CN110180407A - A kind of MULTILAYER COMPOSITE biomass water process film - Google Patents
A kind of MULTILAYER COMPOSITE biomass water process film Download PDFInfo
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- CN110180407A CN110180407A CN201910519136.6A CN201910519136A CN110180407A CN 110180407 A CN110180407 A CN 110180407A CN 201910519136 A CN201910519136 A CN 201910519136A CN 110180407 A CN110180407 A CN 110180407A
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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
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention belongs to membrane for water treatment technical fields, in particular to a kind of 3 layers of compound biomass water process film, 3 tunics are made of biomass basement membrane, high-intensitive cross-linked porous film layer including bottom, the processing film layer of middle layer, the anti-pollution porous membrane layer on surface layer, pass through certain physics between three layers, chemical action is connected as one, greatly improve compound film strength, biomass membrane material prepared by the present invention has biggish water flux, pollution resistance is strong, it can be to the heavy metal in water, the microorganisms such as bacterium, organic matter etc. is effectively filtered out, and membrane substance itself is environmentally friendly, prospect is used with good.
Description
Technical field
The invention belongs to membrane for water treatment technical field, in particular to a kind of environmental protection, it is biomass-based have high water flux,
The membrane for water treatment material for there are excellent results is absorbed for heavy metal ion.
Background technique
It is a new technology that embrane method, which handles waste water,.For a long time, membrane for water treatment according to the hole of film is divided into micro-filtration, ultrafiltration, receives
Filter, reverse osmosis, infiltration tin (stannizing), active transport, electrodialysis etc..Can prepare membrane for water treatment substance have cellulose and its
Spin-off, polyvinylidene fluoride, polysulfones, polypropylene, polyethylene, polyacrylonitrile, polyamide etc., these materials are all hydrophobic mostly
Property, functional group needed for the hydrophobic surface of film lacks separation process.Risen in research recently it is a kind of using biomass as water at
The technology of film is managed, but there are still certain bottlenecks.Main problem are as follows: firstly, the biomass membrane feature of environmental protection is strong, it is from a wealth of sources, it is easy to make
It is standby；Secondly, hydrophily is preferable.But meanwhile biomass film water transmitance is lower, and pollution resistance is poor；Secondly, the official of biomass membrane
It can roll into a ball there is still a need for enriching, film also needs to improve from the binding ability of different pollutants.Again, biomass membrane often has bad machine
Tool performance is easy to cause film rupture in application.The present invention in view of the above-mentioned problems, develops a kind of with superperformance
Biomass combined membrane for water treatment material.
Summary of the invention
This invention address that overcoming, biomass-based membrane for water treatment bad mechanical property, water penetration rate are low, absorb and imitate to pollutant
The problem of fruit difference provides a kind of biomass combined membrane for water treatment.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of MULTILAYER COMPOSITE biomass water process film, is made of 3 layers of biomass basement membrane, the high-intensitive cross-linked porous film including bottom
Layer, the processing film layer of middle layer, surface layer anti-pollution porous membrane layer；
Further, it between the high-intensitive cross-linked porous film layer and processing film layer, handles and leads between film layer and anti-pollution porous membrane layer
Cross physics, chemical action is combined into one.
Further, the high-intensitive cross-linked porous film layer be with sodium alginate, eight arm ammonia salt caged silsesquioxane particles,
Chitosan, pore-foaming agent are primary raw material preparation；
Wherein, the quality of eight arm ammonia salt caged silsesquioxane particles is between the 8.5-16% of sodium alginate quality, chitosan
Quality between the 22.6-36.8% of sodium alginate quality.
Further, the eight arms ammonia salt caged silsesquioxane (Oa-POSS) is the modified product of POSS.This POSS monomer
Because there is the presence of a large amount of ammoniums, so that monomer has good water solubility.Its structural formula is as follows:
Wherein, eight ammoniums in the corner Oa-POSS under certain acidity and alkalinity environment be easier dissociate, formed cation, with
Play the role of the crosslinking agent as calcium ion after sodium alginate mixing, sodium alginate can be connected by ion exchange, thus shape
At gel.Meanwhile there are hydrophobicitys for the main body caged Si-O structure of POSS particle, aggregation forms nano-micrometre in gel
The micropore of rank, the raising that the presence of micropore has conducive to water flux.The presence of POSS plays the role of stress spaced point, also has
Effect improves film strength.
Further, the pore-foaming agent can be aqueous pore-foaming agent such as urea, polyethylene glycol, can also be for example positive fourth of oiliness pore-foaming agent
Alkane, iso-butane, n-hexane, isohexane.
Further, the thickness of the high-intensitive cross-linked porous film layer is between 300-800 microns, the hole area of film between
Between membrane area 30-50%, aperture is between 200-500 microns.
Further, the processing film layer is to be formed sediment with gelatin, N,N-DMAA, chitosan, glutaraldehyde, dialdehyde
Powder, N, N'- methylene-bisacrylamide, polyethylene glycol are primary raw material preparation；
Wherein, between the 18.6-32.2% of gelatin quality, the quality of chitosan is situated between the quality of N,N-DMAA
Between the 32.5-52.6% of gelatin quality, the quality of glutaraldehyde is between the 6.5-10.8% of chitosan mass, dialdehyde starch
Quality between the 14.6-21.4% of chitosan mass, N, the quality of N'- methylene-bisacrylamide is between N, N- diformazan
Between the 3.6-8.4% of base acrylamide quality, the quality of polyethylene glycol is between the 24.5-45% of gelatin quality.
Further, the glutaraldehyde can be used as the crosslinking agent of gelatin and chitosan, dialdehyde starch can be used as the friendship of chitosan
Join agent.
Further, the molecular weight of the polyethylene glycol is between 400-2000.
Further, the thickness of process film is between 200-500 microns, the hole area of film between membrane area 20-40% it
Between, aperture is between 50-500 microns.
Further, the anti-pollution porous membrane layer is with methacrylate grafted chitosan, gelatin and eight arm polyethylene glycol
Caged silsesquioxane particles, polyethylene glycol, crosslinking agent N, N ,-methylene-bisacrylamide, initiator potassium persulfate, catalyst
N, N, N', N'- tetramethylethylenediamine are primary raw material preparation；
Wherein, the quality of methacrylate grafted chitosan is between the 56%-112% of gelatin quality, eight arm polyethylene glycol
The quality of caged silsesquioxane particles is between the 8.5-16.4% of gelatin, and the quality of polyethylene glycol is between methacrylic acid
Between the 12.5-22.5% of ester grafted chitosan quality, crosslinking agent N, N, the quality of-methylene-bisacrylamide is between methyl-prop
Between the 4.5-8.5% of olefin(e) acid ester grafted chitosan quality, initiator potassium persulfate, catalyst n, N, N', N'- tetramethyl second two
The quality of amine is respectively interposed between the 0.15-0.3% and 0.075-0.1% of methacrylate grafted chitosan quality.
Further, the eight arms polyethylene glycol caged silsesquioxane particles (POSS-PEG) are the modified product of POSS.
This POSS monomer is because there is the presence of a large amount of polyethylene glycol (PEG), so that monomer has good water solubility.Its structural formula is such as
Under:
Simultaneously as the presence of end group PEG, is conducive to the combination of the polyethylene glycol in itself and formula, be conducive to uniform pore,
POSS particle is since its hydrophobicity exists, the pore effect being equally beneficial in film, and POSS is conducive to as stress spaced point
The promotion of film dynamic performance.
Further, the thickness of anti-pollution porous membrane layer is between 300-800 microns, and the hole area of film is between membrane area 20-
Between 40%, aperture is between 100-500 microns.
Further, the methacrylate grafted chitosan is prepared by methacrylic acid and chitosan reaction,
Grafting degree is calculated as between 42-68% by grafted chain and chitosan mass ratio, and methacrylate grafted chitosan after branch is added to have
A large amount of double bonds are for reaction.
Further, addition of the anti-pollution porous membrane layer due to POSS particle among film, the presence of acrylic acid cross-linked structure, effectively
The Hydrophile-Lipophile of film is had adjusted, so that film has good antifouling effect.
Further, the preparation process of a kind of MULTILAYER COMPOSITE biomass water process film are as follows:
(1) oils is added as oily phase as substrate in merging aqueous gel block on it in a reservoir；
(2) sodium alginate, chitosan, pore-foaming agent are dissolved in the acetic acid aqueous solution that mass concentration is 3%, solution is instilled into oily phase
In, spread film is formed on gel piece surface layer, instills the eight arm ammonia salt caged times that mass concentration is 4-8% after balance on spread film
Half silicone particles aqueous solution stands 6-12h and forms film I after covering；Wherein, mass fraction of the chitosan in acetic acid aqueous solution
Between 2-4%, eight arm ammonia salt caged silsesquioxane particles aqueous solution volumes of dropwise addition are between the 1/ of acetic acid aqueous solution volume
Between；
(3) by gelatin, N, N- dimethylacrylamide, chitosan, dialdehyde starch, glutaraldehyde, N, N'- methylene bisacrylamide acyl
It is that solution is instilled to the surface of liquid film I in 3% acetic acid aqueous solution that amine, polyethylene glycol, which are dissolved in mass concentration, realizes covering, sprawls flat
6-12h is stood after weighing apparatus and forms liquid film II, wherein gelatin is in the mass fraction in acetic acid aqueous solution between 8.5-12.5%；
It (4) will be dissolved with methacrylate grafted chitosan, gelatin and eight arm polyethylene glycol caged silsesquioxane particles, poly- second
Glycol, crosslinking agent N, N ,-methylene-bisacrylamide, initiator potassium persulfate, catalyst n, N, N', N'- tetramethylethylenediamine
Aqueous solution drop to the surface liquid film II, realize covering, sprawl and stand 12-24h after balance and ultimately form sandwich diaphragm；
Wherein, the mass fraction of gelatin in aqueous solution is between 5.5-8.5%；
(5) after sandwich diaphragm being taken out at -60 DEG C quickly cooling, and vacuumize, dry film obtained, by dry film at 20 DEG C in pure water
6h is dried at 50 DEG C after impregnating 6h, obtains final products after circulation 5 times.
Further, the MULTILAYER COMPOSITE biomass water process film is in two be made of aqueous gel substrate and upper oil phase
It is prepared in two-phase interface in phase system.
Further, the aqueous gel substrate is hydrophilic gel, preferably polyacrylamide gel, carbopol gel.
Further, the upper oil phase is organic oils and close oil based solvent.
Further, the thickness of the upper oil phase is higher than film surface 15cm.
Further, the hydrophily of the every tunic sprawled in the system using hydrogel substrate and on it and oily phase
Pressure is, it can be achieved that every layer is sprawled film forming.
Further, between the high-intensitive cross-linked porous film layer and processing film layer, processing film layer and anti-pollution porous membrane layer it
Between be combined into one by physics, chemical action, this combination is realized by following form:
Firstly, chemical action is as follows: high-intensitive cross-linked porous film layer and processing film layer between, during the preparation process, first at
Type is high-intensitive cross-linked porous film layer, and chitosan therein does not react, and drips in high-intensitive cross-linked porous film layer
Add processing film layer, glutaraldehyde therein, dialdehyde starch can on interface with the chitosan and high-intensitive cross-linked porous in own layer
Certain cross-linking reaction occurs for the chitosan in film layer, forms cross-linked structure；Secondly, processing film layer and anti-pollution porous membrane layer it
Between, during the preparation process, since the top of the processing film layer pre-polymerization liquid of dropwise addition is still oily phase, so there is an engagement in drop
The monomer N,N-DMAA and crosslinking agent N, N'- methylene-bisacrylamide of oil can be more nearly oily phase, on it
There are initiator, catalyst and a small amount of crosslinking agent of double bond crosslinking in the anti-pollution porous membrane layer pre-polymerization liquid of instillation, these substances can
Cause C=C double bond of monomer N, N- dimethylacrylamide in processing film layer, metering system in anti-pollution porous membrane layer on interface
Cross-linking reaction between C=C double bond of acid esters grafted chitosan, so that this two layers formation is whole.
Physical action are as follows: have constituent of chitosan in three layers, there is stronger interaction between each other；Meanwhile as located
There is polyethylene glycol in reason film layer and anti-pollution porous membrane layer, while there is also a variety of interaction of hydrogen bond that can produce in each layer
Component, the above substance will generate stronger Physical interaction.
Further, which is suitable for the absorption of heavy metal ion such as lead, cadmium, boron ion.
Specific embodiment
Illustrative embodiment of the invention described in detail below.But these implementation methods are only exemplary purpose, and
The invention is not limited thereto.
Embodiment 1
A kind of MULTILAYER COMPOSITE biomass water process film is made of 3 layers of biomass basement membrane, and successively the high-intensitive crosslinking including bottom is more
Hole film layer, the processing film layer of middle layer, surface layer anti-pollution porous membrane layer；
The high intensity cross-linked porous film layer is with sodium alginate, eight arm ammonia salt caged silsesquioxane particles, chitosan, oiliness
Pore-foaming agent normal butane is primary raw material preparation；Wherein, the quality of eight arm ammonia salt caged silsesquioxane particles is sodium alginate matter
The 11.5% of amount, the quality of chitosan are the 32.4% of sodium alginate quality.
The high intensity cross-linked porous film layer with a thickness of 400 microns, the hole area of film is the 36.5% of membrane area, aperture
Between 200-400 microns.
The processing film layer is with gelatin, N, N- dimethylacrylamide, chitosan, glutaraldehyde, dialdehyde starch, N, N'-
Methylene-bisacrylamide, polyethylene glycol are primary raw material preparation, wherein the quality of N,N-DMAA is gelatin matter
The 24.5% of amount, the quality of chitosan are the 41.7% of gelatin quality, and the quality of glutaraldehyde is the 8.5% of chitosan mass, and dialdehyde forms sediment
The quality of powder is 18.4%, N of chitosan mass, and the quality of N'- methylene-bisacrylamide is N,N-DMAA matter
The 5.2% of amount, the quality of polyethylene glycol are the 35.4% of gelatin quality, and wherein the molecular weight of polyethylene glycol is 1500.
The process film with a thickness of 300 microns, the hole area of film is membrane area 35%, and aperture is between 50-200 micron
Between.
The anti-pollution porous membrane layer is with methacrylate grafted chitosan, gelatin and eight arm polyethylene glycol caged sesquialter silicon
Oxygen alkane particle, polyethylene glycol, crosslinking agent N, N ,-methylene-bisacrylamide, initiator potassium persulfate, catalyst n, N, N', N'-
Tetramethylethylenediamine is primary raw material preparation, wherein the quality of methacrylate grafted chitosan is the 84% of gelatin quality,
The quality of eight arm polyethylene glycol caged silsesquioxane particles is the 10.6% of gelatin, and the quality of polyethylene glycol is methacrylic acid
The 16.4% of ester grafted chitosan quality, crosslinking agent N, N, the quality of-methylene-bisacrylamide are methacrylate graft shell
The 6.5% of glycan quality, initiator potassium persulfate, catalyst n, N, N', the quality of N'- tetramethylethylenediamine are respectively methyl-prop
The 0.22% and 0.08% of olefin(e) acid ester grafted chitosan quality.
The anti-pollution porous membrane layer with a thickness of 550 microns, the hole area of film is the 25% of membrane area, and aperture is between 200-
Between 400 microns.
The grafting degree of the methacrylate grafted chitosan is calculated as 52% by grafted chain and chitosan mass ratio.
The preparation process of the MULTILAYER COMPOSITE biomass water process film are as follows:
(1) silicone oil is added as substrate in merging polyacrylamide gel block on it in a reservoir, silicone oil with a thickness of
20cm, the viscosity of silicone oil are 500cSt；
At (2) 20 DEG C, sodium alginate, chitosan, pore-foaming agent is dissolved in the acetic acid aqueous solution that mass concentration is 3%, solution is dripped
Enter in oily phase, forms spread film on gel piece surface layer, instill the eight arm ammonia salts that mass concentration is 4.6% on spread film after balance
Caged silsesquioxane particles aqueous solution stands 8h and forms film I after covering；Wherein, quality of the chitosan in acetic acid aqueous solution
Score is 2.5%, and eight arm ammonia salt caged silsesquioxane particles aqueous solution volumes of dropwise addition are the 1/5 of acetic acid aqueous solution volume；
At (3) 40 DEG C, by gelatin, N,N-DMAA, chitosan, dialdehyde starch, glutaraldehyde, N, N'- di-2-ethylhexylphosphine oxide
It is that solution is instilled to the surface of liquid film I in 3% acetic acid aqueous solution that acrylamide, polyethylene glycol, which are dissolved in mass concentration, realizes covering,
6-12h formation liquid film II is stood after sprawling balance, wherein mass fraction of the gelatin in acetic acid aqueous solution is 10.5%；
It, will be dissolved with methacrylate grafted chitosan, gelatin and eight arm polyethylene glycol caged silsesquioxane grains at (4) 40 DEG C
Son, polyethylene glycol, crosslinking agent N, N ,-methylene-bisacrylamide, initiator potassium persulfate, catalyst n, N, N', N'- tetramethyl
The aqueous solution of ethylenediamine drops to the surface liquid film II, realizes covering, sprawl stand after balance 18h ultimately form three layers it is compound
Film；Wherein, the mass fraction of gelatin in aqueous solution is 6.2%；
(5) after sandwich diaphragm being taken out at -60 DEG C quickly cooling, and vacuumize, dry film obtained, by dry film at 20 DEG C in pure water
6h is dried at 50 DEG C after impregnating 6h, obtains final products after circulation 5 times.
Progress water flux test in 1 hour is carried out using the membrane for water treatment at 25 DEG C, under 0.3MPa, it is right at 25 DEG C, 1Mpa
Initial concentration is that 20 μ g/ml cadmium ions and 20 μ g/ml lead ion aqueous solutions carry out retention test, continuous operation for 24 hours, water flux,
It is as shown in table 1 for the interception of cadmium ion and lead ion.
Embodiment 2
A kind of MULTILAYER COMPOSITE biomass water process film is made of 3 layers of biomass basement membrane, and successively the high-intensitive crosslinking including bottom is more
Hole film layer, the processing film layer of middle layer, surface layer anti-pollution porous membrane layer；
The high intensity cross-linked porous film layer is with sodium alginate, eight arm ammonia salt caged silsesquioxane particles, chitosan, oiliness
Pore-foaming agent normal butane is primary raw material preparation；Wherein, the quality of eight arm ammonia salt caged silsesquioxane particles is sodium alginate matter
The 13.2% of amount, the quality of chitosan are the 28.6% of sodium alginate quality.
The high intensity cross-linked porous film layer with a thickness of 500 microns, the hole area of film is the 38.5% of membrane area, aperture
Between 200-500 microns.
The processing film layer is with gelatin, N, N- dimethylacrylamide, chitosan, glutaraldehyde, dialdehyde starch, N, N'-
Methylene-bisacrylamide, polyethylene glycol are primary raw material preparation, wherein the quality of N,N-DMAA is gelatin matter
The 26.9% of amount, the quality of chitosan are the 45.4% of gelatin quality, and the quality of glutaraldehyde is the 8.5% of chitosan mass, and dialdehyde forms sediment
The quality of powder is 16.2%, N of chitosan mass, and the quality of N'- methylene-bisacrylamide is N,N-DMAA matter
The 6.4% of amount, the quality of polyethylene glycol are the 32.1% of gelatin quality, and wherein the molecular weight of polyethylene glycol is 1200.
The process film with a thickness of 350 microns, the hole area of film is membrane area 32%, and aperture is between 50-400 micron
Between.
The anti-pollution porous membrane layer is with methacrylate grafted chitosan, gelatin and eight arm polyethylene glycol caged sesquialter silicon
Oxygen alkane particle, polyethylene glycol, crosslinking agent N, N ,-methylene-bisacrylamide, initiator potassium persulfate, catalyst n, N, N', N'-
Tetramethylethylenediamine is primary raw material preparation, wherein the quality of methacrylate grafted chitosan is gelatin quality
102.6%, the quality of eight arm polyethylene glycol caged silsesquioxane particles is the 12.2% of gelatin, and the quality of polyethylene glycol is methyl
The 13.8% of acrylic ester grafted chitosan mass, crosslinking agent N, N, the quality of-methylene-bisacrylamide are methacrylate
The quality of the 7.2% of grafted chitosan quality, initiator potassium persulfate, catalyst n, N, N', N'- tetramethylethylenediamine is respectively
The 0.25% and 0.085% of methacrylate grafted chitosan quality.
The anti-pollution porous membrane layer with a thickness of 600 microns, the hole area of film is the 32% of membrane area, and aperture is between 150-
Between 300 microns.
The grafting degree of the methacrylate grafted chitosan is calculated as 60.4% by grafted chain and chitosan mass ratio.
The preparation process of the MULTILAYER COMPOSITE biomass water process film are as follows:
(1) silicone oil is added as substrate in merging carbopol gel block on it in a reservoir, silicone oil with a thickness of 25cm,
The viscosity of silicone oil is 100cSt；
At (2) 25 DEG C, sodium alginate, chitosan, pore-foaming agent is dissolved in the acetic acid aqueous solution that mass concentration is 3%, solution is dripped
Enter in oily phase, forms spread film on gel piece surface layer, instill the eight arm ammonia salts that mass concentration is 5.7% on spread film after balance
Caged silsesquioxane particles aqueous solution stands 10h and forms film I after covering；Wherein, quality of the chitosan in acetic acid aqueous solution
Score is 3%, and eight arm ammonia salt caged silsesquioxane particles aqueous solution volumes of dropwise addition are the 1/4 of acetic acid aqueous solution volume；
At (3) 45 DEG C, by gelatin, N,N-DMAA, chitosan, dialdehyde starch, glutaraldehyde, N, N'- di-2-ethylhexylphosphine oxide
It is that solution is instilled to the surface of liquid film I in 3% acetic acid aqueous solution that acrylamide, polyethylene glycol, which are dissolved in mass concentration, realizes covering,
10h formation liquid film II is stood after sprawling balance, wherein mass fraction of the gelatin in acetic acid aqueous solution is 9.5%；
It, will be dissolved with methacrylate grafted chitosan, gelatin and eight arm polyethylene glycol caged silsesquioxane grains at (4) 45 DEG C
Son, polyethylene glycol, crosslinking agent N, N ,-methylene-bisacrylamide, initiator potassium persulfate, catalyst n, N, N', N'- tetramethyl
The aqueous solution of ethylenediamine drops to the surface liquid film II, realizes covering, sprawl stand after balance 15h ultimately form three layers it is compound
Film；Wherein, the mass fraction of gelatin in aqueous solution is 7.5%；
(5) after sandwich diaphragm being taken out at -60 DEG C quickly cooling, and vacuumize, dry film obtained, by dry film at 20 DEG C in pure water
6h is dried at 50 DEG C after impregnating 6h, obtains final products after circulation 5 times.
Progress water flux test in 1 hour is carried out using the membrane for water treatment at 25 DEG C, under 0.3MPa, it is right at 25 DEG C, 1Mpa
Initial concentration is that 20 μ g/ml cadmium ions and 20 μ g/ml lead ion aqueous solutions carry out retention test, continuous operation for 24 hours, water flux,
It is as shown in table 1 for the interception of cadmium ion and lead ion.
Table 1: the water flux of membrane for water treatment is prepared in embodiment 1,2, for the interception of cadmium ion, lead ion
Claims (9)
1. a kind of MULTILAYER COMPOSITE biomass water process film, is made of 3 layers of biomass basement membrane, the high-intensitive cross-linked porous including bottom
Film layer, the processing film layer of middle layer, surface layer anti-pollution porous membrane layer；
It is further characterized in that: between the high intensity cross-linked porous film layer and processing film layer, processing film layer and anti-pollution porous membrane layer
Between be combined into one by physics, chemical action.
2. a kind of MULTILAYER COMPOSITE biomass water process film as described in claim 1, it is characterised in that: the high intensity cross-linked porous
Film layer is to prepare using sodium alginate, eight arm ammonia salt caged silsesquioxane particles, chitosan, pore-foaming agent as primary raw material；Film
Thickness is between 300-800 microns, and the hole area of film is between membrane area 30-50%, and aperture is between 200-500 micron
Between；
Wherein, the quality of eight arm ammonia salt caged silsesquioxane particles is between the 8.5-16% of sodium alginate quality, chitosan
Quality between the 22.6-36.8% of sodium alginate quality.
3. a kind of MULTILAYER COMPOSITE biomass water process film as described in claim 1, it is characterised in that: the processing film layer is with bright
Glue, N, N- dimethylacrylamide, chitosan, glutaraldehyde, dialdehyde starch, N, N'- methylene-bisacrylamide, polyethylene glycol are
Primary raw material preparation；The thickness of film is between 200-500 microns, and the hole area of film is between membrane area 20-40%, aperture
Between 50-500 microns；
Wherein, between the 18.6-32.2% of gelatin quality, the quality of chitosan is situated between the quality of N,N-DMAA
Between the 32.5-52.6% of gelatin quality, the quality of glutaraldehyde is between the 6.5-10.8% of chitosan mass, dialdehyde starch
Quality between the 14.6-21.4% of chitosan mass, N, the quality of N'- methylene-bisacrylamide is between N, N- diformazan
Between the 3.6-8.4% of base acrylamide quality, the quality of polyethylene glycol is between the 24.5-45% of gelatin quality.
4. a kind of MULTILAYER COMPOSITE biomass water process film as described in claim 1, it is characterised in that: the anti-pollution porous membrane layer is
With methacrylate grafted chitosan, gelatin and eight arm polyethylene glycol caged silsesquioxane particles, polyethylene glycol, crosslinking agent
N, N ,-methylene-bisacrylamide, initiator potassium persulfate, catalyst n, N, N', N'- tetramethylethylenediamine are primary raw material system
It is standby；The thickness of film is between 300-800 microns, and the hole area of film is between membrane area 20-40%, and aperture is between 100-500
Between micron；
Wherein, the quality of methacrylate grafted chitosan is between the 56%-112% of gelatin quality, eight arm polyethylene glycol
The quality of caged silsesquioxane particles is between the 8.5-16.4% of gelatin quality, and the quality of polyethylene glycol is between methyl-prop
Between the 12.5-22.5% of olefin(e) acid ester grafted chitosan quality, crosslinking agent N, N, the quality of-methylene-bisacrylamide is between first
Between the 4.5-8.5% of the acrylic ester grafted chitosan mass of base, initiator potassium persulfate, catalyst n, N, N', N'- tetramethyl
The quality of ethylenediamine is respectively interposed between the 0.15-0.3% and 0.075-0.1% of methacrylate grafted chitosan quality.
5. a kind of MULTILAYER COMPOSITE biomass water process film as described in claim 1, it is characterised in that: a kind of MULTILAYER COMPOSITE is raw
Substance membrane for water treatment is prepared in the two-phase interface in the two-phase system being made of aqueous gel substrate and upper oil phase.
6. a kind of MULTILAYER COMPOSITE biomass water process film as described in claim 1, it is characterised in that: a kind of MULTILAYER COMPOSITE is raw
The preparation process of substance membrane for water treatment are as follows:
(1) oils is added as oily phase as substrate in merging aqueous gel block on it in a reservoir；
(2) sodium alginate, chitosan, pore-foaming agent are dissolved in the acetic acid aqueous solution that mass concentration is 3%, solution is instilled into oily phase
In, spread film is formed on gel piece surface layer, instills the eight arm ammonia salt caged times that mass concentration is 4-8% after balance on spread film
Half silicone particles aqueous solution stands 6-12h and forms film I after covering；Wherein, mass fraction of the chitosan in acetic acid aqueous solution
Between 2-4%, eight arm ammonia salt caged silsesquioxane particles aqueous solution volumes of dropwise addition are between the 1/ of acetic acid aqueous solution volume
Between；
(3) by gelatin, N, N- dimethylacrylamide, chitosan, dialdehyde starch, glutaraldehyde, N, N'- methylene bisacrylamide acyl
It is that solution is instilled to the surface of liquid film I in 3% acetic acid aqueous solution that amine, polyethylene glycol, which are dissolved in mass concentration, realizes covering, sprawls flat
6-12h is stood after weighing apparatus and forms liquid film II, wherein gelatin is in the mass fraction in acetic acid aqueous solution between 8.5-12.5%；
It (4) will be dissolved with methacrylate grafted chitosan, gelatin and eight arm polyethylene glycol caged silsesquioxane particles, poly- second
Glycol, crosslinking agent N, N ,-methylene-bisacrylamide, initiator potassium persulfate, catalyst n, N, N', N'- tetramethylethylenediamine
Aqueous solution drop to the surface liquid film II, realize covering, sprawl and stand 12-24h after balance and ultimately form sandwich diaphragm；
Wherein, the mass fraction of gelatin in aqueous solution is between 5.5-8.5%；
(5) after sandwich diaphragm being taken out at -60 DEG C quickly cooling, and vacuumize, dry film obtained, by dry film at 20 DEG C in pure water
6h is dried at 50 DEG C after impregnating 6h, obtains final products after circulation 5 times.
7. a kind of MULTILAYER COMPOSITE biomass water process film as described in claim 1, it is characterised in that: the aqueous gel substrate is
Hydrophilic hydrogel, preferably polyacrylamide hydrogel, polyacrylic acid hydrogel.
8. a kind of MULTILAYER COMPOSITE biomass water process film as described in claim 1, it is characterised in that: the upper oil phase is organic
Oils and close oil based solvent.
9. a kind of MULTILAYER COMPOSITE biomass water process film as described in claim 1, it is characterised in that: the thickness of the upper oil phase
Higher than film surface 15cm.
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