CN108722196A - A kind of magnetic high-intensity and high-tenacity hydrogel and application method for fouling membrane cleaning - Google Patents
A kind of magnetic high-intensity and high-tenacity hydrogel and application method for fouling membrane cleaning Download PDFInfo
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Abstract
A kind of preparation and application of fouling membrane cleaning magnetic coupling hydrogel microsphere, it is using sodium alginate as skeleton, using acrylamide and its derivative as polymerized monomer, sodium metasilicate is dissolved in the water together with polymerized monomer and sodium alginate, ultraviolet initiation acrylamide polymerization, through calcium ion crosslinking in hydrogel in-situ preparation calcium silicates nano-particle, by glucono-δ-lactone aqueous solution soaking, the calcium silicates for generating surface containing mesopore silica gel, to improve the strength and stability of hydrogel.Mineralising in situ generates the intensity that evenly dispersed nanometer calcium silicates improves hydrogel.The present invention prepares microballoon using micro-nano magnetic particle as reinforcing agent, using syringe, very close using its density and water, itself has the advantages that high-intensity and high-tenacity and has better stability, cleaning performance is improved in flow or air-blowing flushing process.Stability significantly improves the composite hydrogel of addition silicate in water, has good application prospect in fouling membrane cleaning field.
Description
Technical field
The present invention relates to a kind of magnetic high-intensity and high-tenacity hydrogels and application method for fouling membrane cleaning, belong to work(
It can material and environmental area.
Background technology
Membrane separation technique has efficient, energy-saving and environmental protection, molecule due to having separation, concentration, purifying and refined function concurrently
Grade filtering and filter process is simple, the features such as easily controllable, therefore, UF membrane becomes most important means in current separation science
One of.Fouling membrane refers in membrane filtration processes, and the particle, colloidal particle or solute transportation in water are since there are physics with film
It adsorbed in film surface or fenestra caused by chemical interaction or mechanism, deposit and membrane aperture is caused to become smaller or block,
Film is set to generate the irreversible change phenomenon of transmission flow and stalling characteristic.Film transparent liquid flux after pollution declines, and filter effect is disliked
Change, the lost of life, cleaning difficulty is big, has seriously affected the working efficiency and economic benefit of ultrafiltration, and pollution and the film for preventing film are clear
Wash a research hotspot as membrane process.In film operational process, pretreatment filtrate, modified membrane, optimization can be taken
The technologies decelerating membrane pollution such as operating condition extends the service life of film, but the film for having polluted, it is necessary to carry out cleaning ability
Elimination or pollution abatement, to ensure the normal treatment effect of reactor.Membrane cleaning has physical cleaning, chemical cleaning, biology cleaning
The methods of.For various forms of fouling membranes, different cleaning methods should be used.
Physical cleaning refers to that artificial, mechanical cleaning and clear water cleaning etc. remove film surface without using any form chemical agent
Any chemical reaction does not occur for the cleaning method of pollutant, entire cleaning process.This method does not introduce new pollutant, cleaning step
It is rapid simple, however this method is only effective to polluting the film at initial stage, cleaning performance cannot be lasting.Sun Zhenlong etc. is cleaned flat with sponge ball
Piece membrane module passes through film surface with waterpower control sponge ball, can remove the pollutant of film surface by force, restore membrane flux substantially
【Environmental project, 2003,21 (2)：7-9】.Civisvanathan etc. to filtering-air blowback the study found that filtering 15min,
Air blowback 15min can obtain best transmission stability and total flux, although this circulate operation cannot fully erased film
Pollution, but compared with continuous operation technique, improve 271% flux【Wat.Sci.Technol., 1997,36 (12)：259-
266.】。
In actual operation, only it is difficult that membrane flux is made to restore completely by physical cleaning, it is necessary to borrow for seriously polluted film
Help chemical cleaning.Chemical cleaning is that certain suitable chemical agent is added in water, and continuous wash cycles, which can be fine
The compound dirt of removing so that membrane flux restores rapidly.Chemical cleaning is typically the pollution level according to film, (secondary with oxidant
Sodium chlorate etc.), sour (hydrochloric acid, sulfuric acid, nitric acid etc.), alkali (sodium hydroxide etc.), complexing agent, surfactant, enzyme, the changes such as detergent
It learns cleaning agent film is impregnated and cleaned, is a kind of opposite most efficient method of removal fouling membrane.Maartens et al. pairs
Discovery when polyethers alum (PES) film progress chemical cleaning polluted by paper pulp and pulp, nonionic surfactant Triton
X.100 the effect cleaned simultaneously with sponge ball is better than nonionic surfactant dodecyl sodium sulfate (SDS) and sodium hydroxide
The mixing of solution is cleaned【J.Membr.Sci., 2002,209：81-89.】.The researchs such as Tong Panrui find that MBR handles dyeing waste water
Pvdf membrane pollution mainly as caused by film surface gel layer, chemical cleaning can restore membrane flux about 90% or more, and use empty
Aeration plus the method for backwash carry out physical cleaning to film and are only capable of restoring membrane flux about 70%【Chinese water supply and drainage, 2006,22
(5)：106-108】.
There is document to report some relatively new cleaning methods in succession in recent years, including introduce into system sponge ball,
Mechanical oscillation, air-blowing, ultrasonic wave, impulse electric field etc..Hundred storehouse of Liu et al. carries out enhanced coagulation/ultrafiltration group technology Membrane cleaning
Research, the Membrane cleaning mode that technique is rushed using the punching of first gas, rear water, test result show：Waterpower cleaning can change to a certain extent
Kind and maintenance membrane flux, the ratio that flux rises after cleaning are 50.6%；Extend waterpower scavenging period and is filtering and cleaning
Increase aeration in journey, each contributes to the recovery of flux.Jin Wei et al. carries out Membrane cleaning using ultrasound and dilute citric acid synergistic effect
Shi Faxian, this method can relatively easily remove the dirt of new film surface, make its flux recovery to the 81% of initial flux, and only use acid
Wash 66.3% that membrane flux can only be made to be restored to initial flux.After impregnating 7h with diluted acid for the film of heavy contamination, using ultrasound
Flux recovery can be made to the 73.2% of initial flux with the collaboration cleaning of dilute citric acid, hence it is evident that higher than without 56.2% when impregnating.
Chemical cleaning is costly, and the chemical agent of addition may cause the damage of water pollution or film, and physical cleaning is only
Effective to the film for polluting initial stage, with the extension of run time, the effect of cleaning is deteriorated, and membrane flux recovery rate is relatively low.With waterpower control
Sponge ball processed passes through film surface, can remove the pollutant of film surface by force, but sponge ball density ratio water is small, is easy to float on water
It is inadequate to the removing dynamics of film surface pollution on face.Sponge ball itself is easy absorption pollutant, and is difficult to recycle.Macromolecule
The multicomponent system that hydrogel is made of polymer three-dimensional network and water.Hydrogel have with density similar in water, can be with water
Stream constantly rinses film surface, and there is hydrogel certain elasticity, antipollution can play preferable cleaning performance.But it is general
Hydrogel intensity is smaller, relatively soft, it is difficult to apply in Membrane cleaning.
Polyacrylamide/the calcium alginate (PAM/CaAlg) of high resiliency and high tenacity of Nature magazine rans in 2012
Double-network hydrogel【Nature, 2012,489 (7414)：133-136】.Although about 90% is water in the hydrogel, its elasticity
It is superpower, 20 times of original length can be stretched to and continuous, can also voluntarily restored to the original state later.Its toughness is also fine,
Hydrogel as one piece is broken disconnected, needs the energy expended and to break disconnected one block of natural rubber similar.Early-stage study system of the present invention
The cleaning of fouling membrane is used for for PAM/CaAlg double-network hydrogel microballoons.But in aqueous solution especially containing monovalent ion
Under environment, the cross-linking ion in the bis- cross-linked network hydrogels of PAM/CaAlg can release, under the mechanical property for causing gel
Drop.If introducing the non-covalent bond such as hydrophobic effect, hydrogen bond, electrostatic attraction and crystallization etc. with self-regeneration function,
It will be helpful to prepare stable high intensity hydrogel.The selection glucono-δ-lactones (GDL) such as normal river are slowly released using its hydrolysis
Release CaSiO3In Ca2+It is crosslinked NaAlg, is prepared for injectable CaAlg/CaSiO3/ GDL composite hydrogels.Pass through change
CaSiO3With the content of GDL, gel time, compression strength and the swelling behavior of composite hydrogel can be regulated and controled【Acta
Biomaterialia, 2013,9 (11)：9107-9117.】.Joerg C.Tiller1 et al. are caused by enzyme in dual network water
Evenly dispersed non-sizing nano-calcium phosphate is formd in gel, and the energy to failure of hydrogel is made to reach 1300J/m2, elasticity modulus
440MPa is reached, but its toughness is relatively low【Nature, 2017,543 (7645)：407-410】.
The present inventor is purple the study found that sodium metasilicate and acrylamide and sodium alginate (NaAlg) are dissolved in the water together
Outer initiation acrylamide polymerization, through calcium ion crosslinking in hydrogel in-situ preparation calcium silicates (CaSiO3) nano-particle, pass through
GDL aqueous solution soakings, GDL hydrolysis release H+, H+With CaSiO3Reaction generates surface containing mesopore silica gel (SiO2) calcium silicates
(CaSiO3@SiO2)。CaSiO3@SiO2Interaction of hydrogen bond occurs with CaAlg and PAM, to improve hydrogel intensity and
Stability.Original position mineralising generates evenly dispersed nanometer CaSiO in PAM/CaAlg3Improve the intensity of hydrogel.Contain
CaSiO3@SiO2PAM/CaAlg hydrogels impregnated in physiological saline 30 days after can also keep energy to failure close to natural cartilage
(9000J/m2), and its swelling ratio is only 1/5th of PAM/CaAlg hydrogels.
Present invention design prepares a kind of fouling membrane cleaning magnetic coupling hydrogel microsphere, and the composite hydrogel is with sodium alginate
Sodium metasilicate is dissolved in together with polymerized monomer and sodium alginate using acrylamide and its derivative as polymerized monomer for skeleton
In water, ultraviolet initiation acrylamide polymerization, through calcium ion crosslinking in hydrogel in-situ preparation calcium silicates (CaSiO3) nanoparticle
Son generates surface containing mesopore silica gel (SiO by GDL aqueous solution soakings2) calcium silicates, to improve the intensity of hydrogel
And stability.Original position mineralising generates evenly dispersed nanometer CaSiO in PAM/CaAlg3Improve the intensity of hydrogel.This hair
Bright to prepare microballoon using syringe using micro-nano magnetic particle as reinforcing agent, very close using its density and water, itself has
High-intensity and high-tenacity and have the advantages that better stability, cleaning performance is improved in flow or air-blowing flushing process.Utilize it
Magnetic and resistant to pollution characteristic is easily recycled use.Compared to PAM/CaAlg hydrogels, the composite hydrogel of silicate is added in water
Middle stability significantly improves, and needs within originally one week the hydrogel for using ionomer again, extends to one and a half months crosslinking now
Once.The fouling membrane clean magnetic coupling hydrogel microsphere preparation method simple process and low cost, can kept dry, film dirt
There is good application prospect in dye cleaning field.
Invention content
In view of the deficiencies of the prior art, the technical issues of present invention intends to solve is that fouling membrane is difficult to physical cleaning, sponge ball
To film surface pollution removing dynamics is inadequate, sponge ball is easy absorption pollutant and is difficult to recycle, Common hydrogels intensity and steady
The problems such as qualitative difference.
The present invention solve the fouling membrane be difficult to physical cleaning, sponge ball to film surface pollution cleanup dynamics not enough, sponge
The technical solution that ball is easy the problems such as absorption pollutant and being difficult to recycles, Common hydrogels strength and stability is poor is that design is a kind of
Fouling membrane cleans magnetic coupling hydrogel.
It is special the present invention provides a kind of magnetic high-intensity and high-tenacity hydrogel and application method for fouling membrane cleaning
Sign is that steps are as follows：
A) 5-15g polymerized monomers, 0.5-2g sodium alginates are weighed, sodium alginate mass percent is 1%-60% silicic acid
Sodium, the chemical cross-linking agent of polymerized monomer mass percent 0.03%-0.15%, is dissolved in 50-100mL deionized waters, stirs together
It mixes and is uniformly dissolved, the micro-nano magnetic particle of polymerized monomer mass percent 1-100% is then added, is obtained after ultrasonic disperse pre-
Copolymer solution；
B) preparing metal mass of ion percentage is the aqueous metal salt of 0.01%-10%, as ion crosslinking agent；
C) configuration quality percentage is 0.1%-6% glucono-δ-lactone solution, as acid treating solution；
D) persulfuric acid of polymerized monomer mass percent 0.1%-5% is added in the pre-polymer solution obtained to step a)
Ammonium, the sodium hydrogensulfite of polymerized monomer mass percent 0.1%-5%, the tetramethyl of polymerized monomer mass percent 0.1%-5%
Base ethylenediamine after being dispersed with stirring uniformly, extracts above-mentioned mixed solution, in N with syringe2The lower injection step b) of protection obtain from
In sub- crosslinking agent, ultraviolet irradiation polymerize 1-60min, obtains a kind of chemically and physically crosslinked hydrogel microsphere；
E) the chemically and physically crosslinked hydrogel microsphere that step d) is obtained is soaked with the acid treating solution that step c) is obtained
0.2-10h is steeped, then 0.2-24h is impregnated with the ion crosslinking agent that step b) is obtained, obtains further crosslinked hydrogel microsphere, it will
After hydrogel microsphere freeze-drying, the microballoon of dry state preservation is obtained；
f）The microballoon preserved using the preceding dry state that obtains step e) adds water-swellable, and it is magnetic multiple to obtain a kind of fouling membrane cleaning
Heshui gel micro-ball puts into the fouling membrane cleaning magnetic coupling hydrogel microsphere after swelling in filtered fluid, in flow or air-blowing
Utilize hydrogel microsphere very close with water in flushing process and the pollutant of flexible advantage cleaning film surface；
G) using the magnetic high-intensity and high-tenacity hydrogel microsphere after 45-90 days because the loss of ion crosslinking agent causes machine
Tool performance declines, and is crosslinked with the aqueous metal salt that step b) is obtained, is then reused again.
Polymerized monomer of the present invention is Diacetone Acrylamide, N-isopropylacrylamide, acrylamide, metering system
Any one in amide, dimethacrylamide, 2- acrylamide-2-methyl propane sulfonics or two or more mixtures, it is described
Aqueous metal salt be zinc chloride, iron chloride, aluminium chloride, calcium chloride, calcium dihydrogen phosphate, calcium sulfate, calcium nitrate, phosphoric acid hydrogen
Any one in calcium, calcium lactate aqueous solution or two or more mixtures.
Chemical cross-linking agent of the present invention be divinylbenzene, diisocyanate, N, N '-methylene-bisacrylamides,
Any one in ethylene glycol dimethacrylate, melamine methylol etherate or two or more mixtures, it is described
Magnetic particle is any one or two or more mixtures in magnetic straight iron powder, magnetic iron ore, positive ferrite.
Specific implementation mode
Specific embodiments of the present invention are described below, but the present invention should not be limited by the examples.
Embodiment 1.
A) 5g Methacrylamides, 0.5g sodium alginates, the sodium metasilicate that sodium alginate mass percent is 1%, first are weighed
The ethylene glycol dimethacrylate of base acrylamide mass percent 0.03%, is dissolved in together in 50mL deionized waters, stirring
It is uniformly dissolved, the magnetic straight iron powder of polymerized monomer mass percent 1% is then added, pre-polymer solution is obtained after ultrasonic disperse；
B) preparing metal mass of ion percentage is 0.01% solder(ing)acid, as ion crosslinking agent；
C) configuration quality percentage is 0.1% glucono-δ-lactone solution, as acid treating solution；
D) persulfuric acid of Methacrylamide mass percent 0.1% is added in the pre-polymer solution obtained to step a)
Ammonium, the sodium hydrogensulfite of Methacrylamide mass percent 0.1%, the tetramethyl of Methacrylamide mass percent 0.1%
Base ethylenediamine after being dispersed with stirring uniformly, extracts above-mentioned mixed solution, in N with syringe2The lower injection step b) of protection obtain from
In sub- crosslinking agent, ultraviolet irradiation polymerize 1min, obtains a kind of chemically and physically crosslinked hydrogel microsphere；
E) the chemically and physically crosslinked hydrogel microsphere that step d) is obtained is soaked with the acid treating solution that step c) is obtained
0.2h is steeped, then 0.2h is impregnated with the solder(ing)acid that step b) is obtained, further crosslinked hydrogel microsphere is obtained, by the water
After gel micro-ball freeze-drying, the microballoon of dry state preservation is obtained；
F) it uses the preceding microballoon for preserving the dry state that step e) is obtained to add water-swellable, it is magnetic again to obtain a kind of fouling membrane cleaning
Heshui gel micro-ball puts into the fouling membrane cleaning magnetic coupling hydrogel microsphere after swelling in filtered fluid, in flow or air-blowing
Utilize hydrogel microsphere very close with water in flushing process and the pollutant of flexible advantage cleaning film surface；
G) using the magnetic high-intensity and high-tenacity hydrogel microsphere after 45 days because the loss of ion crosslinking agent causes machinery
Performance declines, and is crosslinked with the aqueous metal salt that step b) is obtained, is then reused again.
Embodiment 2.
A) 15g acrylamides, 2g sodium alginates are weighed, sodium alginate mass percent is 60% sodium metasilicate, acrylamide
The diisocyanate of mass percent 0.15% is dissolved in together in 100mL deionized waters, and stirring and dissolving is uniform, is then added third
The magnetic iron ore of acrylamide mass percent 100% obtains pre-polymer solution after ultrasonic disperse；
B) calcium chloride water that preparing metal mass of ion percentage is 10%, as ion crosslinking agent；
C) configuration quality percentage is 6% glucono-δ-lactone solution, as acid treating solution；
D) ammonium persulfate of acrylamide mass percent 5%, propylene are added in the pre-polymer solution obtained to step a)
The sodium hydrogensulfite of amide mass percent 5%, the tetramethylethylenediamine of acrylamide mass percent 5% are dispersed with stirring
After even, above-mentioned mixed solution is extracted with syringe, in N2In the ion crosslinking agent that the lower injection step b) of protection is obtained, ultraviolet irradiation
It polymerize 60min, obtains a kind of chemically and physically crosslinked hydrogel microsphere；
E) the chemically and physically crosslinked hydrogel microsphere that step d) is obtained is soaked with the acid treating solution that step c) is obtained
10h is steeped, then is impregnated for 24 hours with the calcium chloride water that step b) is obtained, further crosslinked hydrogel microsphere is obtained, by the water-setting
After the freeze-drying of glue microballoon, the microballoon of dry state preservation is obtained；
F) it uses the preceding microballoon for preserving the dry state that step e) is obtained to add water-swellable, it is magnetic again to obtain a kind of fouling membrane cleaning
Heshui gel micro-ball puts into the fouling membrane cleaning magnetic coupling hydrogel microsphere after swelling in filtered fluid, in flow or air-blowing
Utilize hydrogel microsphere very close with water in flushing process and the pollutant of flexible advantage cleaning film surface；
G) using the magnetic high-intensity and high-tenacity hydrogel microsphere after 90 days because the loss of ion crosslinking agent causes machinery
Performance declines, and is crosslinked with the aqueous metal salt that step b) is obtained, is then reused again.
Embodiment 3.
A) 10g dimethacrylamide, 1g sodium alginates are weighed, sodium alginate mass percent is 5% sodium metasilicate, polymerization
The N of monomer mass percentage 0.1%, N '-methylene-bisacrylamide, are dissolved in 80mL deionized waters, stirring and dissolving is equal together
It is even, the positive ferrite of polymerized monomer mass percent 20% is then added, pre-polymer solution is obtained after ultrasonic disperse；
B) the calcium monohydrogen phosphate aqueous solution that preparing metal mass of ion percentage is 3.5%, as ion crosslinking agent；
C) configuration quality percentage is 2% glucono-δ-lactone solution, as acid treating solution；
D) persulfuric acid of dimethacrylamide mass percent 1% is added in the pre-polymer solution obtained to step a)
Ammonium, the sodium hydrogensulfite of dimethacrylamide mass percent 0.5%, the four of dimethacrylamide mass percent 1%
Methyl ethylenediamine after being dispersed with stirring uniformly, extracts above-mentioned mixed solution, in N with syringe2The lower injection step b) of protection is obtained
In ion crosslinking agent, ultraviolet irradiation polymerize 10min, obtains a kind of chemically and physically crosslinked hydrogel microsphere；
H) the chemically and physically crosslinked hydrogel microsphere that step d) is obtained is soaked with the acid treating solution that step c) is obtained
5h is steeped, then the calcium monohydrogen phosphate aqueous solution soaking 1h obtained with step b), further crosslinked hydrogel microsphere is obtained, by the water-setting
After the freeze-drying of glue microballoon, the microballoon of dry state preservation is obtained；
E) it uses the preceding microballoon for preserving the dry state that step e) is obtained to add water-swellable, it is magnetic again to obtain a kind of fouling membrane cleaning
Heshui gel micro-ball puts into the fouling membrane cleaning magnetic coupling hydrogel microsphere after swelling in filtered fluid, in flow or air-blowing
Utilize hydrogel microsphere very close with water in flushing process and the pollutant of flexible advantage cleaning film surface；
F) the obtained dry microspheres of step f) are added water-swellable using preceding, obtains a kind of fouling membrane and cleans magnetic coupling water-setting
Glue microballoon utilizes hydrogel microsphere by the hydrogel microsphere input filtered fluid after swelling in flow or air-blowing flushing process
Very close with water and flexible advantage cleans the pollutant of film surface；
G) using the magnetic high-intensity and high-tenacity hydrogel microsphere after 60 days because the loss of ion crosslinking agent causes machinery
Performance declines, and is crosslinked with the aqueous metal salt that step b) is obtained, is then reused again.
Embodiment 4.
A) 8g N-isopropylacrylamides, 0.7g sodium alginates are weighed, sodium alginate mass percent is 15% sodium metasilicate, different
The N of propylacrylamide mass percent 0.15%, N '-methylene-bisacrylamide, are dissolved in 60mL deionized waters, stir together
It mixes and is uniformly dissolved, the magnetic straight iron powder of polymerized monomer mass percent 50% is then added, it is molten to obtain prepolymer after ultrasonic disperse
Liquid；
B) calcium nitrate aqueous solution that preparing metal mass of ion percentage is 1%, as ion crosslinking agent；
C) configuration quality percentage is 4% glucono-δ-lactone solution, as acid treating solution；
D) ammonium persulfate of polymerized monomer mass percent 0.5% is added in the pre-polymer solution obtained to step a), it is different
The sodium hydrogensulfite of propylacrylamide percentage 0.2%, the tetramethylethylenediamine of N-isopropylacrylamide percentage 0.6%,
After being dispersed with stirring uniformly, above-mentioned mixed solution is extracted with syringe, in N2The ion crosslinking agent that the lower injection step b) of protection is obtained
In, ultraviolet irradiation polymerize 5min, obtains a kind of chemically and physically crosslinked hydrogel microsphere；
E) the chemically and physically crosslinked hydrogel microsphere that step d) is obtained is impregnated with the acid solution that step c) is obtained
0.5h, then 0.5h is impregnated with the calcium nitrate aqueous solution that step b) is obtained, further crosslinked hydrogel microsphere is obtained, by the water-setting
After the freeze-drying of glue microballoon, the microballoon of dry state preservation is obtained；
F) the obtained dry microspheres of step f) are added water-swellable using preceding, obtains a kind of fouling membrane and cleans magnetic coupling water-setting
Glue microballoon utilizes hydrogel microsphere by the hydrogel microsphere input filtered fluid after swelling in flow or air-blowing flushing process
Very close with water and flexible advantage cleans the pollutant of film surface；
G) using the magnetic high-intensity and high-tenacity hydrogel microsphere after 65 days because the loss of ion crosslinking agent causes machinery
Performance declines, and is crosslinked with the aqueous metal salt that step b) is obtained, is then reused again.
Claims (5)
1. a kind of magnetic high-intensity and high-tenacity hydrogel and application method for fouling membrane cleaning, it is characterized in that steps are as follows：
A) 5-15g polymerized monomers, 0.5-2g sodium alginates are weighed, the sodium metasilicate of sodium alginate mass percent 1%-60% gathers
The chemical cross-linking agent for closing monomer mass percentage 0.03%-0.15%, is dissolved in 50-100mL deionized waters, stirring and dissolving together
Uniformly, the micro-nano magnetic particle of polymerized monomer mass percent 1-100% is then added, it is molten to obtain prepolymer after ultrasonic disperse
Liquid；
B) preparing metal mass of ion percentage is the aqueous metal salt of 0.01%-10%, as ion crosslinking agent；
C) configuration quality percentage is 0.1%-6% glucono-δ-lactone solution, as acid treating solution；
D) ammonium persulfate of polymerized monomer mass percent 0.1%-5% is added in the pre-polymer solution obtained to step a), gathers
Close the sodium hydrogensulfite of monomer mass percentage 0.1%-5%, the tetramethyl second two of polymerized monomer mass percent 0.1%-5%
Amine after being dispersed with stirring uniformly, extracts above-mentioned mixed solution, in N with syringe2The ionomer that the lower injection step b) of protection is obtained
In agent, ultraviolet irradiation polymerize 1-60min, obtains a kind of chemically and physically crosslinked hydrogel microsphere；
E) the chemically and physically crosslinked hydrogel microsphere that step d) is obtained is impregnated with the acid treating solution that step c) is obtained
0.2-10h, then 0.2-24h is impregnated with the ion crosslinking agent that step b) is obtained, further crosslinked hydrogel microsphere is obtained, by this
After hydrogel microsphere freeze-drying, the microballoon of dry state preservation is obtained；
F) it uses the preceding microballoon for preserving the dry state that step e) is obtained to add water-swellable, obtains a kind of fouling membrane cleaning magnetic coupling water
Gel micro-ball is rinsed in the fouling membrane cleaning magnetic coupling hydrogel microsphere input filtered fluid after swelling in flow or air-blowing
Utilize hydrogel microsphere very close with water in the process and the pollutant in flexible advantage cleaning filtered fluid；
G) using the magnetic high-intensity and high-tenacity hydrogel microsphere after 45-90 days because the loss of ion crosslinking agent causes mechanicalness
It can decline, be crosslinked with the aqueous metal salt that step b) is obtained, then reused again.
2. a kind of magnetic high-intensity and high-tenacity hydrogel and application method for fouling membrane cleaning as described in claim 1,
It is characterized in that the polymerized monomer be Diacetone Acrylamide, N-isopropylacrylamide, acrylamide, Methacrylamide,
Any one in dimethacrylamide, 2- acrylamide-2-methyl propane sulfonics or two or more mixtures.
3. a kind of magnetic high-intensity and high-tenacity hydrogel and application method for fouling membrane cleaning as described in claim 1,
It is characterized in that the aqueous metal salt is zinc chloride, iron chloride, calcium chloride, calcium dihydrogen phosphate, calcium sulfate, calcium nitrate, phosphorus
Any one in sour hydrogen calcium aqueous solution or two or more mixtures.
4. a kind of magnetic high-intensity and high-tenacity hydrogel and application method for fouling membrane cleaning as described in claim 1,
It is characterized in that the chemical cross-linking agent is divinylbenzene, diisocyanate, N, N '-methylene-bisacrylamides, dimethyl
Any one in acrylic acid glycol ester, melamine methylol etherate or two or more mixtures.
5. a kind of magnetic high-intensity and high-tenacity hydrogel and application method for fouling membrane cleaning as described in claim 1,
It is characterized in that the magnetic particle is any one or two or more mixing in magnetic straight iron powder, magnetic iron ore, positive ferrite
Object.
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| CN112175205A (en) * | 2019-07-01 | 2021-01-05 | 哈尔滨工业大学 | Magnetic hydrogel, preparation method thereof and 3D printing method |
| CN112774452A (en) * | 2020-12-18 | 2021-05-11 | 武汉艾科滤膜技术有限公司 | Preservation method of ultrafiltration membrane component |
| CN115364693A (en) * | 2021-11-16 | 2022-11-22 | 中国科学院生态环境研究中心 | Method for repairing water treatment performance of polyamide composite membrane |
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