CN103785301A - Cellulose acetate forward osmosis film material and preparation method thereof - Google Patents
Cellulose acetate forward osmosis film material and preparation method thereof Download PDFInfo
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- CN103785301A CN103785301A CN201410050442.7A CN201410050442A CN103785301A CN 103785301 A CN103785301 A CN 103785301A CN 201410050442 A CN201410050442 A CN 201410050442A CN 103785301 A CN103785301 A CN 103785301A
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Abstract
The invention discloses a cellulose acetate forward osmosis film material. The cellulose acetate forward osmosis film material is a dissymmetric film, and is 20-150 micrometers in thickness and 55 to 90 percent in porosity. The cellulose acetate forward osmosis film material is made of cellulose acetate casting film liquid in a film scraping manner by adopting a film scraping machine; the content of cellulose acetate in the cellulose acetate casting film liquid is 5-40wt%, and the balance refers to macromolecule solvents. The cellulose acetate forward osmosis film material disclosed by the invention is suitable for being used in the forward osmosis process, is good in hydrophilcity and has a superthin structure; the porosity of a supporting layer is large; the connectivity of a hole structure is good; the internal concentration polarization can be effectively reduced; the compactness of a surface layer is good; the reject rate of univalency salt is high; small molecules such as trace suspended solids, bacteria and viruses in a water body can be effectively removed; the treatment efficiency is high and the operation cost is low.
Description
Technical field
The present invention relates to macromolecule member material field, relate in particular to a kind of cellulose acetate forward osmosis membrane material and preparation method thereof.
Background technology
Earth surface major part is covered by ocean, and wherein only having 0.8% water resource is drinkable fresh water, faces serious water resource, environment and energy crisis along with environmental pollution day by day seriously causes the whole world.It is the effective way that solves water resources crisis that exploitation account for more than 99% seawater of earth surface.But the reverse osmosis technology that desalinization at present extensively adopts need to apply larger external pressure, energy consumption is higher.The emerging water technology that positive infiltration technology is born for solving this key issue just.Positive infiltration technology is the both sides that solution different osmotic pressure are placed on to pellicle, water spontaneously from Hyposmolality side (feeding liquid) to hyperosmosis side (driving liquid) under the promotion of permeable pressure head, reach driving side solution and be diluted, the process that feed side solution is concentrated.Except being applied to desalinization, positive infiltration technology also can be applicable to a lot of fields of the national industry such as waste water recycling, agricultural irrigation, food, medical treatment, Aero-Space.In positive process of osmosis, the permeable pressure head of pellicle both sides can be more much higher than the motive force in reverse osmosis process, just permeating theoretically and can realize the saturating amount more much higher than counter-infiltration.But because the existence of interior concentration polarization causes the poor Δ π of osmotic pressure,effective eff much smaller than the permeable pressure head Δ π that drives liquid and feeding liquid, reduced to a great extent the motive force of process of osmosis, therefore real fluxes is much smaller than theoretical flux.Interior concentration polarization is because the water or the salt ion that see through pellicle cause to the diffusional resistance that drives liquid and feeding liquid body.So membrane material supporting layer is thinner, diffusional resistance is less, and interior concentration polarization is just more weak, and flux is higher; Cortex is thinner, and hydrone resistance to mass tranfer is less, and flux is higher.In addition, guaranteeing that, under the prerequisite of film-strength, membrane material supporting layer pore structure is more communicated with, aperture is larger, and flux is higher.Therefore, the thickness of membrane material and supporting layer pore structure directly affect the positive permeation flux of membrane material.
Evaluate the performance indications of forward osmosis membrane material except flux, another is the interception capacity of membrane material to salt, is called for short salt rejection.Salt rejection depends primarily on the compactness extent of membrane material cortex.Cortex is completely fine and close, and salt ion can not see through, and hydrone also cannot see through simultaneously, and the aperture of cortex is preferably between 0.4～0.6 nanometer, and salt rejection is the highest.Therefore, developing suitable membrane material is to solve one of key of just permeating interior concentration polarization and rejection, and desirable forward osmosis membrane material should be the membrane material with following characteristics:
(a) cortex has good hydrophily, and flux is high, and antifouling property is good;
(b) cortex aperture is preferably between 0.4～0.6 nanometer, guarantees high salt rejection; Thickness is as far as possible little, improves flux;
(c) supporting layer is as far as possible thin, and porosity is large, and pore structure height is communicated with, and has high mass tranfer coefficient, reduces interior concentration polarization;
(d) there is good mechanical performance and chemical stability;
Early stage positive penetration study adopts reverse osmosis membrane as forward osmosis membrane material, but effect is all undesirable.In the nineties in 20th century, HTI(Hydration Technology Innovations) first company develop business-like FO film, and Patents is WO2006110497A2.It is the cellulose acetate class film [18] being supported by the polyester webs in the middle of embedded film or nonwoven, membrane material smooth surface.Compared with the reverse osmosis membrane surface forming with general interface polymerization, the surface roughness of HTI film is in 36 nanometers, and the roughness on interfacial polymerization film surface is about 100 nanometers.
Patent 103055713A has introduced the preparation method of a kind of pair of cortex cellulose acetate forward osmosis membrane, researcher wishes that the membrane material by preparation with two cortexes stops the salt ion of driving side to immerse in supporting layer pore structure, thereby reduce interior concentration polarization, improve flux.But result shows, two cortexes have just increased the resistance to mass tranfer of water, and flux is significantly reduced, and salt rejection is not significantly improved;
Interfacial polymerization film is also the study hotspot of forward osmosis membrane material at present, and interfacial polymerization film is normally made up of polyamide cortex and thicker polysulfones porous support layer and nonwoven supporting layer.Because polysulfones is porous hydrophobic material, hydrone transmission resistance is therein larger, prepares interfacial polymerization forward osmosis membrane have serious interior concentration polarization phenomenon with hydrophobic material as polysulfones work supports.On the other hand, the polysulfones that it is poor that interfacial polymerization film all adopts hydrophily is made backing material, membrane material low contamination resistance.Patent CN103170257A has introduced and a kind of polysulfones has been carried out to the preparation method for the preparation of polysulfones/polyamide composite film after carboxylated hydrophilic modifying.When but water wetted material supports, interfacial polymerization cortex is inhomogeneous and poor with support associativity, and cortex easily comes off.
The researcher of NUS also attempts to obtain polyeletrolyte cortex by layer-layer self assembly mode, but this film can hold back bivalent cation, for the rejection of a valence state salt ion far below business-like HTI film.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, proposed a kind of preparation method of cellulose acetate forward osmosis membrane; It is good that described ultra-thin cellulose acetate forward osmosis membrane has hydrophily, and interior concentration polarization is little, and positive permeation flux is high, and chlorine resistance is good, to the high advantage of a valence state salt ion rejection.
For achieving the above object and other object, the present invention adopts following technical scheme to realize:
A kind of cellulose acetate forward osmosis membrane material, described cellulose acetate forward osmosis membrane material is a kind of anisotropic membrane;
The thickness of described cellulose acetate forward osmosis membrane material is 20-150 μ m, and porosity is 55%～90%,
Described cellulose acetate forward osmosis membrane material is made by knifing machine knifing by cellulose acetate casting solution, and described casting solution contains the cellulose acetate of 5～40wt.%, and all the other components are macromolecule solvent and additive;
Wherein, described macromolecule solvent is for being selected from tetrachloroethanes, DMF, one or more in 1-METHYLPYRROLIDONE, methyl-sulfoxide, carrene, propylene glycol carbonate and diglycol.
Preferably, casting solution described above also contains volatility additive, described volatility additive is selected from methyl alcohol, one or more in benzene, methyl acetate, ethyl acetate, oxolane, acetone, carbon tetrachloride and n-hexane, the mass ratio of described macromolecule solvent and described volatility additive is 1:0.01～1:2.5.
More preferably, the mass ratio of described macromolecule solvent and described volatility additive is 1:0.01～1:2.
More preferably, the mass ratio of described macromolecule solvent and described volatility additive is 2:1～1:2.
More preferably, described casting solution contains the cellulose acetate of 5%～30wt%, and all the other components are macromolecule solvent and volatility additive.
More preferably, described casting solution contains the Triafol T of 15-25wt%, and all the other components are macromolecule solvent and volatility additive, and wherein, the mass ratio of macromolecule solvent and volatility additive is 2:1～1:2.
Preferably, the thickness of described cellulose acetate forward osmosis membrane material is 20-70 μ m.
Cellulose acetate forward osmosis membrane material described in the present invention is the anisotropic membrane with cortex and supporting layer; The chemical constituent of cortex and supporting layer is identical; Cortex construction densification, aperture is very little, has centrifugation; Supporting layer has netted intercommunicating pore structure.Preferably, the weight average molecular weight of cellulose acetate described above is 5～300,000.
More preferably, the weight average molecular weight of described cellulose acetate is 5～150,000.
Preferably, cellulose acetate described above is Triafol T.
Preferably, cellulose acetate described above is Triafol T and the mixture that is selected from the arbitrary cellulose acetate in cellulose diacetate, cellulose acetate propionate and acetate butyrate fiber, and in described mixture, Triafol T is 1:0～1:3 with the mass ratio that is selected from the arbitrary cellulose acetate in cellulose diacetate, cellulose acetate propionate and acetate butyrate fiber.
More preferably, in described mixture, Triafol T is 1:0～1:2.5 with the mass ratio that is selected from the arbitrary cellulose acetate in cellulose diacetate, cellulose acetate propionate and acetate butyrate fiber.
The invention also discloses a kind of method of preparing cellulose acetate forward osmosis membrane material described above, comprise the steps:
1) casting solution preparation: cellulose acetate is added in macromolecule solvent and volatility additive, carry out stirring and dissolving under 25～50 ℃ of conditions of temperature, form uniform casting solution;
2) casting solution is carried out to deaeration: deaeration temperature is 25～70 ℃;
3) utilize knifing machine knifing: by step 2) in be coated on the glass plate of dried and clean through the casting solution of deaeration processing, form nascent state film by knifing machine knifing, and nascent state film is placed in to temperature is 15～45 ℃, under the air that relative humidity is 20%～80%, volatilize 0-60 second;
4) coagulation bath processing: the nascent state film forming in step 3) is put into coagulation bath phase-splitting and solidify to form membrane material; Wherein, the medium of coagulation bath is selected from the one in the mixture of mixture, alcohols, alcohol and water of water, water and polar solvent; Coagulation bath temperature is 0～50 ℃;
5) post processing: by the membrane material rinsed with deionized water in step 4), remove remaining macromolecule solvent and volatility additive, obtain cellulose acetate forward osmosis membrane material.
Preferably, in step 1), under 25～40 ℃ of conditions of temperature, carry out stirring and dissolving.
Preferably, step 2) in, deaeration temperature is 25～50 ℃.
Preferably, in step 3), it is 20～40 ℃ that nascent state film is placed in to temperature, under the air that relative humidity is 20%～70%, volatilizees 0-60 second.
In step 4), coagulation bath is processed to nascent state film film-forming.
According to the analysis of positive penetration theory and interior concentration polarization, the present invention proposes the relation that affects between forward osmosis membrane material microstructure and positive permeance property as shown in Figure 2, the aperture of cortex directly affects the rejection of film, concentration polarization in skin thickness and supporting layer thickness effect, interior concentration polarization affects the permeation flux of film.Thickness is larger, the water or the salt ion that see through pellicle are larger to the mass transfer diffusional resistance of driving liquid and feeding liquid body, drive the valid density difference on liquid or feeding liquid bulk concentration and pellicle surface larger, show as that osmotic pressure,effective is poor to be reduced, flux reduces, on this basis, and the larger feature of membrane material architectural difference that the present invention obtains according to the casting solution of different solvents, by selecting suitable solvent, obtain the membrane material that porosity is higher.By adding the volatility additive good with coagulation bath compatibility to be conducive to the formation of dense layer surface, on the one hand, add after volatility additive nascent state film within the air section time of staying, after volatility additive volatilization, can improve film surface polymer concentration and be conducive to improve cortex compactness, on the other hand, volatility additive and coagulation bath intermiscibility are good,, to postpone to be separated mechanism film forming, be conducive to the formation of dense layer surface.In addition, the condition such as coagulation bath temperature, air section volatilization time in film forming procedure also has very important impact to membrane structure.The condition that coagulation bath temperature is high is issued to balance empress dowager, and macromolecular chain is wound around tightr, and cortex aperture is less, and flux is lower, and rejection is higher.The air section volatilization time is larger on the connectedness impact of pore structure, and within certain volatilization time, the time is longer, and solvent can effectively improve the connectedness of pore structure to the continuous volatilization of air side in nascent state film, thereby improves water flux.
Particularly, the present invention is by adding one and more than one volatility additives, utilize its volatility in film forming procedure to obtain dense layer surface, utilize rate of volatilization between different additive and the difference with coagulation bath compatibility simultaneously, by regulating the rich phase of content regulation and control film forming procedure mediopellis place macromolecule and stingy generation and the growth conditions of macromolecule of volatile component in casting solution, thereby affect cortex compactness extent, improve salt rejection.
The cellulose acetate forward osmosis membrane material of preparing in the present invention can effectively remove the salinity in water body, take the NaCl of 0.5mol/L as driving liquid, deionized water is feeding liquid, at 25 ℃, under the test condition that charging and driving flow quantity are 1800mL/min, NaCl diffuse in reverse direction flux is 1.93-8.34g/m
2h, infiltration water flux is 5.86-21.38L/m
2h.Preferably, in the present invention, the NaCl diffuse in reverse direction flux of above-mentioned disclosed cellulose acetate forward osmosis membrane material is less than 3g/m
2h, infiltration water flux is greater than 10L/m
2h.
More preferably, under above-mentioned test condition, the NaCl diffuse in reverse direction flux of above-mentioned disclosed cellulose acetate forward osmosis membrane material is 1.73-2.23g/m in the present invention
2h, infiltration water flux is 9.93-15.80L/m
2h.
Be that its flux in guaranteeing high salt rejection is also higher.
To sum up, in the present invention, disclosed cellulose acetate forward osmosis membrane material is applicable to positive process of osmosis, its good hydrophilic property, has superthin structure, and supporting layer porosity is large, and pore structure connectedness is good, can effectively reduce interior concentration polarization; And cortex compactness is good, monovalent salt rejection is high, can also effectively remove the little molecules such as trace suspension thing in water body, bacterium, virus, and treatment effeciency is high, running cost is low.On the basis of disclosed cellulose acetate forward osmosis membrane material, can further be developed as emergent water disposal device in the present invention in addition, as water bag, the Drinking Water Problem while effectively solving natural calamity or army's Field Operational.This material preparation method is simple, and process stabilizing is good, easy and simple to handle, and it has overcome various shortcoming of the prior art, creative, is applicable to commercial Application.
Figure of description
Fig. 1 is the scanning electron microscope (SEM) photograph of the cellulose acetate forward osmosis membrane material of embodiment 6 in the present invention;
Wherein in Fig. 1:
1 is fine and close selective separating,
2 is at the described infracortical supporting layer with netted intercommunicating pore structure.
Fig. 2 is forward osmosis membrane material microstructure and property relationship schematic diagram in the present invention.
The specific embodiment
Below, by specific instantiation explanation embodiments of the present invention, those skilled in the art can understand other advantages of the present invention and effect easily by the disclosed content of this description.The present invention can also be implemented or be applied by the other different specific embodiment, and the every details in this description also can be based on different viewpoints and application, carries out various modifications or change not deviating under spirit of the present invention.
In embodiment, in order to save the energy, reduce costs, in preparation method, operation is generally all carried out at ambient temperature, and the solution of post processing rinsing is selected water.Those skilled in the art can be according to preparing cellulose acetate forward osmosis membrane material under disclosed other conditions in practical operation and the present invention.
In the present embodiment, the preparation method of cellulose acetate forward osmosis membrane material is as follows:
1) casting solution preparation: the Triafol T that is 2:1 by mass ratio and cellulose diacetate mixture 19g add 45g 1-METHYLPYRROLIDONE, in 30g methyl acetate and 6g acetone, carry out stirring and dissolving under 40 ℃ of conditions of temperature, form uniform casting solution;
2) casting solution is carried out to deaeration: deaeration temperature is 25 ℃;
3) utilize knifing machine knifing: by step 2) in be coated on the glass plate of dried and clean through the casting solution of deaeration processing, form nascent state film by knifing machine knifing, and nascent state film is placed in to temperature is 25 ℃, under the air that relative humidity is 65%, volatilize 3 seconds;
4) coagulation bath processing: the nascent state film forming in step 3) is put into coagulation bath phase-splitting and solidify to form membrane material; Wherein, the medium of coagulation bath is water; Coagulation bath temperature is 37 ℃;
5) post processing: by the membrane material rinsed with deionized water in step 4), remove remaining macromolecule solvent and volatility additive, obtain cellulose acetate forward osmosis membrane material.
Prepared cellulose acetate forward osmosis membrane material is treated performance test or structural characterization.
The forward osmosis membrane material of preparing under this condition very easily dewaters, and stops the several seconds just can dewater and bleach in air.
The thickness of described cellulose acetate forward osmosis membrane material is 46 μ m, and porosity is 55%.
Positive permeance property test condition: take the NaCl solution of 1L0.5mol/L as driving liquid, 2L deionized water is feeding liquid, 25 ℃ of temperature, feed velocity 1800mL/min, test 1 hour, and result is got the mean value of latter 50 minutes, and just permeation flux is 5.86 ± 0.50L/m
2h, NaCl diffuse in reverse direction flux is 7.37 ± 0.26g/m
2h.
In the present embodiment, the preparation method of cellulose acetate forward osmosis membrane material is as follows:
1) casting solution preparation: 19g Triafol T is added to 45g 1-METHYLPYRROLIDONE, in 30g methyl acetate and 6g acetone, carry out stirring and dissolving under 25 ℃ of conditions of temperature, form uniform casting solution;
2) casting solution is carried out to deaeration: deaeration temperature is 25 ℃;
3) utilize knifing machine knifing: by step 2) in be coated on the glass plate of dried and clean through the casting solution of deaeration processing, form nascent state film by knifing machine knifing, and nascent state film is placed in to temperature is 25 ℃, under the air that relative humidity is 59%, volatilized for 3 seconds;
4) coagulation bath processing: the nascent state film forming in step 3) is put into coagulation bath phase-splitting and solidify to form membrane material; Wherein, the medium of coagulation bath is selected from water; Coagulation bath temperature is 50 ℃;
5) post processing: by the membrane material rinsed with deionized water in step 4), remove remaining macromolecule solvent and volatility additive, obtain cellulose acetate forward osmosis membrane material.
Prepared cellulose acetate forward osmosis membrane material is put into fresh deionized water, treat performance test or structural characterization.
The thickness of described cellulose acetate forward osmosis membrane material is 38 μ m, and porosity is 58%.
Positive permeance property test condition is identical with embodiment 1, and positive penetration testing result is got the mean value of latter 50 minutes, and positive permeation flux is 8.34 ± 0.48L/m
2h, NaCl diffuse in reverse direction flux is 4.80 ± 0.13g/m
2h.
Embodiment 3
In the present embodiment, the preparation method of cellulose acetate forward osmosis membrane material is as follows:
1) casting solution preparation: 17g Triafol T is added to 50gN-methyl pyrrolidone, in 23g oxolane and 10g acetone, carry out stirring and dissolving under 30 ℃ of conditions of temperature, form uniform casting solution;
2) casting solution is carried out to deaeration: deaeration temperature is 30 ℃;
3) utilize knifing machine knifing: by step 2) in be coated on the glass plate of dried and clean through the casting solution of deaeration processing, form nascent state film by knifing machine knifing, and nascent state film is placed in to temperature is 25 ℃, 5s volatilizees under the air that relative humidity is 57%;
4) coagulation bath processing: the nascent state film forming in step 3) is put into coagulation bath phase-splitting and solidify to form membrane material; Wherein, the medium of coagulation bath is selected from water; Coagulation bath temperature is 0 ℃;
5) post processing: by the membrane material rinsed with deionized water in step 4), remove remaining macromolecule solvent and volatility additive, obtain cellulose acetate forward osmosis membrane material.
Cellulose acetate forward osmosis membrane material is put into fresh deionized water, treat performance test or structural characterization.
The thickness of described cellulose acetate forward osmosis membrane material is 39 μ m, and porosity is 67%.
Positive permeance property test condition is identical with embodiment 1, and positive penetration testing result is got the mean value of latter 50 minutes, and positive permeation flux is 12.15 ± 0.37L/m
2h, NaCl diffuse in reverse direction flux is 2.04 ± 0.05g/m
2h.
Embodiment 4
1) casting solution preparation: 17g Triafol T is added to 50g 1-METHYLPYRROLIDONE, in 23g oxolane and 10g acetone, carry out stirring and dissolving under 30 ℃ of conditions of temperature, form uniform casting solution;
2) casting solution is carried out to deaeration: deaeration temperature is 30 ℃;
3) utilize knifing machine knifing: by step 2) in be coated on the glass plate of dried and clean through the casting solution of deaeration processing, form nascent state film by knifing machine knifing, and nascent state film is placed in to temperature is 25 ℃, under the air that relative humidity is 49%, volatilized for 3 seconds;
4) coagulation bath processing: the nascent state film forming in step 3) is put into coagulation bath phase-splitting and solidify to form membrane material; Wherein, the medium of coagulation bath is selected from water; Coagulation bath temperature is 15 ℃;
5) post processing: by the membrane material rinsed with deionized water in step 4), remove remaining macromolecule solvent and volatility additive, obtain cellulose acetate forward osmosis membrane material.
Cellulose acetate forward osmosis membrane material is put into fresh deionized water, treat performance test or structural characterization.
The thickness of described cellulose acetate forward osmosis membrane material is 34 μ m, and porosity is 58%.
Positive permeance property test condition is identical with embodiment 1, and positive penetration testing result is got the mean value of latter 50 minutes, and positive permeation flux is 10.38 ± 0.45L/m
2h, NaCl diffuse in reverse direction flux is 1.76 ± 0.03g/m
2h.
Embodiment 5
1) casting solution preparation: 17g Triafol T is added to 50gN-methyl pyrrolidone, in 23g oxolane and 10g acetone, carry out stirring and dissolving under 25 ℃ of conditions of temperature, form uniform casting solution;
2) casting solution is carried out to deaeration: deaeration temperature is 25 ℃;
3) utilize knifing machine knifing: by step 2) in be coated on the glass plate of dried and clean through the casting solution of deaeration processing, form nascent state film by knifing machine knifing, and nascent state film is placed in to temperature is 25 ℃, under the air that relative humidity is 54%, volatilize 60 seconds;
4) coagulation bath processing: the nascent state film forming in step 3) is put into coagulation bath phase-splitting and solidify to form membrane material; Wherein, the medium of coagulation bath is selected from water; Coagulation bath temperature is 15 ℃;
5) post processing: by the membrane material rinsed with deionized water in step 4), remove remaining macromolecule solvent and volatility additive, obtain cellulose acetate forward osmosis membrane material.
And then cellulose acetate forward osmosis membrane material is put into fresh deionized water, treat performance test or structural characterization.
The thickness of described cellulose acetate forward osmosis membrane material is 28 μ m, and porosity is 69%.
Positive permeance property test condition is identical with embodiment 1, and positive penetration testing result is got the mean value of latter 50 minutes, and positive permeation flux is 15.24 ± 0.56L/m
2h, NaCl diffuse in reverse direction flux is 1.93 ± 0.04g/m
2h.
Embodiment 6
1) casting solution preparation: 15g Triafol T is added to 50g 1-METHYLPYRROLIDONE, in 26g oxolane and 39g acetone, carry out stirring and dissolving under 40 ℃ of conditions of temperature, form uniform casting solution;
2) casting solution is carried out to deaeration: deaeration temperature is 35 ℃;
3) utilize knifing machine knifing: by step 2) in be coated on the glass plate of dried and clean through the casting solution of deaeration processing, form nascent state film by knifing machine knifing, and nascent state film is placed in to temperature is 30 ℃, 30s volatilizees under the air that relative humidity is 54%;
4) coagulation bath processing: the nascent state film forming in step 3) is put into coagulation bath phase-splitting and solidify to form membrane material; Wherein, the medium of coagulation bath is selected from water; Coagulation bath temperature is 25 ℃;
5) post processing: by the membrane material rinsed with deionized water in step 4), remove remaining macromolecule solvent and volatility additive, obtain cellulose acetate forward osmosis membrane material.
And then cellulose acetate forward osmosis membrane material is put into fresh deionized water, treat performance test or structural characterization.
The thickness of described cellulose acetate forward osmosis membrane material is 23 μ m, and porosity is 79%.
Positive permeance property test condition is identical with embodiment 1, and positive penetration testing result is got the mean value of latter 50 minutes, and positive permeation flux is 11.27 ± 0.45L/m
2h, NaCl diffuse in reverse direction flux is 2.11 ± 0.12g/m
2h.
Embodiment 7
1) casting solution preparation: 18g Triafol T is added to 20g propylene glycol carbonate, in 34g diglycol, 20g carrene and 7g acetone, carry out stirring and dissolving under 40 ℃ of conditions of temperature, form uniform casting solution;
2) casting solution is carried out to deaeration: deaeration temperature is 25 ℃;
3) utilize knifing machine knifing: by step 2) in be coated on the glass plate of dried and clean through the casting solution of deaeration processing, form nascent state film by knifing machine knifing, and nascent state film is placed in to temperature is 25 ℃, 5s volatilizees under the air that relative humidity is 41%;
4) coagulation bath processing: the nascent state film forming in step 3) is put into coagulation bath phase-splitting and solidify to form membrane material; Wherein, the medium of coagulation bath is selected from water; Coagulation bath temperature is 10 ℃;
5) post processing: by the membrane material rinsed with deionized water in step 4), remove remaining macromolecule solvent and volatility additive, obtain cellulose acetate forward osmosis membrane material.
And then cellulose acetate forward osmosis membrane material is put into fresh deionized water, treat performance test or structural characterization.
The thickness of described cellulose acetate forward osmosis membrane material is 28 μ m, and porosity is 64%.
Positive permeance property test condition is identical with embodiment 1, and positive penetration testing result is got the mean value of latter 50 minutes, and positive permeation flux is 15.87 ± 0.45L/m
2h, NaCl diffuse in reverse direction flux is 4.93 ± 0.05g/m
2h.
Embodiment 8
1) casting solution preparation: 5g Triafol T is added to 30g propylene glycol carbonate, in 34g diglycol, 20g carrene and 11g methyl acetate, carry out stirring and dissolving under 40 ℃ of conditions of temperature, form uniform casting solution;
2) casting solution is carried out to deaeration: deaeration temperature is 25 ℃;
3) utilize knifing machine knifing: by step 2) in be coated on the glass plate of dried and clean through the casting solution of deaeration processing, form nascent state film by knifing machine knifing, and nascent state film is placed in to temperature is 25 ℃, 10s volatilizees under the air that relative humidity is 41%;
4) coagulation bath processing: the nascent state film forming in step 3) is put into coagulation bath phase-splitting and solidify to form membrane material; Wherein, the medium of coagulation bath is selected from water; Coagulation bath temperature is 10 ℃;
5) post processing: by the membrane material rinsed with deionized water in step 4), remove remaining macromolecule solvent and volatility additive, obtain cellulose acetate forward osmosis membrane material.
And then cellulose acetate forward osmosis membrane material is put into fresh deionized water, treat performance test or structural characterization.
The thickness of described cellulose acetate forward osmosis membrane material is 35 μ m, and porosity is 58%.
Positive permeance property test condition is identical with embodiment 1, and positive penetration testing result is got the mean value of latter 50 minutes, and positive permeation flux is 10.18 ± 0.60L/m
2h, NaCl diffuse in reverse direction flux is 4.32 ± 0.08g/m
2h.
Embodiment 9
1) casting solution preparation: 18g Triafol T is added to 25g propylene glycol carbonate, in 17g diglycol, carry out stirring and dissolving under 40 ℃ of conditions of temperature, form uniform casting solution;
2) casting solution is carried out to deaeration: deaeration temperature is 25 ℃;
3) utilize knifing machine knifing: by step 2) in be coated on the glass plate of dried and clean through the casting solution of deaeration processing, form nascent state film by knifing machine knifing, and nascent state film is placed in to temperature is 25 ℃, under the air that relative humidity is 41%, volatilize;
4) coagulation bath processing: the nascent state film forming in step 3) is put into coagulation bath phase-splitting and solidify to form membrane material; Wherein, the medium of coagulation bath is selected from water; Coagulation bath temperature is 10 ℃;
5) post processing: by the membrane material rinsed with deionized water in step 4), remove remaining macromolecule solvent and volatility additive, obtain cellulose acetate forward osmosis membrane material.
And then cellulose acetate forward osmosis membrane material is put into fresh deionized water, treat performance test or structural characterization.
The thickness of described cellulose acetate forward osmosis membrane material is 70 μ m, and porosity is 68%.
Positive permeance property test condition is identical with embodiment 1, and positive penetration testing result is got the mean value of latter 50 minutes, and positive permeation flux is 19.35 ± 0.48L/m
2h, NaCl diffuse in reverse direction flux is 4.65 ± 0.12g/m
2h.
Embodiment 10
1) casting solution preparation: 20g Triafol T is added to 15g propylene glycol carbonate, and 5g diglycol in 40g carrene, carries out stirring and dissolving under 40 ℃ of conditions of temperature, forms uniform casting solution;
2) casting solution is carried out to deaeration: deaeration temperature is 25 ℃;
3) utilize knifing machine knifing: by step 2) in be coated on the glass plate of dried and clean through the casting solution of deaeration processing, form nascent state film by knifing machine knifing, and nascent state film is placed in to temperature is 25 ℃, 8S volatilizees under the air that relative humidity is 41%;
4) coagulation bath processing: the nascent state film forming in step 3) is put into coagulation bath phase-splitting and solidify to form membrane material; Wherein, the medium of coagulation bath is selected from water; Coagulation bath temperature is 10 ℃;
5) post processing: by the membrane material rinsed with deionized water in step 4), remove remaining macromolecule solvent and volatility additive, obtain cellulose acetate forward osmosis membrane material.
And then cellulose acetate forward osmosis membrane material is put into fresh deionized water, treat performance test or structural characterization.
The thickness of described cellulose acetate forward osmosis membrane material is 105 μ m, and porosity is 79%.
Positive permeance property test condition is identical with embodiment 1, and positive penetration testing result is got the mean value of latter 50 minutes, and positive permeation flux is 9.63 ± 0.25L/m
2h, NaCl diffuse in reverse direction flux is 3.85 ± 0.06g/m
2h.
Embodiment 11
1) casting solution preparation: 10g Triafol T is added to 30g propylene glycol carbonate, and 20g diglycol in 40g carrene, carries out stirring and dissolving under 30 ℃ of conditions of temperature, forms uniform casting solution;
2) casting solution is carried out to deaeration: deaeration temperature is 25 ℃;
3) utilize knifing machine knifing: by step 2) in be coated on the glass plate of dried and clean through the casting solution of deaeration processing, form nascent state film by knifing machine knifing, and nascent state film is placed in to temperature is 25 ℃, 20s volatilizees under the air that relative humidity is 41%;
4) coagulation bath processing: the nascent state film forming in step 3) is put into coagulation bath phase-splitting and solidify to form membrane material; Wherein, the medium of coagulation bath is selected from water; Coagulation bath temperature is 10 ℃;
5) post processing: by the membrane material rinsed with deionized water in step 4), remove remaining macromolecule solvent and volatility additive, obtain cellulose acetate forward osmosis membrane material.
And then cellulose acetate forward osmosis membrane material is put into fresh deionized water, treat performance test or structural characterization.
The thickness of described cellulose acetate forward osmosis membrane material is 43 μ m, and porosity is 90%.
Positive permeance property test condition is identical with embodiment 1, and positive penetration testing result is got the mean value of latter 50 minutes, and positive permeation flux is 21.38 ± 0.57L/m
2h, NaCl diffuse in reverse direction flux is 4.31 ± 0.09g/m
2h.
Embodiment 12
1) casting solution preparation: 30g Triafol T is added to 25g propylene glycol carbonate, and 15g diglycol in 30g carrene, carries out stirring and dissolving under 30 ℃ of conditions of temperature, forms uniform casting solution;
2) casting solution is carried out to deaeration: deaeration temperature is 25 ℃;
3) utilize knifing machine knifing: by step 2) in be coated on the glass plate of dried and clean through the casting solution of deaeration processing, form nascent state film by knifing machine knifing, and nascent state film is placed in to temperature is 25 ℃, 60s volatilizees under the air that relative humidity is 41%;
4) coagulation bath processing: the nascent state film forming in step 3) is put into coagulation bath phase-splitting and solidify to form membrane material; Wherein, the medium of coagulation bath is selected from water; Coagulation bath temperature is 10 ℃;
5) post processing: by the membrane material rinsed with deionized water in step 4), remove remaining macromolecule solvent and volatility additive, obtain cellulose acetate forward osmosis membrane material.
And then cellulose acetate forward osmosis membrane material is put into fresh deionized water, treat performance test or structural characterization.
The thickness of described cellulose acetate forward osmosis membrane material is 58 μ m, and porosity is 56%.
Positive permeance property test condition is identical with embodiment 1, and positive penetration testing result is got the mean value of latter 50 minutes, and positive permeation flux is 14.85 ± 0.25L/m
2h, NaCl diffuse in reverse direction flux is 2.08 ± 0.12g/m
2h.
In sum, in the inventive method prior art, the technique of disclosed production multicolour section coloured yarn yarn is compared, there is equipment simple, production operation is convenient, good and the advantage of having saved production cost of constant product quality, so the present invention has effectively overcome various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all can, under spirit of the present invention and category, modify or change above-described embodiment.Therefore, such as in affiliated technical field, have and conventionally know that the knowledgeable, not departing from all equivalence modifications that complete under disclosed spirit and technological thought or changing, must be contained by claim of the present invention.
Claims (10)
1. a cellulose acetate forward osmosis membrane material, is characterized in that, described cellulose acetate forward osmosis membrane material is a kind of anisotropic membrane; The thickness of described cellulose acetate forward osmosis membrane material is 20-150 μ m, and porosity is 55%～90%,
Described cellulose acetate forward osmosis membrane material is made by knifing machine knifing by cellulose acetate casting solution, and described casting solution contains the cellulose acetate of 5～40wt.%, and all the other components are macromolecule solvent;
Wherein, described macromolecule solvent is for being selected from tetrachloroethanes, N-N-dimethyl formamide, one or more in 1-METHYLPYRROLIDONE, methyl-sulfoxide, carrene, propylene glycol carbonate and diglycol.
2. cellulose acetate forward osmosis membrane material as claimed in claim 1, it is characterized in that, described casting solution also contains volatility additive, described volatility additive is selected from methyl alcohol, one or more in benzene, methyl acetate, ethyl acetate, oxolane, acetone, carbon tetrachloride and n-hexane, the mass ratio of described macromolecule solvent and described volatility additive is 1:0.01～1:2.5.
3. cellulose acetate forward osmosis membrane material as claimed in claim 1, is characterized in that, the weight average molecular weight of described cellulose acetate is 5～300,000.
4. cellulose acetate forward osmosis membrane material as claimed in claim 2, is characterized in that, described cellulose acetate is Triafol T.
5. cellulose acetate forward osmosis membrane material as claimed in claim 1, it is characterized in that, described cellulose acetate is Triafol T and the mixture that is selected from the arbitrary cellulose acetate in cellulose diacetate, cellulose acetate propionate and acetate butyrate fiber, and in described mixture, Triafol T is 1:0.01～1:3 with the mass ratio that is selected from the arbitrary cellulose acetate in cellulose diacetate, cellulose acetate propionate and acetate butyrate fiber.
6. a method of preparing the cellulose acetate forward osmosis membrane material as described in as arbitrary in claim 1-5, comprises the steps:
1) casting solution preparation: cellulose acetate is added in macromolecule solvent and volatility additive, carry out stirring and dissolving under 25～50 ℃ of conditions of temperature, form uniform casting solution;
2) casting solution is carried out to deaeration: deaeration temperature is 25～70 ℃;
3) utilize knifing machine knifing: by step 2) in be coated on the glass plate of dried and clean through the casting solution of deaeration processing, form nascent state film by knifing machine knifing, and nascent state film is placed in to temperature is 15～45 ℃, under the air that relative humidity is 20%～80%, volatilize 0-60 second;
4) coagulation bath processing: the nascent state film forming in step 3) is put into coagulation bath phase-splitting and solidify to form membrane material; Wherein, the medium of coagulation bath is selected from the one in the mixture of mixture, alcohols, alcohol and water of water, water and polar solvent; Coagulation bath temperature is 0～50 ℃;
5) post processing: by the membrane material rinsed with deionized water in step 4), remove remaining macromolecule solvent and volatility additive, obtain cellulose acetate forward osmosis membrane material.
7. method as claimed in claim 6, is characterized in that, in step 1), under 25～40 ℃ of conditions of temperature, carries out stirring and dissolving.
8. method as claimed in claim 6, is characterized in that step 2) in, deaeration temperature is 25～50 ℃.
9. method as claimed in claim 6, is characterized in that, in step 3), it is 20～40 ℃ that nascent state film is placed in to temperature, under the air that relative humidity is 20%～70%, volatilizees.
10. as described in as arbitrary in claim 1-5, cellulose acetate forward osmosis membrane material is in the application in desalinization field.
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| CN105749765A (en) * | 2016-05-19 | 2016-07-13 | 上海应用技术学院 | Preparation method of high-performance cellulose triacetate forward osmosis membrane |
| CN106166451A (en) * | 2016-06-28 | 2016-11-30 | 安徽松泰包装材料有限公司 | A kind of preparation method of forward osmosis membrane |
| CN106925139A (en) * | 2017-04-02 | 2017-07-07 | 天津大学 | A kind of double layered forward osmosis membrane material preparation method with concave convex rod as porous support materials |
| CN107376666A (en) * | 2017-08-09 | 2017-11-24 | 中国农业大学 | A kind of modified cellulose acetate film and preparation method and application |
| CN114984779A (en) * | 2022-06-24 | 2022-09-02 | 福建农林大学 | Preparation method of high-flux cellulose forward osmosis membrane |
| CN115364692A (en) * | 2022-08-12 | 2022-11-22 | 中国科学院上海高等研究院 | Air filtration composite membrane prepared based on cellulose nanofiber reinforced hydrogel conversion and preparation method thereof |
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| CN115364692A (en) * | 2022-08-12 | 2022-11-22 | 中国科学院上海高等研究院 | Air filtration composite membrane prepared based on cellulose nanofiber reinforced hydrogel conversion and preparation method thereof |
| CN115364692B (en) * | 2022-08-12 | 2023-08-25 | 中国科学院上海高等研究院 | Air filtration composite membrane prepared based on cellulose nanofiber reinforced hydrogel conversion and preparation method thereof |
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