic-hydrophobic balance of film, improved permeability of the membrane and separation selectivity.
Present stage has had in a large number and studies show that, organic-inorganic hybridized osmotic vaporization film and hybrid inorganic-organic gas separation membrane are compared with the pure polymers film, and physical and chemical stability and separating property all improve a lot.But also fewer comparatively speaking to the research of hybrid inorganic-organic reverse osmosis membrane, this is because the preparation method of reverse osmosis membrane and design feature and infiltration evaporation, the composite gas separation of film have a great difference.Reverse osmosis membrane generally prepares by interfacial polymerization, be soluble in the aqueous phase and two kinds of monomers of organic facies carry out polycondensation reaction at the two-phase interface place, polymerization film formation in the extremely short time, therefore, the filling of inorganic particulate just can not prepare composite membrane as phase inversion, particle and casting solution are carried out simple blend, but particle will be scattered in water or organic phase solution, in interfacial polymerization process, make inorganic particle filled in the aramid layer of polymerisation generation.Hybrid inorganic-organic reverse osmosis membrane not only preparation technology is comparatively complicated, particle diameter to the inorganic particulate of filling also has high requirements, this is the very thin thickness (less than 1 μ m) owing to its aramid layer, and therefore the particle diameter of the inorganic particulate of filling must be a Nano grade.
Have research that nanometer grade silica, titanium dioxide granule are added in the reverse osmosis composite membrane, the result shows that the physical stability of film and separating property all improve.But these nano particles do not have pore passage structure, to improving the separating property of film, act on very limited.Nano molecular sieve claims superfine molecular sieves again, and its particle size between 1~100 nanometer, is the crystal that a class has the porous road generally.The molecular simulation result shows that the duct of LTA type molecular sieve of Nano zeolite is Subnano-class (0.42 nanometer), than hydration Na
+, Cl
-The plasma diameter is little, therefore, and to hydration Na
+, Cl
-Plasma has 100% rejection, and hydrone (0.27 nanometer) then can freely pass through its duct simultaneously.Therefore, for the aqueous solution that contains salt ion, have only hydrone can pass through the duct of LTA type molecular sieve of Nano zeolite, salt ion then is trapped.Simultaneously, because LTA type molecular sieve of Nano zeolite surface has certain hydrophily, the adsorption and diffusion of hydrone will be improved.The permeation flux that film is improved in the molecular sieve filled duct that not only can utilize molecular sieve in the PA membrane also can if can be improved the rejection and the chemical stability of film simultaneously.
Because the preparation process of interfacial polymerization film is special, the process that zeolite adds in the reverse osmosis membrane is also sneaked out Cheng Butong together, and when adding to zeolite molecular sieve in water or the oil phase, the process of film forming and the separating effect of film also will be different, but this respect also has the research report.In addition, about how increasing the compatibility between zeolite molecular sieve and the organosilicon/polyamide 6 amine film and improve the dispersion of zeolite molecular sieve in the film, contain the performance of zeolite molecular sieve reverse osmosis composite membrane, be still waiting to do further research with further raising.
Summary of the invention
The invention provides a kind of preparation method who contains the reverse osmosis composite membrane of molecular sieve of Nano zeolite, the water flux of the reverse osmosis composite membrane that makes and salt rejection rate height, mechanical strength is good.
A kind of preparation method who contains the reverse osmosis composite membrane of molecular sieve of Nano zeolite comprises: molecular sieve of Nano zeolite is distributed in the polyamine aqueous solution, obtains mixture A; The polysulfones support membrane is immersed among the said mixture A, the immersion time is 30~60min, take out film and remove solvent, film and polynary solution of acid chloride behind the removal solvent are carried out interface polymerization reaction, and the film after reaction is finished obtains containing the reverse osmosis composite membrane of molecular sieve of Nano zeolite through post processing;
The above-mentioned reverse osmosis composite membrane that contains molecular sieve of Nano zeolite can also adopt following preparation method's preparation, comprising: molecular sieve of Nano zeolite is distributed in the polynary solution of acid chloride, obtains mixture B; The polysulfones support membrane is immersed in the polyamine aqueous solution, the immersion time is 30~60min, take out film and remove solvent, film and said mixture B behind the removal solvent carry out interface polymerization reaction, and the film after reaction is finished obtains containing the reverse osmosis composite membrane of molecular sieve of Nano zeolite through post processing.
The weight ratio of polysulfones support membrane, polyamine and polynary acyl chlorides is 5~20: 10~70: 1.The polysulfones support membrane is selected conventional commercially available prod for use, is the polysulfones porous milipore filter of 30~40 nanometers as commercially available average pore size.
When preparation mixture A and mixture B, mix for guaranteeing molecular sieve of Nano zeolite and corresponding solution, the mixture A and the mixture B thermostatic ultrasonic that contain molecular sieve of Nano zeolite can be handled, the processing time was not less than 10 minutes.
Among mixture A and the mixture B, the weight percent concentration of molecular sieve of Nano zeolite is: 0.001~0.2%, and the weight percent concentration of preferred molecular sieve of Nano zeolite is 0.05~0.2%.
The molecular sieve of Nano zeolite surface has a large amount of hydroxyls, makes molecular sieve of Nano zeolite have hydrophily preferably, helps the dispersion of molecular sieve of Nano zeolite in the aqueous solution.In interfacial polymerization process, molecular sieve of Nano zeolite can be added in the polyamine aqueous solution, also molecular sieve of Nano zeolite can be added in the polynary solution of acid chloride, reaction active groups hydroxyl and acyl chlorides on the molecular sieve of Nano zeolite are had an effect to improve its dispersion in polynary solution of acid chloride.
It is 60~70 nanometer LTA type molecular sieve of Nano zeolite that molecular sieve of Nano zeolite is selected from average grain diameter.LTA type molecular sieve of Nano zeolite.
The weight percent concentration of polyamine is 1~10% in the polyamine aqueous solution, and concentration is unsuitable excessive, and the excessive polyamine dissolving of concentration not exclusively makes in the reverse osmosis composite membrane for preparing at last to have defective easily.
The solvent of polynary solution of acid chloride is selected from C
5~C
8Fat alkane, the weight percent concentration of polynary acyl chlorides is 0.05~0.6% in the polynary solution of acid chloride, concentration is unsuitable excessive, the excessive polynary acyl chlorides dissolving of concentration not exclusively makes in the reverse osmosis composite membrane for preparing at last to have defective equally easily; Preferred solvent is a n-hexane.
Polyamine is preferably m-phenylene diamine (MPD); Polynary acyl chlorides is preferably pyromellitic trimethylsilyl chloride.
The reaction time of interface polymerization reaction is 40~60 seconds.
The method of removing solvent can adopt natural air drying to arrive certain degree or with the solvent of rubber stick rolled film surface with removal film surface.
Film after interface polymerization reaction is finished is through the reverse osmosis composite membrane that dries in the shade, 50~70 ℃ of baking oven heated at constant temperature and rinsing obtain containing molecular sieve of Nano zeolite.
The preparation method who contains the zeolite molecular sieve reverse osmosis composite membrane provided by the invention, the preparation method is simple, and the mechanical strength that contains the zeolite molecular sieve reverse osmosis composite membrane of preparation is good, and salt rejection rate and water flux are higher than polyamide reverse osmose membrane.
Description of drawings
Fig. 1 is the surface scan electron microscope picture of the complex reverse osmosis membrane of embodiment 6 preparations;
Fig. 2 is the surface scan electron microscope picture of the complex reverse osmosis membrane of embodiment 12 preparations.
The specific embodiment
The prepared reverse osmosis composite membrane of the present invention is used for desalination, and salt rejection rate and water flux are two important parameters estimating reverse osmosis composite membrane, and salt rejection rate R is defined as:
Wherein, C
fThe concentration of salt in the water before expression is handled; C
pThe concentration that the back sees through salt in the liquid is handled in expression.
Water flux is defined as: under certain operating condition, see through the volume of the water of elementary membrane area in the unit interval, its unit is L/m
2.h.
The test condition that adopts among the present invention is: the sodium-chloride water solution of 2000ppm, operating pressure are 232psi, and operating temperature is 25 ℃.
The polysulfones support membrane that uses in the embodiment of the invention is the polysulfones porous milipore filter of 30~40 nanometers as average pore size, derives from State Oceanic Administration, Hangzhou Water Treatment Technology Research and Development Center.
Embodiment 1
With average grain diameter is that to be distributed to the 100ml weight percent concentration be in 5% the m-phenylene diamine (MPD) aqueous solution for the LTA type molecular sieve of Nano zeolite of 60 nanometers, guarantee that LTA type zeolite molecular sieve weight percent concentration is 0.006%, ultrasonic processing obtained mixture in 10 minutes under the room temperature; With the 1g average pore size is that the polysulfones porous milipore filter of 30 nanometers directly is immersed in the said mixture, the immersion time is 30min, take out film, treat the moisture natural air drying 0.5h on film top layer, be that 0.4% pyromellitic trimethylsilyl chloride hexane solution 50ml carries out interface polymerization reaction and made composite membrane in 40 seconds with weight percent concentration immediately, composite membrane dried in the shade in air 2 minutes, again through 60 ℃ of baking oven heated at constant temperature 20 minutes, rinsing 10 minutes in 40 ℃ water then, obtain containing the molecular sieve of Nano zeolite reverse osmosis composite membrane, the reverse osmosis composite membrane of preparation is kept in the water.
Embodiment 2
With average grain diameter is that to be distributed to the 100ml weight percent concentration be in 8% the m-phenylene diamine (MPD) aqueous solution for the LTA type molecular sieve of Nano zeolite of 65 nanometers, guarantee that LTA type zeolite molecular sieve weight percent concentration is 0.012%, ultrasonic processing obtained mixture in 20 minutes under the room temperature; With the 1g average pore size is that the polysulfones porous milipore filter of 30 nanometers directly is immersed in the said mixture, the immersion time is 40min, take out film, treat the moisture natural air drying 0.5h on film top layer, be that 0.6% pyromellitic trimethylsilyl chloride hexane solution 50ml carries out interface polymerization reaction 50s and makes composite membrane with weight percent concentration immediately, composite membrane dried in the shade in air 2 minutes, again through 60 ℃ of baking oven heated at constant temperature 20 minutes, rinsing 10 minutes in 40 ℃ water then, obtain containing the molecular sieve of Nano zeolite reverse osmosis composite membrane, the reverse osmosis composite membrane of preparation is kept in the water.
Embodiment 3
With average grain diameter is that to be distributed to the 100ml weight percent concentration be in 5% the m-phenylene diamine (MPD) aqueous solution for the LTA type molecular sieve of Nano zeolite of 70 nanometers, guarantee that LTA type zeolite molecular sieve weight percent concentration is 0.025%, ultrasonic processing obtained mixture in 30 minutes under the room temperature; With the 1g average pore size is that the polysulfones porous milipore filter of 30 nanometers directly is immersed in the said mixture, the immersion time is 40min, take out film, treat the moisture natural air drying 0.5h on film top layer, be that 0.5% pyromellitic trimethylsilyl chloride hexane solution 50ml carries out interface polymerization reaction and made composite membrane in 60 seconds with weight percent concentration immediately, composite membrane dried in the shade in air 2 minutes, again through 60 ℃ of baking oven heated at constant temperature 20 minutes, rinsing 10 minutes in 40 ℃ water then, obtain containing the molecular sieve of Nano zeolite reverse osmosis composite membrane, the reverse osmosis composite membrane of preparation is kept in the water.
Embodiment 4
With average grain diameter is that to be distributed to the 100ml weight percent concentration be in 4% the m-phenylene diamine (MPD) aqueous solution for the LTA type molecular sieve of Nano zeolite of 60 nanometers, guarantee that LTA type zeolite molecular sieve weight percent concentration is 0.05%, ultrasonic processing obtained mixture in 20 minutes under the room temperature; With the 1g average pore size is that the polysulfones porous milipore filter of 30 nanometers directly is immersed in the said mixture, the immersion time is 50min, take out film, treat the moisture natural air drying 0.5h on film top layer, be that 0.4% pyromellitic trimethylsilyl chloride hexane solution 50ml carries out interface polymerization reaction and made composite membrane in 40 seconds with weight percent concentration immediately, composite membrane dried in the shade in air 2 minutes, again through 60 ℃ of baking oven heated at constant temperature 20 minutes, rinsing 10 minutes in 40 ℃ water then, obtain containing the molecular sieve of Nano zeolite reverse osmosis composite membrane, the reverse osmosis composite membrane of preparation is kept in the water.
Embodiment 5
With average grain diameter is that to be distributed to the 100ml weight percent concentration be in 3% the m-phenylene diamine (MPD) aqueous solution for the LTA type molecular sieve of Nano zeolite of 60 nanometers, guarantee that LTA type zeolite molecular sieve weight percent concentration is 0.1%, ultrasonic processing obtained mixture in 30 minutes under the room temperature; With the 1g average pore size is that the polysulfones porous milipore filter of 30 nanometers directly is immersed in the said mixture, the immersion time is 50min, take out film, treat the moisture natural air drying 0.5h on film top layer, be that 0.4% pyromellitic trimethylsilyl chloride hexane solution 50ml carries out interface polymerization reaction and made composite membrane in 50 seconds with weight percent concentration immediately, composite membrane dried in the shade in air 2 minutes, again through 60 ℃ of baking oven heated at constant temperature 20 minutes, rinsing 10 minutes in 40 ℃ water then, obtain containing the molecular sieve of Nano zeolite reverse osmosis composite membrane, the reverse osmosis composite membrane of preparation is kept in the water.
Embodiment 6
With average grain diameter is that to be distributed to the 100ml weight percent concentration be in 3% the m-phenylene diamine (MPD) aqueous solution for the LTA type molecular sieve of Nano zeolite of 60 nanometers, guarantee that LTA type zeolite molecular sieve weight percent concentration is 0.2%, ultrasonic processing obtained mixture in 40 minutes under the room temperature; With the 1g average pore size is that the polysulfones porous milipore filter of 30 nanometers directly is immersed in the said mixture, the immersion time is 40min, take out film, treat the moisture natural air drying 0.5h on film top layer, be that 0.2% pyromellitic trimethylsilyl chloride hexane solution 50ml carries out interface polymerization reaction and made composite membrane in 60 seconds with weight percent concentration immediately, composite membrane dried in the shade in air 2 minutes, again through 60 ℃ of baking oven heated at constant temperature 20 minutes, rinsing 10 minutes in 40 ℃ water then, obtain containing the molecular sieve of Nano zeolite reverse osmosis composite membrane, the reverse osmosis composite membrane of preparation is kept in the water.The molecular sieve of Nano zeolite reverse osmosis composite membrane that contains for preparing is made scanning electron microscope diagram, the result as shown in Figure 1, as can be seen from Figure 1: the surface of film is more smooth, and structure is more loose, is easy to passing through of hydrone.
Comparative Examples 1
With the 1g average pore size is that directly to be immersed in the 100ml weight percent concentration be in 3% the m-phenylene diamine (MPD) aqueous solution for the polysulfones porous milipore filter of 30 nanometers, the immersion time is 40min, take out film, treat the moisture natural air drying 0.5h on film top layer, be that 0.2% pyromellitic trimethylsilyl chloride hexane solution 50ml carries out interface polymerization reaction and made composite membrane in 60 seconds with weight percent concentration immediately, composite membrane dried in the shade in air 2 minutes, again through 60 ℃ of baking oven heated at constant temperature 20 minutes, rinsing 10 minutes in 40 ℃ water then, obtain reverse osmosis composite membrane, the reverse osmosis composite membrane of preparation is kept in the water.
Performance test example 1
At operating pressure is 232psi, operating temperature is under 25 ℃ the condition, respectively with the sodium-chloride water solution of 2000ppm by by the reverse osmosis composite membrane that contains molecular sieve of Nano zeolite that obtains of embodiment 1~6 preparation and the reverse osmosis composite membrane of Comparative Examples 1 preparation, the concentration of the sodium-chloride water solution after the test processes and volume, calculate the water flux and the salt rejection rate of each composite membrane respectively, test result is as shown in table 1: by table 1 result as can be known, the reverse osmosis composite membrane that contains molecular sieve of Nano zeolite that is prepared by embodiment 1~6 is on the basis that guarantees essentially identical salt rejection rate, water flux can improve more than 60%, obviously increases than the reverse osmosis composite membrane water flux that does not contain molecular sieve of Nano zeolite for preparing under the equal conditions.
Table 1
Embodiment 7
With average grain diameter is that the LTA type molecular sieve of Nano zeolite of 60 nanometers is distributed in the hexane solution that the 50ml weight percent concentration is 0.4% pyromellitic trimethylsilyl chloride, guarantee that LTA type zeolite molecular sieve weight percent concentration is 0.006%, ultrasonic processing obtained mixture in 10 minutes under the room temperature; With the 1g average pore size is that directly to be immersed in the 100ml weight percent concentration be in 6% the m-phenylene diamine (MPD) aqueous solution for the polysulfones porous milipore filter of 30 nanometers, the immersion time is 40min, take out film, after extracting with rubber stick roll extrusion support membrane surface, carried out interface polymerization reaction 40 seconds with said mixture, composite membrane dried in the shade in air 2 minutes, again through 60 ℃ of baking oven heated at constant temperature 20 minutes, rinsing 10 minutes in 40 ℃ water then, rinsing obtains containing the molecular sieve of Nano zeolite reverse osmosis composite membrane, prepares reverse osmosis composite membrane and is kept in the water.
Embodiment 8
With average grain diameter is that the LTA type molecular sieve of Nano zeolite of 65 nanometers is distributed in the hexane solution that the 50ml weight percent concentration is 0.3% pyromellitic trimethylsilyl chloride, guarantee that LTA type zeolite molecular sieve weight percent concentration is 0.012%, ultrasonic processing obtained mixture in 10 minutes under the room temperature; With the 1g average pore size is that directly to be immersed in the 100ml weight percent concentration be in 2% the m-phenylene diamine (MPD) aqueous solution for the polysulfones porous milipore filter of 30 nanometers, the immersion time is 40min, take out film, after extracting with rubber stick roll extrusion support membrane surface, carried out interface polymerization reaction 50 seconds with said mixture, composite membrane dried in the shade in air 2 minutes, again through 60 ℃ of baking oven heated at constant temperature 20 minutes, rinsing 10 minutes in 40 ℃ water then, rinsing obtains containing the molecular sieve of Nano zeolite reverse osmosis composite membrane, prepares reverse osmosis composite membrane and is kept in the water.
Embodiment 9
With average grain diameter is that the LTA type molecular sieve of Nano zeolite of 70 nanometers is distributed in the hexane solution that the 50ml weight percent concentration is 0.2% pyromellitic trimethylsilyl chloride, guarantee that LTA type zeolite molecular sieve weight percent concentration is 0.025%, ultrasonic processing obtained mixture in 10 minutes under the room temperature; With the 1g average pore size is that directly to be immersed in the 100ml weight percent concentration be in 4% the m-phenylene diamine (MPD) aqueous solution for the polysulfones porous milipore filter of 30 nanometers, the immersion time is 40min, take out film, after extracting with rubber stick roll extrusion support membrane surface, carried out interface polymerization reaction 60 seconds with said mixture, composite membrane dried in the shade in air 2 minutes, again through 60 ℃ of baking oven heated at constant temperature 20 minutes, rinsing 10 minutes in 40 ℃ water then, rinsing obtains containing the molecular sieve of Nano zeolite reverse osmosis composite membrane, prepares reverse osmosis composite membrane and is kept in the water.
Embodiment 10
With average grain diameter is that the LTA type molecular sieve of Nano zeolite of 60 nanometers is distributed in the hexane solution that the 50ml weight percent concentration is 0.3% pyromellitic trimethylsilyl chloride, guarantee that LTA type zeolite molecular sieve weight percent concentration is 0.05%, ultrasonic processing obtained mixture in 10 minutes under the room temperature; With the 1g average pore size is that directly to be immersed in the 100ml weight percent concentration be in 6% the m-phenylene diamine (MPD) aqueous solution for the polysulfones porous milipore filter of 30 nanometers, the immersion time is 40min, take out film, after extracting with rubber stick roll extrusion support membrane surface, carried out interface polymerization reaction 60 seconds with said mixture, composite membrane dried in the shade in air 2 minutes, again through 60 ℃ of baking oven heated at constant temperature 20 minutes, rinsing 10 minutes in 40 ℃ water then, rinsing obtains containing the molecular sieve of Nano zeolite reverse osmosis composite membrane, prepares reverse osmosis composite membrane and is kept in the water.
Embodiment 11
With average grain diameter is that the LTA type molecular sieve of Nano zeolite of 60 nanometers is distributed in the hexane solution that the 50ml weight percent concentration is 0.4% pyromellitic trimethylsilyl chloride, guarantee that LTA type zeolite molecular sieve weight percent concentration is 0.1%, ultrasonic processing obtained mixture in 10 minutes under the room temperature; With the 1g average pore size is that directly to be immersed in the 100ml weight percent concentration be in 4% the m-phenylene diamine (MPD) aqueous solution for the polysulfones porous milipore filter of 30 nanometers, the immersion time is 40min, take out film, after extracting with rubber stick roll extrusion support membrane surface, carried out interface polymerization reaction 50 seconds with said mixture, composite membrane dried in the shade in air 2 minutes, again through 60 ℃ of baking oven heated at constant temperature 20 minutes, rinsing 10 minutes in 40 ℃ water then, rinsing obtains containing the molecular sieve of Nano zeolite reverse osmosis composite membrane, prepares reverse osmosis composite membrane and is kept in the water.
Embodiment 12
With average grain diameter is that the LTA type molecular sieve of Nano zeolite of 60 nanometers is distributed in the hexane solution that the 50ml weight percent concentration is 0.2% pyromellitic trimethylsilyl chloride, guarantee that LTA type zeolite molecular sieve weight percent concentration is 0.2%, ultrasonic processing obtained mixture in 10 minutes under the room temperature; With the 1g average pore size is that directly to be immersed in the 100ml weight percent concentration be in 3% the m-phenylene diamine (MPD) aqueous solution for the polysulfones porous milipore filter of 30 nanometers, the immersion time is 40min, take out film, after extracting with rubber stick roll extrusion support membrane surface, carried out interface polymerization reaction 50 seconds with said mixture, composite membrane dried in the shade in air 2 minutes, again through 60 ℃ of baking oven heated at constant temperature 20 minutes, rinsing 10 minutes in 40 ℃ water then, rinsing obtains containing the molecular sieve of Nano zeolite reverse osmosis composite membrane, prepares reverse osmosis composite membrane and is kept in the water.The molecular sieve of Nano zeolite reverse osmosis composite membrane that contains for preparing is made scanning electron microscope diagram, the result as shown in Figure 2, as can be seen from Figure 2: the surface of film is more coarse, structure is fine and close more, more helps stoping hydration Na
+, Cl
-Isoionic passing through.
Performance test example 2
The method identical with performance test example 1 tested the molecular sieve of Nano zeolite reverse osmosis composite membrane that contains that embodiment 7~12 prepares, test result is as shown in table 2: by table 2 result as can be known, the present invention prepares, and to contain the molecular sieve of Nano zeolite reverse osmosis composite membrane be that 0.05~0.2% o'clock water flux value and salt rejection rate is all higher at zeolite molecular sieve in weight percent concentration.
Table 2
Claims (10)
1. a preparation method who contains the reverse osmosis composite membrane of molecular sieve of Nano zeolite comprises: molecular sieve of Nano zeolite is distributed in the polyamine aqueous solution, obtains mixture A; The polysulfones support membrane is immersed among the said mixture A, takes out film and remove solvent, film and polynary solution of acid chloride behind the removal solvent are carried out interface polymerization reaction, and reaction is finished after post processing obtains containing the reverse osmosis composite membrane of molecular sieve of Nano zeolite.
2. a preparation method who contains the reverse osmosis composite membrane of molecular sieve of Nano zeolite comprises: molecular sieve of Nano zeolite is distributed in the polynary solution of acid chloride, obtains mixture B; The polysulfones support membrane is immersed in the polyamine aqueous solution, takes out film and remove solvent, film and said mixture B behind the removal solvent carry out interface polymerization reaction, and reaction is finished after post processing obtains containing the reverse osmosis composite membrane of molecular sieve of Nano zeolite.
3. the preparation method who contains the reverse osmosis composite membrane of molecular sieve of Nano zeolite according to claim 1 and 2 is characterized in that, it is 60~70 nanometer LTA type molecular sieve of Nano zeolite that described molecular sieve of Nano zeolite is selected from average grain diameter.
4. the preparation method who contains the reverse osmosis composite membrane of molecular sieve of Nano zeolite according to claim 1 and 2 is characterized in that, the weight ratio of described polysulfones support membrane, polyamine and polynary acyl chlorides is 5~20: 10~70: 1.
5. the preparation method who contains the reverse osmosis composite membrane of molecular sieve of Nano zeolite according to claim 1 and 2 is characterized in that, the weight percent concentration of molecular sieve of Nano zeolite is 0.001~0.2% among described mixture A or the mixture B.
6. the preparation method who contains the reverse osmosis composite membrane of molecular sieve of Nano zeolite according to claim 1 and 2 is characterized in that, the weight percent concentration of polyamine is 1~10% in the described polyamine aqueous solution.
7. the preparation method who contains the reverse osmosis composite membrane of molecular sieve of Nano zeolite according to claim 1 and 2, it is characterized in that, the solvent of described polynary solution of acid chloride is the fat alkane of C5~C8, and the weight percent concentration of polynary acyl chlorides is 0.05~0.6% in the described polynary solution of acid chloride.
8. the preparation method who contains the reverse osmosis composite membrane of molecular sieve of Nano zeolite according to claim 7 is characterized in that, described solvent is a n-hexane.
9. the preparation method who contains the reverse osmosis composite membrane of molecular sieve of Nano zeolite according to claim 1 and 2 is characterized in that, described polyamine is a m-phenylene diamine (MPD); Described polynary acyl chlorides is a pyromellitic trimethylsilyl chloride.
10. the preparation method who contains the reverse osmosis composite membrane of molecular sieve of Nano zeolite according to claim 1 and 2 is characterized in that, the reaction time of described interface polymerization reaction is 40~60 seconds.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201010243109XA CN101940883A (en) | 2010-08-03 | 2010-08-03 | Preparation method of reverse osmosis composite membrane containing nano zeolite molecular sieves |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201010243109XA CN101940883A (en) | 2010-08-03 | 2010-08-03 | Preparation method of reverse osmosis composite membrane containing nano zeolite molecular sieves |
Publications (1)
Publication Number | Publication Date |
---|---|
CN101940883A true CN101940883A (en) | 2011-01-12 |
Family
ID=43433206
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201010243109XA Pending CN101940883A (en) | 2010-08-03 | 2010-08-03 | Preparation method of reverse osmosis composite membrane containing nano zeolite molecular sieves |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101940883A (en) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102794117A (en) * | 2012-07-29 | 2012-11-28 | 北京工业大学 | Preparation method of silazane-modified silicalite-1 molecular sieve filling silicon rubber composite membrane |
CN102794116A (en) * | 2012-06-06 | 2012-11-28 | 复旦大学 | Mesoporous silicon dioxide sphere-polymer nano composite nano-filtration membrane and preparation method thereof |
CN102921300A (en) * | 2012-10-25 | 2013-02-13 | 贵阳时代沃顿科技有限公司 | Agent and method for surface treatment on nanofiltration membrane |
CN103111196A (en) * | 2013-03-04 | 2013-05-22 | 杭州水处理技术研究开发中心有限公司 | Preparation method of nanofiltration membrane |
CN103301756A (en) * | 2013-07-01 | 2013-09-18 | 苏州瀚海高分子有限公司 | Preparation method of nanometer TiO2-PA laminated film |
CN103736404A (en) * | 2014-01-06 | 2014-04-23 | 北京碧水源膜科技有限公司 | Basal membrane of reverse osmosis membrane and preparation method of reverse osmosis membrane |
CN104014255A (en) * | 2014-06-05 | 2014-09-03 | 北京工业大学 | Preparation method for self-assembled modified silicone rubber/inorganic particle alcohol permselective hybrid membrane |
US9212238B2 (en) | 2012-12-28 | 2015-12-15 | Industrial Technology Research Institute | Microparticle, addition agent and filtering membrane |
CN105536560A (en) * | 2015-12-19 | 2016-05-04 | 杭州水处理技术研究开发中心有限公司 | Method for preparing double-layer polysulfone support film of different ingredients and structures |
CN107174982A (en) * | 2017-07-18 | 2017-09-19 | 宁波日新恒力科技有限公司 | A kind of preparation method of the reverse osmosis composite membrane containing octavinyl-POSS |
CN107213798A (en) * | 2017-07-18 | 2017-09-29 | 宁波日新恒力科技有限公司 | A kind of preparation method for the reverse osmosis composite membrane for containing eight amino POSS |
CN109433029A (en) * | 2018-11-15 | 2019-03-08 | 山东大学 | A kind of preparation method of the reverse osmosis membrane of anti-pollution type doped cerium oxide and silver nano-grain |
CN110124536A (en) * | 2019-06-04 | 2019-08-16 | 泰州禾益新材料科技有限公司 | A kind of organic-inorganic bifunctional layer reverse osmosis membrane |
CN111085117A (en) * | 2019-11-28 | 2020-05-01 | 丁水英 | High-water-permeability reverse osmosis membrane and preparation method thereof |
CN112870992A (en) * | 2021-01-13 | 2021-06-01 | 同济大学 | Zeolite membrane and preparation method thereof |
CN113856492A (en) * | 2021-10-26 | 2021-12-31 | 泰州九润环保科技有限公司 | Polyamide reverse osmosis membrane with porous support layer doped with molecular sieve |
CN116159446A (en) * | 2023-03-24 | 2023-05-26 | 泰州九润环保科技有限公司 | Molecular sieve/polyamide mixed matrix membrane |
CN116272421A (en) * | 2023-03-24 | 2023-06-23 | 泰州九润环保科技有限公司 | Molecular sieve/polyamide mixed matrix membrane |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1954901A (en) * | 2005-10-24 | 2007-05-02 | 中国海洋大学 | Polyester amide reverse osmosis compound film and its preparation method |
CN101052459A (en) * | 2004-10-29 | 2007-10-10 | 东丽株式会社 | Composite semipermeable membrane, production process thereof, and element, fluid separation equipment and method for water treatment using the same |
US20100062156A1 (en) * | 2008-04-15 | 2010-03-11 | NanoH+hu 2+l O, Inc. NanoH+hu 2+l O Inc. | Reverse Osmosis Membranes |
-
2010
- 2010-08-03 CN CN201010243109XA patent/CN101940883A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101052459A (en) * | 2004-10-29 | 2007-10-10 | 东丽株式会社 | Composite semipermeable membrane, production process thereof, and element, fluid separation equipment and method for water treatment using the same |
CN1954901A (en) * | 2005-10-24 | 2007-05-02 | 中国海洋大学 | Polyester amide reverse osmosis compound film and its preparation method |
US20100062156A1 (en) * | 2008-04-15 | 2010-03-11 | NanoH+hu 2+l O, Inc. NanoH+hu 2+l O Inc. | Reverse Osmosis Membranes |
Non-Patent Citations (1)
Title |
---|
《Langmuir》 20090615 Mary L. Lind et al Influence of Zeolite Crystal Size on Zeolite-Polyamide Thin Film Nanocomposite Membranes 10139-1014 1-10 第25卷, 第17期 2 * |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102794116A (en) * | 2012-06-06 | 2012-11-28 | 复旦大学 | Mesoporous silicon dioxide sphere-polymer nano composite nano-filtration membrane and preparation method thereof |
CN102794116B (en) * | 2012-06-06 | 2014-10-29 | 复旦大学 | Mesoporous silicon dioxide sphere-polymer nano composite nano-filtration membrane and preparation method thereof |
CN102794117A (en) * | 2012-07-29 | 2012-11-28 | 北京工业大学 | Preparation method of silazane-modified silicalite-1 molecular sieve filling silicon rubber composite membrane |
CN102794117B (en) * | 2012-07-29 | 2014-01-15 | 北京工业大学 | Preparation method of silazane-modified silicalite-1 molecular sieve filling silicon rubber composite membrane |
CN102921300A (en) * | 2012-10-25 | 2013-02-13 | 贵阳时代沃顿科技有限公司 | Agent and method for surface treatment on nanofiltration membrane |
CN102921300B (en) * | 2012-10-25 | 2015-04-22 | 贵阳时代沃顿科技有限公司 | Agent and method for surface treatment on nanofiltration membrane |
US9212238B2 (en) | 2012-12-28 | 2015-12-15 | Industrial Technology Research Institute | Microparticle, addition agent and filtering membrane |
CN103111196A (en) * | 2013-03-04 | 2013-05-22 | 杭州水处理技术研究开发中心有限公司 | Preparation method of nanofiltration membrane |
CN103301756A (en) * | 2013-07-01 | 2013-09-18 | 苏州瀚海高分子有限公司 | Preparation method of nanometer TiO2-PA laminated film |
CN103736404A (en) * | 2014-01-06 | 2014-04-23 | 北京碧水源膜科技有限公司 | Basal membrane of reverse osmosis membrane and preparation method of reverse osmosis membrane |
CN104014255A (en) * | 2014-06-05 | 2014-09-03 | 北京工业大学 | Preparation method for self-assembled modified silicone rubber/inorganic particle alcohol permselective hybrid membrane |
CN104014255B (en) * | 2014-06-05 | 2016-04-13 | 北京工业大学 | The preparation method of the preferential alcohol hybridized film thoroughly of a kind of self-assembled modified silicon rubber/inorganic particulate |
CN105536560A (en) * | 2015-12-19 | 2016-05-04 | 杭州水处理技术研究开发中心有限公司 | Method for preparing double-layer polysulfone support film of different ingredients and structures |
CN105536560B (en) * | 2015-12-19 | 2018-01-16 | 杭州水处理技术研究开发中心有限公司 | A kind of different component and the double-deck polysulfones of structure support membrane preparation method |
CN107213798A (en) * | 2017-07-18 | 2017-09-29 | 宁波日新恒力科技有限公司 | A kind of preparation method for the reverse osmosis composite membrane for containing eight amino POSS |
CN107174982A (en) * | 2017-07-18 | 2017-09-19 | 宁波日新恒力科技有限公司 | A kind of preparation method of the reverse osmosis composite membrane containing octavinyl-POSS |
CN109433029A (en) * | 2018-11-15 | 2019-03-08 | 山东大学 | A kind of preparation method of the reverse osmosis membrane of anti-pollution type doped cerium oxide and silver nano-grain |
CN110124536A (en) * | 2019-06-04 | 2019-08-16 | 泰州禾益新材料科技有限公司 | A kind of organic-inorganic bifunctional layer reverse osmosis membrane |
CN111085117B (en) * | 2019-11-28 | 2021-12-07 | 博格隆(浙江)生物技术有限公司 | High-water-permeability reverse osmosis membrane and preparation method thereof |
CN111085117A (en) * | 2019-11-28 | 2020-05-01 | 丁水英 | High-water-permeability reverse osmosis membrane and preparation method thereof |
CN112870992A (en) * | 2021-01-13 | 2021-06-01 | 同济大学 | Zeolite membrane and preparation method thereof |
CN113856492A (en) * | 2021-10-26 | 2021-12-31 | 泰州九润环保科技有限公司 | Polyamide reverse osmosis membrane with porous support layer doped with molecular sieve |
CN116159446A (en) * | 2023-03-24 | 2023-05-26 | 泰州九润环保科技有限公司 | Molecular sieve/polyamide mixed matrix membrane |
CN116272421A (en) * | 2023-03-24 | 2023-06-23 | 泰州九润环保科技有限公司 | Molecular sieve/polyamide mixed matrix membrane |
CN116159446B (en) * | 2023-03-24 | 2023-11-28 | 泰州九润环保科技有限公司 | Molecular sieve/polyamide mixed matrix membrane |
CN116272421B (en) * | 2023-03-24 | 2024-03-29 | 泰州九润环保科技有限公司 | Molecular sieve/polyamide mixed matrix membrane |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101940883A (en) | Preparation method of reverse osmosis composite membrane containing nano zeolite molecular sieves | |
CN102114392B (en) | Method for preparing reverse osmosis composite membrane containing modified nano-zeolite molecular sieve | |
Bao et al. | Application of amine-functionalized MCM-41 modified ultrafiltration membrane to remove chromium (VI) and copper (II) | |
CN104209022B (en) | A kind of high throughput polyamide/ZIF-8 Nano filtering composite membranes and preparation method thereof | |
Wang et al. | Hydrophilic polymers of intrinsic microporosity as water transport nanochannels of highly permeable thin-film nanocomposite membranes used for antibiotic desalination | |
Vatanpour et al. | Preparation and characterization of nanocomposite PVDF ultrafiltration membrane embedded with nanoporous SAPO-34 to improve permeability and antifouling performance | |
Arthanareeswaran et al. | Effect of silica particles on cellulose acetate blend ultrafiltration membranes: Part I | |
Ehsan Yakavalangi et al. | Effect of surface properties of polysulfone support on the performance of thin film composite polyamide reverse osmosis membranes | |
CN104209021A (en) | Preparation method of aromatic polyamide film modified by ZIF-8 type metal-organic framework material | |
CN105727772B (en) | A kind of complex reverse osmosis membrane and preparation method thereof | |
CN102430349A (en) | Reverse osmosis composite membrane and preparation method thereof | |
JP2010504189A (en) | Porous membrane and manufacturing method thereof | |
Zeng et al. | Fabrication and characterization of an ion-imprinted membrane via blending poly (methyl methacrylate-co-2-hydroxyethyl methacrylate) with polyvinylidene fluoride for selective adsorption of Ru (III) | |
He et al. | Conferring pH-sensitivity on poly (vinylidene fluoride) membrane by poly (acrylic acid-co-butyl acrylate) microgels | |
US20140367326A1 (en) | Thin-film nano-composite membrane with mesoporous silica nanoparticles | |
CN112675715A (en) | Polyamide nano composite film and preparation method and application thereof | |
CN105080367A (en) | Composite nano-filtration membrane containing composite nanoparticles, and preparation method thereof | |
CN107148312A (en) | Separate film structure | |
Xiao et al. | MOFs-mediated nanoscale Turing structure in polyamide membrane for enhanced nanofiltration | |
CN105771685A (en) | Novel metal-organic framework material separation membrane based on carbon nanotube substrate and preparation method thereof | |
Zhou et al. | Preparation of a novel sulfonated polyphenlene sulfone with flexible side chain for ultrafiltration membrane application | |
Zhang et al. | In situ assembly of polyamide/Fe (BTC) nanocomposite reverse osmosis membrane assisted by Fe3+–polyphenolic complex for desalination | |
CN113856492A (en) | Polyamide reverse osmosis membrane with porous support layer doped with molecular sieve | |
CN115845639A (en) | Nanofiltration membrane containing molecular sieve organic composite material intermediate layer and preparation method thereof | |
Hwang et al. | Water treatment by polysulfone membrane modified with tetrahydrofuran and water pressure |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110112 |