CN111686592A - Composite nanofiltration membrane and preparation method thereof - Google Patents
Composite nanofiltration membrane and preparation method thereof Download PDFInfo
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- B01D71/06—Organic material
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Abstract
The invention provides a high-flux composite nanofiltration membrane and a preparation method thereof, wherein a polysulfonamide desalting layer is obtained by interfacial polymerization reaction of polybasic sulfonyl chloride, chlorinated trimellitic anhydride and polyamine so as to improve the acid resistance of the nanofiltration membrane. The chlorinated trimellitic anhydride serving as an additive is added into the oil phase solution to participate in interfacial reaction, so that the porosity of a generated desalting layer can be increased, the finally prepared composite nanofiltration membrane has good acid resistance and high pure water flux, and the preparation process is simple, easy to implement, easy to realize industrialization and wide in application prospect.
Description
Technical Field
The invention relates to a composite nanofiltration membrane and a preparation method thereof, in particular to an acid-resistant composite nanofiltration membrane and a preparation method thereof.
Background
Nanofiltration separation technology is used as a new branch of membrane technology, and has increasingly utility in modern chemical production. In the technical field of membrane separation, compared with a common nanofiltration membrane, the composite nanofiltration membrane has the advantages of good permeability, strong pressure tightness, good selective separation performance and the like due to the unique morphological structure and is widely applied. However, with the development of industry, the systems to be separated become diversified and complicated, and the separation membrane is required to have not only good separation selectivity but also a certain physicochemical stability to maintain a stable separation effect for a long time.
At present, mixed strong acid type waste liquid is often not available, and when such waste liquid is treated by a membrane separation technique, separation membranes such as common Polyamide (PA), Cellulose Acetate (CA) and the like are insufficient due to poor acid resistance. Therefore, the selection of acid-resistant membrane materials, the optimization of membrane preparation processes, and membrane modification have become key factors in solving the above problems.
The pH tolerance range of common composite nanofiltration membranes such as polyamide membranes, cellulose acetate membranes and some commercial membranes is generally 3-10, and the phenomena of chemical bond breakage, membrane microstructure degradation and the like are easily caused when strong-acid feed liquid is treated, so that the separation performance of the membranes is influenced, and the engineering cost is increased by frequently replacing the separation membranes. The Polysulfonamide (PSA) is a high polymer material similar to polyamide, has a pH tolerance range of 1-10, and has good acid resistance. In addition, the whole molecule has a strong conjugation effect, and the sulfonamide bond has excellent hydrolysis resistance relative to an amido bond, so that the polysulfonamide composite nanofiltration membrane has excellent acid resistance and good separation performance, and has good application value in the aspect of preparing the acid-resistant composite nanofiltration membrane.
However, the water flux of the current acid-resistant nanofiltration membrane is generally low, and patent CN105289305A discloses a preparation method of a high-flux acid-resistant nanofiltration membrane, wherein the pure water flux of the prepared nanofiltration membrane under 0.5Mpa is 2.1L/m2h. The pure water flux of the acid-resistant nanofiltration membrane at 0.5MPa is 10-15L/m reported in pHstable thin film composite polymer membranes by interfacial polymerization2h. Therefore, how to improve the acid resistance of the nanofiltration membrane and improve the water flux of the nanofiltration membrane needs to be further researched.
Disclosure of Invention
In order to solve the problems, the invention provides a composite nanofiltration membrane with acid resistance and high flux and a preparation method thereof.
The invention provides a composite nanofiltration membrane which comprises a base membrane and a separation layer, wherein the separation layer is a polysulfonamide layer, and raw materials of the polysulfonamide layer comprise polyamine monomers, polybasic sulfonyl chloride monomers and chlorinated trimellitic anhydride.
The polysulfonamide generated by interfacial polymerization reaction of polyamine and polybasic sulfonyl chloride has strong acid resistance, but the generated polyamide layer has high crosslinking degree and too compact separation layer due to high functionality of the polybasic sulfonyl chloride, and although the polyamide layer has good interception effect, the water flux is seriously influenced. According to the invention, chlorinated trimellitic anhydride is used as an additive to be added into an organic solution, and due to the low functionality, the interface polymerization reaction between a part of polyamine monomers in a water phase and polysulfonamide in an oil phase can be limited, so that the crosslinking degree of a network structure of a separation layer is reduced, the structure of the separation layer is looser, the hydrophilicity and the charge density of a filter membrane can be increased, and the pure water flux of the nanofiltration membrane is obviously improved while the desalting rate is ensured.
According to one embodiment, the mass ratio of the polyamine monomer to the polybasic sulfonyl chloride monomer is 1: 1-4: 1; in one embodiment, the mass ratio of the polyamine monomer to the polybasic sulfonyl chloride monomer is 1: 1-2: 1.
According to one embodiment, the mass ratio of the polybasic sulfonyl chloride monomer to the chlorinated trimellitic anhydride is 10: 1-100: 1; in one embodiment, the mass ratio of the polybasic sulfonyl chloride monomer to the chlorinated trimellitic anhydride is 20: 1-40: 1 or 40: 1-60: 1.
In one embodiment, the polyamine monomer is at least one selected from the group consisting of polyethyleneimine, piperazine, m-phenylenediamine, tetraethylenepentamine and polyvinylamine. As an embodiment, the polyamine monomer is selected from piperazine. By combining the preparation method and the preparation raw materials, the aqueous phase solution prepared from the piperazine has higher stability, can be placed for a long time, and is more beneficial to industrial production.
In one embodiment, the polybasic acid chloride monomer is at least one selected from the group consisting of 1,3, 6-naphthalene trisulfonyl chloride, 1, 6-naphthalene disulfonyl chloride, 2, 6-naphthalene disulfonyl chloride, and 2, 7-naphthalene disulfonyl chloride. As an embodiment, the polybasic acid chloride monomer is selected from 1,3, 6-naphthalene trisulfonyl chloride. By combining the preparation method and the preparation raw materials, the 1,3, 6-naphthalene trisulfonyl chloride has lower cost and is more beneficial to industrial production.
In one embodiment, the base film is made of at least one material selected from polysulfone, polyethersulfone, polytetrafluoroethylene, and polyvinylidene fluoride. As an embodiment, the base film is selected from polytetrafluoroethylene. By combining the preparation method and the preparation raw materials, the polytetrafluoroethylene has better corrosion resistance. The polyethersulfone, polytetrafluoroethylene and polyvinylidene fluoride three base membranes can be purchased from Hangzhou Anno filter equipment, Inc., and have molecular weight cut-off of 10 ten thousand Da, 3 ten thousand Da and 5 ten thousand Da respectively; the preparation method of the polysulfone-based membrane is detailed in the specific embodiment, and the molecular weight cut-off of the polysulfone-based membrane is 5 ten thousand Da.
In one embodiment, the molecular weight cut-off of the base film is 3 to 10 ten thousand Da. In one embodiment, the molecular weight cut-off of the base film is 3 to 5 ten thousand Da. In the invention, if the molecular weight cut-off of the base membrane is too small, namely the aperture of the base membrane is too small, the pure water flux of the obtained composite nanofiltration membrane is too small; if the trapped molecular weight of the base membrane is too large, namely the aperture of the base membrane is too large, the supporting force on the desalting layer is weakened, and the desalting performance of the composite nanofiltration membrane is unstable. The molecular weight cut-off of the base membrane optimized in the invention can enable the obtained composite nanofiltration membrane to achieve the technical effect of the invention.
In the invention, the desalting layer is a polysulfonamide layer.
As an embodiment, the pure water flux of the composite nanofiltration membrane is more than or equal to 24L/m under the conditions that the temperature is 25 ℃ and the pressure is 0.5MPa2h。
In one embodiment, the composite nanofiltration membrane is used for treating Na with the concentration of 0.2g/L under the conditions that the temperature is 25 ℃ and the pressure is 0.5MPa2SO4The salt rejection rate is more than or equal to 80 percent. The cross-linking degree of a network structure of the separation layer can be properly reduced due to larger ionic radius when ions with more than two valences are intercepted, so that the water flux is improved while the desalination rate is ensured2SO4Water flux in saline solution.
The invention provides a preparation method of a composite nanofiltration membrane, wherein a polysulfonamide layer is formed by interfacial polymerization of a polyamine monomer, a polybasic sulfonyl chloride monomer and chlorinated trimellitic anhydride.
The invention provides a preparation method of a composite nanofiltration membrane, which comprises the following steps:
(1) mixing polyamine monomer with water to obtain water phase solution;
(2) mixing a polybasic acyl chloride monomer, chlorinated trimellitic anhydride and an organic solvent to obtain an oil phase solution;
(3) providing a base film, and immersing the base film into an aqueous solution to obtain a coated base film;
(4) and (4) taking the base membrane coated in the step (3) out, immersing the base membrane into the oil phase solution, taking out and drying to obtain the composite nanofiltration membrane.
In the step (1), the polyamine monomer, the surfactant, the acid-binding agent and the water can also be mixed to obtain an aqueous solution.
In one embodiment, the surfactant in step (1) is at least one selected from the group consisting of sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium dodecylbenzenesulfonate, tetrabutylammonium bromide and cetyltrimethylammonium chloride. In one embodiment, the surfactant in step (1) is selected from sodium dodecyl sulfate. In the invention, the surfactant can increase the surface wettability of the basement membrane and is beneficial to uniformly spreading the water phase on the surface of the basement membrane. In addition, the diffusion rate of the water phase monomer into the oil phase in the interfacial polymerization reaction can be increased, thereby increasing the reaction rate.
In one embodiment, in the step (1), the acid-binding agent is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, triethylamine, and 4-dimethylaminopyridine. In one embodiment, the acid scavenger in step (1) is selected from sodium bicarbonate. In the invention, the acid-binding agent can neutralize acid generated by interfacial reaction and promote the continuous proceeding of interfacial polymerization reaction.
In one embodiment, the content of the polyamine monomer in the aqueous phase solution in the step (1) is 0.1% to 1.0% (w/w). In one embodiment, the content of the polyamine monomer in the aqueous phase solution in the step (1) is 0.1% to 0.5% (w/w). In the invention, when the content of the polyamine is too high, the reaction rate of the polyamine monomer and the polybasic acyl chloride on the surface of the base membrane is too high, and the generated desalting layer is too compact, so that the pure water flux of the composite nanofiltration membrane is greatly reduced; when the content of the polyamine is too small, the reaction rate of the polyamine monomer and the polybasic acyl chloride on the surface of the base membrane is too slow, the generated desalting layer is too loose, and the desalting rate is greatly reduced although the pure water flux of the composite nanofiltration membrane is ensured.
In one embodiment, the content of the surfactant in the aqueous phase solution in the step (1) is 0.01% to 1.0% (w/w). In one embodiment, the content of the surfactant in the aqueous phase solution in the step (1) is 0.05% to 0.5% (w/w). In the invention, when the content of the surfactant is too large, the diffusion rate of the water phase monomer is too high, so that the interfacial polymerization reaction is too high, and the generated desalting layer is too compact; when the content of the surfactant is too small, it cannot effectively function to increase wettability of the base film and diffusion rate of the aqueous phase monomer.
In one embodiment, the content of the acid-binding agent in the aqueous phase solution in the step (1) is 0.01-0.5% (w/w). In one embodiment, the content of the acid-binding agent in the aqueous phase solution in the step (1) is 0.05-0.1% (w/w). In the invention, when the content of the acid-binding agent is too large, the progress of interfacial polymerization reaction is inhibited; when the acid scavenger content is too small, the acid generated during the interfacial polymerization reaction cannot be sufficiently neutralized.
As an embodiment, the organic solvent in the step (2) is at least one selected from the group consisting of Isopar G, Isopar E, Isopar H, Isopar L, Isopar M, n-hexane, toluene and cyclohexane. In one embodiment, the organic solvent in step (2) is Isopar G. The Isopar G, Isopar E, Isopar H, Isopar L and Isopar M (Exxon Mobil, Inc. from the manufacturer) are isoalkanes. Compared with other alkanes, Isopar isoparaffin has the advantages of no odor, safety and environmental protection; wherein Isopar G not only has good volatilization speed, but also has higher flash point, so the safety is higher and the drying is easy, and the method is more suitable for industrial production.
In one embodiment, the content of the polyacyl chloride monomer in the oil phase solution in the step (2) is 0.05% to 1.0% (w/w). In one embodiment, the content of the polyacyl chloride monomer in the oil phase solution in the step (2) is 0.1% to 0.5% (w/w). In the invention, when the content of the polyacyl chloride is too large, the reaction rate of the polyamine monomer and the polyacyl chloride on the surface of the base membrane is too high, and the generated desalting layer is too compact, so that the pure water flux of the composite nanofiltration membrane is greatly reduced; when the content of the polyacyl chloride is too small, the reaction rate of the polyamine monomer and the polyacyl chloride on the surface of the base membrane is too slow, the generated desalting layer is too loose, and the desalting rate is greatly reduced although the pure water flux of the composite nanofiltration membrane is ensured.
In one embodiment, the content of the chlorinated trimellitic anhydride in the oil phase solution in the step (2) is 0.001% to 0.1% (w/w). In one embodiment, the content of the chlorinated trimellitic anhydride in the oil phase solution in the step (2) is 0.005% to 0.05% (w/w). When the content of the chlorinated trimellitic anhydride is too large, the structure of a generated desalting layer is too loose, so that the desalting rate is reduced; when the content of the chlorinated trimellitic anhydride is too small, the effect of reducing the degree of crosslinking of the desalted layer cannot be exerted. The invention controls the porosity of the desalting layer by controlling the ratio of the polybasic acyl chloride to the chlorinated trimellitic anhydride, and further controls the pure water flux and the desalting rate of the composite nanofiltration membrane.
In one embodiment, the basement membrane in step (3) is soaked in clear water and then taken out and soaked in the aqueous solution. In the invention, the base membrane is soaked in clear water, so that residual impurities on the base membrane can be removed, the influence of the impurities on the interfacial polymerization reaction is reduced, and the pure water flux and the desalination rate of the prepared composite nanofiltration membrane are further improved.
In one embodiment, the basement membrane is soaked in clear water for 5-24 hours.
In one embodiment, the step (3) is immersed in the aqueous solution for 0.5-20 min; and (4) the immersion time in the step (3) is 5-10 min.
In one embodiment, the base film coated in step (4) is primarily dried and then immersed in the oil phase solution.
As an embodiment, the primary drying temperature is 10 to 50 ℃; the primary drying time is 2-15 min. As an embodiment, the primary drying temperature is 20 to 40 ℃; the primary drying time is 5-10 min.
In one embodiment, the immersion time in the step (4) is 0.5-5.0 min; the drying temperature is 60-120 ℃; the drying time is 1-15 min.
In one embodiment, the immersion time in the step (4) is 1-3 min; the drying temperature is 80-110 ℃; the drying time is 2-10 min.
In the invention, the primary drying in the step (4) is low-temperature drying, and aims to remove redundant water drops on the surface of the basement membrane so as to keep the interface between a water phase and an oil phase smooth, ensure the shape of the finally generated desalting layer to be regular and better ensure the separation performance of the membrane. The drying in the step (4) is high-temperature drying, and the purpose of the drying is to promote interfacial polymerization reaction of the oil phase and the water phase, so that the obtained desalting layer can realize uniform coating.
The invention controls the rate of polymerization reaction between the water phase and the oil phase interface by adjusting the contents of the surfactant, the acid-binding agent, the polyamine and the polybasic acyl chloride, adjusts the crosslinking degree of a desalting layer network structure by adjusting the content of the chlorinated trimellitic anhydride, and controls the porosity of a generated desalting layer in a synergistic way, thereby further improving the pure water flux and the desalting rate of the composite nanofiltration membrane.
The% (w/w) as referred to herein means% (g/g), e.g., 1% (g/g) means that 0.01g of solute is added per 1g of solvent during the preparation.
The invention has the technical effects that:
the composite nanofiltration membrane is prepared by utilizing the excellent acid resistance of the polysulfonamide and the function of adjusting the degree of crosslinking of the network structure of the separation layer by using the trimellitic anhydride chloride, so that the problem of poor acid resistance of a common separation membrane is solved. The generated desalting layer is looser by adding the chlorinated trimellitic anhydride additive into the organic solution, and the hydrophilicity and the charge density of the filter membrane can be increased, so that the pure water flux of the nanofiltration membrane is obviously improved while the desalting rate of the nanofiltration membrane is ensured.
Detailed Description
The following specific examples describe the present invention in detail, however, the present invention is not limited to the following examples.
Preparation of polysulfone-based membranes
(1) Weighing 18 wt% of polysulfone, 72 wt% of N, N-dimethylacetamide and 10 wt% of polyethylene glycol with the molecular weight of 800;
(2) adding polysulfone into N, N-dimethylacetamide at 110 ℃, and stirring for 8 hours until the solution is clear; then adding polyethylene glycol, and stirring for 8h at 50 ℃ to form a membrane casting solution;
(3) filtering the membrane casting solution;
(4) carrying out vacuum defoaming treatment on the filtered membrane casting solution at 30 ℃ for 24 h;
(5) preparing the membrane from the membrane casting solution and polyester non-woven fabric on a membrane coating machine, standing the membrane in air with the temperature of 25-30 ℃ and the humidity of 70-80% for 2-3min, transferring the membrane into a deionized water coagulating bath for solidification, and soaking the membrane in deionized water to obtain the polysulfone ultrafiltration membrane.
Preparation of (II) composite nanofiltration membrane
The prepared composite nanofiltration membranes are pre-pressed for half an hour by pure water under 0.5MPa, and the pure water flux of the membranes is respectively tested by the pure water, and 0.5g/L Na is used2SO4The electrolyte solution of (2) was tested for salt rejection at 25 ℃.
The calculation formula of the pure water flux is shown in (1).
Wherein A ═ π DL (A-effective membrane area, m)2(ii) a D-average diameter of membrane filaments, m; l-the effective length of the membrane filaments, m); t-time required for collecting Q volume of produced fluid, h; q-volume of product fluid collected over time t, L.
The salt rejection calculation method is shown in (2).
Wherein R is the salt rejection of the membrane, Cf-the conductivity of the stock solution,. mu.S/cm; cpConductivity of the produced water,. mu.S/cm.
And (3) repeatedly measuring the composite nanofiltration membrane for 3 times, and taking an average value to obtain the desalination rate of the composite nanofiltration membrane.
Example 1:
(1) mixing 0.25g of piperazine, 0.1g of sodium dodecyl sulfate and 0.075g of triethylamine with 100g of deionized water to obtain an aqueous phase solution;
(2) mixing 0.15G of 1,3, 6-naphthalene trisulfonyl chloride, 0.005G of trimellitic anhydride chloride and 100G of Isopar G to obtain an oil phase solution;
(3) providing a polysulfone ultrafiltration basement membrane with the molecular weight cutoff of 5 ten thousand Da, and immersing the basement membrane into an aqueous solution to obtain a coated basement membrane;
(4) and (4) taking out the base membrane coated in the step (3) after 5 minutes, drying the base membrane at 30 ℃ for 5 minutes, immersing the base membrane into the oil phase solution, taking out the base membrane after 2 minutes, and drying the base membrane at 120 ℃ for 5 minutes to obtain the composite nanofiltration membrane.
And (3) testing results: placing the obtained composite nanofiltration membrane in 10 wt% of H2SO4Soaking in water solution for 10 hr, and testing at 25 deg.C and 0.5Mpa to obtain pure water flux of 26L/m2h, salt rejection of 83%.
Example 2:
(1) mixing 1g of piperazine with 100g of deionized water to obtain an aqueous phase solution;
(2) 0.25g of 1,3, 6-naphthalene trisulfonyl chloride, 0.015g of trimellitic anhydride chloride and 100g of cyclohexane are mixed to obtain an oil phase solution;
(3) providing a polysulfone based membrane with a molecular weight cut-off of 5 ten thousand Da, and immersing the base membrane into an aqueous solution to obtain a coated base membrane;
(4) and (4) taking out the base membrane coated in the step (3) after 5 minutes, drying the base membrane at 30 ℃ for 5 minutes, immersing the base membrane into the oil phase solution, taking out the base membrane after 1 minute, and drying the base membrane at 100 ℃ for 10 minutes to obtain the composite nanofiltration membrane.
And (3) testing results: placing the obtained composite nanofiltration membrane in 10 wt% of H2SO4Soaking in water solution for 10 hr, and testing at 25 deg.C and 0.5Mpa to obtain pure water flux of 26L/m2h, salt rejection of 80%.
Example 3:
(1) mixing 0.15g of tetraethylenepentamine, 0.1g of sodium dodecyl benzene sulfonate and 0.075g of triethylamine with 100g of deionized water to obtain an aqueous phase solution;
(2) mixing 0.15G of 1,3, 6-naphthalene trisulfonyl chloride, 0.005G of trimellitic anhydride chloride and 100G of Isopar G to obtain an oil phase solution;
(3) providing a polysulfone ultrafiltration basement membrane with the molecular weight cutoff of 5 ten thousand Da, and immersing the basement membrane into an aqueous solution to obtain a coated basement membrane;
(4) and (4) taking out the base membrane coated in the step (3) after 5 minutes, drying the base membrane at 30 ℃ for 5 minutes, immersing the base membrane into the oil phase solution, taking out the base membrane after 2 minutes, and drying the base membrane at 120 ℃ for 5 minutes to obtain the composite nanofiltration membrane.
And (3) testing results: placing the obtained composite nanofiltration membrane in 10 wt% of H2SO4Soaking in water solution for 10 hr, and testing at 25 deg.C and 0.5Mpa to obtain pure water flux of 24L/m2h, salt rejection of 84%.
Example 4:
(1) mixing 0.1g of polyethyleneimine, 1g of tetrabutylammonium bromide, 0.01g of sodium hydroxide and 100g of deionized water to obtain an aqueous phase solution;
(2) mixing 0.1g of 1, 6-naphthalene disulfonyl chloride, 0.001g of chlorinated trimellitic anhydride and 100g of n-hexane to obtain an oil phase solution;
(3) providing a polyvinylidene fluoride ultrafiltration base membrane with the molecular weight cutoff of 3 ten thousand Da, and immersing the base membrane into an aqueous phase solution to obtain a coated base membrane;
(4) and (4) taking out the base membrane coated in the step (3) after 20 minutes, drying the base membrane at 50 ℃ for 2 minutes, immersing the base membrane into the oil phase solution, taking out the base membrane after 2 minutes, and drying the base membrane at 120 ℃ for 5 minutes to obtain the composite nanofiltration membrane.
And (3) testing results: will be provided withPlacing the obtained composite nanofiltration membrane in 10 wt% of H2SO4Soaking in water solution for 10 hr, and testing at 25 deg.C and 0.5Mpa to obtain pure water flux of 28L/m2h, salt rejection of 83%.
Example 5:
(1) mixing 1g of m-phenylenediamine, 0.01g of sodium dodecyl benzene sulfonate, 0.5g of sodium bicarbonate and 100g of deionized water to obtain an aqueous solution;
(2) mixing 0.5g of 2, 7-naphthalene disulfonyl chloride, 0.05g of chlorinated trimellitic anhydride and 100g of cyclohexane to obtain an oil phase solution;
(3) providing a polytetrafluoroethylene ultrafiltration basement membrane with the molecular weight cutoff of 3 ten thousand Da, and immersing the basement membrane into an aqueous phase solution to obtain a coated basement membrane;
(4) and (4) taking out the base membrane coated in the step (3) after 0.5 minute, drying the base membrane at 10 ℃ for 15 minutes, immersing the base membrane into the oil phase solution, taking out the base membrane after 0.5 minute, and drying the base membrane at 80 ℃ for 15 minutes to obtain the composite nanofiltration membrane.
And (3) testing results: placing the obtained composite nanofiltration membrane in 10 wt% of H2SO4Soaking in water solution for 10 hr, and testing at 25 deg.C and 0.5Mpa to obtain pure water flux of 24L/m2h, salt rejection of 86%.
Example 6:
(1) mixing 1g of polyvinylamine, 0.1g of 4-dimethylaminopyridine and 0.05g of potassium carbonate with 100g of deionized water to obtain an aqueous phase solution;
(2) mixing 0.25g of 2, 6-naphthalene disulfonyl chloride, 0.01g of chlorinated trimellitic anhydride and 100g of cyclohexane to obtain an oil phase solution;
(3) providing a polyether sulfone ultrafiltration basement membrane with the molecular weight cutoff of 10 ten thousand Da, and immersing the basement membrane into an aqueous phase solution to obtain a coated basement membrane;
(4) and (4) taking out the base membrane coated in the step (3) after 20 minutes, drying the base membrane at 30 ℃ for 5 minutes, immersing the base membrane into the oil phase solution, taking out the base membrane after 1 minute, and drying the base membrane at 100 ℃ for 10 minutes to obtain the composite nanofiltration membrane.
And (3) testing results: placing the obtained composite nanofiltration membrane in 10 wt% of H2SO4Soaking in water solution for 10 hr, and testing at 25 deg.C and 0.5Mpa to obtain pure water flux of 26L/m2h, salt rejection of 84%.
Comparative example 1:
(1) mixing 0.25g of piperazine, 0.1g of sodium dodecyl sulfate and 0.075g of triethylamine with 100g of deionized water to obtain an aqueous phase solution;
(2) mixing 1,3, 5-benzenetricarbonyl chloride (0.15G) with isopar G (100G) to obtain an oil phase solution;
(3) providing a polysulfone ultrafiltration basement membrane with the molecular weight cutoff of 5 ten thousand Da, and immersing the basement membrane into an aqueous solution to obtain a coated basement membrane;
(4) and (4) taking out the base membrane coated in the step (3) after 5 minutes, drying the base membrane at 30 ℃ for 5 minutes, immersing the base membrane into the oil phase solution, taking out the base membrane after 2 minutes, and drying the base membrane at 120 ℃ for 5 minutes to obtain the composite nanofiltration membrane.
And (3) testing results: placing the obtained composite nanofiltration membrane in 10 wt% of H2SO4Soaking in water solution for 10 hr, and testing at 25 deg.C and 0.5Mpa to obtain pure water flux of 93L/m2h, salt rejection of 21%.
Comparative example 2:
(1) mixing 0.25g of piperazine, 0.1g of sodium dodecyl sulfate and 0.075g of triethylamine with 100g of deionized water to obtain an aqueous phase solution;
(2) mixing 1,3, 6-naphthalene trisulfonyl chloride (0.15G) with Isopar G (100G) to obtain an oil phase solution;
(3) providing a polysulfone ultrafiltration basement membrane with the molecular weight cutoff of 5 ten thousand Da, and immersing the basement membrane into an aqueous solution to obtain a coated basement membrane;
(4) and (4) taking out the base membrane coated in the step (3) after 5 minutes, drying the base membrane at 30 ℃ for 5 minutes, immersing the base membrane into the oil phase solution, taking out the base membrane after 2 minutes, and drying the base membrane at 120 ℃ for 5 minutes to obtain the composite nanofiltration membrane.
And (3) testing results: placing the obtained composite nanofiltration membrane in 10 wt% of H2SO4Soaking in water solution for 10 hr, and testing at 25 deg.C and 0.5Mpa to obtain pure water flux of 16L/m2h, salt rejection of 83%.
As can be seen from the comparison of comparative examples 1 and 2, the same amount of H was added at 10 wt%2SO4After the nanofiltration membrane is soaked in the aqueous solution for 10 hours, compared with a common polyamide membrane, the polysulfonamide nanofiltration membrane prepared by using polysulfonyl chloride has the advantages that the desalination rate is greatly improved, and good acid resistance is shown. As can be seen from the comparison results of comparative example 2 and examples 1 to 6, the pure water flux of the composite nanofiltration membrane after the addition of the chlorinated trimellitic anhydride is remarkably improved while the salt rejection rate is maintained.
Claims (22)
1. The composite nanofiltration membrane comprises a base membrane and a separation layer, wherein the separation layer is a polysulfonamide layer, and is characterized in that the raw materials of the polysulfonamide layer comprise polyamine monomers, polybasic sulfonyl chloride monomers and chlorinated trimellitic anhydride.
2. The composite nanofiltration membrane of claim 1, wherein the mass ratio of the polyamine monomer to the polysulfonyl chloride monomer is 1: 1-4: 1.
3. The composite nanofiltration membrane according to claim 1, wherein the mass ratio of the polybasic sulfonyl chloride monomer to the chlorinated trimellitic anhydride is 10: 1-100: 1.
4. The composite nanofiltration membrane of claim 1, wherein the polyamine monomer is selected from at least one of polyethyleneimine, piperazine, m-phenylenediamine, tetraethylenepentamine, and polyvinylamine.
5. The composite nanofiltration membrane according to claim 1, wherein the polybasic acid chloride monomer is at least one selected from the group consisting of 1,3, 6-naphthalene trisulfonyl chloride, 1, 6-naphthalene disulfonyl chloride, 2, 6-naphthalene disulfonyl chloride, and 2, 7-naphthalene disulfonyl chloride.
6. The composite nanofiltration membrane according to claim 1, wherein the raw material of the basement membrane is at least one selected from polysulfone, polyethersulfone, polytetrafluoroethylene and polyvinylidene fluoride.
7. The composite nanofiltration membrane of claim 1, wherein the molecular weight cut-off of the base membrane is between 3 and 10 million Da.
8. The composite nanofiltration membrane of claim 1, wherein the pure water flux of the composite nanofiltration membrane is not less than 24L/m at a temperature of 25 ℃ and a pressure of 0.5MPa2h。
9. The composite nanofiltration membrane of claim 1, wherein the composite nanofiltration membrane is applied to Na with a concentration of 0.2g/L at a temperature of 25 ℃ and a pressure of 0.5MPa2SO4The salt rejection rate is more than or equal to 80 percent.
10. The method for preparing a composite nanofiltration membrane according to claim 1, wherein the polysulfonamide layer is formed by interfacial polymerization of a polyamine monomer, a polysulfonyl chloride monomer and chlorinated trimellitic anhydride.
11. The method of claim 10, comprising the steps of:
(1) mixing polyamine monomer with water to obtain water phase solution;
(2) mixing a polybasic acyl chloride monomer, chlorinated trimellitic anhydride and an organic solvent to obtain an oil phase solution;
(3) providing a base film, and immersing the base film into an aqueous solution to obtain a coated base film;
(4) and (4) taking the base membrane coated in the step (3) out, immersing the base membrane into the oil phase solution, taking out and drying to obtain the composite nanofiltration membrane.
12. The method of claim 11, wherein in the step (1), the polyamine monomer, the surfactant, and the acid-binding agent are mixed with water to obtain an aqueous solution.
13. The method of claim 12, wherein the surfactant in step (1) is at least one selected from the group consisting of sodium dodecylbenzenesulfonate, sodium dodecylsulfate, tetrabutylammonium bromide and cetyltrimethylammonium chloride.
14. The method of claim 12, wherein in step (1), the acid scavenger is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, triethylamine, and 4-dimethylaminopyridine.
15. The method according to claim 11, wherein the content of the polyamine monomer in the aqueous solution of the step (1) is 0.1% to 1.0% (w/w).
16. The method according to claim 11, wherein the organic solvent in the step (2) is at least one selected from the group consisting of Isopar g, Isopar E, Isopar H, Isopar L, Isopar M, n-hexane, toluene and cyclohexane.
17. The method according to claim 11, wherein the content of the polybasic acid chloride monomer in the oil phase solution of step (2) is 0.05% to 1.0% (w/w).
18. The production method according to claim 11, wherein the content of the chlorinated trimellitic anhydride in the oil phase solution in the step (2) is 0.001% to 0.1% (w/w).
19. The preparation method according to claim 11, wherein the basement membrane in the step (3) is soaked in clear water and then taken out and soaked in the aqueous solution, and the soaking time is 5-24 hours.
20. The method according to claim 11, wherein the immersion time in step (3) is 0.5 to 20 min.
21. The method of claim 11, wherein the base film coated in the step (4) is primarily dried and then immersed in the oil phase solution.
22. The method according to claim 11, wherein the immersion time in the step (4) is 0.5-5 min; the drying temperature is 60-120 ℃; the drying time is 1-15 min.
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| CN113559728A (en) * | 2021-07-22 | 2021-10-29 | 中国乐凯集团有限公司 | Acid-resistant composite nanofiltration membrane and preparation method thereof |
| CN114225708A (en) * | 2021-12-08 | 2022-03-25 | 中海油节能环保服务有限公司 | Super-hydrophilic oleophobic separation membrane for oil-water separation and preparation method thereof |
| CN114367203A (en) * | 2022-01-17 | 2022-04-19 | 上海乐纯生物技术有限公司 | Composite ultrafiltration membrane and manufacturing method thereof |
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