CN114130206A - Polyamide composite nanofiltration membrane and preparation method thereof - Google Patents
Polyamide composite nanofiltration membrane and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
Abstract
The invention relates to a polyamide composite nanofiltration membrane and a preparation method thereof. The preparation method of the polyamide composite nanofiltration membrane comprises the following steps: dissolving polysulfone and a pore-forming agent in a first organic solvent to obtain a polysulfone membrane casting solution; forming a membrane from the polysulfone membrane casting solution by a solid-liquid phase conversion method to prepare a polysulfone porous membrane; sequentially dipping the polysulfone porous membrane into a first medium and a second medium to obtain an interfacial polymerization product, wherein the first medium and the second medium are respectively a water phase solution or an oil phase solution, and the first medium and the second medium are different; the water phase solution comprises a water phase monomer, an acid binding agent and a water phase additive, and the oil phase solution comprises an oil phase monomer. The preparation method of the polyamide composite nanofiltration membrane is simple and feasible, the used raw materials are easy to obtain, the performance is stable, the price is low, the raw materials are easy to obtain, and the polyamide composite nanofiltration membrane is suitable for mass production.
Description
Technical Field
The invention relates to a polyamide composite nanofiltration membrane and a preparation method thereof, belonging to the field of water treatment.
Background
Nanofiltration, as a low energy consumption and uniquely selective membrane separation technique, has been increasingly used in a wide variety of industrial fields in recent years, such as: papermaking, printing and dyeing, biopharmaceutical engineering, pretreatment of seawater, municipal sewage treatment, underground water softening and other industries. The high-flux nanofiltration membrane is used as a special nanofiltration membrane which can realize high water yield under low operation pressure, and has great market application requirements for a long time.
However, similar to most water treatment membranes, in the membrane preparation process, in order to maintain high selectivity of the membrane, the water flux of the membrane is inevitably lost to a certain extent, which also affects the popularization and use efficiency of the nanofiltration membrane to a certain extent, and therefore, the research of the high-flux nanofiltration membrane has become a hot spot for the research of workers in the membrane industry.
In the prior art, methods for improving the flux of the composite nanofiltration membrane mainly comprise two main categories of regulation of a supporting layer and regulation of a desalting layer according to different research objects and focus points, wherein the regulation of the supporting layer is mainly started from the design of the porosity and the pore diameter of an ultrafiltration membrane and the hydrophilicity of the surface of the membrane, and the regulation of the desalting layer is mainly regulated by the diffusion rate of monomers and the reaction activity between two-phase monomers in the interfacial polymerization process through a specific technical means. In the prior art, the development of the high-flux nanofiltration membrane is difficult to be compatible with high selectivity.
In cited document 1, a method of adding polydimethylsiloxane as an organic phase additive to a TMC solution to prepare a modified high-flux polyamide membrane is described; the polydimethylsiloxane is selected as the oil phase additive, so that the method is a method for conveniently improving the membrane flux, but for large-scale industrial production, the difficulty in recovering the solvent is increased due to the addition of the additive in the organic solvent, and the method is not beneficial to the industrial green development of energy conservation, emission reduction and cost saving.
Citation 2 discloses a method for preparing a corrosion-resistant high-flux nanofiltration membrane by depositing reduced graphene oxide on a porous ultrafiltration membrane. The corrosion resistance and flux of the membrane surface of the reduced graphene oxide are better improved, but the preparation and purification processes of the reduced graphene oxide are more complex, and the preparation cost is higher.
Citation 3 introduces a method for preparing an aminated polysulfone membrane, and a high-flux piperazine polyamide composite nanofiltration membrane is prepared by using the aminated polysulfone membrane as a support layer. The authors start with the modification of the polysulfone support layer, and prepare an aminated polysulfone ultrafiltration membrane for subsequent interfacial polymerization, and the modified amination of the polysulfone surface significantly improves the flux of the composite membrane, however, the preparation of the aminated coating solution needs to undergo processes such as oxidation-reduction and the like, and the coating solution is not easy to store, thus limiting the application of the preparation method in large-scale industrial production to a certain extent.
Citation 4 discloses a method for preparing a high-flux nanofiltration membrane by using a novel buffer system, wherein an author introduces a water-phase buffer system of tetramethylammonium hydroxide and weak acid into interfacial polymerization reaction, and prepares a nanofiltration membrane with high water flux by regulating and controlling the treatment temperature after the interfacial polymerization, and the water flux is increased by about 37-40% compared with the flux of a conventional CSA/TEA buffer system. However, two coating liquids are used, and the coating liquids are not easy to store, so that the application of the preparation method in large-scale industrial production is limited to a certain extent.
In view of the above problems in the prior art, it is an urgent need to solve the technical problem of developing a nanofiltration membrane with high flux, high selectivity, simple structure and stable performance.
Cited documents:
cited document 1: CN101559354B
Cited document 2: CN106000121B
Cited document 3: CN107158981B
Cited document 4: CN110449045A
Disclosure of Invention
Problems to be solved by the invention
In view of the problems in the prior art, for example: the invention firstly provides a preparation method of a polyamide composite nanofiltration membrane, and the problems of increased solvent recovery difficulty, complex preparation process, expensive raw materials and the like are solved. The preparation method is simple and feasible, and the used raw materials are easy to obtain, stable in performance, cheap and easy to obtain.
Furthermore, the invention also provides a loose polyamide composite nanofiltration membrane with proper thickness, which not only can keep the high rejection rate of divalent inorganic salt ions, but also can greatly improve the membrane flux compared with the conventional nanofiltration membrane.
Means for solving the problems
The invention provides a preparation method of a polyamide composite nanofiltration membrane, which comprises the following steps:
dissolving polysulfone and a pore-forming agent in a first organic solvent to obtain a polysulfone membrane casting solution;
forming a membrane from the polysulfone membrane casting solution by a solid-liquid phase conversion method to prepare a polysulfone porous membrane;
sequentially dipping the polysulfone porous membrane into a first medium and a second medium to obtain an interfacial polymerization product, wherein the first medium and the second medium are respectively a water phase solution or an oil phase solution, and the first medium and the second medium are different; wherein
The water phase solution comprises a water phase monomer, an acid binding agent and a water phase additive, and the oil phase solution comprises an oil phase monomer.
The preparation method comprises the following steps of (1) enabling the polysulfone content to be 15-27 wt%, preferably 16-19 wt% based on the total mass of the polysulfone membrane casting solution; the content of the pore-foaming agent is 0.4-1.0 wt%, preferably 0.4-1.0 wt%; the content of the first organic solvent is 72 to 84 wt%, preferably 80.2 to 83.6 wt%.
According to the preparation method, the pore-foaming agent comprises a high-molecular pore-foaming agent or a small-molecular pore-foaming agent; preferably, the small molecule pore-forming agent comprises one or a combination of two or more of lithium chloride, calcium chloride or water, and the high molecule pore-forming agent comprises one or a combination of two or more of polyethylene glycol, polyvinylpyrrolidone or polyvinyl alcohol;
the first organic solvent comprises one or two of N, N-dimethylformamide and dimethylacetamide.
The preparation method according to the present invention further includes a step of defoaming before the deposition of the polysulfone membrane-casting solution.
The preparation method of the invention is characterized in that the first medium is an aqueous phase solution, the second medium is an oil phase solution, and the first medium or the second medium is immersed for 0.5-1 min.
The preparation method according to the invention, wherein the content of the aqueous phase monomer is 1.0 to 5.0 wt%, preferably 1.0 to 1.6 wt%, based on the total mass of the aqueous phase solution; the content of the acid-binding agent is 1.0-5.0 wt%, preferably 1.0-2 wt%; the content of the water phase additive is 0.1-2.0 wt%, preferably 0.5-0.8 wt%.
The preparation method comprises the following steps of preparing an aqueous phase monomer, wherein the aqueous phase monomer comprises one or more of o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, piperazine, benzidine, 3, 5-diaminobenzoic acid or 5-sulfom-phenylenediamine;
the acid-binding agent comprises one or the combination of more than two of sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate, sodium carbonate or potassium carbonate;
the water phase additive comprises one or the combination of more than two of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polyvinyl alcohol or ethanolamine.
The preparation method according to the invention, wherein the oil phase monomer is added in an amount of 0.1-2.0 wt%, preferably 0.1-0.2 wt%, based on the total mass of the oil phase solution;
the oil phase monomer comprises one or the combination of more than two of tribenzoyl chloride, terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride or 1, 5-dinaphthyl sulfonyl chloride.
The preparation method according to the present invention, wherein the preparation method further comprises a step of post-treatment; preferably, the post-processing comprises: and washing the interfacial polymerization product, soaking in a glycerol aqueous solution, and drying to obtain the polyamide composite nanofiltration membrane.
The invention also provides a polyamide composite nanofiltration membrane, which is characterized by utilizing the nanofiltration membrane as claimed in any one of claims 1 to 9The preparation method is prepared; preferably, the composite nanofiltration membrane is at 25 ℃, 100psi of operating pressure, relative to MgSO4The desalination rate of (2) is not less than 90%, and the flux is above 43 GFD.
ADVANTAGEOUS EFFECTS OF INVENTION
The polyamide composite nanofiltration membrane and the preparation method thereof have at least the following technical effects:
the preparation method of the polyamide composite nanofiltration membrane is simple and feasible, the used raw materials are easy to obtain, the performance is stable, the price is low, the raw materials are easy to obtain, and the polyamide composite nanofiltration membrane is suitable for mass production.
Furthermore, the polyamide composite nanofiltration membrane is proper and loose in thickness, not only can keep high rejection rate of divalent inorganic salt ions, but also can greatly improve membrane flux compared with a conventional nanofiltration membrane.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, "plural" in "plural", and the like means a numerical value of 2 or more unless otherwise specified.
In this specification, the terms "substantially", "substantially" or "substantially" mean an error of less than 5%, or less than 3% or less than 1% as compared to the relevant perfect or theoretical standard.
In the present specification, "%" denotes mass% unless otherwise specified.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
First aspect
The invention provides a preparation method of a polyamide composite nanofiltration membrane, which comprises the following steps:
dissolving polysulfone and a pore-forming agent in a first organic solvent to obtain a polysulfone membrane casting solution;
forming a membrane from the polysulfone membrane casting solution by a solid-liquid phase conversion method to prepare a polysulfone porous membrane;
sequentially dipping the polysulfone porous membrane into a first medium and a second medium to obtain an interfacial polymerization product, wherein the first medium and the second medium are respectively a water phase solution or an oil phase solution, and the first medium and the second medium are different; wherein
The water phase solution comprises a water phase monomer, an acid binding agent and a water phase additive, and the oil phase solution comprises an oil phase monomer.
The preparation method of the polyamide composite nanofiltration membrane is simple and feasible, the used raw materials are easy to obtain, the performance is stable, the price is low, the raw materials are easy to obtain, and the polyamide composite nanofiltration membrane is suitable for mass production. In addition, the polyamide composite nanofiltration membrane is proper and loose in thickness, high rejection rate of divalent inorganic salt ions can be maintained, and membrane flux is greatly improved.
In some embodiments, in order to better enable the polysulfone membrane casting solution to be formed into a membrane by a solid-liquid phase inversion method, the polysulfone content in the polysulfone membrane casting solution is 15-27 wt%, preferably 16-19 wt%, based on the total mass of the polysulfone membrane casting solution; the content of the pore-foaming agent is 0.4-1.0 wt%, preferably 0.4-1.0 wt%; the content of the first organic solvent is 72 to 84 wt%, preferably 80.2 to 83.6 wt%. Specifically, the polysulfone content is 18 wt%, 20 wt%, 22 wt%, 25 wt%, 27 wt%, etc.; the content of the pore-foaming agent is 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt% and the like; the content of the first organic solvent is 74 wt%, 76 wt%, 78 wt%, 80 wt%, 82 wt%, etc. Preferably, the polysulfone membrane casting solution is formulated at an elevated temperature to accelerate the dissolution of the solute. Specifically, the temperature may be 100-.
As for the porogen, in the present invention, the porogen includes a high molecular porogen or a small molecular porogen. The polyamide composite nanofiltration membrane has a proper pore structure by using the pore-forming agent, so that the flux of the composite nanofiltration membrane is improved.
Specifically, the polymeric or small-molecule porogen is not particularly limited, and may be some polymeric or small-molecule porogens commonly used in the art, and specifically, the polymeric porogens include one or a combination of two or more of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), and the like. The micromolecular pore-foaming agent comprises one or the combination of more than two of lithium chloride, calcium chloride or water. However, in view of the requirements of the present invention for pore structure, it is preferred to use polymeric porogens.
Further, in the present invention, the first organic solvent includes one or two of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC).
In some specific embodiments, in order to make the surface structure and the internal structure of the polysulfone porous membrane more suitable for preparing the composite nanofiltration membrane, a defoaming treatment step is further included before the polysulfone membrane casting solution is made into a membrane, in the present invention, all defoaming processes are performed in a vacuum defoaming box, and the vacuum pump pressure is controlled within the range of 0.05-0.1 Mpa.
Further, the polysulfone porous membrane is obtained by forming a membrane from the polysulfone membrane casting solution. In order to obtain the composite nanofiltration membrane with excellent performance, the membrane formation can be performed by performing solid-liquid phase conversion on the prepared polysulfone membrane casting solution. Specifically, the polysulfone membrane casting solution prepared in advance is uniformly coated (e.g. knife coated) on a substrate, the substrate coated with the polysulfone membrane casting solution is slowly immersed into a coagulating bath by controlling the conveying speed, and a porous supporting layer polysulfone membrane is obtained by scraping through a gel curing process, wherein the substrate may be preferably a polyester non-woven fabric.
Preferably, the main component of the coagulation bath is water, and in order to ensure the diffusion rate of the solvent between two phases, the temperature of the coagulation bath is controlled within the range of 10-25 ℃, and the conveying speed is 2-5 m/min.
Further, the polysulfone porous membrane obtained is sequentially immersed in a first medium and a second medium to obtain an interfacial polymerization product, wherein the first medium and the second medium are respectively an aqueous phase solution or an oil phase solution, and the first medium and the second medium are different.
In the present invention, the order of impregnation is not particularly limited, and impregnation may be performed as necessary. Specifically, when the first medium is an aqueous phase solution and the second medium is an oil phase solution, the polysulfone porous membrane is first immersed in the first medium, i.e., the aqueous phase solution, and then the polysulfone porous membrane is immersed in the second medium, i.e., the oil phase solution; when the first medium is an oil phase solution and the second medium is an aqueous phase solution, the polysulfone porous membrane is firstly immersed in the first medium, namely the oil phase solution, and then the polysulfone porous membrane is immersed in the second medium, namely the aqueous phase solution.
In some preferred embodiments, the first medium is an aqueous phase solution and the second medium is an oil phase solution. Namely, the polysulfone porous membrane is immersed in a first medium, namely an aqueous phase solution, and then the polysulfone porous membrane is immersed in a second medium, namely an oil phase solution, so that an interfacial polymerization product with more excellent performance can be obtained, and the adhesion between the surface desalting layer and the supporting layer is firmer.
Further, in order not to affect the efficacy of the composite nanofiltration membrane, the time for immersion is not excessively long, specifically, the time for immersion in the first medium or the second medium may be 0.5 to 1min, for example: 35s, 40s, 45s, 50s, 55s, etc. When the dipping time is 0.5-1min, the high-flux polyamide composite nanofiltration membrane can be obtained. Preferably, when the first medium is an aqueous phase solution and the second medium is an oil phase solution, the first medium may be immersed for 0.5 to 1min, then the surface beads may be drained, and then the second medium may be immersed for 0.5 to 1 min.
For aqueous phase solutions, in the present invention, the aqueous phase solution includes an aqueous phase monomer, an acid scavenger, and an aqueous phase additive. The aqueous phase monomer, acid-binding agent, and aqueous phase additive may be dissolved with water as a solvent to obtain an aqueous phase solution. In the invention, an acid-binding agent is used for neutralizing redundant HCl, and when potassium carbonate or sodium carbonate is used as the acid-binding agent, carbon dioxide formed in the process is beneficial to the formation of a loose desalting layer. The molecular structure of the water phase additive is used, so that the water phase additive has certain alkalinity, HCl generated in interfacial polymerization reaction can be absorbed, the interfacial polymerization reaction is carried out more completely, and a complete and uniform desalting layer is formed more easily.
According to the method, the polyamide composite nanofiltration membrane with proper and loose thickness is prepared through the synergistic effect of the acid-binding agent and the water-phase additive in the reaction mechanism, the prepared membrane can keep the high rejection rate of divalent inorganic salt ions, and the flux of the composite nanofiltration membrane is greatly improved.
In some specific embodiments, the aqueous phase monomer is present in an amount of 1.0 to 5.0 wt.%, preferably 1.0 to 1.6 wt.%, based on the total mass of the aqueous phase solution; the content of the acid-binding agent is 1.0-5.0 wt%, preferably 1.0-2 wt%; the content of the water phase additive is 0.1-2.0 wt%, preferably 0.5-0.8 wt%, and the content of the used solvent water is 92.0-97.9 wt%. Specifically, the content of the aqueous phase monomer may be 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, etc.; the content of the acid-binding agent is 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, etc.; the content of the water phase additive is 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt% and the like; the solvent water is used in an amount of 92.5 wt%, 93 wt%, 93.5 wt%, 94 wt%, 94.5 wt%, 95 wt%, 95.5 wt%, 96 wt%, 97 wt%, etc.
Specifically, in the present invention, the aqueous phase monomer includes one or a combination of two or more of o-phenylenediamine, m-phenylenediamine (MPD), p-phenylenediamine, piperazine, benzidine, 3, 5-diaminobenzoic acid, and 5-sulfometaphenylene diamine. The acid-binding agent comprises one or the combination of more than two of sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate, sodium carbonate or potassium carbonate.
The water phase additive comprises one or the combination of more than two of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polyvinyl alcohol and ethanolamine. The water phase additive used in the invention has simple structure, stable performance, low cost and easy obtaining, can effectively improve the diffusion rate of the water phase monomer to the organic phase interface, and increases the contact surface of two phases.
As for the oil phase solution, in the present invention, the oil phase solution includes an oil phase monomer. The invention uses the second organic solvent to dissolve the oil phase monomer to obtain the oil phase solution. Specifically, the second organic solvent is an alkane solvent and/or a cycloalkane solvent. The addition amount of the oil phase monomer is 0.1-2.0 wt%, preferably 0.1-0.2 wt%, based on the total mass of the oil phase solution; the addition amount of the second organic solvent is 98.0-99.9 wt%. Specifically, the oil phase monomer may be added in an amount of 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, etc.; the second organic solvent may be added in an amount of 98.2 wt%, 98.5 wt%, 98.8 wt%, 99 wt%, 99.2 wt%, 99.5 wt%, etc.
Specifically, in the present invention, the oil phase monomer includes one or a combination of two or more of trimesoyl chloride (TMC), phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, or 1, 5-dinaphthoyl chloride, the alkane solvent includes one or a combination of two of n-hexane, n-heptane, and the like, and the cycloalkane solvent includes one or a combination of two of cyclohexane, methylcyclohexane, and the like.
Further, in some specific embodiments, the preparation method further comprises a post-treatment step, and the final polyamide composite nanofiltration membrane product is obtained through post-treatment. The mode of the post-treatment is not particularly limited, and post-treatment methods generally used in the art, including washing, dipping, drying, and the like, can be used. Specifically, the post-processing includes: and washing the interfacial polymerization product, soaking in a glycerol aqueous solution, and drying to obtain the polyamide composite nanofiltration membrane.
The washing may be carried out using water and/or an organic solvent such as a low boiling point hydrocarbon, alcohol, ether, or ketone, and is preferably carried out using water for 1 to 5 min.
The impregnation comprises the step of impregnating with glycerol aqueous solution, wherein the glycerol aqueous solution has the function of moisturizing the membrane, so that the performance attenuation of the membrane caused by too fast dehydration due to too high temperature in the subsequent drying of the membrane is avoided. Specifically, in the glycerol aqueous solution, the content of the glycerol is 8-15 wt% based on the total mass of the glycerol aqueous solution, and the impregnation time is 1-3 min.
The drying may be carried out under heating or under reduced pressure to obtain dried product, preferably under heating, and the drying temperature may be 60-100 deg.C, and the drying time may be 2-5 min.
Second aspect of the invention
The second aspect of the invention provides a polyamide composite nanofiltration membrane prepared by the preparation method of the first aspect, wherein the composite nanofiltration membrane is prepared at 25 ℃ and 100psi of operating pressure of MgSO (MgSO) in terms of pressure of MgSO (MgSO)4The desalination rate of (2) is not less than 90%, and the flux is above 43 GFD.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The membrane related performance test is carried out according to the standard in the GB/T34242-2017 nanofiltration membrane test method.
Example 1
(1) Preparing a polysulfone membrane casting solution: 855g of polysulfone (19.0 wt%) and 36g of PEG (0.8 wt%) are respectively weighed and added into a beaker containing 3609g of DMF (80.2 wt%) based on the total mass of the polysulfone membrane casting solution, stirred and dissolved at 150 ℃, cooled to room temperature (if bubbles exist in the solution, vacuum defoaming treatment is needed under the negative pressure of 0.06MPa after the solution is cooled to the room temperature), and sealed and placed for later use.
(2) Preparation of a porous support layer: uniformly blade-coating the polysulfone membrane casting solution prepared in the step (1) on a polyester non-woven fabric, controlling the conveying speed to slowly immerse the non-woven fabric coated with the membrane casting solution into a coagulating bath, and scraping to obtain a porous support layer polysulfone membrane through a gel curing process; wherein the coagulation bath is deionized water, and the temperature of the coagulation bath is controlled at about 18 deg.C and the conveying speed is 4m/min to ensure the diffusion rate of the solvent between two phases.
(3) Preparing an aqueous phase solution: weighing m-phenylenediamine (MPD) (1.6 wt%), K2CO3(1.5 wt%), ethanolamine (0.5 wt%), and pure water (96.4 wt%) was added to prepare an aqueous solution.
(4) Preparing an oil phase solution: based on the total mass of the oil phase solution, 0.2 wt% of TMC is weighed and prepared into an organic phase solution, and the solvent is n-hexane (99.8 wt%).
(5) Interfacial polymerization and post-treatment process: and (3) immersing the polysulfone porous membrane prepared in the step (2) into a water phase solution for 1min, taking out, draining surface water drops, immersing the polysulfone porous membrane into an oil phase solution for 0.5min, washing the polysulfone porous membrane with deionized water for 2min after taking out, immersing the polysulfone porous membrane in a glycerol water solution with 15% of glycerol content for 2min, and finally drying the membrane at 80 ℃ for 2min to prepare the composite nanofiltration membrane.
(6) And (3) testing the performance of the membrane: placing the composite nanofiltration membrane obtained in the above steps in a mold for performance test, wherein the test pressure is 100psi, and the raw water concentration is MgSO4 2000ppm, the measured properties are shown in Table 1 below:
TABLE 1
Example 2
(1) Preparing a polysulfone membrane casting solution: 855g of polysulfone (19.0 wt%) and 72g of PEG (1.6 wt%) are respectively weighed and added into a beaker containing 3573g of DMF (79.4 wt%), stirred and dissolved at 150 ℃ until the polysulfone and PEG are completely dissolved, and the solution is cooled to room temperature (if bubbles exist in the solution, the solution is subjected to vacuum defoaming treatment under the negative pressure of 0.06MPa after being cooled to the room temperature), sealed and placed for later use.
(2) Preparation of a porous support layer: uniformly blade-coating the polysulfone membrane casting solution prepared in the step (1) on a polyester non-woven fabric, controlling the conveying speed to slowly immerse the non-woven fabric coated with the membrane casting solution into a coagulating bath, and scraping to obtain a porous support layer polysulfone membrane through a gel curing process; wherein the coagulation bath is deionized water, and the temperature of the coagulation bath is controlled at about 18 deg.C and the conveying speed is 4m/min to ensure the diffusion rate of the solvent between two phases.
(3) Preparing an aqueous phase solution: weighing m-phenylenediamine (MPD) (1.6 wt%), K2CO3(1.5 wt%), ethanolamine (0.5 wt%) was added to pure water (96.4 wt%) to prepare an aqueous solution.
(4) Preparing an oil phase solution: based on the total mass of the oil phase solution, 0.2 wt% of TMC is weighed and prepared into an organic phase solution, and the solvent is n-hexane (99.8 wt%).
(5) Interfacial polymerization and post-treatment process: and (3) immersing the polysulfone porous membrane prepared in the step (2) into a water phase solution for 1min, taking out, draining surface water drops, immersing the polysulfone porous membrane into an oil phase solution for 0.5min, washing the polysulfone porous membrane with deionized water for 2min after taking out, immersing the polysulfone porous membrane in a glycerol water solution with 15% of glycerol content for 2min, and finally drying the membrane at 80 ℃ for 2min to prepare the composite nanofiltration membrane.
(6) And (3) testing the performance of the membrane: placing the composite nanofiltration membrane obtained in the step into a mould for performance test, and testing the pressure to be 100 DEGpsi, raw water concentration MgSO42000ppm, the measured properties are shown in Table 2 below:
TABLE 2
Example 3
(1) Preparing a polysulfone membrane casting solution: 855g of polysulfone (19.0 wt%) and 36g of PVP (0.8 wt%) are respectively weighed and added into a beaker containing 3609g of DMF (80.2 wt%) based on the total mass of the polysulfone membrane casting solution, stirred and dissolved at 150 ℃, cooled to room temperature (if bubbles exist in the solution, vacuum defoaming treatment is needed under the negative pressure of 0.06MPa after the solution is cooled to the room temperature), and sealed and placed for later use.
(2) Preparation of a porous support layer: uniformly blade-coating the polysulfone membrane casting solution prepared in the step (1) on a polyester non-woven fabric, controlling the conveying speed to slowly immerse the non-woven fabric coated with the membrane casting solution into a coagulating bath, and scraping to obtain a porous support layer polysulfone membrane through a gel curing process; wherein the coagulation bath is deionized water, and the temperature of the coagulation bath is controlled at about 18 deg.C and the conveying speed is 4m/min to ensure the diffusion rate of the solvent between two phases.
(3) Preparing an aqueous phase solution: weighing m-phenylenediamine (MPD) (1.6 wt%), K2CO3(1.5 wt%), ethanolamine (0.5 wt%) was added to pure water (96.4 wt%) to prepare an aqueous solution;
(4) preparing an oil phase solution: weighing 0.2 wt% of TMC (TMC) based on the total mass of the oil phase solution to prepare an organic phase solution, wherein the solvent is n-hexane (99.8 wt%);
(5) interfacial polymerization and post-treatment process: soaking the polysulfone porous membrane prepared in the step (2) in the water phase solution for 1min, taking out, draining surface water drops, soaking the polysulfone porous membrane in the oil phase solution for 0.5min, taking out, washing the polysulfone porous membrane with deionized water for 2min, soaking the polysulfone porous membrane in a glycerol water solution with 15% of glycerol content for 2min, and finally drying the membrane at 80 ℃ for 2min to obtain the composite nanofiltration membrane;
(6) and (3) testing the performance of the membrane: putting the composite nanofiltration membrane obtained in the step into a mould for carrying outPerformance test, test pressure 100psi, raw water concentration MgSO42000ppm, measured properties are shown in Table 3 below:
TABLE 3
Example 4
(1) Preparing a polysulfone membrane casting solution: 855g of polysulfone (19.0 wt%) and 36g of PEG (0.8 wt%) are respectively weighed and added into a beaker containing 3609g of DMF (80.2 wt%) based on the total mass of the polysulfone membrane casting solution, stirred and dissolved at 150 ℃, cooled to room temperature (if bubbles exist in the solution, vacuum defoaming treatment is needed under the negative pressure of 0.06MPa after the solution is cooled to the room temperature), and sealed and placed for later use.
(2) Preparation of a porous support layer: uniformly blade-coating the polysulfone membrane casting solution prepared in the step (1) on a polyester non-woven fabric, controlling the conveying speed to enable the non-woven fabric coated with the membrane casting solution to be slowly immersed into a coagulating bath, and scraping to obtain the porous supporting layer polysulfone membrane through a gel curing process, wherein the coagulating bath is deionized water, the temperature of the coagulating bath is controlled at 18 ℃ for ensuring the diffusion rate of a solvent between two phases, and the conveying speed is 4 m/min.
(3) Preparing an aqueous phase solution: weighing m-phenylenediamine (MPD) (1.6 wt%), K2CO3(2.0 wt%), ethanolamine (0.5 wt%) was added to pure water (96.4 wt%) to prepare an aqueous solution.
(4) Preparing an oil phase solution: based on the total mass of the oil phase solution, 0.2 wt% of TMC is weighed and prepared into an organic phase solution, and the solvent is n-hexane (99.8 wt%).
(5) Interfacial polymerization and post-treatment process: and (3) immersing the polysulfone porous membrane prepared in the step (2) into a water phase solution for 1min, taking out, draining surface water drops, immersing the polysulfone porous membrane into an oil phase solution for 0.5min, washing the polysulfone porous membrane with deionized water for 2min after taking out, immersing the polysulfone porous membrane in a glycerol water solution with 15% of glycerol content for 2min, and finally drying the membrane at 80 ℃ for 2min to prepare the composite nanofiltration membrane.
(6) And (3) testing the performance of the membrane: compounding the obtained productPlacing the composite nanofiltration membrane in a mold for performance test, wherein the test pressure is 100psi, and the raw water concentration is MgSO42000ppm, measured properties are shown in Table 4 below:
TABLE 4
Example 5
(1) Preparing a polysulfone membrane casting solution: 855g of polysulfone (19.0 wt%) and 36g of PEG (0.8 wt%) are respectively weighed and added into a beaker containing 3609g of DMF (80.2 wt%) based on the total mass of the polysulfone membrane casting solution, stirred and dissolved at 150 ℃, cooled to room temperature (if bubbles exist in the solution, vacuum defoaming treatment is needed under the negative pressure of 0.06MPa after the solution is cooled to the room temperature), and sealed and placed for later use.
(2) Preparation of a porous support layer: uniformly blade-coating the polysulfone membrane casting solution prepared in the step (1) on a polyester non-woven fabric, controlling the conveying speed to enable the non-woven fabric coated with the membrane casting solution to be slowly immersed into a coagulating bath, and scraping to obtain the porous supporting layer polysulfone membrane through a gel curing process, wherein the coagulating bath is deionized water, the temperature of the coagulating bath is controlled to be about 18 ℃ for ensuring the diffusion rate of a solvent between two phases, and the conveying speed is 4 m/min.
(3) Preparing an aqueous phase solution: weighing m-phenylenediamine (MPD) (1.0 wt%), K2CO3(2.0 wt%), ethanolamine (0.8 wt%) was added to pure water (96.2 wt%) to prepare an aqueous solution.
(4) Preparing an oil phase solution: 0.12 wt% TMC was weighed out and prepared as an organic phase solution in n-hexane (99.88 wt%).
(5) Interfacial polymerization and post-treatment process: and (3) immersing the polysulfone porous membrane prepared in the step (2) into a water phase solution for 1min, taking out, draining surface water drops, immersing the polysulfone porous membrane into an oil phase solution for 0.5min, washing the polysulfone porous membrane with deionized water for 2min after taking out, immersing the polysulfone porous membrane in a glycerol water solution with 15% of glycerol content for 2min, and finally drying the membrane at 80 ℃ for 2min to prepare the composite nanofiltration membrane.
(6) And (3) testing the performance of the membrane: compounding the obtained productPlacing the composite nanofiltration membrane in a mold for performance test, wherein the test pressure is 100psi, and the raw water concentration is MgSO42000ppm, measured properties are shown in Table 5 below:
TABLE 5
Example 6
(1) Preparing a polysulfone membrane casting solution: 855g of polysulfone (19.0 wt%) and 36g of PEG (0.8 wt%) are respectively weighed and added into a beaker containing 3609g of DMF (80.2 wt%) based on the total mass of the polysulfone membrane casting solution, stirred and dissolved at 150 ℃, cooled to room temperature (if bubbles exist in the solution, vacuum defoaming treatment is needed under the negative pressure of 0.06MPa after the solution is cooled to the room temperature), and sealed and placed for later use.
(2) Preparation of a porous support layer: uniformly blade-coating the polysulfone membrane casting solution prepared in the step (1) on a polyester non-woven fabric, controlling the conveying speed to enable the non-woven fabric coated with the membrane casting solution to be slowly immersed into a coagulating bath, and scraping to obtain the porous supporting layer polysulfone membrane through a gel curing process, wherein the coagulating bath is deionized water, the temperature of the coagulating bath is controlled to be about 18 ℃ for ensuring the diffusion rate of a solvent between two phases, and the conveying speed is 4 m/min.
(3) Preparing an aqueous phase solution: weighing m-phenylenediamine (MPD) (1.0 wt%), K2CO3(2 wt%), ethanolamine (0.8 wt%) was added to pure water (96.2 wt%) to prepare an aqueous solution.
(4) Preparing an oil phase solution: based on the total mass of the oil phase solution, 0.1 wt% of TMC, 0.02 wt% of TMC and isophthaloyl dichloride are weighed to prepare an organic phase solution, and the solvent of the organic phase solution is n-hexane (99.88 wt%).
(5) Interfacial polymerization and post-treatment process: and (3) immersing the polysulfone porous membrane prepared in the step (2) into a water phase solution for 1min, taking out, draining surface water drops, immersing the polysulfone porous membrane into an oil phase solution for 0.5min, washing the polysulfone porous membrane with deionized water for 2min after taking out, immersing the polysulfone porous membrane in a glycerol water solution with 15% of glycerol content for 2min, and finally drying the membrane at 80 ℃ for 2min to prepare the composite nanofiltration membrane.
(6) And (3) testing the performance of the membrane: placing the composite nanofiltration membrane obtained in the above steps in a mold for performance test, wherein the test pressure is 100psi, and the raw water concentration is MgSO42000ppm, the measured properties are shown in Table 6 below:
TABLE 6
Example 7
(1) Preparing a polysulfone membrane casting solution: 855g of polysulfone (19.0 wt%) and 36g of PEG (0.8 wt%) are respectively weighed and added into a beaker containing 3609g of DMF (80.2 wt%) based on the total mass of the polysulfone membrane casting solution, stirred and dissolved at 150 ℃, cooled to room temperature (if bubbles exist in the solution, vacuum defoaming treatment is needed under the negative pressure of 0.06MPa after the solution is cooled to the room temperature), and sealed and placed for later use.
(2) Preparation of a porous support layer: uniformly blade-coating the polysulfone membrane casting solution prepared in the step (1) on a polyester non-woven fabric, controlling the conveying speed to enable the non-woven fabric coated with the membrane casting solution to be slowly immersed into a coagulating bath, and scraping to obtain the porous supporting layer polysulfone membrane through a gel curing process, wherein the coagulating bath is deionized water, the temperature of the coagulating bath is controlled to be about 18 ℃ for ensuring the diffusion rate of a solvent between two phases, and the conveying speed is 4 m/min.
(3) Preparing an aqueous phase solution: weighing m-phenylenediamine (MPD) (1.0 wt%), K2CO3(2 wt%), ethanolamine (0.8 wt%) was added to pure water (96.2 wt%) to prepare an aqueous solution.
(4) Preparing an oil phase solution: based on the total mass of the oil phase solution, 0.12 wt% of TMC is weighed to prepare an organic phase solution, and the solvent is cyclohexane (99.88 wt%).
(5) Interfacial polymerization and post-treatment process: and (3) immersing the polysulfone porous membrane prepared in the step (2) into a water phase solution for 1min, taking out, draining surface water drops, immersing the polysulfone porous membrane into an oil phase solution for 0.5min, washing the polysulfone porous membrane with deionized water for 2min after taking out, immersing the polysulfone porous membrane in a glycerol water solution with 15% of glycerol content for 2min, and finally drying the membrane at 80 ℃ for 2min to prepare the composite nanofiltration membrane.
(6) And (3) testing the performance of the membrane: placing the composite nanofiltration membrane obtained in the above steps in a mold for performance test, wherein the test pressure is 100psi, and the raw water concentration is MgSO42000ppm, measured properties are shown in Table 7 below:
TABLE 7
Example 8
(1) Preparing a polysulfone membrane casting solution: 855g of polysulfone (19.0 wt%) and 36g of PEG (0.8 wt%) are respectively weighed and added into a beaker containing 3609g of DMF (80.2 wt%) based on the total mass of the polysulfone membrane casting solution, stirred and dissolved at 150 ℃, cooled to room temperature (if bubbles exist in the solution, vacuum defoaming treatment is needed under negative pressure of at least 0.06MPa after the solution is cooled to the room temperature), and sealed and placed for later use.
(2) Preparation of a porous support layer: uniformly blade-coating the polysulfone membrane casting solution prepared in the step (1) on a polyester non-woven fabric, controlling the conveying speed to enable the non-woven fabric coated with the membrane casting solution to be slowly immersed into a coagulating bath, and scraping to obtain the porous supporting layer polysulfone membrane through a gel curing process, wherein the coagulating bath is deionized water, the temperature of the coagulating bath is controlled to be about 18 ℃ for ensuring the diffusion rate of a solvent between two phases, and the conveying speed is 4 m/min.
(3) Preparing an aqueous phase solution: weighing m-phenylenediamine (MPD) (1.0 wt%), K2CO3(2 wt%), ethanolamine (0.8 wt%) was added to pure water (96.2 wt%) to prepare an aqueous solution.
(4) Preparing an oil phase solution: based on the total mass of the oil phase solution, 0.12 wt% of TMC is weighed to prepare an organic phase solution, and the solvent is methylcyclohexane (99.88 wt%).
(5) Interfacial polymerization and post-treatment process: and (3) immersing the polysulfone porous membrane prepared in the step (2) into a water phase solution for 1min, taking out, draining surface water drops, immersing the polysulfone porous membrane into an oil phase solution for 0.5min, washing the polysulfone porous membrane with deionized water for 2min after taking out, immersing the polysulfone porous membrane in a glycerol water solution with 15% of glycerol content for 2min, and finally drying the membrane at 80 ℃ for 2min to prepare the composite nanofiltration membrane.
(6) And (3) testing the performance of the membrane: placing the composite nanofiltration membrane obtained in the above steps in a mold for performance test, wherein the test pressure is 100psi, and the raw water concentration is MgSO42000ppm, measured properties are shown in Table 8 below:
TABLE 8
As can be seen from examples 1-8, the composite nanofiltration membrane prepared by the preparation method disclosed by the invention has the advantages of being capable of resisting MgSO (MgSO) at 25 ℃ and under the operation pressure of 100psi4The desalination rate of the composite nanofiltration membrane is not lower than 90 percent, the flux of the composite nanofiltration membrane is more than 43GFD, and the thickness of the desalination layer can be more than 80nm, which is obviously superior to that of the conventional membrane in the prior art.
It should be noted that, although the technical solutions of the present invention are described in specific embodiments, those skilled in the art can understand that the present invention should not be limited thereto.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen in order to best explain the principles of the embodiments, the practical application, or improvements made to the technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (10)
1. The preparation method of the polyamide composite nanofiltration membrane is characterized by comprising the following steps of:
dissolving polysulfone and a pore-forming agent in a first organic solvent to obtain a polysulfone membrane casting solution;
forming a membrane from the polysulfone membrane casting solution by a solid-liquid phase conversion method to prepare a polysulfone porous membrane;
sequentially dipping the polysulfone porous membrane into a first medium and a second medium to obtain an interfacial polymerization product, wherein the first medium and the second medium are respectively a water phase solution or an oil phase solution, and the first medium and the second medium are different; wherein
The water phase solution comprises a water phase monomer, an acid binding agent and a water phase additive, and the oil phase solution comprises an oil phase monomer.
2. The process according to claim 1, wherein the polysulfone is present in an amount of 15-27 wt.%, preferably 16-19 wt.%, based on the total mass of the polysulfone dope solution; the content of the pore-foaming agent is 0.4-1.0 wt%, preferably 0.4-1.0 wt%; the content of the first organic solvent is 72 to 84 wt%, preferably 80.2 to 83.6 wt%.
3. The preparation method according to claim 1 or 2, wherein the porogen comprises a high molecular porogen or a small molecular porogen; preferably, the small molecule pore-forming agent comprises one or a combination of two or more of lithium chloride, calcium chloride or water, and the high molecule pore-forming agent comprises one or a combination of two or more of polyethylene glycol, polyvinylpyrrolidone or polyvinyl alcohol;
the first organic solvent comprises one or two of N, N-dimethylformamide and dimethylacetamide.
4. The production method according to any one of claims 1 to 3, further comprising a step of defoaming the polysulfone membrane-casting solution before the deposition thereof.
5. The method according to any one of claims 1 to 4, wherein the first medium is an aqueous phase solution, the second medium is an oil phase solution, and the immersion time in the first medium or the second medium is 0.5 to 1 min.
6. The method according to any one of claims 1 to 5, wherein the aqueous phase monomer is present in an amount of 1.0 to 5.0 wt.%, preferably 1.0 to 1.6 wt.%, based on the total mass of the aqueous phase solution; the content of the acid-binding agent is 1.0-5.0 wt%, preferably 1.0-2 wt%; the content of the water phase additive is 0.1-2.0 wt%, preferably 0.5-0.8 wt%.
7. The production method according to any one of claims 1 to 6, wherein the aqueous phase monomer comprises one or a combination of two or more of o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, piperazine, benzidine, 3, 5-diaminobenzoic acid, or 5-sulfom-phenylenediamine;
the acid-binding agent comprises one or the combination of more than two of sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate, sodium carbonate or potassium carbonate;
the water phase additive comprises one or the combination of more than two of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polyvinyl alcohol or ethanolamine.
8. The production method according to any one of claims 1 to 7, characterized in that the oil phase monomer is added in an amount of 0.1 to 2.0 wt%, preferably 0.1 to 0.2 wt%, based on the total mass of the oil phase solution;
the oil phase monomer comprises one or the combination of more than two of tribenzoyl chloride, terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride or 1, 5-dinaphthyl sulfonyl chloride.
9. The production method according to any one of claims 1 to 8, characterized by further comprising a step of post-treatment; preferably, the post-processing comprises: and washing the interfacial polymerization product, soaking in a glycerol aqueous solution, and drying to obtain the polyamide composite nanofiltration membrane.
10. A polyamide composite nanofiltration membrane, which is prepared by the preparation method of any one of claims 1 to 9; preferably, the composite nanofiltration membrane is at 25 ℃, 100psi of operating pressure, relative to MgSO4Salt rejection ratio of (2)Not less than 90%, and flux over 43 GFD.
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