CN104248914A - Reverse osmosis membrane and preparation method thereof - Google Patents
Reverse osmosis membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a reverse osmosis membrane, a preparation method of the reverse osmosis membrane, and the reverse osmosis membrane prepared by the method. The reverse osmosis membrane comprises a support layer and a separation layer stacked together, the separation layer comprises sulfonated poly aryl ether sulphone with the structure shown as any of formula (I), (II) and (III) and inorganic particles; wherein n is an integer equal to or greater than 1, preferably n is equal to or greater than 1 and equal to or less than 100; m is greater than 0 and less than 1, r is greater than 0 and less than 1, m+r=1; s is greater than 0 and less than 1, t is greater than 0 and less than 1, and s+t=1; the reverse osmosis membrane has both high salt cutting rate, high water flux and strong chlorine resistance.
Description
Technical field
The present invention relates to a kind of reverse osmosis membrane, a kind of preparation method of reverse osmosis membrane and the reverse osmosis membrane that prepared by the method.
Background technology
UF membrane occurs 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 is exactly diffusion barrier.For perforated membrane, the size according to membrane aperture can be divided into microfiltration membranes, milipore filter, NF membrane and reverse osmosis membrane.
Wherein, reverse osmosis membrane is because having good separation performance to organic molecule and inorganic ion, safety, environmental protection, the advantage such as easy to operate and one of key technology becoming water treatment.Up to now, reverse osmosis membrane be mainly used in the field such as to prepare in seawater 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, that is, be made up of separating layer and supporting layer.Wherein, the preparation method of composite membrane mainly contains: weak solution cladding process, interfacial polymerization and Plasma Polymerization etc.The current composite membrane be widely used in water treatment field mainly takes the mode of interfacial polymerization, such as, polyamide film can be compound to micropore and support counterdie surface.But the chemical constitution of polyamide makes the chlorine-resistant property of such composite membrane very weak, and the permission of all commercial polyamide composite films to free chlorine is almost nil, thus adds film pretreatment cost and reduce its service life.Therefore, the chlorine-resistant property improving film is one of vital task of current reverse osmosis membrane research.
Research shows, sulfonated polyether sulfone has acidproof, alkaline-resisting and chlorine resistance preferably, has good application prospect in film field.US4818387 discloses a kind of sulfonated polyether sulfone composite membrane and preparation method thereof.Test result shows, the sulfonated polyether sulfone composite membrane adopting dip coating to prepare has 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, 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
The object of this invention is to provide a kind of new reverse osmosis membrane, a kind of preparation method of reverse osmosis membrane and the reverse osmosis membrane that prepared by the method.
The invention provides a kind of reverse osmosis membrane, described reverse osmosis membrane comprises the supporting layer and separating layer that stack together, wherein, described separating layer contain there is formula (I), any one sulfonated polyether sulphone in structure shown in (II) and (III) and inorganic particulate;
Wherein, n is the integer of >=1, preferably 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 a kind of preparation method of reverse osmosis membrane, wherein, the method comprises the following steps:
(1) sulfonated polyether sulphone of any one the drying had in structure shown in formula (I), (II) and (III) is dissolved in solvent, and the solution obtained is mixed with inorganic particulate, be prepared into coating liquid;
(2) described coating liquid is coated on supporting layer, then carries out heat cure;
Wherein, n is the integer of >=1, preferably 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, inorganic particulate inside has pore passage structure and hydrophilic ability uniquely, on the other hand, being incorporated into by inorganic particulate to have of the present inventionly has in the sulfonated polyether sulphone of ad hoc structure, add the roughness on the reverse osmosis membrane surface prepared by the present invention, increase the surface area of the reverse osmosis membrane prepared by the present invention, thus the water flux of the reverse osmosis membrane prepared by the present invention is significantly improved, namely, reverse osmosis membrane provided by the invention has higher water flux and higher salt-stopping rate, and show stronger chlorine-resistant property (namely, oxidation resistent susceptibility).
Other features and advantages of the present invention are 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 forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one 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
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Reverse osmosis membrane provided by the invention comprises the supporting layer and separating layer that stack together, it is characterized in that, described separating layer contain there is formula (I), any one sulfonated polyether sulphone in structure shown in (II) and (III) and inorganic particulate;
Wherein, n is the integer of >=1, preferably 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, is preferably 1.0-2.0mmol/g.The ion exchange capacity of described sulfonated polyether sulphone refers to sulfonic molal quantity in 1g sulfonated polyether sulphone, and acid base titration method can be adopted to measure.
According to the present invention, above-mentioned formula (I) can be commercially available to the sulfonated polyether sulphone of structure formula (III) Suo Shi, and such as, shown in formula (I), the sulfonated polyether sulphone of structure can purchased from Yan Jin Technology Co., Ltd.; Also can prepare according to various method well known in the art, will repeat no more at this.
According to the present invention, although the thickness of described supporting layer and described separating layer all can carry out selecting and changing in wider scope, but two-layerly can play better coordinated effect to make this, enabling obtained reverse osmosis membrane 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 separating layer is 100-500 nanometer; More preferably in situation, the thickness of described supporting layer is 40-150 micron, and the thickness of described separating layer is 100-300 nanometer.
According to the present invention, higher salt-stopping rate, higher water flux and stronger chlorine-resistant property is had better concurrently in order to enable obtained reverse osmosis membrane, under preferable case, in described separating layer, the weight ratio of described sulfonated polyether sulphone and described inorganic particulate can be 1-100:1, more preferably, in situation, in described separating layer, 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 this inorganic particulate crystal structure inside has pore passage structure and has hydrophily.Under preferable case, in order to make obtained reverse osmosis membrane, there is the water penetration improved further, also namely there is higher water flux, described inorganic particulate selects attapulgite, its reason is: attapulgite is a kind of nanometer porous road lenticular zeopan, and be different from the phyllosilicates such as imvite, crystal is bar-shaped or filamentary structure, there is regular, fixed-size one-dimensional channels in its crystal structure inside, hydrone can access aperture road; And, single crystal is tiny bar-shaped, needle-like and threadiness, when disperseing, rod-like fibre can keep multi-faceted deposit drying regularly in felted thing thing after, form the inhomogenous secondary space of size between agglomerate, make more hydrone can through hole.Further preferably, described inorganic particulate is the attapulgite after roasting, and sintering temperature is 200-600 DEG C, is preferably 300-500 DEG C, is more preferably 400 DEG C; Roasting time is 1-10 hour, is preferably 2-5 hour, is 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 particulate, and when described particulate is spherical, then the size of described particulate refers to the diameter of this particulate.
According to the present invention, described supporting layer variously can have certain aperture and intensity and can be used in the supporting layer of reverse osmosis membrane for existing, usually can for having the milipore filter that non-woven fabrics supports, forming the polymeric material of milipore filter 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) sulfonated polyether sulphone of any one the drying had in structure shown in formula (I), (II) and (III) is dissolved in solvent, and the solution obtained is mixed with inorganic particulate, be prepared into coating liquid;
(2) described coating liquid is coated on supporting layer, then carries out heat cure;
Wherein, n is the integer of >=1, preferably 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 the present invention to described coating liquid is not particularly limited, but have higher salt-stopping rate, higher water flux and stronger chlorine-resistant property better concurrently to enable obtained reverse osmosis membrane, under preferable case, the consumption of described coating liquid makes the thickness of described separating layer be 100-500 nanometer, is preferably 100-300 nanometer.In addition, the thickness of supporting layer also can be selected in wider scope, such as, can be 40-200 micron, is preferably 40-150 micron.
According to the present invention, as mentioned above, described supporting layer variously can have certain aperture and intensity and can be used in the supporting layer of reverse osmosis membrane for existing, usually can for having the milipore filter that non-woven fabrics supports, forming the polymeric material of milipore filter is 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 % by weight, under preferable case, the consumption of described sulfonated polyether sulphone is 0.5-5 % by weight; The consumption of described inorganic particulate can be 0.001-1 % by weight, and under preferable case, the consumption of described inorganic particulate is 0.005-0.5 % by weight; The weight ratio of described sulfonated polyether sulphone and described inorganic particulate can be 1-100:1, and under preferable case, 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 with describe above identical.
According to the present invention, described solvent can be the existing inert media that described phenolphthalein type sulfonated polyether sulphone and additive can be dissolved, such as, can be selected from formic acid, acetic acid, methyl alcohol, ethanol, glycol monoethyl ether, glycol dimethyl ether, acetone and deionized water one or more.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, most preferably is 7:2:1.
In addition, in order to make the reverse osmosis membrane that obtains more smooth, preferably, before the preparation method of reverse osmosis membrane provided by the invention is also included in and is coated on supporting layer by coating liquid, by fixing for described supporting layer on a glass.
The condition of the present invention to described heat cure is not particularly limited, as long as described coating liquid can be made to solidify.Such as, the condition of described heat cure comprise temperature can for 20-120 DEG C, the time can for 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.
Below 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 measure;
(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 2.0MPa, records the pure water transit dose of described reverse osmosis membrane in 1h under 25 DEG C of conditions, and obtained by following formulae discovery at pressure:
J=Q/ (At), wherein, J is pure water flux, the effective film area (m of Q to be pure water transit dose (L), A be reverse osmosis membrane
2), 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, be 2.0MPa at pressure, record the change in concentration of sodium chloride in the former aqueous solution of sodium chloride and permeate that initial concentration in 1h is 2000ppm under 25 DEG C of conditions, and obtained by following formulae discovery:
R=(C
p-C
f)/C
p× 100%, wherein, R is salt-stopping rate, C
pfor the concentration of sodium chloride in stoste, C
ffor the concentration of sodium chloride in permeate.
Embodiment 1
This embodiment is for illustration of reverse osmosis membrane provided by the invention and preparation method thereof.
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 the mixed solvent of formic acid, glycol monoethyl ether and the deionized water composition that total amount is 100g (wherein, the weight ratio of formic acid, glycol monoethyl ether and deionized water is 7:2:1) in, after filtration, add 0.01g roasting attapulgite of 2 hours (average particle size particle size is 10nm) at temperature is 400 DEG C, after ultrasonic disperse, make coating weak solution.By bisphenol-a polysulfone milipore filter (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 separating layer thickness is the C-SPAES complex reverse osmosis membrane of 300 nanometers.
This reverse osmosis membrane is soaked 24 hours in water, then, under 2.0MPa, the condition of 25 DEG C, records the water flux of this reverse osmosis membrane in 1h; And the change in concentration of sodium chloride in initial liquid and permeate in 1h, according to above-mentioned formula, calculate salt-stopping rate, the results are shown 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 the mixed solvent of formic acid, glycol dimethyl ether and the deionized water composition that total amount is 100g (wherein, the weight ratio of formic acid, glycol dimethyl ether and deionized water is 7:2:1) in, after filtration, add 0.05g roasting attapulgite of 2 hours (average particle size particle size is 20nm) at temperature is 400 DEG C, after ultrasonic disperse, make coating weak solution.Bisphenol-a polysulfone milipore filter 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 separating layer thickness is the C-SPAES complex reverse osmosis membrane of 100 nanometers.
This reverse osmosis membrane is soaked 24 hours in water, then, under 2.0MPa, the condition of 25 DEG C, records the water flux of this reverse osmosis membrane in 1h; And the change in concentration of sodium chloride in initial liquid and permeate in 1h, according to above-mentioned formula, calculate salt-stopping rate, the results are shown 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 the mixed solvent of formic acid, glycol monoethyl ether and the acetone composition that total amount is 100g (wherein, the weight ratio of formic acid, glycol monoethyl ether and acetone is 7:2:1) in, after filtration, add 0.02g roasting attapulgite of 2 hours (average particle size particle size is 12nm) at temperature is 400 DEG C, after ultrasonic disperse, make coating weak solution.Bisphenol-a polysulfone milipore filter 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, obtaining supporting layer thickness is 140 microns, and separating layer thickness is the C-SPAES complex reverse osmosis membrane of 200 nanometers.
This reverse osmosis membrane is soaked 24 hours in water, then, under 2.0MPa, the condition of 25 DEG C, records the water flux of this reverse osmosis membrane in 1h; And the change in concentration of sodium chloride in initial liquid and permeate in 1h, according to above-mentioned formula, calculate salt-stopping rate, the results are shown 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 the mixed solvent of acetic acid, glycol monoethyl ether and the deionized water composition that total amount is 100g (wherein, the weight ratio of acetic acid, glycol monoethyl ether and deionized water is 7:2:1) in, after filtration, add 0.1g roasting attapulgite of 2 hours (average particle size particle size is 15nm) at temperature is 400 DEG C, after ultrasonic disperse, make coating weak solution.Bisphenol-a polysulfone milipore filter 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, obtaining supporting layer thickness is 140 microns, and separating layer thickness is the C-SPAES complex reverse osmosis membrane of 400 nanometers.
This reverse osmosis membrane is soaked 24 hours in water, then, under 2.0MPa, the condition of 25 DEG C, records the water flux of this reverse osmosis membrane in 1h; And the change in concentration of sodium chloride in initial liquid and permeate in 1h, according to above-mentioned formula, calculate salt-stopping rate, the results are shown 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 the mixed solvent of acetic acid, glycol dimethyl ether and the acetone composition that total amount is 100g (wherein, the weight ratio of acetic acid, glycol dimethyl ether and acetone is 8:1:1) in, after filtration, add 0.125g roasting attapulgite of 2 hours (average particle size particle size is 18nm) at temperature is 400 DEG C, after ultrasonic disperse, make coating weak solution.Bisphenol-a polysulfone milipore filter 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, obtaining supporting layer thickness is 140 microns, and separating layer thickness is the C-SPAES complex reverse osmosis membrane of 500 nanometers.
This reverse osmosis membrane is soaked 24 hours in water, then, under 2.0MPa, the condition of 25 DEG C, records the water flux of this reverse osmosis membrane in 1h; And the change in concentration of sodium chloride in initial liquid and permeate in 1h, according to above-mentioned formula, calculate salt-stopping rate, the results are shown 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 the mixed solvent of formic acid, glycol monoethyl ether and the ethanol composition that total amount is 100g (wherein, the weight ratio of formic acid, glycol monoethyl ether and ethanol is 6:3:1) in, after filtration, add 0.05g roasting attapulgite of 2 hours at temperature is 400 DEG C, after ultrasonic disperse, make coating weak solution.Bisphenol-a polysulfone milipore filter 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 layer thickness is 140 microns, and separating layer thickness is the P-SPAES complex reverse osmosis membrane of 100 nanometers.
This reverse osmosis membrane is soaked 24 hours in water, then, under 2.0MPa, the condition of 25 DEG C, records the water flux of this reverse osmosis membrane in 1h; And the change in concentration of sodium chloride in initial liquid and permeate in 1h, according to above-mentioned formula, calculate salt-stopping rate, the results are shown 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 the mixed solvent of formic acid, glycol monoethyl ether and the deionized water composition that total amount is 100g (wherein, the weight ratio of formic acid, glycol monoethyl ether and deionized water is 7:2:1) in, after filtration, add 0.05g roasting attapulgite of 2 hours (average particle size particle size is 20nm) at temperature is 400 DEG C, after ultrasonic disperse, make coating weak solution.Bisphenol-a polysulfone milipore filter 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, obtaining supporting layer thickness is 140 microns, and separating layer thickness is the SPAES complex reverse osmosis membrane of 100 nanometers.
This reverse osmosis membrane is soaked 24 hours in water, then, under 2.0MPa, the condition of 25 DEG C, records the water flux of this reverse osmosis membrane in 1h; And the change in concentration of sodium chloride in initial liquid and permeate in 1h, according to above-mentioned formula, calculate salt-stopping rate, the results are shown in Table 1.
Comparative example 1
Identical with the preparation method of embodiment 1, institute's difference is that the C-SPAES prepared applies in weak solution the attapulgite after not adding roasting, the C-SPAES complex reverse osmosis membrane obtained.
Identical also with embodiment 1 of the method for testing of this reverse osmosis membrane, the results are shown in Table 1.
Table 1
As can be seen from the result of above embodiment 1-7, reverse osmosis membrane provided by the invention has excellent water flux and salt-stopping rate, 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 well concurrently, has prospects for commercial application.Further, as can be seen from the comparing result of embodiment 1-7 and comparative example 1, the water flux not adding the reverse osmosis membrane of the attapulgite after roasting is lower, and this can reduce the product water efficiency of film, waste energy, this can limit the commercial Application of this reverse osmosis membrane to a great extent.
In addition, Fig. 1 is the scanning electron microscope (SEM) photograph of reverse osmosis membrane of the attapulgite that do not adulterate prepared by comparative example 1, and Fig. 2 is the scanning electron microscope (SEM) photograph of the reverse osmosis membrane of the doping attapulgite prepared according to embodiments of the invention 2, 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 more coarse, and this caused because attapulgite is embedded in reverse osmosis membrane, and the increase of surface roughness increases the specific area of reverse osmosis membrane, and this is also one of reason increasing this reverse osmosis membrane water flux.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (12)
1. a reverse osmosis membrane, described reverse osmosis membrane comprises the supporting layer and separating layer that stack together, it is characterized in that, described separating layer contain there is formula (I), any one sulfonated polyether sulphone in structure shown in (II) and (III) and inorganic particulate;
Wherein, n is the integer of >=1, preferably 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.
2. reverse osmosis membrane according to claim 1, wherein, the thickness of described supporting layer is 40-200 micron, and be preferably 40-150 micron, the thickness of described separating layer is 100-500 nanometer, is preferably 100-300 nanometer.
3. reverse osmosis membrane according to claim 1, wherein, in described separating layer, the weight ratio of described sulfonated polyether sulphone and described inorganic particulate is 1-100:1, is preferably 1-50:1.
4. the reverse osmosis membrane according to claim 1 or 3, wherein, described inorganic particulate is the attapulgite after roasting, and the particle size of described inorganic particulate is 10-20nm.
5. reverse osmosis membrane according to claim 4, wherein, described sintering temperature is 200-600 DEG C, and roasting time is 1-10 hour.
6. a preparation method for reverse osmosis membrane, the method comprises the following steps:
(1) sulfonated polyether sulphone of any one the drying had in structure shown in formula (I), (II) and (III) is dissolved in solvent, and the solution obtained is mixed with inorganic particulate, be prepared into coating liquid;
(2) described coating liquid is coated on supporting layer, then carries out heat cure;
Wherein, n is the integer of >=1, preferably 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.
7. preparation method according to claim 6, wherein, the thickness of described supporting layer is 40-200 micron, and be preferably 40-150 micron, the consumption of described coating liquid makes the thickness of described separating layer be 100-500 nanometer, is preferably 100-300 nanometer.
8. preparation method according to claim 6, wherein, with the gross weight of described coating liquid for benchmark, the consumption of described sulfonated polyether sulphone is 0.5-10 % by weight, be preferably 0.5-5 % by weight, the consumption of described inorganic particulate is 0.001-1 % by weight, is preferably 0.005-0.5 % by weight; The weight ratio of described sulfonated polyether sulphone and described inorganic particulate is 1-100:1, is preferably 1-50:1.
9. preparation method according to claim 6, wherein, described inorganic particulate is the attapulgite after roasting, and the particle size of described inorganic particulate is 10-20nm.
10. preparation method according to claim 6, wherein, described solvent be in formic acid, acetic acid, methyl alcohol, ethanol, glycol monoethyl ether, glycol dimethyl ether, acetone and deionized water any one or multiple.
11. preparation methods according to claim 6, wherein, the condition of described heat cure comprises that temperature is 20-120 DEG C, the time is 5-50 minute.
12. reverse osmosis membranes prepared by the method in claim 6-11 described in any one.
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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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| 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 |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107413196A (en) * | 2017-04-19 | 2017-12-01 | 天津大学 | Forward osmosis membrane preparation method and method for treating pesticide wastewater by using forward osmosis membrane |
| CN107413196B (en) * | 2017-04-19 | 2019-12-13 | 天津大学 | forward osmosis membrane preparation method and method for treating pesticide wastewater by using forward osmosis membrane |
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| CN104248914B (en) | 2016-06-29 |
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