CN105879701A - Two-dimensional nano-material layer embedded novel composite forward osmosis (FO) membrane and preparation method thereof - Google Patents
Two-dimensional nano-material layer embedded novel composite forward osmosis (FO) membrane and preparation method thereof Download PDFInfo
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- CN105879701A CN105879701A CN201610295300.6A CN201610295300A CN105879701A CN 105879701 A CN105879701 A CN 105879701A CN 201610295300 A CN201610295300 A CN 201610295300A CN 105879701 A CN105879701 A CN 105879701A
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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
- 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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- 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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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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
- B01D71/56—Polyamides, e.g. polyester-amides
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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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
- B01D2325/24—Mechanical properties, e.g. strength
Abstract
The invention discloses a novel composite forward osmosis (FO) membrane with high water flux and high salt rejection characteristics, which is obtained by a two-dimensional nano-material layer embedding method, and a preparation method thereof. The novel composite FO membrane aims at solving the bottleneck problems of the existing FO membranes during application that the water flux is low, the internal concentration polarization is severe, salt solutes of a sucked solution are in reverse diffusion and the like. The novel composite FO membrane disclosed by the invention is based on the original thin-skin-layer composite membrane structure, and a layer of continuous, porous (the pore size is smaller than 1nm) and ultrathin (the thickness is smaller than 1nm) two-dimensional nano-material is embedded between a supporting layer and a separating power so as to form a sandwich-like novel structure which consists of the supporting layer, the two-dimensional nano-material embedded layer and the separating power. According to the novel composite FO membrane, the water flux and salt rejection of the prepared FO membrane are greatly improved by making full use of excellent water permeability and salt rejection capability of the two-dimensional nano-material, the internal concentration polarization is effectively reduced, and the reverse diffusion of the salt solutes of the sucked solution is inhibited.
Description
Technical field
The invention belongs to technical field of membrane separation, be specifically related to NEW TYPE OF COMPOSITE forward osmosis membrane of a kind of two-dimension nano materials inlay and preparation method thereof.
Background technology
Just permeating (FO) is a kind of new membrane isolation technics developed rapidly in recent years, have that process is spontaneous, simple to operate, energy-conserving and environment-protective, can the advantage such as operation at normal temperatures and pressures, showing huge potential using value in the field such as chemical technology, biological engineering, medicine processing, drug release, metallurgical processing, petroleum-based energy, food processing, military engineering, Aero-Space, desalinization, waste water process, sludge condensation, prospect is the most wide.
But; FO technology exists water flux concentration polarization low, interior (ICP) in actual applications, and problem makes it be difficult to scale industrialization with salt solute back-mixing is serious, effluent quality is poor, energy consumption is high, separation efficiency is low etc., and producing of these problems is the most relevant with the separating property of FO membrane material.Compound (TFC) FO film of FO technology many uses thin skin layer at present, it is mainly made up of porous support layer and thin stratum disjunctum.In general, the stratum disjunctum of preferable TFC FO film should have high water flux, high salt retains, the characteristic of less salt back-mixing；Supporting layer then should be the thinnest and resistance to mass tranfer is little, to improve water flux and to reduce ICP.But being constrained to scarcity and the deficiency of preparation technology of current good membranes material, the supporting layer of the TFC FO film that FO technology is used is the thickest, is easily caused serious ICP；And stratum disjunctum to the infiltration of water and to retain salt solute be shifting relation, high water flux process is usually associated with the back-mixing of salt solute, causes the problems such as the pollution of former water, fouling membrane aggravation.To this, people attempt being modified TFC FO film optimization to meet practical application request, improve water flux to a certain extent.But, the modified optimization method of current TFC FO film still suffers from problems with: the stratum disjunctum of (1) Modified Membrane often leads to salt solute back-mixing seriously to improve water flux, and the back-mixing controlling salt solute then will be to sacrifice water flux as cost；(2) modified supporting layer can control ICP to a certain extent and improve water flux, and salt solute back-mixing problem yet suffers from.It can be seen that existing TFC FO membrane modifying method is still without solving well to draw the key issue that liquid salt solute back-mixing this restriction FO develops further.Therefore, develop have high water flux, low draw liquid salt solute back-mixing characteristics new membrane be promote FO film develop further with application important channel.
The fast development of two-dimension nano materials in recent years is that the structure design of novel FO film provides new Research Thinking, and the preparation for high water flux, the low FO film drawing liquid solute back-mixing brings probability.
Two-dimension nano materials refers to only maintain in the dimension of one, z direction the material of nanoscale, and it has broad application prospects in multiple fields because of physicochemical property uniqueness.As a example by typical two-dimension nano materials Graphene, Graphene is to be currently known the thinnest, the hardest two dimensional crystal, it is only a carbon atom thickness, its lattice is the hexagon surrounded by six carbon atom, there is the advantages such as high carrier mobility, high transmission rate, excellent electrical and thermal conductivity, paid close attention to widely in fields such as military affairs, Aero-Space, microelectronics industry and information industries.After Graphene two dimension basal plane introduces nano-pore, available a kind of ultra-thin, two-dimentional porous film material porous graphene that mechanical performance is strong, porous graphene pore size makes it have selectivity sieving actoion to various sizes of ion and molecule with the difference of arrangement mode, therefore of great interest in water treatment by membrane (reverse osmosis, just infiltration etc.) field.(the Nano Letter such as Cohen-Tanugi, 2012, research 12:3602) shows, porous graphene is when desalinization, the existence of bore edges hydroxyl is greatly improved salt rejection rate, comparing with traditional reverse osmosis membrane, the porous graphene rate of filtration under same operation pressure wants fast 2-3 the order of magnitude；The research of Surwade etc. (Nature Nanotechnology, 2015,10:459) shows the salt rejection rate of almost 100% when showing porous graphene aperture less than 1 nm, the highest water flux can reach 106 g/m2.It is contemplated that, if possess excellent release can porous graphene substitute traditional reverse osmosis membrane, NF membrane etc. when desalinization, sewage disposal, it is possible to resolve the problems such as energy consumption is high, and fouling membrane is serious；When being used for FO as ultra-thin separation film, can effectively eliminate ICP, solve to draw the reverse diffusion problem of liquid solute, and obtain ultrahigh water flux.Additionally, deepening continuously and developing along with Material Field scientific research, may find that or prepare more porous graphene that is similar in the future this ultra-thin, stable and there is the excellent two-dimension nano materials selecting separation property, bring new prospect for Membrane Separation for Water Treatment.
But from the point of view of reality application angle, ultra-thin two-dimension nano materials is individually used for FO Technology and is difficulty with at present, but after two-dimension nano materials is combined dexterously with existing FO film, then can obtain and a kind of there is high water flux, the low NEW TYPE OF COMPOSITE FO film drawing liquid solute air-teturning mixed characteristic.NEW TYPE OF COMPOSITE FO film can effectively utilize the two-dimension nano materials rejection to ion, will draw liquid side salt solute retention, suppresses its back-mixing, and reduces ICP to a certain extent, improves water flux.
Summary of the invention
For solving the water flux concentration polarization low, interior and draw the problems such as the liquid reverse diffusing phenomenon of salt solute are serious present in the actual application of current existing forward osmosis membrane, the present invention is combined forward osmosis membrane structure based on original thin skin layer, it is proposed that a kind of method of NEW TYPE OF COMPOSITE forward osmosis membrane that two-dimension nano materials inlay has between supporting layer and stratum disjunctum high water flux and high salt-stopping rate feature with acquisition.
For realizing the acquisition of above-mentioned NEW TYPE OF COMPOSITE forward osmosis membrane, the invention provides following preparation method: first with the preparation of the method such as inversion of phases, electrostatic spinning, there is certain mechanical strength permeable supporting layer；Secondly, two-dimension nano materials is compounded in supporting layer upper surface by the way of lotus electrostatic and substrate shift and combines and obtains the structure compound counterdie for " supporting layer-two-dimension nano materials layer "；Finally, obtain, by the methods such as interfacial polymerization, polyelectrolyte self assembly compound-split layer on the two-dimension nano materials layer of compound counterdie, the NEW TYPE OF COMPOSITE forward osmosis membrane that structure is " supporting layer-two-dimension nano materials inlay-stratum disjunctum ".
Two-dimension nano materials inlay used in the present invention is continuous whole, porous and pore size are ultra-thin (thickness is only monatomic size or less than 1 nm) material of 0.5-1.5 nm, in NEW TYPE OF COMPOSITE forward osmosis membrane, have the effect that (1) improves salt-stopping rate, improve and just permeating effluent quality.Hole on two-dimension nano materials allows hydrone freely to pass through, and the relatively large ion of pair radius is (such as Na+、Ca2+、Mg2+、SO4 2-Deng) there is crown_interception, the ion of the material liquid side that can will transmit through stratum disjunctum retains further, improves the salt-stopping rate of NEW TYPE OF COMPOSITE forward osmosis membrane.(2) mechanical strength of film is improved.Two-dimension nano materials excellent in mechanical performance, it embeds the mechanical strength that can significantly improve NEW TYPE OF COMPOSITE forward osmosis membrane.(3) liquid solute back-mixing is drawn in suppression, reduces ICP, improves water flux.The liquid solute ions of drawing spread to material liquid side can be trapped in supporting layer by two-dimension nano materials inlay by the crown_interception of ion, and suppression reduces ICP while drawing liquid solute back-mixing, improves the water flux of film.
NEW TYPE OF COMPOSITE forward osmosis membrane proposed by the invention can be applicable to the environmental technology fields such as desalinization, sludge condensation, stain disease process, and can be realized with density by the pore size of regulation two-dimension nano materials according to the difference of application, the water flux of NEW TYPE OF COMPOSITE forward osmosis membrane and the regulation and control of salt-stopping rate.
Accompanying drawing explanation
Fig. 1 is the preparation process of the NEW TYPE OF COMPOSITE forward osmosis membrane described in the specific embodiment of the invention one.
Detailed description of the invention
Detailed description of the invention one: the preparation method of NEW TYPE OF COMPOSITE forward osmosis membrane realizes according to following steps: (1) prepares supporting layer: by polysulfones, N, dinethylformamide and N-Methyl pyrrolidone mix with the mass ratio of 12:22:66, stand 12 h deaerations after stirring 8 h in dry conditions, obtain homogeneous casting solution.With coating device, casting solution is painted on clean glass plate equably the liquid film of 100 μ m-thick, immediately the glass plate scribbling liquid film smoothly being immersed 10 min in deionized water makes liquid film change into immobilon-p, with deionized water immobilon-p rinsed well completely and be placed at 105 DEG C being dried 20 min, obtain the supporting layer being dried.(2) the compound counterdie of preparation: use rubber bar to carry out friction charged to dry supporting layer, subsequently supporting layer upper surface is closely adhered on two dimension porous graphene at the bottom of cuprio.Down by being fitted with two dimension porous graphene (thickness 0.34 nm, aperture 0.5-1.5 nm) substrate at the bottom of the cuprio of supporting layer, swim on the ferric chloride etching liquid of 2.5 wt.%, and on liquid level, be forced into 0.15 MPa with nitrogen.After 2 h, being etched completely away at the bottom of cuprio, picked up by supporting layer, now two dimension porous graphene has been compounded in supporting layer upper surface, obtain the compound counterdie of " supporting layer-two-dimension nano materials layer " structure, be combined counterdie surface 10 times to remove remaining etching liquid with deionized water rinsing.Compound counterdie after finally rinsing is placed at 105 DEG C dries 12 h, is stored in dry place standby.(3) compound-split layer: the dry composite counterdie obtained in step (2) is immersed in the m-diaminobenzene. aqueous solution of 3 wt.% and take out after 2 min, after removing compound counterdie excess surface drop with rubber cylinder, the upper surface of compound counterdie and the normal hexane being dissolved with 0.2 wt.% pyromellitic trimethylsilyl chloride are fully contacted 1 min, the two-dimentional porous graphene surface making compound counterdie occurs interface polymerization reaction to generate polyamide stratum disjunctum, with deionized water, the monomer that stratum disjunctum surface is reacted the most completely is rinsed well, finally give by supporting layer, class " sandwich " the type NEW TYPE OF COMPOSITE forward osmosis membrane that two dimension porous graphene inlay and polyamide stratum disjunctum are constituted.
Detailed description of the invention two: present embodiment and detailed description of the invention one difference are that the casting solution of step (1) is that polysulfones, Polyethylene Glycol (mean molecule quantity is 400 Da), N,N-dimethylformamide and N-Methyl pyrrolidone are mixed with the mass ratio of 12:6:19:63.Other step and parameter are identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one difference are that the glass plate scribbling liquid film in step (1) is smoothly immersed in the N-Methyl pyrrolidone and deionized water mixed solution that volume ratio is 3:97.Other step and parameter are identical with detailed description of the invention one.
Detailed description of the invention four: present embodiment and detailed description of the invention one difference are the ammonium persulfate solution that etching liquid at the bottom of the cuprio used in step (2) is 8.0 wt.%.Other step and parameter are identical with detailed description of the invention one.
Detailed description of the invention five: present embodiment and detailed description of the invention one difference are in step (2) that the ethanol water using volume fraction to be 50% rinses compound counterdie surface and removes remaining etching liquid.Other step and parameter are identical with detailed description of the invention one.
Detailed description of the invention six: present embodiment and detailed description of the invention one difference are that the m-diaminobenzene. concentration of aqueous solution used in step (3) is 3.4 wt.%.Other step and parameter are identical with detailed description of the invention one.
Detailed description of the invention seven: during present embodiment and detailed description of the invention one difference are that in step (3), pyromellitic trimethylsilyl chloride is dissolved in the Isopar-G solution that Exxon Mobil Corporation produces, in the organic phase solution formed, the concentration of pyromellitic trimethylsilyl chloride is 0.15 wt.%.Other step and parameter are identical with detailed description of the invention one.
Detailed description of the invention eight: present embodiment and detailed description of the invention one difference are in step (3) that the compound upper surface of counterdie is 2 min with the time of contact of the normal hexane being dissolved with 0.2 wt.% pyromellitic trimethylsilyl chloride.Other step and parameter are identical with detailed description of the invention one.
Claims (7)
- NEW TYPE OF COMPOSITE forward osmosis membrane the most proposed by the invention, it is characterised in that described compound forward osmosis membrane is three-decker, particularly as follows: play the supporting layer of mechanical support effect；Have loose structure and pore diameter range 0.5-1.5 nm, there is high water-permeability and the high two-dimension nano materials inlay cutting salt feature；Allowing hydrone to pass through and have certain stratum disjunctum cutting salt characteristic, described two-dimension nano materials inlay is between supporting layer and stratum disjunctum.
- 2. NEW TYPE OF COMPOSITE forward osmosis membrane as claimed in claim 1, it is characterized in that: the material of described supporting layer includes polysulfones, polypropylene, SPSF, carboxylation polysulfones, polyether sulfone, polyether-ketone, sulfonated polyether-ether-ketone, poly (aryl ether sulfone ketone), poly (arylene ether nitrile) ketone, copolyether sulfone, polyimides, Polyetherimide, sulfonation poly-phenylene ether, polyacrylonitrile, polybenzimidazoles, cellulose acetate, Triafol T, acetylbutyrylcellulose, cellulose acetate propionate, Kynoar, polyester, aquaporin, polyvinylpyrrolidone, polyvinyl alcohol, Polyethylene Glycol, titanium dioxide, silicon dioxide, silver nano-grain, poly-dopamine, polymine, one or more in CNT；Described two-dimension nano materials inlay is the one in Graphene, graphene oxide, porous graphene, fluorographite, phosphorus alkene, silene, germanium alkene, stannum alkene, boron alkene, TiOx nano page, zinc-oxide nano page, manganese oxide nanometer page, perovskite nanometer page, niobates nanometer page, hexagonal boron nitride.
- 3. the preparation method of NEW TYPE OF COMPOSITE forward osmosis membrane as claimed in claim 1, comprise the following steps: the first step, prepare supporting layer, concrete operation method is: by polymer with 6.0-12.0 wt.%, additive dissolves in a solvent with 0-8.0 wt.%, after stirring 8-10 h, the casting solution that static 10-24 h is uniformly mixed, after utilizing coating device that casting solution is painted on clean glass plate the liquid film of 100-200 μ m-thick, at once glass plate is immersed in the coagulation bath of 20-40 DEG C, after 10 min, liquid film is frozen into polymeric film and departs from glass plate, with deionized water, polymeric film is rinsed well repeatedly, i.e. obtain the supporting layer of described NEW TYPE OF COMPOSITE forward osmosis membrane；Second step, two-dimension nano materials is compounded on supporting layer, obtain " supporting layer-two-dimension nano materials layer " compound counterdie, concrete operation method is: supporting layer is the most dried, make it charged with rubber bar in the lower surface friction of supporting layer, subsequently the upper surface of charged supporting layer is fitted on the two-dimension nano materials of strip substrate, the strip substrate two-dimension nano materials substrate of supporting layer will be fitted with down, float on the etching liquid of 10-20 wt.%, and on liquid level, it is forced into 0.10-0.15 MPa with nitrogen, after substrate is etched away completely, with upper surface 3-10 time of deionized water rinsing supporting layer, finally give compound counterdie；3rd step, compound-split layer on the two-dimension nano materials layer of compound counterdie, be there is the NEW TYPE OF COMPOSITE forward osmosis membrane of " supporting layer-two-dimension nano materials layer-stratum disjunctum " structure, concrete operation method is: is immersed in the polyamine aqueous solution that mass fraction is 3-5% by the compound counterdie prepared in step 2 and takes out after 2 min, the two-dimension nano materials layer side of the compound counterdie taken out is contacted 1 min with the polynary acyl chlorides organic phase solution that mass fraction is 0.1-0.2%, two-dimension nano materials layer surface is made to occur the interface polymerization reaction of polyamine and polynary acyl chlorides to form stratum disjunctum, finally with deionized water, unreacted monomer is rinsed well, be there is the NEW TYPE OF COMPOSITE forward osmosis membrane of " supporting layer-two-dimension nano materials inlay-stratum disjunctum " structure.
- 4. the preparation method of NEW TYPE OF COMPOSITE forward osmosis membrane as claimed in claim 3, it is characterized in that: different according to described NEW TYPE OF COMPOSITE forward osmosis membrane application, as desalinization, sludge condensation or membrane bioreactor, the water flux of described NEW TYPE OF COMPOSITE forward osmosis membrane and the regulation and control of salt-stopping rate realize with hole density by regulating the pore size of described two-dimension nano materials inlay.
- 5. the preparation method of NEW TYPE OF COMPOSITE forward osmosis membrane as claimed in claim 3, it is characterised in that: described polymer is one or more in polysulfones, polypropylene, SPSF, carboxylation polysulfones, polyether sulfone, polyether-ketone, sulfonated polyether-ether-ketone, poly (aryl ether sulfone ketone), poly (arylene ether nitrile) ketone, copolyether sulfone, polyimides, Polyetherimide, sulfonation poly-phenylene ether, polyacrylonitrile, polybenzimidazoles, cellulose acetate, Triafol T, acetylbutyrylcellulose, cellulose acetate propionate, Kynoar, polyester, aquaporin；Described additive is one or more in polyvinylpyrrolidone, polyvinyl alcohol, Polyethylene Glycol, titanium dioxide, silicon dioxide, silver nano-grain, poly-dopamine, polymine, CNT；Described solvent is one or more in dimethylformamide, dimethyl acetylamide, N-Methyl pyrrolidone, dimethyl sulfoxide, tetramethyl sulfoxide, acetone, oxolane；Described coagulation bath is deionized water, ethanol or contains the deionized water solution of one or more in dimethylformamide, dimethyl acetylamide, N-Methyl pyrrolidone, dimethyl sulfoxide, tetramethyl sulfoxide, acetone, oxolane；The substrate of described strip substrate two-dimension nano materials is copper, nickel or polymethyl methacrylate；Described substrate etching liquid is ammonium persulfate solution, the aqueous solution of iron chloride or acetone；Described polyamine is polymine, p-phenylenediamine, piperazine or m-diaminobenzene.；Described polynary acyl chlorides is paraphthaloyl chloride, pyromellitic trimethylsilyl chloride or 3,3,5,5-biphenyl tetracarboxylic acyl chlorides.
- 6. NEW TYPE OF COMPOSITE forward osmosis membrane preparation method as claimed in claim 3, it is characterised in that: the described method preparing supporting layer be sintering process, pulling method, track etching method, sol-gal process, vapour deposition method, coating process, phase inversion, method of electrostatic spinning or make in aforementioned manners in preparation process by cross-linking modified, graft modification, the method for doping vario-property acquisition supporting layer.
- 7. NEW TYPE OF COMPOSITE forward osmosis membrane preparation method as claimed in claim 3, it is characterised in that: the described method of compound-split layer on the two-dimension nano materials layer of compound counterdie be interfacial polymerization, polyelectrolyte self-assembly method or make in aforementioned manners in preparation process by cross-linking modified, graft modification, the method for doping vario-property acquisition stratum disjunctum.
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