CN101574629B - Method for preparing polyvinyl alcohol/polyether sulfone pervaporation composite membrane - Google Patents
Method for preparing polyvinyl alcohol/polyether sulfone pervaporation composite membrane Download PDFInfo
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- CN101574629B CN101574629B CN2008101062300A CN200810106230A CN101574629B CN 101574629 B CN101574629 B CN 101574629B CN 2008101062300 A CN2008101062300 A CN 2008101062300A CN 200810106230 A CN200810106230 A CN 200810106230A CN 101574629 B CN101574629 B CN 101574629B
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- polyvinyl alcohol
- polyether sulfone
- pva
- separating layer
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Abstract
The invention relates to a method for preparing a polyvinyl alcohol/polyether sulfone (PVA/PES) pervaporation composite membrane. The method comprises the following steps: placing and soaking PES in 0.05 to 5 weight percent borax aqueous solution for 6 to 12 hours; dissolving PVA dissolved in deionized water at a temperature of between 80 and 95 DEG C to prepare casting solution of which the mass concentration of the PVA is 1 to 7 weight percent; cooling the casting solution to between 20 and 25 DEG C; placing the treated PES in the PVA casting solution; preparing a PVA separation layer with the thickness of 1 to 8 microns on PES base membrane and then drying at a temperature of between 20 and 25 DEG C so as to obtain composite membrane; and placing the obtained composite membrane in acetone solution containing glutaraldehyde accounting for 5 to 20 volume percent of the total volume and HCl accounting for 0.1 to 0.15 volume percent of the total volume and treating for 0.5 to 5 hours at a temperature of between 20 and 50 DEG C. The preparation method has the advantages of simple process and easily controlled condition. The membrane is applicable to the separation of water/glycol mixture, and the permeation flux of the composite membrane can be up to 445 g/(m<2>h).
Description
Technical field
The present invention relates to a kind of branch dried up/preparation method of the polyvinyl alcohol/alcohol/polyether sulfone pervaporation composite membrane of organic (water/ethylene glycol) mixture.
Background technology
In order to develop high-throughout pervaporation water permeable membrane, many researchers reduce film thickness by preparing asymmetrical membrane structure.This film is made of the active separating layer and the porose supporting layer of ultra-thin densification, active cortex and supporting layer can be made of different materials, so its every layer material can both be optimized separately, active cortex can be optimized to desirable selection permeability, and supporting layer can reach best intensity and pressure tightness.Thereby can also keep good chemistry and heat endurance when making film after compound have high selectivity and permeation flux.
Usually the supporting layer of composite membrane is the asymmetric milipore filter that makes by phase-inversion technologies, and is wherein common with the supporting layer that polysulfones, polyether sulfone, SPSF, polyacrylonitrile, polyimides and PVDF membrane material are made.The active separating layer material of pervaporation dehydration composite membrane is hydrophilic macromolecular material such as polyvinyl alcohol, shitosan, polyacrylic acid etc.The problem that exists is hydrophilic relatively water permeable membrane material, the milipore filter material hydrophobicity of supporting layer is stronger, cause low interface interaction power is arranged between hydrophilic active separating layer and the hydrophobic supporting layer, cause the hydrophilic active separating layer to be difficult to evenly be coated to support layer surface, and between active separating layer and supporting layer interface, form defective easily, influence the separating property of film.Improve the hydrophilic and caking property of supporting layer thus and come interface interaction power between enhanced activity separating layer and the supporting layer to become the focus of people's research, main method has: (1) is used all has the coupling agent of affinity or surfactant-modified to hydrophilic active separating layer and hydrophobic supporting layer; (2) supporting layer is carried out body or surface hydrophilic modification to improve its surperficial energy.
One of pervaporation dehydration composite membrane key is exactly the structural stability of composite membrane, because hydrophilic active separating layer easy swelling in the aqueous solution.If active separating layer is different with the supporting layer degree of swelling, will produce stress at the interface.After stress surpassed certain critical value, active layer and supporting layer will break away from.Therefore the regulation and control of interface interaction power are keys of preparation penetrating and distilling composite membranes and ultra-thin active separating layer between active separating layer and the supporting layer.
Summary of the invention
The purpose of this invention is to provide a kind of interfacial reaction crosslinking agent that the treated introducing of polyether sulfone supporting layer and active separating layer are had reactivity, increase the interface interaction power between composite membrane supporting layer and the active separating layer, thereby improve the pervaporation performance of polyvinyl alcohol osmotic evaporation film and the preparation method of a kind of polyvinyl alcohol/alcohol/polyether sulfone pervaporation composite membrane of stability.
The preparation method of polyvinyl alcohol/alcohol/polyether sulfone pervaporation composite membrane of the present invention realizes as follows:
(1) supporting layer modification: with molecular cut off is that the polyether sulfone supporting layer of 20000-30000 places the interfacial reaction crosslinking agent borax solution of 0.05-5wt% to soak 6-12 hour, takes out, and dries;
(2) preparation of active separating layer casting solution: the polyvinyl alcohol of the degree of polymerization 1650～2500 is dissolved in the 80-95 ℃ of deionized water, make the casting solution that the polyvinyl alcohol mass concentration is 1-7wt%, be cooled to 20-25 ℃,, standby after the deaeration with screen filtration to remove impurity;
(3) preparation of composite membrane: will place the active separating layer membrane liquid of step (2) preparation through the polyether sulfone supporting layer (PES) that step (1) is handled, making thickness by dip coating on the polyether sulfone basement membrane is the active separating layer of 1-8 μ m polyvinyl alcohol (PVA), is prepared composite membrane after 20-25 ℃ of drying;
(4) the surface-crosslinked processing of the active separating layer of composite membrane: the prepared composite membrane of step (3) placed to contain account for the acetone soln that cumulative volume is 5-20vol% glutaraldehyde (GA) and 0.1-0.15vol%HCl, treatment temperature is 20-50 ℃, processing time is 0.5-5 hour, obtains surface-crosslinked polyvinyl alcohol/alcohol/polyether sulfone pervaporation composite membrane.
The invention has the advantages that: it is simple that this method prepares the composite membrane process, and condition is easily controlled.The pervaporation of the surface-crosslinked polyvinyl alcohol/polyether sulfone composite membrane that makes divides dried up and the ethylene glycol mixture, has higher permeation flux.Existing surface-crosslinked polyvinyl alcohol homogeneous membrane only is 211g/ (m to the permeation flux of water and ethylene glycol mixture
2And the prepared surface-crosslinked polyvinyl alcohol/polyether sulfone composite membrane of the present invention can reach 445g/ (m to the permeation flux of water and ethylene glycol mixture h),
2H).
The specific embodiment
Embodiment 1
The preparation of polyvinyl alcohol/alcohol/polyether sulfone pervaporation composite membrane (film 1)
Take by weighing the 7.5g degree of polymerization and be 1750 polyvinyl alcohol (PVA) and 492.5g deionized water and put into there-necked flask, put into 90 ℃ water bath with thermostatic control and heat, the 900r/min rotating speed stirs dissolving down 1 hour.All reduce to 25 ℃ after the dissolving, remove by filter insoluble matter, standing and defoaming is made mass concentration and is 1.5% the active separating layer casting solution of polyvinyl alcohol.
Molecular cut off is that 25000 poly (ether sulfone) film is that (10cm * 10cm) soaked 2 days in deionized water removes the glycerine in the striping, 20-25 ℃ of drying to supporting layer.Place the 0.1wt% borax solution to soak absorption 12 hours dried poly (ether sulfone) film, take out 20-25 ℃ of drying.PES supporting layer after handling is fixed on the glass plate, uses rubber belt sealing all around, place the active separating layer casting solution reaction of the 1.5wt%PVA for preparing absorption 5min then, take out, 20-25 ℃ of drying 12 hours.After treating active separating layer bone dry, place and contain that to account for cumulative volume be the 15vol% glutaraldehyde and account for the acetone soln that cumulative volume is 0.12vol%HCl, descended crosslinked 3 hours at 40 ℃, crosslinked finishing taken out composite membrane distilled water flushing three times, promptly obtain surface-crosslinked polyvinyl alcohol/polyether sulfone composite membrane (film 1), by the scanning electron microscopic observation of composite membrane section being learnt the active separating layer average thickness of PVA is 1 μ m.It is 20% water and ethylene glycol mixture that this composite membrane is used to separate water quality concentration, and the mass concentration of per-meate side water is reached more than 91.45%, and total permeation flux can reach 756g/ (m
2H) more than.
Embodiment 2
The preparation of polyvinyl alcohol/alcohol/polyether sulfone pervaporation composite membrane (film 2)
Experimentation is identical with embodiment one with condition, it is 2wt% that present embodiment only changes the active separating layer casting solution of PVA concentration, surface-crosslinked polyvinyl alcohol/polyether sulfone the composite membrane (film 2) of gained learns that by the scanning electron microscopic observation of composite membrane section the active separating layer average thickness of PVA is 1.5 μ m.It is 20% water and ethylene glycol mixture that this composite membrane is used to separate water quality concentration, and the mass concentration of per-meate side water is reached more than 99.09%, and total permeation flux can reach 427g/ (m
2H) more than.
Embodiment 3
The preparation of polyvinyl alcohol/alcohol/polyether sulfone pervaporation composite membrane (film 3)
Experimentation is identical with embodiment one with condition, it is 3wt% that present embodiment only changes the active separating layer casting solution of PVA concentration, surface-crosslinked polyvinyl alcohol/polyether sulfone the composite membrane (film 3) of gained learns that by the scanning electron microscopic observation of composite membrane section the active separating layer average thickness of PVA is 2.5 μ m.It is 20% water and ethylene glycol mixture that this composite membrane is used to separate water quality concentration, and the mass concentration of per-meate side water is reached more than 98.50%, and total permeation flux can reach 412g/ (m
2H) more than.
Embodiment 4
The preparation of polyvinyl alcohol/alcohol/polyether sulfone pervaporation composite membrane (film 4)
Experimentation is identical with embodiment one with condition, it is 5wt% that present embodiment only changes the active separating layer casting solution of PVA concentration, surface-crosslinked polyvinyl alcohol/polyether sulfone the composite membrane (film 4) of gained learns that by the scanning electron microscopic observation of composite membrane section the active separating layer average thickness of PVA is 4.0 μ m.It is 20% water and ethylene glycol mixture that this composite membrane is used to separate water quality concentration, and the mass concentration of per-meate side water is reached more than 97.72%, and total permeation flux can reach 281g/ (m
2H) more than.
Embodiment 5
The preparation of polyvinyl alcohol/alcohol/polyether sulfone pervaporation composite membrane (film 5)
Experimentation is identical with embodiment one with condition, it is 7wt% that present embodiment only changes the active separating layer casting solution of PVA concentration, surface-crosslinked polyvinyl alcohol/polyether sulfone the composite membrane (film 5) of gained learns that by the scanning electron microscopic observation of composite membrane section the active separating layer average thickness of PVA is 7.0 μ m.It is 20% water and ethylene glycol mixture that this composite membrane is used to separate water quality concentration, and the mass concentration of per-meate side water is reached more than 94.78%, and total permeation flux can reach 218g/ (m
2H) more than.
Comparative Examples 1
The preparation of polyvinyl alcohol/alcohol/polyether sulfone pervaporation composite membrane (film 6)
Take by weighing the 10g degree of polymerization and be 1750 polyvinyl alcohol and 490g deionized water and put into there-necked flask, put into 90 ℃ water bath with thermostatic control and heat, the 900r/min rotating speed stirs dissolving down 1 hour.All reduce to 25 ℃ after the dissolving, remove by filter insoluble matter, standing and defoaming, making mass concentration is the active separating layer casting solution of polyvinyl alcohol of 2.0wt%.
Molecular cut off is that 25000 poly (ether sulfone) film is that (10cm * 10cm) soaked 2 days in deionized water removes the glycerine in the striping, 20-25 ℃ of drying to supporting layer.Place the 5vol% glutaraldehyde water solution to soak absorption 12 hours dried poly (ether sulfone) film, take out 20-25 ℃ of drying.PES supporting layer after handling is fixed on the glass plate, uses rubber belt sealing all around, place the active separating layer casting solution reaction of the 2.0wt%PVA for preparing absorption 5min then, take out, 20-25 ℃ of drying 12 hours.After treating active separating layer bone dry, place and contain that to account for cumulative volume be the 15vol% glutaraldehyde and account for the acetone soln that cumulative volume is 0.12vol%HCl, descended crosslinked 3 hours at 40 ℃, crosslinked taking-up distilled water flushing three times that finish, can make surface-crosslinked polyvinyl alcohol/polyether sulfone composite membrane (film 6), learn the active separating layer average thickness of PVA 3.5 μ m by the scanning electron microscopic observation of composite membrane section.It is 20% water and ethylene glycol mixture that this composite membrane is used to separate water quality concentration, and the mass concentration of per-meate side water is reached more than 95.45%, and total permeation flux can reach 393g/ (m
2H) more than.
Comparative Examples 2
The preparation of surface-crosslinked polyvinyl alcohol homogeneous membrane (film 7)
Take by weighing the 5g degree of polymerization and be 1750 polyvinyl alcohol and 50g deionized water and put into there-necked flask, put into 90 ℃ water bath with thermostatic control and heat, the 900r/min rotating speed stirs dissolving down 1 hour.All reduce to 25 ℃ after the dissolving, remove by filter insoluble matter, standing and defoaming is made the polyvinyl alcohol water solution that mass concentration is 10wt%, and striking film forming on glass plate was 20-25 ℃ of drying 24 hours.Film taken off to place contain that to account for cumulative volume be the 15vol% glutaraldehyde and account for the acetone soln that cumulative volume is 0.12vol%HCl, descended crosslinked 3 hours at 40 ℃, crosslinked taking-up distilled water flushing three times that finish place acetone soln further to remove the glutaraldehyde of face remnants.Be used to separate water quality concentration and be 20% water and ethylene glycol mixture, the mass concentration of per-meate side water is reached more than 99.58%, total permeation flux can reach 211g/ (m
2H) more than.
Table 1 is depicted as the prepared film 1 of embodiment, and film 2, film 3, film 4, the prepared film 6 of film 5 and Comparative Examples, the pervaporation of film 7 divide dried up and permeation flux and separation factor result ethylene glycol mixture.
Table 1
Claims (1)
1. the preparation method of a polyvinyl alcohol/alcohol/polyether sulfone pervaporation composite membrane is characterized in that: realize as follows:
(1) supporting layer modification: with molecular cut off is that the polyether sulfone supporting layer of 20000-30000 places the interfacial reaction crosslinking agent borax solution of 0.05-5wt% to soak 6-12 hour, takes out, and dries;
(2) preparation of active separating layer casting solution: the polyvinyl alcohol of the degree of polymerization 1650～2500 is dissolved in the 80-95 ℃ of deionized water, make the casting solution that the polyvinyl alcohol mass concentration is 1-7wt%, be cooled to 20-25 ℃,, standby after the deaeration with screen filtration to remove impurity;
(3) preparation of composite membrane: will place the active separating layer casting solution of step (2) preparation through the polyether sulfone supporting layer that step (1) is handled, making thickness by dip coating on the polyether sulfone basement membrane is the active separating layer of 1-8 μ m polyvinyl alcohol, is prepared composite membrane after 20-25 ℃ of drying;
(4) the surface-crosslinked processing of the active separating layer of composite membrane: the prepared composite membrane of step (3) placed to contain account for the acetone soln that cumulative volume is 5-20vol% glutaraldehyde and 0.1-0.15vol%HCl, treatment temperature is 20-50 ℃, processing time is 0.5-5 hour, obtains surface-crosslinked polyvinyl alcohol/alcohol/polyether sulfone pervaporation composite membrane.
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| CN102794117B (en) * | 2012-07-29 | 2014-01-15 | 北京工业大学 | Preparation method of silazane-modified silicalite-1 molecular sieve filling silicon rubber composite membrane |
| CN105080352B (en) * | 2014-04-24 | 2017-09-26 | 中国石油化工股份有限公司 | A kind of complex reverse osmosis membrane and preparation method |
| WO2016077827A1 (en) | 2014-11-14 | 2016-05-19 | Rensselaer Polytechnic Institute | Synthetic membranes and methods of use thereof |
Citations (5)
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| CN1249204A (en) * | 1998-09-26 | 2000-04-05 | 中国石化齐鲁石油化工公司 | Osmosis vaporizing compound membrane and application thereof |
| EP1306121A1 (en) * | 2000-07-27 | 2003-05-02 | ASAHI MEDICAL Co., Ltd. | Modified hollow-fiber membrane |
| CN1843594A (en) * | 2006-03-20 | 2006-10-11 | 天津大学 | Method for preparing facilitated transport membrane of branched neopentyl ethylene diamine for CO2 separation |
| CN101003005A (en) * | 2006-12-21 | 2007-07-25 | 天津大学 | Method for preparing ultrafiltration film of poly-ether-sulfone and anti-protein-contamination type |
| EP1718400B1 (en) * | 2004-02-19 | 2008-04-16 | Membrana GmbH | High-flux dialysis membrane with an improved separation behaviour |
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2008
- 2008-05-09 CN CN2008101062300A patent/CN101574629B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249204A (en) * | 1998-09-26 | 2000-04-05 | 中国石化齐鲁石油化工公司 | Osmosis vaporizing compound membrane and application thereof |
| EP1306121A1 (en) * | 2000-07-27 | 2003-05-02 | ASAHI MEDICAL Co., Ltd. | Modified hollow-fiber membrane |
| EP1718400B1 (en) * | 2004-02-19 | 2008-04-16 | Membrana GmbH | High-flux dialysis membrane with an improved separation behaviour |
| CN1843594A (en) * | 2006-03-20 | 2006-10-11 | 天津大学 | Method for preparing facilitated transport membrane of branched neopentyl ethylene diamine for CO2 separation |
| CN101003005A (en) * | 2006-12-21 | 2007-07-25 | 天津大学 | Method for preparing ultrafiltration film of poly-ether-sulfone and anti-protein-contamination type |
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