CN115245758B - Composite forward osmosis membrane and preparation method and application thereof - Google Patents
Composite forward osmosis membrane and preparation method and application thereof Download PDFInfo
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- CN115245758B CN115245758B CN202110466664.7A CN202110466664A CN115245758B CN 115245758 B CN115245758 B CN 115245758B CN 202110466664 A CN202110466664 A CN 202110466664A CN 115245758 B CN115245758 B CN 115245758B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/002—Forward osmosis or direct osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0095—Drying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a composite forward osmosis membrane, a preparation method and application thereof. The forward osmosis membrane sequentially comprises a bottom layer, a porous supporting layer and an active separating layer, wherein the active separating layer is an aromatic polyamide layer, the porous supporting layer is divided into a sub-layer and a surface layer, the surface layer is of a small-hole structure with narrow pore diameter distribution, and the sub-layer is attached to the bottom layer and is of a highly-communicated three-dimensional network porous structure. The porous supporting layer is prepared by an atomization pretreatment auxiliary non-solvent induced phase separation method. The forward osmosis membrane has higher water flux and lower reverse diffusion salt flux, the preparation process is convenient and simple, continuous preparation can be realized, industrialization is easy, and the forward osmosis membrane has wide application in the fields of sewage treatment, sea water desalination, membrane bioreactor, reduced pressure power generation, food processing, medicine enrichment and the like, and has great industrial application prospect.
Description
Technical Field
The invention relates to the field of separation membranes, in particular to a composite forward osmosis membrane, a preparation method of the forward osmosis membrane and application of the forward osmosis membrane in a water treatment process.
Background
Forward osmosis is an osmotically driven membrane separation process that utilizes an osmotic pressure gradient to allow water to spontaneously permeate a semi-permeable membrane from a Feed Solution (FS) side of lower osmotic pressure to a Draw Solution (DS) side of higher osmotic pressure. In the forward osmosis process, the feed solution is concentrated and the draw solution is diluted. The drawing agent is recycled by reverse osmosis or distillation, and purified water is obtained.
Forward osmosis membranes are the core of forward osmosis processes, and the quality of their performance determines whether the forward osmosis process can be used on a large scale. The thin layer composite forward osmosis membrane is formed by compositing an ultrathin skin layer on the surface of a porous supporting layer, has unique advantages, such as ultrathin skin layer, strong thermal stability, difficult biodegradation, capability of respectively and optimally combining the supporting layer and the skin layer, and the like, and is increasingly receiving extensive attention of scholars.
A concentration polarization phenomenon which cannot be ignored is generated in the forward osmosis process, and the performance of the forward osmosis membrane is greatly affected, so that the industrialization progress of the forward osmosis membrane is also limited by the concentration polarization. And the internal concentration polarization phenomenon which restricts the performance of the forward osmosis membrane is closely related to the performance and structural parameters of the membrane supporting layer. In general, a support layer with higher porosity, better penetration of pores and thinner thickness is more beneficial to reduce the internal concentration polarization phenomenon in the forward osmosis process, thereby obtaining higher water flux. In the literature of Industrial & Engineering Chemistry Research,2016,55:5327-5334, silica nanoparticles are introduced into a polyethersulfone supporting layer, and then the silica nanoparticles are removed by hydrofluoric acid etching to prepare a novel composite forward osmosis membrane. This approach can form interconnected, highly porous support layers. A porous polyethylene film is used as a supporting layer material in the document Journal of Membrane Science,2017,544:213-220, so that a composite forward osmosis film with high permeability and mechanical durability is prepared. The highly open, internally interconnected pore structure of the porous polyethylene support layer complements its thinner thickness, which is beneficial to slow down the internal concentration polarization phenomenon, thereby improving the water flux of the membrane. Chinese patent (CN 112090290A) adds hollow nanocapsules into the casting solution to prepare the forward osmosis membrane supporting layer through phase inversion, and the hollow nanocapsules provide more water channels for the forward osmosis membrane and reduce mass transfer resistance and pore tortuosity. As for the liquid separation membrane, it is well known that a method of modifying a support layer by introducing an additive such as a nano porous material to obtain more water transport channels is not easy for long-term use and industrialization of the membrane, and also increases production costs. Other porous membranes with high porosity, such as electrostatic spinning membranes (Environmental Science & Technology,2005 (39): 7 684-7 691), organic-inorganic hybrid metal mesh membranes (CN 110280222A), etc., which can be used for the composite membrane support layer, have the problems of narrow separation application range, complex preparation process, lower membrane preparation efficiency, high cost, etc.
Therefore, the development of a simple and efficient method for preparing the forward osmosis composite membrane with high porosity and high penetration structure support layer has very important practical significance and commercial value.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a composite forward osmosis membrane and a preparation method thereof, and application of the composite forward osmosis membrane in the field of water treatment.
The invention aims to provide a composite forward osmosis membrane which sequentially comprises a bottom layer, a porous supporting layer and an active separating layer, wherein the active separating layer is an aromatic polyamide layer, the porous supporting layer is divided into a sub-layer and a surface layer, the surface layer is of a small pore structure with narrow pore diameter distribution, and the sub-layer is attached to the bottom layer and is of a highly-communicated three-dimensional network porous structure.
The composite forward osmosis membrane comprises a three-layer structure of a bottom layer, a porous supporting layer and an active separating layer, wherein the porous supporting layer is positioned between the bottom layer and the active separating layer and mainly provides mechanical strength and a fluid transmission channel; the active separation layer mainly plays a role in separation and screening.
The materials of the bottom layer may include, but are not limited to: nonwoven fabrics, woven fabrics, polyester screens, electrospun silk films and other porous support materials.
The active separation layer is formed by interfacial polymerization of an aromatic amine compound containing two or more amino groups and an acid chloride compound containing two or more acid chloride groups on the support layer.
Preferably, the active separation layer is prepared by performing interfacial polymerization reaction on an aromatic polyfunctional amine compound and an aromatic polyfunctional acyl chloride compound, wherein the aromatic polyfunctional amine compound is preferably at least one of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 1,3, 5-diaminobenzene, 1,2, 4-diaminobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminotoluene, 2, 4-diaminoanisole, amol and xylylenediamine, and the aromatic polyfunctional acyl chloride compound is preferably at least one of terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride, biphenyl dicarboxylic acid chloride, benzene disulfonyl chloride and trimesoyl chloride.
The porous support layer is prepared by adopting an atomization pretreatment auxiliary non-solvent induced phase separation method, and is characterized in that the process of preparing the porous support layer by inducing phase separation is divided into two steps, and the atomization pretreatment process is combined with non-solvent induced phase separation, namely, the film forming is firstly remained in an atomization liquid drop bath for partial induced phase separation, and then enters a non-solvent coagulation bath for complete phase separation.
The polymer for preparing the porous support layer is at least one selected from polyvinyl chloride, polysulfone, polyethersulfone, sulfonated polyethersulfone, polyacrylonitrile, cellulose acetate, polyvinylidene fluoride, polyimide, polyacrylic acid, polylactic acid, polyamide, chitosan, polyetherimide, polystyrene, polyolefin, polyester, polytrifluoroethylene, silicone resin, acrylonitrile-styrene copolymer and modified polymers thereof.
The porous supporting layer is of an asymmetric structure and is provided with a thin surface layer and a sub-layer attached to the bottom layer, and the sub-layer is of a bicontinuous highly-communicated three-dimensional network porous structure, so that water transmission resistance can be reduced, and water flux can be increased; the surface layer is attached to the active separation layer.
The average pore diameter of the surface layer of the porous supporting layer is 5-100 nm.
The supporting layer sub-layer is of a three-dimensional network porous structure which is mutually communicated, and the pore structure is highly communicated and has larger porosity. The cross section of the support layer sub-layer is a polymer fiber skeleton and a hole structure with basically consistent morphology along the film thickness direction, namely the sub-layer cross section is a structure with the polymer fiber skeleton and the same type of holes distributed along the film thickness direction. For example, ultrafiltration membranes obtained by conventional non-solvent phase separation methods often have different types of pore structures present in the cross-section of the sub-layer at the same time, typically comprising a sponge-like pore structure and a large finger-like pore structure.
The porosity of the ultrafiltration membrane is 40 to 90%, preferably 60 to 90%, more preferably 70 to 80%.
The thickness of the bottom layer is 50-300 mu m, the thickness of the porous support layer sub-layer is 10-60 mu m, the thickness of the surface layer of the porous support layer is 0.5-5 mu m, and the thickness of the active separation layer is 5-200 nm.
The second object of the present invention is to provide a method for preparing the composite forward osmosis membrane, comprising the steps of:
1) Dissolving components including a polymer of the porous support layer in a solvent to prepare a casting solution;
2) Scraping and casting the casting solution on the bottom layer;
3) Carrying out atomization pretreatment, wherein the atomization pretreatment stays in an atomized liquid drop bath, the bottom surface faces to atomized liquid drops, and the surface of the protective film coated with the casting solution is not contacted with the atomized liquid drops;
4) Immersing in a coagulating bath to obtain the porous support layer;
5) Contacting the porous support layer sequentially with an aqueous phase solution containing an aromatic polyfunctional amine compound and an organic phase solution containing an aromatic polyfunctional acyl chloride compound;
6) And drying and heat treating to obtain the composite forward osmosis membrane.
In the step 1), the solid content of the polymer in the casting film liquid is 6-20 wt%, preferably 8-18 wt%.
In step 1), the polymer may be selected from polymer materials for filtration membranes as usual in the art. The polymeric materials used may include, but are not limited to: polyvinyl chloride, polysulfone, polyethersulfone, sulfonated polyethersulfone, polyacrylonitrile, cellulose acetate, polyvinylidene fluoride, polyimide, polyacrylic acid, polylactic acid, polyamide, chitosan, polyetherimide, polystyrene, polyolefin, polyester, polytrifluoroethylene, silicone resin, acrylonitrile-styrene copolymer, and the like, and at least one of the polymers modified by the same.
The casting solution can also contain common additives and the like.
The film-forming additive is a polymer material which is miscible in the film-forming polymer good solvent and has hydrophilicity, and can include but is not limited to: at least one of chitosan, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, glycerol, propylene glycol, acetone, polyoxyethylene polyoxypropylene ether block copolymer, etc. The membrane-forming additives may also include conventional inorganic salt porogens, poor solvents, and/or various inorganic nanoparticles such as nanoscale inorganic fillers required in typical filtration membrane preparation processes, including but not limited to: zinc chloride, lithium chloride, magnesium chloride, lithium bromide, water, various small molecule alcohols, and the like; the inorganic filler is manganese dioxide, silicon dioxide, zinc oxide, etc.
The amount of the film-forming additive used is a conventional amount, and in the present invention, it is preferable that: the concentration of the polymer additive is 1-200 g/L; the concentration of the small molecule additive is 0.5-50 g/L.
In the step 1), the solvent is a good solvent capable of dissolving the film-forming polymer and the film-forming additive, and the solvent comprises at least one of N, N-dimethylformamide, N-dimethylacetamide, acetone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethyl sulfoxide, tetrahydrofuran, dioxane, acetonitrile, chloroform, polarclean solvent, triethyl phosphate, trimethyl phosphate, hexamethyl ammonium phosphate, tetramethyl urea, acetonitrile, toluene, hexane, octane and the like, and the preparation time and the preparation temperature of the casting solution are determined according to the casting material.
In the step 2), the casting solution is uniformly coated on the bottom layer for film scraping.
The primer material required for coating the casting solution can be a support layer material or a base material used as a coating polymer solution in the prior art, and can include, but is not limited to: nonwoven fabrics, woven fabrics, polyester screens, electrospun silk films and other porous support materials.
In the step 2), the wet film is coated with the casting solution, and the thickness is not particularly limited, but the thickness of the scratch film is preferably 50 to 500. Mu.m, more preferably 75 to 300. Mu.m.
The porous supporting layer used in the invention is prepared by adopting an atomization pretreatment auxiliary non-solvent induced phase separation method. I.e. first stay in the atomized droplet bath for partially induced phase separation, and then enter the non-solvent coagulation bath for complete phase separation.
The present invention provides a great distinction from Vapor Induced Phase Separation (VIPS), which refers to the phase separation that occurs under certain high humidity (or saturation humidity) conditions, without involving an atomized droplet bath.
In the step 3), the atomization pretreatment is that after the casting solution is coated, the bottom layer of the film faces to atomized liquid drops, the atomized liquid drops stay in contact with the atomized liquid drops for a certain time, and the surface of the film coated with the casting solution is protected from contacting with the atomized liquid drops. The method of obtaining the atomized liquid droplet bath is not particularly limited, and various conventional methods of liquid atomization, such as pressure atomization, rotary disk atomization, high-pressure air stream atomization, ultrasonic atomization, and the like, may be employed.
The atomization pretreatment time is preferably 1s to 60s, more preferably 2s to 40s.
The size of the droplets in the droplet bath is preferably 1 to 50. Mu.m, more preferably 5 to 20. Mu.m.
The required atomization amount per unit membrane area is 2-50L/m 2 H is preferably 10 to 20L/m 2 ·h。
The liquid drops in the atomization pretreatment are poor solvents of the casting film polymer, and can be single components such as water, ethanol, glycol and the like, can also be composed of water and polar aprotic solvents, surfactants or other solvents, and can also be solution of salt, acid and alkali.
The mode that the surface of the protective film coated with the casting film liquid does not contact with atomized liquid drops can adopt conventional methods such as shielding protection, blowing protection and the like.
The coagulation bath in the step 4) is a poor solvent of the casting film polymer, and can be single components such as water, ethanol, glycol and the like, or can be mixed by water and a polar aprotic solvent or other solvents, such as sodium hydroxide aqueous solution.
In step 5), the porous support layer is sequentially contacted with an aqueous phase solution of a compound containing two or more amino groups and an organic phase solution containing two or more acid chloride acyl chloride compounds to perform interfacial polymerization.
The compound containing two or more amino groups is one or more of aromatic polyfunctional amine compounds. The aromatic polyfunctional amine compound is preferably at least one of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 1,3, 5-triaminobenzene, 1,2, 4-triaminobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminotoluene, 2, 4-diaminoanisole, amiphenol, and xylylenediamine.
The concentration of the aromatic polyfunctional amine compound in the aqueous solution is 1.0-2.5 w/v%.
The contact time of the porous supporting layer and the aqueous phase solution is 5-150 seconds.
The acyl chloride compound containing two or more acyl chloride groups is one or more of aromatic polyfunctional acyl chloride compounds; the aromatic polyfunctional acyl chloride compound is preferably at least one of terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride, biphenyldicarboxylic acid chloride, benzenedisulfonyl chloride and trimesoyl chloride.
The organic solvent of the organic phase solution is one or more of n-hexane, cyclohexane, trifluorotrichloroethane, n-heptane, n-octane, toluene, ethylbenzene and ISOPAR solvent oil.
The concentration of the aromatic polyfunctional acyl chloride compound in the organic phase solution is 0.05-0.15 w/v%.
The contact time of the porous supporting layer and the organic phase solution is 5-150 seconds.
In the step 6), the temperature of the heat treatment is 25-70 ℃ and the time is 1-5 minutes.
The process for preparing the active separation layer in the present invention may be preferably performed as follows:
a) Contacting the porous support layer with an aqueous solution of an aromatic compound containing two or more amino groups;
b) Removing excessive aqueous solution on the surface of the porous support layer after being infiltrated by the aqueous solution, wherein the method for removing the excessive aqueous solution can be selected from but not limited to a wind spraying method, a rolling method and the like;
c) The porous support layer treated in step (b) is contacted with an organic phase solution containing two or more acid chloride acyl chloride compounds.
d) Drying, heat treatment and water washing to obtain the composite forward osmosis membrane.
The invention further provides the composite forward osmosis membrane obtained by the preparation method.
The fourth purpose of the invention is to provide the application of the composite forward osmosis membrane or the composite forward osmosis membrane obtained by the preparation method in the fields of sewage treatment, sea water desalination, membrane bioreactor, reduced pressure power generation, food processing, medicine enrichment and the like.
Compared with the prior art, the invention is characterized in that:
the forward osmosis membrane support layer prepared by the method disclosed by the invention has a special structure, has a small pore separation surface layer with narrow pore size distribution and a sublayer with a bicontinuous high through hole structure, has larger porosity, can effectively optimize the structural parameters of the forward osmosis membrane, reduces the internal concentration polarization phenomenon in the forward osmosis process, reduces mass transfer resistance, increases a mass transfer channel, and greatly improves the permeation flux of the membrane. The invention only needs to add the atomization pretreatment process on the basis of the traditional non-solvent phase inversion method for preparing the composite membrane supporting layer. The forward osmosis membrane has the characteristics of high water flux, low reverse diffusion salt flux, simple preparation process, easily available raw materials, low cost and the like, can be used for continuously preparing forward osmosis membrane materials on a large scale, and is easy for industrial application. The method has wide application space in the fields of sewage treatment, sea water desalination, membrane bioreactor, reduced pressure power generation, food processing, drug enrichment and the like, and has good application prospect.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a cross-sectional view showing the porous support layer of the composite forward osmosis membrane obtained in example 5.
FIG. 2 is a surface topography of the composite forward osmosis membrane obtained in example 5.
FIG. 3 is a cross-sectional view showing the morphology of the support layer of the composite forward osmosis membrane obtained in comparative example 1.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure still fall within the scope of the present invention.
In addition, the specific features described in the following embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, so long as the concept of the present invention is not deviated, and the technical solution formed thereby is a part of the original disclosure of the present specification, and also falls within the protection scope of the present invention.
According to a preferred embodiment of the present invention, the preparation method of the composite forward osmosis membrane may be performed as follows:
1') dissolving a component containing a polymer in a solvent to prepare a casting solution;
2') scraping and casting the casting solution on the supporting layer to form a film;
3') carrying out atomization pretreatment, namely, staying in an atomized liquid drop bath for a certain time, wherein the bottom layer is faced to the atomized liquid drops, and the surface of the protective film coated with the casting film liquid does not contact the atomized liquid drops;
4') immersing in a coagulation bath to obtain the polymer support layer;
5') contacting the porous support layer with an aqueous solution of an aromatic compound containing two or more amino groups after dilution for a period of 5 to 150 seconds;
6') rolling the porous support layer which is infiltrated by the aqueous phase solution by using a rubber roller, and removing redundant aqueous phase solution;
7') contacting the porous support layer infiltrated by the aqueous phase solution with an organic phase solution containing acyl chloride compounds of two or more acyl chloride groups for 5-150 seconds, and generating a compact functional layer on the surface of the porous support layer through interfacial polymerization reaction;
8') finally naturally drying the porous support layer immersed in the organic phase solution in air, then carrying out post-treatment for 1-5 minutes at a certain temperature, and washing with water to obtain the forward osmosis composite membrane.
Water flux, back diffusion salt flux are important parameters for evaluating forward osmosis composite membranes.
The water flux of a membrane is a parameter characterizing the permeability of the membrane, and refers to the volume of water passing through the membrane per unit area in unit time, commonly used units L/m 2 H. The prepared forward osmosis composite membrane is placed in a testing device, and the volume of water in raw material liquid reaching the drawing liquid side through the forward osmosis membrane in a certain time is measured at room temperature, and the specific calculation method is as follows:
J w ＝ΔV/Δt·A m
wherein:
J w -water flux (L/m) 2 ·h)；
DeltaV-the volume change (L) of the raw material liquid in the t time;
A m area of test membrane (m 2 )；
Δt-test time (h).
The back diffusion salt flux is a parameter for representing the separation performance of the composite membrane, and is commonly used in units of g/m 2 h. And (3) testing the change of the electric conductivity in the raw material liquid by using an electric conductivity meter, and calculating the back diffusion flux by using a standard curve. The calculation method comprises the following steps:
J s ＝(C t V t -C 0 V 0 )/Δt·A m
wherein:
J s -back-diffusing salt flux (g/m) 2 ·h)；
C t -the concentration (g/L) of the feed solution at time t;
V t -the volume (L) of the feed solution at time t;
C 0 -concentration of feed solution at time t=0 (g/L);
V 0 -volume of feed solution (L) at time t=0;
A m area of test membrane (m 2 )；
Δt-test time (h).
The water flux and the reverse diffusion salt flux of the forward osmosis composite membrane are tested on a forward osmosis test device. The test conditions were as follows: at 25℃with 1M MgCl 2 And (3) taking deionized water as a raw material liquid as a drawing liquid, and testing the water flux and the reverse diffusion salt flux of the forward osmosis composite membrane by a forward osmosis testing device.
In the embodiment of the invention, all chemical reagents are commercial products, and no special purification treatment exists unless the chemical reagents are independently proposed.
Spraying equipment: the ultrasonic humidifier is Haoqi HQ-JS130H.
Example 1
(1) Preparing a supporting layer: 12g of polyacrylonitrile is dissolved in 88g of DMF solvent, heated and stirred at 50 ℃ to form a uniform solution, and vacuumized and defoamed; then a continuous film scraping machine is adopted to scrape and coat the film on non-woven fabrics, the thickness of a feeler gauge is controlled to be 150 mu m during coating, then the back surface of the film after coating faces to a liquid drop bath obtained by ultrasonic atomization of deionized water, the film stays in the liquid drop bath for 20s, and the surface of the film coated with casting film liquid is protectedThe atomized liquid drops are not contacted, and the atomization amount of the unit area of the film is 6.2L/m 2 H; immersing the film into deionized water coagulation bath to completely phase separate; and washing with water to obtain the support layer.
(2) Preparing a composite film: weighing a certain amount of aqueous phase monomer m-phenylenediamine (MPD) in a volumetric flask, and using deionized water to fix the volume to a scale, and performing ultrasonic dissolution to obtain a uniform aqueous phase solution containing 2w/v% of MPD. A certain amount of organic phase monomer trimesoyl chloride (TMC) is weighed into a volumetric flask, the volume is fixed to the scale by using ISOPAR solvent oil, and the organic phase monomer trimesoyl chloride (TMC) is dissolved into a uniform organic phase solution containing 0.1w/v% TMC by ultrasonic. Using the polyacrylonitrile porous support membrane prepared in the step (1), and performing soaking contact with the aqueous phase solution for 60 seconds. Then the excess aqueous phase solution is poured off, the surface of the film is dried by a clean rubber roller, and then the film is soaked and contacted with the trimesoyl chloride organic phase solution for 60 seconds. And then pouring out the redundant organic phase solution, airing the formed polyamide layer in the air, and performing post-treatment for 4min at normal temperature to obtain the composite forward osmosis membrane. The prepared composite forward osmosis membrane is stored in deionized water and tested for standby.
In the composite forward osmosis membrane obtained in example 1, the thickness of the bottom layer was 85 μm, the thickness of the porous support layer sub-layer was 43 μm, the thickness of the porous support layer surface layer was 2.2 μm, and the thickness of the active separation layer was 45nm. The average pore diameter of the surface layer of the supporting layer is 16nm. The porosity of the porous support layer was 72%.
Example 2
(1) Preparing a supporting layer: a forward osmosis membrane support layer was prepared in the same manner as in example 1, except that in the preparation of the forward osmosis membrane support layer of step (1), the atomization amount of atomized droplets used in the atomization pretreatment stage was 10L/m 2 ·h。
(2) Preparing a composite film: the same as in example 1.
In the composite forward osmosis membrane obtained in example 2, the thickness of the bottom layer was 85 μm, the thickness of the porous support layer sub-layer was 45 μm, the thickness of the porous support layer surface layer was 2.1 μm, and the thickness of the active separation layer was 43nm. The average pore diameter of the surface layer of the supporting layer is 17nm. The porosity of the porous support layer was 75%.
Example 3
(1) Preparing a supporting layer: a forward osmosis membrane support layer was prepared as in example 1, except that during the preparation of the forward osmosis membrane support layer of step (1), the atomization amount of atomized droplets used in the atomization pretreatment stage was 17L/m 2 ·h。
(2) Preparing a composite film: the same as in example 1.
In the composite forward osmosis membrane obtained in example 3, the thickness of the bottom layer was 85 μm, the thickness of the porous support layer sub-layer was 47 μm, the thickness of the porous support layer surface layer was 1.9 μm, and the thickness of the active separation layer was 42nm. The average pore diameter of the surface layer of the supporting layer is 18nm. The porosity of the porous support layer was 79%.
Example 4
(1) Preparing a supporting layer: a forward osmosis membrane support layer was prepared as in example 3, except that during the preparation of the forward osmosis membrane support layer of step (1), the back surface of the coated membrane was ultrasonically atomized toward deionized water in an atomization pretreatment stage to obtain a droplet bath, and the droplet bath was left for 10 seconds.
(2) Preparing a composite film: the same as in example 1.
In the composite forward osmosis membrane obtained in example 4, the thickness of the bottom layer was 85 μm, the thickness of the porous support layer sub-layer was 45 μm, the thickness of the porous support layer surface layer was 2.1 μm, and the thickness of the active separation layer was 44nm. The average pore diameter of the surface layer of the supporting layer is 17nm. The porosity of the porous support layer was 74%.
Example 5
(1) Preparing a supporting layer: a forward osmosis membrane support layer was prepared as in example 3, except that the back side of the coated membrane was ultrasonically atomized toward deionized water in the atomization pretreatment stage to obtain a droplet bath, and the droplet bath was left for 30s. The cross-sectional morphology of the porous support layer of the forward osmosis membrane is shown in figure 1, and the surface morphology of the forward osmosis membrane is shown in figure 2.
(2) Preparing a composite film: the same as in example 1.
In the composite forward osmosis membrane obtained in example 5, the thickness of the bottom layer was 85 μm, the thickness of the porous support layer sub-layer was 47 μm, the thickness of the porous support layer surface layer was 1.6 μm, and the thickness of the active separation layer was 40nm. The average pore diameter of the surface layer of the supporting layer is 24nm. The porosity of the porous support layer was 83%.
Example 6
(1) Preparing a supporting layer: dissolving 12g of polysulfone in 88g of polarclean solvent, heating and stirring to form a uniform solution at 100 ℃, and vacuumizing and defoaming; then a continuous film scraping machine is adopted to scrape and coat the film on non-woven fabrics, the thickness of a feeler gauge is controlled to be 150 mu m during coating, then the back surface of the film after coating faces to a liquid drop bath obtained by ultrasonic atomization of deionized water, the film stays in the liquid drop bath for 4s, the surface of the film coated with casting film liquid is protected from contacting atomized liquid drops, and the atomization amount of the film per unit area is 17L/m 2 H; immersing the film into deionized water coagulation bath to completely phase separate; and washing with water to obtain the support layer.
(2) Preparing a composite film: the same as in example 1.
In the composite forward osmosis membrane obtained in example 6, the thickness of the bottom layer was 85 μm, the thickness of the porous support layer sub-layer was 45 μm, the thickness of the porous support layer surface layer was 1.6 μm, and the thickness of the active separation layer was 44nm. The average pore diameter of the surface layer of the supporting layer is 22nm. The porosity of the porous support layer was 73%.
Example 7
(1) A forward osmosis membrane was prepared as in example 6, except that during the forward osmosis membrane support layer preparation, the back side of the coated membrane was ultrasonically atomized toward deionized water to obtain a droplet bath in which the droplet bath was left for 6s during the atomization pretreatment stage.
(2) Preparing a composite film: the same as in example 1.
In the composite forward osmosis membrane obtained in example 7, the thickness of the bottom layer was 85 μm, the thickness of the porous support layer sub-layer was 49 μm, the thickness of the porous support layer surface layer was 1.4 μm, and the thickness of the active separation layer was 41nm. The average pore diameter of the surface layer of the supporting layer is 26nm. The porosity of the porous support layer was 75%.
Comparative example 1
(1) A forward osmosis membrane was prepared according to the method of example 3, except that during the preparation of the forward osmosis membrane support layer, the ultrafiltration membrane was directly immersed in a solvent coagulation bath to perform complete phase separation without an atomization pretreatment stage, and the support layer was obtained after water washing, the cross-sectional morphology of the support layer being shown in FIG. 3.
(2) Preparing a composite film: the same as in example 3.
In the composite forward osmosis membrane obtained in comparative example 1, the thickness of the active separation layer was 50nm. The average pore diameter of the supporting layer is 13nm. The porosity of the support layer was 70%.
Comparative example 2
(1) A forward osmosis membrane was prepared according to the method of example 6, except that during the preparation of the forward osmosis membrane support layer, the ultrafiltration membrane was directly immersed in a solvent coagulation bath to perform complete phase separation without an atomization pretreatment stage, and the support layer was obtained after washing with water.
(2) Preparing a composite film: the same as in example 6.
In the composite forward osmosis membrane obtained in comparative example 2, the thickness of the active separation layer was 52nm. The average pore diameter of the support layer was 16nm. The porosity of the support layer was 67%.
The composite forward osmosis membranes prepared in examples 1-7 and comparative examples 1-2 were used for water flux, reverse diffusion salt flux and salt rejection performance tests.
The water flux and the reverse diffusion salt flux of the forward osmosis composite membrane were tested on a forward osmosis test system.
At 25℃with 1M MgCl 2 The water solution is used as a drawing liquid, deionized water is used as a raw material liquid, and the water flux and the reverse diffusion salt flux of the composite forward osmosis membrane are tested by a forward osmosis testing device. The results obtained are shown in Table 1.
TABLE 1
From the test results of the above examples and comparative examples, it can be seen that the composite forward osmosis membrane prepared by using the support layer after the atomization pretreatment has excellent water flux, and the forward osmosis membrane water flux is significantly improved on the basis of keeping the back diffusion salt flux low. When the atomization time continues to increase, the pore diameter of the surface of the support layer gradually increases, so that a complete polyamide separation layer is not easy to form in the interfacial polymerization process, and the back diffusion salt flux is increased sharply, so that the membrane performance is reduced. It can be seen from examples 1-3 that the permeation flux of the forward osmosis membrane increases with increasing atomization. In addition, the atomization pretreatment process can be applied to various polymer film-making materials, and can effectively improve the permeability of the composite film.
Claims (20)
1. The composite forward osmosis membrane sequentially comprises a bottom layer, a porous supporting layer and an active separating layer, wherein the active separating layer is an aromatic polyamide layer; the porous supporting layer is divided into a sub-layer and a surface layer, the surface layer is of a small-hole structure with narrow pore diameter distribution, and the sub-layer is attached to the bottom layer and is of a through three-dimensional network porous structure;
the composite forward osmosis membrane is prepared by the following steps:
1) Dissolving components including a polymer of the porous support layer in a solvent to prepare a casting solution;
2) Scraping and casting the casting solution on the bottom layer;
3) Carrying out atomization pretreatment, wherein the atomization pretreatment stays in an atomized liquid drop bath, the bottom surface faces to atomized liquid drops, the surface of the protective film coated with casting film liquid does not contact the atomized liquid drops, the atomization pretreatment time is 6 s-20 s, and the required atomization amount per unit film area is 10-20L/m 2 ·h；
4) Immersing in a coagulating bath to obtain the porous support layer;
5) Contacting the porous support layer sequentially with an aqueous phase solution containing an aromatic polyfunctional amine compound and an organic phase solution containing an aromatic polyfunctional acyl chloride compound;
6) And drying and heat treating to obtain the composite forward osmosis membrane.
2. The composite forward osmosis membrane of claim 1, wherein:
the bottom layer is at least one of non-woven fabric, spun fabric, polyester screen mesh and electrostatic spinning film; and/or the number of the groups of groups,
the polymer of the porous supporting layer is selected from at least one of polyvinyl chloride, polysulfone, polyethersulfone, sulfonated polyethersulfone, polyacrylonitrile, cellulose acetate, polyvinylidene fluoride, polyimide, polyacrylic acid, polylactic acid, polyamide, chitosan, polyetherimide, polystyrene, polyolefin, polyester, polytrifluoroethylene, silicone resin, acrylonitrile-styrene copolymer and modified polymers thereof.
3. The composite forward osmosis membrane of claim 1, wherein:
the average pore diameter of the surface layer of the porous supporting layer is 5-100 nm; and/or the number of the groups of groups,
the porosity of the porous supporting layer is 40-90%.
4. A composite forward osmosis membrane according to claim 3, characterized in that:
the porosity of the porous supporting layer is 60-90%.
5. The composite forward osmosis membrane of claim 1, wherein:
the thickness of the bottom layer is 50-300 mu m, the thickness of the porous support layer sub-layer is 10-60 mu m, the thickness of the surface layer of the porous support layer is 0.5-5 mu m, and the thickness of the active separation layer is 5-200 nm.
6. The composite forward osmosis membrane of claim 1, wherein:
the active separation layer is prepared by performing interfacial polymerization reaction on an aromatic polyfunctional amine compound and an aromatic polyfunctional acyl chloride compound.
7. The composite forward osmosis membrane of claim 6, wherein:
the aromatic polyfunctional amine compound is at least one of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 1,3, 5-triaminobenzene, 1,2, 4-triaminobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminotoluene, 2, 4-diaminoanisole, amiphenol and xylylenediamine, and the aromatic polyfunctional acyl chloride compound is at least one of terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride, biphenyl dicarboxylic acid chloride, benzene disulfonyl chloride and trimesoyl chloride.
8. A method of preparing a composite forward osmosis membrane according to any one of claims 1 to 7, comprising the steps of:
1) Dissolving components including a polymer of the porous support layer in a solvent to prepare a casting solution;
2) Scraping and casting the casting solution on the bottom layer;
3) Carrying out atomization pretreatment, wherein the atomization pretreatment stays in an atomized liquid drop bath, the bottom surface faces to atomized liquid drops, and the surface of the protective film coated with the casting solution is not contacted with the atomized liquid drops;
4) Immersing in a coagulating bath to obtain the porous support layer;
5) Contacting the porous support layer sequentially with an aqueous phase solution containing an aromatic polyfunctional amine compound and an organic phase solution containing an aromatic polyfunctional acyl chloride compound;
6) And drying and heat treating to obtain the composite forward osmosis membrane.
9. The method for preparing a composite forward osmosis membrane according to claim 8, wherein: in the step (1) of the process,
the solid content of the polymer in the casting film liquid is 6-20wt%; and/or the number of the groups of groups,
the solvent is a good solvent for the polymer.
10. The method for preparing a composite forward osmosis membrane according to claim 9, characterized in that:
the solid content of the polymer in the casting film liquid is 8-18 wt%.
11. The method for preparing a composite forward osmosis membrane according to claim 8, wherein:
in step 2), the thickness of the scratch film is 50-500 μm.
12. The method for preparing a composite forward osmosis membrane according to claim 11, characterized in that:
the thickness of the scraping film is 75-300 mu m.
13. The method for preparing a composite forward osmosis membrane according to claim 8, wherein: in the step 3) of the method,
the size of the liquid drops in the liquid drop bath is 1-50 mu m; and/or the number of the groups of groups,
the atomization pretreatment time is 6 s-20 s; and/or the number of the groups of groups,
the required atomization amount per unit membrane area is 10-20L/m 2 H; and/or the number of the groups of groups,
the droplets are poor solvents for the polymer.
14. The method for preparing a composite forward osmosis membrane according to claim 13, characterized in that:
the size of the droplets in the droplet bath is 5-20 mu m.
15. The method for preparing a composite forward osmosis membrane according to claim 8, wherein:
in step 4), the coagulation bath is a poor solvent for the polymer.
16. The method for producing a composite forward osmosis membrane according to any one of claims 9 or 13 or 15, characterized in that:
the good solvent of the polymer is at least one selected from N, N-dimethylformamide, N-dimethylacetamide, acetone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethyl sulfoxide, tetrahydrofuran, dioxane, acetonitrile, chloroform, polarclean solvent, triethyl phosphate, trimethyl phosphate, hexamethyl ammonium phosphate, tetramethyl urea, acetonitrile, toluene, hexane and octane; and/or the number of the groups of groups,
the poor solvent of the polymer is at least one selected from water, ethanol and ethylene glycol.
17. The method for preparing a composite forward osmosis membrane according to claim 8, wherein: in the step 5) of the method,
the concentration of the aromatic polyfunctional amine compound in the aqueous phase solution is 1.0-2.5 w/v%; and/or the number of the groups of groups,
the contact time of the porous supporting layer and the aqueous phase solution is 5-150 seconds; and/or the number of the groups of groups,
the concentration of the aromatic polyfunctional acyl chloride compound in the organic phase solution is 0.05-0.15 w/v%; and/or the number of the groups of groups,
the contact time of the porous supporting layer and the organic phase solution is 5-150 seconds.
18. The method for preparing a composite forward osmosis membrane according to claim 8, wherein: in the step 6) of the process, the process is carried out,
the temperature of the heat treatment is 25-70 ℃ and the time is 1-5 minutes.
19. A composite forward osmosis membrane obtainable by a process according to any one of claims 8 to 18.
20. Use of a composite forward osmosis membrane according to any one of claims 1 to 7 or a composite forward osmosis membrane obtained by a process according to any one of claims 8 to 18 in the fields of sewage treatment, sea water desalination, membrane bioreactors, reduced pressure power generation, food processing, and drug enrichment.
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| CN202110466664.7A CN115245758B (en) | 2021-04-28 | 2021-04-28 | Composite forward osmosis membrane and preparation method and application thereof |
| PCT/CN2021/127029 WO2022183751A1 (en) | 2021-03-05 | 2021-10-28 | Double-continuous high-pass polymer ultrafiltration membrane, preparation method therefor, and application thereof |
| CA3212478A CA3212478A1 (en) | 2021-03-05 | 2021-10-28 | Bicontinuous highly interconnected porous polymer ultrafiltration membrane as well as preparation method and application thereof |
| BR112023017730A BR112023017730A2 (en) | 2021-03-05 | 2021-10-28 | CONTINUOUS DOUBLE PASSAGE POLYMER ULTRAFILTRATION MEMBRANE, METHOD OF PREPARATION THEREOF AND ITS APPLICATION THEREOF |
| KR1020237034171A KR20230154961A (en) | 2021-03-05 | 2021-10-28 | Dual continuous high-pass polymer ultrafiltration membrane and its manufacturing method and application |
| CN202180005381.0A CN115335139A (en) | 2021-03-05 | 2021-10-28 | Dual-continuous high-through polymer ultrafiltration membrane and preparation method and application thereof |
| JP2023553555A JP2024509442A (en) | 2021-03-05 | 2021-10-28 | Bicontinuous highly interconnected polymer ultrafiltration membranes and their preparation methods and applications |
| EP21928825.5A EP4302865A1 (en) | 2021-03-05 | 2021-10-28 | Double-continuous high-pass polymer ultrafiltration membrane, preparation method therefor, and application thereof |
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