CN1332739C - Method for preparing vinol hollow-fiber type penetration gasifying film - Google Patents
Method for preparing vinol hollow-fiber type penetration gasifying film Download PDFInfo
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- CN1332739C CN1332739C CNB2004100740356A CN200410074035A CN1332739C CN 1332739 C CN1332739 C CN 1332739C CN B2004100740356 A CNB2004100740356 A CN B2004100740356A CN 200410074035 A CN200410074035 A CN 200410074035A CN 1332739 C CN1332739 C CN 1332739C
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Abstract
The present invention discloses a method for preparing polyvinyl alcoholhollow fiber type penetration gasifying films, which comprises the steps that firstly, polyvinyl alcohol resin, water, alcohol and ketone alcohol are uniformly mixed in a stirring vessel and are dissolved to obtain film casting solution. Secondly, the stirring vessel is pumped to form vacuum, the prepared film casting solution is defoamed in a vacuum environment, and nitrogen gas is charged into the stirring vessel. A valve and a metering pump at the bottom of the stirring vessel are opened and started, the film casting solution flows to the metering pump under the pressure of the nitrogen gas in the vessel and enters an annular spraying nozzle through the metering pump, and nitrogen gas is charged into a core of the annular spraying nozzle. The film casting solution is sprayed out from the annular spraying nozzle and enters a gel bath through a gas gap to be solidified and shaped. Thirdly, the surface of a polyvinyl alcohol hollow fiber film is coated with water solution of crosslinking agents, and then, crosslinking is carried out. The preparing method of the present invention can eliminate the problem that when composite films are coated and manufactured, pin hole technology, etc. are easy to be unstable.
Description
Technical field
The present invention relates to polyvinyl alcohol is the preparation method of the doughnut formula water osmotic vaporizing membrane penetrated preferably of membrane material.
Background technology
Infiltration evaporation is a kind of novel membrane separation technique, it utilize the difference of the diffusion velocity in the surface dissolution of polymeric membrane for separation and film of each component in the mixed liquor and reach optionally separate and the enrichment mixed liquor in the purpose of a certain component.Compare with traditional handicraft, the outstanding feature of this technology is the separative efficiency height, energy consumption is low, process is simple, easy to operate, free from environmental pollution etc.; And might realize the separation of insurmountable nearly boiling point mixed liquor of general conventional method or azeotrope.Recent two decades comes, and infiltration evaporation has become the effective ways that chemical industry separates and reclaim mixed liquor, and is widely used in industrial fields such as bio-pharmaceuticals, food industry and environmental protection.
Separate the difference that mixed liquor is formed according to desire, infiltrating and vaporizing membrane generally can be divided into water penetrated preferably film, organic liquor penetrated preferably film and organic liquor/organic liquor diffusion barrier three classes.Wherein, water penetrated preferably film has obtained practical application, as is used for liquid hydrocarbon dehydration production high-purity organic liquor, particularly ethanol, isopropyl alcohol and ethylene glycol.
The membrane material of water osmotic vaporizing membrane penetrated preferably is representative with polyvinyl alcohol (being called for short PVA), its organic solvent resistance is good, separating property stable, Germany GFT company nineteen eighty-three at first realized crosslinked PVA composite membrane separating alcohol/aqueous systems industrialization (German Pat:DE3220570A1,1983-12-01).The PVA infiltrating and vaporizing membrane of commercial Application generally is made into flat, is assembled into membrane module with stainless steel again.The loading density of plate type membrane assembly is low, and film device will occupy bigger space; Stainless steel costs an arm and a leg, and has increased the cost of investment of equipment; And device is heavier, inconvenient installation.Compare with plate type membrane assembly, doughnut formula membrane module loading density is big, cost is low, installation weight is light, installation easily.Existing doughnut PVA infiltrating and vaporizing membrane adopts the preparation method of composite membrane.At first produce the milipore filter of doughnut formula, surperficial at milipore filter then by dip coating polyvinyl alcohol cortex.So just obtain the PVA osmosis vaporizing compound membrane, milipore filter only plays the effect of porous support layer.Like this hollow-fibre membrane of Zhi Zuoing will by two the step just can finish, complex manufacturing technology, and the coating the PVA thin layer be difficult to uniformity, pin hole appears easily, these factors all can influence the infiltration evaporation performance (selectivity and permeability) of PVA film.
Summary of the invention
The object of the present invention is to provide the preparation method of the PVA doughnut formula infiltrating and vaporizing membrane of once-forming.The PVA infiltrating and vaporizing membrane of this form has a dense layer surface and porous support layer, and two-layer membrane material all is a polyvinyl alcohol.Dense layer surface plays the infiltration evaporation centrifugation, and porous support layer only plays the effect of mechanical support.Hollow-fibre membrane of the present invention can once-forming, has avoided coating to make composite membrane and has occurred technology problem of unstable such as pin hole easily.
The preparation method of polyvinyl alcohol doughnut formula infiltrating and vaporizing membrane of the present invention, carry out as follows:
1) preparation of casting solution
Polyvinyl alcohol resin 8 weight portions, water 28～34 weight portions, alcohol 1～6 weight portion and keto-alcohol 2～10 weight portions are mixed in stirred tank, and dissolving is made into casting solution under 70～90 ℃.
PVA is a commercial resin, and number-average molecular weight is 70,000～200, between 000 (with 70,000～110,000 is advisable).The degree of hydrolysis of PVA is 88% or 99%, does not have specific (special) requirements.Described alcohol for example comprises: ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol, ethylene glycol, diethylene glycol (DEG), triethylene glycol and tetraethylene glycol etc., preferred alcohol.Described keto-alcohol refers to contain simultaneously the molecule of hydroxyl and carbonyl, and the present invention selects diacetone alcohol for use.
2) making of hollow-fibre membrane
Stirred tank is vacuumized, and vacuum is pressed between 90～120Pa, allows the deaeration 20 minutes to 1 hour in vacuum environment of the casting solution for preparing.Charge into nitrogen to stirred tank then, nitrogen pressure reaches 0.8～1.2 kilograms per centimeter in still
2Open valve and measuring pump at the bottom of the stirred tank, flow to measuring pump under the nitrogen pressure of casting solution in still, and enter the ring nozzle of the logical nitrogen of SMIS through measuring pump, casting solution sprays from ring nozzle, solidifies setting in the coagulation bath through entering behind one section air gap.The logical nitrogen of the SMIS of ring nozzle has the shape of doughnut to keep finished product.
Coagulation bath is by ketone, as compositions such as butanone, methyl ethyl ketone, methyl propyl ketone, ethyl octyl group ketone, the preferred butanone of the present invention, temperature between 10～40 ℃, preferred 15～20 ℃.
3) crosslinked, the curing of film
The present invention adopts film surface chemistry cross-linking method.Crosslinking agent can use formaldehyde, acetaldehyde, valeral, glutaraldehyde, maleic acid, maleic anhydride, citric acid, oxalic acid etc., and the aqueous solution that crosslinking agent will be mixed with weight portion 0.1～5% just can be applied to the present invention.Cross-linking step is as follows, with the aqueous solution of crosslinking agent coating PVA hollow-fibre membrane surface, then hollow-fibre membrane is placed under 100～120 ℃ the temperature crosslinkedly, and crosslinking time is at 1 second to 30 minutes, preferred 10 seconds to 3 minutes.
The PVA doughnut formula infiltrating and vaporizing membrane that is obtained after above-mentioned three steps is infiltrating and vaporizing membrane of the present invention.
Description of drawings
Fig. 1 is the outer surface electromicroscopic photograph of embodiment 1
Fig. 2 is the inner surface electromicroscopic photograph of embodiment 1
Fig. 3 is the outer surface electromicroscopic photograph of embodiment 2
Fig. 4 is the inner surface electromicroscopic photograph of embodiment 2
Fig. 5 is the outer surface electromicroscopic photograph of embodiment 3
The specific embodiment
Embodiment 1
Polyvinyl alcohol (degree of polymerization 2400～2500, degree of hydrolysis 98～99%) 800 grams are dissolved in ethanol 200g, and diacetone alcohol 800g in the mixed solvent that water 3000g forms, promptly becomes uniform spinning solution after 90 ℃ of following stirring and dissolving.
After the spinning solution deaeration that will obtain with said method, constant temperature is at 80 ℃, and 50 ℃ of ejections down, the nozzle SMIS leads to 50 ℃ of nitrogen from the nozzle of the two-layer ring type structure of external diameter 1.65mm, internal diameter 0.8mm.It behind walking 10cm in 20 ℃, 90% humidification district, is immersed in 20 ℃ the butanone coagulation bath and obtain hollow fiber membrane, spinning speed 4.5m/min.
At the PVA macaroni yarn surface applied glutaraldehyde water solution (weight portion 1%) that solidifies, place then under 110 ℃ of environment and solidified 30 seconds, promptly obtain PVA doughnut formula infiltrating and vaporizing membrane.Outer surface is fine and close PVA cortex, and inner surface is spongy pore structure.Accompanying drawing one is the outer surface electromicroscopic photograph of present embodiment, does not have loose structure.Accompanying drawing two is inner surface electromicroscopic photographs of present embodiment, is spongy loose structure.
Embodiment 2
Polyvinyl alcohol (degree of polymerization 2400～2500, degree of hydrolysis 98～99%) 800 grams are dissolved in ethanol 400g, and diacetone alcohol 400g in the mixed solvent that water 3200g forms, promptly becomes uniform spinning solution after 90 ℃ of following stirring and dissolving.
After the spinning solution deaeration that will obtain with said method, remain on 80 ℃, 50 ℃ of ejections down, the nozzle SMIS leads to 50 ℃ of nitrogen from the nozzle of the two-layer ring type structure of external diameter 1.65mm, internal diameter 0.8mm.It behind traveling 10cm in 20 ℃, 90% humidification district, is imported 20 ℃ hydrogel and obtain hollow fiber membrane, spinning speed 4.5m/min in bathing.
At the PVA macaroni yarn surface applied glutaraldehyde water solution (weight portion 1%) that solidifies, place then under 110 ℃ of environment and solidified 30 seconds, promptly obtain PVA doughnut formula infiltrating and vaporizing membrane.Outer surface is fine and close PVA cortex, and inner surface is the finger-like pore structure.Accompanying drawing three is outer surface electromicroscopic photographs of present embodiment, does not have loose structure.Accompanying drawing four is inner surface electromicroscopic photographs of present embodiment, is the finger-like loose structure.
Embodiment 3 (Comparative Examples)
Polyvinyl alcohol (degree of polymerization 2400～2500, degree of hydrolysis 98～99%) 800 grams are dissolved in diacetone alcohol 800g, in the mixed solvent that water 3200g forms, promptly become uniform spinning solution after 90 ℃ of following stirring and dissolving.
After the spinning solution deaeration that will obtain with said method, remain on 80 ℃, 50 ℃ of ejections down, the nozzle SMIS leads to 50 ℃ of nitrogen from the nozzle of the two-layer ring type structure of external diameter 1.65mm, internal diameter 0.8mm.It behind traveling 10cm in 20 ℃, 90% humidification district, is imported in 20 ℃ the butanone coagulation bath and obtain hollow fiber membrane, spinning speed 4.5m/min.
At the PVA macaroni yarn surface applied glutaraldehyde water solution (weight portion 1%) that solidifies, place then under 110 ℃ of environment and solidified 30 seconds, promptly obtain PVA doughnut formula film.Outer surface is a loose structure.Accompanying drawing five is outer surface electromicroscopic photographs of present embodiment, loose structure occurs.
Embodiment 4 (Comparative Examples)
Polyvinyl alcohol (degree of polymerization 2400～2500, degree of hydrolysis 98～99%) 800 grams are dissolved in ethanol 400g, and diacetone alcohol 400g in the mixed solvent that water 3200g forms, promptly becomes uniform spinning solution after 90 ℃ of following stirring and dissolving.
After the spinning solution deaeration that will obtain with said method, remain on 80 ℃, 50 ℃ of ejections down, the nozzle SMIS leads to 50 ℃ of nitrogen from the nozzle of the two-layer ring type structure of external diameter 1.65mm, internal diameter 0.8mm.Behind traveling 10cm in 20 ℃, 90% humidification district, the water that imports 20 ℃ is as spinning hollow fiber membrane in the coagulation bath with it, and the film silk is difficult to solidified forming, can't make the infiltrating and vaporizing membrane of doughnut formula.
Claims (5)
1. the preparation method of polyvinyl alcohol doughnut formula infiltrating and vaporizing membrane, carry out as follows:
1) preparation of casting solution
Polyvinyl alcohol resin 8 weight portions, water 28～34 weight portions, alcohol 1～6 weight portion and keto-alcohol 2～10 weight portions are mixed in stirred tank, and dissolving is made into casting solution under 70～90 ℃;
2) making of hollow-fibre membrane
Stirred tank is vacuumized, and vacuum is pressed between 90～120Pa, allows the casting solution deaeration in vacuum environment for preparing charge into nitrogen to stirred tank then to 1 hour in 20 minutes, and nitrogen pressure reaches 0.8～1.2 kilograms per centimeter in still
2, open valve and measuring pump at the bottom of the stirred tank, flow to measuring pump under the nitrogen pressure of casting solution in still, and enter the ring nozzle of the logical nitrogen of SMIS through measuring pump, casting solution sprays from ring nozzle, solidifies setting in the coagulation bath through entering behind one section air gap;
3) crosslinked, the curing of film
With the aqueous solution of crosslinking agent coating polyvinyl alcohol hollow-fibre membrane surface, then hollow-fibre membrane is placed under 100～120 ℃ the temperature crosslinkedly, crosslinking time was at 1 second to 30 minutes.
2. according to the preparation method of claim 1, it is characterized in that: described alcohol is ethanol, and described ketone is diacetone alcohol.
3. according to the preparation method of claim 1, it is characterized in that: described coagulation bath is a butanone, and temperature is between 10～40 ℃.
4. according to the preparation method of claim 1, it is characterized in that: described crosslinking agent is formaldehyde, acetaldehyde, valeral, glutaraldehyde, maleic acid, maleic anhydride, citric acid or oxalic acid, and the weight portion concentration of the aqueous solution of described crosslinking agent is 0.1～5%.
5. according to the preparation method of claim 1, it is characterized in that: described crosslinking time is 10 seconds to 3 minutes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100740356A CN1332739C (en) | 2004-09-01 | 2004-09-01 | Method for preparing vinol hollow-fiber type penetration gasifying film |
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| CNB2004100740356A CN1332739C (en) | 2004-09-01 | 2004-09-01 | Method for preparing vinol hollow-fiber type penetration gasifying film |
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| CN1332739C true CN1332739C (en) | 2007-08-22 |
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| CN102327743B (en) * | 2010-07-12 | 2013-04-03 | 华东理工大学 | Preparation method of bifunctional hollow fibrous membrane with strong acidic catalysis and pervaporation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4806189A (en) * | 1984-08-13 | 1989-02-21 | Monsanto Company | Composite fluid separation membranes |
| JPH0824602A (en) * | 1994-07-08 | 1996-01-30 | Chikyu Kankyo Sangyo Gijutsu Kenkyu Kiko | Surface-improve gas separation membrane and its preparation |
| US6500233B1 (en) * | 2000-10-26 | 2002-12-31 | Chevron U.S.A. Inc. | Purification of p-xylene using composite mixed matrix membranes |
| CN1509804A (en) * | 2002-12-26 | 2004-07-07 | 天津工业大学膜科学与技术研究所 | Method for preparing composite hollow fibre membrane |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4806189A (en) * | 1984-08-13 | 1989-02-21 | Monsanto Company | Composite fluid separation membranes |
| JPH0824602A (en) * | 1994-07-08 | 1996-01-30 | Chikyu Kankyo Sangyo Gijutsu Kenkyu Kiko | Surface-improve gas separation membrane and its preparation |
| US6500233B1 (en) * | 2000-10-26 | 2002-12-31 | Chevron U.S.A. Inc. | Purification of p-xylene using composite mixed matrix membranes |
| CN1509804A (en) * | 2002-12-26 | 2004-07-07 | 天津工业大学膜科学与技术研究所 | Method for preparing composite hollow fibre membrane |
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