CN111097294B - Preparation method of nanofiltration membrane for reclaimed water treatment - Google Patents
Preparation method of nanofiltration membrane for reclaimed water treatment Download PDFInfo
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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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0095—Drying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- 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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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Abstract
The invention relates to the field of preparation of semipermeable membranes, and discloses a preparation method of a nanofiltration membrane for reclaimed water treatment, which comprises the following steps: adding polyacyl chloride into an oil phase solvent, namely ethylcyclohexane, and preparing an oil phase solution, wherein the mass concentration of the polyacyl chloride in the oil phase solution is 0.1-0.2%; adding polyamine and a water-soluble additive into deionized water to prepare an aqueous phase solution, wherein the mass concentration of the polyamine in the aqueous phase solution is 0.2-0.4%, and the mass concentration of the water-soluble additive is 0.05-2%; respectively carrying out contact reaction on the supporting base film with the water phase solution and the oil phase solution to obtain a pretreated membrane; and cleaning the pretreated membrane, soaking in glycerol and drying to obtain the nanofiltration membrane. According to the invention, the water-soluble additive is added into the aqueous phase solution, so that the polyamide functional layer with large aperture and high free volume is easily formed, and the water flux can be effectively improved while the retention rate of the nanofiltration membrane on organic polyethylene glycol is ensured.
Description
Technical Field
The invention relates to the field of preparation of semipermeable membranes, in particular to a preparation method of a nanofiltration membrane for reclaimed water treatment.
Background
The nanofiltration membrane is a novel separation semipermeable membrane which is produced in the late 80 s, has the molecular weight cutoff between a reverse osmosis membrane and an ultrafiltration membrane, is about 200 plus 2000Da, and can cut off nano-scale (0.001 micron) substances. Nanofiltration membrane separation is generally carried out at normal temperature, has no phase change, no chemical reaction and no damage to biological activity, can effectively intercept divalent and high-valent ions and small molecules with relative molecular mass higher than 200, so that a large part of monovalent inorganic salt permeates, similar amino acid and protein can be separated, separation of high molecular weight and low molecular weight organic matters is realized, and the cost is lower than that of the traditional process.
Although the nanofiltration semipermeable membrane has various advantages in the field of water treatment, including the fields of underground water hardness removal, surface water organic matter removal, chromaticity, organic and inorganic liquid separation and concentration, dye purification, concentration and desalination, natural medicine separation and concentration and the like, the nanofiltration semipermeable membrane has wide application prospect, but the nanofiltration membrane of various manufacturers in the market generally has low water flux, and the water flux is seriously attenuated along with the prolonging of the service time. In order to solve the phenomenon, a new high-flux nanofiltration membrane needs to be developed. In the process of preparing the high-flux nanofiltration membrane, a plurality of researchers add assistants or nanoparticles into the water phase and the oil phase to increase the hydrophilicity of the membrane surface and the effective area of the membrane, so that the flux is improved, and meanwhile, the antibacterial performance of the membrane is improved.
For example, a "functional monomer of membrane containing hexafluoroisopropanol group and a method for preparing the nanofiltration membrane" disclosed in the chinese patent literature, whose publication No. CN102527265B, first designs and synthesizes a class of 1-hydroxy-1-trifluoromethyl-2, 2, 2-trifluoroethyl dianiline compounds as additives to be added into an aqueous phase, and a fluorine-containing nanofiltration membrane is obtained by interfacial polymerization, and the prepared nanofiltration semipermeable membrane has good interception effect and high flux on divalent salt ions, and has strong tolerance on free chlorine.
The publication No. CN106621850A discloses that firstly, attapulgite-nano silver composite inorganic powder is prepared and mixed into an oil phase solution, so that the polyamide nanofiltration membrane containing the attapulgite-nano silver composite inorganic powder is prepared through interfacial polymerization.
However, some methods of the researchers still have certain defects, namely the nanofiltration membrane cannot reach high water flux, the lifting amplitude is small, the cost and the treatment process difficulty are increased, meanwhile, a loose desalting layer is generated due to side reactions of other small molecules introduced in the reaction, the density of the desalting layer is reduced, the molecular interception of the membrane is obviously reduced, and therefore the membrane performance lifting effect is not obvious. And the practical long-term and stable production cannot be met.
Disclosure of Invention
The invention provides a preparation method of a nanofiltration membrane for treating regenerated water, which aims to overcome the problems that when the flux of a nanofiltration membrane in the prior art is low and is seriously attenuated along with the prolonging of service time, the flux is improved by adding an auxiliary agent or nanoparticles into a water-oil phase, the improvement amplitude is small, the cost and the treatment process difficulty are increased, and the side reaction of other small molecules can be introduced to generate a loose desalting layer, the density of the desalting layer is reduced, so that the molecular rejection rate of the membrane is obviously reduced, and the practical long-term and stable production cannot be met.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nanofiltration membrane for reclaimed water treatment comprises the following steps:
(1) preparing an oil phase solution: adding polyacyl chloride into an oil phase solvent, namely ethylcyclohexane, and stirring and dissolving to obtain an oil phase solution, wherein the mass concentration of the polyacyl chloride in the oil phase solution is 0.1-0.2%;
(2) preparing an aqueous solution: respectively adding polyamine and a water-soluble additive with different solubility with the polyamine in the oil phase solution into deionized water, and uniformly stirring to obtain a water phase solution, wherein the mass concentration of the polyamine in the water phase solution is 0.2-0.4%, and the mass concentration of the water-soluble additive is 0.05-2%;
(3) contact reaction: pouring the water phase solution onto the supporting base film, pouring out the redundant water phase solution on the supporting base film after soaking, and blowing clean the redundant water phase solution on the surface and the back of the supporting base film until no water drops exist on the surface of the supporting base film; then contacting the surface of the supporting base film with an oil phase solution, and obtaining a pretreatment membrane after contact reaction;
(4) and (3) post-treatment: and pre-drying and cleaning the pre-treated membrane, soaking in glycerol, and finally drying to obtain the nanofiltration membrane.
According to the method, the nanofiltration membrane is prepared by utilizing the interfacial polymerization reaction of the water phase solution and the oil phase solution, the polyamine and the water-soluble additive in the water phase solution and the polybasic acyl chloride in the oil phase solution can generate the interfacial polymerization reaction on the surface of the supporting base membrane to generate the ultrathin polyamide functional layer with the selective separation function, the supporting base membrane enables the prepared nanofiltration membrane to have good strength and pressure tightness, and the polyamide functional layer enables the prepared nanofiltration membrane to have good selective permeability.
In the reaction process, the generated polyamide layer can hinder the diffusion process of the polyamine and the added water-soluble additive from the water phase to the oil, so that the diffusion rate of the two monomers in the water phase is reduced, the density of the polyamide layer is also continuously improved along with the thickening of the reaction, the diffusion of the water-phase monomer is further prevented, and the polymerization reaction rate is reduced. If the water-soluble additive is not added, the generated polyamide functional layer is too dense, so that the water flux of the nanofiltration membrane is low, and the use requirement is not met.
According to the method, a certain mass of water-soluble additive is added when the water-phase solution is prepared in the step (2), and due to the fact that the solubility of the polyamine and the water-soluble additive in the oil phase is different, the molecular structure characteristics and the steric hindrance are different, the activity of the formed polyamide functional layer is different, so that the polyamide functional layer with large aperture and high free volume is easy to form after the water-soluble additive is added in the water-phase solution, and the water flux of the nanofiltration membrane can be effectively improved. The compactness of the polyamide functional layer is lower along with the increase of the adding amount of the water-soluble additive, and if the amount of the water-soluble additive is too large, the water flux of the nanofiltration membrane is improved, but the rejection rate is insufficient. The water-soluble additive with proper addition amount is adopted, the water flux and the molecular rejection rate of the prepared nanofiltration membrane are both good, and the practical long-term and stable production can be met in the treatment process of the reclaimed water.
In the step (3), the supporting base membrane is soaked by the water-phase solution to enable the surface and the pores of the supporting base membrane to be rich in the water-phase solution, then the supporting base membrane is contacted with the oil-phase solution to enable the water-phase solution and the oil-phase solution to carry out interfacial polymerization reaction to generate an ultrathin polyamide functional layer, and selective permeability is endowed to the nanofiltration membrane. And (4) finally, after the post-treatment in the step (4), accelerating interfacial polymerization, improving the overall crosslinking degree of polyamide, and completely volatilizing an oil phase solvent, wherein the finally prepared nanofiltration membrane has good strength, pressure tightness, organic substance interception rate and water flux.
Preferably, the polyamine in step (2) is piperazine. Piperazine is diamine containing aliphatic chains, molecular chains of piperazine are softer, and a polyamide functional layer with large aperture and high free volume is easy to form, so that the prepared nanofiltration membrane has good permeability.
Preferably, the water-soluble additive in step (2) is: 3, 5-dimethyl-1, 2-phenylenediamine, 2, 5-diaminotoluene dihydrochloride, 4-methoxy-m-phenylenediamine, 4-bromo-o-phenylenediamine, 4-bromo-3-fluoro-1, 2-phenylenediamine, 2-nitro-1, 4-phenylenediamine, N-methyl-4, 4 '-methylenedianiline, N-methyl-1, 2-phenylenediamine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, N-isopropylethylenediamine, m-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 4' -diaminodiphenylamine, melamine, pentamethyldiethylenetriamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, 1,3, 5-triaminobenzene, 1,2, 4-triaminobenzene, di-and tri-aminotoluene, 2,4, 6-triaminopyrimidine, 2,4, 5-triaminopyrimidine, 4,5, 6-triaminopyrimidine, 2,4,5, 6-tetraaminopyrimidine. The substances are selected as water-soluble additives, have different solubilities with polyamine in an oil phase solution and have different molecular structures and steric hindrance with polyamine, so that a polyamide functional layer with large aperture and high free volume is easily formed, and the water flux of the nanofiltration membrane is effectively improved.
Preferably, after dissolving the polyamine and the water-soluble additive in the step (2), hydrochloric acid or sodium hydroxide solution is added to adjust the pH value of the aqueous phase solution to 2-12. Within the pH range, the prepared nanofiltration membrane has optimal performance.
Preferably, the polybasic acid chloride in the step (1) is trimesoyl chloride. Trimesoyl chloride is selected as an oil phase solution, and can be subjected to interface reaction with polyamine and a water-soluble additive, so that a polyamide functional layer with large aperture and high free volume is effectively generated.
Preferably, the supporting base membrane in the step (3) is a porous polysulfone supporting base membrane. The porous polysulfone is used as a supporting base film, so that the prepared nanofiltration membrane has good strength and pressure tightness.
Preferably, the soaking time of the supporting base membrane and the aqueous phase solution in the step (3) is 10-30 s. Within the time range, the method can ensure full infiltration on the premise of high production efficiency, so that the surface of the supporting base film and the film pores are rich in aqueous phase solution, and the subsequent contact reaction is facilitated.
Preferably, the contact reaction time of the supporting base membrane with the oil phase solution in the step (3) is 10 to 30 s. In the contact reaction time, the water phase solution and the oil phase solution can generate an interface reaction to generate an ultrathin polyamide functional layer, and the polyamide functional layer is not fully generated in too short time, so that the selective permeability of the nanofiltration membrane is influenced; too long a time results in too thick a polyamide functional layer, which reduces the performance of the film.
Preferably, the post-treatment step in step (4) is: pre-drying the membrane after contact reaction in a drying oven at 50-70 deg.C for 1-2min, washing with 70-90 deg.C hot water for 4-6min, taking out, soaking in 7-9% glycerol for 1-3min, and oven drying at 50-70 deg.C. Firstly, pre-drying the membrane subjected to the contact reaction for a period of time, on one hand, accelerating interfacial polymerization and improving the overall crosslinking degree of polyamide, on the other hand, volatilizing an oil phase solvent and terminating the interfacial polymerization reaction; then soaking the membrane in glycerol to prevent the membrane pores from shrinking to reduce water flux; and finally, carrying out final drying to obtain the nanofiltration membrane with excellent performance.
Therefore, the beneficial effects of the invention are as follows: the method comprises the steps of preparing a nanofiltration membrane by utilizing an interfacial polymerization reaction of a water phase solution and an oil phase solution, wherein polyamine and a water-soluble additive in the water phase solution and polyacyl chloride in the oil phase solution can generate an interfacial polymerization reaction on the surface of a supporting base membrane to generate an ultrathin polyamide functional layer with a selective separation function, and after the water-soluble additive is added in the water phase solution, the polyamide functional layer with large aperture and high free volume is easy to form due to the difference of solubility, molecular structure characteristics and steric hindrance of the polyamine and the water-soluble additive in the oil phase, so that the water flux of the nanofiltration membrane can be effectively improved, and the retention rate of organic matters cannot be reduced by controlling the addition quality of the water-soluble additive.
Detailed Description
The invention is further described with reference to specific embodiments.
Example 1:
a preparation method of a nanofiltration membrane for reclaimed water treatment comprises the following steps:
(1) preparing an oil phase solution: adding trimesoyl chloride into an oil phase solvent, namely ethylcyclohexane, and stirring and dissolving to obtain an oil phase solution, wherein the mass concentration of the trimesoyl chloride in the oil phase solution is 0.15%;
(2) preparing an aqueous solution: adding piperazine and m-xylylenediamine into deionized water respectively, stirring at high speed for 0.5h until the piperazine and the m-xylylenediamine are completely dissolved, adding hydrochloric acid to adjust the pH value of the solution to 4, and stirring uniformly to obtain an aqueous phase solution, wherein the mass concentration of the piperazine in the aqueous phase solution is 0.3%, and the mass concentration of the m-xylylenediamine in the aqueous phase solution is 0.2%;
(3) contact reaction: pouring the water phase solution on the porous polysulfone support base membrane, after the water phase solution is contacted for 20s, pouring the redundant water phase solution on the porous polysulfone support base membrane, and blowing the redundant water phase solution on the surface and the back surface of the porous polysulfone support base membrane by using an air knife to clean, wherein no water drop exists on the surface of the porous polysulfone support base membrane; then contacting the surface of the porous polysulfone support base membrane with an oil phase solution, and carrying out contact reaction for 20s to obtain a pretreated membrane;
(4) and (3) post-treatment: predrying the membrane subjected to the contact reaction in a drying oven at 60 ℃ for 1min, washing with hot water at 80 ℃ for 5min, taking out, soaking in glycerol with the mass concentration of 8% for 2min, taking out, and drying at 60 ℃ to obtain the nanofiltration membrane.
Example 2:
example 2 differs from example 1 in that hydrochloric acid was added in step (2) of example 2 to adjust the pH of the solution to 2, and the rest was the same as in example 1.
Example 3:
example 3 differs from example 1 in that hydrochloric acid was added in step (2) of example 3 to adjust the pH of the solution to 5, and the rest was the same as in example 1.
Example 4:
example 4 is different from example 1 in that hydrochloric acid was added to adjust the pH of the solution to 7 in step (2) of example 4, and the rest was the same as in example 1.
Example 5:
example 5 differs from example 1 in that the pH of the solution was adjusted to 9 by adding sodium hydroxide solution in step (2) of example 5, and the rest is the same as in example 1.
Example 6:
example 6 differs from example 1 in that the pH of the solution was adjusted to 12 by adding sodium hydroxide solution in step (2) of example 6, and the rest is the same as in example 1.
Example 7:
example 7 is different from example 1 in that the mass concentration of xylylenediamine in the aqueous solution of example 7 was 0.05%, and the other points are the same as those in example 1.
Example 8:
example 8 is different from example 1 in that the mass concentration of xylylenediamine in the aqueous solution of example 8 was 0.12%, and the other points are the same as those in example 1.
Example 9:
example 9 is different from example 1 in that the mass concentration of xylylenediamine in the aqueous solution of example 9 was 0.16%, and the other points are the same as those in example 1.
Example 10:
example 10 is different from example 1 in that the mass concentration of xylylenediamine in the aqueous solution of example 10 was 0.25%, and the other points are the same as those in example 1.
Example 11:
example 11 is different from example 1 in that the mass concentration of xylylenediamine in the aqueous solution of example 11 was 0.35%, and the other points are the same as those in example 1.
Example 12:
example 12 is different from example 1 in that the mass concentration of xylylenediamine in the aqueous solution of example 12 was 0.5%, and the other points are the same as those in example 1.
Example 13:
example 13 is different from example 1 in that the mass concentration of xylylenediamine in the aqueous solution of example 13 was 2%, and the other points are the same as those in example 1.
Example 14:
(1) preparing an oil phase solution: adding trimesoyl chloride into an oil phase solvent, namely ethylcyclohexane, and stirring and dissolving to obtain an oil phase solution, wherein the mass concentration of the polybasic acyl chloride in the oil phase solution is 0.1%;
(2) preparing an aqueous solution: adding piperazine and 3, 5-dimethyl-1, 2-phenylenediamine into deionized water respectively, stirring at a high speed for 0.5h until the piperazine and the 3, 5-dimethyl-1, 2-phenylenediamine are completely dissolved, adding hydrochloric acid to adjust the pH value of the solution to 4, and stirring uniformly to obtain an aqueous phase solution, wherein the mass concentration of the piperazine in the aqueous phase solution is 0.2%, and the mass concentration of the 3, 5-dimethyl-1, 2-phenylenediamine in the aqueous phase solution is 0.2%;
(3) contact reaction: pouring the water phase solution on the porous polysulfone support base membrane, after the water phase solution is contacted for 10s, pouring the redundant water phase solution on the porous polysulfone support base membrane, and blowing the redundant water phase solution on the surface and the back surface of the porous polysulfone support base membrane clean by using an air knife, wherein no water drop exists on the surface of the porous polysulfone support base membrane; then contacting the surface of the porous polysulfone support base membrane with an oil phase solution, and carrying out contact reaction for 10s to obtain a pretreated membrane;
(4) and (3) post-treatment: predrying the membrane subjected to the contact reaction in a drying oven at 50 ℃ for 2min, washing with hot water at 70 ℃ for 6min, taking out, soaking in glycerol with the mass concentration of 7% for 3min, taking out, and drying at 50 ℃ to obtain the nanofiltration membrane.
Example 15:
(1) preparing an oil phase solution: adding trimesoyl chloride into an oil phase solvent, namely ethylcyclohexane, and stirring and dissolving to obtain an oil phase solution, wherein the mass concentration of the polybasic acyl chloride in the oil phase solution is 0.2%;
(2) preparing an aqueous solution: adding piperazine and 2, 5-diaminotoluene dihydrochloride into deionized water respectively, stirring at a high speed for 0.5h until the piperazine and the 2, 5-diaminotoluene dihydrochloride are completely dissolved, adding hydrochloric acid to adjust the pH value of the solution to 4, and stirring uniformly to obtain an aqueous phase solution, wherein the mass concentration of piperazine in the aqueous phase solution is 0.2%, and the mass concentration of 2, 5-diaminotoluene dihydrochloride is 0.2%;
(3) contact reaction: pouring the water phase solution on the porous polysulfone support base membrane, after the water phase solution is contacted for 30s, pouring the redundant water phase solution on the porous polysulfone support base membrane, and blowing the redundant water phase solution on the surface and the back surface of the porous polysulfone support base membrane by using an air knife to clean, wherein no water drop exists on the surface of the porous polysulfone support base membrane; then contacting the surface of the porous polysulfone support base membrane with an oil phase solution, and obtaining a pretreated membrane after a contact reaction for 30 s;
(4) and (3) post-treatment: predrying the membrane subjected to the contact reaction in a drying oven at 70 ℃ for 1min, washing with hot water at 90 ℃ for 4min, taking out, soaking in 9% glycerol for 1min, taking out, and drying at 70 ℃ to obtain the nanofiltration membrane.
Example 16:
example 16 is different from example 1 in that 4-methoxy-m-phenylenediamine is used as a water-soluble additive in example 16, and the rest is the same as in example 1.
Example 17:
example 17 differs from example 1 in that 4-bromoo-phenylenediamine is used as the water-soluble additive in example 17, and the other steps are the same as in example 1.
Example 18:
example 18 differs from example 1 in that 4-bromo-3-fluoro-1, 2-phenylenediamine is used as the water-soluble additive in example 18, and the rest is the same as in example 1.
Example 19:
example 19 differs from example 1 in that 2-nitro-1, 4-phenylenediamine is used as the water-soluble additive in example 19, and the rest is the same as in example 1.
Example 20:
example 20 is different from example 1 in that N-methyl-4, 4' -methylenedianiline was used as the water-soluble additive in example 20, and the rest was the same as in example 1.
Example 21:
example 21 is different from example 1 in that N-methyl-1, 2-phenylenediamine is used as the water-soluble additive in example 21, and the rest is the same as in example 1.
Example 22:
example 22 is different from example 1 in that ethylenediamine was used as the water-soluble additive in example 22, and the rest was the same as in example 1.
Example 23:
example 23 differs from example 1 in that propylene diamine was used as the water-soluble additive in example 23, and the rest was the same as in example 1.
Example 24:
example 24 is different from example 1 in that butanediamine was used as the water-soluble additive in example 24, and the rest was the same as in example 1.
Example 25:
example 25 is different from example 1 in that pentamethylenediamine was used as the water-soluble additive in example 25, and the rest was the same as in example 1.
Example 26:
example 26 is different from example 1 in that N-isopropylethylenediamine was used as the water-soluble additive in example 26, and the rest was the same as in example 1.
Example 27:
example 27 is different from example 1 in that m-phenylenediamine is used as the water-soluble additive in example 27, and the rest is the same as in example 1.
Example 28:
example 28 differs from example 1 in that p-xylylenediamine was used as the water-soluble additive in example 28, and the other steps are the same as in example 1.
Example 29:
example 29 differs from example 1 in that the water-soluble additive in example 29 is melamine, and the rest is the same as in example 1.
Example 30:
example 30 is different from example 1 in that pentamethyldiethylenetriamine is used as the water-soluble additive in example 30, and the rest is the same as in example 1.
Example 31:
example 31 is different from example 1 in that tetraethylenepentamine is used as the water-soluble additive in example 31, and the rest is the same as in example 1.
Example 32:
example 32 differs from example 1 in that the water-soluble additive of example 32 employs pentaethylenehexamine, and the rest is the same as in example 1.
Example 33:
example 33 is different from example 1 in that 1,3, 5-triaminobenzene is used as the water-soluble additive in example 33, and the rest is the same as in example 1.
Example 34:
example 34 is different from example 1 in that 1,2, 4-triaminobenzene is used as the water-soluble additive in example 34, and the rest is the same as example 1.
Example 35:
example 35 differs from example 1 in that 2,4, 6-triaminopyrimidine was used as the water-soluble additive in example 35, and the rest was the same as in example 1.
Example 36:
example 36 differs from example 1 in that 2,4, 5-triaminopyrimidine was used as the water-soluble additive in example 36, and the rest was the same as in example 1.
Example 37:
example 37 differs from example 1 in that 4,5, 6-triaminopyrimidine was used as the water-soluble additive in example 37, and the rest was the same as in example 1.
Example 38:
example 38 differs from example 1 in that 2,4,5, 6-tetraaminopyrimidine was used as the water-soluble additive in example 38, and the rest was the same as in example 1.
Example 39:
example 39 is different from example 1 in that diethylenetriamine was used as the water-soluble additive in example 39, and the rest is the same as in example 1.
Example 40:
example 40 differs from example 1 in that 4,4' -diaminodiphenylamine was used as the water-soluble additive in example 40, and the rest was the same as in example 1.
Comparative example 1:
comparative example 1 is different from example 1 in that m-xylylenediamine is not added in comparative example 1, and the rest is the same as in example 1.
The nanofiltration membranes prepared in the above examples and comparative examples were subjected to performance tests under the following conditions: the cross-flow filtration test was carried out with 500ppm of an aqueous solution of polyethylene glycol (PEG, average molecular weight 400Da) at a test pressure of 0.30MPa and a test temperature of 25 ℃. The test results are shown in table 1.
Table 1: and (5) testing the performance of the nanofiltration membrane.
As can be seen from table 1, in examples 1 to 6, the pH of the aqueous phase solution was changed, the water flux of the nanofiltration membrane prepared was gradually decreased and the retention rate of PEG-400 was gradually increased with the increase of pH, and the comprehensive performance of the nanofiltration membrane was optimized at a pH of 5 in the aqueous phase solution. The interfacial polymerization reaction is easier to proceed towards the direction of generating polyamide with the increase of the pH value of the aqueous phase solution, which is beneficial to generating polyamide molecules, the crosslinking degree is high, the compactness of the polyamide primary layer is increased, the lamellar structure of the functional layer is reduced and the density is increased, and the thickening of the functional layer causes the low water flux and the high retention rate of the prepared nanofiltration membrane.
In examples 7-13, the mass of the water-soluble additive, m-xylylenediamine, was changed, and as the concentration of m-xylylenediamine increased, the flux of the semipermeable membrane increased and the salt rejection rate decreased. This is due to the fact that as the concentration of m-xylylenediamine increases, the polyamide functional layer becomes less dense, resulting in an increase in flux and a decrease in rejection of the semipermeable membrane.
In examples 14 to 40, the nanofiltration membranes prepared using the different water-soluble additives of the present invention exhibited good overall performance in terms of water flux and rejection rate. In the comparative example 1, the water-soluble additive is not added, so that the water flux of the prepared nanofiltration membrane is greatly reduced compared with that in the example.
Claims (7)
1. A preparation method of a nanofiltration membrane for reclaimed water treatment is characterized by comprising the following steps:
(1) preparing an oil phase solution: adding polyacyl chloride into an oil phase solvent, namely ethylcyclohexane, and stirring and dissolving to obtain an oil phase solution, wherein the mass concentration of the polyacyl chloride in the oil phase solution is 0.1-0.2%;
(2) preparing an aqueous solution: respectively adding polyamine and a water-soluble additive with different solubility with the polyamine in the oil phase solution into deionized water, and uniformly stirring to obtain a water phase solution, wherein the mass concentration of the polyamine in the water phase solution is 0.2-0.4%, and the mass concentration of the water-soluble additive is 0.05-2%; the water-soluble additive is m-xylylenediamine; dissolving polyamine and water-soluble additive, adding hydrochloric acid or sodium hydroxide solution to adjust the pH value of the water phase solution to 2-12;
(3) contact reaction: pouring the water phase solution onto the supporting base film, pouring out the redundant water phase solution on the supporting base film after soaking, and blowing clean the redundant water phase solution on the surface and the back of the supporting base film until no water drops exist on the surface of the supporting base film; then contacting the surface of the supporting base film with an oil phase solution, and obtaining a pretreatment membrane after contact reaction;
(4) and (3) post-treatment: and pre-drying and cleaning the pre-treated membrane, soaking in glycerol, and finally drying to obtain the nanofiltration membrane.
2. The method as set forth in claim 1, wherein the polyamine in the step (2) is piperazine.
3. The method for preparing nanofiltration membrane for reclaimed water treatment according to claim 1, wherein the polybasic acid chloride is trimesoyl chloride in the step (1).
4. The method of claim 1, wherein the supporting base membrane in the step (3) is a porous polysulfone supporting base membrane.
5. The method for preparing nanofiltration membrane for reclaimed water treatment according to claim 1 or 4, wherein the soaking time of the support base membrane and the aqueous solution in the step (3) is 10-30 s.
6. The method for preparing nanofiltration membrane for reclaimed water treatment according to claim 1 or 4, wherein the contact reaction time of the support base membrane and the oil phase solution in the step (3) is 10 to 30 s.
7. The method for preparing nanofiltration membrane for reclaimed water treatment according to claim 1, wherein the post-treatment step in the step (4) comprises the following steps: pre-drying the membrane after contact reaction in a drying oven at 50-70 deg.C for 1-2min, washing with 70-90 deg.C hot water for 4-6min, taking out, soaking in 7-9% glycerol for 1-3min, and oven drying at 50-70 deg.C.
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