CN104248914B - A kind of reverse osmosis membrane and preparation method thereof - Google Patents
A kind of reverse osmosis membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of reverse osmosis membrane, the preparation method of a kind of reverse osmosis membrane and the reverse osmosis membrane prepared by the method.Described reverse osmosis membrane includes the supporting layer and the stratum disjunctum that stack together, and wherein, described stratum disjunctum contains any one the sulfonated polyether sulphone and inorganic particulate that have in structure shown in formula I, (II) and (III)；Wherein, n is the integer of >=1, it is preferable that 1≤n≤100；M is 0 < m < 1, r is 0 < r < 1, and m+r=1；S is 0 < s < 1, t is 0 < t < 1, and s+t=1；Reverse osmosis membrane provided by the invention can have higher salt-stopping rate, higher water flux and stronger chlorine-resistant property well concurrently.
Description
Technical field
The present invention relates to a kind of reverse osmosis membrane, the preparation method of a kind of reverse osmosis membrane and the reverse osmosis membrane prepared by the method.
Background technology
Membrance separation is to occur in 20 beginnings of the century, and a kind of separation technology emerged rapidly after the sixties in 20th century.The core of membrane separation technique separates film exactly.For perforated membrane, micro-filtration membrane, ultrafilter membrane, NF membrane and reverse osmosis membrane can be divided into according to the size of membrane aperture.
Wherein, reverse osmosis membrane becomes one of key technology of water process because having the advantages such as the good separation performance to organic molecule and inorganic ion, safe and environment-friendly, easy operation.Up to now, reverse osmosis membrane be mainly used in the field such as prepare in sea water and brackish water desalination, water softening, middle Water Sproading, Industrial Wastewater Treatment and ultra-pure water.At present, on market, the reverse osmosis membrane of 90% is composite membrane, i.e. be made up of stratum disjunctum and supporting layer.Wherein, the preparation method of composite membrane mainly has: weak solution cladding process, interfacial polymerization and Plasma Polymerization etc..It is currently widely used for the composite membrane in water treatment field and mainly takes the mode of interfacial polymerization, for instance, it is possible to polyamide film is compound to micropore and supports counterdie surface.But, the chemical constitution of polyamide makes the chlorine-resistant property of such composite membrane very weak, and all commercial polyamide composite films are almost nil to the permission of free chlorine, thus adding film pretreatment cost and reducing its service life.Therefore, the chlorine-resistant property of raising film is one of vital task of current reverse osmosis membrane research.
Research shows, sulfonated polyether sulfone has acidproof, alkaline-resisting preferably and chlorine resistance, has good application prospect in film field.US4818387 discloses a kind of sulfonated polyether sulfone composite membrane and preparation method thereof.Test result shows, adopts sulfonated polyether sulfone composite membrane prepared by dip coating to have extraordinary chlorine-resistant, oxidation resistent susceptibility.CN101721926A discloses a kind of sulfonation containing naphthyridine ketone structure copolymerization aryl ether sulfone composite membrane and preparation method thereof, and such composite membrane has good separation property, water penetration and chlorine resistance.
Although sulfonated polyether sulphone complex reverse osmosis membrane shows good section salt and useful oxidative resistance, but this sulfonated polyether sulphone complex reverse osmosis membrane water penetration is poor, and this also counteracts that the process of its industrialization.
Therefore, along with the reach of science, novel reverse osmosis membrane has become the focus of research.
Summary of the invention
It is an object of the invention to provide a kind of new reverse osmosis membrane, the preparation method of a kind of reverse osmosis membrane and the reverse osmosis membrane prepared by the method.
The invention provides a kind of reverse osmosis membrane, described reverse osmosis membrane includes the supporting layer and the stratum disjunctum that stack together, wherein, described stratum disjunctum contains any one the sulfonated polyether sulphone and inorganic particulate that have in structure shown in formula I, (II) and (III)；
Wherein, n is the integer of >=1, it is preferable that 1≤n≤100；M is 0 < m < 1, r is 0 < r < 1, and m+r=1；S is 0 < s < 1, t is 0 < t < 1, and s+t=1.
The preparation method that present invention also offers a kind of reverse osmosis membrane, wherein, the method comprises the following steps:
(1) any one the dry sulfonated polyether sulphone having in structure shown in formula I, (II) and (III) is dissolved in solvent, and the solution obtained is mixed with inorganic particulate, prepare into coating liquid；
(2) described coating liquid is coated on supporting layer, then carries out heat cure；
Wherein, n is the integer of >=1, it is preferable that 1≤n≤100；M is 0 < m < 1, r is 0 < r < 1, and m+r=1；S is 0 < s < 1, t is 0 < t < 1, and s+t=1.
Present invention also offers the reverse osmosis membrane prepared by said method.
The present inventor finds through further investigation, on the one hand, there is inside inorganic particulate pore passage structure and hydrophilic ability uniquely, on the other hand, inorganic particulate is incorporated in the sulfonated polyether sulphone with ad hoc structure with the present invention, add the roughness on reverse osmosis membrane surface prepared by the present invention, increase the surface area of reverse osmosis membrane prepared by the present invention, so that the water flux of the reverse osmosis membrane prepared by the present invention significantly improves, namely, reverse osmosis membrane provided by the invention has higher water flux and higher salt-stopping rate, and show higher chlorine-resistant property (namely, oxidation resistent susceptibility).
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below.In the accompanying drawings:
Fig. 1 is the SEM scanning electron microscope (SEM) photograph of the reverse osmosis membrane according to comparative example 1 preparation；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the reverse osmosis membrane according to embodiments of the invention 2 preparation.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
Reverse osmosis membrane provided by the invention includes the supporting layer and the stratum disjunctum that stack together, it is characterised in that described stratum disjunctum contains any one the sulfonated polyether sulphone and inorganic particulate that have in structure shown in formula I, (II) and (III)；
Wherein, n is the integer of >=1, it is preferable that 1≤n≤100；M is 0 < m < 1, r is 0 < r < 1, and m+r=1；S is 0 < s < 1, t is 0 < t < 1, and s+t=1.
In above-mentioned formula (II) and (III), m, r, s and t refer to the sulfonation degree of sulfonated polyether sulphone.
In the present invention, the ion exchange capacity of described sulfonated polyether sulphone can be 0.5-2.5mmol/g, it is preferred to 1.0-2.0mmol/g.The ion exchange capacity of described sulfonated polyether sulphone refers to sulfonic molal quantity in 1g sulfonated polyether sulphone, it is possible to adopt acid base titration method to be measured.
According to the present invention, above-mentioned formula (I) can be commercially available to the sulfonated polyether sulphone of structure shown in formula (III), for instance, shown in formula (I), the sulfonated polyether sulphone of structure can purchased from Yan Jin Technology Co., Ltd.；Can also prepare according to various methods well known in the art, will not be described in great detail at this.
According to the present invention, although the thickness of described supporting layer and described stratum disjunctum all can carry out selecting and changing in wider scope, but so that this two-layer can play better coordinated effect, enables obtained reverse osmosis membrane to have higher salt-stopping rate, higher water flux and stronger chlorine-resistant property better concurrently, under preferable case, the thickness of described supporting layer is 40-200 micron, and the thickness of described stratum disjunctum is 100-500 nanometer；More preferably, in situation, the thickness of described supporting layer is 40-150 micron, and the thickness of described stratum disjunctum is 100-300 nanometer.
According to the present invention, in order to enable obtained reverse osmosis membrane to have higher salt-stopping rate, higher water flux and stronger chlorine-resistant property better concurrently, under preferable case, in described stratum disjunctum, the weight ratio of described sulfonated polyether sulphone and described inorganic particulate can be 1-100:1, more preferably, in situation, in described stratum disjunctum, the weight ratio of described sulfonated polyether sulphone and described inorganic particulate can be 1-50:1.
According to the present invention, described inorganic particulate is not particularly limited, as long as having pore passage structure inside this inorganic particulate crystal structure and having hydrophilic.Under preferable case, in order to make obtained reverse osmosis membrane have the water penetration of improvement further, namely there is higher water flux, described inorganic particulate selects attapulgite, its reason is: attapulgite is a kind of nanometer porous road lenticular zeopan, is different from the phyllosilicates such as montmorillonite, and crystal is bar-shaped or filamentary structure, there is regular, fixed-size one-dimensional channels inside its crystal structure, hydrone can access aperture road；And, single crystal is tiny bar-shaped, needle-like and threadiness, and when dispersion, rod-like fibre can keep multi-faceted and deposit after drying regularly in felted thing thing, forms the inhomogenous secondary space of size between agglomerate so that more hydrone can pass through hole.It is further preferred that described inorganic particulate is the attapulgite after roasting, sintering temperature is 200-600 DEG C, it is preferred to 300-500 DEG C, more preferably 400 DEG C；Roasting time is 1-10 hour, it is preferred to 2-5 hour, more preferably 2 hours.
According to the present invention, the particle size of described inorganic particulate can be 10-20nm.In the present invention, described particle size refers to the maximum linear distance between two differences on described microgranule, and when described microgranule is spherical, then the size of described microgranule refers to the diameter of this microgranule.
According to the present invention, described supporting layer can be the existing various supporting layers having certain aperture and intensity and can be used in reverse osmosis membrane, can being generally have the ultrafilter membrane that non-woven fabrics supports, the polymeric material of composition ultrafilter membrane can be one or more in phenolphthalein type polyarylether sulfone, polyether sulfone and bisphenol-a polysulfone.
The preparation method of reverse osmosis membrane provided by the invention, the method comprises the following steps:
(1) any one the dry sulfonated polyether sulphone having in structure shown in formula I, (II) and (III) is dissolved in solvent, and the solution obtained is mixed with inorganic particulate, prepare into coating liquid；
(2) described coating liquid is coated on supporting layer, then carries out heat cure；
Wherein, n is the integer of >=1, it is preferable that 1≤n≤100；M is 0 < m < 1, r is 0 < r < 1, and m+r=1；S is 0 < s < 1, t is 0 < t < 1, and s+t=1.
The consumption of described coating liquid is not particularly limited by the present invention, but in order to enable obtained reverse osmosis membrane to have higher salt-stopping rate, higher water flux and stronger chlorine-resistant property better concurrently, under preferable case, the consumption of described coating liquid makes the thickness of described stratum disjunctum be 100-500 nanometer, it is preferred to 100-300 nanometer.Additionally, the thickness of supporting layer can also select in wider scope, for instance, it is possible to for 40-200 micron, it is preferred to 40-150 micron.
According to the present invention, as mentioned above, described supporting layer can be the existing various supporting layers having certain aperture and intensity and can be used in reverse osmosis membrane, can being generally have the ultrafilter membrane that non-woven fabrics supports, the polymeric material of composition ultrafilter membrane be one or more in phenolphthalein type polyarylether sulfone, polyether sulfone and bisphenol-a polysulfone.
According to the present invention, in described coating liquid, the content of each component can carry out selecting and changing in wider scope, such as, with the gross weight of described coating liquid for benchmark, the consumption of described sulfonated polyether sulphone can be 0.5-10 weight %, under preferable case, the consumption of described sulfonated polyether sulphone is 0.5-5 weight %；The consumption of described inorganic particulate can be 0.001-1 weight %, it is preferable that in situation, and the consumption of described inorganic particulate is 0.005-0.5 weight %；The weight ratio of described sulfonated polyether sulphone and described inorganic particulate can be 1-100:1, it is preferable that in situation, and the weight ratio of described sulfonated polyether sulphone and described inorganic particulate is 1-50:1.
In described method provided by the invention, described inorganic particulate is identical with described above.
According to the present invention, described solvent can be the existing inert media that can described phenolphthalein type sulfonated polyether sulphone and additive be dissolved, for example, it is possible to one or more in formic acid, acetic acid, methanol, ethanol, glycol monoethyl ether, glycol dimethyl ether, acetone and deionized water.Preferably, described solvent is the mixed solvent of formic acid, glycol monoethyl ether and deionized water, and wherein, the weight ratio of formic acid, glycol monoethyl ether and deionized water can be 6-8:1-3:1, it is most preferred that for 7:2:1.
Additionally, so that the reverse osmosis membrane arrived is more smooth, it is preferable that the preparation method of reverse osmosis membrane provided by the invention is additionally included in before being coated on supporting layer by coating liquid, is fixed on a glass by described supporting layer.
The condition of described heat cure is not particularly limited by the present invention, solidifies as long as enabling to described coating liquid.Such as, the condition of described heat cure include temperature can be 20-120 DEG C, the time can be 5-50 minute；Preferably, temperature can be 70 DEG C, the time can be 30 minutes.
Present invention also offers the reverse osmosis membrane prepared by said method.
Hereinafter will be described the present invention by embodiment.
In the following Examples and Comparative Examples:
(1) ion exchange capacity of sulfonated polyether sulphone adopts acid base titration method to be measured；
(2) water flux of reverse osmosis membrane is tested by the following method and is obtained: loaded by reverse osmosis membrane in membrane cisterna, is the pure water transit dose recording described reverse osmosis membrane in 1h under 2.0MPa, 25 DEG C of conditions at pressure, and is obtained by below equation calculating:
J=Q/ (A t), wherein, J is pure water flux, and Q is pure water transit dose (L), A is the effective film area (m of reverse osmosis membrane2), t is the time；
(3) salt-stopping rate of reverse osmosis membrane is tested by the following method and is obtained: loaded by reverse osmosis membrane in membrane cisterna, it is under 2.0MPa, 25 DEG C of conditions, record the concentration change of sodium chloride in the former aqueous solution of sodium chloride and permeate that initial concentration in 1h is 2000ppm at pressure, and is obtained by below equation calculating:
R=(Cp-Cf)/Cp× 100%, wherein, R is salt-stopping rate, CpFor the concentration of sodium chloride, C in stock solutionfFor the concentration of sodium chloride in permeate.
Embodiment 1
This embodiment is used for reverse osmosis membrane provided by the invention and preparation method thereof is described.
By dried for the 1.0g sulfonated polyether sulphone C-SPAES(with structure shown in formula I purchased from Yan Jin Technology Co., Ltd., n is 85, ion exchange capacity is 1.37mmol/g) be dissolved in total amount be the formic acid of 100g, glycol monoethyl ether and deionized water composition mixed solvent (wherein, the weight ratio of formic acid, glycol monoethyl ether and deionized water is 7:2:1) in, after filtration, adding 0.01g is the roasting attapulgite of 2 hours at 400 DEG C (average particle size particle size is 10nm) in temperature, makes coating weak solution after ultrasonic disperse.By bisphenol-a polysulfone ultrafilter membrane (purchased from Zhejiang MEY Technology Co., Ltd., the trade mark is PS20, thickness is 140 microns, lower same) fix on a glass, the coating weak solution prepared is brushed equably at ultrafiltration membrane surface, then heat treatment 30 minutes at 70 DEG C, the layer thickness that is supported is 140 microns, and stratum disjunctum thickness is the C-SPAES complex reverse osmosis membrane of 300 nanometers.
This reverse osmosis membrane is soaked 24 hours in water, then, 2.0MPa, 25 DEG C when, record the water flux of this reverse osmosis membrane in 1h；And the concentration change of sodium chloride in initial liquid and permeate in 1h, according to above-mentioned formula, calculating salt-stopping rate, result is in Table 1.
Embodiment 2
By dried for the 1.0g sulfonated polyether sulphone C-SPAES(with structure shown in formula I purchased from Yan Jin Technology Co., Ltd., n is 85, ion exchange capacity is 1.37mmol/g) be dissolved in total amount be the formic acid of 100g, glycol dimethyl ether and deionized water composition mixed solvent (wherein, the weight ratio of formic acid, glycol dimethyl ether and deionized water is 7:2:1) in, after filtration, adding 0.05g is the roasting attapulgite of 2 hours at 400 DEG C (average particle size particle size is 20nm) in temperature, makes coating weak solution after ultrasonic disperse.Bisphenol-a polysulfone ultrafilter membrane is fixed on a glass, the coating weak solution prepared is brushed equably at ultrafiltration membrane surface, then heat treatment 30 minutes under 70 ° of C, the layer thickness that is supported is 140 microns, and stratum disjunctum thickness is the C-SPAES complex reverse osmosis membrane of 100 nanometers.
This reverse osmosis membrane is soaked 24 hours in water, then, 2.0MPa, 25 DEG C when, record the water flux of this reverse osmosis membrane in 1h；And the concentration change of sodium chloride in initial liquid and permeate in 1h, according to above-mentioned formula, calculating salt-stopping rate, result is in Table 1.
Embodiment 3
By dried for the 1.0g sulfonated polyether sulphone C-SPAES(with structure shown in formula I purchased from Yan Jin Technology Co., Ltd., n is 85, ion exchange capacity is 1.37mmol/g) be dissolved in total amount be the formic acid of 100g, glycol monoethyl ether and acetone composition mixed solvent (wherein, the weight ratio of formic acid, glycol monoethyl ether and acetone is 7:2:1) in, after filtration, adding 0.02g is the roasting attapulgite of 2 hours at 400 DEG C (average particle size particle size is 12nm) in temperature, makes coating weak solution after ultrasonic disperse.Bisphenol-a polysulfone ultrafilter membrane is fixed on a glass, the coating weak solution prepared is brushed equably at ultrafiltration membrane surface, then heat treatment 30 minutes under 70 ° of C, obtain supporting that layer thickness is 140 microns, stratum disjunctum thickness is the C-SPAES complex reverse osmosis membrane of 200 nanometers.
This reverse osmosis membrane is soaked 24 hours in water, then, 2.0MPa, 25 DEG C when, record the water flux of this reverse osmosis membrane in 1h；And the concentration change of sodium chloride in initial liquid and permeate in 1h, according to above-mentioned formula, calculating salt-stopping rate, result is in Table 1.
Embodiment 4
By dried for the 1.0g sulfonated polyether sulphone C-SPAES(with structure shown in formula I purchased from Yan Jin Technology Co., Ltd., n is 85, ion exchange capacity is 1.37mmol/g) be dissolved in total amount be the acetic acid of 100g, glycol monoethyl ether and deionized water composition mixed solvent (wherein, the weight ratio of acetic acid, glycol monoethyl ether and deionized water is 7:2:1) in, after filtration, adding 0.1g is the roasting attapulgite of 2 hours at 400 DEG C (average particle size particle size is 15nm) in temperature, makes coating weak solution after ultrasonic disperse.Bisphenol-a polysulfone ultrafilter membrane is fixed on a glass, the coating weak solution prepared is brushed equably at ultrafiltration membrane surface, then heat treatment 30 minutes under 70 ° of C, obtain supporting that layer thickness is 140 microns, stratum disjunctum thickness is the C-SPAES complex reverse osmosis membrane of 400 nanometers.
This reverse osmosis membrane is soaked 24 hours in water, then, 2.0MPa, 25 DEG C when, record the water flux of this reverse osmosis membrane in 1h；And the concentration change of sodium chloride in initial liquid and permeate in 1h, according to above-mentioned formula, calculating salt-stopping rate, result is in Table 1.
Embodiment 5
By dried for the 1.0g sulfonated polyether sulphone C-SPAES(with structure shown in formula I purchased from Yan Jin Technology Co., Ltd., n is 85, ion exchange capacity is 1.37mmol/g) be dissolved in total amount be the acetic acid of 100g, glycol dimethyl ether and acetone composition mixed solvent (wherein, the weight ratio of acetic acid, glycol dimethyl ether and acetone is 8:1:1) in, after filtration, adding 0.125g is the roasting attapulgite of 2 hours at 400 DEG C (average particle size particle size is 18nm) in temperature, makes coating weak solution after ultrasonic disperse.Bisphenol-a polysulfone ultrafilter membrane is fixed on a glass, the coating weak solution prepared is brushed equably at ultrafiltration membrane surface, then heat treatment 30 minutes under 70 ° of C, obtain supporting that layer thickness is 140 microns, stratum disjunctum thickness is the C-SPAES complex reverse osmosis membrane of 500 nanometers.
This reverse osmosis membrane is soaked 24 hours in water, then, 2.0MPa, 25 DEG C when, record the water flux of this reverse osmosis membrane in 1h；And the concentration change of sodium chloride in initial liquid and permeate in 1h, according to above-mentioned formula, calculating salt-stopping rate, result is in Table 1.
Embodiment 6
By dried for the 1.0g sulfonated polyether sulphone P-SPAES(with structure shown in formula I purchased from Yan Jin Technology Co., Ltd., m is 0.5, r is 0.5, ion exchange capacity is 1.39mmol/g) be dissolved in total amount be the formic acid of 100g, glycol monoethyl ether and ethanol composition mixed solvent (wherein, the weight ratio of formic acid, glycol monoethyl ether and ethanol is 6:3:1) in, after filtration, adding 0.05g is the roasting attapulgite of 2 hours at 400 DEG C in temperature, makes coating weak solution after ultrasonic disperse.Bisphenol-a polysulfone ultrafilter membrane is fixed on a glass (average particle size particle size is 20nm), the coating weak solution prepared is brushed equably at ultrafiltration membrane surface, then heat treatment 30 minutes under 70 ° of C, obtaining supporting that layer thickness is 140 microns, stratum disjunctum thickness is the P-SPAES complex reverse osmosis membrane of 100 nanometers.
This reverse osmosis membrane is soaked 24 hours in water, then, 2.0MPa, 25 DEG C when, record the water flux of this reverse osmosis membrane in 1h；And the concentration change of sodium chloride in initial liquid and permeate in 1h, according to above-mentioned formula, calculating salt-stopping rate, result is in Table 1.
Embodiment 7
By dried for the 1.0g sulfonated polyether sulphone SPAES(with structure shown in formula I purchased from Yan Jin Technology Co., Ltd., s is 0.5, t is 0.5, ion exchange capacity is 1.32mmol/g) be dissolved in total amount be the formic acid of 100g, glycol monoethyl ether and deionized water composition mixed solvent (wherein, the weight ratio of formic acid, glycol monoethyl ether and deionized water is 7:2:1) in, after filtration, adding 0.05g is the roasting attapulgite of 2 hours at 400 DEG C (average particle size particle size is 20nm) in temperature, makes coating weak solution after ultrasonic disperse.Bisphenol-a polysulfone ultrafilter membrane is fixed on a glass, the coating weak solution prepared is brushed equably at ultrafiltration membrane surface, then heat treatment 30 minutes under 70 ° of C, obtain supporting that layer thickness is 140 microns, stratum disjunctum thickness is the SPAES complex reverse osmosis membrane of 100 nanometers.
This reverse osmosis membrane is soaked 24 hours in water, then, 2.0MPa, 25 DEG C when, record the water flux of this reverse osmosis membrane in 1h；And the concentration change of sodium chloride in initial liquid and permeate in 1h, according to above-mentioned formula, calculating salt-stopping rate, result is in Table 1.
Comparative example 1
Identical with the preparation method of embodiment 1, the C-SPAES coating weak solution of be different in that preparation does not add the attapulgite after roasting, the C-SPAES complex reverse osmosis membrane obtained.
The method of testing of this reverse osmosis membrane is also identical with embodiment 1, and result is in Table 1.
Table 1
Can be seen that from the result of above example 1-7, reverse osmosis membrane provided by the invention has water flux and the salt-stopping rate of excellence, as can be seen here, reverse osmosis membrane provided by the invention has stronger chlorine-resistant property, namely, reverse osmosis membrane provided by the invention can have higher salt-stopping rate, higher water flux and stronger chlorine-resistant property, great prospects for commercial application well concurrently.Further, from the comparing result of embodiment 1-7 and comparative example 1 it can be seen that the water flux of the reverse osmosis membrane of attapulgite after not adding roasting is relatively low, this can reduce the product water efficiency of film, the waste energy, this can limit the commercial Application of this reverse osmosis membrane to a great extent.
Additionally, Fig. 1 is the scanning electron microscope (SEM) photograph of the reverse osmosis membrane of the undoped p attapulgite of comparative example 1 preparation, and Fig. 2 is the scanning electron microscope (SEM) photograph of the reverse osmosis membrane of the doping attapulgite according to embodiments of the invention 2 preparation, as seen from Figure 1, this reverse osmosis membrane has surfacing, flawless feature；As seen from Figure 2, this reverse osmosis membrane surface ratio is rougher, and this is caused owing to attapulgite is embedded in reverse osmosis membrane, and the increase of surface roughness increases the specific surface area of reverse osmosis membrane, and this is also one of reason increasing this reverse osmosis membrane water flux.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode.In order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (15)
1. a reverse osmosis membrane, described reverse osmosis membrane includes the supporting layer and the stratum disjunctum that stack together, it is characterized in that, described stratum disjunctum contains any one the sulfonated polyether sulphone and inorganic particulate that have in structure shown in formula I, (II) and (III), described inorganic particulate is the attapulgite after roasting, the particle size of described inorganic particulate is 10-20nm, in described stratum disjunctum, the weight ratio of described sulfonated polyether sulphone and described inorganic particulate is 1-100:1；
Wherein, n is the integer of >=1；M is 0 < m < 1, r is 0 < r < 1, and m+r=1；S is 0 < s < 1, t is 0 < t < 1, and s+t=1.
2. reverse osmosis membrane according to claim 1, wherein, in structure shown in formula I, 1≤n≤100.
3. reverse osmosis membrane according to claim 1 and 2, wherein, the thickness of described supporting layer is 40-200 micron, and the thickness of described stratum disjunctum is 100-500 nanometer.
4. reverse osmosis membrane according to claim 3, wherein, the thickness of described supporting layer is 40-150 micron, and the thickness of described stratum disjunctum is 100-300 nanometer.
5. reverse osmosis membrane according to claim 1, wherein, in described stratum disjunctum, the weight ratio of described sulfonated polyether sulphone and described inorganic particulate is 1-50:1.
6. reverse osmosis membrane according to claim 1, wherein, described sintering temperature is 200-600 DEG C, and roasting time is 1-10 hour.
7. a preparation method for reverse osmosis membrane, the method comprises the following steps:
(1) any one the dry sulfonated polyether sulphone having in structure shown in formula I, (II) and (III) is dissolved in solvent, and the solution obtained is mixed with inorganic particulate, prepare into coating liquid, described inorganic particulate is the attapulgite after roasting, the particle size of described inorganic particulate is 10-20nm, and the weight ratio of described sulfonated polyether sulphone and described inorganic particulate is 1-100:1；
(2) described coating liquid is coated on supporting layer, then carries out heat cure, to form the stratum disjunctum containing described sulfonated polyether sulphone and described inorganic particulate on described supporting layer；
Wherein, n is the integer of >=1；M is 0 < m < 1, r is 0 < r < 1, and m+r=1；S is 0 < s < 1, t is 0 < t < 1, and s+t=1.
8. preparation method according to claim 7, wherein, in structure shown in formula I, 1≤n≤100.
9. the preparation method according to claim 7 or 8, wherein, the thickness of described supporting layer is 40-200 micron, and the consumption of described coating liquid makes the thickness of described stratum disjunctum be 100-500 nanometer.
10. preparation method according to claim 9, wherein, the thickness of described supporting layer is 40-150 micron, and the consumption of described coating liquid makes the thickness of described stratum disjunctum be 100-300 nanometer.
11. the preparation method according to claim 7 or 8, wherein, with the gross weight of described coating liquid for benchmark, the consumption of described sulfonated polyether sulphone is 0.5-10 weight %, and the consumption of described inorganic particulate is 0.001-1 weight %.
12. preparation method according to claim 11, wherein, with the gross weight of described coating liquid for benchmark, the consumption of described sulfonated polyether sulphone is 0.5-5 weight %, and the consumption of described inorganic particulate is 0.005-0.5 weight %；The weight ratio of described sulfonated polyether sulphone and described inorganic particulate is 1-50:1.
13. the preparation method according to claim 7 or 8, wherein, described solvent be in formic acid, acetic acid, methanol, ethanol, glycol monoethyl ether, glycol dimethyl ether, acetone and deionized water any one or multiple.
14. the preparation method according to claim 7 or 8, wherein, the condition of described heat cure include temperature be 20-120 DEG C, the time be 5-50 minute.
15. the reverse osmosis membrane that the method described in any one in claim 7-14 prepares.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1071100A (en) * | 1991-09-27 | 1993-04-21 | 中国科学院大连化学物理研究所 | The preparation of sulfonated polyary-ether-sulfone nanometer filter film |
| US6177011B1 (en) * | 1996-03-18 | 2001-01-23 | Nitto Denko Corporation | Composite reverse osmosis membrane having a separation layer with polyvinyl alcohol coating and method of reverse osmotic treatment of water using the same |
| CN101721926A (en) * | 2009-12-01 | 2010-06-09 | 大连理工大学 | Sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone and preparation method thereof |
| CN102683731A (en) * | 2011-03-18 | 2012-09-19 | 韩国科学技术研究院 | Electrolyte membrane for fuel cell, and membrane-electrode assembly and fuel cell including the same |
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| JPS614505A (en) * | 1984-06-15 | 1986-01-10 | Nitto Electric Ind Co Ltd | Polysulfone composite semipermeable membrane and its manufacture |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1071100A (en) * | 1991-09-27 | 1993-04-21 | 中国科学院大连化学物理研究所 | The preparation of sulfonated polyary-ether-sulfone nanometer filter film |
| US6177011B1 (en) * | 1996-03-18 | 2001-01-23 | Nitto Denko Corporation | Composite reverse osmosis membrane having a separation layer with polyvinyl alcohol coating and method of reverse osmotic treatment of water using the same |
| CN101721926A (en) * | 2009-12-01 | 2010-06-09 | 大连理工大学 | Sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone and preparation method thereof |
| CN102683731A (en) * | 2011-03-18 | 2012-09-19 | 韩国科学技术研究院 | Electrolyte membrane for fuel cell, and membrane-electrode assembly and fuel cell including the same |
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