CN110124533A - A kind of anti-polluting oil-water separation ultra-filtration membrane and preparation method thereof that gel micro-ball is modified - Google Patents
A kind of anti-polluting oil-water separation ultra-filtration membrane and preparation method thereof that gel micro-ball is modified Download PDFInfo
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- CN110124533A CN110124533A CN201910519122.4A CN201910519122A CN110124533A CN 110124533 A CN110124533 A CN 110124533A CN 201910519122 A CN201910519122 A CN 201910519122A CN 110124533 A CN110124533 A CN 110124533A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
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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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- 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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- 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
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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Abstract
The present invention relates to a kind of modified anti-polluting oil-water separation ultra-filtration membranes and preparation method thereof of gel micro-ball, gel micro-ball is prepared with the vinyl monomer in side group respectively containing carboxylic group and amide group, it first passes around free radical polymerization and forms random copolymer, the network structure of physical crosslinking is formed between strand side group by hydrogen bond Supramolecular self assembly, microspherulite diameter is adjustable within the scope of 50-500nm；Membrane surface carries out carboxylated (- COOH) by UV photoinitiated grafting polymerization and is modified, and the amide group (- CONH with microsphere surface2) connected by hydrogen bond action.The present invention provides a kind of new thinking for hydrophobic ultrafiltration membrane surface hydrophilic modifying and for water-oil separating, the Modified Membrane has preferable hydrophily and underwater oleophobic performance, in oil water separation process, it can effectively reduce oil droplet in the adherency of film surface, be expected to be used for the separation of oil-in-water emulsion.
Description
Technical field
The invention belongs to the preparation method of the modified high-molecular membrane material in water treatment field, in particular to a kind of gel micro-ball
Modified anti-polluting oil-water separation ultra-filtration membrane and preparation method thereof.
Background technique
The oil-containing generated with the fast development of industrial technology, the production processes such as petroleum, daily use chemicals, weaving, leather and plating
Sewage increases year by year, and the processing of oily wastewater is not solved.Oily wastewater can be with according to the difference of oil droplet size
It is divided into oil slick, dispersed oil, oil emulsion and dissolved oil, wherein oil emulsion is since the package of surfactant is so as to steadily
In the presence of and be difficult to be merged into larger oil droplet, the general method with standing is also difficult to separate it from waste water.In order to effectively
Oily wastewater pollution is reduced, it must be effectively separated before discharge oil water mixture especially oil hydrosol.UF membrane skill
Art has important influence in fields such as petrochemical industries, and oily matter on the one hand can be recycled, energy saving；On the other hand it can make water
Body purification, reaches discharge standard, to reduce the harm to environment.Traditional separation membrane material is mostly hydrophobic polymer matrix
Membrane material, is easy absorption oil droplet when handling the low oil-in-water emulsion of oil content, in film surface and fenestra so as to cause fouling membrane,
The rapid decaying of membrane flux is in turn resulted in, membrane lifetime is reduced.Therefore, in order to further increase the separation of oil emulsion oil-water mixture
Efficiency, increases the recovery rate of membrane flux, and then prolongs its service life, and needs to improve the oil rub resistance pollutant performance of film, that is, reduces
Adhesiveness of the oil molecule in film surface.
In recent years, there is the film of hydrophilic/oleophobic properties excellent antipollution is shown in oil water separation process on surface
Property.Common method of modifying has blending and modifying, modification by copolymerization and surface modified.Chinese invention patent (application number
CN104607060A it) discloses hydrophilic to improve its using inorganic nano-particle and PVDF admixture of powder method preparation Modified Membrane
Method, but nanoparticle specific surface area is larger is easy to reunite together, and there are inorganic nano-particles to be unevenly distributed in film
The problems such as.Chinese invention patent (application number CN106492655A) disclose using silica by chemical bond be grafted PVDF from
And improve the hydrophily of filter membrane, to improve its antifouling property, but this method destroys the chemical bond of film forming matter itself, drop
The problems such as low mechanical property of film.Therefore, around surface, a large amount of research has been done in modification to many scholars.Chinese invention patent
(application number CN104474930A) is disclosed through sulfydryl-epoxy and sulfydryl-alkene addition reaction one-step method in polyvinylidene fluoride film
Surface is crosslinked one layer of hydrogel by chemical bond, can effectively improve the stability of gel.But this method preparation process it is complicated and
Gel layer, which can block fenestra, causes flux to decline.Chinese invention patent (application number CN105218852A) discloses a kind of technique letter
Single self assembly polystyrene-carboxylic acid (PS-COOH) microballoon functional composite membrane, this method are quiet by microballoon and porous film surface
Electrical forces are prepared into functional composite membrane, are expected to be applied to measure the field of antigen concentration on a biosensor.But if logical
It crosses this method preparation Modified Membrane and is applied to oil hydrosol seperation film field, the composite membrane is steady in different acid or alkali environment use processes
It surely can be impacted.
The monomer that the present invention contains carboxylic group using side group and side group contains amide group is modifying agent, through free radical polymerization
Random copolymer is formed, forms the reticular structure microballoon of physical crosslinking, microballoon table between strand side group by Supramolecular self assembly
A large amount of carboxylic group and amide group are contained in face, and the basement membrane of exposed amide group and surface carboxylation is connect by hydrogen bond action
Branch is in separation membrane surface.The free hydrophilic radical in part is easy on the strand of the gel micro-ball and water molecules, thus in film
Surface forms hydrated sheath, and keeps prolonged stability, and then improves oily wastewater separating effect and extend making for seperation film
Use the service life.It is compared with the traditional method, film prepared by the present invention has many advantages, such as easy to operate, and antipollution effect is significant.The present invention
For hydrophobic film surface hydrophilic modifying and provide a kind of new thinking for water-oil separating, can be super by intermolecular hydrogen bonding
Molecular self-assembling forms the modifying agent of gel, can be used for film surface hydrophilic modifying.The Modified Membrane has preferable hydrophilic
Property and underwater oleophobic performance can effectively reduce oil droplet in the adherency of film surface in oil water separation process, be expected to be used for oil-in-water
The separation of lotion.
Summary of the invention
Vinyl monomer of the present invention using side group respectively containing carboxyl and amide group is modifying agent, through free radical polymerization shape
The reticular structure microballoon of physical crosslinking is formed at random copolymer and by Supramolecular self assembly between side group, and microsphere surface contains
A large amount of carboxylic group and amide group, partial size 50-500nm；With Kynoar (PVDF), polyethylene (PE) or polypropylene
(PP) etc. polyolefins commercial membranes of materials or be basement membrane from film, carry out its surface using UV photoinitiated grafting polymerization
Carboxyl (- COOH) is modified；The amide group (- CONH exposed with gel micro-ball2) linked by hydrogen bond action, so that obtaining can
Antipollution ultrafiltration membrane for water-oil separating.The preparation of above-mentioned anti-pollution separation membrane mainly comprises the steps that
1. the preparation of gel micro-ball: by taking methacrylic acid (MAAc) and Methacrylamide (MAAm) monomer as an example,
1) a certain amount of MAAc, MAAm and distilled water are weighed, is added sequentially in the three-necked flask for being placed in 70 DEG C of water-baths；
2) plus spherical condensation tube and mechanical stirring paddle form experimental provision, and are stirred, revolving speed be 2000r/min with
On；
3) N is passed through under flask sealing state2Deoxygenation 30min or more；
4) initiator azodiisobutyronitrile (AIBN) is added, reacts 270min, gel micro-ball is made；
5) above-mentioned gel micro-ball aqueous solution is placed in bag filter and is dialysed, the time is 2 days or more, changes one every 12h
Secondary water；
6) gel micro-ball obtained after dialysis is placed in large beaker, and it is standby as dispersing agent and distilled water that ethyl alcohol is added
With.
The mass ratio of MAAc and MAAm is 1: 3-1: 0.3 in the step 1)；Distilled water additional amount and total monomer quality it
Than being 50: 1；
The ratio of AIBN additional amount and monomer gross mass is 1: 20 in the step 4)；
The mixed solution that the gel micro-ball prepared in the step 6) is placed in dehydrated alcohol and distilled water mass ratio is 1: 2
In, microballoon and mixed solution mass ratio are 1: 1000.
2. the preparation of antipollution water-oil separationg film:
1) basement membrane is rinsed with methanol solution, then is placed in the methanol solution containing benzophenone (BP), is impregnated certain
Naturally dry is taken out after time；
2) acrylic acid (AA) and iron ammonium sulfate (FAS) are dissolved in distilled water, then pour into mixed liquor in valve bag,
It is passed through nitrogen deoxygenation, the film dried is immersed, is sealed；
3) film after sealing is put irradiates certain time in the UV lamp, takes the film out, with the mixed solution pair of first alcohol and water
Film is impregnated to remove unreacted monomer；
4) film is placed in sand core filter, the gel micro-ball solution of certain volume is poured into during vacuum filtration, coagulated
Glue microballoon grafts on film surface by the hydrogen bond action between amide group and the carboxylic acid group of film surface；
5) it takes the film out, after being cleaned again with the mixed solution of first alcohol and water to film, is dried in vacuo spare.
Above-mentioned steps 1) in basement membrane can be the commercial membranes of the olefines such as PVDF, PE or PP or from being film-made, aperture is big
Small is 0.1-0.45 μm, diameter 3-10cm；BP concentration is 0.1-1.0mol/L, soaking time 1-2h；
Above-mentioned steps 2) in the quality of AA be the mass ratio of 0.1-0.5g, AA and FAS be 1: 0.2, distilled water additional amount with
The mass ratio of AA is 20: 1, leads to the time of nitrogen deoxygenation in 30min or more；
Above-mentioned steps 3) in ultraviolet lamp power be 300-500W, irradiation time 5-15min；
Above-mentioned steps 4) in gel micro-ball solution volume be 10-100mL.
The present invention has following advantageous effects: film surface hydrophily improves, underwater oil resistant drop adsorption capacity enhancing, and
It is easy to operate, addition chemical cross-linking agent is not needed, the structure of gel micro-ball and membrane separating property are stablized under acid-base condition, are used for
Membrane flux recovery rate is high in oil hydrosol separation process, and separating property is good, to make the high recycling rate of seperation film.This belongs to
A kind of novel oil rub resistance pollution hydrophilic modifying seperation film, is particularly suitable for the oil emulsion separation of small particle.
Detailed description of the invention
Fig. 1 is the scanning electricity of P (MAAc-co-MAAm) the gel micro-ball Modified Membrane and PVDF basement membrane that prepare in case study on implementation 1
Mirror comparison diagram.
Fig. 2 is P (MAAc-co-MAAm) the gel micro-ball Modified Membrane prepared in case study on implementation 1 and PVDF basement membrane to underwater oil
Drip adhesion test figure.
Fig. 3 is the grease cream of P (MAAc-co-MAAm) the gel micro-ball Modified Membrane and PVDF basement membrane that prepare in case study on implementation 1
Liquid flux loop test comparison diagram.
Fig. 4 is the grease cream of P (MAAc-co-MAAm) the gel micro-ball Modified Membrane and PVDF basement membrane that prepare in case study on implementation 1
Liquid flux recovery rate data comparison figure.
Specific embodiment
Embodiment 1:
(1) synthesis of P (MAAc-co-MAAm) gel micro-ball:
1) MAAc (0.50g), MAAm (0.50g) and 50mL distilled water be added to three-necked flask (volume 250mL, 70 DEG C
Water-bath) in；
2) add spherical condensation tube and mechanical stirring paddle to be assembled into experimental provision on three-necked flask, start to stir and sealing
N is passed through under state2Deoxygenation 30min；
3) AIBN (0.05g) is added into the mixture after above-mentioned stirring, reacts 270min；
4) it after completion of the reaction, is placed in bag filter and carries out dialysis 2 days or more, and change a water every 12h；
5) gel micro-ball that above-mentioned dialysis is completed is placed in the beaker of 1000mL, be added 800mL distilled water and 150mL without
Water-ethanol；It is spare to be prepared into gel micro-ball.
(2) preparation of antipollution water-oil separationg film:
It 1) is 0.1 μm by aperture, the former film of PVDF business that diameter is 5cm is rinsed with methanol solution；
2) pvdf membrane after cleaning is placed in the methanol solution (0.4mol/L) of benzophenone (BP) and is impregnated, taken after 1.5h
Naturally dry out；
3) by AA (0.30g), FAS (0.05g) and 50mL distilled water are made into mixed solution, be placed in valve bag,
Logical nitrogen 30min, the pvdf membrane dried is immersed, is sealed；
4) valve bag after sealing is placed under the ultraviolet lamp of 500W, is taken the film out after irradiating 15min with first alcohol and water
Mixed solution impregnates to remove unreacted monomer film；
5) film is placed in sand core filter, the gel micro-ball solution of 60mL is poured into during vacuum filtration, gel is micro-
Ball grafts on film surface by the hydrogen bond action between amide group and the carboxylic acid group of film surface；
6) it completes after filtering, takes the film out, after being cleaned again with the mixed solution of first alcohol and water to film, vacuum drying
It is spare.
Embodiment 2:
(1) synthesis of P (MAAc-co-MAAm) gel micro-ball: with embodiment 1.
(2) preparation of antipollution water-oil separationg film:
It 1) is 0.22 μm by aperture, the former film of PVDF business that diameter is 5cm, which is placed in methanol solution, to be cleaned；
2) pvdf membrane after cleaning is placed in the methanol solution (0.4mol/L) of benzophenone and is impregnated, taken out certainly after 1.5h
So dry；
3) by AA (0.6g), FAS (0.05g) and 50mL distilled water are made into mixed solution, be placed in valve bag, lead to
The pvdf membrane dried is immersed, is sealed by nitrogen 30min；
4) valve bag after sealing is placed under the ultraviolet lamp of 300W, is taken the film out after irradiating 15min, with first alcohol and water
Mixed solution impregnates to remove unreacted monomer film；
5) film is placed in sand core filter, the gel micro-ball solution of 30mL is poured into during vacuum filtration, gel is micro-
Ball grafts on film surface by the hydrogen bond action between amide group and the carboxylic acid group of film surface；
6) it completes after filtering, takes the film out, after being cleaned again with the mixed solution of first alcohol and water to film, vacuum drying
It is spare.
Experimental comparison's example:
It is 0.22 μm by average pore size, the former film of PVDF business that diameter is 5cm is rinsed with methanol solution, is then carried out
Vacuum drying, PVDF blank ultrafiltration membrane needed for obtaining this experiment.
Experiment effect:
A kind of anti-polluting oil-water separation ultra-filtration membrane that gel micro-ball is modified is prepared in present invention design, and the ultrafiltration membrane is under water
Small to oil droplet adsorptivity, high for membrane flux recovery rate in oil hydrosol separation process, separating property is good, and film in use process
Stability is good.Test is compared using sample prepared by case study on implementation 1 to obtain:
(1) sample surfaces prepared by case study on implementation 1 are uniformly grafted with gel micro-ball (referring to Figure of description 1), explanation
Film surface is successfully grafted gel micro-ball；
(2) to film oil droplet adhesion test, sample prepared by case study on implementation 1 prepares sample to oil droplet compared to Experimental comparison's example
Adhesiveness be greatly reduced (referring to Figure of description 2), this illustrates that it has more excellent oil resistant drop adhesion property；
(3) sample prepared by case study on implementation 1 carries out oil hydrosol flux loop test, after circulation is up to 1.5 hours three times,
Initial flux is only from 439.8Lm2·h-1Drop to 401.6Lm2·h-1；And the sample of Experimental comparison's example preparation is by three times
Seriously polluted after same circulation, initial flux is from 841.4Lm2·h-1Drop to 382.4Lm2·h-1(referring to specification
Attached drawing 3), illustrate that modified film properties are more stable.
(4) in addition, the sample of Experimental comparison's example preparation is after above three loop test, flux recovery rate drops to
45.5%, and sample prepared by case study on implementation 1, the flux recovery rate of Modified Membrane maintain always 90% or more (referring to specification
Attached drawing 4), this illustrates that modified seperation film has more excellent oil resistant drop pollution capacity.
Claims (4)
1. a kind of modified anti-polluting oil-water separation ultra-filtration membrane of gel micro-ball, it is characterised in that basement membrane is olefines film, and gel is micro-
Ball is the reticular structure for forming random copolymer by free radical polymerization and having physical crosslinking；Microballoon is grafted by hydrogen bond action
In the film surface of carboxylated, to obtain the antipollution ultrafiltration membrane with water-oil separating performance；The ultrafiltration membrane is under water to oil droplet
Adsorptivity is small, and high for membrane flux recovery rate in oil hydrosol separation process, separating property is good, and membrane stability in use process
It is good.
2. a kind of modified anti-polluting oil-water separation ultra-filtration membrane of gel micro-ball according to claim 1, it is characterised in that alkene
Hydro carbons basement membrane be selected from commercial membranes or from film one of, specific material be selected from Kynoar (PVDF), polyethylene (PE) or
One of polypropylene (PP) film, pore size are 0.1-0.45 μm, diameter 3-10cm.
3. a kind of modified anti-polluting oil-water separation ultra-filtration membrane of gel micro-ball according to claim 1, it is characterised in that solidifying
Glue microballoon by strand side group amide group and carboxylic group formed based on Supramolecular self assembly, and microsphere surface contains greatly
The carboxylic group and amide group of amount, partial size 50-500nm, it is specific the preparation method is as follows:
1) a certain amount of MAAc, MAAm and distilled water are weighed, is added sequentially in the three-necked flask for being placed in 70 DEG C of water-baths；
2) add spherical condensation tube and mechanical stirring paddle to form experimental provision, and be stirred, revolving speed is 2000r/min or more；
3) N is passed through under flask sealing state2Deoxygenation 30min or more；
4) initiator azodiisobutyronitrile (AIBN) is added, reacts 270min, obtains gel micro-ball；
5) above-mentioned gel micro-ball aqueous solution is placed in bag filter and is carried out dialysis 2 days or more, change a water every 12h；
6) gel micro-ball obtained after dialysis is placed in large beaker, and it is spare as dispersing agent and distilled water that ethyl alcohol is added.
The mass ratio of MAAc and MAAm is 1: 3-1: 0.3 in the step 1)；The ratio between distilled water additional amount and total monomer quality are
50:1；
The ratio of AIBN additional amount and monomer gross mass is 1: 20 in the step 4)；
In the mixed solution that the gel micro-ball prepared in the step 6) is placed in dehydrated alcohol and distilled water mass ratio is 1: 2,
Microballoon and mixed solution mass ratio are 1: 1000.
4. a kind of modified anti-polluting oil-water separation ultra-filtration membrane of gel micro-ball according to claim 1, preparation method are pressed
Following step carries out:
1) basement membrane is rinsed with methanol solution, then is placed in the methanol solution containing benzophenone (BP), and immersion takes after a certain period of time
Naturally dry out；
2) acrylic acid (AA) and iron ammonium sulfate (FAS) are dissolved in distilled water, then pour into mixed liquor in valve bag, be passed through
Nitrogen deoxygenation immerses the film dried, is sealed；
3) film after sealing is put and irradiates certain time in the UV lamp, takes the film out, with the mixed solution of first alcohol and water to film into
Row is impregnated to remove unreacted monomer；
4) film is placed in sand core filter, the gel micro-ball solution of 10-100mL is poured into during vacuum filtration, gel is micro-
Ball grafts on film surface by the hydrogen bond action between amide group and the carboxylic acid group of film surface；
5) it takes the film out, after being cleaned again with the mixed solution of first alcohol and water to film, is dried in vacuo spare.
Above-mentioned steps 1) in BP concentration be 0.1-1.0mol/L, soaking time 1-2h；
Above-mentioned steps 2) in the quality of AA be the mass ratio of 0.1-0.5g, AA and FAS be 1: 0.2, distilled water additional amount and AA's
Mass ratio is 20: 1, leads to the time of nitrogen deoxygenation in 30min or more；
Above-mentioned steps 3) in ultraviolet lamp power be 300-500W, irradiation time 5-15min.
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| CN118236871A (en) * | 2024-02-27 | 2024-06-25 | 浙江开创环保科技股份有限公司 | Sewage filtering device and filtering method |
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| CN114471176A (en) * | 2021-12-09 | 2022-05-13 | 华南师范大学 | Super-hydrophilic composite membrane for realizing separation of emulsified oil and preparation method and application thereof |
| CN118236871A (en) * | 2024-02-27 | 2024-06-25 | 浙江开创环保科技股份有限公司 | Sewage filtering device and filtering method |
| CN118236871B (en) * | 2024-02-27 | 2024-09-20 | 浙江开创环保科技股份有限公司 | Sewage filtering device and filtering method |
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