CN115253698A - Preparation method of fiber-reinforced hollow fiber nanofiltration membrane - Google Patents

Preparation method of fiber-reinforced hollow fiber nanofiltration membrane Download PDF

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Publication number
CN115253698A
CN115253698A CN202110477631.2A CN202110477631A CN115253698A CN 115253698 A CN115253698 A CN 115253698A CN 202110477631 A CN202110477631 A CN 202110477631A CN 115253698 A CN115253698 A CN 115253698A
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China
Prior art keywords
parts
nanofiltration membrane
fiber
hollow fiber
mass
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CN202110477631.2A
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Chinese (zh)
Inventor
李梁梁
胡晓宇
高旭
王春浩
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Tianjin Motimo Membrane Technology Co Ltd
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Tianjin Motimo Membrane Technology Co Ltd
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Priority to CN202110477631.2A priority Critical patent/CN115253698A/en
Publication of CN115253698A publication Critical patent/CN115253698A/en
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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
    • 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
    • B01D69/08—Hollow fibre membranes
    • 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
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention belongs to the field of membrane preparation, and particularly relates to a preparation method of a fiber-reinforced hollow fiber nanofiltration membrane, which comprises the following steps: 1) Coating a base film: soaking the braided tube component with a solvent which is the same as the feed liquid; after the material is completely discharged, the material liquid is pushed out of the braided tube component from top to bottom by using nitrogen; standing, immersing in deionized water for curing, cleaning to obtain a coated base film, and immersing in deionized water again for later use; 2) Preparing a desalting functional layer: soaking the coated base film in an aqueous phase solution for 5-60s from bottom to top, and then draining the aqueous phase; standing for 2min; then the oil phase solution is reacted for 1-20min from bottom to top to push out the soaked coated base film, and the oil phase is emptied; blowing with hot air at 80 deg.C for 10s to obtain product; the breaking strength of the fiber-reinforced hollow fiber nanofiltration membrane obtained by the preparation method of the fiber-reinforced hollow fiber nanofiltration membrane is remarkably improved. Greatly reduces the broken wire rate and obviously improves the pressure resistance.

Description

Preparation method of fiber-reinforced hollow fiber nanofiltration membrane
Technical Field
The invention belongs to the field of membrane preparation, and particularly relates to a preparation method of a fiber-reinforced hollow fiber nanofiltration membrane.
Background
The hollow fiber nanofiltration membrane is usually in a self-supporting structure, namely a base membrane is used for bearing pressure, and a desalination function layer is used for removing salts and small molecules. To achieve a certain pressure resistance, the base membrane needs to have a sufficient thickness, but the thicker the base membrane, the lower the water flux, and the membrane performance cannot be further improved. Meanwhile, in order to ensure the water yield, the tensile strength along the radial direction of the fiber is limited, so that the yarn breakage can be inevitable in the long-term use process.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a fiber-reinforced hollow fiber nanofiltration membrane.
In order to realize the purpose, the invention adopts the technical scheme that:
a preparation method of a fiber-reinforced hollow fiber nanofiltration membrane comprises the following steps:
1) Coating a base film: soaking the braided tube component with a solvent which is the same as the feed liquid; after the material is completely discharged, the material liquid is pushed out of the braided tube assembly from top to bottom by using nitrogen; standing, immersing in deionized water for curing, cleaning to obtain a coated base film, and immersing in deionized water again for later use;
the feed liquid comprises the following components in parts by mass: 18-33 parts of main material, 0-5 parts of forming auxiliary agent and 100 parts of solvent; preferably, the molding auxiliary comprises 25 parts by mass of a main material, 3 parts by mass of a molding auxiliary and 100 parts by mass of a solvent;
2) Preparing a desalting functional layer: soaking the coated base film in an aqueous phase solution from bottom to top for 5-60s, preferably, soaking for 20s, and draining the aqueous phase; standing for 2min; then the oil phase solution is reacted for 1-20min from bottom to top, the soaked coating base membrane is pushed out, and the oil phase is emptied; blowing with hot air at 80 deg.C for 10s to obtain product;
the aqueous phase solution comprises the following components in parts by mass: 0.1-16 parts of polyamine compound, 0.01-5 parts of proton absorbent, 0.01-3 parts of polymerization accelerator and 100 parts of deionized water; the oil phase solution comprises 0.01-4 parts by mass of polyfunctional acyl chloride, 0.01-5 parts by mass of halogenated hydrocarbon and 100 parts by mass of organic solvent.
Preferably, the aqueous phase solution comprises the following components in parts by mass: 2-4 parts of polyamine compound, 0.1-0.5 part of proton absorbent, 0.2 part of polymerization accelerator and 100 parts of deionized water; the oil phase solution contains 0.4 part by mass of polyfunctional acyl chloride, 0.8 part by mass of halogenated hydrocarbon and 100 parts by mass of organic solvent.
The main material is one of polysulfone, polyethersulfone and polyvinylidene fluoride.
The forming auxiliary agent is one of lithium chloride, polyoxyethylene 400, glycol and polyvinylpyrrolidone.
The solvent is one of Dimethylacetamide (DMAC), dimethylformamide (DMF) or N-methylpyrrolidone (NMP).
The polyamine compound is one or a mixture of more of phenylenediamine, piperazine, homopiperazine, ethylenediamine, hexamethylenediamine, melamine, 1, 2-cyclohexanediamine, aminoethyl piperazine, o-phenylenediamine, p-phenylenediamine, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine and 4,4' -diphenyldiamine.
The polymerization accelerator is one of polyvinylpyrrolidone, poly (methyl) acrylamide, polyhydroxyethyl methacrylate and polypropylene glycol.
The proton absorbent is one of triethylamine, triethylene diamine, trimethylamine, N, N' -dimethyl piperazine, sodium hydroxide, potassium hydroxide, sodium phosphate and sodium carbonate.
The polyfunctional acyl chloride is one of trimesoyl chloride, adipoyl chloride and sebacoyl chloride.
The organic solvent is one of isoparaffin, normal hexane, cyclohexane and heptane.
The halogenated hydrocarbon is one of chloroform, dichloromethane, bromoform, dibromomethane, iodoform and diiodomethane.
Compared with the prior art, the invention has the beneficial effects that:
the breaking strength of the fiber-reinforced hollow fiber nanofiltration membrane obtained by the preparation method of the fiber-reinforced hollow fiber nanofiltration membrane is remarkably improved. Greatly reduces the broken wire rate and obviously improves the pressure resistance.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the preferred embodiments.
Example 1: the feed liquid formula is as follows: 25 parts by mass of polysulfone, 3 parts by mass of lithium chloride and 100 parts by mass of dimethylacetamide. Stirred at 60 ℃ for 24 hours and then left to stand for 24 hours.
Coating a base film: the braided tube assembly was first soaked with the same solvent as the feed solution for 5min. After purging, the feed liquid is pushed out of the module from top to bottom under a certain pressure using nitrogen. Standing for 60s, soaking in deionized water, curing for 10min, cleaning, and soaking in deionized water again for use.
The water phase formula comprises: comprises 2 parts by mass of piperazine, 0.5 part by mass of triethylamine, 0.2 part by mass of polyvinylpyrrolidone and 100 parts by mass of deionized water.
The oil phase formula comprises: comprises 0.4 part by mass of trimesoyl chloride, 0.5 part by mass of dichloromethane and 100 parts by mass of n-hexane.
Preparing a desalting functional layer: soaking the coated base film obtained in the step 1) for 20 seconds from bottom to top by using an aqueous phase solution, and then draining the aqueous phase. Standing for 2min. And pushing the soaked coated base membrane in an oil phase solution from bottom to top, reacting for 2min, and then emptying the oil phase. Blowing with hot air at 80 deg.C for 10s to obtain the final product.
Example 2: the feed liquid formula is as follows: 25 parts by mass of polysulfone, 400,3 parts by mass of polyoxyethylene and 100 parts by mass of dimethylacetamide. The rest was the same as in example 1.
Example 3: the water phase formula comprises: comprises 2 parts by mass of m-phenylenediamine, 0.5 part by mass of triethylamine, 0.2 part by mass of polyvinylpyrrolidone and 100 parts by mass of deionized water. The rest is the same as in example 1.
Example 4: the water phase formula comprises: comprises 2 parts by mass of 1, 4-cyclohexanediamine, 0.5 part by mass of triethylamine, 0.2 part by mass of polyvinylpyrrolidone and 100 parts by mass of deionized water. The rest is the same as in example 1.
Example 5: the water phase formula comprises: comprises piperazine 2 weight portions, sodium hydroxide 0.1 weight portions, polyvinylpyrrolidone 0.2 weight portions and deionized water 100 weight portions. The rest was the same as in example 1.
Example 6: the water phase formula comprises: comprises 2 parts by mass of piperazine, 0.5 part by mass of sodium phosphate, 0.2 part by mass of polyvinylpyrrolidone and 100 parts by mass of deionized water. The rest is the same as in example 1.
Example 7: the water phase formula comprises: comprises 4 parts by mass of piperazine, 0.5 part by mass of triethylamine, 0.2 part by mass of polyvinylpyrrolidone and 100 parts by mass of deionized water. The rest was the same as in example 1.
Example 8: the oil phase formula comprises: comprises 0.8 mass part of trimesoyl chloride, 0.5 mass part of dichloromethane and 100 mass parts of normal hexane. The rest is the same as in example 1.
Example 9: the oil phase formula comprises: comprises 0.4 parts by mass of trimesoyl chloride, 0.5 parts by mass of dichloromethane and 100 parts by mass of isoparaffin. The rest is the same as in example 1.
Example 10: preparing a desalting functional layer: the aqueous solution was allowed to soak for 20 seconds from the bottom up, and then the aqueous phase was drained. Standing for 2min. Then the oil phase solution is reacted for 2min from bottom to top, and the oil phase is emptied. The rest was the same as in example 1.
Comparative example 1 the base film coating process was not wet out and the rest was the same as in example 1.
Comparative example 2 the base film coating process was not left to stand, and the rest was the same as in example 1.
Comparative example 3 the desalination function layer was prepared without hot air blowing, and the procedure was otherwise the same as in example 1.
Nanofiltration membrane separation performance test method
Testing liquid: the test was carried out using a 2000mg/L magnesium sulfate solution.
The operating parameters are as follows: a nanofiltration membrane evaluator is adopted for testing, the pressure is 0.5MPa, the temperature is 25 ℃, the pH =7.0, and the recovery rate is 15%.
Calculating the formula:
the retention rate R = (CI-CO)/CI x 100%, wherein CI is water inlet conductance, and CO is water outlet conductance;
flux F = V/(a × T), where V is water production volume, a is membrane area, and T is measurement time.
Table 1 shows the results of the runs of the different examples and comparative examples.
TABLE 1
Magnesium sulfate,% Water flux, L/(m)2*h)
Example 1 97 46
Example 2 98 42
Example 3 97 45
Example 4 97 43
Example 5 96 47
Example 6 97 41
Example 7 95 40
Example 8 98 38
Example 9 96 39
Example 10 97 44
Comparative example 1 35 62
Comparative example 2 92 8
Comparative example 3 88 27
From the data, it can be seen that the membrane material with good performance can be obtained by adopting the fiber reinforced hollow fiber nanofiltration membrane.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.

Claims (10)

1. A preparation method of a fiber-reinforced hollow fiber nanofiltration membrane is characterized by comprising the following steps:
1) Coating a base film: soaking the braided tube component with a solvent which is the same as the feed liquid; after the material is completely discharged, the material liquid is pushed out of the braided tube assembly from top to bottom by using nitrogen; standing, immersing in deionized water for curing, cleaning to obtain a coated base film, and immersing in deionized water again for later use;
the feed liquid comprises the following components in parts by mass: 18-33 parts of main material, 0-5 parts of forming auxiliary agent and 100 parts of solvent;
2) Preparing a desalting functional layer: soaking the coated base film in an aqueous phase solution for 5-60s from bottom to top, and then draining the aqueous phase; standing for 2min, reacting the oil phase solution from bottom to top for 1-20min, pushing out the soaked coated base film, and draining the oil phase; blowing with hot air at 80 deg.C for 10s to obtain product;
the aqueous phase solution comprises the following components in parts by mass: 0.1-16 parts of polyamine compound, 0.01-5 parts of proton absorbent, 0.01-3 parts of polymerization accelerator and 100 parts of deionized water; the oil phase solution comprises 0.01-4 parts by mass of polyfunctional acyl chloride, 0.01-5 parts by mass of halogenated hydrocarbon and 100 parts by mass of organic solvent.
2. The method for preparing the fiber-reinforced hollow fiber nanofiltration membrane according to claim 1, wherein the main material is one of polysulfone, polyethersulfone and polyvinylidene fluoride.
3. The method for preparing the fiber-reinforced hollow fiber nanofiltration membrane according to claim 1, wherein the molding aid is one of lithium chloride, polyoxyethylene 400, ethylene glycol and polyvinylpyrrolidone.
4. The method for preparing the fiber-reinforced hollow fiber nanofiltration membrane according to claim 1, wherein the solvent is one of Dimethylacetamide (DMAC), dimethylformamide (DMF) or N-methylpyrrolidone (NMP).
5. The method for preparing a fiber-reinforced hollow fiber nanofiltration membrane according to claim 1, wherein the polyamine compound is one or more of phenylenediamine, piperazine, homopiperazine, ethylenediamine, hexamethylenediamine, melamine, 1, 2-cyclohexanediamine, aminoethylpiperazine, o-phenylenediamine, p-phenylenediamine, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, and 4,4' -diphenyldiamine.
6. The method for preparing the fiber-reinforced hollow fiber nanofiltration membrane according to claim 1, wherein the polymerization accelerator is one of polyvinylpyrrolidone, poly (meth) acrylamide, polyhydroxyethyl methacrylate, and polyallylamine.
7. The method for preparing a fiber-enhanced hollow fiber nanofiltration membrane according to claim 1, wherein the proton absorbent is one of triethylamine, triethylene diamine, trimethylamine, N, N' -dimethylpiperazine, sodium hydroxide, potassium hydroxide, sodium phosphate and sodium carbonate.
8. The method for preparing a fiber-enhanced hollow fiber nanofiltration membrane according to claim 1, wherein the polyfunctional acid chloride is one of trimesoyl chloride, adipoyl chloride and sebacoyl chloride.
9. The method for preparing the fiber-enhanced hollow fiber nanofiltration membrane according to claim 1, wherein the organic solvent is one of isoparaffin, n-hexane, cyclohexane and heptane.
10. The method for preparing the fiber-reinforced hollow fiber nanofiltration membrane according to claim 1, wherein the halogenated hydrocarbon is one of chloroform, dichloromethane, bromoform, dibromomethane, iodoform and diiodomethane.
CN202110477631.2A 2021-04-29 2021-04-29 Preparation method of fiber-reinforced hollow fiber nanofiltration membrane Pending CN115253698A (en)

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CN202110477631.2A CN115253698A (en) 2021-04-29 2021-04-29 Preparation method of fiber-reinforced hollow fiber nanofiltration membrane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110477631.2A CN115253698A (en) 2021-04-29 2021-04-29 Preparation method of fiber-reinforced hollow fiber nanofiltration membrane

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CN115253698A true CN115253698A (en) 2022-11-01

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