CN112108016A - Preparation method of spider-web-structure-imitated oil-water separation membrane - Google Patents
Preparation method of spider-web-structure-imitated oil-water separation membrane Download PDFInfo
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- CN112108016A CN112108016A CN202011087563.0A CN202011087563A CN112108016A CN 112108016 A CN112108016 A CN 112108016A CN 202011087563 A CN202011087563 A CN 202011087563A CN 112108016 A CN112108016 A CN 112108016A
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- carboxymethyl cellulose
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- water separation
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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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides an oil-water separation membrane imitating a spider web structure and a preparation method thereof. The polymer film is taken as a base film, carboxymethyl cellulose (CMC) is taken as a modifier to carry out functional modification on the polymer film, the modified film with the spider-web-like structure is prepared by introducing the modified film into the surface of the film in an etherification self-crosslinking mode, and the carboxymethyl cellulose forms a hydrogel layer on the surface of the polymer film by utilizing the carboxymethyl cellulose self-crosslinking, thereby realizing the functional modification on the surface of the film. Compared with an unmodified polymer membrane, the carboxymethyl cellulose (CMC) polymer membrane prepared by the invention has higher separation performance, anti-pollution performance and mechanical performance, and has certain reference value for the research of the modification of the separation membrane.
Description
Technical Field
The invention belongs to the technical field of separation membrane modification, and particularly relates to a preparation method of an oil-water separation membrane imitating a spider web structure.
Background
Oil-water pollution and frequent oil spill accidents caused by oily industrial wastewater become the most urgent environmental problems all over the world, and oil-water separation is one of the research hotspots which are currently concerned at home and abroad. The traditional oil-water separation method such as a centrifugal method, an air flotation method, a biological method, an adsorption method, a gravity method and the like has the defects of low efficiency, low selectivity, high operation cost and the like, and an oil-water separation technology which is simple to operate and is environment-friendly is urgently needed. The membrane separation technology has the advantages of environmental friendliness, low energy consumption, high efficiency and the like, membrane-method oil-water separation is well attracted by researchers and enterprises, and a large number of research reports are reported in recent years, but how to obtain an oil-water separation membrane material with high separation performance, pollution resistance and mechanical performance is still one of the common problems in the field. The special rough form and wettability of the membrane surface have great influence on the adhesive force of pollutants, and the improvement of the comprehensive performance of the oil-water separation membrane by modifying the membrane surface is still an important direction worthy of exploration.
The hydrogel is a gel taking water as a dispersion system, has a macromolecular network structure, can absorb water to generate a swelling phenomenon, and cannot be dissolved. Because of its good biocompatibility, hydrogels are widely used in the fields of bioengineering and medicine. Due to the high hydrophilicity and good biocompatibility of the hydrogel, the hydrogel has good application prospect in the field of hydrophilic modification of polymer membranes. By means of membrane surface grafting and membrane surface coating, the hydrogel modified membrane with high hydrophilicity and high separation performance, pollution resistance and mechanical performance can be prepared.
Disclosure of Invention
The invention aims to provide an oil-water separation membrane with an imitation spider web structure and high separation performance, pollution resistance and mechanical performance and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows:
the invention provides a preparation method of an oil-water separation membrane imitating a spider web structure, which comprises the following steps:
coating a mixed aqueous solution of 0.1-2 wt% of carboxymethyl cellulose and 5-15 wt% of polyvinylpyrrolidone on the surface of a polymer base membrane, thermally crosslinking for 0.5-2h at 30-60 ℃, then immersing into an ethanol solution containing a crosslinking agent for further crosslinking, wherein the concentration of the crosslinking agent is 0.5-2 wt%, crosslinking for 4-12 h at 40-80 ℃, soaking in water for 12-48 h, and freeze-drying to obtain the spider-web-structure-simulated oil-water separation membrane.
Preferably, the polymer-based membrane in the above step is a polysulfone membrane, a polyvinylidene fluoride membrane or a polyacrylonitrile membrane with a molecular weight cutoff of 100000-3000000 Da.
Preferably, the molecular weight of the polyvinylpyrrolidone in the step is 3000-3000000 Da.
Preferably, step 5 is performed. The cross-linking agent is glyoxal, glutaraldehyde, adipaldehyde, or epichlorohydrin.
The oil-water separation membrane with the spider web-like structure is prepared by the method.
The invention has the advantages that:
according to the oil-water separation membrane with the imitated spider web structure, the surface of the polymer membrane is coated with a carboxymethyl cellulose solution, the polymer membrane is introduced through self-crosslinking, the hydrophilicity of the polymer membrane is improved, and compared with the polymer membrane before modification, the formed oil-water separation membrane with the imitated spider web structure has long-time stability and optimizes comprehensive performances such as surface hydrophilicity, separability and mechanical property of the polymer membrane. The method has certain reference value for the modification research of the separation membrane with higher separation performance, pollution resistance and mechanical performance.
Drawings
The following description is made in further detail with reference to the accompanying drawings and embodiments of the present invention.
FIG. 1 is an electron microscope picture of 10000 times of surface morphology of an oil-water separation membrane with an artificial spider web structure prepared by coating carboxymethyl cellulose with different concentrations in examples 1, 2, 3 and 4.
FIG. 2 shows the water contact angle test results of the simulated spider web structure oil-water separation membranes prepared by coating different concentrations of carboxymethyl cellulose in examples 1, 2, 3 and 4.
FIG. 3 shows the results of oil flux and retention tests of simulated spider web oil-water separation membranes prepared by coating different concentrations of carboxymethyl cellulose in examples 1, 2, 3 and 4.
FIG. 4 shows the results of mechanical property tests of simulated spider web-structured oil-water separation membranes prepared by coating carboxymethyl cellulose with different concentrations in examples 1, 2, 3 and 4.
Detailed description of the invention
The present invention will be described in detail with reference to specific examples, but the present invention is not limited to the examples.
The preparation inspects the influence of the content of the carboxymethyl cellulose on the surface structure of the membrane, and finds that the content of the carboxymethyl cellulose has great influence on the surface structure of the finally obtained membrane, and the membrane is in a spider-web-like structure.
Example 1:
a preparation method of an oil-water separation membrane imitating a spider web structure comprises the following steps:
1) dissolving 1.25g of polyvinylpyrrolidone in 25ml of pure water, stirring at normal temperature for 6 hours, standing and defoaming to obtain a modifier solution;
2) dissolving 1.96g of epichlorohydrin in 100ml of ethanol, and adjusting the pH of an epichlorohydrin ethanol solution to 10 by using a sodium hydroxide aqueous solution to obtain a uniform cross-linking agent solution;
3) inverting the modifier solution on the surface of the polyvinylidene fluoride membrane, uniformly scraping and coating by using a 100-micron scraper, putting the polyvinylidene fluoride membrane into an oven, performing thermal crosslinking for 0.5h at 40 ℃, taking out the polyvinylidene fluoride membrane, immersing the polyvinylidene fluoride membrane into the crosslinker solution for further crosslinking, then putting the polyvinylidene fluoride membrane into the oven at 60 ℃ for crosslinking for 8h, taking out the polyvinylidene fluoride membrane, immersing the polyvinylidene fluoride membrane in pure water for 24h, and performing freeze drying to obtain the spider-web-structure-simulated oil-water separation membrane (M-0).
Example 2:
a preparation method of an oil-water separation membrane imitating a spider web structure comprises the following steps:
1) dissolving 0.125g of carboxymethyl cellulose and 1.25g of polyvinylpyrrolidone in 25ml of pure water, stirring at normal temperature for 6 hours, standing and defoaming to obtain a modifier solution;
2) this step is the same as step 2) in example 1;
3) the step is the same as the step 3) in the embodiment 1, and the oil-water separation membrane (M-1) imitating the spider web structure is obtained.
Example 3:
a preparation method of an oil-water separation membrane imitating a spider web structure comprises the following steps:
1) dissolving 0.25g of carboxymethyl cellulose and 1.25g of polyvinylpyrrolidone in 25ml of pure water, stirring for 6 hours at normal temperature, standing and defoaming to obtain a modifier solution;
2) this step is the same as step 2) in example 1;
3) the step is the same as the step 3) in the embodiment 1, and the oil-water separation membrane (M-2) imitating the spider web structure is obtained.
Example 4:
a preparation method of an oil-water separation membrane imitating a spider web structure comprises the following steps:
1) dissolving 0.375g of carboxymethyl cellulose and 1.25g of polyvinylpyrrolidone in 25ml of pure water, stirring for 6 hours at normal temperature, standing and defoaming to obtain a modifier solution;
2) this step is the same as step 2) in example 1;
3) the step is the same as the step 3) in the embodiment 1, and the oil-water separation membrane (M-3) imitating the spider web structure is obtained.
Claims (5)
1. A preparation method of an oil-water separation membrane imitating a spider web structure is characterized in that carboxymethyl cellulose is coated on the surface of a polymer membrane, a hydrogel layer is formed on the surface of the membrane through carboxymethyl cellulose esterification and crosslinking, and the polymer membrane with higher oil-water separation performance, pollution resistance and mechanical performance is prepared after the membrane coated with the carboxymethyl cellulose is subjected to freeze drying.
2. The method according to claim 1, characterized in that it comprises in particular the steps of: coating a mixed aqueous solution of 0.1-2 wt% of carboxymethyl cellulose and 5-15 wt% of polyvinylpyrrolidone on the surface of a polymer base membrane, thermally crosslinking for 0.5-2h at 30-60 ℃, then immersing into an ethanol solution containing a crosslinking agent for further crosslinking, wherein the concentration of the crosslinking agent is 0.5-2 wt%, crosslinking for 4-12 h at 40-80 ℃, soaking in water for 12-48 h, and freeze-drying to obtain the spider-web-structure-simulated oil-water separation membrane.
3. The method according to claim 2, wherein the polymer-based membrane is a polysulfone membrane, a polyvinylidene fluoride membrane or a polyacrylonitrile membrane with a molecular weight cut-off of 100000-3000000 Da.
4. The method according to claim 2, wherein the polyvinylpyrrolidone has a molecular weight in the range of 3000 to 3000000 Da.
5. The method of claim 2, wherein the crosslinking agent is glyoxal, glutaraldehyde, adipaldehyde, or epichlorohydrin.
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Citations (11)
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| CN101445609A (en) * | 2008-11-14 | 2009-06-03 | 武汉大学 | Hydroscopic cellulose hydrogel and preparation method thereof |
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| CN103111096A (en) * | 2013-01-24 | 2013-05-22 | 清华大学 | Responsive oil and water separation net film with underwater super lipophobicity property and preparation method thereof |
| CN103157299A (en) * | 2013-03-26 | 2013-06-19 | 清华大学 | Oil-water separation mesh film with acid-base salt stabilizing function and with underwater super-oleophobic property and preparation method thereof |
| CN104474930A (en) * | 2014-11-25 | 2015-04-01 | 天津工业大学 | Anti-pollution oil-water separation film and preparation method thereof |
| CN106362438A (en) * | 2016-11-22 | 2017-02-01 | 新奥生态环境治理有限公司 | Oil-water separation film and application thereof |
| CN106745507A (en) * | 2016-12-30 | 2017-05-31 | 常州碳星科技有限公司 | A kind of resistant to pollution oil-water separation mesh film and preparation method thereof |
| CN107050927A (en) * | 2017-04-27 | 2017-08-18 | 苏州捷尔沃科技有限公司 | Composite structured oil-water separation mesh film and preparation method thereof |
| CN107080976A (en) * | 2017-06-15 | 2017-08-22 | 河北工业大学 | A kind of preparation method with the oil-water separation mesh film of superoleophobic property under water |
| CN107200853A (en) * | 2017-05-27 | 2017-09-26 | 武汉理工大学 | A kind of dendrimer/carboxymethyl cellulose superabsorbent hydrogel and its preparation and application |
| CN108854583A (en) * | 2018-06-05 | 2018-11-23 | 江苏大学 | A kind of preparation method of the hydrophily water-oil separationg film of imitative spider web frame |
-
2020
- 2020-10-13 CN CN202011087563.0A patent/CN112108016A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445609A (en) * | 2008-11-14 | 2009-06-03 | 武汉大学 | Hydroscopic cellulose hydrogel and preparation method thereof |
| CN102029079A (en) * | 2010-10-29 | 2011-04-27 | 中国科学院化学研究所 | Underwater super-oleophobic oil-water separation mesh membrane as well as preparation method and application thereof |
| CN103111096A (en) * | 2013-01-24 | 2013-05-22 | 清华大学 | Responsive oil and water separation net film with underwater super lipophobicity property and preparation method thereof |
| CN103157299A (en) * | 2013-03-26 | 2013-06-19 | 清华大学 | Oil-water separation mesh film with acid-base salt stabilizing function and with underwater super-oleophobic property and preparation method thereof |
| CN104474930A (en) * | 2014-11-25 | 2015-04-01 | 天津工业大学 | Anti-pollution oil-water separation film and preparation method thereof |
| CN106362438A (en) * | 2016-11-22 | 2017-02-01 | 新奥生态环境治理有限公司 | Oil-water separation film and application thereof |
| CN106745507A (en) * | 2016-12-30 | 2017-05-31 | 常州碳星科技有限公司 | A kind of resistant to pollution oil-water separation mesh film and preparation method thereof |
| CN107050927A (en) * | 2017-04-27 | 2017-08-18 | 苏州捷尔沃科技有限公司 | Composite structured oil-water separation mesh film and preparation method thereof |
| CN107200853A (en) * | 2017-05-27 | 2017-09-26 | 武汉理工大学 | A kind of dendrimer/carboxymethyl cellulose superabsorbent hydrogel and its preparation and application |
| CN107080976A (en) * | 2017-06-15 | 2017-08-22 | 河北工业大学 | A kind of preparation method with the oil-water separation mesh film of superoleophobic property under water |
| CN108854583A (en) * | 2018-06-05 | 2018-11-23 | 江苏大学 | A kind of preparation method of the hydrophily water-oil separationg film of imitative spider web frame |
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