CN1481928A - hydrophilic organic-inorganic compounded pervaporation separating film and method for making the same - Google Patents
hydrophilic organic-inorganic compounded pervaporation separating film and method for making the same Download PDFInfo
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- CN1481928A CN1481928A CNA031419224A CN03141922A CN1481928A CN 1481928 A CN1481928 A CN 1481928A CN A031419224 A CNA031419224 A CN A031419224A CN 03141922 A CN03141922 A CN 03141922A CN 1481928 A CN1481928 A CN 1481928A
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Abstract
The present invention is one kind of composite separating film with inorganic porous film as carrier and hydrophilic polymer as active layer. The inorganic film carrier selected has proper pore size and porosity and has high activity reaction radical on the surface. By means of free radical reaction, hydrophilic olefin monomer is grafted in chemical bonding mode onto the surface of inorganic porous film carrier to form a superthin separating layer with high selectivity. The composite organic-inorganic separating film has high stability, high separating performance and wide application range. It may be used in dewatering, purifying and concentration of most organic solvent except strong alkali organic solvent.
Description
Technical field
The invention belongs to the diffusion barrier technical field, being specifically related to a kind of is carrier with the microporous inorganic film, and hydrophilic polymer is efficient hydrophile organic-abio compound permeation evaporating and separating membrane of active layer and preparation method thereof.
Background technology
The pervaporation membrane separation technique is specifically designed to the separation of liquid mixture, is specially adapted to separating of the azeotropic mixture liquid mixture close with boiling point, has characteristics such as efficient, energy-conservation, pollution-free, is a kind of isolation technics that development potentiality is arranged very much.But up to now, this technology is in industrial application and unsatisfactory.Tracing it to its cause, mainly is that separation costs is higher, thereby lacks competitiveness because the separating property of film is lower.
The separating effect of pervaporation has confidential relation with the character of diffusion barrier.Concerning the hydrophily diffusion barrier, its basic demand is:
Under operating condition, film has sufficiently high mechanical strength and anti-solvent stability in processed aqueous organopolysiloxane;
Film has high as far as possible selectivity to component to be removed in the mixture (water), and promptly the content of water in the penetrating fluid that separated film removes should be high more good more;
Film has permeability as well as possible to water, and promptly the amount of the penetrating fluid that removes through diffusion barrier in the unit interval wants big, with guarantor unit's membrane area higher production capacity is arranged.
At present, commercial hydrophilic penetrating and evaporating film mainly contains two kinds, and a kind of is to be the organic film of homogeneous that raw material is made with the hydrophily high polymer, and a kind of is to be the inoranic membrane that raw material is made with the A type molecular sieve.
Commercial hydrophilic polymer film such as composite membrane of polyvinyl alcohol, though very excellent separation selectivity is arranged, permeability of the membrane is poor, the water separation capability of film is hundreds of g/m only
2H.Therefore, equipment investment expense and production cost are all very high, and becoming influences the main cause of pervaporation isolation technics in industrial extensive use.And the film made from the hydrophily high polymer has significant swelling in the stronger solution of polarity, and film strength, separating property and service life all significantly decrease, and the application of film is very limited.
With the hydrophilic inorganic film that A type molecular sieve is made, have that selectivity is good, good penetrability and a high advantage of stability, be a kind of osmotic evaporating and separating membrane of high comprehensive performance.But, the preparation process complexity of this film, the specification requirement height, yield rate is low, and by contrast, the preparation cost height of film is difficult to promote equally.And the kind of molecular screen membrane is more single, and adaptability is also relatively poor.
Summary of the invention
The object of the present invention is to provide a kind of separation selectivity and good penetrability, stability height, hydrophilic osmotic evaporating and separating membrane that cost of manufacture is low and preparation method thereof.
The hydrophilic osmotic evaporating and separating membrane that the present invention proposes, be a kind of organic and inorganic composite membrane, it is a base material with the microporous inorganic film, passes through the chemical graft method on it, be formed with the hydrophilic polymer active layer that connects with chemical chain, this polymer active layer thickness is a nanoscale.This organic and inorganic hydrophilic composite film is used for the dehydration of organic solvent, and very high separation selectivity is not only arranged, and good flux and stability are arranged.
Be applicable to that but microporous inorganic film base material of the present invention is the inorganic porous material that a large amount of reaction active groups are contained on a kind of surface, its matrix must have good heat endurance and chemical stability in separated medium.Any composition that constitutes this inorganic material film can be with processed solution mixture generation chemical reaction and dissolution, in use can destroyed or stripping.Among the present invention, the composition that is used as the microporous barrier base material mainly contains α or gama-alumina (Al
2O
3), zirconia ZrO
2, silica SiO
2, titanium dioxide TiO
2, silicate, cordierite and based on molecular screen membrane of aluminium oxide or silica etc.
Among the present invention, be that surfacing, micropore size are little, void content is high to the basic demand of microporous inorganic film base material.Usually, the aperture of film should be less than 0.5 micron, and preferably less than 0.1 micron, void content should be higher than 20%, preferably is higher than 40%.The thickness of film should be less than 2 centimetres, preferably less than 0.5 centimetre.
Among the present invention, the microporous inorganic film can be a homogeneous membrane, also can be composite membrane.Homogeneous membrane is used with a kind of inorganic material and is made, and has the microcellular structure of symmetry.Composite membrane is that compound again one deck microporous layers is made on the micropore homogeneous membrane, has asymmetric microcellular structure.By contrast, composite membrane is more suitable for the present invention.On the one hand, composite membrane reduces greatly to the material of basement membrane and the requirement of the pore size and the uniformity, thereby the micropore size of most commercial can reduce preparation cost as the basement membrane of composite membrane less than 1 micron inoranic membrane greatly.On the other hand, the structure of compound inorganic microporous layers is more even on the film, is more suitable for and forms and can regulate in the larger context.Composite microporous layer can be used method preparations such as sol-gel process, vapour deposition process or infusion process.The thickness of microporous layers usually should be less than 50 microns, preferably less than 10 microns.The aperture of microporous layers and porosity should reach the requirement of homogeneous membrane, and promptly the aperture of film should be less than 0.5 micron, and preferably less than 0.1 micron, void content should be higher than 20%, preferably is higher than 40%.The thickness of film should be less than 2 centimetres, preferably less than 0.5 centimetre.
Among the present invention, the microporous inorganic film can have different shapes, as flat sheet membrane or tubular membrane.
Among the present invention, the surface of microporous inorganic film is all contained and is had higher chemically active group, as hydroxyl or amido etc.These have the group of reactivity, can be that inoranic membrane component itself has, also can be by the oxidation on film surface, hydrolysis or other chemical reactions introduced.
The preparation method of above-mentioned hydrophilic inorganic-organic compound osmotic evaporating and separating membrane that the present invention proposes is as follows: with above-mentioned microporous inorganic film is base material, adopt the chemical graft method on its surface, formation with chemical bond linkage, have very high score from the hydrophilic graft polymer layer of activity, thereby obtain composite membrane.
Among the present invention, the monomer that is used for graft reaction mainly is some olefinic monomers that contain hydrophilic group.As vinyl pyrrolidone, vinylpyridine, acrylic acid, methacrylic acid, acrylamide etc., can be as the raw material of preparation hydrophily organic and inorganic composite membrane organic layer.
The graft polymerization reaction of hydrophilic monomer carries out in solvent, preferably is solvent with water.Monomer concentration generally in 1%～80% (weight ratio, down together), is preferably 2%～50%.Initator as graft polymerization reaction is water-soluble radical reaction initator commonly used, for example persulfate, ammonium ceric nitrate, persulfate-sulfite oxidation reduction system.The temperature of graft reaction is decided on used initator, is generally-50 ℃～100 ℃, best 25 ℃～90 ℃.Reaction time was generally 0.5～10 hour.
In order to improve reaction efficiency and the percent grafting of polymer monomer, can carry out preliminary treatment earlier to microporous inorganic film surface on microporous inorganic film surface.The used reagent of preliminary treatment can with the active group effect on inoranic membrane surface, and can therefore introduce and can further carry out the required active group of graft reaction.The used reagent of preliminary treatment contains unsaturated bond usually simultaneously and can carry out the reactive activity group with the hydroxyl or the amido on inoranic membrane surface, as alkoxyl, epoxy radicals, anhydride group etc.Double bond containing organo silane coupling agent, unsaturated acid anhydride (as maleic anhydride) etc. can be used as inoranic membrane surface-treated reagent.Wherein double bond containing organo silane coupling agent is specially adapted to the graft polymerization reaction of hydrophily vinyl monomer among the present invention.
Among the present invention, the surface preparation of microporous inorganic film is normally carried out in high boiling organic solvent, as toluene, dimethylbenzene, ethyl acetate etc.Being used for pretreated chemical reagent should be greater than 1% in the concentration of solution, best more than 10%.Treatment temperature is preferably in more than 50 ℃ more than 25 ℃.Processing time is more than 0.5 hour, and is best more than 2 hours.
The organic and inorganic composite membrane that the present invention makes is a kind of hydrophilic osmotic evaporating and separating membrane of function admirable, is applicable to dehydration, the purifying and concentrated of the most of organic solvents except that the strong basicity organic solvent.The solvent that is suitable for has alcohols: as methyl alcohol, ethanol, isopropyl alcohol, butanols etc., and ethers: as ether, oxolane etc., ketone: as butanone, cyclohexanone etc., acids: as acetate, acrylic acid etc.; The ester class: as ethyl acetate, acrylate and methacrylate etc., other solvents: as pyridine, acrylonitrile etc.
The dewatering of the diffusion barrier that the present invention makes is measured in small-sized pervaporation pond.The volume of osmotic cell is 100ml, and diameter is 5cm, is made by stainless steel material.Magnetic stirrer, heater and thermostat are housed in the osmotic cell.The outlet of osmotic cell links to each other with vavuum pump with cold-trap.In osmotic cell, add 50ml solution during operation.The vacuum of system is 150Pa, and probe temperature is 30 ℃.Penetrating fluid is collected with cold-trap, regularly switches.With gas chromatography determination solution (c
0) and penetrating fluid (c ') in water content; Measure the weight (W) of penetrating fluid with weight method, and calculate penetrating fluid flux J, be i.e. the weight of the penetrating fluid that removes of the film that is per hour amassed by unit plane.Computing formula is as follows:
(unit: kg/h*m
2)
Wherein, W is the weight of the penetrating fluid collected in the cold-trap, and A is a membrane area, and t is the time interval of sampling.
The weight percentage c ' of the selectivity water of diffusion barrier in penetrating fluid (%) represents.
Compare with present commercial organic polymer films or inoranic membrane, main feature of the present invention is,
1, the mechanical strength of film and chemical stability height.The organic and inorganic composite membrane of the present invention's preparation is grafted on hydrophily organic monomer molecule on the microporous inorganic film by chemical bond, and the polymer active layer of formation also passes through crosslinking Treatment.Therefore organic active layer is stable very good, can not dissolve in boiling water and organic acid.
2, the selectivity of film and permeability are all very good.Active layer of the present invention is to prepare by the chemical graft method on microporous inorganic film surface.Good hydrophilic property, the thickness of active layer little (only a few nanometer).Chemical bonding structure between the monomer of high-hydrophilic, ultra-thin separating layer and separating layer and inoranic membrane basement membrane makes the film that makes that good selectivity and very high permeation flux be arranged.It is a kind of osmotic evaporating and separating membrane of excellent performance.
3, the adaptability of film is good.The present invention can change the separating property of active separating layer by changing the character and the structure of chemical graft monomer.Therefore, be applicable to the separation of ORGANIC SOLVENT MIXTURES of different nature.
4, the preparation method of film is simple, cost of manufacture is cheap.The present invention is not high to the structural requirement of microporous inorganic basement membrane, therefore, and low cost of manufacture.
The specific embodiment
Embodiment 1:
Present embodiment uses the micropore ceramics film of being produced by Nanjing University of Technology, and its main material is Al
2O
3The about 3mm of the thickness of microporous barrier, area are 1cm
2The aperture of this microporous barrier is about 50nm, and the pure water infiltration capacity under 150Pa vacuum is 540L/m
2H.
This film is placed the three-neck flask that spherical condensation tube is housed, add 20g toluene and 2g γ-methacryloxypropyl three TMOSs then.Added hot reflux 5 hours.After the cooling, microporous barrier is taken out, use toluene, ethanol, water that the surface washing of film is clean successively, to remove unreacted silane.
Micropore ceramics film through silane treatment places the 150mL there-necked flask, adds 8% acrylamide aqueous solution 50mL, potassium peroxydisulfate 0.06g.Under nitrogen protection, 80 ℃ were reacted 1 hour.Reaction finishes back hot deionized water washing three times.Place 120 ℃ of baking ovens to dry then.
Embodiment 2:
Present embodiment uses synthetic voluntarily zeolite composite membrane.This film is that the analcime microporous layers of compound one deck 10 μ m on cordierite carrier is prepared from.The thickness of microporous barrier is about 3mm, and area is 1cm
2The aperture of this microporous barrier is less than 10nm, and the pure water infiltration capacity under 150Pa vacuum is about 350L/m
2H.
This film is placed the three-neck flask that spherical condensation tube is housed, add 20g toluene and 2g γ-methacryloxypropyl three TMOSs then.Added hot reflux 5 hours.After the cooling, microporous barrier is taken out, use toluene, ethanol, water that the surface washing of film is clean successively, to remove unreacted silane.
Micro-pore zeolite composite membrane through silane treatment places the 150mL there-necked flask, adds 8% acrylamide aqueous solution 50mL, potassium peroxydisulfate 0.06g.Under nitrogen protection, 80 ℃ were reacted 1 hour.Reaction finishes back hot deionized water washing three times.Place 120 ℃ of baking ovens to dry then.
Embodiment 3:
Present embodiment uses the cordierite film of being produced by non-metal chemical mechinery works, Yixing.The average pore size of film is 2 μ m.The thickness of microporous barrier is 3mm, and area is 1cm
2With the surface of vapour deposition process at the cordierite film, coated one layer thickness is the silica gel microporous barrier of 20 μ m～30 μ m.The pure water infiltration capacity of composite membrane under 150Pa vacuum is 380L/m
2H.
This film is placed the three-neck flask that spherical condensation tube is housed, add 20g toluene and 2g γ-methacryloxypropyl three TMOSs then.Added hot reflux 5 hours.After the cooling, microporous barrier is taken out, use toluene, ethanol, water that the surface washing of film is clean successively, to remove unreacted silane.
Micropore cordierite composite membrane through silane treatment places the 150mL there-necked flask, adds 10% acrylic acid aqueous solution 50mL, potassium peroxydisulfate 0.06g.Under nitrogen protection, 80 ℃ were reacted 1 hour.Reaction finishes back hot deionized water washing three times.Then, place 120 ℃ of baking ovens to dry.
Embodiment 4:
To place osmotic cell, tight seal with micropore ceramics/polyacrylamide composite membrane that embodiment 1 makes.In osmotic cell, add 50mL concentration then and be 95% ethanol water.At 30 ℃, separate under the 150Pa vacuum.Collect penetrating fluid with liquid nitrogen cold trap.Experimental result is as follows: water content in the penetrating fluid:＞90%, and penetrating fluid flux: 2.5kg/m
2H.
Embodiment 5:
To place osmotic cell, tight seal with molecular sieve/polyacrylamide composite membrane that embodiment 2 makes.In osmotic cell, add 50mL concentration then and be 95% ethanol water.At 30 ℃, separate under the 150Pa vacuum.Collect penetrating fluid with liquid nitrogen cold trap.Experimental result is as follows: water content in the penetrating fluid:＞92%, and penetrating fluid flux: 2kg/m
2H.
Embodiment 6:
To place osmotic cell, tight seal with silica/polyacrylic acid composite membrane that embodiment 3 makes.In osmotic cell, add 50mL concentration then and be 95% ethanol water.At 30 ℃, separate under the 150Pa vacuum.Collect penetrating fluid with liquid nitrogen cold trap.Experimental result is as follows: water content in the penetrating fluid:＞99.5%, and penetrating fluid flux: 1.8kg/m
2H.
Embodiment 7:
To place osmotic cell, tight seal with silica/polyacrylic acid composite membrane that embodiment 3 makes.In osmotic cell, add 50mL concentration then and be 99% methanol aqueous solution.At 30 ℃, separate under the 150Pa vacuum.Collect penetrating fluid with liquid nitrogen cold trap.Experimental result is as follows: water content in the penetrating fluid:＞99.5%, and penetrating fluid flux: 1kg/m
2H.
Embodiment 8:
To place osmotic cell, tight seal with silica/polyacrylic acid composite membrane that embodiment 3 makes.In osmotic cell, add 50mL concentration then and be 90% isopropanol water solution.At 30 ℃, separate under the 150Pa vacuum.Collect penetrating fluid with liquid nitrogen cold trap.Experimental result is as follows: water content in the penetrating fluid:＞99.5%, and penetrating fluid flux: 1.1kg/m
2H.
Claims (12)
1, a kind of hydrophile organic-abio compound permeation evaporating and separating membrane is characterized in that it is a base material with the microporous inorganic film, by the chemical graft method, is formed with the hydrophilic polymer active layer that connects with chemical chain on it; The aperture of this microporous inorganic film is less than 0.5 micron, and porosity is higher than 20%, and thickness is less than 2 centimetres, and this polymer active layer thickness is a nanoscale.
2, diffusion barrier according to claim 1, it is characterized in that but the microporous inorganic film base material is the inorganic porous material that reactivity is contained on a kind of surface, comprise α or gama-alumina, zirconia, silica, titanium dioxide, silicate, cordierite and based on the molecular screen membrane of aluminium oxide or silica.
3, diffusion barrier according to claim 1 is characterized in that the microporous inorganic film base material is a homogeneous membrane, or is compounded with the composite membrane of a microporous layers that on homogeneous membrane the thickness of this microporous layers is less than 50 microns.
4, diffusion barrier according to claim 1, the reaction monomers that it is characterized in that forming the polymer active layer is the olefinic monomer that contains hydrophilic group.
5, diffusion barrier according to claim 1, the aperture that it is characterized in that the microporous inorganic film base material is less than 0.1 micron, and porosity is higher than 40%, and thickness is less than 0.5 centimetre.
6, a kind of preparation method as one of claim 1-5 described diffusion barrier, it is characterized in that concrete steps are as follows: with above-mentioned microporous inorganic film is base material, adopt the chemical graft method on its surface, formation is with hydrophilic graft polymer layer chemical bond linkage, that have isolating active, thereby obtains required composite membrane; The monomer that is used for graft reaction is the olefinic monomer that contains hydrophilic group, graft polymerization reaction carries out in solvent, and monomer weight concentration is 1%-80%, and initator is water-soluble radical reaction initator commonly used, reaction temperature is-50 ℃～100 ℃, and the reaction time is 0.5～10 hour.
7, preparation method according to claim 6 is characterized in that the initator as graft reaction is persulfate, ammonium ceric nitrate, persulfate-sulfite oxidation reduction system.
8, preparation method according to claim 6, the weight concentration that it is characterized in that reaction monomers is 2-50%, reaction temperature is 25-90 ℃.
9, preparation method according to claim 6 is characterized in that preliminary treatment is carried out on microporous inorganic film surface earlier, and the used reagent of preliminary treatment is to contain unsaturated bond simultaneously and can carry out the reactive activity gene with the hydroxyl or the amido on inoranic membrane surface.
10, preparation method according to claim 9 is characterized in that the reagent of the organic film surface preparation of micropore adopts organo silane coupling agent, the unsaturated acid anhydride that contains two keys.
11, preparation method according to claim 9, it is characterized in that the organic film surface preparation of micropore carries out in high boiling organic solvent, these organic solvents are toluene, dimethylbenzene, ethyl acetate, its concentration in solution should be greater than 1%, treatment temperature is more than 25 ℃, and the processing time is more than 0.5 hour.
12, preparation method according to claim 11 is characterized in that the weight concentration of organic solvent in solution is more than 10%, and treatment temperature is more than 50 ℃, and the processing time is more than 2 hours.
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| CN103028331A (en) * | 2013-01-03 | 2013-04-10 | 盐城工学院 | Preparation method of hydroxyethyl cellulose-silicon dioxide pervaporation hybrid membrane |
| CN103861466A (en) * | 2012-12-17 | 2014-06-18 | 中国科学院大连化学物理研究所 | Preparation method of hydrophilic separation membrane |
| CN103877834A (en) * | 2012-12-20 | 2014-06-25 | 财团法人工业技术研究院 | Dehumidification System |
| CN104959043A (en) * | 2015-06-25 | 2015-10-07 | 北京天恒盛通科技发展有限公司 | Preparation method and application of organic liquid separation net film based on wettability differences |
| CN105903360A (en) * | 2016-06-17 | 2016-08-31 | 安庆市天虹新型材料科技有限公司 | Antibacterial stain-resistant polyvinylidene fluoride composite film |
| CN104722208B (en) * | 2013-12-24 | 2017-09-15 | Oci有限公司 | Utilize the pervaporation system of glycol ether dehydration organic/inorganic compound film |
| CN107519766A (en) * | 2017-08-17 | 2017-12-29 | 河南科技大学 | A kind of polymer matrix Ceramic excessive filtration composite coating material and preparation method thereof, application |
| CN111266022A (en) * | 2020-01-17 | 2020-06-12 | 吉林大学 | Preparation method of flexible titanium dioxide nanowire film |
| CN111629816A (en) * | 2017-11-09 | 2020-09-04 | 加州大学评议会 | Asymmetric composite membranes and uses thereof |
| WO2021248900A1 (en) * | 2020-06-12 | 2021-12-16 | 三达膜科技（厦门）有限公司 | High-flux modified titanium oxide composite ultrafiltration membrane and application thereof |
| US11541153B2 (en) | 2017-12-01 | 2023-01-03 | The Regents Of The University Of California | Biofouling resistant coatings and methods of making and using the same |
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2003
- 2003-07-29 CN CNA031419224A patent/CN1481928A/en active Pending
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| CN103861466B (en) * | 2012-12-17 | 2016-06-01 | 中国科学院大连化学物理研究所 | The preparation method of a kind of wetting ability separatory membrane |
| CN103861466A (en) * | 2012-12-17 | 2014-06-18 | 中国科学院大连化学物理研究所 | Preparation method of hydrophilic separation membrane |
| US9815020B2 (en) | 2012-12-20 | 2017-11-14 | Industrial Technology Reserach Institute | Dehumidification system |
| CN103877834A (en) * | 2012-12-20 | 2014-06-25 | 财团法人工业技术研究院 | Dehumidification System |
| CN103877834B (en) * | 2012-12-20 | 2016-08-10 | 财团法人工业技术研究院 | Dehumidification system |
| CN103028331A (en) * | 2013-01-03 | 2013-04-10 | 盐城工学院 | Preparation method of hydroxyethyl cellulose-silicon dioxide pervaporation hybrid membrane |
| CN104722208B (en) * | 2013-12-24 | 2017-09-15 | Oci有限公司 | Utilize the pervaporation system of glycol ether dehydration organic/inorganic compound film |
| CN104959043B (en) * | 2015-06-25 | 2018-07-03 | 北京天恒盛通科技发展有限公司 | Organic liquid separate mesh membrane preparation method and purposes based on infiltration sex differernce |
| CN104959043A (en) * | 2015-06-25 | 2015-10-07 | 北京天恒盛通科技发展有限公司 | Preparation method and application of organic liquid separation net film based on wettability differences |
| CN105903360A (en) * | 2016-06-17 | 2016-08-31 | 安庆市天虹新型材料科技有限公司 | Antibacterial stain-resistant polyvinylidene fluoride composite film |
| CN107519766A (en) * | 2017-08-17 | 2017-12-29 | 河南科技大学 | A kind of polymer matrix Ceramic excessive filtration composite coating material and preparation method thereof, application |
| CN111629816A (en) * | 2017-11-09 | 2020-09-04 | 加州大学评议会 | Asymmetric composite membranes and uses thereof |
| US11541153B2 (en) | 2017-12-01 | 2023-01-03 | The Regents Of The University Of California | Biofouling resistant coatings and methods of making and using the same |
| US11807701B2 (en) | 2019-06-05 | 2023-11-07 | The Regents Of The University Of California | Biofouling resistant coatings and methods of making and using the same |
| CN111266022A (en) * | 2020-01-17 | 2020-06-12 | 吉林大学 | Preparation method of flexible titanium dioxide nanowire film |
| WO2021248900A1 (en) * | 2020-06-12 | 2021-12-16 | 三达膜科技（厦门）有限公司 | High-flux modified titanium oxide composite ultrafiltration membrane and application thereof |
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