CN103446898B - Alginate-base organic-inorganic composite hydrogel filtering membrane and preparation method thereof - Google Patents
Alginate-base organic-inorganic composite hydrogel filtering membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an alginate-base organic-inorganic composite hydrogel filtering membrane, which is designed and prepared aiming at the problems of low mechanical strength, high probability of deformation, low flux and the like of a pure ionic cross-linked hydrogel filtering membrane. According to the filtering membrane, sodium alginate is used as a membrane forming substrate, micro-nano inorganic particles are used as a reinforcing agent and a pore-enlarging agent, and the composite hydrogel membrane which is obtained after cross-linking of a cross-linking agent and elution of a pore-forming agent has better stability and mechanical performance than the pure ionic cross-linked alginate hydrogel membrane. The mechanical strength and the pore size of the membrane are adjusted by changing the type, the particle diameter size and the added amount of the micro-nano inorganic particles and the type and the concentration of the ionic cross-linking agent. The composite hydrogel filtering membrane is prepared through a simple preparation process and is low in cost; no organic waste liquid is produced; the obtained hydrogel flat membrane can resist the pressure of 0.1-0.6 MPa; the alginate hydrogel is dissolved after being subjected to soaking treatment of a sodium citrate solution; expensive micro-nano inorganic particles can be recovered through simple precipitation separation.
Description
Technical field
The present invention relates to a kind of alginic acid alkali organo-mineral complexing hydrogel filter membrane and preparation method thereof, belong to environment functional material and film field.
Background technology
Conventional film filtering material very easily causes large molecule, colloid, electrolyte etc. in film surface or film inside irreversible deposition due to the hydrophobicity of itself, causes fouling membrane that the flux of film is constantly declined, so that membrane separating process can not normally carry out.For the feature of the lyophobic dusts such as the easy adsorbed proteins of polymer film surface, the effective ways alleviating fouling membrane are the surface naturies improving film, as chargedization on film surface or the hydrophiling etc. of hydrophobic film.
Blending and modifying is a kind of short-cut method of improvement film properties of learning from other's strong points to offset one's weaknesses on existing membrane material basis.By blended with hydrophilic macromolecule, hydrophilic component is introduced in casting solution system, thus film properties is improved.It is constant that blend film not only can maintain original rejection, and pure water flux, resistance tocrocking and fungus resistance all reach and significantly promote.Be usually used in blended with improve membrane permeability can and the macromolecule of separating property mainly contain following several: polyethylene glycol (PEG), polymethyl methacrylate (PMMA), sulfonated polystyrene, polyvinyl alcohol (PVA), SPSF (SPS), polysulfones (PS), polyacrylonitrile (PAN), nylon 6, polyvinyl acetate (PVAc) and chloromethyl polysulphone (CMPS) etc., they are blended from hydrophobic polymeric has respectively obtained the microfiltration membranes and milipore filter that are applicable to different separation system.The people such as Su Yanlei can significantly improve resistance tocrocking and the permeance property [J.Membr.Sci., 2008,322 (1): 171-177] of film with the copolymer-modified poly (ether-sulfone) ultrafiltration membrane of Phosphorylcholine.
Surface coating modified is the water soluble polymer or the surfactant that contain functional group by applying last layer on film surface, can introduce one deck functional polymer layer method of modifying on the surface of film.At film surface coating layer of surface activating agent, the hydrophily of film can be improved equally, improve membrane flux, but the surfactant of the coating on film surface can come off gradually along with the prolongation of time, thus cause the decline of membrane flux, until modified effect completely loses.Composite membrane has been prepared in the surface that shitosan (CS) is coated in polyether sulfone (PES) milipore filter, nylon-6 microfiltration membranes and PVDF microfiltration membranes by the people such as Sun Xiuzhen, in this three classes composite membrane, the performance of PVDF-CS composite membrane is the most excellent, under the operating condition of 0.25MPa, room temperature, the development of 98.4%[shitosan ultrafiltration composite membrane is reached to the rejection of PEG-20000, ocean, the East Sea, 1999,17 (2): 21-25].
Surface graft modification is the method that another large class effectively can improve polymer film surface character, generally cause means by plasma, light, irradiation, electron beam etc. and form avtive spot on film surface, this avtive spot causes other function monomer to be more further polymerized at film surface grafting, gives polymer film surface with the character of grafted polymer.The feature of surface graft modification is that modification occurs over just within several nanometers of film superficial layer, while imparting film surface is with the character of grafted polymer, do not affect the character of material body, and combine with chemical bond between the macromolecular chain of grafting with film surface and make modified effect more firm.The people such as Hsueh have prepared AA-PVDF-DMAEA Bipolar Membrane by plasma graft, the side grafting anionic monomer acrylic acid of pvdf membrane, and opposite side is grafted cation monomeric acrylic-N then, N-dimethyl amine ester.Due to the surface having Ionomer to cover graft copolymer membrane, the pure water contact angle of graft copolymer membrane is made significantly to decline [J.Membr.Sci., 2003,219:1-13].
Improve the hydrophily of film at present mainly through blending and modifying, surface coating and surface graft modification, thus improve the antifouling property of film.But blending and modifying complex process, surface coating easily comes off, and surface graft modification is difficult to obtain uniform Modified Membrane.The improvement of film self-characteristic and the exploitation of new membrane material are the focuses of research both at home and abroad, mainly through following 3 aspects: the exploitation of (1) novel high flux membrane material (as metal film); (2) modification of organic film material, to improve flux and antifouling property; (3) Organic inorganic film is manufactured.
Nano inoganic particle is as Al
2o
3particle, TiO
2particle and SiO
2particles etc. can be used for improving film hydrophily.With the film that the casting solution containing this kind of particle is obtained, perfectly combining the heat-resisting quantity of inorganic material, hydrophily and high molecular pliability, is a kind of novel hydrophilic organic/inorganic substances compound membrane.Inorganic material has high strength due to it, high rigidity, and the green grass or young crops that high rigidity is subject to people as structural material narrows, and the toughness that organic material has then had and elasticity, easily shape.Maria Arsuaga J passes through TiO
2, Al
2o
3and ZrO
2nano particle has carried out modification to PES film.The metal oxide of embedding makes the structure of film more open and porous, and antifouling property and the long-term flux stability of modification caudacoria are significantly improved [J.Membr.Sci., 2013,428:131-141].Daraei P etc. has prepared Fe by phase in version method
3o
4/ MWCNT/PES, PANI/Fe
3o
4/ PES and Fe
3o
4/ PES film.Mixed matrix film properties is detected, the three kinds of film Fe cast in magnetic field by pure water flux and pollution parameters
3o
4/ MWCNT/PES, PANI/Fe
3o
4/ PES and Fe
3o
4/ PES pure water flux improves 15%, 29% and 96% respectively.Water contact angle is measured and is confirmed PANI/Fe
3o
4the hydrophily [Sep.Sci.Technol., 2013,109:111-121] that composite membrane is superior.
Research shows, the hydrophily of film is better, then its contamination resistance is stronger, has occurred some in recent years at film surface coating hydrogel to alleviate the document of fouling membrane.Young-Hye La etc. is pore-foaming agent with polyvinyl alcohol under the existence of sensitising agent, utilize ultraviolet irradiation to be cross-linked and go out hydrophilic gel layer at polysulphone super-filter membrane surface construction, this hydrophilic gel layer reveals remarkable hydrophily and permeability, excellent contamination resistance [J.Membr.Sci. is shown for oil water mixture and bovine serum albumin, 2012,401:306-312].Chen Xiaolin etc. use sodium alginate as surface-active layer material, with glutaraldehyde as cross linker, with polysulfones (PSF) and polyacrylonitrile (PAN) for supporting layer, prepare a kind of novel nanofiltration membrane with negative electric charge [Chinese Marine University's journal, 2010,40 (10): 85-89].We are bibliography [Nature in work before, 2012, 489 (7414): 133-136] a kind of Hybridization hydrogel flat membrane for water filtration has been prepared, this Flat Membrane take sodium alginate as macromolecular scaffold, with acrylamide and derivative thereof for polymerization single polymerization monomer, add chemical cross-linking agent and ion crosslinking agent, take water soluble compound as pore-foaming agent, initiated polymerization forms two cross-linked network hydrogels of high-intensity high-tenacity, the Flat Membrane obtained after washing away pore-foaming agent is for water filtration, there is high hydrophily and excellent resistance tocrocking [201310112790.8].But after being through the polymerisation of monomer, pore-foaming agent is partially grafted, is difficult to wash-out, the membrane flux therefore obtained is very little, and unreacted monomer has had a strong impact on the water quality after membrane filtration.We attempted taking sodium alginate as matrix, take calcium chloride as crosslinking agent, be that pore-foaming agent prepares calcium alginate hydrogel Flat Membrane with water soluble polymer, find that pore-foaming agent can by abundant wash-out, flux significantly improves, but pure ionomer hydrogel filter membrane poor stability, and mechanical strength is low, film is being subject to pressure thinning thus is making Pore Blocking, and therefore under the pressure of more than 0.16MPa, flux almost no longer increases with pressure and increases.
Low for pure ionomer hydrogel filter membrane mechanical strength, the problems such as film is easily out of shape, and flux is low, the present invention designs a kind of alginic acid alkali organo-mineral complexing hydrogel filter membrane.This filter membrane take into sodium alginate as film base material, with micro-nano inorganic particulate for reinforcing agent and expanding agent, be cross-linked through ion crosslinking agent, the compound water congealing glued membrane obtained after wash-out pore-foaming agent has than the better stability of pure ionomer alginate hydrogel film and mechanical performance.By changing the kind of micro-nano inorganic particulate, the kind of particle size and consumption and ion crosslinking agent and the mechanical strength of concentration adjustment film and fenestra size.This composite aquogel film preparation technique is simple, cost is low, does not have organic liquid waste to produce, and aquagel membrane can the pressure of resistance to 0.1-0.6MPa, and after sodium citrate solution immersion treatment, alginate hydrogel dissolves, and is separated the micro-nano inorganic particulate of recyclable costliness through simple precipitation.
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is that film surface is easily polluted, pure ionomer hydrogel filter membrane mechanical strength is low, the problems such as film is easily out of shape, and flux is low.
The present invention solves the easily pollution of described film surface, pure ionomer hydrogel filter membrane mechanical strength is low, and the technical scheme of the problems such as film is easily out of shape, and flux is low is a kind of alginic acid alkali organo-mineral complexing hydrogel filter membrane of design and preparation method thereof.
The invention provides a kind of alginic acid alkali organo-mineral complexing hydrogel filter membrane and preparation method thereof, it is characterized in that comprising the following steps:
A) 1-5g sodium alginate is taken, the pore-foaming agent of sodium alginate mass percent 1%-100%, the micro-nano inorganic particulate of sodium alginate mass percent 0.01-100%, pour into together in deionized water, stirring and dissolving, ultrasonic disperse is even, is positioned over after leaving standstill froth breaking in the closed container of 4 DEG C-30 DEG C and obtains casting solution:
B) preparing metal mass of ion percentage is the aqueous metal salt of 0.01%-10%, as ion crosslinking agent;
C) casting solution that step a) obtains is poured on the sheet glass of dry cleansing, the uniform film that thickness is 20-2000 μm is scraped with knifing rod, vacuum outgas is steeped, step b is dipped into together with sheet glass) in the ionomer agent solution that obtains, reaction 0.1-24h, obtains the organo-mineral complexing aquagel membrane of the ionomer containing pore-foaming agent;
D) by step c) the organo-mineral complexing aquagel membrane of ionomer containing pore-foaming agent that obtains at 4 DEG C-90 DEG C with deionized water concussion wash-out 8-48h, removing pore-foaming agent and unreacted ion crosslinking agent, obtain alginic acid alkali organo-mineral complexing hydrogel filter membrane.
Aqueous metal salt of the present invention is any one or two or more mixture in zinc chloride, barium chloride, iron chloride, aluminium chloride, calcium chloride, calcium dihydrogen phosphate, calcium nitrate aqueous solution; Described inorganic nano-particle is any one or two or more mixture in titanium dioxide, silica, kaolin, magnesium hydroxide, alundum (Al2O3), zirconia, tri-iron tetroxide, calcium carbonate, barium sulfate, imvite, graphene oxide, Graphene, CNT, and the particle diameter of inorganic particulate is between 5nm-150 μm; Described pore-foaming agent is any one or two or more mixture in polyacrylamide, PVP, polyethylene glycol, urea, polyvinyl alcohol, PVP, gelatin, water soluble starch, and pore-foaming agent molecular weight is between 60-100000.
Preparation technology is simple for this composite aquogel filter membrane, cost is low, organic liquid waste is not had to produce, the hydrogel Flat Membrane obtained can the pressure of resistance to 0.1-0.6MPa, and after sodium citrate solution immersion treatment, alginate hydrogel dissolves, through the micro-nano inorganic particulate of the recyclable costliness of simple precipitate and separate.Film can be degradable by microorganism after abandoning, and can not cause environmental hazard.
Detailed description of the invention
Introduce specific embodiments of the invention below, but the present invention is not by the restriction of embodiment.
Embodiment 1. 1 kinds of calcium alginates/silica organo-mineral complexing hydrogel filter membrane and preparation method thereof
A) 5g sodium alginate is taken, the polyacrylamide pore-foaming agent of sodium alginate mass percent 100%, pour in 100ml deionized water together, then add the nano silicon of sodium alginate mass percent 100%, stirring and dissolving obtains casting solution after being evenly positioned over and leaving standstill froth breaking in the closed container of 25 DEG C;
B) preparing calcium ion mass percent is the calcium chloride water of 5%, as ion crosslinking agent;
C) casting solution is poured on the sheet glass of dry cleansing, scrapes with knifing rod the uniform film that thickness is 500 μm, be dipped into step b together with sheet glass) in the calcium chloride water that obtains, reaction 12h, obtains the hydrogel Flat Membrane of ionomer;
D) by step c) the hydrogel Flat Membrane of ionomer that obtains is with deionized water concussion wash-out 24h at 50 DEG C, and removing polyacrylamide and unreacted calcium ion, obtain calcium alginate/silica organo-mineral complexing hydrogel filter membrane.
Embodiment 2. 1 kinds of aluminium alginates/imvite organo-mineral complexing hydrogel filter membrane and preparation method thereof
A) 1g sodium alginate is taken, the PVP pore-foaming agent of sodium alginate mass percent 50%, pour in 100ml deionized water together, then add the nano imvite of sodium alginate mass percent 80%, stirring and dissolving obtains casting solution after being evenly positioned over and leaving standstill froth breaking in the closed container of 25 DEG C;
B) preparing aluminium ion mass percent is the aluminum chloride aqueous solution of 8%, as ion crosslinking agent;
C) casting solution is poured on the sheet glass of dry cleansing, the uniform film that thickness is 2000 μm is scraped with knifing rod, step b is dipped into together with sheet glass) in the ionomer agent solution that obtains, reaction 15h, obtains the hydrogel Flat Membrane of ionomer;
D) by step c) the hydrogel Flat Membrane of ionomer that obtains is with deionized water concussion wash-out 12h at 25 DEG C, and removing PVP and unreacted aluminium ion, obtain aluminium alginate/imvite organo-mineral complexing hydrogel filter membrane.
Embodiment 3. 1 kinds of ferric alginates/zirconia organo-mineral complexing hydrogel filter membrane and preparation method thereof
A) 5g sodium alginate is taken, the polyvinyl alcohol pore-foaming agent of sodium alginate mass percent 10%, pour in 100ml deionized water together, then add the nano zircite of sodium alginate mass percent 60%, stirring and dissolving obtains casting solution after being evenly positioned over and leaving standstill froth breaking in the closed container of 25 DEG C;
B) preparing iron ion mass percent is the ferric chloride in aqueous solution of 4%, as ion crosslinking agent;
C) casting solution is poured on the sheet glass of dry cleansing, the uniform film that thickness is 20 μm is scraped with knifing rod, step b is dipped into together with sheet glass) in the ionomer agent solution that obtains, reaction 15h, obtains the hydrogel Flat Membrane of ionomer;
D) by step c) the hydrogel Flat Membrane of ionomer that obtains is with deionized water concussion wash-out 16h at 25 DEG C, and removing iron ion and unreacted crosslinking agent, obtain ferric alginate/zirconia organo-mineral complexing hydrogel filter membrane.
Embodiment 4. 1 kinds of alginic acid zinc/graphene oxide organo-mineral complexing hydrogel filter membrane and preparation method thereof
A) 3.5g sodium alginate is taken, the polyvinyl alcohol pore-foaming agent of sodium alginate mass percent 20%, pour in 100ml deionized water together, then add the graphene oxide of sodium alginate mass percent 0.01%, stirring and dissolving obtains casting solution after being evenly positioned over and leaving standstill froth breaking in the closed container of 25 DEG C;
B) preparing zinc ion mass percent is the solder(ing)acid of 3.5%, as ion crosslinking agent;
C) casting solution is poured on the sheet glass of dry cleansing, the uniform film that thickness is 100 μm is scraped with knifing rod, step b is dipped into together with sheet glass) in the ionomer agent solution that obtains, reaction 12h, obtains the hydrogel Flat Membrane of ionomer;
D) by step c) the hydrogel Flat Membrane of ionomer that obtains is with deionized water concussion wash-out 24h at 25 DEG C, and removing polyvinyl alcohol and unreacted zinc ion, obtain alginic acid zinc/graphene oxide organo-mineral complexing hydrogel filter membrane.
Claims (4)
1. a preparation method for alginic acid alkali organo-mineral complexing hydrogel filter membrane, is characterized in that comprising the following steps:
A) 1-5g sodium alginate is taken, the pore-foaming agent of sodium alginate mass percent 1%-100%, the micro-nano inorganic particulate of sodium alginate mass percent 0.01-100%, pour into together in deionized water, stirring and dissolving, ultrasonic disperse is even, is positioned over after leaving standstill froth breaking in the closed container of 4 DEG C-30 DEG C and obtains casting solution;
B) preparing metal mass of ion percentage is the aqueous metal salt of 0.01%-10%, as ion crosslinking agent;
C) casting solution that step a) obtains is poured on the sheet glass of dry cleansing, the uniform film that thickness is 20-2000 μm is scraped with knifing rod, vacuum outgas is steeped, step b is dipped into together with sheet glass) in the ionomer agent solution that obtains, reaction 0.1-24h, obtains the organo-mineral complexing aquagel membrane of the ionomer containing pore-foaming agent;
D) by step c) the organo-mineral complexing aquagel membrane of ionomer containing pore-foaming agent that obtains at 4 DEG C-90 DEG C with deionized water concussion wash-out 8-48h, removing pore-foaming agent and unreacted ion crosslinking agent, obtain alginic acid alkali organo-mineral complexing hydrogel filter membrane.
2. the preparation method of a kind of alginic acid alkali organo-mineral complexing hydrogel filter membrane as claimed in claim 1, is characterized in that described aqueous metal salt is any one or two or more mixture in zinc chloride, barium chloride, iron chloride, aluminium chloride, calcium chloride, copper sulphate, calcium nitrate aqueous solution.
3. the preparation method of a kind of alginic acid alkali organo-mineral complexing hydrogel filter membrane as claimed in claim 1, is characterized in that described micro-nano inorganic particulate is SiO
2, TiO
2, Al
2o
3, Fe
2o
3, Fe
3o
4, ZnO, CuO, clay, CNT, Graphene, one or more mixtures in calcium carbonate, the particle diameter of inorganic particulate is between 5nm-150 μm.
4. the preparation method of a kind of alginic acid alkali organo-mineral complexing hydrogel filter membrane as claimed in claim 1, it is characterized in that described pore-foaming agent is any one or two or more mixture in polyacrylamide, PVP, polyethylene glycol, urea, polyvinyl alcohol, APEO, gelatin, water soluble starch, pore-foaming agent molecular weight is between 60-100000.
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| CN113908812A (en) * | 2021-10-15 | 2022-01-11 | 成都工业学院 | Spherical hydrogel filler based on fly ash and preparation method thereof |
| CN114797471B (en) * | 2022-05-11 | 2023-02-03 | 武汉大学 | Crustacean charcoal/sodium alginate composite gel nanofiltration membrane as well as preparation method and application thereof |
| CN114835944B (en) * | 2022-07-04 | 2022-09-20 | 广东省科学院生态环境与土壤研究所 | Energy-consumption self-sufficient type efficient photothermal evaporation nano-particle porous membrane and preparation method and application thereof |
| CN115651274B (en) * | 2022-10-31 | 2024-03-26 | 淮阴工学院 | Preparation method of clay-based composite hydrogel for solar seawater desalination |
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| US7045062B1 (en) * | 2003-01-21 | 2006-05-16 | Seventy-Seventh Meridian Corporation, Llc | Pervaporation membranes and methods of use |
| CN102743981A (en) * | 2012-07-18 | 2012-10-24 | 盐城工学院 | Preparation and application of sodium alginate pervaporation hybrid membrane |
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