CN113731192A - Hydrophilic ultrafiltration membrane for oil-water separation and preparation method thereof - Google Patents
Hydrophilic ultrafiltration membrane for oil-water separation and preparation method thereof Download PDFInfo
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- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 60
- 238000000926 separation method Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
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- 238000002156 mixing Methods 0.000 claims abstract description 17
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- 239000002904 solvent Substances 0.000 claims description 6
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- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
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- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 4
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- 239000011148 porous material Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
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- CKCGJBFTCUCBAJ-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propyl acetate Chemical compound CCOC(C)COC(C)COC(C)=O CKCGJBFTCUCBAJ-UHFFFAOYSA-N 0.000 claims description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
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- 238000005809 transesterification reaction Methods 0.000 abstract 1
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Images
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- 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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- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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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
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
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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
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/025—Finger pores
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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
- B01D2325/24—Mechanical properties, e.g. strength
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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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明提供了一种用于油水分离的亲水性超滤膜及其制备方法，通过聚甲基丙烯酸甲酯与成膜聚合物共混制备共混膜，再通过酯交换反应将乙二醇接枝到膜表面，制备亲水性超滤膜，在含油污水处理、物料浓缩等分离领域展示出良好的抗污染能力。本发明所述的用于油水分离的亲水性超滤膜的制备方法制备过程简单，条件温和，便于工业化放大，具有良好的工业应用价值。The invention provides a hydrophilic ultrafiltration membrane for oil-water separation and a preparation method thereof. The blended membrane is prepared by blending polymethyl methacrylate and a film-forming polymer, and then ethylene glycol is prepared by transesterification. It is grafted to the surface of the membrane to prepare a hydrophilic ultrafiltration membrane, which shows good anti-pollution ability in the separation fields of oily sewage treatment and material concentration. The preparation method of the hydrophilic ultrafiltration membrane for oil-water separation of the present invention is simple in preparation process, mild in conditions, convenient for industrialization and enlargement, and has good industrial application value.
Description
Technical Field
The invention belongs to the technical field of polymer separation membranes, and particularly relates to a hydrophilic ultrafiltration membrane for oil-water separation and a preparation method thereof.
Background
The oil-water mixture has wide sources, has serious influence on ecological environment and production process, and needs to be efficiently separated from the aspects of environmental protection, resource recycling, safe production and the like. The traditional oil-water separation technology comprises methods of air floatation, flocculation, adsorption, electric dehydration, chemical demulsification and the like, and the technologies usually consume a large amount of energy and add chemical agents to generate a large amount of sludge. The ultrafiltration membrane separation technology belongs to a physical method, does not need an additional medicament, has simple treatment process, can remove emulsified oil and dissolved oil which are difficult to treat, and is an ideal oil-water separation technology.
At present, hydrophobic materials such as polysulfone, polyethersulfone and polyvinylidene fluoride are mostly adopted for the organic ultrafiltration membrane, so that the ultrafiltration membrane is hydrophobic. In practical application, the filtration resistance is continuously increased due to the pollution of the membrane, the filtration flux of the membrane is seriously attenuated, and the membrane is frequently cleaned and has high cost. In the oil-water separation process, the membrane pollution phenomenon is particularly obvious. Researches show that hydrophilic modification of the separation membrane is the key for improving the anti-pollution capability of the separation membrane, and the current main hydrophilic modification methods comprise a blending modification technology and a surface modification technology.
The blending modification is a process of adding one or more substances on the basis of the original membrane material and preparing a macroscopically uniform material by mixing. It not only retains the original properties of the original material, but also can overcome the defects of the original material. These modifying materials structurally comprise hydrophilic segments and hydrophobic segments, the hydrophilic segments will automatically concentrate on the membrane surface due to high hydrophilicity during the gel process, and the hydrophobic segments will intertwine with the membrane material and be fixed in the membrane.
The surface modification technology is used for improving the hydrophilicity and the flux of the ultrafiltration membrane through surface reaction and improving the pollution resistance of the membrane. The surface modification method of the membrane mainly comprises the following steps: adsorption method, surface coating method, surface chemical reaction method, low-temperature plasma modification method, ray irradiation modification method, photo-grafting modification method, etc. The adsorption method and the surface coating method are relatively simple to operate, the modifier is physically coated on the surface of the ultrafiltration membrane to be adsorbed on the surface of the ultrafiltration membrane, but the modifier gradually falls off from the surface of the ultrafiltration membrane along with the prolonging of the operation time, and a permanent modification effect cannot be obtained. The surface chemical reaction can fix the modified monomer, the modifier can be grafted to the surface of the ultrafiltration membrane, and the modifier is connected with the polymer through a covalent bond, so that the ultrafiltration membrane has good stability, but the chemical modification process is complex, pretreatment is required, and the modification range is limited; the low-temperature plasma surface modification is a film modification method which is developed rapidly in recent years, is relatively simple to operate and is not easy to pollute air, but modification equipment is relatively complex, the modification mechanism is not clear, and purposeful modification is difficult to carry out; ultraviolet radiation graft polymerization is a common ultrafiltration membrane surface modification method, ultraviolet light is not easy to be absorbed by a polymer membrane, but can be absorbed by a photoinitiator to initiate reaction, so that the purpose of surface modification can be achieved, the material body is not influenced, but the photoinitiator and the catalyst are required to be added, and the grafting rate is not easy to control. The interfacial crosslinking polymerization is a novel ultrafiltration membrane surface modification technology at present, and is characterized in that macromolecules for surface hydrophilic modification are firstly adsorbed on the surface of an ultrafiltration membrane, and then the hydrophilic modification macromolecules are crosslinked by a crosslinking agent to form a network structure so as to improve the stability of the modification macromolecules on the surface of the membrane. The method has the advantages of simple operation, low requirement on equipment, good stability of the hydrophilic modified polymer on the surface of the membrane and wide application range.
The separation layer of the ultrafiltration membrane is thin and is easily damaged by harsh environment, so that the performance of the separation membrane is reduced. Therefore, the ideal separation membrane modification technology has the characteristics of mild reaction conditions, simple equipment and convenience for process amplification. Surface chemical grafting has better stability than other modification techniques, but requires specific chemical sites for surface chemical grafting of separation membranes. The traditional separation membrane material has strong chemical stability, is not easy to carry out chemical grafting reaction, and can generate active sites only by activation. However, the activation process of the separation membrane often causes the breakage of the membrane-forming polymer chain, which affects the membrane pore structure and mechanical properties of the separation membrane. Therefore, if active groups can be introduced into the separation membrane through a blending technology to provide active sites for chemical grafting, and the chemical grafting can be performed under mild reaction conditions to facilitate industrial scale-up, the method is an ideal separation membrane surface modification technology.
Disclosure of Invention
In view of the above, in order to solve the above problems, the invention provides a preparation method of a hydrophilic ultrafiltration membrane for oil-water separation, which has mild reaction conditions, simple process, environmental protection and convenience for industrial amplification, wherein the hydrophilic ultrafiltration membrane has good hydraulic stability, strong pollution resistance, high water flux and good hydrophilicity and can obtain a good separation effect in the process of treating oily sewage by blending polymethyl methacrylate and a film-forming polymer and grafting ethylene glycol onto the surface of the membrane through ester exchange reaction.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a hydrophilic ultrafiltration membrane for oil-water separation comprises the following steps:
s1, mixing the film-forming polymer with polymethyl methacrylate to prepare a blended film;
and S2, grafting ethylene glycol to the surface of the blend membrane through ester exchange reaction to obtain the target product hydrophilic ultrafiltration membrane.
Further, the S1 specifically includes: dissolving a film-forming polymer, polymethyl methacrylate and an additive in a solvent, uniformly mixing to obtain a film-forming solution, and preparing a blended film by adopting an immersion sedimentation method after vacuum defoaming;
the S2 specifically includes: and soaking the blend membrane in an ethylene glycol solution, and grafting ethylene glycol to the surface of the blend membrane through ester exchange reaction to obtain the hydrophilic ultrafiltration membrane.
Further, the film-forming polymer is polysulfone, polyethersulfone, polyvinylidene fluoride or polyvinyl chloride;
further, the solvent is dimethylacetamide, dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide.
Further, the additive is a water-soluble additive, a water-insoluble additive, an inorganic salt compound or a combination thereof; the water-soluble additive is one or more of ethylene glycol, propylene glycol, glycerol, triethylene glycol, polyethylene glycol (200, 400 and 600), polyvinylpyrrolidone, polyvinyl butyral and polyvinyl acetate; the water-insoluble additive is one or more of propylene carbonate, gamma-butyrolactone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monoethyl ether acetate and dipropylene glycol monoethyl ether acetate; the inorganic salt compound is one or more of lithium chloride, lithium nitrate and calcium nitrate.
Further, the sum of the mass of the film forming polymer and the mass of the polymethyl methacrylate accounts for 5-30% of the total mass of the film forming solution, the mass of the additive accounts for 0.5-20% of the total mass of the film forming solution, and the balance is the solvent; wherein the mass ratio of the film-forming polymer to the polymethyl methacrylate is 0.05: 1-20: 1.
Further, in the process of preparing the membrane preparation solution, the reaction temperature is 5-120 ℃, and the time is 1-50 h; in the process of preparing the blend membrane by adopting an immersion sedimentation method, the membrane is replaced by deionized water for 24 hours after being formed.
Further, the glycol solution contains water and a catalyst; the catalyst accounts for 0.0001-5% of the total mass of the glycol solution, and the water accounts for 0.0001-5% of the total mass of the glycol solution.
Further, the catalyst is alkaline inorganic salt, specifically one or more of sodium hydroxide, potassium hydroxide or calcium hydroxide.
Further, the time of the ester exchange reaction is 0.5-50 h, and the temperature of the ester exchange reaction is 5-80 ℃.
A hydrophilic ultrafiltration membrane for oil-water separation is an asymmetric structure of a finger-shaped pore support body.
Further, the hydrophilic ultrafiltration membrane is a flat membrane or a hollow fiber membrane.
Compared with the prior art, the hydrophilic ultrafiltration membrane for oil-water separation and the preparation method thereof have the following advantages:
(1) the preparation method of the hydrophilic ultrafiltration membrane for oil-water separation has mild reaction conditions and simple process, active groups are introduced into the separation membrane through a blending technology, active sites are provided for chemical grafting, the reaction conditions of ester exchange reaction are mild, industrial amplification is facilitated, and the preparation method is an ideal separation membrane surface modification technology and has good industrial application value;
(2) the hydrophilic ultrafiltration membrane for oil-water separation has good hydraulic stability, strong pollution resistance, high water flux and good hydrophilicity, the blending membrane is prepared by mixing the membrane forming polymer and polymethyl methacrylate, and ethylene glycol is grafted to the surface of the blending membrane through ester exchange reaction, so that the hydrophilicity and the pollution resistance of the membrane are improved, and the hydrophilic ultrafiltration membrane has good application value in the fields of oily sewage treatment, material concentration and municipal sewage treatment.
Drawings
FIG. 1 is a photograph showing a cross section of a hollow fiber type hydrophilic ultrafiltration membrane according to an embodiment of the present invention;
FIG. 2 is a cross-sectional photograph of a flat-plate type hydrophilic ultrafiltration membrane according to an embodiment of the present invention
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
Preparation:
adding 32g of polysulfone, 20g of polymethyl methacrylate and 8g of polyethylene glycol (molecular weight is 400) into 240g of dimethylacetamide, stirring at 70 ℃ for 24 hours to completely dissolve the materials to obtain a membrane preparation solution, defoaming in vacuum, and preparing the hollow fiber membrane by an immersion precipitation method under the following specific spinning conditions:
spinning temperature is 80 ℃, dry spinning distance is 70mm, core liquid is deionized water, and core liquid flow is 0.8 ml/min-1The gel bath is water, the water bath temperature is 50 ℃, and the blending membrane is obtained after deionized water washing.
Adding 5g of deionized water and 5g of sodium hydroxide into 200g of ethylene glycol to obtain an ethylene glycol solution, soaking the blended membrane into the ethylene glycol solution, and reacting at 60 ℃ for 20 hours to obtain the target product, namely the hollow fiber type hydrophilic ultrafiltration membrane.
And (3) performance testing:
the pure water flux of the hollow fiber type hydrophilic ultrafiltration membrane obtained in example 1 was 150 L.m-2·h-1The bovine serum albumin retention rate is 75.5%, and the water contact angle is 34 °.
Oil-water separation test is carried out on the produced water of the oil field, before the test, the oil content in the produced water of the oil field is 120ppm, the suspended particle content is 60ppm, and the median of the particle size is 3 microns.
After filtration with the hollow fiber hydrophilic ultrafiltration membrane prepared in example 1, the oil content in the permeate was less than 10ppm, the suspended particle content was 1ppm, and the median particle size was less than 1 micron. FilmThe water flux in the oily sewage is 30 L.m-2·h-1The flow recovery of the membrane after simple flushing was 85%.
Example 2
Preparation:
adding 36g of polysulfone, 18g of polymethyl methacrylate and 8g of ethylene glycol into 238g of dimethylacetamide, stirring at 80 ℃ for 24 hours to completely dissolve the materials to obtain a membrane preparation solution, defoaming in vacuum, and preparing the hollow fiber membrane by an immersion precipitation method under the following specific spinning conditions:
spinning temperature is 50 ℃, dry spinning distance is 100mm, core liquid is deionized water, and core liquid flow is 1.0 ml/min-1The gel bath is water, the water bath temperature is 50 ℃, and the blending membrane is obtained after deionized water washing.
1g of deionized water and 1g of sodium hydroxide are added into 200g of ethylene glycol to obtain ethylene glycol solution, the blended membrane is soaked into the ethylene glycol solution and reacts for 24 hours at the temperature of 60 ℃, and the target product is the hollow fiber type hydrophilic ultrafiltration membrane.
And (3) performance testing:
the pure water flux of the hollow fiber type hydrophilic ultrafiltration membrane obtained in example 2 was 200 L.m-2·h-1Bovine serum albumin retention was 55.5% and water contact angle was 40 °.
Oil-water separation test is carried out on the produced water of the oil field, before the test, the oil content in the produced water of the oil field is 120ppm, the suspended particle content is 60ppm, and the median of the particle size is 3 microns.
After the hollow fiber type hydrophilic ultrafiltration membrane prepared in example 2 is used for filtration, the oil content in the permeate is less than 16ppm, the content of suspended particles is 2ppm, and the median particle size is less than 1 micron. The water flux of the membrane in the oil-containing wastewater is 30 L.m-2·h-1The flow recovery of the membrane after simple flushing was 75%.
Example 3
Adding 32g of polysulfone, 18g of polymethyl methacrylate and 3g of lithium nitrate into 247g of dimethylformamide, stirring at 80 ℃ for 24 hours to completely dissolve the materials to obtain a membrane-forming solution, defoaming in vacuum, and scraping a flat membrane by an immersion sedimentation method, wherein the specific membrane-scraping conditions are as follows:
the temperature of the film preparation liquid is 50 ℃, the height of a scraper is 200 mu m, the film scraping speed is 0.1 m/s, the temperature of the gel bath is 15 ℃, and the blend film is obtained after deionized water washing.
1g of deionized water and 2g of sodium hydroxide are added into 200g of ethylene glycol to obtain ethylene glycol solution, the blend membrane is soaked into the ethylene glycol solution and reacts for 24 hours at the temperature of 60 ℃, and a target product is a flat plate type hydrophilic ultrafiltration membrane.
And (3) performance testing:
the pure water flux of the flat-plate type hydrophilic ultrafiltration membrane prepared in example 3 was 280L · m-2·h-1Bovine serum albumin retention rate was 35.5% and water contact angle was 48 °.
Oil-water separation test is carried out on the produced water of the oil field, before the test, the oil content in the produced water of the oil field is 100ppm, the suspended particle content is 50ppm, and the median of the particle size is 3 microns.
After filtration with the flat plate hydrophilic ultrafiltration membrane prepared in example 3, the oil content in the permeate was less than 14ppm, the suspended particle content was 2ppm, and the median particle size was less than 1 micron. The water flux of the membrane in the oil-containing wastewater is 35 L.m-2·h-1The recovery rate of the membrane flow after simple flushing was 73%.
Example 4
Preparation:
adding 51g of polyvinylidene fluoride, 18g of polymethyl methacrylate and 9g of propylene glycol into 222g of dimethylformamide, stirring at 70 ℃ for 24 hours to completely dissolve the materials to obtain a membrane preparation solution, defoaming in vacuum, and scraping a flat membrane by an immersion sedimentation method, wherein the specific membrane scraping conditions are as follows:
the temperature of the film-forming liquid is 60 ℃, the height of a scraper is 150 mu m, the film-scraping speed is 0.15m/s, the gel bath is water, the water bath temperature is 15 ℃, and the blended film is obtained after deionized water washing.
1g of deionized water and 2g of sodium hydroxide are added into 200g of ethylene glycol to obtain ethylene glycol solution, the blend membrane is soaked into the ethylene glycol solution and reacts for 24 hours at the temperature of 60 ℃, and a target product is a flat plate type hydrophilic ultrafiltration membrane.
And (3) performance testing:
the pure water flux of the flat-plate hydrophilic ultrafiltration membrane prepared in example 4 was 300 L.m-2·h-1Bovine serum albumin retention was 45.5% and water contact angle was 45 °.
Oil-water separation test is carried out on the produced water of the oil field, the oil content in the produced water of the oil field before the test is 90ppm, the suspended particle content is 50ppm, and the median of the particle size is 2 microns.
After filtration with the flat plate hydrophilic ultrafiltration membrane prepared in example 4, the oil content in the permeate was less than 15ppm, the suspended particle content was 1.5ppm, and the median particle size was less than 1 micron. The water flux of the membrane in the oily sewage is 32 L.m-2·h-1The recovery rate of the membrane flow after simple washing was 70%.
Comparative example 1
Preparation:
32g of polysulfone and 20g of polymethyl methacrylate are added into 248g of dimethylacetamide, stirred for 24 hours at 70 ℃ and completely dissolved to obtain a membrane preparation solution, and after vacuum defoaming, the hollow fiber membrane is prepared by an immersion precipitation method, wherein the specific spinning conditions are as follows:
spinning temperature is 80 ℃, dry spinning distance is 70mm, core liquid is deionized water, and core liquid flow is 0.8 ml/min-1The gel bath is water, the water bath temperature is 50 ℃, and the cellulose hollow fiber membrane is obtained after deionized water washing.
And (3) performance testing:
the spun cellulose hollow fiber membrane is washed in flowing deionized water for 24 hours and then placed in 50 percent glycerol aqueous solution for standby, a scanning electron microscope shows that the membrane is in an asymmetric structure, and the pure water flux of the membrane is 120 L.m-2·h-1The bovine serum albumin retention rate was 42.5% and the water contact angle was 78 °.
Oil-water separation test is carried out on the produced water of the oil field, before the test, the oil content in the produced water of the oil field is 120ppm, the suspended particle content is 60ppm, and the median of the particle size is 3 microns.
After the cellulose hollow fiber membrane filtration, the oil content in the permeated liquid is less than 10ppm, the content of suspended particles is 1ppm, and the median particle size is less than 1 micron. The water flux of the membrane in the oily sewage is 10 L.m-2·h-1The flow recovery of the membrane after simple flushing was 40%.
Comparative example 2
Preparation:
stirring 36g of polyvinylidene fluoride, 12 g of polymethyl methacrylate and 152g of dimethylacetamide at 80 ℃ for 24 hours to completely dissolve the polyvinylidene fluoride, obtaining a membrane preparation solution, defoaming in vacuum, and scraping a flat membrane by an immersion sedimentation method, wherein the specific membrane hanging conditions are as follows:
the temperature of the feed liquid is 60 ℃, the height of the scraper is 200 mu m, the film scraping speed is 0.15m/s, the temperature of the gel bath is 15 ℃, and the blending film is obtained after the deionized water washing.
And (3) performance testing:
the spun flat membrane is washed in flowing deionized water for 24 hours and then placed in 50 percent glycerol aqueous solution for standby, a scanning electron microscope shows that the membrane has an asymmetric structure, and the pure water flux of the membrane is 120 L.m-2·h-1Bovine serum albumin retention rate is 65.5%, and water contact angle is 80 °.
Oil-water separation test is carried out on the produced water of the oil field, before the test, the oil content in the produced water of the oil field is 120ppm, the suspended particle content is 60ppm, and the median of the particle size is 3 microns.
After the flat membrane filtration, the oil content in the permeate is less than 20ppm, the suspended particle content is 1ppm, and the median particle size is less than 1 micron. The water flux of the membrane in the oily sewage is 10 L.m-2·h-1The flow recovery rate of the separation membrane after simple washing was 30%.
As can be seen from the performance test parts of the examples and the comparative examples, the hollow fiber type and flat plate type hydrophilic ultrafiltration membranes described in the examples have strong anti-pollution capability and high water flux, and the flow recovery rate of the membranes after oily sewage treatment and simple flushing is far higher than that of the separation membranes prepared in the comparative examples. The cross-sectional structures of the hollow fiber type and plate type hydrophilic ultrafiltration membranes prepared in examples are shown in fig. 1 and 2.
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 (10)
1. A preparation method of a hydrophilic ultrafiltration membrane for oil-water separation is characterized by comprising the following steps:
s1, mixing the film-forming polymer with polymethyl methacrylate to prepare a blended film;
and S2, grafting ethylene glycol to the surface of the blend membrane through ester exchange reaction to obtain the target product hydrophilic ultrafiltration membrane.
2. The method for preparing the hydrophilic ultrafiltration membrane for oil-water separation according to claim 1, wherein:
the S1 specifically includes: dissolving a film-forming polymer, polymethyl methacrylate and an additive in a solvent, uniformly mixing to obtain a film-forming solution, and preparing a blended film by adopting an immersion sedimentation method after vacuum defoaming;
the S2 specifically includes: and soaking the blend membrane in an ethylene glycol solution, and grafting ethylene glycol to the surface of the blend membrane through ester exchange reaction to obtain the hydrophilic ultrafiltration membrane.
3. The method for preparing the hydrophilic ultrafiltration membrane for oil-water separation according to claim 2, wherein: the film-forming polymer is polysulfone, polyethersulfone, polyvinylidene fluoride or polyvinyl chloride; the solvent is dimethyl acetamide, dimethyl formamide, N-methyl pyrrolidone or dimethyl sulfoxide.
4. The method for preparing the hydrophilic ultrafiltration membrane for oil-water separation according to claim 2, wherein: the additive is water-soluble additive, water-insoluble additive, inorganic salt compound or their combination; the water-soluble additive is one or more of ethylene glycol, propylene glycol, glycerol, triethylene glycol, polyethylene glycol, polyvinylpyrrolidone, polyvinyl butyral and polyvinyl acetate; the water-insoluble additive is one or more of propylene carbonate, gamma-butyrolactone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monoethyl ether acetate and dipropylene glycol monoethyl ether acetate; the inorganic salt compound is one or more of lithium chloride, lithium nitrate and calcium nitrate.
5. The method for preparing the hydrophilic ultrafiltration membrane for oil-water separation according to claim 2, wherein: the sum of the mass of the film forming polymer and the polymethyl methacrylate accounts for 5-30% of the total mass of the film forming solution, the mass of the additive accounts for 0.5-20% of the total mass of the film forming solution, and the balance is the solvent; wherein the mass ratio of the film-forming polymer to the polymethyl methacrylate is 0.05: 1-20: 1.
6. The method for preparing the hydrophilic ultrafiltration membrane for oil-water separation according to claim 2, wherein: in the process of preparing the membrane preparation solution, the reaction temperature is 5-120 ℃, and the time is 1-50 h; in the process of preparing the blend membrane by adopting an immersion sedimentation method, the membrane is replaced by deionized water for 24 hours after being formed.
7. The method for preparing the hydrophilic ultrafiltration membrane for oil-water separation according to claim 2, wherein: the glycol solution contains water and a catalyst; the catalyst accounts for 0.0001-5% of the total mass of the glycol solution, and the water accounts for 0.0001-5% of the total mass of the glycol solution.
8. The method for preparing the hydrophilic ultrafiltration membrane for oil-water separation according to claim 7, wherein: the catalyst is one or more of sodium hydroxide, potassium hydroxide or calcium hydroxide.
9. The method for preparing the hydrophilic ultrafiltration membrane for oil-water separation according to claim 2, wherein: the time of the ester exchange reaction is 0.5-50 h, and the temperature of the ester exchange reaction is 5-80 ℃.
10. The hydrophilic ultrafiltration membrane for oil-water separation prepared by the method of any one of claims 1 to 9, wherein: the hydrophilic ultrafiltration membrane is of a finger-shaped pore support asymmetric structure; preferably, the hydrophilic ultrafiltration membrane is a flat membrane or a hollow fiber membrane.
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