CN101992033A - Method for preparing polyimide hollow fiber pervaporation membrane and application thereof - Google Patents
Method for preparing polyimide hollow fiber pervaporation membrane and application thereof Download PDFInfo
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- CN101992033A CN101992033A CN2009100659836A CN200910065983A CN101992033A CN 101992033 A CN101992033 A CN 101992033A CN 2009100659836 A CN2009100659836 A CN 2009100659836A CN 200910065983 A CN200910065983 A CN 200910065983A CN 101992033 A CN101992033 A CN 101992033A
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Abstract
The invention belongs to the technical field of membrane separation and relates to a method for preparing a polyimide hollow fiber pervaporation membrane and an application thereof. The polyimide hollow fiber pervaporation membrane is prepared by spinning, cooling and drying and is applied to removing water from alcohol solvents. The polyimide hollow fiber pervaporation membrane prepared by using the method of the invention ensures that the water-separating degree in the alcohol solvents is high. Besides, the manufacturing cost and the use cost are both low.
Description
Technical field
The invention belongs to the membrane separation technique field, relate to a kind of preparation method and application thereof that is used for the polyimides doughnut infiltrating and vaporizing membrane that alcohols solvent dewaters.
Technical background
The alcoholic solvent of anhydrous level is absolutely necessary in fields such as petrochemical industry, fine chemistry industry, medication chemistry, daily-use chemical industry and new forms of energy, therefore with moisture a small amount of or micro-in the organic solvent from, thereby obtain anhydrous level alcoholic solvent be most important in the above-mentioned field also be one of modal unit process.When the mixture of alcohol and water reaches the azeotropic balance, traditional handicraft be adopt moisture that technology such as azeotropic distillation, extracting rectifying or molecular sieve adsorption will be wherein from, and then obtaining anhydrous grade alcoholic solvent, the common ground of these technology is highly energy-consumings, manually-operated cost height.The infiltration evaporation membrane technology that grow up nearly decades since in the process of its a small amount of or minor amount of water in separating alcoholic solvent intrinsic low energy consumption, do not introduce advantages such as the 3rd component, blowdown are few, obtained people's generally approval.Inorganic ceramic material can high temperature resistant, anti-solvent, resistance to chemical attack, but the manufacturing cost height of film costs an arm and a leg, and is unfavorable for large-scale promotion application.And the organic high molecular layer cost is low, and low price can large-scale promotion application.Current main membrane material has CAM, PS membrane, poly (ether sulfone) film, polypropylene cyanogen, polyvinylidene fluoride film etc., and serviceability temperature all can not surpass 70 ℃, is not suitable for being used for separating the water in the alcoholic solution.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is used for the polyimides doughnut infiltrating and vaporizing membrane that dewaters from alcohols solvent, and the application of passing through doughnut infiltrating and vaporizing membrane water in separating alcoholic solution of this method output, use the separation degree height of the polyimides doughnut infiltrating and vaporizing membrane of this preparation method's production, and one-tenth produces and use cost is cheap to water in the alcohols solvent.
The preparation method of polyimides doughnut infiltrating and vaporizing membrane comprises the steps:
(1) according to following parts by weight casting film solution: polyimide acid 10-24, polyvinylpyrrolidone 0.1-4, nonsolvent additive 10-25, polar organic solvent 79.9-47;
(2) above-mentioned casting film solution is injected the doughnut spinning-drawing machine, extrude from spinning head under the air pressure effect through press filtration, extruded velocity is 1-80m/min;
(3) the nascent hollow-fibre membrane that will extrude after 5-150cm distance, soaked 0.2-4 hour in temperature is 0-85 ℃ water-bath in air, and wherein filling liquid is a water, and the flow velocity of water is 1-100ml/min;
(4) with 200-400 ℃ of heating 1-6 hour in baking oven of polyimide acid hollow-fibre membrane.
Described polyimide acid by etc. fragrance two phthalic anhydrides and the fragrant diphenylamines of mol ratio form through prepared in reaction, fragrance two phthalic anhydrides are: the raw material of one or more in pyromellitic acid anhydride or biphenyl dianhydride or diphenyl ether dianhydride or benzophenone dianhydride or diphenyl sulfone dianhydride or hexafluoro isopropyl diphthalic anhydrides or the triphen bis ether tetracarboxylic acid dianhydride mixes, the fragrance diphenylamines is: p-phenylenediamine (PPD) or m-phenylene diamine (MPD) or 2,4-toluenediamine or 3,4-toluenediamine or 2,6-toluenediamine or 2,5-dimethyl phenylene diamine or 2,6-dimethyl phenylene diamine or 2,4,6-trimethylbenzene diamines or tetramethyl-para-phenylene diamine or benzidine or MDA or 2, a kind of in two [4-(3-amino-benzene oxygen) phenyl] propane of 2-.
The molecular weight of described polyvinylpyrrolidone is 1000-200000.
Described nonsolvent additive is a kind of in glycerine or ethanol or the ethylene glycol.
Described polar organic solvent is selected from N-methyl pyrrolidone or N, dinethylformamide or N, a kind of in N-dimethylacetylamide or the methyl-sulfoxide.
The application of polyimides doughnut infiltrating and vaporizing membrane, polyimides doughnut infiltrating and vaporizing membrane is used for the permeable membrane of infiltration vaporization membrane module, is applied to dewater in the alcohols solvent, and alcohols solvent is: methyl alcohol or ethanol or propyl alcohol or butanols or amylalcohol.
The application of polyimides doughnut infiltrating and vaporizing membrane, polyimides doughnut infiltrating and vaporizing membrane are measured the permeation flux of water greater than 3x10 in 70-150 ℃ temperature range
-7Mol/m
2SPa, for the separation factor of alcohol greater than 200.
The present invention mainly adopts polyimide acid as major ingredient, and polyimide acid is one of best high-molecular organic material of combination property, high temperature resistant reaching more than 400 ℃, long-term serviceability temperature is between-200-300 ℃, acidproof, organic solvent-resistant, good mechanical performance.The heat endurance of polyimides and the character of organic solvent-resistant make it might use the preparation infiltrating and vaporizing membrane and are used for separating water in the alcoholic solution.By the polyimides doughnut infiltrating and vaporizing membrane of above-mentioned preparation method's output, after measured in 70-150 ℃ temperature range the permeation flux of water greater than 3x10
-7Mol/m
2SPa, for the separation factor of alcohol all greater than 200.
The specific embodiment:
Embodiment 1
The preparation method of polyimides doughnut infiltrating and vaporizing membrane comprises the steps:
1. get 31 gram diphenyl ether dianhydrides, 32 gram benzophenone dianhydrides, and get 43 gram benzidines, be that solvent 20 ℃ of stirring reactions in flask made polyimide acid in 10 hours with 320 gram N-methyl pyrrolidones.In flask, add molecular weight then and be 15000 polyvinylpyrrolidone, glycerine, N-methyl pyrrolidone, obtain casting film solution after the mixing, various proportion of raw materials are as follows for (percentage of following each raw material is the percentage that accounts for mixed casting film solution) in the casting film solution: polyimide acid 14%, polyvinylpyrrolidone 2%, glycerine 15%, N-methyl pyrrolidone 69%.
2. above-mentioned casting film solution is injected the doughnut spinning-drawing machine, casting film solution is extruded from the spinning head of doughnut spinning-drawing machine under the air pressure effect, and extruded velocity is 14m/min;
3. the nascent hollow-fibre membrane that will extrude after 80cm distance, soaked 2 hours in temperature is 20 ℃ water bath in air, and wherein the flow velocity of filling liquid water is 10ml/min.
With the polyimide acid hollow-fibre membrane in baking oven 300 ℃ the heating 2 hours.
The outer diameter of the polyimide acid hollow-fibre membrane by the above-mentioned steps output is 2mm, and inner diameter is 1.6mm.At 105 ℃ of permeation fluxs that record water is 8x10
-7Mol/m
2SPa is 340 for the ethanol separation factor.
Embodiment 2
Getting 32 gram benzophenone dianhydrides and 20 gram MDAs, is that solvent 20 ℃ of stirring reactions of room temperature in flask made polyimide acid in 24 hours with 120 gram N-methyl pyrrolidones.In flask, add molecular weight then and be 20000 polyvinylpyrrolidone, ethanol, N-methyl pyrrolidone, obtain casting film solution after the mixing, various proportion of raw materials are as follows for (percentage of following each raw material is the percentage that accounts for mixed casting film solution) in the casting film solution: polyimide acid 20%, polyvinylpyrrolidone 2%, ethanol 12%, N-methyl pyrrolidone 66%.
2. above-mentioned casting film solution is injected the doughnut spinning-drawing machine, casting film solution is extruded from the spinning head of doughnut spinning-drawing machine under the air pressure effect, and extruded velocity is 10m/min;
3. the nascent hollow-fibre membrane that will extrude after 50cm distance, soaked 1 hour in temperature is 20 ℃ water-bath in air, and wherein the flow velocity of filling liquid water is 14ml/min.
With the polyimide acid hollow-fibre membrane in baking oven 300 ℃ the heating 2 hours.
The outer diameter of the polyimide acid hollow-fibre membrane by the above-mentioned steps output is 1.5mm, and inner diameter is 1.3m.At 130 ℃ of permeation fluxs that record water is 9x10
-7Mol/m
2SPa is 310 for the isopropyl alcohol separation factor.
Embodiment 3
Get 21.8 gram pyromellitic acid anhydrides and 10.8 gram p-phenylenediamine (PPD), with 100 gram N, dinethylformamide is that solvent 100 ℃ of stirring reactions in flask made polyimide acid in 10 hours.In flask, add molecular weight then and be 200000 polyvinylpyrrolidone, ethylene glycol, N, dinethylformamide, obtain casting film solution after the mixing, various proportion of raw materials are as follows for (percentage of following each raw material is the percentage that accounts for mixed casting film solution) in the casting film solution: polyimide acid 10%, polyvinylpyrrolidone 0.1%, ethylene glycol 10%, N, dinethylformamide 79.9%.
2. above-mentioned casting film solution is injected the doughnut spinning-drawing machine, casting film solution is extruded from the spinning head of doughnut spinning-drawing machine under the air pressure effect, and extruded velocity is 1m/min;
3. the nascent hollow-fibre membrane that will extrude after 5cm distance, soaked 0.2 hour in temperature is 1 ℃ water bath in air, and wherein the flow velocity of filling liquid water is 1ml/min.
With the polyimide acid hollow-fibre membrane in baking oven 380 ℃ the heating 1 hour.
The outer diameter of the polyimide acid hollow-fibre membrane by the above-mentioned steps output is 1.0mm, and inner diameter is 0.8mm.At 125 ℃ of permeation fluxs that record water is 4x10
-7Mol/m
2SPa is 270 for the n-butanol separation factor.
Embodiment 4
Get 29.4 gram biphenyl dianhydrides and 10.8 gram m-phenylene diamine (MPD)s, with 80 gram N, the N-dimethylacetylamide is that solvent 80 ℃ of stirring reactions in flask made polyimide acid in 10 hours.In flask, add molecular weight then and be 45000 polyvinylpyrrolidone, ethylene glycol, N, the N-dimethylacetylamide, obtain casting film solution after the mixing, various proportion of raw materials are as follows for (percentage of following each raw material is the percentage that accounts for mixed casting film solution) in the casting film solution: polyimide acid 24%, polyvinylpyrrolidone 4%, ethylene glycol 25%, N, N-dimethylacetylamide 47%.
2. above-mentioned casting film solution is injected the doughnut spinning-drawing machine, casting film solution is extruded from the spinning head of doughnut spinning-drawing machine under the air pressure effect, and extruded velocity is 80m/min;
3. the nascent hollow-fibre membrane that will extrude after 150cm distance, soaked 4 hours in temperature is 85 ℃ water-bath in air, and wherein the flow velocity of filling liquid water is 100ml/min.
With the polyimide acid hollow-fibre membrane in baking oven 400 ℃ the heating 6 hours.
The outer diameter of the polyimide acid hollow-fibre membrane by the above-mentioned steps output is 1.1mm, and inner diameter is 0.9mm.At 150 ℃ of permeation fluxs that record water is 3x10
-7Mol/m
2SPa is 206 for the n-amyl alcohol separation factor.
Embodiment 5
Get 35.8 gram diphenyl sulfone dianhydride and 12.3 grams 2, the 4-toluenediamine is that solvent 20 ℃ of stirring reactions in flask made polyimide acid in 10 hours with 150 gram methyl-sulfoxides.In reactor, add molecular weight then and be 1000 polyvinylpyrrolidone, ethylene glycol, methyl-sulfoxide, obtain casting film solution after the mixing, various proportion of raw materials are as follows for (percentage of following each raw material is the percentage that accounts for mixed casting film solution) in the casting film solution: polyimide acid 11%, polyvinylpyrrolidone 3%, ethylene glycol 11%, methyl-sulfoxide 75%.
2. above-mentioned casting film solution is injected the doughnut spinning-drawing machine, casting film solution is extruded from the spinning head of doughnut spinning-drawing machine under the air pressure effect, and extruded velocity is 40m/min;
3. the nascent hollow-fibre membrane that will extrude after 100cm distance, soaked 2 hours in temperature is 60 ℃ water-bath in air, and wherein the flow velocity of filling liquid water is 50ml/min.
With the polyimide acid hollow-fibre membrane in baking oven 200 ℃ the heating 2 hours.
The outer diameter of the polyimide acid hollow-fibre membrane by the above-mentioned steps output is 2.6mm, and inner diameter is 2.3mm.At 70 ℃ of permeation fluxs that record water is 3x10
-7Mol/m
2SPa is 640 for the methyl alcohol separation factor.
Embodiment 6
44.4 gram hexafluoro isopropyl diphthalic anhydrides and 12.2 grams 3 such as get, the 4-toluenediamine is that solvent 20 ℃ of stirring reactions in flask made polyimide acid in 10 hours with 180 gram N-methyl pyrrolidones.In flask, add molecular weight then and be 100000 polyvinylpyrrolidone, glycerine, N-methyl pyrrolidone, obtain casting film solution after the mixing, various proportion of raw materials are as follows for (percentage of following each raw material is the percentage that accounts for mixed casting film solution) in the casting film solution: polyimide acid 12%, polyvinylpyrrolidone 1%, glycerine 12%, N-methyl pyrrolidone 75%.
2. above-mentioned casting film solution is injected the doughnut spinning-drawing machine, casting film solution is extruded from the spinning head of doughnut spinning-drawing machine under the air pressure effect, and extruded velocity is 50m/min;
3. the nascent hollow-fibre membrane that will extrude after 110cm distance, soaked 1 hour in temperature is 70 ℃ water-bath in air, and wherein the flow velocity of filling liquid water is 60ml/min.
With the polyimide acid hollow-fibre membrane in baking oven 300 ℃ the heating 3 hours.
The outer diameter of the polyimide acid hollow-fibre membrane by the above-mentioned steps output is 3.5mm, and inner diameter is 3.3mm.At 110 ℃ of permeation fluxs that record water is 14x10
-7Mol/m
2SPa is 210 for the isopropyl alcohol separation factor.
In the present embodiment 3, the 4-toluenediamine is also available 2, and the 6-toluenediamine substitutes, and effect is identical.
Embodiment 7
Get 40.2 gram triphen bis ether tetracarboxylic acid dianhydrides and 19.7 grams 2, the 5-dimethyl phenylene diamine, with 150 gram N, dinethylformamide is that solvent 20 ℃ of stirring reactions in flask made polyimide acid in 10 hours.In reactor, add molecular weight then and be 150000 polyvinylpyrrolidone, glycerine, N, dinethylformamide, obtain casting film solution after the mixing, various proportion of raw materials are as follows for (percentage of following each raw material is the percentage that accounts for mixed casting film solution) in the casting film solution: polyimide acid 15%, polyvinylpyrrolidone 0.5%, glycerine 13%, N, dinethylformamide 71.5%.
2. above-mentioned casting film solution is injected the doughnut spinning-drawing machine, casting film solution is extruded from the spinning head of doughnut spinning-drawing machine under the air pressure effect, and extruded velocity is 50m/min;
3. the nascent hollow-fibre membrane that will extrude after 120cm distance, soaked 3 hours in temperature is 80 ℃ water-bath in air, and wherein the flow velocity of filling liquid water is 80ml/min.
With the polyimide acid hollow-fibre membrane in baking oven 350 ℃ the heating 5 hours.
The outer diameter of the polyimide acid hollow-fibre membrane by the above-mentioned steps output is 2mm, and inner diameter is 1.6mm.At 115 ℃ of permeation fluxs that record water is 6x10
-7Mol/m
2SPa is 240 for the ethanol separation factor.
In the present embodiment 3, the 4-toluenediamine is also available 2, and the 6-dimethyl phenylene diamine substitutes, and effect is identical.
Embodiment 8
Get 40.2 gram triphen bis ether tetracarboxylic acid dianhydrides and 15 grams 2,4,6-trimethylbenzene diamines, with 120 gram N, dinethylformamide is that solvent 20 ℃ of stirring reactions in flask made polyimide acid in 10 hours.In reactor, add molecular weight then and be 30000 polyvinylpyrrolidone, glycerine, N, dinethylformamide, obtain casting film solution after the mixing, various proportion of raw materials are as follows for (percentage of following each raw material is the percentage that accounts for mixed casting film solution) in the casting film solution: polyimide acid 13%, polyvinylpyrrolidone 0.8%, glycerine 14%, N, dinethylformamide 72.2%.
2. above-mentioned casting film solution is injected the doughnut spinning-drawing machine, casting film solution is extruded from the spinning head of doughnut spinning-drawing machine under the air pressure effect through press filtration, and extruded velocity is 60m/min;
3. the nascent hollow-fibre membrane that will extrude after 10cm distance, soaked 1.5 hours in temperature is 10 ℃ water-bath in air, and wherein the flow velocity of filling liquid water is 60ml/min.
With the polyimide acid hollow-fibre membrane in baking oven 250 ℃ the heating 6 hours.
The outer diameter of the polyimide acid hollow-fibre membrane by the above-mentioned steps output is 2.1mm, and inner diameter is 1.9mm.At 90 ℃ of permeation fluxs that record water is 6x10
-7Mol/m
2SPa is 440 for the methyl alcohol separation factor.
Embodiment 9
Get 31 gram diphenyl ether dianhydrides and 41 grams 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-, with 150 gram N, the N-dimethylacetylamide is that solvent 20 ℃ of stirring reactions in flask made polyimide acid in 10 hours.In reactor, add molecular weight then and be 30000 polyvinylpyrrolidone, glycerine, N, the N-dimethylacetylamide, obtain casting film solution after the mixing, various proportion of raw materials are as follows for (percentage of following each raw material is the percentage that accounts for mixed casting film solution) in the casting film solution: polyimide acid 16%, polyvinylpyrrolidone 0.9%, glycerine 19%, N, N-dimethylacetylamide 64.1%.
2. above-mentioned casting film solution is injected the doughnut spinning-drawing machine, casting film solution is extruded from the spinning head of doughnut spinning-drawing machine under the air pressure effect, and extruded velocity is 70m/min;
3. the nascent hollow-fibre membrane that will extrude after 70cm distance, soaked 0.5 hour in temperature is 40 ℃ water-bath in air, and wherein the flow velocity of filling liquid water is 70ml/min.
With the polyimide acid hollow-fibre membrane in baking oven 200 ℃ the heating 2.5 hours.
The outer diameter of the polyimide acid hollow-fibre membrane by the above-mentioned steps output is 2.3mm, and inner diameter is 2mm.At 125 ℃ of permeation fluxs that record water is 13x10
-7Mol/m
2SPa is 338 for the n-butanol separation factor.
Embodiment 10
Get 6.4 gram benzophenone dianhydrides, 35.5 gram hexafluoro isopropyl diphthalic anhydrides, and get 41 grams 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-are that solvent 20 ℃ of stirring reactions in flask made polyimide acid in 10 hours with 160 gram methyl-sulfoxides.In reactor, add molecular weight then and be in 1000 polyvinylpyrrolidone, glycerine, the methyl-sulfoxide, obtain casting film solution after the mixing, various proportion of raw materials are as follows for (percentage of following each raw material is the percentage that accounts for mixed casting film solution) in the casting film solution: polyimide acid 17%, polyvinylpyrrolidone 0.2%, glycerine 18%, methyl-sulfoxide 64.8%.
2. above-mentioned casting film solution is injected the doughnut spinning-drawing machine, casting film solution is extruded from the spinning head of doughnut spinning-drawing machine under the air pressure effect through press filtration, and extruded velocity is 20m/min;
3. the nascent hollow-fibre membrane that will extrude after 15cm distance, soaked 2.5 hours in temperature is 50 ℃ water-bath in air, and the flow velocity of its SMIS liquid water is 20ml/min.
With the polyimide acid hollow-fibre membrane in baking oven 320 ℃ the heating 1.5 hours.
The outer diameter of the polyimide acid hollow-fibre membrane by the above-mentioned steps output is 2.1mm, and inner diameter is that 1.9mm is 18x10 at 125 ℃ of permeation fluxs that record water
-7Mol/m
2SPa, isopropyl alcohol is 230 to the separation factor of water.
Embodiment 11
Get 8.8 gram biphenyl dianhydrides, 21.7 gram diphenyl ether dianhydrides, and get 20 gram MDAs, with 80 gram N, dinethylformamide is that solvent 20 ℃ of stirring reactions in flask made polyimide acid in 10 hours.In reactor, add molecular weight then and be 50000 polyvinylpyrrolidone, ethanol, N, dinethylformamide, obtain casting film solution after the mixing, various proportion of raw materials are as follows for (percentage of following each raw material is the percentage that accounts for mixed casting film solution) in the casting film solution: polyimide acid 18%, polyvinylpyrrolidone 0.3%, ethanol 20%, N, dinethylformamide 61.7%.
2. above-mentioned casting film solution is injected the doughnut spinning-drawing machine, casting film solution is extruded from the spinning head of doughnut spinning-drawing machine under the air pressure effect through press filtration, and extruded velocity is 30m/min;
3. the nascent hollow-fibre membrane that will extrude after 90cm distance, soaked 3.5 hours in temperature is 30 ℃ water-bath in air, and the flow velocity of its SMIS liquid water is 30ml/min.
With the polyimide acid hollow-fibre membrane in baking oven 260 ℃ the heating 3.5 hours.
The outer diameter of the polyimide acid hollow-fibre membrane by the above-mentioned steps output is 1.8mm, and inner diameter is 1.5mm.At 80 ℃ of permeation fluxs that record water is 5x10
-7Mol/m
2SPa is 285 for the methyl alcohol separation factor.
Embodiment 12
Get 14.3 gram diphenyl sulfone dianhydride, 19.2 gram benzophenone dianhydrides, and get 41 grams 2, and two [4-(3-amino-benzene oxygen) phenyl] propane of 2-, with 130 gram N, dinethylformamide is that solvent 20 ℃ of stirring reactions in flask made polyimide acid in 10 hours.In reactor, add molecular weight then and be 80000 polyvinylpyrrolidone, ethanol, N, dinethylformamide, obtain casting film solution after the mixing, various proportion of raw materials are as follows for (percentage of following each raw material is the percentage that accounts for mixed casting film solution) in the casting film solution: polyimide acid 19%, polyvinylpyrrolidone 0.6%, ethanol 16%, N, dinethylformamide 64.4%.
2. above-mentioned casting film solution is injected the doughnut spinning-drawing machine, casting film solution is extruded from the spinning head of doughnut spinning-drawing machine under the air pressure effect through press filtration, and extruded velocity is 20m/min;
3. the nascent hollow-fibre membrane that will extrude after 60cm distance, soaked 1.8 hours in temperature is 20 ℃ water-bath in air, and the flow velocity of its SMIS liquid water is 40ml/min.
With the polyimide acid hollow-fibre membrane in baking oven 320 ℃ the heating 4.5 hours.
The outer diameter of the polyimide acid hollow-fibre membrane by the above-mentioned steps output is 2.4mm, and inner diameter is 2.1mm.At 105 ℃ of permeation fluxs that record water is 18x10
-7Mol/m
2SPa is 320 for the ethanol separation factor.
Embodiment 13
Get 10.9 the gram pyromellitic acid anhydrides, 15.5 the gram diphenyl ether dianhydrides and and 12.2 the gram 3, the 4-toluenediamine, with 60 the gram N, the N-dimethylacetylamide is that solvent 20 ℃ of stirring reactions in flask made polyimide acid in 10 hours.In reactor, add molecular weight then and be 1000 polyvinylpyrrolidone, ethanol, N, the N-dimethylacetylamide, obtain casting film solution after the mixing, various proportion of raw materials are as follows for (percentage of following each raw material is the percentage that accounts for mixed casting film solution) in the casting film solution: polyimide acid 21%, polyvinylpyrrolidone 0.7%, ethanol 16%, N, N-dimethylacetylamide 62.3%.
2. above-mentioned casting film solution is injected the doughnut spinning-drawing machine, casting film solution is extruded from the spinning head of doughnut spinning-drawing machine under the air pressure effect through press filtration, and extruded velocity is 35m/min;
3. the nascent hollow-fibre membrane that will extrude after 65cm distance, soaked 1.8 hours in temperature is 30 ℃ water-bath in air, and the flow velocity of its SMIS liquid water is 90ml/min.
With the polyimide acid hollow-fibre membrane in baking oven 170 ℃ the heating 2.3 hours.
The outer diameter of the polyimide acid hollow-fibre membrane by the above-mentioned steps output is 2mm, and inner diameter is 1.8mm.At 125 ℃ of permeation fluxs that record water is 4x10
-7Mol/m
2SPa is 230 for tert-butyl alcohol separation factor.
Embodiment 14
Get 8.9 gram hexafluoro isopropyl diphthalic anhydrides, 32 gram triphen bis ether tetracarboxylic acid dianhydrides, and get 12.2 grams 2, the 6-toluenediamine is that solvent 20 ℃ of stirring reactions in flask made polyimide acid in 10 hours with 80 gram methyl-sulfoxides.In reactor, add molecular weight then and be 20000 polyvinylpyrrolidone, ethanol, methyl-sulfoxide, obtain casting film solution after the mixing, various proportion of raw materials are as follows for (percentage of following each raw material is the percentage that accounts for mixed casting film solution) in the casting film solution: polyimide acid 22%, polyvinylpyrrolidone 2%, ethanol 24%, methyl-sulfoxide 52%.
2. above-mentioned casting film solution is injected the doughnut spinning-drawing machine, casting film solution is extruded from the spinning head of doughnut spinning-drawing machine under the air pressure effect through press filtration, and extruded velocity is 35m/min;
3. the nascent hollow-fibre membrane that will extrude after 130cm distance, soaked 2.6 hours in temperature is 65 ℃ water-bath in air, and the flow velocity of its SMIS liquid water is 55ml/min.
With the polyimide acid hollow-fibre membrane in baking oven 185 ℃ the heating 2.2 hours.
The outer diameter of the polyimide acid hollow-fibre membrane by the above-mentioned steps output is 2mm, and inner diameter is 1.6mm.At 125 ℃ of permeation fluxs that record water is 10x10
-7Mol/m
2SPa is 225 for the n-amyl alcohol separation factor.
Embodiment 15
Get 32 gram benzophenone dianhydrides and 41 grams 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-, with 120 gram N, dinethylformamide is that solvent 20 ℃ of stirring reactions in flask made polyimide acid in 10 hours.In reactor, add molecular weight then and be 1000 polyvinylpyrrolidone, ethanol, N, dinethylformamide, obtain casting film solution after the mixing, various proportion of raw materials are as follows for (percentage of following each raw material is the percentage that accounts for mixed casting film solution) in the casting film solution: polyimide acid 23%, polyvinylpyrrolidone 4%, ethanol 22%, N, dinethylformamide 51%.
2. above-mentioned casting film solution is injected the doughnut spinning-drawing machine, casting film solution is extruded from the spinning head of doughnut spinning-drawing machine under the air pressure effect through press filtration, and extruded velocity is 55m/min;
3. the nascent hollow-fibre membrane that will extrude after 140cm distance, soaked 3.6 hours in temperature is 80 ℃ water-bath in air, and the flow velocity of its SMIS liquid water is 85ml/min.
With the polyimide acid hollow-fibre membrane in baking oven 320 ℃ the heating 5.5 hours.
The outer diameter of the polyimide acid hollow-fibre membrane by the above-mentioned steps output is 2.3mm, and inner diameter is 2.0mm, is 11x10 at 90 ℃ of permeation fluxs that record water
-7Mol/m
2SPa is 438 for separation factor.
Claims (7)
1. the preparation method of polyimides doughnut infiltrating and vaporizing membrane is characterized in that preparation process comprises the steps:
(1) according to following parts by weight casting film solution: polyimide acid 10-24, polyvinylpyrrolidone 0.1-4, nonsolvent additive 10-25, polar organic solvent 79.9-47;
(2) above-mentioned casting film solution is injected the doughnut spinning-drawing machine, extrude from spinning head under the air pressure effect through press filtration, extruded velocity is 1-80m/min;
(3) the nascent hollow-fibre membrane that will extrude after 5-150cm distance, soaked 0.2-4 hour in temperature is 0-85 ℃ water-bath in air, and wherein filling liquid is a water, and the flow velocity of water is 1-100ml/min;
(4) with 200-400 ℃ of heating 1-6 hour in baking oven of polyimide acid hollow-fibre membrane.
2. the preparation method of polyimides doughnut infiltrating and vaporizing membrane according to claim 1, it is characterized in that: described polyimide acid by etc. fragrance two phthalic anhydrides and the fragrant diphenylamines of mol ratio form through prepared in reaction, fragrance two phthalic anhydrides are: the raw material of one or more in pyromellitic acid anhydride or biphenyl dianhydride or diphenyl ether dianhydride or benzophenone dianhydride or diphenyl sulfone dianhydride or hexafluoro isopropyl diphthalic anhydrides or the triphen bis ether tetracarboxylic acid dianhydride mixes, the fragrance diphenylamines is: p-phenylenediamine (PPD) or m-phenylene diamine (MPD) or 2,4-toluenediamine or 3,4-toluenediamine or 2,6-toluenediamine or 2,5-dimethyl phenylene diamine or 2,6-dimethyl phenylene diamine or 2,4,6-trimethylbenzene diamines or tetramethyl-para-phenylene diamine or benzidine or MDA or 2, a kind of in two [4-(3-amino-benzene oxygen) phenyl] propane of 2-.
3. the preparation method of polyimides doughnut infiltrating and vaporizing membrane according to claim 1 is characterized in that: the molecular weight of described polyvinylpyrrolidone is 1000-200000.
4. the preparation method of polyimides doughnut infiltrating and vaporizing membrane according to claim 1 is characterized in that: described nonsolvent additive is a kind of in glycerine or ethanol or the ethylene glycol.
5. the preparation method of polyimides doughnut infiltrating and vaporizing membrane according to claim 1, it is characterized in that: described polar organic solvent is selected from N-methyl pyrrolidone or N, dinethylformamide or N, a kind of in N-dimethylacetylamide or the methyl-sulfoxide.
6. the application of polyimides doughnut infiltrating and vaporizing membrane according to claim 1, it is characterized in that: polyimides doughnut infiltrating and vaporizing membrane is used for the permeable membrane of infiltration vaporization membrane module, be applied to dewater in the alcohols solvent, alcohols solvent is: methyl alcohol or ethanol or propyl alcohol or butanols or amylalcohol.
7. the application of polyimides doughnut infiltrating and vaporizing membrane according to claim 7 is characterized in that: polyimides doughnut infiltrating and vaporizing membrane is measured the permeation flux of water greater than 3x10 in 70-150 ℃ temperature range
-7Mol/m
2SPa, for the separation factor of alcohol greater than 200.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218316A (en) * | 2014-11-28 | 2016-01-06 | 杭州奇纯膜技术有限公司 | A kind of hollow fiber pervaporation membrane prepares the device and method of dehydrated alcohol |
| CN105294396A (en) * | 2014-11-28 | 2016-02-03 | 杭州奇纯膜技术有限公司 | Device and method for preparing anhydrous n-propanol through hollow fiber pervaporation membrane |
| CN109173753A (en) * | 2018-09-20 | 2019-01-11 | 中国乐凯集团有限公司 | Casting solution, ultrafiltration membrane, reverse osmosis composite membrane or Nano filtering composite membrane |
| CN109433021A (en) * | 2018-11-28 | 2019-03-08 | 常州大学 | Have both the osmosis vaporizing compound membrane and preparation method thereof of solvent resistance and excellent small molecular alcohol separating property |
| CN112867556A (en) * | 2018-10-22 | 2021-05-28 | 日东电工株式会社 | Separation membrane and membrane separation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1231941A (en) * | 1998-04-16 | 1999-10-20 | 中国科学院大连化学物理研究所 | Preparation of asymmetrical hollow polyimide fibre membrane |
| CN1911494A (en) * | 2005-08-11 | 2007-02-14 | 中国石油天然气股份有限公司 | Preparation method of polyimide nanometer filtering membrane |
| CN101480583A (en) * | 2008-12-30 | 2009-07-15 | 天邦膜技术国家工程研究中心有限责任公司 | Method for preparing novel polyetherimide hollow fiber film |
-
2009
- 2009-08-28 CN CN2009100659836A patent/CN101992033A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1231941A (en) * | 1998-04-16 | 1999-10-20 | 中国科学院大连化学物理研究所 | Preparation of asymmetrical hollow polyimide fibre membrane |
| CN1911494A (en) * | 2005-08-11 | 2007-02-14 | 中国石油天然气股份有限公司 | Preparation method of polyimide nanometer filtering membrane |
| CN101480583A (en) * | 2008-12-30 | 2009-07-15 | 天邦膜技术国家工程研究中心有限责任公司 | Method for preparing novel polyetherimide hollow fiber film |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218316A (en) * | 2014-11-28 | 2016-01-06 | 杭州奇纯膜技术有限公司 | A kind of hollow fiber pervaporation membrane prepares the device and method of dehydrated alcohol |
| CN105294396A (en) * | 2014-11-28 | 2016-02-03 | 杭州奇纯膜技术有限公司 | Device and method for preparing anhydrous n-propanol through hollow fiber pervaporation membrane |
| CN109173753A (en) * | 2018-09-20 | 2019-01-11 | 中国乐凯集团有限公司 | Casting solution, ultrafiltration membrane, reverse osmosis composite membrane or Nano filtering composite membrane |
| CN112867556A (en) * | 2018-10-22 | 2021-05-28 | 日东电工株式会社 | Separation membrane and membrane separation method |
| CN109433021A (en) * | 2018-11-28 | 2019-03-08 | 常州大学 | Have both the osmosis vaporizing compound membrane and preparation method thereof of solvent resistance and excellent small molecular alcohol separating property |
| CN109433021B (en) * | 2018-11-28 | 2021-06-18 | 常州大学 | Pervaporation composite membrane with solvent resistance and excellent small molecular alcohol separation performance and preparation method thereof |
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