CN103182252A - Novel composite forward osmosis membrane and preparation method thereof - Google Patents
Novel composite forward osmosis membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a novel composite forward osmosis membrane and a preparation method thereof. The preparation method comprises the following steps: coating a casting solution on a low-density non-woven fabric and carrying out phase inversion in a gel bath so as to obtain a porous supporting layer; and allowing an aqueous solution of polyamine and an organic solution of polyacyl chloride to react on the porous supporting layer to form an ultrathin separating layer so as to obtain the composite forward osmosis membrane with a three-layer structure consisting of a low-density non-woven fabric layer, the porous supporting layer and the ultrathin separating layer. According to the invention, through hydrophilic modification of the porous supporting layer and modification of the ultrathin separating layer on the surface, the thickness of the compact ultrathin separating layer is reduced, and water flux is improved. The novel composite forward osmosis membrane prepared in the invention can be used in the process of forward osmosis and has high membrane flux and a high retention rate.
Description
Technical field
The invention belongs to water treatment with the preparation field of polymeric membrane, be specifically related to just permeate (Forward Osmosis, FO) preparation method of film for the NEW TYPE OF COMPOSITE of positive process of osmosis.
Background technology
The forward osmosis membrane separation process is a kind of new membrane isolation technics that grew up in the last few years, compare with traditional pressure-driven type membrane process, positive process of osmosis does not need impressed pressure, energy consumption is less, process is lower to the pollution level of film, the rate of recovery of process is higher, and environmental effect close friend is because these advantages of positive process of osmosis make fields such as it concentrates at desalinization, bitter desalination, food, generating, medicine control release that wide development space be arranged.
Forward osmosis membrane is the core of positive process of osmosis, and can the quality of its performance determining positive process of osmosis obtain large-scale application.The research that is applied in the forward osmosis membrane in the positive process of osmosis at present is less, the commodity forward osmosis membrane has only U.S. Hydration Technology Inc. company by phase inversion production, relevant patent is WO2006110497A2, material selection cellulose acetate class, make the restriction that is subjected to Treatment Solution pH condition in its application process, and its membrane flux is lower.
Reverse osmosis membrane accounts for 85% of film market in the diffusion barrier market at present, the preparation process development of reverse osmosis membrane is comparatively ripe, the commodity reverse osmosis membrane can reach very high flux, therefore positive process of osmosis will replace traditional pressure-driven type membrane process and need further study forward osmosis membrane and make it reach higher film properties, and comprehensively the advantage that its energy consumption is low just might realize its wide application value in film market.Therefore develop high flux, high performance forward osmosis membrane has great importance to the forward osmosis membrane process.
The principal element of restriction membrane flux is the interior concentration polarization phenomenon that occurs in the process in the porous support layer in the positive process of osmosis, therefore its existence makes the forward osmosis membrane flux far below theoretical membrane flux, will improve the interior concentration polarization phenomenon in the flux reduction process as far as possible of forward osmosis membrane.Compound forward osmosis membrane is owing to can be optimized counterdie and surface-active separating layer respectively in the preparation process, make its structure reduce interior concentration polarization effect as far as possible to the influence of water flux, make the high-throughout forward osmosis membrane of its easier preparation, and can select for use different materials to be applied in the different solution systems, because the advantage of compound forward osmosis membrane, exploration is studied to the preparation of compound forward osmosis membrane by a lot of research institutions in the world at present, but generally, the raising of the flux of forward osmosis membrane is not very big.Therefore, need a kind of preparation method of novel compound forward osmosis membrane, on the basis of optimizing compound forward osmosis membrane structure, further improve the water flux of positive process of osmosis.
Summary of the invention
The objective of the invention is provides a kind of NEW TYPE OF COMPOSITE forward osmosis membrane and preparation method thereof at the deficiency of existing forward osmosis membrane technology of preparing, mainly is that porous support layer by optimizing compound forward osmosis membrane and the physico-chemical property of surperficial superthin layer are realized.
The invention provides a kind of preparation method of novel compound forward osmosis membrane, technical conceive is as follows: adopt certain dissolution with solvents polymer, it is dissolved under the heating stirring condition, obtain the casting solution of homogeneous transparent; The low-density polyester support is pasted on glass plate, adopted certain thickness scraper that casting solution is coated on the supporting layer, inversion of phases film forming in coagulation bath; Support counterdie in preparation adopts novel interfacial polymerization method (adding certain density additive in water and/or organic phase) to carry out the preparation of ultra-thin separating layer, and it is carried out certain heat treatment, obtains novel compound forward osmosis membrane.And randomly, in described casting solution, add the hydrophilic nano particle of certain pore size and particle diameter, adopt the ultrasonic nano particle that makes in casting solution, to carry out homodisperse step.
A first aspect of the present invention provides a kind of compound forward osmosis membrane, is three-decker, comprising: low-density nonwoven fabric layer, porous support layer and ultra-thin separating layer, described porous support layer are between described low-density nonwoven fabric layer and the ultra-thin separating layer.
In another preference, the thickness of described low-density nonwoven fabric layer is 80 μ m-110 μ m, is made density＜50g/m by polyester
3
In another preference, described porous support layer is made by polymer, and described polymer is polysulfones, polyether sulfone, SPSF, polysulfonamides, poly (aryl ether sulfone ketone), poly (arylene ether nitrile) ketone, copolyether sulfone, Kynoar, polyacrylonitrile or cellulose acetate class.
The counterdie average pore size is at 20nm-80nm, and thickness is at 120 μ m-180 μ m.
In another preference, described ultra-thin separating layer is compact texture, and thickness is 60nm～180nm, is made in described porous support layer reaction by the polyamine aqueous solution and polynary acyl chlorides organic solution.
Described ultra-thin separating layer refers to polymer substance, multivalent ion even monovalent ion are had the separation of thin layers of higher interception capacity, wherein, the rejection of monovalent ion is reached more than 95%.
In another preference, described polyamine is piperazine and derivative, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine (PPD), equal benzene triamine, binary fatty amine or polyhydric aliphatic amine;
Described polynary acyl chlorides is o-phthaloyl chloride, m-phthaloyl chloride, paraphthaloyl chloride or pyromellitic trimethylsilyl chloride.
In another preference, described binary fatty amine is ethylenediamine.
A second aspect of the present invention provides the preparation method of compound forward osmosis membrane, said method comprising the steps of:
(1) casting solution is coated on the low-density nonwoven fabric layer, inversion of phases obtains porous support layer in coagulation bath;
(2) on described porous support layer, the polyamine aqueous solution and the reaction of polynary acyl chlorides organic solution form described ultra-thin separating layer.
In another preference, described casting solution is formulated in organic solvent by polymer dissolution, wherein, described polymer is polysulfones, polyether sulfone, SPSF, polysulfonamides, poly (aryl ether sulfone ketone), poly (arylene ether nitrile) ketone, copolyether sulfone, Kynoar, polyacrylonitrile, cellulose acetate or its combination, described solvent is N, dinethylformamide, N, N-dimethylacetylamide, N-methyl pyrrolidone, chloroform or their mixture.
In another preference, described polyamine is piperazine and derivative, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine (PPD), equal benzene triamine, binary fatty amine or polyhydric aliphatic amine;
Described polynary acyl chlorides is o-phthaloyl chloride, m-phthaloyl chloride, paraphthaloyl chloride or pyromellitic trimethylsilyl chloride.
In another preference, described binary fatty amine is ethylenediamine.
Further, described method also comprises step:
(3) described ultra-thin separating layer is heat-treated.
The composite membrane of interface polymerization reaction preparation is heat-treated 5-10min under 90-110 ℃ of condition make and react completely.
Further, preceding in described step (1), comprise also adding the step of hydrophilic nanoparticles in the casting solution that the concentration of described hydrophilic nanoparticles is 0.04w/w%-2w/w%.
In another preference, described hydrophilic nanoparticles is the hydrophilic particles with loose structure, and size is 1～10nm, is TiO
2Nano particle, SiO
2Nano particle, imvite, zeolite molecular sieve or organic metal alkoxide.Described organic metal alkoxide is aluminium isopropoxide, tetraisopropoxy titanium or phenyl triethoxysilane.
In another preference, the concentration of described casting solution is 14%-22w/v%; The concentration of described polyamine is 1.0%-2.5w/w%; The concentration of described polynary acyl chlorides is 0.06%-0.15w/v%.
In another preference, also be added with additive in the described polyamine aqueous solution and/or the described polynary acyl chlorides organic solution, the concentration of described additive is 0.04%-2%, and described additive is the hydrophilic particles with loose structure, and size is 1～10nm, is TiO
2Nano particle, SiO
2Nano particle, imvite, zeolite molecular sieve or organic metal alkoxide.
Described organic metal alkoxide is aluminium isopropoxide, tetraisopropoxy titanium or phenyl triethoxysilane.
Compared with prior art, the invention has the advantages that:
1) preparation technology of the present invention has carried out certain improvement on the basis of traditional interfacial polymerization method, by adding certain additive, increases the aquaporin in the surperficial superthin layer, makes the compound forward osmosis membrane for preparing have higher water flux.
2) the present invention adopts the hydrophilic nano particle of certain pore size to join in the casting solution, make the just infiltration for preparing support counterdie and have hydrophily preferably, thereby reduce the interior concentration polarization phenomenon in the positive process of osmosis greatly, improve the water flux of compound forward osmosis membrane largely.
The specific embodiment
The present inventor is through extensively and in depth research, the unexpected discovery, porous support layer by optimizing compound forward osmosis membrane and the physico-chemical property of surperficial superthin layer, can obtain to have higher water flux, and can reduce the compound forward osmosis membrane of the interior concentration polarization phenomenon in the positive process of osmosis greatly.On this basis, finished the present invention.
Compound forward osmosis membrane (compound FO film)
Compound forward osmosis membrane of the present invention is three-decker, comprising: low-density nonwoven fabric layer, porous support layer and ultra-thin separating layer, described low-density nonwoven fabric are between described porous support layer and the ultra-thin separating layer.
The thickness of described low-density nonwoven fabric layer is 80 μ m-110 μ m, is made by materials such as nylon, polyamide fibre, acrylic fibers, and its density is lower than 50g/m3 than at present much lower for separating of the nonwoven density of film backing material.
In a preference, the polyester material with 30%-50% perforate degree is made the low-density nonwoven fabric layer, as backing material.
Can adopt the commercial goods, as the big weighing apparatus filter cloth in Hangzhou Co., Ltd, DPP and JPP series are as the low-density nonwoven fabric layer.
Described porous support layer is made by polymer, and described polymer is polysulfones, polyether sulfone, SPSF, polysulfonamides, poly (aryl ether sulfone ketone), poly (arylene ether nitrile) ketone, copolyether sulfone, Kynoar, polyacrylonitrile or cellulose acetate class.
The average pore size of concrete porous support layer is 20-80nm, and thickness is 120 μ m-180 μ m..
Described ultra-thin separating layer is compact texture, and thickness is 60nm～180nm, is made in described porous support layer reaction by the polyamine aqueous solution and polynary acyl chlorides organic solution.
In another preference, the thickness of described ultra-thin separating layer is 80nm～150nm, and preferably, the thickness of described ultra-thin separating layer is 90nm～120nm.
Ultra-thin separating layer of the present invention refers to: the separation of thin layers that polymer substance, multivalent ion even monovalent ion is had higher interception capacity.
Described polyamine is piperazine and derivative, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine (PPD), equal benzene triamine, binary fatty amine or polyhydric aliphatic amine;
Described polynary acyl chlorides is o-phthaloyl chloride, m-phthaloyl chloride, paraphthaloyl chloride or pyromellitic trimethylsilyl chloride.
In another preference, described binary fatty amine is ethylenediamine.
The preparation method of compound forward osmosis membrane
The preparation method of compound forward osmosis membrane provided by the invention may further comprise the steps:
(1) casting solution is coated on the low-density nonwoven fabric layer, inversion of phases obtains porous support layer in coagulation bath;
(2) on described porous support layer, the polyamine aqueous solution and the reaction of polynary acyl chlorides organic solution form described ultra-thin separating layer, thereby obtain described compound forward osmosis membrane.
Described casting solution is formulated in organic solvent by polymer dissolution, wherein, described polymer is polysulfones, polyether sulfone, SPSF, polysulfonamides, poly (aryl ether sulfone ketone), poly (arylene ether nitrile) ketone, copolyether sulfone, Kynoar, polyacrylonitrile or cellulose acetate class and their mixture, described solvent is N, dinethylformamide, N, organic solvent and/or their mixtures such as N-dimethylacetylamide, N-methyl pyrrolidone, chloroform.
Described coagulation bath is the mixture of deionized water or solvent and deionized water, described solvent is N, dinethylformamide, N, organic solvent and/or their mixtures such as N-dimethylacetylamide, N-methyl pyrrolidone, chloroform, concentration＜50v/v%, preferably, concentration＜30v/v%, more preferably, concentration＜20v/v%, even concentration＜10v/v%.
Described polyamine is piperazine and derivative, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine (PPD), equal benzene triamine, binary fatty amine or polyhydric aliphatic amine;
Described polynary acyl chlorides is o-phthaloyl chloride, m-phthaloyl chloride, paraphthaloyl chloride or pyromellitic trimethylsilyl chloride.
In another preference, described binary fatty amine is ethylenediamine.
The concentration of described casting solution is 14%-22w/v%; The concentration of described polyamine is 1.0%-2.5w/v%; The concentration of described polynary acyl chlorides is 0.06%-0.15w/v%.
Further, described method also comprises step:
(3) described compound forward osmosis membrane is heat-treated.
In another preference, compound forward osmosis membrane is heat-treated 5-10min make and to react completely under 90-110 ℃ of condition.
Further, preceding in described step (1), comprise also adding the step of hydrophilic nanoparticles in the casting solution that the concentration of described hydrophilic nanoparticles is 0.04%-2%.
In another preference, described hydrophilic nanoparticles is the hydrophilic particles with loose structure, and size is 1～10nm, is TiO
2Nano particle, SiO
2Nano particle, imvite, zeolite molecular sieve or organic metal alkoxide.Described organic metal alkoxide is aluminium isopropoxide, tetraisopropoxy titanium, phenyl triethoxysilane etc.
Further, also be added with additive in the described polyamine aqueous solution and/or the described polynary acyl chlorides organic solution, the concentration of described additive is 0.04%-2%, and described additive is the hydrophilic particles with loose structure, and size is 1～10nm, is TiO
2Nano particle, SiO
2Nano particle, imvite, zeolite molecular sieve or organic metal alkoxide.
Described organic metal alkoxide is aluminium isopropoxide, tetraisopropoxy titanium, phenyl triethoxysilane etc.
Unless otherwise defined, employed all specialties are identical with the meaning that scientific words and one skilled in the art are familiar with in the literary composition.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The usefulness that preferable implementation method described in the literary composition and material only present a demonstration.
The above-mentioned feature that the present invention mentions, or the feature that embodiment mentions can any combination.All features that this case specification discloses can with any composition forms and usefulness, each feature that discloses in the specification can anyly provide the alternative characteristics of identical, impartial or similar purpose to replace.Therefore except special instruction is arranged, the feature that discloses only is the general example of equalization or similar features.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example is usually according to normal condition or the condition of advising according to manufacturer.
Embodiment 1
Take by weighing the 16g polysulfones, be dissolved in 84g by N, in the mixed solvent that N-dimethylacetylamide and PEG-400 form, be made into polymer concentration and be 18% counterdie casting solution.Adding 2g hydrophilic nano particle imvite formation imvite concentration is 2% novel counterdie casting solution in the counterdie casting solution for preparing, and disperses 30min to obtain the finely dispersed novel counterdie casting solution of nano particle in ultrasonic.Adopt novel counterdie casting solution on low-density nonwoven supporting layer, adopt certain thickness scraper to carry out knifing, put into coagulation bath deionized water gel film forming, obtain polysulfones ultrafiltration counterdie.
In the organic phase solvent n-hexane of interface polymerization reaction, add hydrophilic nanoparticles NaA type molecular sieve as the additive of organic phase, be made into the solution that contains nano particle 0.4%, measure mixed solvent 100ml, add 0.15g pyromellitic trimethylsilyl chloride (TMC), after the stirring and dissolving as novel organic phase, carry out interface polymerization reaction with 1.5% m-phenylene diamine (MPD) reactant aqueous solution at the polysulfones counterdie of preparation and generate active separation of thin layers, in 100-110 ℃ heated at constant temperature case, heat-treat and make that the active thin layer of preparation is stable, compound forward osmosis membrane deionized water rinsing after the processing, remove unreacted solvent, obtain novel compound forward osmosis membrane, be kept in the deionized water standby.
Embodiment 2
Take by weighing the 2.5g o-phenylenediamine and be mixed with 2.5% the o-phenylenediamine aqueous solution, the nano particle CNT that adds 0.2g is mixed with that to contain concentrations of nanoparticles be 0.2% aqueous phase solution, react with 0.15% pyromellitic trimethylsilyl chloride organic phase solution, carry out interface polymerization reaction at the polysulfones ultrafiltration counterdie for preparing (preparation of embodiment 1 phase inversion) and generate the novel active superthin layer, it is to heat-treat in 100-110 ℃ the heated at constant temperature case makes that the active thin layer of preparation is stable, compound forward osmosis membrane deionized water rinsing after the processing, remove unreacted solvent, obtain novel compound forward osmosis membrane, be kept in the deionized water standby.
Embodiment 3
Take by weighing the 1.5g p-phenylenediamine (PPD) and be mixed with 1.5% the p-phenylenediamine (PPD) aqueous solution, the nano particle SiO2 nano particle that adds 0.2g is mixed with that to contain concentrations of nanoparticles be 0.2% aqueous phase solution; Measure mixed solvent 100ml, add 0.08g pyromellitic trimethylsilyl chloride (TMC), after the stirring and dissolving as novel organic phase, adding the 0.4g nano particle is made into and contains 0.4% nano particle, contain 0.08% pyromellitic trimethylsilyl chloride organic phase solution reaction, carry out interface polymerization reaction at the polysulfones ultrafiltration counterdie for preparing (preparation of embodiment 1 phase inversion) and generate the novel active superthin layer, it is to heat-treat in 100-110 ℃ the heated at constant temperature case makes that the active thin layer of preparation is stable, compound forward osmosis membrane deionized water rinsing after the processing, remove unreacted solvent, obtain novel compound forward osmosis membrane, be kept in the deionized water standby.
Embodiment 4
Take by weighing the mixture (part by weight 1: 3) of 18g polyether sulfone and polysulfones, be dissolved in 82g by N, in the mixed solvent that N-dimethylacetylamide and PEG-400 form, be made into polyether sulfone-polysulfones concentration and be 18% counterdie casting solution.Adding 0.4g hydrophilic nano particle phenyl triethoxysilane formation metal alkoxide concentration is 0.4% novel counterdie casting solution in the counterdie casting solution for preparing, and disperses 30min to obtain the finely dispersed novel counterdie casting solution of nano particle in ultrasonic.Adopt novel counterdie casting solution on low-density nonwoven supporting layer, adopt certain thickness scraper to carry out knifing, put into coagulation bath (N, the mixture of N-dimethylacetylamide and deionized water, N wherein, the concentration of N-dimethylacetylamide is 8vol%) in the gel film forming, obtain novel counterdie.
Take by weighing the 1.8g m-phenylene diamine (MPD) and be mixed with 1.8% the m-phenylene diamine (MPD) aqueous solution, the nano particle phenyl triethoxysilane that adds 0.2g is mixed with that to contain metal alkoxide concentration be 0.2% aqueous phase solution, react with 0.06% pyromellitic trimethylsilyl chloride organic phase hexane solution, carry out interface polymerization reaction at the polyether sulfone for preparing-polysulfones ultrafiltration counterdie and generate the novel active superthin layer, it is to heat-treat in 100-110 ℃ the heated at constant temperature case makes that the active thin layer of preparation is stable, compound forward osmosis membrane deionized water rinsing after the processing, remove unreacted solvent, obtain novel compound forward osmosis membrane, be kept in the deionized water standby.
Embodiment 5
Take by weighing the 14g sulfonated polyether sulfone, be dissolved in 86g by N, in the mixed solvent that N-dimethylacetylamide and PEG-400 form, be made into polysulfones concentration and be 18% counterdie casting solution.Adding 0.4g hydrophilic nano particle NaA type molecular sieve formation nano particle concentration is 0.4% novel counterdie casting solution in the counterdie casting solution for preparing, and disperses 30min to obtain the finely dispersed novel counterdie casting solution of nano particle in ultrasonic.Adopt novel counterdie casting solution on low-density nonwoven supporting layer, adopt certain thickness scraper to carry out knifing, put into coagulation bath deionized water gel film forming, obtain novel counterdie.
Measure mixed solvent 100ml, add the 0.12g paraphthaloyl chloride, after the stirring and dissolving as novel organic phase, adding 0.4g nano particle NaA type molecular sieve is made into and contains 0.4% nano particle, contain 0.12% pyromellitic trimethylsilyl chloride organic phase hexane solution reaction, carry out interface polymerization reaction at the novel sulfonated polyether sulfone ultrafiltration counterdie for preparing and generate the novel active superthin layer, it is to heat-treat in 100-110 ℃ the heated at constant temperature case makes that the active thin layer of preparation is stable, compound forward osmosis membrane deionized water rinsing after the processing, remove unreacted solvent, obtain novel compound forward osmosis membrane, be kept in the deionized water standby.
Embodiment 6
Take by weighing the 20g SPSF, be dissolved in 80g by N, in the mixed solvent that N-dimethylacetylamide and PEG-400 form, be made into SPSF concentration and be 18% counterdie casting solution.Adding 0.4g metal alkoxide tetraisopropoxy titanium formation metal alkoxide concentration is 0.4% novel counterdie casting solution in the counterdie casting solution for preparing, and disperses 30min to obtain the finely dispersed novel counterdie casting solution of nano particle in ultrasonic.Adopt novel counterdie casting solution on low-density nonwoven supporting layer, adopt certain thickness scraper to carry out knifing, put into coagulation bath (N, the mixture of N-dimethylacetylamide and deionized water, N wherein, the concentration of N-dimethylacetylamide is 20vol%) in the gel film forming, obtain novel counterdie.
Take by weighing the equal benzene triamine of 2.2g and be mixed with 2.2% equal benzene three amine aqueous solutions, the metal alkoxide tetraisopropoxy titanium that adds 0.2g is mixed with that to contain metal alkoxide concentration be 0.2% aqueous phase solution; Measure mixed solvent 100ml, add the 0.08g o-phthaloyl chloride, after the stirring and dissolving as novel organic phase, adding the 0.4g nano particle is made into and contains 0.4% nano particle, contain 0.08% o-phthaloyl chloride organic phase solution reaction, carry out interface polymerization reaction at the novel sulfonated polysulfones ultrafiltration counterdie for preparing and generate the novel active superthin layer, it is to heat-treat in 100-110 ℃ the heated at constant temperature case makes that the active thin layer of preparation is stable, compound forward osmosis membrane deionized water rinsing after the processing, remove unreacted solvent, obtain novel compound forward osmosis membrane, be kept in the deionized water standby.
The test of embodiment 7 water fluxes
7.1 polysulfones counterdie flux test
As tested object, step is as follows with the polysulfones counterdie of embodiment preparation, unmodified counterdie:
A, the polysulfones counterdie is put in the membrane cisterna of milipore filter water flux tester, in carrying out under the 0.2MPa pressure more than the precompressed 30min;
Film after b, the precompressed is adjusted to 0.1MPa with pressure and carries out the water flux test, the volume of resulting water in the weighing certain hour scope.The computing formula of water flux is:
Water flux (L.m
-2.h
-1)=V
Water(L)/(S
Film(m
2) * t (h))
7.2 compound forward osmosis membrane flux test
As tested object, step is as follows with the NEW TYPE OF COMPOSITE forward osmosis membrane of embodiment preparation, unmodified compound forward osmosis membrane:
A. compound forward osmosis membrane is positioned in the forward osmosis membrane flux testing arrangement, as drawing liquid, deionized water carries out the forward osmosis membrane performance test as material liquid with NaCl solution;
B. note with electronic balance and draw liquid side quality situation of change in time;
C. calculate the flux magnitude of compound forward osmosis membrane according to the flux computing formula of milipore filter.
The water flux test result of counterdie and composite membrane is as shown in table 1.
Table 1 water flux test result
Table 1 experimental result shows: the water flux of the novel porous support counterdie that the present invention is prepared had improved about 70-130LMH more originally, after carrying out interfacial polymerization and preparing compound forward osmosis membrane, the more unmodified compound forward osmosis membrane of novel forward osmosis membrane water flux under identical test system has improved about 3-8LMH, reduces the interior concentration polarization phenomenon in the positive process of osmosis.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned instruction content of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. a compound forward osmosis membrane is characterized in that, described compound forward osmosis membrane is three-decker, comprising: low-density nonwoven fabric layer, porous support layer and ultra-thin separating layer, described porous support layer are between described low-density nonwoven fabric layer and the ultra-thin separating layer.
2. compound forward osmosis membrane as claimed in claim 1 is characterized in that, the thickness of described low-density nonwoven fabric layer is 80 μ m-110 μ m, is made density＜50g/m by polyester
3
3. compound forward osmosis membrane as claimed in claim 1, it is characterized in that, described porous support layer is made by polymer, and described polymer is polysulfones, polyether sulfone, SPSF, polysulfonamides, poly (aryl ether sulfone ketone), poly (arylene ether nitrile) ketone, copolyether sulfone, Kynoar, polyacrylonitrile or cellulose acetate class.
4. compound forward osmosis membrane as claimed in claim 1 is characterized in that, described ultra-thin separating layer is compact texture, and thickness is 60nm～180nm, is made in described porous support layer reaction by the polyamine aqueous solution and polynary acyl chlorides organic solution.
5. compound forward osmosis membrane as claimed in claim 4 is characterized in that, described polyamine is piperazine and derivative, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine (PPD), equal benzene triamine, binary fatty amine or polyhydric aliphatic amine;
Described polynary acyl chlorides is o-phthaloyl chloride, m-phthaloyl chloride, paraphthaloyl chloride or pyromellitic trimethylsilyl chloride.
6. the preparation method of compound forward osmosis membrane as claimed in claim 1 is characterized in that, said method comprising the steps of:
(1) casting solution is coated on the low-density nonwoven fabric layer, inversion of phases obtains porous support layer in coagulation bath;
(2) on described porous support layer, the polyamine aqueous solution and the reaction of polynary acyl chlorides organic solution form described ultra-thin separating layer.
7. preparation method as claimed in claim 6 is characterized in that, described method also comprises step:
(3) described ultra-thin separating layer is heat-treated.
8. preparation method as claimed in claim 6 is characterized in that, and is preceding in described step (1), also comprises adding the step of hydrophilic nanoparticles in the casting solution, and the concentration of described hydrophilic nanoparticles is 0.04w/w%-2w/w%.
9. preparation method as claimed in claim 6 is characterized in that, the concentration of described casting solution is 14w/w%-22w/v%; The concentration of described polyamine is 1.0w/w%-2.5w/w%; The concentration of described polynary acyl chlorides is 0.06%-0.15w/v%.
10. preparation method as claimed in claim 6, it is characterized in that, also be added with additive in the described polyamine aqueous solution and/or the described polynary acyl chlorides organic solution, the concentration of described additive is 0.04w/w%-2w/w%, described additive is the hydrophilic particles with loose structure, size is 1～10nm, is TiO
2Nano particle, SiO
2Nano particle, imvite, zeolite molecular sieve or organic metal alkoxide.
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| CN103816811A (en) * | 2014-02-26 | 2014-05-28 | 宁波莲华环保科技股份有限公司 | Preparation method of organic forward-osmosis membrane |
| CN104001434A (en) * | 2014-06-13 | 2014-08-27 | 中国海洋大学 | Forward osmosis membrane and preparation method thereof |
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| CN114797495A (en) * | 2022-05-16 | 2022-07-29 | 陕西鼎澈膜科技有限公司 | Production and manufacturing method of high-pressure nanofiltration membrane |
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