CN111229050B - Preparation method of composite membrane - Google Patents
Preparation method of composite membrane Download PDFInfo
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Abstract
The invention relates to a preparation method of a composite membrane, wherein oil phase reaction monomers and water phase reaction monomers participating in polymerization reaction are respectively led in from two sides of a porous base membrane and then contact at the opening of the membrane hole through the membrane hole to carry out interfacial polymerization reaction. The concentration and the supply quantity of the two reaction monomers are convenient to control, the reaction speed and the reaction degree of the two reaction monomers can be respectively controlled, and the bottleneck of the prior art is broken through, so that the aggregation structure of the crosslinking layer is easy to regulate and control, and the composite membrane with higher removal rate is obtained.
Description
Technical Field
The invention belongs to the field of separation membranes, relates to a reverse osmosis membrane and nanofiltration membrane preparation technology, and particularly relates to a preparation method of a composite membrane.
Background
At present, most commercialized reverse osmosis membranes, nanofiltration membranes and the like are composite membranes, wherein an extremely thin composite layer is constructed on the surface of a porous base membrane, and the composite layer provides a selective separation function of the composite membrane. In the prior art, a compact composite layer with a separation function, which is not easy to fall off on the surface of a membrane, is formed by the interfacial polymerization reaction of a reaction monomer in an oil phase and a reaction monomer in water phase. In order to increase the membrane flux, it is necessary to minimize the thickness of the composite layer. In order to improve the selective separation, i.e., the rejection, of the composite membrane, it is desirable to minimize the polymerization defects on the composite layer.
For example, in the existing preparation method of reverse osmosis membrane and nanofiltration membrane, a layer of aqueous phase solution containing amine compounds is coated on the surface of a porous basement membrane, and then a layer of oil phase solution containing acid chloride compounds is coated on the surface of the porous basement membrane, when the oil phase solution contacts the aqueous phase solution, the amine compounds in the aqueous phase solution and the acid chloride compounds in the oil phase solution undergo interfacial polymerization reaction, so as to form a polyamide polymer composite layer on the surface of the porous basement membrane, as shown in fig. 1, in order to ensure the separation performance of the composite membrane, a complete and defect-free composite layer 3 needs to be formed on the surface of the basement membrane. When the porous base membrane 1 has macropores 8 or the aqueous phase solution and the oil phase solution are not uniformly distributed, defects 4 are generated, as shown in fig. 2, in order to avoid the defects, the thickness of the composite layer needs to be increased, so that the thickness of the composite layer is difficult to reduce, and the membrane flux is difficult to further improve. Meanwhile, as an important factor for controlling the interfacial polymerization reaction, the supply amount and the supply speed of the amine-containing compound in the aqueous phase solution and the acid chloride-containing compound in the oil phase solution are not easy to control, and the concentrations of the amine-containing compound in the aqueous phase solution and the acid chloride-containing compound in the oil phase solution are not easy to realize stable control during industrial production. In addition, because of the limitation of the current interfacial polymerization reaction mode, the currently prepared reverse osmosis membrane and nanofiltration membrane are generally flat membranes which are easy to industrially produce, and it is difficult to obtain hollow fiber reverse osmosis membrane and hollow fiber nanofiltration membrane which are easy to industrially produce through the interfacial polymerization reaction.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a composite membrane.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a process for preparing composite membrane includes such steps as respectively introducing the oil-phase reaction monomer and water-phase reaction monomer which take part in polymerization reaction from both sides of porous base membrane, passing through the pores of membrane, and contact at the opening of said pores for interfacial polymerization reaction.
The method comprises the following specific steps:
firstly, wetting a porous base membrane from the permeation side of the porous base membrane by water to fill liquid water in membrane pores;
secondly, flowing an oil phase solution containing an oil phase reaction monomer on the front surface of the porous base membrane, wherein the oil phase solution covers the outer side of the membrane pores;
thirdly, discharging water on the permeation side of the porous base membrane; and (2) introducing a water phase solution containing water phase reaction monomers into the permeation side of the porous base membrane, diffusing the reaction monomers in the water phase solution into the membrane pores, contacting the reaction monomers in the oil phase solution at the openings of the membrane pores to generate interfacial polymerization reaction, forming crosslinking reactants at the openings of the membrane pores, and plugging the membrane pores by the hole-cap-shaped crosslinking layer, thereby preparing the composite membrane.
And the oil phase reaction monomer is a binary or ternary acyl chloride compound, specifically trimesoyl chloride, phthaloyl chloride, isophthaloyl chloride, succinoyl chloride, cyanuric chloride and trichloroisocyanuric acid.
And the water phase reaction monomer is a binary or ternary amine compound, specifically p-xylylenediamine, piperazine, m-phenylenediamine, o-xylylenediamine, s-triazine and the like.
The mass percentage of the oil phase reaction monomer in the oil phase solution is 0.05-0.30 wt%, preferably 0.05-0.10 wt%.
The mass percentage of the aqueous phase reaction monomer in the aqueous phase solution is 0.20-1.0 wt%, preferably 0.20-0.40 wt%.
And the reaction time of the water phase reaction monomer and the oil phase reaction monomer is 15-30 min.
Preferably, the oil phase solution containing the oil phase reaction monomer is a normal hexane oil phase solution with the mass percentage of 0.05-0.10 wt% of trimesoyl chloride and a n-decane oil phase solution with the mass percentage of 0.05-0.10 wt% of trimesoyl chloride.
Preferably, the aqueous phase solution containing the aqueous phase reaction monomer is an aqueous phase solution containing 0.20-0.40 wt% of p-xylylenediamine, 0.20-0.40 wt% of piperazine and 0.20-0.40 wt% of m-phenylenediamine.
The oil phase solution is n-hexane, and can also be high in viscosity, such as kerosene, n-decane, etc., to control the reaction speed.
Various components such as a surfactant, graphene, carbon nano tubes, an organic metal framework material, a molecular sieve material, immobilized protein and the like can be added into the oil phase solution and the water phase solution to further regulate and control the aggregation state structure of the cross-linking layer so as to obtain a composite membrane with higher removal rate and higher membrane flux.
In order to improve the adhesion firmness of the pore caps on the surface of the porous base membrane, a reaction monomer in an oil phase or a reaction monomer in a water phase can be selected, and at least one of the reaction monomer and the reaction monomer can generate chemical bonding reaction with the porous base membrane material.
The porous base membrane material is a conventional ultramicro filter membrane material, such as polysulfone, polyethersulfone, polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride, polypropylene, polyethylene, polytetrafluoroethylene, cellulose acetate and the like. The prepared composite membrane is in the shape of hollow fiber type, plate frame type, roll type or tube type.
The method can also be used for preparing composite membranes such as gas separation membranes, pervaporation separation membranes and the like, and can also be applied to surface modification of porous membranes.
The invention has the advantages and positive effects that:
1. because two reaction monomers are respectively led in from two sides of the porous base membrane, the concentration and the supply quantity of the two reaction monomers are convenient to control, the reaction speed and the reaction degree of the two reaction monomers can be respectively controlled, the bottleneck of the prior art is broken through, and the aggregation structure of the crosslinking layer is easy to regulate and control, so that the composite membrane with higher removal rate is obtained;
2. only a cross-linking layer similar to a hole cap is formed at the opening of the membrane hole, and the hole can react to form a hole cap to block the membrane hole, so that a complete composite layer is not required to be formed on the surface of the porous base membrane, the defect of the composite layer is not easy to generate, and the composite membrane with higher removal rate can be obtained;
3. only a hat-like cross-linked layer is formed at the opening of the membrane hole to block the membrane hole, so that the technical requirement on the porous base membrane is reduced, the membrane hole can be blocked even if a large hole exists, the defect that the large hole easily generates a composite layer due to the fact that a complete composite layer is required to be formed on the surface of the porous base membrane is avoided, and the composite membrane with higher removal rate is obtained;
4. the reaction temperature of the oil phase solution and the water phase solution can be respectively controlled, so that the respective control of the interfacial polymerization reaction speed and the reaction degree is realized, and the composite membrane with higher removal rate can be obtained;
5. because the pores of the porous base membrane can directly influence the membrane flux of the composite membrane, the invention only forms a hat-like cross-linking layer at the openings of the membrane pores to block the membrane pores, and can select the porous base membrane with larger pore diameter, thereby obtaining larger membrane flux;
6. only a hat-like cross-linked layer is formed at the opening of the membrane hole to block the membrane hole, and a complete composite layer is not required to be formed on the surface of the porous base membrane, so that the thickness of the composite layer can be further reduced, and the membrane flux is improved;
7. because two reactants are respectively led in from two sides of the porous base membrane, the hollow fiber composite membrane can be conveniently prepared, and the internal pressure type or external pressure type hollow fiber composite membrane is obtained;
8. the concentration and the supply quantity of the two reaction monomers are convenient to control, thereby being beneficial to industrial stable production and simultaneously reducing the production cost;
9. because the oil phase solution and the water phase solution can be in a flowing state, compared with the prior art that the water phase solution and the oil phase solution are respectively coated on the same side of the membrane, the water phase solution and the oil phase solution can be respectively coated on the two sides of the membrane according to the prior art, and then the water phase solution and the oil phase solution can be respectively introduced into the permeation side flow channel and the stock solution side flow channel of the membrane component to carry out interfacial polymerization reaction after the preparation of the membrane component of the porous base membrane is finished, namely, the porous base membrane component is prepared firstly, and the preparation of the composite membrane is finished at the later stage.
Drawings
FIG. 1 is a schematic structural view of a composite membrane prepared by a conventional method;
FIG. 2 is a schematic diagram of a defect structure of a composite membrane prepared by a conventional method;
FIG. 3 is a schematic structural view of a first step of the present invention of wetting a porous base membrane with water from the permeate side of the porous base membrane;
FIG. 4 is a schematic structural view of a second step of covering the outside of the membrane pores with oily liquid according to the present invention;
FIG. 5 is a schematic structural diagram of the third step of diffusing the water phase reaction monomer into the pores of the membrane according to the present invention;
FIG. 6 is a schematic structural diagram of a composite membrane prepared according to the present invention.
In the figure, 1 is a porous base membrane, 2 is a membrane pore of the porous base membrane, 3 is a composite layer, 4 is a composite layer defect, 5 is water, 6 is an oil phase solution, 7 is a water phase solution, 8 is a large-size membrane pore of the porous base membrane, and 9 is the composite layer of the invention.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, which are illustrative only and not limiting, and the scope of the present invention is not limited thereby.
A method for preparing a composite membrane, as shown in FIGS. 3-6, comprises a first step of wetting a porous base membrane 1 from a permeable side thereof with water to fill pores 2 with liquid water 5; secondly, flowing an oil phase solution 6 containing an oil phase reaction monomer (such as binary or ternary acyl chloride compounds) on the surface (front surface) of the porous basement membrane, wherein the oily liquid can not enter membrane pores spontaneously and only covers the outer sides of the membrane pores; and thirdly, discharging water on the permeation side of the porous base membrane, introducing an aqueous phase solution 7 containing aqueous phase reaction monomers (such as binary or ternary amine compounds) into the permeation side of the porous base membrane, wherein the reaction monomers (amine compounds) in the aqueous phase solution diffuse into the membrane pores, contact with the reaction monomers (acyl chloride compounds) in the oil phase solution at the openings of the membrane pores, and perform interfacial polymerization reaction to form hat-like cross-linked reactants at the openings of the membrane pores, and the hat-like cross-linked layer 9 blocks the membrane pores 2 and the large-size membrane pores 8, so that the separation membrane such as the reverse osmosis membrane, the nanofiltration membrane and the like is prepared.
Comparative example 1
The method comprises the steps of coating a water phase solution containing 0.40 wt% of p-xylylenediamine on the surface (front surface) of a polysulfone flat porous basement membrane, and then coating a normal hexane oil phase solution containing 0.10 wt% of trimesoyl chloride to prepare the flat reverse osmosis composite membrane by adopting the prior art. Under the test pressure of 1.5MPa, the retention rate of 1000mg/L sodium chloride aqueous solution is 95 percent, and the pure water membrane flux is 21L/m2.h。
Example 1
Firstly, coating pure water on the transmission side of a polysulfone flat porous base membrane to wet the porous base membrane, filling liquid water in membrane pores, then continuously coating a normal hexane oil phase solution containing 0.10 wt% of trimesoyl chloride on the surface (front side) of the porous base membrane, thirdly, continuously coating a water phase solution containing 0.40 wt% of p-xylylenediamine on the transmission side of the porous base membrane for 15 minutes to diffuse p-phenylenediamine in the water phase solution into the membrane pores, enabling the openings of the membrane pores to be in contact with trimesoyl chloride reaction monomers in the oil phase solution to generate interfacial polymerization reaction, forming a pore cap-shaped cross-linking layer at the openings of the membrane pores, and plugging the membrane pores, thereby preparing the flat reverse osmosis membrane. Under the test pressure of 1.5MPa, the retention rate of 1000mg/L sodium chloride aqueous solution is 98 percent, and the pure water membrane flux is 28L/m2H. Both membrane flux and rejection were improved compared to comparative example 1.
Example 2
A flat reverse osmosis membrane was prepared using a 0.08 wt% concentration aqueous n-hexane phase solution of trimesoyl chloride, and 0.20 wt% concentration of p-xylylenediamine, otherwise prepared under the conditions of example 1. Under the test pressure of 1.5MPa, the retention rate of 1000mg/L sodium chloride aqueous solution is 98 percent, and the pure water membrane flux is 38L/m2. h. The reaction monomer concentration was reduced and the membrane flux was further increased compared to example 1.
Example 3
Firstly, coating pure water on the permeation side of a polysulfone flat porous base membrane to wet the porous base membrane, filling liquid water in membrane pores,and then continuously coating a normal hexane oil phase solution containing 0.08 wt% of trimesoyl chloride on the surface (front surface) of the porous base membrane, and in the third step, continuously coating a water phase solution containing 0.25 wt% of piperazine on the permeation side of the porous base membrane, so that the piperazine in the water phase solution is diffused into membrane pores, and is contacted with trimesoyl chloride reaction monomers in the oil phase solution at the openings of the membrane pores to generate interfacial polymerization reaction, and a pore-cap-shaped cross-linking layer is formed at the openings of the membrane pores to plug the membrane pores, thereby preparing the flat nanofiltration membrane. Under the test pressure of 0.3MPa, the retention rate of the sodium sulfate aqueous solution is 1000mg/L, the pure water membrane flux is 48L/m2.h。
Example 4
Introducing 25 ℃ pure water into a permeation side pipeline or a stock solution side pipeline of the roll-type ultrafiltration membrane component to wet a porous base membrane, filling liquid water into membrane pores, discharging the water in the roll-type ultrafiltration membrane component out of the membrane component, introducing a 15 ℃ n-hexane oil phase solution containing 0.08 wt% of trimesoyl chloride from a stock solution inlet of the roll-type ultrafiltration membrane component, flowing out from a stock solution outlet of the roll-type ultrafiltration membrane component, circulating the oil phase on the stock solution side of the roll-type ultrafiltration membrane component by an oil phase circulating pump, introducing a 25 ℃ water phase solution containing 0.30 wt% of m-phenylenediamine from one side of a water production end of the roll-type ultrafiltration membrane component, flowing out from the other side port of the water production end of the roll-type ultrafiltration membrane component, and circulating the water phase on the water production side of the roll-type ultrafiltration membrane component by a water phase circulating pump. And after 30 minutes, stopping the circulation of the oil phase solution and the water phase solution, and discharging the oil phase solution and the water phase solution out of the roll-type membrane component to prepare the roll-type reverse osmosis membrane component. Under the test pressure of 1.5MPa, the retention rate of 1000mg/L sodium chloride aqueous solution is 97 percent, and the pure water membrane flux is 32L/m2.h。
Example 5
Introducing 25 ℃ pure water into the tube side of a hollow fiber ultrafiltration membrane component of cellulose diacetate until water flows out of the shell side of the hollow fiber ultrafiltration membrane component, then discharging the water of the tube side and the shell side of the hollow fiber ultrafiltration membrane component out of the membrane component, then introducing a 25 ℃ n-hexane oil phase solution containing 0.07 wt% of trimesoyl chloride from the shell side inlet of the hollow fiber ultrafiltration membrane component through an oil phase circulating pump, and then introducing the n-hexane oil phase solution from the hollow fiber ultrafiltration membrane componentAnd (3) allowing the water to flow out from a shell pass outlet of the hollow fiber ultrafiltration membrane component, introducing a 25 ℃ water phase solution containing 0.25 wt% of m-phenylenediamine from a tube pass inlet of the hollow fiber ultrafiltration membrane component through a water phase circulating pump, and allowing the water phase solution to flow out from a tube pass outlet of the hollow fiber ultrafiltration membrane component. And after 30 minutes, stopping the circulation of the oil phase solution and the water phase solution, and discharging the oil phase solution and the water phase solution out of the hollow fiber membrane component, thereby preparing the external pressure hollow fiber reverse osmosis membrane component. Under the test pressure of 1.5MPa, the retention rate of 1000mg/L sodium chloride aqueous solution is 98 percent, and the pure water membrane flux is 20L/m2.h。
Example 6
Introducing 25 ℃ pure water into a tube side of a polyvinyl chloride hollow fiber ultrafiltration membrane component until water flows out of a shell side of the hollow fiber ultrafiltration membrane component, then discharging the water of the tube side and the shell side of the hollow fiber ultrafiltration membrane component out of the membrane component, introducing a 25 ℃ n-decane oil phase solution containing 0.07 wt% of trimesoyl chloride from a tube side inlet of the hollow fiber ultrafiltration membrane component through an oil phase circulating pump, flowing out of a tube side outlet of the hollow fiber ultrafiltration membrane component, then introducing a 25 ℃ water phase solution containing 0.25 wt% of piperazine from a shell side inlet of the hollow fiber ultrafiltration membrane component through a water phase circulating pump, and flowing out of a shell side outlet of the hollow fiber ultrafiltration membrane component. And after 30 minutes, stopping the circulation of the oil phase solution and the water phase solution, and discharging the oil phase solution and the water phase solution out of the hollow fiber membrane component so as to prepare the internal pressure hollow fiber nanofiltration membrane component. Under the test pressure of 0.3MPa, the retention rate of the sodium sulfate aqueous solution is 1000mg/L, the pure water membrane flux is 45L/m2.h。
Although the embodiments of the present invention and the accompanying drawings are disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the disclosure of the embodiments and the accompanying drawings.
Claims (9)
1. A preparation method of a composite film is characterized by comprising the following steps: introducing an oil phase reaction monomer and a water phase reaction monomer which participate in polymerization reaction from two sides of the porous base membrane respectively, wherein the oil phase reaction monomer covers the outer side of the membrane hole, the water phase reaction monomer diffuses into the membrane hole, and contacts with the oil phase reaction monomer at the opening of the membrane hole to carry out interfacial polymerization reaction to form a hole-hat-shaped cross-linked layer;
the method comprises the following steps:
firstly, wetting a porous base membrane from the permeation side of the porous base membrane by water to fill liquid water in membrane pores;
secondly, flowing an oil phase solution containing an oil phase reaction monomer on the front surface of the porous base membrane, wherein the oil phase solution covers the outer side of the membrane pores;
and thirdly, after water on the permeation side of the porous base membrane is discharged, introducing a water phase solution containing a water phase reaction monomer into the permeation side of the porous base membrane, diffusing the reaction monomer in the water phase solution into the membrane hole, contacting the reaction monomer in the oil phase solution at the opening of the membrane hole to perform interfacial polymerization reaction, forming a cross-linking reactant at the opening of the membrane hole, and plugging the membrane hole by a hole-cap-shaped cross-linking layer, thereby preparing the composite membrane.
2. A method of making a composite membrane according to claim 1, wherein: the oil phase reaction monomer is a binary or ternary acyl chloride compound.
3. A method of making a composite membrane according to claim 1, wherein: the water phase reaction monomer is a binary or ternary amine compound.
4. A method of making a composite membrane according to claim 1, wherein: the oil phase solution is normal hexane, kerosene, n-decane and cyclohexane.
5. A method of making a composite membrane according to claim 1, wherein: and adding a compound for regulating the aggregation state structure of the cross-linked layer into the oil phase solution and/or the water phase solution.
6. A method of making a composite membrane according to claim 5, wherein: the compound for regulating the aggregation structure of the cross-linked layer is one or a mixture of more than two of a surfactant, graphene, a carbon nano tube, an organic metal framework material and a molecular sieve material.
7. A method of making a composite membrane according to claim 1, wherein: the oil phase reaction monomer and/or the water phase reaction monomer are/is a monomer which has chemical bonding reaction with the porous base membrane material.
8. A method of making a composite membrane according to claim 1, wherein: the membrane material is one or a mixture of more than two of polysulfone, polyethersulfone, polyacrylonitrile, polyvinyl chloride, polyvinylidene fluoride, polypropylene, polyethylene, polytetrafluoroethylene and cellulose acetate; the prepared composite membrane is in the shape of hollow fiber type, plate frame type, roll type or tube type.
9. A method of making a composite membrane according to claim 1, wherein: the prepared composite membrane is used for reverse osmosis membranes, nanofiltration membranes, gas separation membranes and pervaporation separation membranes.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010068833.7A CN111229050B (en) | 2020-01-21 | 2020-01-21 | Preparation method of composite membrane |
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| CN202010068833.7A CN111229050B (en) | 2020-01-21 | 2020-01-21 | Preparation method of composite membrane |
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| CN111249919B (en) * | 2020-02-19 | 2021-09-24 | 天津工业大学 | Hydrophobic membrane surface modification method |
| CN112076714A (en) * | 2020-09-28 | 2020-12-15 | 合肥学院 | Method for preparing composite membrane by interfacial polymerization reaction and reaction device |
| CN114432896A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of nanofiltration membrane |
| CN112892234A (en) * | 2021-02-05 | 2021-06-04 | 天津工业大学 | Regeneration and repair method of composite membrane assembly |
| CN114028958A (en) * | 2021-12-17 | 2022-02-11 | 启成（江苏）净化科技有限公司 | Preparation method for improving desalination rate of reverse osmosis membrane |
| CN114682105B (en) * | 2022-06-02 | 2022-08-23 | 天津大学 | Preparation method and application of strong-polarity-resistant organic solvent nanofiltration membrane |
| CN114797504B (en) * | 2022-06-07 | 2023-05-26 | 青岛科技大学 | Sulfonated polyamide/hydrophobic polymer composite membrane and preparation method and application thereof |
| CN115569526B (en) * | 2022-12-07 | 2023-03-10 | 湖南沁森高科新材料有限公司 | Preparation method of multilayer stepped polyamide composite separation membrane |
| CN115945078B (en) * | 2023-02-22 | 2023-09-12 | 泰州南潇新材料科技有限公司 | Preparation method of hollow fiber polyamide membrane |
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