CN110124533B - Gel microsphere modified anti-pollution oil-water separation ultrafiltration membrane and preparation method thereof - Google Patents
Gel microsphere modified anti-pollution oil-water separation ultrafiltration membrane and preparation method thereof Download PDFInfo
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- CN110124533B CN110124533B CN201910519122.4A CN201910519122A CN110124533B CN 110124533 B CN110124533 B CN 110124533B CN 201910519122 A CN201910519122 A CN 201910519122A CN 110124533 B CN110124533 B CN 110124533B
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- B01D17/02—Separation of non-miscible liquids
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- 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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- 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
- B01D71/26—Polyalkenes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- B01D2325/36—Hydrophilic membranes
Abstract
The invention relates to a gel microsphere modified anti-pollution oil-water separation ultrafiltration membrane and a preparation method thereof, wherein gel microspheres are prepared from vinyl monomers respectively containing carboxyl groups and amide groups on side groups, random copolymers are formed by free radical polymerization, a physically cross-linked network structure is formed between the side groups of a molecular chain through hydrogen bond supermolecule self-assembly, and the particle size of the microspheres is adjustable within the range of 50-500 nm; the surface of the base membrane is modified by carboxylation (-COOH) through an ultraviolet light initiated graft polymerization method and is linked with an amide group (-CONH) on the surface of the microsphere2) Through hydrogen bonding. The invention provides a new idea for hydrophilic modification of the surface of a hydrophobic ultrafiltration membrane and oil-water separation, the modified membrane has better hydrophilicity and underwater oleophobic property, can effectively reduce the adhesion of oil drops on the membrane surface in the oil-water separation process, and is expected to be used for the separation of oil-in-water emulsions.
Description
Technical Field
The invention belongs to a preparation method of a modified polymer membrane material in the field of water treatment, and particularly relates to a gel microsphere modified anti-pollution oil-water separation ultrafiltration membrane and a preparation method thereof.
Background
With the rapid development of industrial technology, the oily sewage generated in the production processes of petroleum, daily chemicals, textiles, leather, electroplating and the like is increased year by year, and the treatment of the oily sewage is not thoroughly solved. The oily sewage can be divided into oil slick, dispersed oil, emulsified oil and dissolved oil according to the difference of the grain sizes of oil drops, wherein the emulsified oil can exist stably and is difficult to be combined into large oil drops due to the coating of a surfactant, and the emulsified oil is difficult to be separated from the waste water by a standing method. In order to effectively reduce oil and water pollution, oil and water mixture, especially oil and water emulsion, must be effectively separated before being discharged. The membrane separation technology has important influence in the fields of petrochemical industry and the like, and on one hand, the oil substances can be recovered, and the energy is saved; on the other hand, the water body can be purified to reach the discharge standard so as to reduce the harm to the environment. Most of traditional separation membrane materials are hydrophobic polymer base membrane materials, and when oil-in-water emulsions with low oil content are processed, oil drops are easily adsorbed on the surface and the inside of membrane pores of the membrane, so that membrane pollution is caused, membrane flux is rapidly attenuated, and the service life of the membrane is shortened. Therefore, in order to further improve the separation efficiency of the emulsified oil-water mixture, increase the recovery rate of the membrane flux, and further extend the service life thereof, it is necessary to improve the anti-fouling performance of the membrane, that is, to reduce the adhesion of oil molecules to the membrane surface.
In recent years, membranes having hydrophilic/oleophobic properties on the surface have exhibited excellent anti-contamination properties in oil-water separation processes. Common modification methods are blend modification, copolymerization modification and surface modification. The Chinese invention patent (application No. CN104607060A) discloses a method for preparing a modified membrane by using a blending method of inorganic nanoparticles and PVDF powder to improve the hydrophilicity of the membrane, but the specific surface area of the nanoparticles is large, the nanoparticles are easy to agglomerate together, and the problems of uneven distribution of the inorganic nanoparticles in the membrane and the like exist. The Chinese invention patent (application No. CN106492655A) discloses that the hydrophilicity of a filtering membrane is improved by utilizing silicon dioxide to graft PVDF through chemical bonds so as to improve the anti-pollution performance of the filtering membrane, but the method destroys the chemical bonds of a membrane forming substance and reduces the mechanical property of the membrane. Therefore, many scholars have conducted extensive research around surface modification. The Chinese patent of invention (application No. CN104474930A) discloses that a layer of hydrogel is crosslinked on the surface of a polyvinylidene fluoride membrane through chemical bonds by a one-step method of mercapto-epoxy and mercapto-alkene addition reactions, and the stability of the hydrogel can be effectively improved. However, the method is complicated in preparation process and the gel layer blocks the pores of the membrane to cause a decrease in flux. Chinese invention patent (application No. CN105218852A) discloses a self-assembly polystyrene-carboxylic acid (PS-COOH) microsphere functional composite membrane with simple process, the method prepares the functional composite membrane through the electrostatic acting force on the surfaces of the microsphere and the porous membrane, and the method is expected to be applied to the field of measuring the antigen concentration on a biosensor. However, if the modified membrane prepared by the method is applied to the field of oil-water emulsion separation membranes, the stability of the composite membrane can be influenced in the use process of different acid-base environments.
The invention takes a monomer with a side group containing a carboxyl group and a side group containing an amide group as a modifier, and a random copolymer is formed by free radical polymerization, a physically cross-linked network structure microsphere is formed among the side groups of a molecular chain through supermolecule self-assembly, the surface of the microsphere contains a large amount of carboxyl groups and amide groups, and the exposed amide groups and a surface carboxylated base membrane are grafted on the surface of a separation membrane through the action of hydrogen bonds. Part of free hydrophilic groups on the molecular chain of the gel microsphere are easy to combine with water molecules, so that a hydration layer is formed on the surface of the membrane, the stability of the membrane is kept for a long time, the separation effect of the oily sewage is improved, and the service life of the separation membrane is prolonged. Compared with the traditional method, the membrane prepared by the invention has the advantages of simple operation, obvious pollution resistance effect and the like. The invention provides a new idea for hydrophilic modification of a hydrophobic membrane surface and application of the hydrophilic modification to oil-water separation, and the modifier which can form gel through intermolecular hydrogen bond supermolecule self-assembly can be used for hydrophilic modification of the membrane surface. The modified membrane has better hydrophilicity and underwater oleophobic performance, can effectively reduce the adhesion of oil drops on the surface of the membrane in the oil-water separation process, and is expected to be used for the separation of oil-in-water emulsions.
Disclosure of Invention
The invention takes vinyl monomers with side groups respectively containing carboxyl and amide groups as a modifier and carries out free radical polymerizationForming random copolymer and forming physically cross-linked network structure microspheres through self-assembly of supermolecules among side groups, wherein the surfaces of the microspheres contain a large amount of carboxyl groups and amide groups, and the particle size is 50-500 nm; taking a polyolefin commercial film or a self-made film made of polyvinylidene fluoride (PVDF), Polyethylene (PE) or polypropylene (PP) and other materials as a base film, and performing carboxyl (-COOH) modification on the surface of the base film by adopting an ultraviolet light initiated graft polymerization method; and amide groups (-CONH) exposed by the gel microspheres2) Linked by hydrogen bond action, thereby obtaining the anti-pollution ultrafiltration membrane which can be used for oil-water separation. The preparation of the anti-pollution separation membrane mainly comprises the following steps:
1. preparation of gel microspheres: taking methacrylic acid (MAAc) and methacrylamide (MAAm) monomers as examples,
1) weighing a certain amount of MAAc, MAAm and distilled water, and sequentially adding the MAAc, the MAAm and the distilled water into a three-neck flask arranged in a 70 ℃ water bath kettle;
2) adding a spherical condenser pipe and a mechanical stirring paddle to form an experimental device, and stirring at a rotating speed of more than 2000 r/min;
3) introducing N in the flask in a sealed state2Deoxidizing for more than 30 min;
4) adding an initiator Azobisisobutyronitrile (AIBN), and reacting for 270min to obtain gel microspheres;
5) placing the gel microsphere aqueous solution in a dialysis bag for dialysis for more than 2 days, and changing water every 12 h;
6) and (3) placing the gel microspheres prepared after dialysis into a big beaker, and adding ethanol serving as a dispersing agent and distilled water for later use.
The mass ratio of MAAc to MAAm in the step 1) is 1: 3-1: 0.3; the ratio of the addition of the distilled water to the total monomer mass is 50: 1;
the ratio of the AIBN addition amount to the total mass of the monomers in the step 4) is 1: 20;
the gel microspheres prepared in the step 6) are placed in a mixed solution with the mass ratio of absolute ethyl alcohol to distilled water being 1: 2, and the mass ratio of the microspheres to the mixed solution is 1: 1000.
2. Preparing an anti-pollution oil-water separation membrane:
1) washing the base membrane with methanol solution, placing the base membrane in methanol solution containing Benzophenone (BP), soaking for a certain time, taking out and naturally drying;
2) dissolving Acrylic Acid (AA) and Ferrous Ammonium Sulfate (FAS) in distilled water, pouring the mixed solution into a self-sealing bag, introducing nitrogen for oxygen discharge, immersing in an air-dried film, and sealing for storage;
3) irradiating the sealed membrane under an ultraviolet lamp for a certain time, taking out the membrane, and soaking the membrane by using a mixed solution of methanol and water to remove unreacted monomers;
4) placing the membrane in a sand core filter, pouring a certain volume of gel microsphere solution in the vacuum filtration process, and grafting the gel microspheres on the surface of the membrane through the hydrogen bond action between amide groups and carboxylic acid groups on the surface of the membrane;
5) the membrane was taken out, washed again with a mixed solution of methanol and water, and then dried in vacuum for future use.
The basement membrane in the step 1) can be a commercial membrane or a self-made membrane of olefins such as PVDF, PE or PP, the pore size is 0.1-0.45 μm, and the diameter is 3-10 cm; the BP concentration is 0.1-1.0mol/L, and the soaking time is 1-2 h;
in the step 2), the mass of AA is 0.1-0.5g, the mass ratio of AA to FAS is 1: 0.2, the mass ratio of the addition amount of distilled water to AA is 20: 1, and the time for introducing nitrogen and discharging oxygen is more than 30 min;
the power of the ultraviolet lamp in the step 3) is 300-;
the volume of the gel microsphere solution in the step 4) is 10-100 mL.
The invention has the following beneficial technical effects: the method has the advantages of improving the hydrophilicity of the membrane surface, enhancing the underwater oil drop adsorption resistance, along with simple operation, no need of adding a chemical cross-linking agent, stable structure and membrane separation performance of the gel microspheres under the acid-base condition, high membrane flux recovery rate and good separation performance when being used in the oil-water emulsion separation process, thereby ensuring high recycling rate of the separation membrane. The hydrophilic modified separating membrane is a novel oil pollution resistant hydrophilic modified separating membrane, and is particularly suitable for separating emulsified oil with small particle size.
Drawings
FIG. 1 is a comparative scanning electron microscope image of P (MAAc-co-MAAm) gel microsphere modified membrane and PVDF-based membrane prepared in example 1.
Fig. 2 is a graph showing the adhesion of the P (MAAc-co-MAAm) gel microsphere modified membrane and the PVDF-based membrane prepared in example 1 to underwater oil droplets.
FIG. 3 is a comparison graph of the oil-water emulsion flux cycling tests of the P (MAAc-co-MAAm) gel microsphere modified membrane and the PVDF-based membrane prepared in example 1.
FIG. 4 is a graph comparing the flux recovery data of oil-water emulsions of P (MAAc-co-MAAm) gel microsphere modified membrane prepared in example 1 and PVDF-based membrane.
Detailed Description
Example 1:
(1) synthesis of P (MAAc-co-MAAm) gel microspheres:
1) MAAc (0.50g), MAAm (0.50g) and 50mL of distilled water were added to a three-necked flask (250 mL capacity, 70 ℃ water bath);
2) adding a spherical condenser tube and a mechanical stirring paddle on a three-neck flask to assemble an experimental device, starting stirring and introducing N in a sealed state2Deoxidizing for 30 min;
3) AIBN (0.05g) was added to the stirred mixture and reacted for 270 min;
4) after the reaction is finished, putting the mixture into a dialysis bag for dialysis for more than 2 days, and changing water every 12 hours;
5) putting the gel microspheres subjected to dialysis into a 1000mL beaker, and adding 800mL of distilled water and 150mL of absolute ethyl alcohol; preparing the gel microspheres for later use.
(2) Preparing an anti-pollution oil-water separation membrane:
1) a PVDF commercial raw membrane with the aperture of 0.1 mu m and the diameter of 5cm is washed by a methanol solution;
2) soaking the cleaned PVDF membrane in a methanol solution (0.4mol/L) of Benzophenone (BP), taking out after 1.5h, and naturally drying;
3) preparing AA (0.30g), FAS (0.05g) and 50mL of distilled water into a mixed solution, then placing the mixed solution into a self-sealing bag, introducing nitrogen for 30min, immersing the dried PVDF membrane, and sealing and storing;
4) placing the sealed self-sealing bag under a 500W ultraviolet lamp, irradiating for 15min, taking out the membrane, and soaking the membrane with a mixed solution of methanol and water to remove unreacted monomers;
5) placing the membrane in a sand core filter, pouring 60mL of gel microsphere solution in the vacuum filtration process, and grafting the gel microspheres on the surface of the membrane through the hydrogen bond action between amide groups and carboxylic acid groups on the surface of the membrane;
6) and after the filtration is finished, taking out the membrane, washing the membrane again by using a mixed solution of methanol and water, and drying in vacuum for later use.
Example 2:
(1) synthesis of P (MAAc-co-MAAm) gel microspheres: the same as in example 1.
(2) Preparing an anti-pollution oil-water separation membrane:
1) washing a PVDF commercial raw membrane with the aperture of 0.22 mu m and the diameter of 5cm in a methanol solution;
2) soaking the cleaned PVDF membrane in a benzophenone methanol solution (0.4mol/L), taking out after 1.5h, and naturally drying;
3) preparing AA (0.6g), FAS (0.05g) and 50mL of distilled water into a mixed solution, then placing the mixed solution into a self-sealing bag, introducing nitrogen for 30min, immersing the dried PVDF membrane, and sealing and storing;
4) placing the sealed self-sealing bag under a 300W ultraviolet lamp, irradiating for 15min, taking out the membrane, and soaking the membrane with a mixed solution of methanol and water to remove unreacted monomers;
5) placing the membrane in a sand core filter, pouring 30mL of gel microsphere solution in the vacuum filtration process, and grafting the gel microspheres on the surface of the membrane through the hydrogen bond action between amide groups and carboxylic acid groups on the surface of the membrane;
6) and after the filtration is finished, taking out the membrane, washing the membrane again by using a mixed solution of methanol and water, and drying in vacuum for later use.
Experimental comparative example:
a PVDF blank ultrafiltration membrane required for the experiment was obtained by washing a PVDF commercial raw membrane having an average pore diameter of 0.22 μm and a diameter of 5cm with a methanol solution and then vacuum-drying.
The experimental effect is as follows:
the gel microsphere modified anti-pollution oil-water separation ultrafiltration membrane designed and prepared by the invention has small adsorbability on oil drops underwater, high membrane flux recovery rate in the oil-water emulsion separation process, good separation performance and good membrane stability in the use process. Comparative tests were carried out using the samples prepared in example 1 to obtain:
(1) the sample prepared in the embodiment 1 is uniformly grafted with gel microspheres on the surface (see the attached figure 1 in the specification), which shows that the gel microspheres are successfully grafted on the surface of the membrane;
(2) for the film oil drop adhesion test, the adhesion of the sample prepared in the embodiment 1 to oil drops is greatly reduced compared with the sample prepared in the experimental comparative example (see the attached figure 2 in the specification), which shows that the sample has excellent oil drop adhesion resistance;
(3) example 1 the sample prepared was subjected to an oil-water emulsion flux cycling test, and after three cycles for up to 1.5 hours, the initial flux was only 439.8L m2·h-1Down to 401.6 L.m2·h-1(ii) a The sample prepared in the experimental comparative example is seriously polluted after three times of same cycles, and the initial flux is 841.4 L.m2·h-1Down to 382.4 L.m2·h-1(see the attached figure 3 in the specification), and the modified membrane is more stable in performance.
(4) In addition, the flux recovery rate of the sample prepared in the experimental comparative example is reduced to 45.5% after the three-cycle test, while the flux recovery rate of the modified membrane of the sample prepared in the embodiment 1 is always maintained above 90% (see the attached figure 4 in the specification), which indicates that the modified separation membrane has excellent oil drop pollution resistance.
Claims (4)
1. A gel microsphere modified anti-pollution oil-water separation ultrafiltration membrane is characterized in that a base membrane is an olefin membrane, a monomer with a side group containing a carboxyl group and a side group containing an amide group is used as a modifier, the modifier monomer is polymerized by free radicals to form a random copolymer, the side groups of molecular chains form physically cross-linked network structure microspheres through supermolecule self-assembly, the surfaces of the microspheres contain a large number of carboxyl groups and amide groups, and the exposed amide groups on the surfaces of the microspheres are grafted on the surface of the base membrane subjected to carboxylation modification through hydrogen bond interaction, so that the anti-pollution ultrafiltration membrane with oil-water separation performance is obtained; the ultrafiltration membrane has small adsorbability on oil drops underwater, high membrane flux recovery rate in the oil-water emulsion separation process, good separation performance and good membrane stability in the use process.
2. The gel microsphere modified anti-pollution oil-water separation ultrafiltration membrane as claimed in claim 1, wherein the olefin-based membrane is selected from one of commercial membranes and self-made membranes, and is selected from one of polyvinylidene fluoride, polyethylene or polypropylene membranes, and has a pore size of 0.1-0.45 μm and a diameter of 3-10 cm.
3. The gel microsphere modified anti-pollution oil-water separation ultrafiltration membrane as claimed in claim 1, wherein the modifier monomer is a monomer with a side group containing a carboxyl group and a side group containing an amide group, methacrylic acid and methacrylamide are subjected to free radical polymerization to form a random copolymer, and mechanical stirring is combined to form a physically crosslinked gel microsphere, multiple hydrogen bond interactions exist between the amide group and the carboxyl group on the side group of the molecular chain of the microsphere, the surface of the microsphere contains a large amount of carboxyl groups and amide groups, and the particle size is 50-500nm, and the preparation method comprises the following steps:
1) weighing a certain amount of methacrylic acid, methacrylamide and distilled water, and sequentially adding the methacrylic acid, the methacrylamide and the distilled water into a three-neck flask arranged in a 70 ℃ water bath kettle;
2) adding a spherical condenser pipe and a mechanical stirring paddle to form an experimental device, and stirring at a rotating speed of more than 2000 r/min;
3) introducing N in the flask in a sealed state2Deoxidizing for more than 30 min;
4) adding an initiator azobisisobutyronitrile, and reacting for 270min to obtain gel microspheres;
5) putting the gel microsphere aqueous solution into a dialysis bag for dialysis for more than 2 days, and changing water every 12 hours;
6) putting the gel microspheres prepared after dialysis into a big beaker, and adding ethanol as a dispersing agent and distilled water for later use;
the mass ratio of the methacrylic acid to the methacrylamide in the step 1) is 1: 3-1: 0.3; the ratio of the addition of the distilled water to the total monomer mass is 50: 1;
the ratio of the addition amount of the azodiisobutyronitrile to the total mass of the monomers in the step 4) is 1: 20;
the gel microspheres prepared in the step 6) are placed in a mixed solution with the mass ratio of absolute ethyl alcohol to distilled water being 1: 2, and the mass ratio of the microspheres to the mixed solution is 1: 1000.
4. The anti-pollution oil-water separation ultrafiltration membrane modified by the gel microspheres as claimed in claim 1, wherein the carboxylation modification method on the surface of the basement membrane is carried out according to the following steps:
1) washing the base membrane with a methanol solution, placing the base membrane in a methanol solution containing benzophenone, soaking for a certain time, taking out and naturally drying;
2) dissolving acrylic acid and ammonium ferrous sulfate in distilled water, then pouring the mixed solution into a self-sealing bag, introducing nitrogen for oxygen discharge, immersing the self-sealing bag into an air-dried film, and sealing and storing the self-sealing bag;
3) irradiating the sealed membrane under an ultraviolet lamp for a certain time, taking out the membrane, and soaking the membrane by using a mixed solution of methanol and water to remove unreacted monomers;
4) placing the membrane in a sand core filter, pouring 10-100mL of gel microsphere solution in the vacuum filtration process, and grafting the gel microspheres on the surface of the membrane through the hydrogen bond action between amide groups and carboxylic acid groups on the surface of the membrane;
5) taking out the membrane, cleaning the membrane again by using a mixed solution of methanol and water, and drying the membrane in vacuum for later use;
in the step 1), the concentration of the benzophenone is 0.1-1.0mol/L, and the soaking time is 1-2 h;
in the step 2), the mass of acrylic acid is 0.1-0.5g, the mass ratio of acrylic acid to ammonium ferrous sulfate is 1: 0.2, the mass ratio of the addition amount of distilled water to acrylic acid is 20: 1, and the time for introducing nitrogen and discharging oxygen is more than 30 min;
the power of the ultraviolet lamp in the step 3) is 300-500W, and the irradiation time of the ultraviolet lamp is 5-15 min.
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