CN115945078B - Preparation method of hollow fiber polyamide membrane - Google Patents
Preparation method of hollow fiber polyamide membrane Download PDFInfo
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- CN115945078B CN115945078B CN202310148355.4A CN202310148355A CN115945078B CN 115945078 B CN115945078 B CN 115945078B CN 202310148355 A CN202310148355 A CN 202310148355A CN 115945078 B CN115945078 B CN 115945078B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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Abstract
Compared with the prior art, the preparation method has the advantages that the polyamide layer with macropores is firstly prepared, the polyacrylonitrile support membrane with the hydrophilicity improved by alkali decomposition is used for adsorbing more aqueous phase monomers again, the flow rate is controlled so that the aqueous phase monomers are only adsorbed by the support membrane, and therefore, the second interfacial polymerization can occur in the macropores of the polyamide, the compactness of the polyamide layer is improved, the membrane thickness is hardly improved, and the advantages of the hollow fiber membrane are combined, so that the membrane flux is remarkably improved.
Description
Technical Field
The application relates to a preparation method of a membrane material, in particular to a preparation method of a hollow fiber polyamide membrane.
Background
Polyamide (PA) is a common separation membrane material that is commonly used in nanofiltration, reverse osmosis, forward osmosis, and other separation processes. Recently, due to its excellent physicochemical properties, many researchers have tried to apply it to pervaporation for separation of organic matter and water, with good results, but the above-mentioned researches are generally found in journal paper because it requires a special monomer or complicated modification operation, and is not suitable for industrial production. Patent application publication No. CN1951549A discloses a polyamide composite membrane, which is prepared by continuously loading 3-4 polyamide layers on a polyamide RO membrane, but the method has high mass transfer resistance and low permeation flux due to stacking a plurality of polyamide layers, and also does not meet the industrial requirements.
The existing polyamide membrane is generally a support membrane and is often a flat membrane, when the polyamide membrane is applied to pervaporation, the flat membrane brings the defects of lower flux and low filling density, and the hollow fiber membrane can improve the filling density and the mass transfer flux of the membrane due to the special form of the hollow fiber membrane, but the hollow fiber polyamide membrane is not applied to organic matter dehydration at present.
Disclosure of Invention
Therefore, the application provides a preparation method of the polyamide membrane applied to pervaporation dehydration, which does not need special monomers and complex post-modification operation, greatly improves the flux of pervaporation and has higher application potential.
The application aims at providing a preparation method of a hollow fiber polyamide membrane, which comprises the following process steps:
1) Sequentially soaking a polyamine I aqueous phase solution and an aromatic polybasic acyl chloride I organic phase solution I after sealing two ends of a polyacrylonitrile hollow fiber membrane to generate a polyamide macroporous through interfacial polymerization reaction on the surface of the polyacrylonitrile hollow fiber membrane, wherein the contact time is sequentially 5-20s and 2-10s;
2) Opening the two ends of the polyacrylonitrile hollow fiber membrane to seal, and continuously passing 0.1-1mol/L alkali solution through the two ends of the polyacrylonitrile hollow fiber membrane to convert the nitrile group of the polyacrylonitrile support membrane into carboxyl and amide groups;
3) Continuously passing the aqueous phase solution of the polyamine II through two ends of the polyacrylonitrile hollow fiber membrane after the polyacrylonitrile hollow fiber membrane is dried so that the polyacrylonitrile hollow fiber membrane adsorbs the aqueous phase solution of the polyamine II;
4) Sealing the two ends of the polyacrylonitrile hollow fiber membrane, and then immersing the polyacrylonitrile hollow fiber membrane in an aromatic polybasic acyl chloride II organic phase solution to enable polybasic amine II and polybasic acyl chloride II to continue to undergo interfacial polymerization at a polyamide macroporous part to form a compact pore, wherein the immersion time is 20-100s;
5) The polyacrylonitrile hollow fiber membrane is subjected to heat treatment to obtain a hollow fiber polyamide membrane.
Preferably, the polyacrylonitrile hollow fiber membrane has a weight average molecular weight of 50000-500000, an average pore diameter of 0.03-0.5 μm and an inner diameter of 2-4mm.
Preferably, the flow time is controlled to be 10-50 seconds in the step 2), and the flow rate is controlled to be 20-80mL/min.
Preferably, the flow time is controlled to be 10-100s in the step 3), and the flow rate is controlled to be 5-50mL/min.
Preferably, the polyamine I is piperazine or fatty amine, and the concentration is 0.5-2wt%; the aromatic polybasic acyl chloride I is isophthaloyl dichloride, terephthaloyl dichloride or phthalic acid dichloride, the concentration is 0.1-1wt%, and the organic phase is one of cyclohexane, n-hexane, n-heptane and octane.
Preferably, the polyamine II is m-phenylenediamine, p-phenylenediamine or o-phenylenediamine, the concentration is 3-5wt%, and the aqueous solution of the polyamine II further comprises 0.2-0.5wt% of acid binding agent and 0.1-1wt% of surfactant; the aromatic polybasic acyl chloride II is trimesoyl chloride with the concentration of 2-5wt%.
Preferably, steps 3) and 4) are repeated 1-2 times before step 5).
Preferably, the heat treatment temperature of step 5) is 50-80 ℃ and the drying is carried out for 5-24 hours.
It is a second object of the present application to provide a hollow fiber polyamide membrane comprising a modified polyacrylonitrile support membrane and a single polyamide membrane layer.
The application also aims to provide an application of the hollow fiber polyamide membrane in the aspect of dehydrating pervaporation organic matters.
Compared with the prior art that the density of the membrane is improved by adopting a plurality of polyamide membrane layers, the application firstly prepares the polyamide layer with macropores, utilizes the polyacrylonitrile support membrane with the hydrophilicity improved by alkali decomposition to adsorb more aqueous phase monomers again, and controls the flow rate to ensure that the aqueous phase monomers are only adsorbed by the support membrane, so that the second interfacial polymerization can occur in the macropores of the polyamide, thereby improving the compactness of the polyamide layer and hardly improving the membrane thickness, and combining the advantages of the hollow fiber membrane, thereby obviously improving the membrane flux.
Drawings
FIG. 1 is an SEM characterization of the polyamide membrane of example 1 (left-cross section, right-surface).
Detailed Description
In order to make the objects, technical schemes and advantages of the present application more apparent, the high-strength and high-flux hollow fiber membranes of the present application and the method for preparing the same will be described in further detail with reference to examples and comparative examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
Example 1
1) Taking a polyacrylonitrile hollow fiber membrane, wherein the weight average molecular weight is 800000, the average pore diameter is 0.2 mu m, the inner diameter is 3.3mm, taking piperazine and water which are dissolved in water as a polyamine I aqueous phase solution with the concentration of 0.5wt%, and taking isophthaloyl dichloride and cyclohexane which are mixed as an aromatic polybasic acyl chloride I solution with the concentration of 0.8 wt%; sealing the two ends of the polyacrylonitrile hollow fiber membrane by using polytetrafluoroethylene adhesive tapes,
firstly, dipping polyamine I aqueous phase solution for 10s, and then dipping the polyamide I aqueous phase solution into aromatic polybasic acyl chloride I organic phase solution I5s to perform interfacial polymerization reaction on the surface of a polyacrylonitrile hollow fiber membrane to generate a polyamide macroporous;
2) Opening two ends of a polyacrylonitrile hollow fiber membrane to seal, continuously passing 0.5mol/L sodium hydroxide solution through the two ends of the polyacrylonitrile hollow fiber membrane through a diaphragm pump to convert the nitrile group of a polyacrylonitrile support membrane into carboxyl and amide groups, controlling the circulation time to be 20 seconds, and controlling the flow rate to be 50mL/min;
3) Drying the polyacrylonitrile hollow fiber membrane; dissolving 5wt% of m-phenylenediamine, 0.2wt% of sodium carbonate and 0.5wt% of N-methylpyrrolidone in water to form a polyamine II aqueous phase solution, and continuously providing power for the polyamine II aqueous phase solution through two ends of a polyacrylonitrile hollow fiber membrane by using a diaphragm pump so that the polyamine II aqueous phase solution is adsorbed by the polyacrylonitrile hollow fiber membrane;
4) Dissolving trimesoyl chloride in n-hexane to form an aromatic polybasic acyl chloride II organic phase solution with the concentration of 3.5wt%, sealing two ends of a polyacrylonitrile hollow fiber membrane, and then soaking the polyacrylonitrile hollow fiber membrane in the aromatic polybasic acyl chloride II organic phase solution to enable polybasic amine II and polybasic acyl chloride II to continue to undergo interfacial polymerization at a polyamide macroporous site to form a compact pore, wherein the soaking time is 50s;
5) And drying the polyacrylonitrile hollow fiber membrane for 12 hours at 60 ℃ to obtain the hollow fiber polyamide membrane.
SEM characterization of the example 1 film showed that the polyamide layer was a single layer structure with dense pores. The hollow fiber polyamide membrane was used for pervaporation isopropyl alcohol (IPA) dehydration characterization, the feed liquid comprising 90wt% isopropyl alcohol and 10wt% water, the temperature being 80 ℃, the operating temperature being room temperature, the vacuum degree being 400Pa, the feed side pressure being 0.1MPa. Characterized in that the hollow fiber polyamide membrane flux is 226g/m 2 H, the water content in the permeate is 81.25% by weight.
Example 2
The remaining conditions were the same as in example 1, and steps 3) and 4) were repeated twice just before step 5), resulting in a hollow fiber polyamide membrane flux of 97.3g/m 2 H, the water content in the permeate is 96.56% by weight.
Comparative example 1
The other conditions were the same as in example 1 except that step (2) was omitted, and the hollow fiber polyamide membrane flux was 120.3g/m 2 H, the water content in the permeate is 80.23% by weight.
Comparative example 2
The remaining conditions were the same as in example 1, except that the sequences of steps 1) and 2) were interchanged, and the resulting hollow fiber polyamide membrane flux was 130.8g/m 2 H, the water content in the permeate is 51.35% by weight.
Comparative example 3
The other conditions were the same as in example 1 except that in step 3), the hollow fiber membrane of polyacrylonitrile was immersed in the aqueous solution of polyamine II for 20 seconds, and the flux of the hollow fiber polyamide membrane was 137.3g/m 2 H, the water content in the permeate was 37.33wt%.
The present application is not limited to the above-mentioned preferred embodiments, and any person who can obtain other various products under the teaching of the present application can make any changes in shape or structure, and all the technical solutions that are the same or similar to the present application fall within the scope of the present application.
Claims (10)
1. The preparation method of the hollow fiber polyamide membrane is characterized in that the hollow fiber polyamide membrane is used for pervaporation dehydration, and the preparation method comprises the following process steps:
1) Sealing two ends of a polyacrylonitrile hollow fiber membrane, sequentially soaking a polyamine I aqueous phase solution and an aromatic polybasic acyl chloride I organic phase solution I to generate a polyamide macroporous through interfacial polymerization reaction on the surface of the polyacrylonitrile hollow fiber membrane;
2) Opening the two ends of the polyacrylonitrile hollow fiber membrane to seal, and continuously passing 0.1-1mol/L alkali solution through the two ends of the polyacrylonitrile hollow fiber membrane to convert the nitrile group of the polyacrylonitrile support membrane into carboxyl and amide groups;
3) Continuously passing the aqueous phase solution of the polyamine II through two ends of the polyacrylonitrile hollow fiber membrane after the polyacrylonitrile hollow fiber membrane is dried so that the polyacrylonitrile hollow fiber membrane adsorbs the aqueous phase solution of the polyamine II;
4) Sealing the two ends of the polyacrylonitrile hollow fiber membrane, and then immersing the polyacrylonitrile hollow fiber membrane in an aromatic polybasic acyl chloride II organic phase solution to enable polybasic amine II and polybasic acyl chloride II to continue to undergo interfacial polymerization at a polyamide macroporous part to form a compact pore, wherein the immersion time is 20-100s;
5) The polyacrylonitrile hollow fiber membrane is subjected to heat treatment to obtain a hollow fiber polyamide membrane.
2. The method for producing a hollow fiber polyamide membrane according to claim 1, characterized in that the polyacrylonitrile hollow fiber membrane has a weight average molecular weight of 50000 to 500000, an average pore diameter of 0.03 to 0.5 μm, and an inner diameter of 2 to 4mm.
3. The method for producing a hollow fiber polyamide membrane according to claim 1, wherein the flow time is controlled to be 10 to 50 seconds and the flow rate is controlled to be 20 to 80mL/min in step 2).
4. The method for producing a hollow fiber polyamide membrane according to claim 1, wherein the flow time is controlled to be 10 to 100 seconds and the flow rate is controlled to be 5 to 50mL/min in step 3).
5. The method for producing a hollow fiber polyamide membrane according to claim 1, characterized in that the polyamine I is piperazine or fatty amine at a concentration of 0.5 to 2wt%; the aromatic polybasic acyl chloride I is isophthaloyl dichloride, terephthaloyl dichloride or phthalic acid dichloride, the concentration is 0.1-1wt%, and the organic phase is one of cyclohexane, n-hexane, n-heptane and octane.
6. The method for preparing the hollow fiber polyamide membrane according to claim 1, wherein the polyamine II is m-phenylenediamine, p-phenylenediamine or o-phenylenediamine, the concentration is 3-5wt%, and the aqueous solution of the polyamine II further comprises 0.2-0.5wt% of an acid binding agent and 0.1-1wt% of a surfactant; the aromatic polybasic acyl chloride II is trimesoyl chloride with the concentration of 2-5wt%.
7. The method for producing a hollow fiber polyamide membrane according to claim 1, characterized in that steps 3) and 4) are repeated 1 to 2 times before step 5) is performed.
8. The method for producing a hollow fiber polyamide membrane according to claim 1, wherein the heat treatment temperature in step 5) is 50 to 80 ℃ and is dried for 5 to 24 hours.
9. A hollow fiber polyamide membrane prepared according to the preparation method of any one of claims 1 to 8, characterized in that the hollow fiber polyamide membrane comprises a modified polyacrylonitrile support membrane and a single polyamide membrane layer.
10. Use of a hollow fiber polyamide membrane according to claim 9 for dewatering pervaporation organics.
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|---|---|---|---|---|
| JPH07284639A (en) * | 1994-04-20 | 1995-10-31 | Toyobo Co Ltd | Production of composite hollow membrane |
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| CN114471181A (en) * | 2021-12-29 | 2022-05-13 | 北京工业大学 | Preparation method of high-permeability zwitterionic hollow fiber nanofiltration membrane |
| CN115105965A (en) * | 2021-03-17 | 2022-09-27 | 中国科学院过程工程研究所 | Method for eliminating defects of hollow fiber gas separation membrane module |
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2023
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| JPH07284639A (en) * | 1994-04-20 | 1995-10-31 | Toyobo Co Ltd | Production of composite hollow membrane |
| CN106268371A (en) * | 2016-08-08 | 2017-01-04 | 贵阳时代沃顿科技有限公司 | A kind of polyacrylonitrile hollow fiber ultrafilter membrane and preparation method thereof |
| CN106621855A (en) * | 2017-01-18 | 2017-05-10 | 南京湶膜科技有限公司 | Preparation method of reverse osmosis composite membrane and reverse osmosis composite membrane |
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| CN114471181A (en) * | 2021-12-29 | 2022-05-13 | 北京工业大学 | Preparation method of high-permeability zwitterionic hollow fiber nanofiltration membrane |
| CN115518525A (en) * | 2022-10-13 | 2022-12-27 | 常州大学 | Preparation method and application of in-situ secondary interfacial polymerization hydrophilic modified ultrathin composite membrane |
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