CN113457475A - Polyacrylonitrile/nano whisker composite ultrafiltration membrane and preparation method thereof - Google Patents
Polyacrylonitrile/nano whisker composite ultrafiltration membrane and preparation method thereof Download PDFInfo
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- CN113457475A CN113457475A CN202110776694.8A CN202110776694A CN113457475A CN 113457475 A CN113457475 A CN 113457475A CN 202110776694 A CN202110776694 A CN 202110776694A CN 113457475 A CN113457475 A CN 113457475A
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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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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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
- B01D67/0013—Casting processes
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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Abstract
The invention relates to a polyacrylonitrile/nano whisker composite ultrafiltration membrane and a preparation method thereof, wherein the method comprises the following steps: 1. preparing bamboo shoot shell nanowhiskers; 2. preparing a membrane casting solution by using bamboo shoot shell nanowhiskers; 3. pouring the casting film liquid on a clean and smooth glass plate, and uniformly and stably scraping the film by using a self-made film scraper to keep the thickness of the casting film liquid film at 150-250 microns; 4. transferring the membrane casting liquid membrane into a coagulating bath, coagulating the membrane casting liquid membrane by a phase inversion method, transferring the coagulated membrane casting liquid membrane into deionized water, replacing the deionized water every eight hours, and soaking for three days to obtain the polyacrylonitrile/nano cellulose ultrafiltration membrane. The method of the invention has simple and convenient operation, the addition of the nano crystal whisker improves the hydrophilicity of the ultrafiltration membrane, and the excellent high strength and Young modulus of the nano crystal whisker improve the strength of the ultrafiltration membrane.
Description
Technical Field
The invention relates to the field of ultrafiltration membranes, in particular to a polyacrylonitrile/nano whisker composite ultrafiltration membrane and a preparation method thereof.
Background
Water is an important resource in our lives, but the world faces not only the shortage of water resources but also the problem of water quality at present, and the membrane technology is more and more important in the aspects of industrial wastewater, biological medicine and the like due to the advantages of high efficiency, simple process, low energy consumption and the like. Polyacrylonitrile has the advantages of good resistance to organic solvents, hydrolysis resistance, aging resistance and the like, and is often used as a raw material for preparing membranes. The nano-cellulose has the excellent characteristics of high strength, high modulus, degradability, sustainability and the like, and if the nano-cellulose is added into a membrane preparation process by a reasonable method, the hydrophilicity and the mechanical property of the ultrafiltration membrane can be remarkably changed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polyacrylonitrile/nano whisker composite ultrafiltration membrane and a preparation method thereof.
The technical scheme for solving the technical problems is as follows:
the preparation method of the polyacrylonitrile/nano whisker composite ultrafiltration membrane comprises the following steps:
step 1, preparing bamboo shoot shell nanowhiskers;
step 2, placing polyacrylonitrile powder in a drying oven to be dried for 20-25h at the temperature of 60-70 ℃, then placing the nano-whiskers in an N, N dimethylacetamide solution to prepare a nano-whisker solution with the mass concentration of 0.2-1%, then adding the polyacrylonitrile powder with the mass fraction of 10-20% into the nano-whisker solution to obtain a mixed solution, and then heating the mixed solution in a constant-temperature water bath at the temperature of 60 ℃ for 3h to obtain a casting solution;
step 3, cooling and defoaming the obtained casting solution at room temperature for more than 12-14h, pouring the completely defoamed casting solution on a clean and smooth glass plate under the conditions of room temperature and 50-60% of air relative humidity, and uniformly and stably scraping the film by using a self-made film scraper to keep the thickness of a casting film liquid film at 250 microns of 150-;
and 4, transferring the casting membrane liquid membrane into a coagulating bath, coagulating the casting membrane liquid membrane by using a phase inversion method, transferring the coagulated casting membrane liquid membrane into deionized water, replacing the deionized water every eight hours, and soaking for three days to obtain the polyacrylonitrile/nano-cellulose ultrafiltration membrane.
Further, the preparation method of the bamboo shoot shell nanowhisker comprises the following steps:
step 1.1, placing bamboo shoot shells in warm water at 40-60 ℃, drying the bamboo shoot shells, and then putting the bamboo shoot shells into a bath with a bath ratio of 1: heating in water bath at 50-70 deg.C for 40-60 hr, and adding 1-3mL/L sulfuric acid for 1-3 hr; drying the processed bamboo shoot shells in a drying oven at the temperature of 60-80 ℃;
step 1.2, placing the bamboo shoot shells treated in the last step into a hydrogen peroxide solution for treatment for 2-3h, and adding thiourea, a sodium polyphosphate auxiliary agent and 1-3% of sodium hydroxide in mass percentage;
step 1.3, placing the bamboo shoot shells processed in the last step into dimethyl sulfoxide liquid, wherein the bath ratio is 1: 40-60 ℃, stirring at the temperature of 40-60 ℃, performing suction filtration by using a vacuum pump, washing with deionized water to be neutral, and drying in a drying oven at the temperature of 60-80 ℃;
and step 1.4, preparing the bamboo shoot shell treated in the last step into the bamboo shoot shell cellulose nanowhisker by a TEMPO oxidation method.
Further, in the step 2, the concentration of the nano-cellulose whisker solution is 0.6%.
Further, the mass fraction of polyacrylonitrile in the mixed solution in the step 3 is 15%.
The polyacrylonitrile/nano whisker composite ultrafiltration membrane is prepared by the method.
The invention has the beneficial effects that: the method of the invention has simple and convenient operation, the addition of the nano crystal whisker improves the hydrophilicity of the ultrafiltration membrane, and the excellent high strength and Young modulus of the nano crystal whisker improve the strength of the ultrafiltration membrane.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
The preparation method of the polyacrylonitrile/nano whisker composite ultrafiltration membrane comprises the following steps:
(1) extraction of bamboo shoot shell fiber
Cleaning bamboo shoot shell in 50 deg.C warm water to remove surface fluff and impurities, oven drying in oven, cutting the dried bamboo shoot shell into small pieces (longitudinal 30mm, cross section 2 × 2mm), adding 2mL/LH at bath ratio of 1:402SO4Heating in 60 deg.C water bath for 1h, washing bamboo shoot shell with clear water at normal temperature to neutral, oven drying at 70 deg.C in oven, collecting 5g of processed bamboo shoot shell, decocting at 95 deg.C, 18g/L sodium hydroxide and 40mL/L hydrogen peroxide in water bath at bath ratio of 1:40 for 150min, and adding 2mL/LH2SO4And (3) carrying out acid washing to neutralize the alkaline solution on the surface of the fiber at a bath ratio of 1:20, and finally washing with clear water at normal temperature to be neutral and drying to obtain the bamboo shoot shell fiber.
(2) Preparation of bamboo shoot shell nano crystal whisker
Crushing the extracted bamboo shoot shell fibers, and sieving the crushed bamboo shoot shell fibers with a 60-mesh sieve to obtain 0.03mm fiber powder, wherein the bath ratio is 1: treating in 30 parts of dimethyl sulfoxide for 6 hours at 50 ℃, then washing to be neutral by using a centrifugal machine, and putting the obtained sample into a 70 ℃ oven for drying. The bath ratio is 1: 100, adding 0.042g of TEMPO and 0.6g of NaBr, dropwise adding a certain amount of NaClO solution with the concentration of 12%, adjusting the pH value to 10-11, uniformly stirring for 3 hours, keeping the pH value stable, adding 5mL of absolute ethyl alcohol to end the reaction, centrifuging the obtained solution in a centrifuge at 5000rpm for 5min, repeatedly washing for 5-6 times until the solution is neutral, removing the supernatant in a centrifuge tube, taking a precipitate, and performing solid-to-liquid ratio of 1: 150, and dispersing in a high-speed homogenizer at 10000rpm for 10min to obtain the nano-whisker suspension liquid. Freezing at-20 deg.C for 1 day, taking out, placing in a freeze drier, drying for 2 days, and taking out to obtain white bamboo shoot shell nanowhisker.
(4) Preparation of polyacrylonitrile/nano cellulose ultrafiltration membrane
Putting polyacrylonitrile powder in a drying oven at 60 ℃ for drying for 24h, weighing a certain amount of nano-crystal whiskers in N, N-dimethylacetamide solution to prepare solution with the concentration of 0%, 0.2%, 0.4%, 0.6%, 0.8% and 1%, dispersing for 30min by ultrasonic waves until the nano-cellulose whiskers are uniformly dispersed in the solvent, adding 15 percent of polyacrylonitrile powder by mass percentage, heating in a constant-temperature water bath at 60 ℃ for 3h, cooling and defoaming the obtained casting solution at room temperature for 12h, at room temperature, the relative humidity of air is maintained between 50 and 60 percent, the casting solution after complete defoaming is poured on a clean and smooth glass plate, a self-made film scraper is used for uniformly and stably scraping the film to keep the thickness of the film at about 200 microns, the film is quickly transferred into a coagulating bath, and (3) converting the casting solution into a film by using a phase inversion method, transferring the film into deionized water, and soaking for three days at intervals of eight hours. As the nanocellulose is gradually increased to 1%, the water flux of the ultrafiltration membrane is gradually reduced from 125.88L/m 2h of the original pure polyacrylonitrile to 90.41L/m2 h. The mechanical performance of the ultrafiltration membrane can be obviously enhanced by adding the nano-whiskers, the Young modulus of the ultrafiltration membrane is increased from 103.60M (Pa) to 193.78M (Pa) when the content of the nano-whiskers is 0-1%, the tensile strength is increased from 2.72M (Pa) to 3.52M (Pa), the performance of the ultrafiltration membrane is better when the content of the nano-whiskers is 1%, and the Young modulus and the tensile strength of the ultrafiltration membrane are respectively increased by 87.04% and 27.9% compared with those of a pure polyacrylonitrile membrane.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. The preparation method of the polyacrylonitrile/nano whisker composite ultrafiltration membrane is characterized by comprising the following steps:
step 1, preparing bamboo shoot shell nanowhiskers;
step 2, placing polyacrylonitrile powder in a drying oven to be dried for 20-25h at the temperature of 60-70 ℃, then placing the nano-whiskers in an N, N dimethylacetamide solution to prepare a nano-whisker solution with the mass concentration of 0.2-1%, then adding the polyacrylonitrile powder with the mass fraction of 10-20% into the nano-whisker solution to obtain a mixed solution, and then heating the mixed solution in a constant-temperature water bath at the temperature of 60 ℃ for 3h to obtain a casting solution;
step 3, cooling and defoaming the obtained casting solution at room temperature for more than 12-14h, pouring the completely defoamed casting solution on a clean and smooth glass plate under the conditions of room temperature and 50-60% of air relative humidity, and uniformly and stably scraping the film by using a self-made film scraper to keep the thickness of a casting film liquid film at 250 microns of 150-;
and 4, transferring the casting membrane liquid membrane into a coagulating bath, coagulating the casting membrane liquid membrane by using a phase inversion method, transferring the coagulated casting membrane liquid membrane into deionized water, replacing the deionized water every eight hours, and soaking for three days to obtain the polyacrylonitrile/nano-cellulose ultrafiltration membrane.
2. The preparation method of polyacrylonitrile/nanowhisker composite ultrafiltration membrane according to claim 1, wherein the preparation method of the bamboo shoot shell nanowhisker comprises the following steps:
step 1.1, placing bamboo shoot shells in warm water at 40-60 ℃, drying the bamboo shoot shells, and then putting the bamboo shoot shells into a bath with a bath ratio of 1: heating in water bath at 50-70 deg.C for 40-60 hr, and adding 1-3mL/L sulfuric acid for 1-3 hr; drying the processed bamboo shoot shells in a drying oven at the temperature of 60-80 ℃;
step 1.2, placing the bamboo shoot shells treated in the last step into a hydrogen peroxide solution for treatment for 2-3h, and adding thiourea, a sodium polyphosphate auxiliary agent and 1-3% of sodium hydroxide in mass percentage;
step 1.3, placing the bamboo shoot shells processed in the last step into dimethyl sulfoxide liquid, wherein the bath ratio is 1: 40-60 ℃, stirring at the temperature of 40-60 ℃, performing suction filtration by using a vacuum pump, washing with deionized water to be neutral, and drying in a drying oven at the temperature of 60-80 ℃;
and step 1.4, preparing the bamboo shoot shell processed in the last step by using a TEMPO oxidation method to obtain the bamboo shoot shell nanowhisker.
3. The method for preparing the polyacrylonitrile/nanowhisker composite ultrafiltration membrane according to claim 1, wherein in the step 2, the concentration of the nanowhisker solution is 0.6%.
4. The preparation method of the polyacrylonitrile/nanowhisker composite ultrafiltration membrane according to claim 1, wherein the mass fraction of polyacrylonitrile in the mixed solution of the step 3 is 15%.
5. A polyacrylonitrile/nanowhisker composite ultrafiltration membrane, characterized by being prepared by the method of any one of claims 1 to 4.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115925304A (en) * | 2022-11-25 | 2023-04-07 | 邯郸浩翔新型建材有限公司 | Special square and round granule machine-made sand for high-strength concrete |
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| CN101074287A (en) * | 2007-06-27 | 2007-11-21 | 东华大学 | Production of cellulose/polyacrylonitrile homogeneous mixed solution |
| CN106366350A (en) * | 2016-08-29 | 2017-02-01 | 张东 | Method for preparing hemodialysis membrane containing bamboo shoot fibers |
| US20180086851A1 (en) * | 2015-11-12 | 2018-03-29 | The Research Foundation For The State University Of New York | Production of carboxylated nanocelluloses |
| CN108771978A (en) * | 2018-07-09 | 2018-11-09 | 海南立昇净水科技实业有限公司 | It is a kind of to utilize nano cellulose crystal blending and modifying ultrafiltration membrane preparation method |
| CN110523302A (en) * | 2019-08-16 | 2019-12-03 | 华南理工大学 | A kind of composite membrane and its preparation method and application of doping Cellulose nanocrystal palpus |
| CN112663381A (en) * | 2020-12-09 | 2021-04-16 | 武汉纺织大学 | Preparation method of bamboo shoot shell cellulose nanowhisker |
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- 2021-07-09 CN CN202110776694.8A patent/CN113457475A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074287A (en) * | 2007-06-27 | 2007-11-21 | 东华大学 | Production of cellulose/polyacrylonitrile homogeneous mixed solution |
| US20180086851A1 (en) * | 2015-11-12 | 2018-03-29 | The Research Foundation For The State University Of New York | Production of carboxylated nanocelluloses |
| CN106366350A (en) * | 2016-08-29 | 2017-02-01 | 张东 | Method for preparing hemodialysis membrane containing bamboo shoot fibers |
| CN108771978A (en) * | 2018-07-09 | 2018-11-09 | 海南立昇净水科技实业有限公司 | It is a kind of to utilize nano cellulose crystal blending and modifying ultrafiltration membrane preparation method |
| CN110523302A (en) * | 2019-08-16 | 2019-12-03 | 华南理工大学 | A kind of composite membrane and its preparation method and application of doping Cellulose nanocrystal palpus |
| CN112663381A (en) * | 2020-12-09 | 2021-04-16 | 武汉纺织大学 | Preparation method of bamboo shoot shell cellulose nanowhisker |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115925304A (en) * | 2022-11-25 | 2023-04-07 | 邯郸浩翔新型建材有限公司 | Special square and round granule machine-made sand for high-strength concrete |
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