CN100586539C - Dynamic self-assembled process for preparing low-pressure high-throughput charged nanofiltration membrane - Google Patents
Dynamic self-assembled process for preparing low-pressure high-throughput charged nanofiltration membrane Download PDFInfo
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Abstract
The invention discloses a method for preparing low-voltage high-flux charged nano-filtration membrane by dynamic self-assembly, which is characterized in that polymer ultra-filtration membrane is taken as a basic film; polycation electrolyte and polyanion electrolyte are alternatively and dynamically self-assembled on the surface of the basic film to gain a selective separation layer and to prepare the nano-filtration membrane of charged surface; wherein, the used ultra-filtration membrane molecular weight cutoff is less than 0.1 million; the ultra-filtration membrane material is surface-charged or modified-charged polymer. Nano-filtration membrane preparation by polyelectrolyte dynamic self-assembly has high efficiency, simple and convenient method and controllable assembly process and film structure; pure water solution is used in the whole preparation process, which is green and environmental protective; the applicable polyelectrolyte has a plurality of types; the separation films with different performances can be obtained by adjusting the types of the polyelectrolyte and the assembly conditions. Furthermore, the prepared nano-filtration membrane has low operation pressure, high removal rate on high valence inorganic salts and far greater flux than the current commercial nano-filtration membrane and the nano-filtration membrane preparation method has good application prospect.
Description
Technical field
The invention belongs to the NF membrane technical field, be specifically related to the method that a kind of dynamic self assembly prepares low-pressure high-throughput charged nanofiltration membrane.This method is applicable to that the polyelectrolyte of different charges carries out self assembly.Conditions such as the kind by changing the assembling number of plies, polyelectrolyte, solution concentration, built-up time obtain the controlled NF membrane of performance.Adopt dynamic self assembly greatly to improve packaging efficiency, have characteristics simple to operate, that reaction is controlled.And the operating pressure of preparation gained NF membrane is low, and to the removal efficiency height of high price inorganic salts, flux is a kind of NF membrane preparation method with applications well prospect much larger than present commercialization NF membrane.
Background technology
Nanofiltration (Nanofiltration) is a kind of pressure drive membrane separation process between counter-infiltration and ultrafiltration, the pore diameter range of NF membrane is about several nanometers, monovalention and molecular weight are removed relatively poor less than 200 organic matter, and divalence or multivalent ion and the organic matter of molecular weight between 200～500 are had higher removal efficiency.Can be widely used in water softening, drink water purifying, improve water quality, the profit degree of depth is separated, useless (liquid) water treatment and reuse, classification, the purifying of chemical industry such as seawater is softening in advance, dyestuff, antibiotic, polypeptide, polysaccharide and biological products and the field such as concentrate.
For the water flux that improves film reduces operating pressure, people often prepare composite nanometer filtering film.Promptly cover one deck selective separation layer as thin as a wafer in the bigger membrane surface of the better flux of intensity.The preparation method mainly contains cladding process, interfacial polymerization, chemical vapour deposition technique, plasma method, uv photo initiated grafting polymerization etc., and commercial prod is in the majority with interfacial polymerization.Membrane material comprises crosslinked fragrant polyamides ammonium, S-PES, S-PPESK, polyvinyl alcohol etc.But the operating pressure of product is many more than 0.5MPa at present, and flux is 30L/m
2.h about, the NF-40HF film of Filmtec company is when operating pressure is 0.9MPa, and flux only is 4.32L/m
2.h.In addition, in said method, interfacial polymerization is strict to monomer, and product quality is wayward; Uv photo initiated grafting polymerization middle-ultraviolet lamp irradiation can exert an influence to film strength, therefore adopts new material, new method to obtain the low-pressure high-throughput NF membrane and is subject to people's attention day by day.In recent years, the someone adopts static self assembly to prepare NF membrane, but generally assembles number of plies height, usually at 5 more than the bilayer, have in addition reach 50-60 double-deck.For example in the Bemd Tieke work reported for preparing the zero defect film, the assembling number of plies even reach 60 bilayers, built-up time is long, efficient is low, is unsuitable for suitability for industrialized production, and because the increase of the number of plies causes operating pressure to increase.It is raw material with the high polyelectrolyte of charge density that the present invention adopts the method for dynamic self assembly, is 2 when double-deck in the assembling number of plies, and the NF membrane of preparation gained is when operating pressure is 0.2MPa, to 1000mg/LNa
2SO
4Removal efficiency be 91.64%, flux is 54.31L/m
2.h, when pressure increased to 0.8MPa, flux reached 106.62/m
2.h, removal efficiency is 89.23%.The whole process of preparation time is less than 30min, has greatly improved packaging efficiency, is fit to use in the actual production.
Summary of the invention
The purpose of this invention is to provide the method that a kind of dynamic self assembly prepares low-pressure high-throughput charged nanofiltration membrane.
Dynamically to prepare the method for low-pressure high-throughput charged nanofiltration membrane be to be basement membrane with the polymer milipore filter in self assembly, replace dynamic self assembly by polycation electrolyte and polyanion electrolyte in membrane surface and obtain selective separation layer, make the charged NF membrane in surface, wherein used milipore filter molecular cut off is less than 100,000, the milipore filter material be the surface charged or after modification charged polymer.
Concrete steps are as follows:
1) polycation electrolyte and polyanion electrolyte are made into the aqueous solution with deionized water dissolving respectively, the mass percent concentration of polycation electrolyte solution, polyanion electrolyte solution is 0.1%～3.5%, add inorganic salts respectively in polycation electrolyte solution and the polyanion electrolyte solution, inorganic salt concentration is 0.1M～3.0M, regulates pH=1～7;
2) polymer milipore filter basement membrane being fixed on a bottom has in the container of porous support layer, face up, in container, add a kind of polyelectrolyte solution then, when membrane surface bear electricity, a kind of polyelectrolyte solution that adds is a kind of polycation electrolyte solution, when membrane surface lotus positive electricity, a kind of polyelectrolyte solution that adds is a kind of polyanion electrolyte solution, solution is being subjected under the external pressure effect, stir, pass through electrostatic interaction, hydrophobic force, hydrogen bond, the polyelectrolyte opposite in the membrane surface assembling with the membrane surface charge, built-up time is 1-60min;
3) polyelectrolyte solution taking-up step 2) adds deionized water in container, stir, and water cleans face, and scavenging period is 1-6min;
4) take out deionized water, add and step 2 in the container) in the opposite another kind of polyelectrolyte solution of a kind of polyelectrolyte solution charge, when step 2) when the polyelectrolyte solution that adds is polycation electrolyte solution, then the another kind of polyelectrolyte solution of step 4) adding is a polyanion electrolyte solution, when step 2) when the polyelectrolyte solution that adds is polyanion electrolyte solution, then the another kind of polyelectrolyte solution of step 4) adding is a polycation electrolyte solution, solution is being subjected under the external pressure effect, stir, pass through electrostatic interaction, hydrophobic force, hydrogen bond action, in step 2) a kind of polyelectrolyte surface-assembled on the another kind of polyelectrolyte of step 4), built-up time is 1-45min, it is double-deck to obtain 1 assembling, and the built-up time of 1 bilayer is 2～80min;
5) the another kind of polyelectrolyte solution in the taking-up step 4) adds deionized water in container, stirs, and water cleans face, and scavenging period is 1-6min, takes out deionized water;
Repeating step 2)-step 5) 1-4 time, when basement membrane lotus positive electricity, according to the dynamic layer assembly of the sequence alternate of polyanion electrolyte, polycation electrolyte, when basement membrane bear electricity, according to the dynamic layer assembly of the sequence alternate of polycation electrolyte, polyanion electrolyte, wherein, the suffered external pressure size of solution is 0.01MPa～0.8MPa during assembling.
The double-deck number of described assembling is 1～5 bilayer.The time of 1 bilayer of assembling is 2～60min.Polycation electrolyte is polymine, polyvinylamine, poly diallyldimethylammonium chloride, and poly-N, N '-dimethyl diallyl ammonium chloride, polyanion electrolyte are kayexalate, kayexalate-maleic acid (salt) copolymer.
The beneficial effect that the present invention has
The dynamic self assembly of polyelectrolyte prepares NF membrane efficient height, method is easy, and assembling process and membrane structure are controlled, and whole process is used pure water solution, environmental protection; The polyelectrolyte kind that is suitable for is many, by kind and the different diffusion barrier of assembling condition available energy of regulating polyelectrolyte.And the operating pressure of preparation gained NF membrane is low, and to the removal efficiency height of high price inorganic salts, flux is a kind of NF membrane preparation method with applications well prospect much larger than present commercialization NF membrane.
The specific embodiment
The present invention is the method that adopts the dynamic self assembly of polyelectrolyte, directly by charged milipore filter or after modification charged milipore filter prepare NF membrane.Be characterized in method by the dynamic self assembly of polyelectrolyte, the charged situation that changes film comprises structure of charge and carrying capacity, surface isolation layer etc., the nanofiltration performance of film is changed on a large scale, the polyelectrolyte kind that is suitable for is many, and can carry out the NF membrane that multiple combination obtains different separating properties.The water flux of product is big, and to the removal efficiency height of high price salt, the Selective Separation performance is good.
Charged polymer milipore filter all can be used as basement membrane after most charged or modifications.As polyacrylonitrile, sulfonated polyether sulfone, sulfonated polyether-ether-ketone etc., also can be the blend or the copolymer of above-mentioned polymer and other polymer.
Among the present invention, the milipore filter molecular cut off that is suitable for is less than 100,000.
Dynamic self-assembling technique of the present invention, be meant that polyelectrolyte solution is being subjected under the external pressure effect, stir, between polyelectrolyte and the basement membrane, the package technique that relies on interactions such as electrostatic interaction, hydrophobic force, hydrogen bond to combine between the polyelectrolyte of different charges, the suffered external pressure size of solution is 0.01MPa～0.8MPa during assembling.
Among the present invention, used polycation electrolyte is polymine, polyvinylamine, poly diallyldimethylammonium chloride, poly-N, N '-dimethyl diallyl ammonium chloride, polyanion electrolyte is kayexalate, kayexalate-maleic acid (salt) copolymer, and the mass percent concentration of polyelectrolyte solution is 0.1%～3.5%.
According to the present invention, the charge that changes the outermost layer polyelectrolyte can obtain the different NF membrane of separating property.
The separating property of the NF membrane of the present invention preparation is to test in diameter is the lucite osmotic cell of 5.5cm, adopts the cross-flow method.Probe temperature is a room temperature, and test job pressure is 0.2～0.8MPa.Permeability of the membrane is used in the water flux of film under this condition or has the water flux under the salt existence to represent (unit: L/m
2H); The selective permeation of film is the NaCl of 1000mg/L with film to concentration, Na
2SO
4, MgCl
2The removal efficiency of solution characterizes.
Embodiment 1:
The used milipore filter of present embodiment is that molecular cut off is 50,000 through polyacrylonitrile (PAN) milipore filter behind the alkali modification.
Dynamically self assembly is to carry out in the bottom that a diameter is 9cm has the rustless steel container of porous support layer.With the film surface of milipore filter up, the edge is fixed, and is placed in the container, carries out self assembly according to the following steps:
1) poly diallyldimethylammonium chloride (Mw=60,000) is used deionized water dissolving, be made into concentration and be 0.2% solution, add NaCl then in poly diallyldimethylammonium chloride solution, the concentration of NaCl solution is 0.5M, and the pH value that drips the concentrated hydrochloric acid regulator solution again is 2.5; Kayexalate (Mw=70,000) is used deionized water dissolving, be made into 0.4% the aqueous solution, in kayexalate solution, add CaCl then
2, CaCl
2The concentration of solution is 0.5M, and the pH value that drips the concentrated hydrochloric acid regulator solution is 2.5; Kayexalate-maleic acid (salt) (Mw=20,000) is used deionized water dissolving, be made into 1.66% the aqueous solution, add CaCl at kayexalate-maleic acid (salt) solution then
2, CaCl
2The concentration of solution is 0.5M, and the pH value that drips the concentrated hydrochloric acid regulator solution is 2.5;
2) the PAN milipore filter behind alkali modification is fixed in the container, face up, the aqueous solution that in container, adds 0.2% poly diallyldimethylammonium chloride then, 0.1MPa down, stir poly diallyldimethylammonium chloride solution, by effects such as electrostatic interaction, hydrophobic force, hydrogen bonds, poly diallyldimethylammonium chloride in the membrane surface assembling, built-up time is 5min;
3) take out poly diallyldimethylammonium chloride solution, add deionized water in container, stir, water cleans, and scavenging period is 1min;
4) take out deionized water, in container, add 0.4% kayexalate solution, 0.1MPa down, stir kayexalate solution, by effects such as electrostatic interaction, hydrophobic force, hydrogen bonds, kayexalate on the poly diallyldimethylammonium chloride surface-assembled, built-up time are 2min, and it is double-deck to obtain 1 assembling thus;
5) take out kayexalate solution, add deionized water in container, stir, water cleans, and scavenging period is 1min, takes out deionized water;
Repeating step 2 again)-step 5) 1 time, carry out the two-wheeled assembling altogether and obtain two bilayers, wherein take turns the 0.4% kayexalate solution that step 4) is used in the assembling and change 1.66% kayexalate-maleic acid (salt) copolymer solution into second, with the deionized water rinse products repeatedly to remove not in conjunction with the polyelectrolyte that gets on.This film is to NaCl, Na
2SO
4, MgCl
2Separating property see Table 1, operating pressure is to Na
2SO
4The influence of separating property sees Table 2.
Embodiment 2:
The used milipore filter of present embodiment is a PES-SPES blend milipore filter, and molecular cut off is 30,000.
Dynamically self assembly is to carry out in the bottom that a diameter is 9cm has the rustless steel container of porous support layer.With the film surface of PES-SPES blend milipore filter up, the edge is fixed, and is placed in the container, carries out self assembly according to the following steps:
1) poly diallyldimethylammonium chloride (Mw=60,000) is used deionized water dissolving, be made into concentration and be 0.2% solution, add NaCl then, the concentration of NaCl solution is 0.5M, and the pH value that drips the concentrated hydrochloric acid regulator solution again is 2.3; Kayexalate (Mw=70,000) is used deionized water dissolving, be made into 0.4% the aqueous solution, add CaCl then
2, make CaCl
2The concentration of solution is 0.5M, and the pH value that drips the concentrated hydrochloric acid regulator solution is 2.3;
2) PES-SPES blend milipore filter is fixed in the container, face up, the aqueous solution that in container, adds 0.2% poly diallyldimethylammonium chloride then, 0.1MPa down, stir poly diallyldimethylammonium chloride solution, by effects such as electrostatic interaction, hydrophobic force, hydrogen bonds, poly diallyldimethylammonium chloride in the membrane surface assembling, built-up time is 5min;
3) take out poly diallyldimethylammonium chloride solution, add deionized water in container, stir, water cleans, and scavenging period is 1min;
4) take out deionized water, in container, add 0.4% kayexalate solution, 0.1MPa down, stir polyelectrolyte solution, by effects such as electrostatic interaction, hydrophobic force, hydrogen bonds, kayexalate on the poly diallyldimethylammonium chloride surface-assembled, built-up time are 2min, and it is double-deck to obtain 1 assembling thus;
5) take out kayexalate solution, add deionized water in container, stir, water cleans, and scavenging period is 1min, takes out deionized water;
Repeating step 2 again)-step 5) 4 times, carry out 5 altogether and take turns assembling, obtain 5 bilayers, at last with the rinsed with deionized water NF membrane repeatedly to remove not in conjunction with the polyelectrolyte that gets on.This film is to NaCl, Na
2SO
4, MgCl
2Separating property see Table 1.
Embodiment 3:
Press the condition of embodiment 1, adopting through polyacrylonitrile (PAN) milipore filter behind the alkali modification is basement membrane, and molecular cut off is 50,000.The concentration of kayexalate-maleic acid (salt) copolymer solution is 3.22%.This film is to NaCl, Na
2SO
4, MgCl
2Separating property see Table 1.
Embodiment 4:
Press the condition of embodiment 1, adopting PES-SPES blend milipore filter is basement membrane, and molecular cut off is 30,000.By the step 2 among the embodiment 1)-after step 5) assembling obtains a bilayer, repeating step 2)-step 5) 4 times, carry out 5 altogether and take turns assembling, obtain 5 bilayers.Wherein last 1 takes turns that 0.4% kayexalate solution changes 1.66% kayexalate-maleic acid (salt) copolymer solution in the step 4) of assembling, with rinsing in the deionized water repeatedly to remove not in conjunction with the polyelectrolyte that gets on.This film is to NaCl, Na
2SO
4, MgCl
2Separating property see Table 1
Embodiment 5:
Press the condition of embodiment 1, assemble one deck poly diallyldimethylammonium chloride at last again.With rinsing sodium filter membrane in the deionized water repeatedly to remove not in conjunction with the polyelectrolyte that gets on.This film is to NaCl, Na
2SO
4, MgCl
2Separating property see Table 1, operating pressure is to MgCl
2The influence of separating property sees Table 3.
The separating property of gained NF membrane among table 1 embodiment
Annotate: operating pressure is 0.4MPa, and test is 1000mg/L with inorganic salt concentration, and R is the removal efficiency of salt, and F is a flux.
The prepared NF membrane of table 2 embodiment 1 under different pressures to 1000mg/LNa
2SO
4Removal efficiency and flux
Removal efficiency and the flux to 1000mg/L MgCl2 of NF membrane under different pressures that table 3 embodiment 5 is prepared
Claims (3)
1. a dynamic self assembly prepares the method for low-pressure high-throughput charged nanofiltration membrane, it is characterized in that with the polymer milipore filter be basement membrane, replace dynamic self assembly by polycation electrolyte and polyanion electrolyte in membrane surface and obtain selective separation layer, make the charged NF membrane in surface, wherein used milipore filter molecular cut off is less than 100,000, the milipore filter material be the surface charged or after modification charged polymer; Concrete steps are as follows:
1) polycation electrolyte and polyanion electrolyte are made into the aqueous solution with deionized water dissolving respectively, the mass percent concentration of polycation electrolyte solution, polyanion electrolyte solution is 0.1%～3.5%, add inorganic salts respectively in polycation electrolyte solution and the polyanion electrolyte solution, inorganic salt concentration is 0.1M～3.0M, regulates pH=1～7;
2) polymer milipore filter basement membrane being fixed on a bottom has in the container of porous support layer, face up, in container, add a kind of polyelectrolyte solution then, when membrane surface bear electricity, a kind of polyelectrolyte solution that adds is a kind of polycation electrolyte solution, when membrane surface lotus positive electricity, a kind of polyelectrolyte solution that adds is a kind of polyanion electrolyte solution, solution is being subjected under the external pressure effect, stir, pass through electrostatic interaction, hydrophobic force, hydrogen bond, the polyelectrolyte opposite in the membrane surface assembling with the membrane surface charge, built-up time is 1-60min;
3) polyelectrolyte solution taking-up step 2) adds deionized water in container, stir, and water cleans face, and scavenging period is 1-6min;
4) take out deionized water, add and step 2 in the container) in the opposite another kind of polyelectrolyte solution of a kind of polyelectrolyte solution charge, when step 2) when the polyelectrolyte solution that adds is polycation electrolyte solution, then the another kind of polyelectrolyte solution of step 4) adding is a polyanion electrolyte solution, when step 2) when the polyelectrolyte solution that adds is polyanion electrolyte solution, then the another kind of polyelectrolyte solution of step 4) adding is a polycation electrolyte solution, solution is being subjected under the external pressure effect, stir, pass through electrostatic interaction, hydrophobic force, hydrogen bond action, in step 2) a kind of polyelectrolyte surface-assembled on the another kind of polyelectrolyte of step 4), built-up time is 1-45min, it is double-deck to obtain 1 assembling, and the built-up time of 1 bilayer is smaller or equal to 80min greater than 2;
5) the another kind of polyelectrolyte solution in the taking-up step 4) adds deionized water in container, stirs, and water cleans face, and scavenging period is 1-6min, takes out deionized water;
Repeating step 2)-step 5) 1-4 time, when basement membrane lotus positive electricity, according to the dynamic layer assembly of the sequence alternate of polyanion electrolyte, polycation electrolyte, when basement membrane bear electricity, according to the dynamic layer assembly of the sequence alternate of polycation electrolyte, polyanion electrolyte, wherein, the suffered external pressure size of solution is 0.01MPa～0.8MPa during assembling.
2. a kind of dynamic self assembly according to claim 1 prepares the method for low-pressure high-throughput charged nanofiltration membrane, and the built-up time that it is characterized in that 1 bilayer of described assembling is smaller or equal to 60min greater than 2.
3. a kind of dynamic self assembly according to claim 1 prepares the method for low-pressure high-throughput charged nanofiltration membrane, it is characterized in that described polycation electrolyte is polymine, polyvinylamine, poly diallyldimethylammonium chloride, poly-N, N '-dimethyl diallyl ammonium chloride, polyanion electrolyte are kayexalate, kayexalate-maleic acid.
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| Preparation of polyelectrolyte multilayer membranes bydynamic layer-by-layer process for pervaporation separation ofalcohol/water mixtures. Guojun Zhang etal.Journal of Membrane Science,Vol.280 . 2006 |
| Preparation of polyelectrolyte multilayer membranes bydynamic layer-by-layer process for pervaporation separation ofalcohol/water mixtures. Guojun Zhang etal.Journal of Membrane Science,Vol.280. 2006 * |
| Self-assembled nano-structured polyelectrolyte compositemembranes for pervaporation. Zhaoqi Zhu etal.Materials Science and Engineering C,Vol.26 . 2006 |
| Self-assembled nano-structured polyelectrolyte compositemembranes for pervaporation. Zhaoqi Zhu etal.Materials Science and Engineering C,Vol.26. 2006 * |
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| CN101274222A (en) | 2008-10-01 |
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