CN110841494A - Amphoteric composite forward osmosis membrane and preparation method and application thereof - Google Patents
Amphoteric composite forward osmosis membrane and preparation method and application thereof Download PDFInfo
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- CN110841494A CN110841494A CN201911154908.7A CN201911154908A CN110841494A CN 110841494 A CN110841494 A CN 110841494A CN 201911154908 A CN201911154908 A CN 201911154908A CN 110841494 A CN110841494 A CN 110841494A
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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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- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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
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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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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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
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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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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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 relates to an amphoteric composite forward osmosis membrane, wherein a porous support membrane adopted by the membrane is a super-hydrophilic polyvinylidene fluoride membrane; a polyamide layer is formed on the porous support membrane, and a zwitterion layer is formed on the polyamide layer. According to the invention, the zwitterion layer is formed by an amino group through a zwitterionization reaction, and the superhydrophilic characteristic of the polyvinylidene fluoride membrane prepared by phase separation induced by water vapor, the nanometer water channel of the catechol derivative modified graphene oxide, and the strong hydration and charge performance of the zwitterionization skin layer are improved greatly while the low back-mixed salt flux is maintained.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to an amphoteric composite forward osmosis membrane and a preparation method and application thereof.
Background
The forward osmosis membrane method seawater desalination technology is a prospective technology for solving the problem of water resources, which is emerging in recent years. Forward osmosis refers to a process in which water is transferred from one end of a low osmotic pressure solution to one end of a high osmotic pressure solution through a selective semipermeable membrane, solute or ions are trapped, and forward osmosis is a spontaneous osmosis process which does not need external pressure drive and can screen out harmful substances such as inorganic salts, heavy metals, microorganisms and the like in a water body.
A common forward osmosis membrane is a composite membrane consisting of a lower porous support membrane and an upper ultrathin polyamide skin layer formed on a substrate by interfacial polymerization. For example, CN 104001434 a discloses a forward osmosis membrane, in which the support layer is a screen and the skin layer is a polyamide layer compounded on the screen. The preparation method comprises the following steps: 1) preparing a water phase solution and an oil phase solution; wherein the solute in the aqueous phase solution is a small molecular compound containing amino and/or a long-chain macromolecule containing amino; the solute of the oil phase solution is a micromolecular substance containing acyl chloride, and the solvent is normal hexane and an isoparaffin solvent; 2) cleaning the screen by using the solution, and then drying the screen at low temperature for later use; 3) placing the screen mesh treated in the step 2) on the upper surface of the water phase, slowly and uniformly adding the oil phase on the upper surface of the water phase, standing for reaction, taking out the product after the reaction is finished, and immersing the product into deionized water to finish the preparation.
It is believed that the lower support membrane provides mechanical strength to the composite membrane and the upper skin layer directly determines the separation performance of the forward osmosis membrane. Recent research results demonstrate that the pore size, porosity and hydrophilicity of the support membrane have a significant impact on the permeability performance of the forward osmosis membrane. The traditional support membrane is a polysulfone and polyether sulfone ultrafiltration membrane prepared by a non-solvent (water) induced phase separation method, and has the advantages of smooth and compact membrane surface, small specific surface area, low aperture ratio and wide aperture distribution; the water contact angle is often more than 80 degrees, which is not beneficial to the diffusion of water phase monomers on the surface of the membrane in the interfacial polymerization process, and easily causes the non-uniformity and the many defects of a polyamide layer. Such a support membrane often causes low flux of the composite forward osmosis membrane, and the concentration polarization is severe due to the slow diffusion speed of the draw solution.
Therefore, it is necessary to develop a new forward osmosis membrane with higher water permeation flux and lower back mixed salt flux (high salt rejection).
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide an amphoteric composite forward osmosis membrane, which is prepared by a method of water vapor induced phase separation to form a superhydrophilic polyvinylidene fluoride support membrane having a high porosity and a catechol derivative-modified graphene oxide surface, and further synthesized on the support membrane by interfacial polymerization to form a polyamide layer, and formed on the polyamide layer by a zwitterionic reaction to form an amphoteric ion layer. Based on the high porosity provided by the polyvinylidene fluoride supporting membrane, the ultra-fast water transfer nano-water channel provided by the graphene oxide and the synergistic effect of the strong hydration layer provided by the amphoteric ion layer, the synthesized amphoteric forward osmosis composite membrane has high water permeation flux, low back-mixed salt flux and pollution resistance.
The second purpose of the invention is to provide a preparation method of the amphoteric composite forward osmosis membrane corresponding to the first purpose.
The invention also aims to provide application of the amphoteric composite forward osmosis membrane.
In order to achieve one of the above purposes, the technical scheme adopted by the invention is as follows:
an amphiphilic composite forward osmosis membrane, comprising:
the porous support membrane is a super-hydrophilic polyvinylidene fluoride membrane;
a polyamide layer formed on the porous support membrane; and
a zwitterionic layer formed on the polyamide layer by reacting a zwitterionic reagent with the amine groups of the polyamide layer.
In some preferred embodiments of the present invention,
the porous support membrane is a catechol derivative modified graphene oxide modified super-hydrophilic polyvinylidene fluoride membrane, and is preferably a catechol derivative modified graphene oxide modified super-hydrophilic polyvinylidene fluoride membrane prepared by a water vapor induced phase separation membrane method.
In some preferred embodiments of the present invention, the zwitterionic reagent is selected from at least one of 1, 3-propanesultone, 3-bromopropionic acid, 4-bromobutyric acid, 5-bromovaleric acid and 7-bromoheptanoic acid.
The inventor of the application discovers in research that the super-hydrophilic polyvinylidene fluoride membrane is prepared by a water vapor induced phase separation method, wherein the catechol derivative modified graphene oxide has good interface adhesion capability, can be embedded into a polyvinylidene fluoride membrane body and/or deposited on the surface of the polyvinylidene fluoride membrane, provides a nano water channel with super-high water transfer rate, and can also improve the roughness, porosity and hydrophilicity of the surface of the membrane to form the super-hydrophilic membrane surface, so that the fast diffusion of an extraction solution is effectively promoted, the concentration polarization is weakened, the water flux of a forward osmosis membrane is improved, and the anti-pollution capability of the membrane is improved; in addition, the interlayer spacing of the graphene oxide can be further regulated and controlled through the alcohol bath and salt bath treatment, so that the ion selectivity and the salt rejection rate of the graphene are further improved. The catechol derivative modified graphene oxide adhered to the surface of the polyvinylidene fluoride can also improve the bonding firmness between the polyvinylidene fluoride supporting film and the uniform and defect-free polyamide layer obtained by interfacial polymerization; furthermore, after the amino group contained in the synthetic polyamide layer (especially the surface contacted with the polyvinylidene fluoride support membrane) is subjected to zwitterionization treatment, the super-strong hydration capability and charge property of the zwitterionic polymer are utilized to promote the conduction and transportation of water molecules and improve the ion selectivity, so that the amphoteric composite forward osmosis membrane with high water flux and low back-mixing salt flux is finally obtained.
In some preferred embodiments of the present invention, when the amphoteric composite forward osmosis membrane uses 1mol/L sodium chloride solution as a draw solution and pure water as a supply solution, the pure water flux is 1Lm-2h-1～100Lm-2h-1Preferably 40 L.m-2·h-1～70L·m-2·h-1The flux of the back-mixed salt is 1 g.m-2·h-1～30g·m-2·h-1Preferably 1 g.m-2·h-1～25g·m-2·h-1。
In order to achieve the second purpose, the invention adopts the following technical scheme:
the preparation method of the amphoteric composite forward osmosis membrane comprises the following steps:
1) providing a porous support membrane;
2) forming a polyamide layer on the porous support membrane by reacting an aqueous phase solution containing an aqueous phase monomer with an oil phase solution containing an oil phase monomer;
3) forming a zwitterionic layer on the polyamide layer by reacting a zwitterionic reagent with amine groups of the polyamide layer,
in some preferred embodiments of the present invention, the porous support membrane is prepared by a method comprising:
1a) providing a mixed solution containing graphene oxide, catechol derivatives, polyamine, polyvinylidene fluoride and an organic solvent;
1b) forming the mixed solution into a liquid film;
1c) inducing the liquid film to generate phase separation by using water vapor so as to partially remove the organic solvent in the liquid film and obtain a gel film;
1d) and sequentially carrying out alcohol bath treatment and salt bath treatment on the gel film to obtain the porous support film.
According to the present invention, the above mixed solution may be prepared by a method comprising the steps of:
firstly, uniformly dispersing graphene oxide in an organic solvent, then adding a catechol derivative, polyamine and polyvinylidene fluoride, and reacting for 1-24 h at 80 ℃.
In some preferred embodiments of the present invention, the content of the graphene oxide in the mixed solution is 5mg to 1g, based on 100mL of the organic solvent.
In some preferred embodiments of the present invention, the content of the catechol derivative in the mixed solution is 5mg to 10g, based on 100mL of the organic solvent.
In some preferred embodiments of the present invention, the polyamine is contained in an amount of 5mg to 10g, based on 100mL of the organic solvent in the mixed solution.
In some preferred embodiments of the present invention, the content of the polyvinylidene fluoride in the mixed solution is 5g to 25g based on 100mL of the organic solvent.
In some preferred embodiments of the present invention, the catechol derivative is selected from at least one of dopamine, catechol, tannic acid, and juglone.
In some preferred embodiments of the present invention, the polyamine is selected from at least one of polyethyleneimine, gamma-aminopropyltriethoxysilane, and amino-cage polysilsesquioxane.
In some preferred embodiments of the present invention, the organic solvent is selected from at least one of N-methylpyrrolidone, N '-dimethylformamide, N' -dimethylacetamide, triethyl phosphate, trimethyl phosphate, and dimethylsulfoxide.
In some preferred embodiments of the present invention, in step 1b), the mixed solution is coated on a surface of a non-woven fabric, so that the mixed solution forms a liquid film.
In some preferred embodiments of the present invention, in step 1c), the method for inducing the phase separation of the liquid film by using water vapor comprises exposing the liquid film to air with humidity of 60% to 100% for 5s to 2 h.
In some preferred embodiments of the present invention, in step 1d), the alcohol used in the alcohol bath treatment is selected from C1-C4The alcohol of (b) is preferably at least one of methanol, ethanol, isopropanol and n-butanol.
In some preferred embodiments of the present invention, in step 1d), the salt solution used in the salt bath treatment is at least one of an aqueous sodium chloride solution, an aqueous potassium chloride solution, an aqueous magnesium sulfate solution, and an aqueous sodium sulfate solution.
In some preferred embodiments of the present invention, in step 2), the porous support membrane is immersed in an aqueous phase solution containing an aqueous phase monomer for 0.5 to 10min, then immersed in an oil phase solution containing an oil phase monomer for 10 to 5min, then taken out, and subjected to heat treatment, thereby forming a polyamide layer on the porous support membrane.
According to the invention, the porous support membrane is soaked in the aqueous phase solution containing the aqueous phase monomer for 0.5-10 min, then taken out, drained of water on the surface of the porous support membrane, and then soaked in the oil phase solution containing the oil phase monomer for 10 s-5 min.
According to the invention, the temperature of the heat treatment is 80-120 ℃, and the time is 1-30 min.
In some preferred embodiments of the present invention, the concentration of the aqueous phase monomer in the aqueous phase solution is 0.2g/L to 10 g/L.
In some preferred embodiments of the present invention, the concentration of the oil phase monomer in the oil phase solution is 0.2g/L to 10 g/L.
In some preferred embodiments of the present invention, the aqueous phase monomer is at least one selected from the group consisting of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, and piperazine, and the solvent of the aqueous phase solution is water.
In some preferred embodiments of the present invention, the oil phase monomer is selected from at least one of trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride.
In some preferred embodiments of the present invention, the solvent of the oil phase solution is n-hexane.
In some preferred embodiments of the present invention, in step 3),
and (2) soaking the porous support membrane with the polyamide layer in a reaction solution containing a zwitterionization reagent at the temperature of 35-45 ℃ for 2-24 h, so as to form the zwitterion layer on the polyamide layer.
In some preferred embodiments of the present invention, the concentration of the zwitterionic reagent in the reaction solution is in the range of 10g/L to 100 g/L.
In some preferred embodiments of the present invention, the zwitterionic reagent is selected from at least one of 1, 3-propanesultone, 3-bromopropionic acid, 4-bromobutyric acid, 5-bromovaleric acid and 7-bromoheptanoic acid.
In some preferred embodiments of the present invention, the solvent of the reaction solution is ethanol.
In order to achieve the third purpose, the invention adopts the following technical scheme:
a forward osmosis treatment system comprising:
the membrane comprises a semipermeable membrane unit formed by the amphoteric composite forward osmosis membrane, a first area and a second area which are separated by the semipermeable membrane unit, a supply part for supplying low osmotic pressure supply liquid to the first area, a supply part for supplying high osmotic pressure draw liquid to the second area, and transmembrane fluid flow from the first area to the second area is formed under the driving of osmotic pressure difference on two sides of the semipermeable membrane.
The invention also provides a sewage treatment method, which comprises the following steps: by using the forward osmosis treatment system, water moves from low osmotic pressure sewage to high osmotic pressure drawing liquid, and then water is recovered from the high osmotic pressure drawing liquid.
The invention also provides a seawater desalination method, which comprises the following steps: by using the forward osmosis treatment system, water moves from the low osmotic pressure seawater to the high osmotic pressure drawing liquid, and then water is recovered from the high osmotic pressure drawing liquid.
The invention has the advantages that at least the following aspects are achieved:
(1) according to the invention, water vapor is adopted to induce phase separation, and meanwhile, the catechol derivative modified graphite oxide is utilized to construct the surface of the super-hydrophilic polyvinylidene fluoride membrane with a micro-nano structure, so that a support membrane is endowed with a large porosity and a high nano water channel, the rapid evacuation of a salt solution is promoted, the concentration polarization is reduced, the membrane resistance is reduced, and the water flux of a forward osmosis membrane is improved;
(2) compared with the supporting membrane of the traditional forward osmosis composite membrane, the aqueous phase solution is easy to spread on the surface of the super-hydrophilic polyvinylidene fluoride membrane in the interfacial polymerization process, a polyamide-amine layer formed by interfacial polymerization is uniform and free of defects, the interfacial adhesion with the polyvinylidene fluoride membrane is strong, and the stability of the membrane and the rejection rate of inorganic salts are ensured;
(3) the good hydrophilicity, charge property and pollution resistance of zwitterions are utilized to realize the performance upgrade of the polyamide layer, and the water permeation flux, the salt retention rate and the pollution resistance of the membrane are improved while the low back-mixed salt flux of the forward osmosis membrane is kept.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
Wherein, the permeability of the prepared forward osmosis membrane is characterized by a set of forward osmosis system. The forward osmosis system comprises a rectangular forward osmosis membrane pool (the effective membrane area is A ═ 4.5 cm)2) The membrane comprises a semipermeable membrane unit formed by a forward osmosis membrane, a semi-membrane pool called a first area and a semi-membrane pool called a second area which are separated by the semipermeable membrane unit, and further comprises a supply part for supplying low osmotic pressure supply liquid to the first area and a supply part for supplying high osmotic pressure extraction liquid to the second area, wherein the two supply parts respectively comprise a liquid storage tank, a circulating pump, a supply pipe, a pressure gauge, a valve and the like. The two sides of the membrane are connected by piping to circulate to the semipermeable membrane, thereby generating a flow of fluid from the low osmotic pressure solution side to the high osmotic pressure solution side and increasing the amount of solution on the high osmotic pressure side. All tests used 1mol/L sodium chloride solution as draw solution (draw solution) and pure water as feed solution (feed solution) with the polyamide layer of the composite membrane facing the feed solution side, and then the forward osmosis process was started at a liquid circulation rate of 0.6L/min and 25 ℃. Monitoring the volume change (Δ V) and the salt concentration (Δ C) of the feed liquid over a given time interval (Δ t), wherein the salt concentration change is obtained by detecting the solution conductivity change, thereby calculating the pure water permeation flux (Jw, Lm)-2h-1) And back-mix salt flux (Js, gm)-2h-1)，Jw＝ΔV/(AΔt)，Js＝ΔCV/(AΔt)。
Some of the raw material information used in the examples and comparative examples below is polyvinylidene fluoride (Solef PVDF1015, suwei usa), graphene oxide (powder, > 99%, shanghai avastin reagent), polyethyleneimine (weight average molecular weight 10000, 99%, shanghai avastin reagent), dopamine (dopamine hydrochloride, 98%, shanghai avastin reagent), tannic acid, catechol (assay pure, shanghai avastin reagent), juglone (> 98%, shanghai shidande), gamma-amino-propenotriethoxysilane (98%, alfa aesar china), m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, piperazine, trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride (> 98%, TCI shanghai), 1, 3-propanesultone (99%, shanghai avastin reagent).
Example 1
(1) Uniformly dispersing 5mg of graphene oxide in 100mL of N-methylpyrrolidone, adding 5mg of dopamine, 5mg of polyethyleneimine and 5g of polyvinylidene fluoride, reacting at 80 ℃ for 1h, uniformly coating the mixture on the surface of a non-woven fabric to obtain a liquid film, then exposing the liquid film to humid air with the humidity of 60% for 5s, carrying out water vapor induced phase separation, immersing the liquid film into methanol, taking out the liquid film, and immersing the liquid film into a sodium chloride aqueous solution to obtain a super-hydrophilic polyvinylidene fluoride film;
(2) immersing a polyvinylidene fluoride membrane into an aqueous solution of m-phenylenediamine with the concentration of 0.2g/L, taking out after soaking for 30s, draining water on the surface of the polyvinylidene fluoride membrane, immersing into a n-hexane solution with the concentration of 0.2g/L trimesoyl chloride, taking out after reacting for 1min, putting into an oven, and carrying out heat treatment at 90 ℃ for 3min to obtain a polyamide composite membrane;
(3) and (2) immersing the polyamide composite membrane into an ethanol solution of 1, 3-propane sultone with the concentration of 10g/L, taking out after soaking for 2h at 40 ℃, and cleaning to obtain the amphoteric composite forward osmosis membrane.
As a result of the tests, the forward osmosis membrane prepared in this example had a pure water flux of 4Lm when 1mol/L sodium chloride solution was used as the draw solution and pure water was used as the feed solution-2h-1The flux of the back-mixed salt is 21gm-2h-1。
Example 2
(1) Uniformly dispersing 1g of graphene oxide in 100mL of N, N' -dimethylformamide, adding 10g of catechol, 10g of gamma-amino propylene triethoxysilane and 25g of polyvinylidene fluoride, reacting at 80 ℃ for 24 hours, uniformly coating the mixture on the surface of a non-woven fabric to obtain a liquid film, then exposing the liquid film to humid air with the humidity of 100% for 2 hours to generate water vapor induced phase separation, immersing the liquid film in ethanol, taking out the liquid film, and immersing the liquid film in a potassium chloride aqueous solution to obtain a super-hydrophilic polyvinylidene fluoride film;
(2) immersing a polyvinylidene fluoride membrane into an o-phenylenediamine aqueous solution with the concentration of 10g/L, taking out after immersing for 10min, draining water on the surface of the polyvinylidene fluoride membrane, immersing into a terephthaloyl chloride n-hexane solution with the concentration of 10g/L, taking out after reacting for 5min, and carrying out heat treatment at 90 ℃ for 3min to obtain a polyamide composite membrane;
(3) and (3) immersing the polyamide composite membrane into 100g/L ethanol solution of 3-bromopropionic acid, taking out after immersing for 24h at 40 ℃, and cleaning to obtain the amphoteric composite forward osmosis membrane.
It was found that the forward osmosis membrane prepared in this example had a pure water flux of 42 L.m when 1mol/L sodium chloride solution was used as the draw solution and pure water was used as the feed solution-2·h-1The flux of the back-mixed salt is 20 g.m-2·h-1。
Example 3
(1) Uniformly dispersing 0.1g of graphene oxide in 100mLN, N' -dimethylacetamide, adding 1g of tannic acid, 2g of amino-cage polysilsesquioxane and 15g of polyvinylidene fluoride, reacting at 80 ℃ for 8 hours, uniformly coating the mixture on the surface of non-woven fabric to obtain a liquid film, then exposing the liquid film to humid air with the humidity of 100% for 0.5 hour, carrying out water vapor induced phase separation, immersing the liquid film in isopropanol, taking out the liquid film, and immersing the liquid film in a magnesium chloride aqueous solution to obtain a super-hydrophilic polyvinylidene fluoride film;
(2) immersing a polyvinylidene fluoride membrane into an aqueous solution of p-phenylenediamine with the concentration of 2g/L, taking out after soaking for 5min, draining water on the surface of the polyvinylidene fluoride membrane, immersing the polyvinylidene fluoride membrane into a n-hexane solution of isophthaloyl dichloride with the concentration of 0.3g/L, taking out after reacting for 1min, and carrying out heat treatment for 5min at the temperature of 90 ℃ to obtain a polyamide composite membrane;
(3) and (3) immersing the polyamide composite membrane into 50g/L ethanol solution of 4-bromobutyric acid, taking out after immersing for 12h at 40 ℃, and cleaning to obtain the amphoteric composite forward osmosis membrane.
It was found that the forward osmosis membrane prepared in this example had a pure water flux of 46 L.m when 1mol/L sodium chloride solution was used as the draw solution and pure water was used as the feed solution-2·h-1The flux of the back-mixed salt is 23 g.m-2·h-1。
Example 4
(1) Uniformly dispersing 0.2g of graphene oxide in 100mL of triethyl phosphate, adding 0.2g of juglone, 3g of polyethyleneimine and 20g of polyvinylidene fluoride, reacting at 80 ℃ for 15 hours, uniformly coating the mixture on the surface of non-woven fabric to obtain a liquid film, exposing the liquid film to humid air with the humidity of 80% for 15s, carrying out water vapor induced phase separation, immersing the liquid film in n-butyl alcohol, taking out the liquid film, and immersing the liquid film in a magnesium sulfate aqueous solution to obtain a super-hydrophilic polyvinylidene fluoride film;
(2) immersing a polyvinylidene fluoride membrane into a piperazine water solution with the concentration of 5g/L, taking out after soaking for 5min, draining water on the surface of the polyvinylidene fluoride membrane, immersing the polyvinylidene fluoride membrane into a phthaloyl chloride n-hexane solution with the concentration of 1.5g/L, taking out after reacting for 2.5min, and carrying out heat treatment for 3min at the temperature of 100 ℃ to obtain a polyamide composite membrane;
(3) and (3) immersing the polyamide composite membrane into an ethanol solution of 5-bromovaleric acid with the concentration of 30g/L, taking out after immersing for 18h at 40 ℃, and cleaning to obtain the amphoteric composite forward osmosis membrane.
It was found that the forward osmosis membrane prepared in this example had a pure water flux of 59 L.m with 1mol/L sodium chloride solution as the draw solution and pure water as the feed solution-2·h-1The flux of the back-mixed salt is 6 g.m-2·h-1。
Example 5
(1) Uniformly dispersing 0.5g of graphene oxide in 100mL of trimethyl phosphate, adding 5g of dopamine, 5g of polyethyleneimine and 12g of polyvinylidene fluoride, reacting at 80 ℃ for 8 hours, uniformly coating the mixture on the surface of non-woven fabric to obtain a liquid film, then exposing the liquid film to humid air with the humidity of 100% for 1 hour to generate water vapor induced phase separation, immersing the liquid film into ethanol, taking out the liquid film, and immersing the liquid film into a sodium sulfate aqueous solution to obtain a super-hydrophilic polyvinylidene fluoride film;
(2) immersing a polyvinylidene fluoride membrane into an aqueous solution of m-phenylenediamine with the concentration of 7g/L, taking out after soaking for 7min, draining water on the surface of the polyvinylidene fluoride membrane, immersing the polyvinylidene fluoride membrane into a n-hexane solution with the concentration of 8g/L trimesoyl chloride, taking out after reacting for 1min, and carrying out heat treatment at 100 ℃ for 3min to obtain a polyamide composite membrane;
(3) and (3) immersing the polyamide composite membrane into an ethanol solution of 7-bromoheptanoic acid with the concentration of 40g/L, taking out after 20 hours of immersion at 40 ℃, and cleaning to obtain the amphoteric composite forward osmosis membrane.
It was found that the forward osmosis membrane prepared in this example had a pure water flux of 65 L.m when 1mol/L sodium chloride solution was used as the draw solution and pure water was used as the feed solution-2·h-1The flux of the back-mixed salt is 24 g.m-2·h-1。
Example 6
(1) Uniformly dispersing 0.3g of graphene oxide in 100mL of dimethyl sulfoxide, adding 3g of dopamine, 9g of polyethyleneimine and 14g of polyvinylidene fluoride, reacting at 80 ℃ for 16h, uniformly coating the mixture on the surface of non-woven fabric to obtain a liquid membrane, then exposing the liquid membrane to humid air with the humidity of 100% for 1.5h, carrying out water vapor induced phase separation, immersing the liquid membrane into ethanol, taking out the liquid membrane, and immersing the liquid membrane into a sodium sulfate aqueous solution to obtain a super-hydrophilic polyvinylidene fluoride membrane;
(2) immersing a polyvinylidene fluoride membrane into an m-phenylenediamine aqueous solution with the concentration of 2g/L, taking out after soaking for 4min, draining water on the surface of the polyvinylidene fluoride membrane, immersing the polyvinylidene fluoride membrane into a n-hexane solution with the concentration of 1.5g/L trimesoyl chloride, taking out after reacting for 3min, and carrying out heat treatment for 3min at the temperature of 90 ℃ to obtain a polyamide composite membrane;
(3) and (3) immersing the polyamide composite membrane into an ethanol solution of 7-bromoheptanoic acid with the concentration of 60g/L, taking out after soaking for 5h at 40 ℃, and cleaning to obtain the amphoteric composite forward osmosis membrane.
It was found that the forward osmosis membrane prepared in this example had a pure water flux of 46 L.m when 1mol/L sodium chloride solution was used as the draw solution and pure water was used as the feed solution-2·h-1The flux of the back-mixed salt is 3 g.m-2·h-1。
Example 7
(1) Uniformly dispersing 0.2g of graphene oxide in 100mL of dimethyl sulfoxide, adding 0.5g of dopamine, 1g of polyethyleneimine and 12g of polyvinylidene fluoride, reacting at 80 ℃ for 10 hours, uniformly coating the mixture on the surface of a non-woven fabric to obtain a liquid membrane, then exposing the liquid membrane to humid air with the humidity of 100% for 5 minutes to generate water vapor induced phase separation, immersing the liquid membrane into ethanol, taking out the liquid membrane, and immersing the liquid membrane into a sodium chloride aqueous solution to obtain a super-hydrophilic polyvinylidene fluoride membrane;
(2) immersing a polyvinylidene fluoride membrane into an aqueous solution of piperazine with the concentration of 5g/L, taking out after soaking for 4min, draining water on the surface of the polyvinylidene fluoride membrane, immersing the polyvinylidene fluoride membrane into a n-hexane solution with the concentration of 3g/L trimesoyl chloride, taking out after reacting for 1min, and carrying out heat treatment at 90 ℃ for 3min to obtain a polyamide composite membrane;
(3) and (3) immersing the polyamide composite membrane into an ethanol solution of 1, 3-propane sultone with the concentration of 30g/L, taking out after soaking for 12h at 40 ℃, and cleaning to obtain the amphoteric composite forward osmosis membrane.
As a result of the tests, the forward osmosis membrane prepared in this example exhibited a pure water flux of 50 L.m when 1mol/L sodium chloride solution was used as the draw solution and pure water was used as the feed solution-2·h-1The flux of the back-mixed salt is 8 g.m-2·h-1。
Comparative example 1
This comparative example is essentially the same as example 7, except that: graphene oxide and dopamine were not added. The forward osmosis membrane obtained in this comparative example had a sodium chloride solution of 1mol/L as a draw solution and pure water as a feed solution, and the pure water flux was 1.2 L.m-2·h-1The flux of the back-mixed salt is 88 g.m-2·h-1。
Comparative example 2
This comparative example is essentially the same as example 7, except that: the liquid film was not placed in a humid atmosphere with a humidity of 100%, but was placed under a dry nitrogen atmosphere for 5 min. The forward osmosis membrane obtained in this comparative example had a sodium chloride solution of 1mol/L as a draw solution and pure water as a feed solution, and the pure water flux was 2.3 L.m-2·h-1The flux of the back-mixed salt is 69 g.m-2·h-1。
Comparative example 3
This comparative example is essentially the same as example 7, except that: the polyamide composite membrane is not subjected to zwitterionization treatment. The forward osmosis membrane obtained in this comparative example had a sodium chloride solution of 1mol/L as a draw solution and pure water as a feed solution, and had a pure water flux of 18.3 L.m-2·h-1The flux of the back-mixed salt is 27 g.m-2·h-1。
In addition, the inventors also conducted experiments with other raw materials and conditions and the like listed in the present specification by referring to the manner of example 1 to example 7, and also produced a composite forward osmosis membrane with high water flux and low back-mixed salt flux.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. An amphiphilic composite forward osmosis membrane, comprising:
the porous support membrane is a super-hydrophilic polyvinylidene fluoride membrane;
a polyamide layer formed on the porous support membrane; and
a zwitterionic layer formed on the polyamide layer by reacting a zwitterionic reagent with the amine groups of the polyamide layer.
2. The amphiphilic composite forward osmosis membrane according to claim 1, wherein the porous support membrane is a catechol derivative-modified graphene oxide-modified superhydrophilic polyvinylidene fluoride membrane, preferably a catechol derivative-modified graphene oxide-modified superhydrophilic polyvinylidene fluoride membrane prepared by a water vapor induced phase separation membrane process; and/or
The zwitterionic reagent is selected from at least one of 1, 3-propane sultone, 3-bromopropionic acid, 4-bromobutyric acid, 5-bromovaleric acid and 7-bromoheptanoic acid.
3. The amphoteric composite forward osmosis membrane according to claim 1 or 2, characterized in thatWhen the amphoteric composite forward osmosis membrane takes 1mol/L sodium chloride solution as an absorption liquid and pure water as a supply liquid, the pure water flux is 1Lm-2h-1～100Lm-2h-1Preferably 40 L.m-2·h-1～70L·m-2·h-1The flux of the back-mixed salt is 1 g.m-2·h-1～30g·m-2·h-1Preferably 1 g.m-2·h-1～25g·m-2·h-1。
4. A method of preparing an amphoteric composite forward osmosis membrane according to any one of claims 1 to 3, comprising the steps of:
1) providing a porous support membrane;
2) forming a polyamide layer on the porous support membrane by reacting an aqueous phase solution containing an aqueous phase monomer with an oil phase solution containing an oil phase monomer;
3) forming a zwitterionic layer on the polyamide layer by reacting a zwitterionic reagent with amine groups of the polyamide layer,
preferably, the water phase monomer is selected from at least one of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine and piperazine, the oil phase monomer is selected from at least one of trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride, and the zwitterionic reagent is selected from at least one of 1, 3-propane sultone, 3-bromopropionic acid, 4-bromobutyric acid, 5-bromovaleric acid and 7-bromoheptanoic acid;
preferably, the porous support membrane is prepared by a method comprising the steps of:
1a) providing a mixed solution containing graphene oxide, catechol derivatives, polyamine, polyvinylidene fluoride and an organic solvent;
1b) forming the mixed solution into a liquid film;
1c) inducing the liquid film to generate phase separation by using water vapor so as to partially remove the organic solvent in the liquid film and obtain a gel film;
1d) and sequentially carrying out alcohol bath treatment and salt bath treatment on the gel film to obtain the porous support film.
5. The preparation method according to claim 4, wherein the content of the graphene oxide is 5mg to 1g, and/or the content of the catechol derivative is 5mg to 10g, and/or the content of the polyamine is 5mg to 10g, and/or the content of the polyvinylidene fluoride is 5g to 25g, based on 100mL of the organic solvent in the mixed solution; preferably, the first and second electrodes are formed of a metal,
the catechol derivative is selected from at least one of dopamine, catechol, tannic acid and juglone; and/or
The polyamine is selected from at least one of polyethyleneimine, gamma-amino propylene triethoxysilane and amino-cage polysilsesquioxane; and/or
The organic solvent is at least one selected from N-methyl pyrrolidone, N '-dimethylformamide, N' -dimethylacetamide, triethyl phosphate, trimethyl phosphate and dimethyl sulfoxide.
6. The production method according to claim 4 or 5,
in the step 1b), the mixed solution is coated on the surface of non-woven fabric, so that the mixed solution forms a liquid film; and/or
In the step 1c), the method for inducing the liquid film to generate the phase separation by using the water vapor comprises the steps of exposing the liquid film to air with the humidity of 60-100% for 5 s-2 h; and/or
In step 1d), the alcohol used in the alcohol bath treatment is selected from C1-C4Preferably at least one of methanol, ethanol, isopropanol and n-butanol; and/or the salt solution adopted in the salt bath treatment is at least one of a sodium chloride aqueous solution, a potassium chloride aqueous solution, a magnesium sulfate aqueous solution and a sodium sulfate aqueous solution.
7. The production method according to any one of claims 4 to 6, wherein, in step 2),
soaking the porous support membrane in a water phase solution containing a water phase monomer for 0.5-10 min, then soaking in an oil phase solution containing an oil phase monomer for 10 s-5 min, then taking out, and carrying out heat treatment, thereby forming a polyamide layer on the porous support membrane;
preferably, the concentration of the aqueous phase monomer in the aqueous phase solution is 0.2 g/L-10 g/L; the solvent of the aqueous phase solution is water; and/or
In the oil phase solution, the concentration of the oil phase monomer is 0.2 g/L-10 g/L; the solvent of the oil phase solution is n-hexane.
8. The production method according to any one of claims 4 to 7, wherein, in step 3),
soaking the porous support membrane with the polyamide layer in a reaction solution containing an amphoteric ionization reagent at the temperature of 35-45 ℃ for 2-24 h, thereby forming an amphoteric ion layer on the polyamide layer; preferably, the first and second electrodes are formed of a metal,
the concentration of the zwitterionic reagent in the reaction solution is 10 g/L-100 g/L; the solvent of the reaction solution is preferably ethanol.
9. A forward osmosis treatment system comprising:
a semipermeable membrane unit formed by the amphoteric composite forward osmosis membrane according to any one of claims 1 to 3 or the amphoteric composite forward osmosis membrane prepared by the preparation method according to any one of claims 4 to 8, a first region and a second region partitioned by the semipermeable membrane unit, a supply section for supplying a low osmotic pressure supply liquid to the first region, a supply section for supplying a high osmotic pressure draw liquid to the second region, and a transmembrane fluid flow from the first region to the second region driven by an osmotic pressure difference across the semipermeable membrane.
10. A method of sewage treatment or seawater desalination comprising: use of the forward osmosis treatment system of claim 9 to recover water from the high osmotic pressure draw after moving water from the low osmotic pressure contaminated water or from the low osmotic pressure seawater to the high osmotic pressure draw.
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