CN109550401A - A kind of membrane distillation composite material - Google Patents
A kind of membrane distillation composite material Download PDFInfo
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- CN109550401A CN109550401A CN201710878698.0A CN201710878698A CN109550401A CN 109550401 A CN109550401 A CN 109550401A CN 201710878698 A CN201710878698 A CN 201710878698A CN 109550401 A CN109550401 A CN 109550401A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
- B01D2323/345—UV-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- 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
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Abstract
The present invention relates to film distillation technology fields, provide a kind of membrane distillation composite material, it is made of hydrophobic porous material layer and hydrophilic porous material layer, the hole of hydrophobic porous material layer and hydrophilic porous material layer is 3 D stereo connection, hydrophobic porous material layer is that 3 D stereo is connected to Kong Jun of the hydrophilic porous material layer at interface, this kind of material considerably increases the specific surface area of material, facilitate hydrone diffuse through and the condensation of water, so that more hydrones pass through composite membrane, realize big membrane flux, and it is not easy to plug in, reduce impact force, with longer service phase, it is suitble to industrial applications.
Description
Technical field
The present invention relates to film distillation technology fields, and in particular to a kind of membrane distillation composite material.
Background technique
Membrane distillation is a kind of novel isolation technics, is using hydrophobic microporous membrane two sides steam pressure difference as mass transfer force
Membrane separating process.Membrane distillation because have can operate under normal pressure, equipment is simple, operation is easy, low operation temperature, using low product
The advantages that position heat source (such as solar energy, underground heat, waste heat), rejection are high and can handle high concentration solution, so being widely used in height
Preparation, ethanol dehydration, food processing, wastewater treatment, brackish water desalination and the sea water desalination of pure water.Membrane distillation method can be by pole
The inorganic salt solution of high concentration is handled, and water obtained is very pure, this is that existing several industrial desalination technologies are difficult to
Reach, it is to solving the problems, such as that the Sustainable Socioeconomic Developments such as current water scarcity, energy-saving and emission-reduction, water environment treatment have
It is significant.With the development of this century material technology and film manufacturing technology, film distillation technology is attracted wide attention.
Membrane distillation is the core of distillation device with film, and people have carried out numerous studies to membrane distillation film, developed poly-
Vinylidene (PVDF), polytetrafluoroethylene (PTFE) and polypropylene (PP), in recent years also in research composite membrane, such as
CN103372378 A " a kind of membrane distillation hydrophilic/hydrophobic composite membrane " proposes a kind of hydrophilic layer, hydrophobic layer and non-woven fabrics support
The membrane distillation composite membrane that layer is combined.Its hydrophilic layer contacts material liquid when work, this kind of membrane distillation hydrophilic/hydrophobic is compound
Film has the characteristics that antipollution is strong, high mechanical strength, but membrane flux is still smaller, when raw water temperature reaches 70 DEG C, membrane flux
Just reach 16L/m2h.CN 103492059B " complex thin film and relative manufacturing process for thin-film distillation " provide including
The compound hydrophilic/hydrophobic film of hydrophilic polymer layer and hydrophobic polymer layer, the film include fluorinated surface
Modified macromer, and the manufacturing method of this kind of film is provided, but this kind of thin-film hydrophobic angle is less than normal, hydrophilic angle is bigger than normal, affects
Membrane flux, when feeding temperature is 50 DEG C, membrane flux most great talent reaches 19.4L/m2h.CN 103998115B " is used for membrane distillation
Three layers of hydrophobe-hydrophile film of application " propose one kind by hydrophobicity electro spinning nano fiber layer, microporous layers, hydrophily back sheet group
At the adjacent distilland in the outer surface of hydrophobicity electro spinning nano fiber layer, hydrophobicity electro spinning nano fiber layer has more micro- than described
For the bigger contact angle of the contact angle of aperture layer to prevent the wettings of the microporous layers, the outer surface of hydrophily back sheet is adjacent for connecing
The distillate area of distillate is received, hydrophily back sheet has contact angle more smaller than the contact angle of the microporous layers to increase in institute
The absorption at back sheet to vapor is stated, when feeding temperature is 50 DEG C, membrane flux most great talent reaches 7.7Kg/m2h。
Existing a variety of membrane distillations are smaller with membrane flux, are not suitable for industrial applications, the film that preliminary works use at present
The membrane flux of distillation film only reaches 10L/m when feeding temperature is 70 DEG C2h。
Summary of the invention:
The object of the present invention is to provide a kind of membrane distillation composite materials of suitable industrial applications.
Another object of the present invention is to provide a kind of membrane components of suitable industrial applications.
Researcher's discovery, about membrane distillation composite membrane, due to compound, the pore structure of each material of two kinds of materials itself,
Influence of the pore structure at especially two kinds Material cladding interfaces for membrane flux is very huge.For example, two kinds of interface material
The connection structure in hole.
The object of the invention is achieved through the following technical solutions:
A kind of membrane distillation composite material, is made of hydrophobic porous material layer and hydrophilic porous material layer, it is critical that described
The hole of hydrophobic porous material layer is 3 D stereo connection, and the hole of the hydrophilic porous material layer is 3 D stereo connection, institute
It is that 3 D stereo is connected to that hydrophobic porous material layer, which is stated, with hole of the hydrophilic porous material layer at interface, i.e., in interface
The hole that the aperture of place, the aperture on hydrophobic porous material layer surface and adjacent hydrophilic porous material layer surface is constituted is three-dimensional connects
Logical；And be with its connected ratio 70% or more be preferred, that is, the hole gross area 70% of the hydrophobic porous material layer at interface with
It is upper to be connected to hole of the hydrophilic porous material layer at interface.Porous hydrophobic material mentioned by the present invention refers to material surface
Water contact angle is greater than 90 °, and hydrophilic porous material refers to the water contact angle of material surface less than 90 °.Mesoporous of the present invention is three-dimensional vertical
The structure of body connection considerably increases the specific surface area of material, and the diffusion for facilitating hydrone for hydrophobic porous material layer is logical
It crosses, facilitates the condensation of water for hydrophilic porous material layer.With regard to hydrophobic porous material layer and hydrophilic porous material layer connection and
Speech, if only together by two kinds of Material claddings, the pore structure design of two kinds of interface material is unreasonable, although by hydrophobic
The water vapour of porous material layer can also be moistened absorption by hydrophilic porous material layer, but its processed in units amount can be then greatly reduced.
The interface connection structure that the hole of two kinds of materials is connected at interface using mutual 3 D stereo by the present invention, is easy to hydrone
Diffusion reduces impact force, has so that more hydrones realize big membrane flux, and be not easy to plug in by composite membrane
Longer service phase, to be suitble to industrial applications.
Furtherly, the membrane distillation composite material, the hydrophobic porous material layer and the hydrophilic porous material
Layer is integrated composite material, the integrated composite refer to same raw material be made with hydrophobic porous material layer with
The material of hydrophilic porous material layer, to realize that the hole of hydrophobic porous material layer and the hole of hydrophilic porous material layer are basic at interface
Bigger membrane flux is realized in all connections.
Furtherly, the water contact angle of the membrane distillation composite material, the hydrophobic porous material layer surface is
110 ° or more, the big water contact angle on hydrophobic porous material layer surface helps to improve vapor flux or/and the institute of process object
The water contact angle for stating hydrophilic porous material layer surface is 30 ° hereinafter, facilitating the condensation of steam isolated, and improves industrialization rule
The treating capacity of mould.
Furtherly, the water contact angle of the membrane distillation composite material, the hydrophobic porous material layer surface is
150 ° or more, when the water contact angle of the hydrophilic porous material layer surface is 5 ° or less, this composite membrane can significantly improve film
Flux, is more suitable industrially scalable application.
Furtherly, the membrane distillation composite material, the cavity wall rough surface in the hole of the hydrophobic porous material layer
It spends Ra value and is not less than 20nm not less than 20nm or/and the cavity wall surface roughness Ra value in hydrophilic porous material layer hole, increase
The specific surface area of material, facilitates hydrone in the diffusion and condensation of material internal, makes it have bigger membrane flux, thus
Greatly improve the processed in units amount for meeting industrial applications.
In order to further increase industrially scalable, processed in units amount is improved, the hydrophobic porous material layer multi-stage porous is made
Material, or/and make the hydrophilic porous material layer multilevel hole material；The multilevel hole material is divided according to the size in hole
Grade, junior hole in the cavity wall in higher level hole, holes at different levels respectively be interconnected and with other grade of Kong Liantong.
Furtherly, the membrane distillation composite material, the hydrophobic porous material layer are microporous teflon membran,
This kind of film has good hydrophobic performance, is advantageously implemented the cavity wall of big membrane flux or/and hydrophilic porous material layer hole
There is TiO on surface2Coating helps to improve the hydrophilicity of hydrophilic porous material, facilitates the condensation of water, both materials carry out
It is more conducive to improve industrial treatment amount after compound.
Furtherly, the membrane distillation is integrated composite material with composite material, using microporous teflon membran
The cavity wall surface roughness Ra value of material, hole is not less than 20nm, in the segment thickness of the microporous teflon membran material
The cavity wall surface preparation TiO2 coating in hole forms hydrophilic porous material layer, the cavity wall surface roughness Ra in hydrophilic porous material layer hole
Value is not less than 20nm, this kind of composite material significantly improves membrane flux.
Another object of the present invention uses following scheme: membrane module is fabricated to composite material using above-mentioned membrane distillation,
For membrane distillation, the hydrophobic porous material layer of composite material is contacted with the raw material hot side of membrane module, hydrophilic porous material layer and film
The liquid cold side contact that component distills out, this kind of membrane module have big membrane flux, and industrial applications effect is particularly significant.
Composite material of the present invention is by the hydrophobic porous material layer and hydrophilic porous material that hole is that 3 D stereo is connected to
Layer is constituted, and increases the specific surface area of material, and will be at the interface of hydrophobic porous material layer and the hydrophilic porous material layer
Hole mutual 3 D stereo connection, realize various dimensions connection, the present invention is in separation in use, can make more hydrones successfully
By the composite material, and at interface, also very little, water wetted material accelerate the condensation of water to resistance, can significantly improve this
The membrane flux of material.Since its is reasonable in design, hydrone is small by resistance wherein, reduces impact force, the present invention can
Without supporting layer, it is still able to maintain good structural stability in use, and treating capacity is big, stain resistance is strong, when military service
It is long, especially suitable for industrial applications.
Detailed description of the invention
Below in conjunction with attached drawing, the present invention is further elaborated with embodiment.
Fig. 1 is inventive film distillation composite structure schematic diagram；
Fig. 2 is the structural schematic diagram of hole unit at the interface of hydrophobic porous material layer and hydrophilic porous material layer in embodiment 2.
Specific embodiment
Specific embodiment based on the technical solution of the present invention, gives detailed embodiment, but guarantor of the invention
Shield range is not limited only to embodiment disclosed below, when not departing from and changing above-mentioned technical idea of the invention, according to ability
The ordinary technical knowledge and/or customary means in domain, it is clear that the replacement or change of diversified forms can also be made, and should all be included in
Within the scope of the present invention.
In Fig. 1,1 is hydrophobic porous material layer, and 2 be hydrophilic porous material layer, 3 for hydrophobic porous material layer with it is hydrophilic porous
The interface of material layer.
In Fig. 2,4 be a Kong Dan at the interface 3 of hydrophobic porous material layer in embodiment 2 and hydrophilic porous material layer
Meta structure, in figure, 5 be the cavity wall of the hole unit, and interface 3 intersects with the cavity wall 5 of hole unit, intersection point A, B, C, D, E, F, friendship
The region 6 on 3 one side of interface is hydrophobic porous material layer region, and the region 7 of 3 another side of interface is hydrophilic porous material layer
Region.
Embodiment 1
A kind of membrane distillation composite material, is made of hydrophobic porous material layer and hydrophilic porous material layer, the hydrophobic porous material
The bed of material is commercially available polyvinylidene fluoride microporous film, and through detecting, porosity 82%, aperture is 2 μm -4 μm, and hole is 3 D stereo
Connection, film thickness be 50 μm, through with Pu Saite detection device Co., Ltd PT-705D contact angle measurement according to operation manual
Test, the water contact angle on hydrophobic porous material layer surface are 113 °；Hydrophilic porous material layer is polyimides microporous barrier, porosity
It is 84%, aperture is 5 μm -9 μm, and hole is 3 D stereo connection, which is: molten in the mixing of tetrahydrofuran and benzene
Ratio by mass part of addition thermoplastic polyimide powder in agent, in the mixed solvent tetrahydrofuran and benzene is 1:10, and solution is dense
Degree is 20g/L, is sufficiently stirred under inflated with nitrogen, and it is 10mL/min, mixing speed 300rpm that nitrogen, which is passed through speed, keeps it completely molten
Solution, with scraper, coating thermoplastic polyimide solution forms film on dry support basement membrane, and thickness sets film at 50 μm
In temperature at 10 DEG C, humidity forms microporous barrier in 90% environment, measures polyimides micropore film water by above-mentioned test method and connects
Feeler is 47 °；Use HR-5198 glue as bonding agent by hydrophobic porous material layer polyvinylidene fluoride microporous film and hydrophilic porous material
Membrane distillation composite material is made in bed of material polyimides microporous barrier bonding, using FEI Co., U.S. FIB/SEM focused ion/electricity
The sub- micro- Electronic Speculum HELIOS NanoLab600i of two-beam detects composite material polyvinylidene fluoride microporous film and polyimides microporous barrier
Interface, the connected ratio in the hole in the hole and polyimides microporous barrier of polyvinylidene fluoride microporous film reaches 72% at interface.It will
The composite material is used for membrane distillation membrane module, and hydrophobic porous material layer polyvinylidene fluoride microporous film is contacted with raw material hot side, parent
Water porous material layer polyimides microporous barrier is contacted with the liquid cold side distilled out, this kind of membrane module has big membrane flux, is used
In processing 1wt%NaCl aqueous solution, when hot side NaCl aqueous temperature is 80 DEG C, and cold side water temperature is 20 DEG C, membrane flux reaches
75L/m2h。
Using 50 μm of polyimide plastic films as substrate, film is irradiated with high-energy heavy ion, is hung down with substrate surface
Histogram is 80 ° to irradiation incidence angle is formed by, and obtaining pore density range is every square centimeter 108It is a, use wavelength for
The ultraviolet light polyimide film of 200-365nm, 80 joules/cm of exposure dose2, then film is dipped in and fills NaOH-
In the container of KMnO solution system, temperature is 80 DEG C, time 70min, and obtaining micropore size is 2 μm -4 μm, and micropore is in approximation
Cylinder, axis is vertical with film surface, and same structure is produced with similar method from another side, uniform pore diameter is led on one side in hole
And the polyvinylidene fluoride microporous film of thickness, select YJ-22 polyimides adhesive as bonding agent by polyvinylidene fluoride microporous film
It is Nian Jie with polyimides microporous barrier, it is detected with same method, the hole of polyvinylidene fluoride microporous film and polyimides are micro- at interface
The connected ratio in the hole of pore membrane reaches 40%, and when carrying out membrane distillation according to above-mentioned condition, membrane flux only reaches 19 L/m2H, membrane flux
Very little.
When the aperture of polyimides micropore film preparation is 2 μm -4 μm, porosity 84%, hole is 3 D stereo connection, thick
Degree is 50 μm, and hydrophobic porous material layer is polyvinylidene fluoride microporous film, and porosity 82%, aperture is 2 μm -4 μm, and hole is three-dimensional
Solid connection, film thickness is 50 μm, and bonding agent selects YJ-22 polyimides adhesive, remaining material parameter is constant, with same
Method detects, and the connected ratio in the hole in the hole and polyimides microporous barrier of polyvinylidene fluoride microporous film reaches 42% at interface.According to
When above-mentioned condition carries out membrane distillation, membrane flux only reaches 36 L/m2H, it is clear that same when this membrane flux is for industrial applications
The time of the high composite material of the time of sample treating capacity more aforementioned connected ratio rises appreciably.
Embodiment 2
A kind of membrane distillation composite material, is made of hydrophobic porous material layer and hydrophilic porous material layer, wherein described hydrophobic more
Porous materials layer is microporous polypropylene membrane, and porosity 85%, aperture is 4 μm -8 μm, and hole is 3 D stereo connection, water contact angle
146°；Hydrophilic porous material layer is microporous polypropylene membrane, and the surface of cavity wall is impregnated of polyacrylic acid/nano silica, parent
The water contact angle of water porous material layer surface is 28 °, porosity 82%, and hole is that uniformly, aperture is 3 μm -6 μm, and hole is three-dimensional
Solid connection；The composite material is the microporous polypropylene membrane for using same hole 3 D stereo to be connected to (overall thickness is 160 μm)
Form on 50% thickness of one side impregnated of polyacrylic acid/nano silica hydrophilic coating, i.e., hydrophobic porous material layer with it is hydrophilic
Porous material layer is integrated composite, and the unit three-dimensional in the hole at interface is connected to schematic diagram referring to fig. 2, as seen from the figure,
The hole 4 is connected to the equal 3 D stereo in the hole in the hole of hydrophobic porous material layer and hydrophilic porous material layer, hydrophobic more at interface
The connected ratio in the hole of Porous materials layer and hydrophilic porous material layer reaches 91% according to the detection method detection of embodiment 1.According to implementation
The condition of example 1 carries out membrane distillation, which is used for membrane distillation membrane module, hydrophobic porous material layer connects with raw material hot side
Touching, hydrophilic porous material layer are contacted with the liquid cold side distilled out, this kind of membrane module has big membrane flux, and membrane flux reaches
113L/m2h。
Embodiment 3
A kind of membrane distillation composite material, is made of hydrophobic porous material layer and hydrophilic porous material layer, the hydrophobic porous material
The bed of material is polyvinylidene fluoride microporous film, and porosity 86%, aperture is 1 μm -2 μm, and hole is 3 D stereo connection, water contact angle
151 °, film thickness is 50 μm；Hydrophilic porous material layer is polyimides microporous barrier, is prepared according to 1 method of embodiment, and porosity is
84%, aperture is 5 μm -9 μm, and hole is 3 D stereo connection, and by plasma treatment, 4.5 ° of water contact angle, film thickness is 100 μ
m；Use HR-5198 glue as bonding agent by hydrophobic porous material layer polyvinylidene fluoride microporous film and hydrophilic porous material strata acyl
Membrane distillation composite material is made in imines microporous barrier, according to 1 method of embodiment detection composite material polyvinylidene fluoride microporous film and
The interface of polyimides microporous barrier, the hole of the connection at interface are 3 D stereo connections, gather inclined fluorine at interface
The connected ratio in the hole in the hole and polyimides microporous barrier of ethylene microporous barrier reaches 80%.Film steaming is carried out according to the condition of embodiment 1
It evaporates, which is used for membrane distillation membrane module, hydrophobic porous material layer is contacted with raw material hot side, hydrophilic porous material layer
It is contacted with the liquid cold side distilled out, this kind of membrane module has big membrane flux, and membrane flux reaches 136L/m2h。
Embodiment 4
A kind of membrane distillation composite material, is made of hydrophobic porous material layer and hydrophilic porous material layer, the hydrophobic porous material
The bed of material is SiO2/ polyvinylidene fluoride microporous film, porosity 85%, aperture are 0.8 μm -2 μm, and hole is 3 D stereo connection, water
155 ° of contact angle, film thickness be 60 μm, preparation method is: at room temperature, according to 20 wt% concentration by Kynoar powder (Mw=
400,000-600,000, it is purchased from Shanghai Dong Fu Chemical Industry Science Co., Ltd) it is added to N, in N '-dimethylformamide, according still further to
SiO2SiO is added in the ratio that nanoparticle and Kynoar powder weight ratio are 1.6:12Nanoparticle, ultrasound point after being completely dissolved
Dissipate and continuously stir 12h, Kynoar/N of acquisition, N '-dimethylformamide/SiO2Nano-particle solution is molten as spinning
Liquid；Above-mentioned spinning solution is subjected to electrostatic spinning, by aluminium foil as collector, electrostatic spinning voltage is 15KV, collects distance and is
14cm obtains SiO2/ polyvinylidene fluoride microporous film, with Switzerland TRIMOS SA measuring technique company's T RIMOS TR-Scan-P
The cavity wall surface of the non-contact microscopic appearance measuring instrument random scanning micropore membrane micropore vestibule, calculates roughness by device software
Ra value, surface roughness Ra value are not less than 22nm；Hydrophilic porous material layer is same as Example 3, use HR-5198 glue as
Bonding agent is by hydrophobic porous material layer SiO2/ polyvinylidene fluoride microporous film and hydrophilic porous material strata acid imide microporous barrier bonding
Membrane distillation composite material is made, detects composite material polyvinylidene fluoride microporous film according to 1 method of embodiment and polyimides is micro-
The interface of pore membrane, the hole of the connection at interface are 3 D stereo connection, polyvinylidene fluoride microporous film at interface
Hole and the connected ratio in hole of polyimides microporous barrier reach 82%；Membrane distillation is carried out according to the condition of embodiment 1, this is compound
Material is used for membrane distillation membrane module, hydrophobic porous material layer contacts with raw material hot side, hydrophilic porous material layer and distills out
The contact of liquid cold side, this kind of membrane module have big membrane flux, and membrane flux reaches 141L/m2h。
Embodiment 5
A kind of membrane distillation composite material, is made of hydrophobic porous material layer and hydrophilic porous material layer, wherein described hydrophobic more
Porous materials layer is microporous polypropylene membrane, and porosity 88%, aperture is 3 μm -6 μm, 148 ° of water contact angle；Hydrophilic porous material layer
For microporous polypropylene membrane, impregnated of polyacrylic acid/nanometer titanium dioxide silicon coating, cavity wall surface is coarse knot on the surface of cavity wall
Structure is detected with 4 test method of embodiment, and cavity wall surface roughness Ra value is not less than 23nm, the water of hydrophilic porous material layer surface
Contact angle is 22 °, porosity 82%, and aperture is 1 μm -4 μm, and hole is 3 D stereo connection, which is using same
The microporous polypropylene membrane (overall thickness is 200 μm) of hole 3 D stereo connection is on 60% thickness of one side impregnated of polyacrylic acid/receive
Rice silica hydrophilic coating forms, similar embodiment 2, the hole in hole and hydrophobic porous material layer at interface and hydrophilic porous
The equal 3 D stereo in the hole of material layer is connected to, the connected ratio in the hole of hydrophobic porous material layer and hydrophilic porous material layer at interface
Reach 90% according to the detection method detection of embodiment 1.Membrane distillation is carried out according to the condition of embodiment 1, which is used for
Membrane distillation membrane module, hydrophobic porous material layer are contacted with raw material hot side, hydrophilic porous material layer and the liquid cold side distilled out
Contact, this kind of membrane module have big membrane flux, and membrane flux reaches 127L/m2h。
Embodiment 6
A kind of membrane distillation composite material, is made of hydrophobic porous material layer and hydrophilic porous material layer, the hydrophobic porous material
The bed of material is polyvinylidene fluoride microporous film, will referring to the method preparation in CN106669458A " a kind of polytetrafluoroethylfiber fiber film "
Raw material polytetrafluoroethylene (PTFE) is changed to Kynoar, and polyvinylidene fluoride microporous film is multilevel hole material, overall porosity 85%, and first
Grade hole aperture is 0.9 μm -2 μm, and there are also the second hole of 10nm-15nm in the cavity wall in first order hole, holes at different levels are respectively mutually interconnected
It is logical and with other grade of Kong Liantong；153 ° of its water contact angle, film thickness are 70 μm；Hydrophilic porous material layer is polyimides micropore
Film, referring to method preparation in embodiment 1,38 ° of water contact angle, porosity 85%, hole is that uniformly, aperture is 2 μm -4 μm, hole
It is that 3 D stereo is connected to, film thickness is 110 μm；It is as bonding agent that hydrophobic porous material layer is poly- inclined by HR-5198 glue
Membrane distillation composite material is made in fluoride microporous film and the bonding of hydrophilic porous material strata acid imide microporous barrier, according to embodiment
1 method detects the interface of composite material polyvinylidene fluoride microporous film and polyimides microporous barrier, the connection at interface
Hole is 3 D stereo connection, the connected ratio in the hole in the hole and polyimides microporous barrier of polyvinylidene fluoride microporous film at interface
Reach 78%.Membrane distillation is carried out according to the condition of embodiment 1, which is used for membrane distillation membrane module, hydrophobic porous material
The bed of material is contacted with raw material hot side, and hydrophilic porous material layer is contacted with the liquid cold side distilled out, this kind of membrane module has big film
Flux, membrane flux reach 145L/m2h。
Embodiment 7
A kind of membrane distillation composite material, is made of hydrophobic porous material layer and hydrophilic porous material layer, the hydrophobic porous material
The bed of material is polyvinylidene fluoride microporous film, same as Example 3；Hydrophilic porous material layer is polyimides microporous barrier, reference
Method preparation in CN106669458A " a kind of polytetrafluoroethylfiber fiber film ", is changed to polyimides for raw material polytetrafluoroethylene (PTFE),
Polyimides microporous barrier is multilevel hole material, and overall porosity 82%, first order hole aperture is 2 μm -4 μm, the cavity wall in first order hole
It is upper there are also the second hole of 10nm-15nm, holes at different levels be respectively interconnected and with other grade of Kong Liantong；17 ° of water contact angle, film thickness
Degree is 120 μm；By HR-5198 glue as bonding agent by hydrophobic porous material layer polyvinylidene fluoride microporous film and hydrophilic porous
Membrane distillation composite material is made in the bonding of material layer polyimides microporous barrier, poly- inclined according to 1 method of embodiment detection composite material
The interface of fluoride microporous film and polyimides microporous barrier, the hole of the connection at interface are 3 D stereo connections,
The connected ratio in the hole of polyvinylidene fluoride microporous film and the hole of polyimides microporous barrier reaches 81% at interface.According to embodiment 1
Condition carries out membrane distillation, which is used for membrane distillation membrane module, and hydrophobic porous material layer is contacted with raw material hot side, parent
Water porous material layer is contacted with the liquid cold side distilled out, this kind of membrane module has big membrane flux, and membrane flux reaches 143L/
m2h。
Embodiment 8
A kind of membrane distillation composite material, is made of hydrophobic porous material layer and hydrophilic porous material layer, the hydrophobic porous material
The bed of material is microporous teflon membran, and preparation method is: according to the ratio that mass fraction is 4 wt% by 3 grams of super high molecular weights
Polyethylene glycol oxide powder is dissolved in 40 DEG C of deionized water, mechanical stirring 3h, and polyethylene oxide solutions are made, are cooled to room
The ptfe emulsion of 62 wt% containing 97 grams is added in polyethylene oxide solutions by temperature, and mechanical stirring 1h forms uniform
Spinning solution, then using steel wire (90 mesh) as supporter, with the spinning solution electrostatic spinning, wherein voltage, collect distance and
Flow velocity is respectively 10 kV, 20 cm and 0.002 mm/s, and the tunica fibrosa of collection is placed on vacuum drying oven, 70 DEG C of baking 6h, then
Carry out 380 DEG C of heat treatment 10min in high temperature furnace, obtain microporous teflon membran, porosity 87%, hole be uniformly,
Aperture is 0.7 μm -2 μm, and hole is that 3 D stereo is connected to, 155 ° of water contact angle；Hydrophilic porous material layer is in 60% thickness of one side
Above-mentioned microporous teflon membran (overall thickness be 190 μm) cavity wall surface with CN1284833C " before being with butyl titanate
Method provided by the preparation method of the ultra hydrophilic coat of titanium dioxide of drive body " prepares TiO2Coating becomes hydrophilic porous material
Layer, the water contact angle of hydrophilic porous material layer surface are 4.8 °, porosity 83%, and hole is that uniformly, aperture is 0.4 μm of -0.9 μ
M, hole are 3 D stereo connections, and the hole of the connection at interface is 3 D stereo connection, hydrophobic porous at interface
The connected ratio in the hole of material layer and hydrophilic porous material layer reaches 92% according to the detection method detection of embodiment 1, the hydrophobic porous
Material layer is integrated composite material with the composite material that hydrophilic porous material layer is constituted, and carries out film according to the condition of embodiment 1
Distillation, is used for membrane distillation membrane module for the composite material, hydrophobic porous material layer is contacted with raw material hot side, hydrophilic porous material
Layer is contacted with the liquid cold side distilled out, this kind of membrane module has big membrane flux, and membrane flux reaches 165L/m2H, through testing,
The service phase of the composite material has reached 35 months.
Embodiment 9
The embodiment similar embodiment 7, difference are the cavity wall in the hole that hydrophobic porous material layer is microporous teflon membran
Surface is coarse structure, and cavity wall surface roughness Ra value is 65nm, and cavity wall surface is full of particle, particle and particles stick, is dredged
The contact angle of water porous material layer surface and water is 172 °, using CN104906968A " a kind of polytetrafluoroethylene film and its preparation
Method preparation in method ", the cavity wall surface Ra value of hydrophilic porous material layer are 32nm, hydrophilic porous material layer surface and water
Contact angle is 2.4 °.Membrane distillation is carried out according to the condition of embodiment 1, which is used for membrane distillation membrane module, it is hydrophobic
Porous material layer is contacted with raw material hot side, and hydrophilic porous material layer is contacted with the liquid cold side distilled out, this kind of membrane module has
Big membrane flux, membrane flux reach 178L/m2H, through testing, the service phase of the composite material has reached 38 months.
Claims (12)
1. a kind of membrane distillation composite material, is made of hydrophobic porous material layer and hydrophilic porous material layer, it is characterised in that: institute
State the hole of hydrophobic porous material layer, the hole of the hydrophilic porous material layer and the hydrophobic porous material layer and described hydrophilic more
Kong Jun of the Porous materials layer at interface is 3 D stereo connection.
2. membrane distillation composite material as described in claim 1, it is characterised in that: the hole connected ratio at the interface is
70% or more.
3. membrane distillation composite material as claimed in claim 1 or 2, it is characterised in that: the hydrophobic porous material layer and institute
Hydrophilic porous material layer is stated as integrated composite material.
4. the membrane distillation composite material as described in claims 1 or 2 or 3, it is characterised in that: the hydrophobic porous material layer table
The water contact angle in face is 110 ° or more；Or/and the water contact angle of the hydrophilic porous material layer surface is 30 ° or less.
5. membrane distillation composite material as claimed in claim 4, it is characterised in that: the water on the hydrophobic porous material layer surface
Contact angle is 150 ° or more；Or/and the water contact angle of the hydrophilic porous material layer surface is 5 ° or less.
6. membrane distillation composite material according to any one of claims 1 to 5, it is characterised in that: described hydrophobic more
The roughness Ra value on the cavity wall surface in the hole of Porous materials layer is not less than 20nm；Or/and the cavity wall in hydrophilic porous material layer hole
Surface Ra value is not less than 20nm.
7. the membrane distillation composite material as described in claim 1 to 6 any claim, it is characterised in that: described hydrophobic more
Porous materials layer is multilevel hole material or/and hydrophilic porous material layer hole is multilevel hole material, the multilevel hole material according to
The size in hole is classified, junior hole in the cavity wall in higher level hole, holes at different levels respectively be interconnected and with other grade of Kong Liantong.
8. the membrane distillation composite material as described in claim 1 to 7 any claim, it is characterised in that: described hydrophobic more
Porous materials layer is microporous teflon membran.
9. the membrane distillation composite material as described in claim 1 to 8 any claim, it is characterised in that: described hydrophilic more
There is TiO2 coating on the cavity wall surface in Porous materials layer hole.
10. the membrane distillation composite material as described in 1,2,4 to 7 any claim of claim, it is characterised in that: described multiple
Condensation material is integrated composite material, and material uses microporous teflon membran material, the cavity wall surface roughness Ra value in hole
Not less than 20nm, the cavity wall surface preparation TiO2 coating in the hole of the segment thickness of the microporous teflon membran material is formed
The cavity wall surface roughness Ra value of hydrophilic porous material layer, hydrophilic porous material layer hole is not less than 20nm.
11. using the membrane module of the membrane distillation composite material as described in claim 1-10 any claim.
12. membrane module as claimed in claim 11, it is characterised in that: the hydrophobic porous material layer and film group of the composite material
The raw material hot side of part contacts, and hydrophilic porous material layer is contacted with the liquid cold side that membrane module distills out.
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|---|---|---|---|
| CN201710878698.0A CN109550401A (en) | 2017-09-26 | 2017-09-26 | A kind of membrane distillation composite material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710878698.0A CN109550401A (en) | 2017-09-26 | 2017-09-26 | A kind of membrane distillation composite material |
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Family
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| CN201710878698.0A Pending CN109550401A (en) | 2017-09-26 | 2017-09-26 | A kind of membrane distillation composite material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112108007A (en) * | 2020-09-24 | 2020-12-22 | 中原工学院 | Polytetrafluoroethylene nanofiber filtering material and processing method thereof |
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| US4419242A (en) * | 1980-02-04 | 1983-12-06 | International Power Technology, Inc. | Composite membrane for a membrane distillation system |
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| CN103464007A (en) * | 2012-06-05 | 2013-12-25 | 通用电气公司 | Asymmetric ePTFE membrane |
| US9346021B2 (en) * | 2008-12-02 | 2016-05-24 | Membrane Distillation Desalination Ltd., Co. | Composite membranes for membrane distillation and related methods of manufacture |
| CN106669457A (en) * | 2015-11-11 | 2017-05-17 | 重庆润泽医药有限公司 | Polytetrafluoroethylene ultrafine fiber membrane |
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2017
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4419242A (en) * | 1980-02-04 | 1983-12-06 | International Power Technology, Inc. | Composite membrane for a membrane distillation system |
| CN1284833C (en) * | 2005-04-07 | 2006-11-15 | 上海交通大学 | Method for preparing ultra hydrophilic coat of titanium dioxide by using tetrabutyl titanatc as precursor |
| US9346021B2 (en) * | 2008-12-02 | 2016-05-24 | Membrane Distillation Desalination Ltd., Co. | Composite membranes for membrane distillation and related methods of manufacture |
| CN103464007A (en) * | 2012-06-05 | 2013-12-25 | 通用电气公司 | Asymmetric ePTFE membrane |
| CN106669457A (en) * | 2015-11-11 | 2017-05-17 | 重庆润泽医药有限公司 | Polytetrafluoroethylene ultrafine fiber membrane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112108007A (en) * | 2020-09-24 | 2020-12-22 | 中原工学院 | Polytetrafluoroethylene nanofiber filtering material and processing method thereof |
| CN112108007B (en) * | 2020-09-24 | 2022-07-26 | 中原工学院 | Polytetrafluoroethylene nanofiber filtering material and processing method thereof |
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