CN111939775A - Preparation method of solvent-resistant reverse osmosis composite membrane - Google Patents
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Abstract
The invention discloses a method for preparing a solvent-resistant polyamide composite membrane by utilizing a photocatalytic modification technology. More specifically, inorganic photocatalytic nano materials are introduced into a polysulfone bottom membrane and a polyamide ultrathin composite layer in the composite membrane, and free radicals are generated by ultraviolet illumination or electron beam irradiation to improve the crosslinking degree in each layer and between interface layers of the composite membrane, so that the composite membrane has better solvent resistance than a pure polyamide composite membrane, and meanwhile, the oxidation resistance and high temperature resistance are also improved.
Description
Technical Field
The invention belongs to the technical field of preparation of separation membrane materials, relates to a preparation method of a reverse osmosis composite membrane, and particularly relates to a preparation method of a solvent-resistant and high-temperature-resistant Polyamide (PA) reverse osmosis composite membrane.
Background
Energy and environmental issues, including the safe water crisis, global warming, and energy supply atrophy, have attracted considerable attention in recent years. To date, various technologies have been initially explored to obtain clean water, capture "greenhouse" gases, and find alternative energy sources. Membrane separation has become one of the most important technologies by solving some of the pressing problems described above. Membrane separation Technology is becoming more and more important in the separation industry, applicable to the separation of various molecular weight components in the gas or liquid phase, with the particular advantage that no heating is required and therefore the energy usage is much lower than in conventional thermal separation processes (Basic Principles of Membrane Technology, second edition, m.mulder, Kluwer academic press, Dordrecht, p 564). The membrane separation comprises microfiltration, ultrafiltration, nanofiltration and reverse osmosis, and Reverse Osmosis (RO) is the most widely applied seawater desalination technology in the world at present, and compared with other technologies, the efficiency is higher, the cost is lower, and the reverse osmosis accounts for 65% of the total amount of all seawater desalination devices in the world.
The performance of RO membranes depends to a large extent on the membrane material and structure, and most commercial RO membranes are Thin Film Composites (TFCs) made of polymers with high mechanical, thermal and chemical stability. The composite membranes currently widely used in the water treatment industry mainly adopt an interfacial polymerization mode to compound a polyamide film on the surface of a microporous support basement membrane. The general process is described in detail in the original us patent 4277344. Firstly, polysulfone is coated on polyester non-woven fabric to form a microporous base membrane, the microporous base membrane is immersed into a diamine or polyamine aqueous solution, then excess amine solution on the surface of the membrane is removed by methods of wind showering, rolling and the like, and the microporous base membrane is immersed into an organic nonpolar solution of polyacyl chloride to perform interfacial polymerization reaction with acyl chloride, so that a compact polyamide ultrathin active layer with a separation function is formed on the surface, and after film formation, full washing and proper heat curing treatment can be performed to improve the membrane performance. Polysulfone in the polyamide composite membrane structure is a non-crosslinked linear structure, so that in the process of treating wastewater containing organic solvents, particularly solvents of polysulfone materials such as amides, alkanones and sulfoxides, the solvents have swelling effect on the polysulfone, membrane pores are greatly shrunk, and water flux is rapidly attenuated. The same problem exists in the treatment of high temperature wastewater, which greatly limits the application range of polyamide composite membranes.
Therefore, there is an urgent need for a solvent-resistant and high-temperature-resistant separation membrane technology that is energy-saving and environmentally friendly.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problem that the solvent resistance and high temperature resistance of a reverse osmosis membrane limit the application range of the reverse osmosis membrane, the invention aims to provide a preparation method of a solvent-resistant high temperature-resistant reverse osmosis composite membrane; the inorganic photocatalytic nano material is introduced into the membrane layer by the method, and free radicals are generated by illumination to perform oxidation-reduction reaction, so that the membrane has better structural stability than a pure polymer reverse osmosis membrane, and the hydrophilicity and the pollution resistance of the membrane are improved.
The technical scheme is as follows: the invention provides a preparation method of a solvent-resistant polyamide reverse osmosis composite membrane, which comprises the following steps:
(1) preparing a Dimethylformamide (DMF) solution containing an inorganic photocatalytic nano material and polysulfone, coating the solution on the surface of non-woven fabric by using a scraper or an extrusion method to form a wet polysulfone film, staying in the air for a period of time, and then entering a coagulating tank of a pure water coagulating bath to form a porous polysulfone support film;
(2) contacting the porous polysulfone support membrane prepared in the step (1) with an aqueous solution (water phase) containing an inorganic photocatalytic nano material and a monomer m-phenylenediamine; removing the excessive m-phenylenediamine solution on the surface of the porous polysulfone support membrane, and then reacting the m-phenylenediamine solution with a normal hexane solution (organic phase) containing an inorganic photocatalytic nano material and monomer trimesoyl chloride to form a membrane containing a polyamide layer; and removing the trimesoyl chloride solution which is not completely reacted on the surface of the membrane containing the polyamide layer by using excessive n-hexane, and carrying out heat treatment to obtain the solvent-resistant Polyamide (PA) reverse osmosis composite membrane.
In the step (1) and the step (2), the inorganic photocatalytic nano material is one or more of TiO2, La2O3, CeO2, MnO2, ZrO2, ZnO, SnO2, ZnS, CuS, FeS, Ag2S, CdS, C3N4 and modified compounds thereof; preferably, the modified compound is graphene oxide modified TiO2 nanoparticles with a chemical formula of TiO2GO-TiO2NPs。
In the step (1), in a Dimethylformamide (DMF) solution containing the inorganic photocatalytic nano material and polysulfone: polysulfone (PSF) is used as a membrane material, Dimethylformamide (DMF) is used as a solvent, and the weight percentage of the Polysulfone (PSF) is 13-19 wt%; the inorganic photocatalytic nanomaterial is 0-5wt%, preferably 0.1-5.0wt%, and more preferably 0.3-2.0 wt% of the total amount of polysulfone and dimethylformamide.
In the step (1), when the wet polysulfone film stays in the air and/or after the polysulfone film leaves a coagulation tank of a pure water coagulation bath, an ultraviolet lamp or an electron accelerator is used for irradiating; the time of staying in the air is 2-30 s.
Preferably, the wavelength of the ultraviolet lamp is 157-436nm, the irradiation is carried out for 5-600s, and the distance from the light source to the surface of the film is 0.5-1000 mm; the electron accelerator has energy of 1KeV-5MeV, and irradiates for 1-300s, and the distance from the light source to the surface of the film is 0.5-1000 mm.
In the step (2), in the aqueous solution containing the inorganic photocatalytic nano material and the monomer m-phenylenediamine, the concentration of the m-phenylenediamine is 1.5 to 3.0wt%, and the content of the inorganic photocatalytic nano material is 0 to 0.2wt%, preferably 0.005 to 0.1wt%, and more preferably 0.01 to 0.1 wt%; reacting in the solution for 10-120 s.
In the step (2), in the n-hexane solution containing the inorganic photocatalytic nano material and the monomer trimesoyl chloride, the concentration of the trimesoyl chloride is 0.05 to 0.20 weight percent, the content of the inorganic photocatalytic nano material is 0 to 0.2 weight percent, preferably 0.005 to 0.1 weight percent, and more preferably 0.01 to 0.1 weight percent; reacting in the solution for 5-30 s.
In the step (2), the heat treatment temperature is 50-120 ℃, and the heat treatment time is 1-10 min.
In the step (2), after excessive m-phenylenediamine solution on the surface of the porous polysulfone support membrane reacts with n-hexane solution (organic phase) containing inorganic photocatalytic nano material and monomer trimesoyl chloride, and/or after heat treatment, an ultraviolet lamp or an electron accelerator is used for irradiation.
Preferably, the wavelength of the ultraviolet lamp is 248-365nm, the irradiation is carried out for 5-600s, and the distance from the light source to the surface of the membrane is 0.5-1000 mm; the electron accelerator has energy of 1KeV-5MeV, and irradiates for 1-300s, and the distance from the light source to the surface of the film is 0.5-1000 mm.
The invention also provides a solvent-resistant reverse osmosis composite membrane, which comprises a polyamide layer and a polysulfone layer which are mutually connected in an abutting mode, wherein the polyamide layer and the polysulfone layer are internally dispersed with photoactive nano-particles respectively.
Has the advantages that:
the invention provides a preparation method of a solvent-resistant reverse osmosis composite membrane, wherein a Polyamide (PA) thin layer is synthesized by interfacial polymerization of m-phenylenediamine and trimesoyl chloride. The inorganic photocatalytic nano material is introduced into the membrane layer, and free radicals are generated by illumination to form a cross-linked structure between polysulfone molecules or between the polysulfone molecules and polyamide molecules, so that the polysulfone molecules or the polyamide molecules have better structural stability than a general reverse osmosis membrane, and the solvent resistance and the high temperature resistance of the composite membrane are improved.
Second, surface modification allows for improved dispersion of metal oxide nanoparticles in the relevant solution, such as GO modified TiO compared TO ordinary TO2 nanoparticles2The nano particles can obtain better dispersibility in the polysulfone membrane casting solution and the monomer solution in the compounding process.
Drawings
FIG. 1 is a schematic structural view of a solvent-resistant polyamide reverse osmosis composite membrane;
FIG. 2 is a process diagram of a porous polysulfone support membrane forming process;
FIG. 3 is a diagram of a process for forming a solvent-resistant Polyamide (PA) reverse osmosis composite membrane;
fig. 4 is a synthesis scheme of graphene oxide modified TiO2 nanoparticles;
FIG. 5 is an electron micrograph of a cross section of a composite film obtained in comparative example (top) and example 8 (bottom);
FIG. 6 is an AFM photograph of the surface of the composite films obtained in comparative example (top) and example 8 (bottom).
Detailed Description
The following are preferred embodiments of the present invention, which are intended to be illustrative only and not limiting, and all changes and modifications which come within the meaning and range of equivalency of the claims are to be embraced therein:
the preparation method of the graphene oxide modified TiO2 nano-particles comprises the following steps:
and pouring a certain amount of graphene oxide into a beaker filled with 50 mL of deionized water, rapidly stirring, sealing the beaker by using a sealing film, and putting the beaker into an ultrasonic instrument for 2 hours of ultrasonic treatment. Then transferring a certain amount of hydrochloric acid (HCL) and sulfuric acid (H) by using a transfer pipette2SO4) Titanium tetrachloride (TiCl)4) Adding the solution into the above water solution, magnetically stirring for 1 hr, and ultrasonic treating for 30 min. And transferring the ultrasonic solution into an inner container of a polytetrafluoroethylene hydrothermal kettle, and carrying out hydrothermal treatment at 180 ℃ for 24 hours. After the water is heated, the mixture is washed to be neutral for a plurality of times. Freeze drying for 24 h. The test piece is placed in a dry environment for standby.
Preparing a support base film doped with graphene oxide modified TiO2 nanoparticles:
mixing a certain amount of polysulfone resin (PSF) and the synthesized GO-TiO2And dissolving and dispersing NPs in dimethyl formamide (DMF) with a certain mass, stirring at 60 ℃ until PSF is completely dissolved, and defoaming in vacuum at room temperature for 8 hours. Coating the defoamed casting solution uniformly onPreparing a thin layer of casting film liquid with a certain thickness on a non-woven fabric with the thickness of 100um, soaking the thin layer of casting film liquid into a constant-temperature gel bath (pure water) after the thin layer of casting film liquid is kept for a period of time at room temperature, washing the thin layer of casting film liquid in another pure water for a certain period of time, and rolling the thin layer of casting film liquid for later.
Preparing a graphene oxide modified TiO2 nanoparticle doped polyamide composite membrane:
preparing a certain amount of nano particles, m-phenylenediamine and water into a transparent aqueous solution; preparing a certain amount of nano particles, trimesoyl chloride and anhydrous n-hexane water into a transparent organic solution; soaking the basement membrane in a m-phenylenediamine solution for a certain time, then taking out, removing the excessive m-phenylenediamine solution on the surface of the basement membrane, and then contacting and reacting with a trimesoyl chloride solution for a certain time to form a membrane containing a polyamide layer; and removing the incompletely reacted trimesoyl chloride solution on the surface of the membrane containing the polyamide layer by using excessive n-hexane, then carrying out heat treatment curing, washing and rolling to obtain the polyamide reverse osmosis composite membrane.
Example 1: 2wt% of GO-TiO2NPs were dispersed in the casting solution containing 18wt% of polysulfone and 80 wt% of dimethylformamide, and the other base films were manufactured and compounded under the same conditions as in the comparative example, and the results are shown in Table 1. The rejection rate of NaCl after DMF treatment is 95.1%, and the water flux is 0.70M3/M2D. The detailed results and the DMF insoluble solids content are shown in Table 1.
Example 2: other film formation conditions were the same as in example 1, and the polysulfone wet film was irradiated with a deuterium ultraviolet lamp (254 nm) for 20 seconds before entering a pure water coagulation bath. The test conditions are the same as the comparative example, the rejection rate of NaCl after DMF treatment is 97.9 percent, and the water flux is 0.87M3/M2D. The detailed results and the DMF insoluble solids content are shown in Table 1.
Example 3: other film forming conditions were the same as in example 1, and the polysulfone film was irradiated with a deuterium ultraviolet lamp for 120 seconds while being put into a pure water coagulation bath. The test conditions are the same as the comparative example, the rejection rate of NaCl after DMF treatment is 98.2 percent, and the water flux is 0.92M3/M2D. The detailed results and the DMF insoluble solids content are shown in Table 1.
Example 4: other film formation conditions were the same as in example 3, and after the composite film formation, the surface of the film was irradiated with a deuterium ultraviolet lamp for 120 seconds before heating and curing. The test conditions are the same as the comparative example, the rejection rate of NaCl after DMF treatment is 98.4 percent, and the water flux is 0.98M3/M2D. The detailed results and the DMF insoluble solids content are shown in Table 1.
Example 5: other film forming conditions were the same as in example 3, and the surface of the composite film was irradiated with a deuterium ultraviolet lamp (254 nm) for 60 seconds during film formation. The test conditions are the same as the comparative example, the rejection rate of NaCl after DMF treatment is 98.2 percent, and the water flux is 1.23M3/M2D. The detailed results and the DMF insoluble solids content are shown in Table 1.
Example 6: the polysulfone film was exposed to an electron accelerator of 10KeV for 120 seconds while being put into a pure water coagulation bath under the same conditions as in example 1. The test conditions were the same as the comparative example, and the rejection rate of NaCl after DMF treatment was 97.5%, and the water flux was 1.02M3/M2D. The detailed results and the DMF insoluble solids content are shown in Table 1.
Example 7: the other film formation conditions were the same as in example 6, and the surface of the film was irradiated with an electron accelerator of 10KeV for 200 seconds in the composite film formation washing process. The test conditions were the same as the comparative example, and the rejection rate of NaCl after DMF treatment was 95.2%, and the water flux was 1.45M3/M2D. The detailed results and the DMF insoluble solids content are shown in Table 1.
Example 8: the conditions for preparing the polysulfone base membrane are the same as those in example 3, and the water phase monomer of the composite membrane contains 0.02 percent of GO-TiO2NPs and 2% m-phenylenediamine, organic phase monomer containing 0.01% TiO2Nano particles and 0.1% trimesoyl chloride, and irradiating the surface of the composite membrane for 600 seconds by using a deuterium ultraviolet lamp in the cleaning process of the composite membrane. The test conditions were the same as the comparative example, and the rejection rate of NaCl after DMF treatment was 97.3%, and the water flux was 1.45M3/M2D. The detailed results and the DMF insoluble solids content are shown in Table 1.
Examples 9-17 show the solvent resistance of composite films obtained with different types and amounts of photoactive material additives and different irradiation conditions, detailed in Table 1.
Comparative example 18% by weight ofPolysulfone is dissolved in 82wt% N, N-dimethyl formamide solvent, heated and stirred until the polysulfone is completely dissolved, and the solution is cooled to room temperature after vacuum defoaming. And scraping a wet film with the thickness of about 150 microns on the surface of the polyester non-woven fabric with the thickness of 100 microns through a film casting machine, staying in air for a certain time, and immersing into a pure water coagulating bath to form a polysulfone supporting basement membrane with the thickness of about 60 microns. The polysulfone base film was immersed in an aqueous solution containing 2.0% m-phenylenediamine for 2 minutes, and the surface was pressed to a half-dry state with a rubber roll and then immersed in a 0.1% n-hexane solution of trimesoyl chloride for 20 seconds. Taken out and put into a container 110oC, treating the membrane in an oven for 10 minutes, and then thoroughly cleaning the membrane with an alkaline solution, an acid solution, an alcohol solution and pure water in sequence to test the performance of the membrane. The composite film obtained in this comparative example was found to be 25oC, under the test conditions of 1000ppm NaCl aqueous solution, 1.5MPa pressure and 15% recovery rate (referred to as the standard test conditions), the rejection rate of NaCl is 99.0%, and the water flux is 1.1M3/M2D. The membrane was cycled in an aqueous solution containing 10000ppm DMF at a pressure of 1.0MPa above and a recovery of 15% for 24 hours, and after washing with pure water for 1 hour, the rejection of NaCl was reduced to 94.0% and the flux of water was 0.63M, as measured by standard test conditions3/M2D. The detailed results and the DMF insoluble solids content are shown in Table 1.
Film Performance testing
The reverse osmosis membrane sheets prepared in examples 1 to 3 and the comparative example were prepared into 4040 standard roll-type membrane elements, and a reverse osmosis operation experiment was performed to test the corresponding salt rejection and water flux.
Initial conditions were tested: 1000ppm NaCl in water, operating pressure 150psi, recovery 15%. The pure water flux is a water flux at a standard temperature (25 ℃ C.) corrected by a temperature coefficient.
Test for solvent resistance
4040 the membrane element was cleaned with pure water at 60Psi for 30min, and then with pure water containing 1% DMF and 1000ppm NaCl at an operating pressure of 150Psi with a 15% recovery. The pure water flux is the water flux at the standard temperature (25 ℃) after being corrected by the temperature coefficient and is continuously tested for 24 hours, and the water flux and the salt rejection are recorded and calculated.
Detection of DMF insoluble solid content in composite film
The composite film was carefully peeled from the nonwoven layer, dried in a 100C vacuum oven for 4 hours, weighed accurately (W1 g), and wrapped with a clean dry nickel mesh of known weight (W0 g). The samples were placed in a soxhlet extractor with 6 samples per set of extractor. Adding 200ml DMF, heating and refluxing for more than 48 hours, taking out the sample after the solvent is cooled to room temperature, placing the sample in a beaker, and washing the sample by using a proper amount of absolute ethyl alcohol. Drying in an oven at 100 deg.C for more than 4 hr, taking out the sample, cooling in a drier for more than 30min, and accurately weighing the total weight W of nickel mesh and gel2。
DMF insoluble solids content = (W)2–W0）/W1×100%
The DMF insoluble components in the composite membrane comprise a polyamide layer, inorganic nano particles and gel generated after irradiation.
TABLE 1
Claims (11)
1. A preparation method of a solvent-resistant polyamide reverse osmosis composite membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing a Dimethylformamide (DMF) solution containing an inorganic photocatalytic nano material and polysulfone, coating the solution on the surface of non-woven fabric by using a scraper or an extrusion method to form a wet polysulfone film, staying in the air for a period of time, and then entering a coagulating tank of a pure water coagulating bath to form a porous polysulfone support film;
(2) contacting the porous polysulfone support membrane prepared in the step (1) with an aqueous solution (water phase) containing an inorganic photocatalytic nano material and a monomer m-phenylenediamine; removing the excessive m-phenylenediamine solution on the surface of the porous polysulfone support membrane, and then reacting the m-phenylenediamine solution with a normal hexane solution (organic phase) containing an inorganic photocatalytic nano material and monomer trimesoyl chloride to form a membrane containing a polyamide layer; and removing the trimesoyl chloride solution which is not completely reacted on the surface of the membrane containing the polyamide layer by using excessive n-hexane, and carrying out heat treatment to obtain the solvent-resistant Polyamide (PA) reverse osmosis composite membrane.
2. The method for preparing a solvent-resistant polyamide reverse osmosis composite membrane according to claim 1, wherein the method comprises the following steps: in the step (1) and the step (2), the inorganic photocatalytic nano material is one or more of TiO2, La2O3, CeO2, MnO2, ZrO2, ZnO, SnO2, ZnS, CuS, FeS, Ag2S, CdS, C3N4 and modified compounds thereof; preferably, the modified compound is graphene oxide modified TiO2 nanoparticles, and the expression is GO-TiO2NPs。
3. The method for preparing a solvent-resistant polyamide reverse osmosis composite membrane according to claim 1, wherein the method comprises the following steps: in the step (1), in a Dimethylformamide (DMF) solution containing the inorganic photocatalytic nano material and polysulfone: polysulfone (PSF) is used as a membrane material, Dimethylformamide (DMF) is used as a solvent, and the content of the Polysulfone (PSF) accounts for 13-19 wt% of the total amount of the polysulfone and the dimethylformamide; the inorganic photocatalytic nanomaterial is 0-5wt%, preferably 0.1-5.0wt%, and more preferably 0.3-2.0 wt% of the total amount of polysulfone and dimethylformamide.
4. The method for preparing a solvent-resistant polyamide reverse osmosis composite membrane according to claim 1, wherein the method comprises the following steps: in the step (1), when the wet polysulfone film stays in the air and/or after the polysulfone film leaves a coagulation tank of a pure water coagulation bath, an ultraviolet lamp or an electron accelerator is used for irradiating; the time of staying in the air is 1-30 s.
5. The method for preparing a solvent-resistant polyamide reverse osmosis composite membrane according to claim 4, wherein the method comprises the following steps: the wavelength of the ultraviolet lamp is 157-436nm, the irradiation is carried out for 5-600s, and the distance from the light source to the surface of the film is 0.5-1000 mm; the electron accelerator has energy of 1KeV-5MeV, and irradiates for 1-300s, and the distance from the light source to the surface of the film is 0.5-1000 mm.
6. The method for preparing a solvent-resistant polyamide reverse osmosis composite membrane according to claim 1, wherein the method comprises the following steps: in the step (2), in the aqueous solution containing the inorganic photocatalytic nano material and the monomer m-phenylenediamine, the concentration of the m-phenylenediamine is 1.5 to 3.0wt%, and the content of the inorganic photocatalytic nano material is 0 to 0.2wt%, preferably 0.005 to 0.1wt%, and more preferably 0.01 to 0.1 wt%; reacting in the solution for 10-120 s.
7. The method for preparing a solvent-resistant polyamide reverse osmosis composite membrane according to claim 1, wherein the method comprises the following steps: in the step (2), in the n-hexane solution containing the inorganic photocatalytic nano material and the monomer trimesoyl chloride, the concentration of the trimesoyl chloride is 0.05 to 0.20 weight percent, the content of the inorganic photocatalytic nano material is 0 to 0.2 weight percent, preferably 0.005 to 0.1 weight percent, and more preferably 0.01 to 0.1 weight percent; reacting in the solution for 5-30 s.
8. The method for preparing a solvent-resistant polyamide reverse osmosis composite membrane according to claim 1, wherein the method comprises the following steps: in the step (2), the heat treatment temperature is 50-120 ℃, and the heat treatment time is 1-10 min.
9. The method for preparing a solvent-resistant polyamide reverse osmosis composite membrane according to claim 1, wherein the method comprises the following steps: in the step (2), after excessive m-phenylenediamine solution on the surface of the porous polysulfone support membrane reacts with n-hexane solution (organic phase) containing inorganic photocatalytic nano material and monomer trimesoyl chloride, and/or after heat treatment, an ultraviolet lamp or an electron accelerator is used for irradiation.
10. The method for preparing a solvent-resistant polyamide reverse osmosis composite membrane according to claim 9, wherein the method comprises the following steps: the wavelength of the ultraviolet lamp is 157-436nm, the irradiation is carried out for 5-600s, and the distance from the light source to the surface of the film is 0.5-1000 mm; the electron accelerator has energy of 1KeV-5MeV, and irradiates for 1-300s, and the distance from the light source to the surface of the film is 0.5-1000 mm.
11. A solvent-resistant reverse osmosis composite membrane is characterized in that: the light-activated nano particle material comprises a polyamide layer and a polysulfone layer which are mutually abutted, wherein light-activated nano particles are dispersed in the polyamide layer and the polysulfone layer respectively.
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