CN100427191C - Production of hollow fibrous air single external skin separating film with polyether sulphone - Google Patents
Production of hollow fibrous air single external skin separating film with polyether sulphone Download PDFInfo
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- CN100427191C CN100427191C CNB2005101121428A CN200510112142A CN100427191C CN 100427191 C CN100427191 C CN 100427191C CN B2005101121428 A CNB2005101121428 A CN B2005101121428A CN 200510112142 A CN200510112142 A CN 200510112142A CN 100427191 C CN100427191 C CN 100427191C
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- polyether sulfone
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Abstract
The present invention discloses a preparation method for a hollow fibrous gas separating film with a single external layer of polyether sulfone, which comprises the following procedures: a film casting solution is prepared from a ternary system of polyether sulfone (PES), a solvent and an additive; then a hollow fibrous gas separating film with a single external layer of polyether sulfone is prepared by a spinning technique with a dry spray and wet spinning method. The present invention is convenient and reliable. Hollow fibrous gas separating films with a single external layer of polyether sulfone, which have different fluxes and selectivity can be prepared by adopting the present invention. The prepared hollow fibrous gas separating film with a single external layer of polyether sulfone can be widely applied to gas separation, such as air rich in oxygen, air rich in nitrogen, CO2 elimination in natural gas, H2 recovering in synthesis gas, etc. in the industrial field.
Description
Technical field
The present invention relates to a kind of hollow-fiber film, more particularly relate to a kind of preparation method of single exodermis polyether sulfone doughnut gas separation membrane.
Background technology
At present, asymmetric hollow-fibre membrane is widely used in the gas separation.U.S. Monsanto Company has developed polysulfones-silicon rubber hollow fiber composite membrane separator before and after 1970, and is successfully used to synthetic ammonia release gas recovery hydrogen, becomes the sign that gas membrane Seperation Technology obtains industrial applications.People such as Henis and Tripodi adopted the resin rubber coating technology to improve the asymmetric membrane cosmetic bug before and after 1980 and obtains remarkable progress at aspects such as membrane material, cyclone separator arrangement and application development process again.Chinese patent CN02133032.8, name is called " cellulose hollow fiber gas separation membrane and preparation thereof ", and to disclose a kind of employings a water N-methyl morpholine oxide be the direct dissolving cellulos of solvent, and the method that phase inversion is spun into the cellulose hollow film is immersed in employing then.Preparation process is as follows: 1) at 80～110 ℃ of MMNOH with 80～93wt%
2O and cellulose mixed dissolution, deaeration, the transparent casting solution of cellulose concentration 7～20wt%; 2) with immersing phase inversion spinning hollow membrane; 3) residual solvent in the flush away film; 4) air dry in the air of relative humidity 40%～90% gets the dry state hollow membrane.This method utilizes native cellulose to be raw material, and membrane material has certain limitation.Current, polyether sulfone (PES) is considered to one of a kind of more promising membrane material, it has good separating property and chemistry and heat endurance and higher separating property, and the gas that can be used for industrial circle separates, and removes CO as oxygen enriching, the rich nitrogen of air, natural gas
2, synthesis gas reclaims H
2Etc. the aspect.Therefore, study single exodermis polyether sulfone doughnut gas separation membrane and become one of focus of this area.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of easy single exodermis polyether sulfone (PES) doughnut gas separation membrane.
The technical solution used in the present invention: a kind of preparation method of single exodermis polyether sulfone doughnut gas separation membrane comprises the following steps:
(a) preparation casting solution
With mass percent be 29%～35%, mean molecule quantity is 50000～150000 polyether sulfone, with mass percent be that 57% the solvent and the additive of surplus join in the container respectively, through dissolving, stir with general mixer and to obtain casting solution after mixing at least three hours, described solvent is selected from one or more the mixture in dimethyl formamide, dimethylacetylamide, the N-methyl pyrrolidone, and described additive is selected from one or more the mixture in methyl alcohol, ethanol, propyl alcohol, the glycerine;
(b) preparation doughnut asymmetric membrane
The casting solution that step a makes is squeezed into outer tube between the annulus of making the film shower nozzle by Compressed Gas, interior pipe at system film shower nozzle injects the inner gel medium simultaneously, it in the coagulation bath outer gel media, in, the temperature of outer gel media is 0～30 ℃, described casting solution and inner gel medium are injected in the coagulation bath simultaneously, casting solution is frozen into single exodermis polyether sulfone hollow-fibre membrane in coagulation bath, described inner gel medium is selected from 50～98% the dimethyl formamide aqueous solution, the dimethylacetylamide aqueous solution, the mixture of one or more in the N-methyl pyrrolidone aqueous solution, described outer gel media is a deionized water.
The diameter of inner pipe of described system film shower nozzle is 0.2～0.6mm, and the outer tube diameter of described system film shower nozzle is 0.5～1.0mm, and the liquid level distance L of described system film shower nozzle and coagulation bath is 0～30mm.
Single exodermis polyether sulfone hollow-fibre membrane that step b is made further soaked into 3 hours in methyl alcohol, ethanol or hexane solution, can play a protective role to single exodermis polyether sulfone hollow-fibre membrane.
The invention has the beneficial effects as follows: the present invention adopt polyether sulfone (PES), solvent and additive ternary system to be mixed with casting solution and do two main processes of spray-wet spinning spinning very easy made single exodermis polyether sulfone doughnut gas separation membrane.Adopt the present invention to prepare to have different flux and polyether sulfone (PES) doughnut gas separation membrane optionally.The gas that prepared polyether sulfone (PES) doughnut gas separation membrane can be widely used in industrial circle separates, and removes CO as oxygen enriching, the rich nitrogen of air, natural gas
2, synthesis gas reclaims H
2Etc. the aspect.
Description of drawings
Fig. 1 is system film shower nozzle and film-forming process schematic diagram;
Fig. 2 a is 100 times of stereoscan photographs of outer single skin PES doughnut gas separation membrane structural membrane section;
Fig. 2 b is 300 times of stereoscan photographs of outer single skin PES doughnut gas separation membrane structural membrane section;
Fig. 2 c is 5000 times of stereoscan photographs of outer single skin PES doughnut gas separation membrane structural membrane section;
Fig. 2 d is 10000 times of stereoscan photographs of outer single skin PES doughnut gas separation membrane structural outer surface;
Fig. 2 e is the hungry surperficial 2000 times of stereoscan photographs of outer single skin PES doughnut gas separation membrane structure.
The specific embodiment
1 couple of the present invention describes in further detail in conjunction with the accompanying drawings: a kind of preparation method of single exodermis polyether sulfone doughnut gas separation membrane comprises the following steps:
(a) preparation casting solution: with mass percent be 29%～35%, mean molecule quantity is 50000～150000 polyether sulfone, with mass percent be that 57% the solvent and the additive of surplus join in the container respectively, through dissolving, stir with general mixer and to obtain casting solution after mixing at least three hours, described solvent is selected from one or more the mixture in dimethyl formamide, dimethylacetylamide, the N-methyl pyrrolidone, and described additive is selected from one or more the mixture in methyl alcohol, ethanol, propyl alcohol, the glycerine;
(b) preparation doughnut asymmetric membrane: the casting solution that step a makes is squeezed into outer tube (3) between the annulus of making film shower nozzle (5) by Compressed Gas, interior pipe (2) at system film shower nozzle (5) injects the inner gel medium simultaneously, be outer gel media in the coagulation bath (6), in, the temperature of outer gel media is 0～30 ℃, described casting solution and inner gel medium are injected in the coagulation bath (6) simultaneously, casting solution is frozen into single exodermis polyether sulfone hollow-fibre membrane in coagulation bath (6), described inner gel medium is selected from 50～98% the dimethyl formamide aqueous solution, the dimethylacetylamide aqueous solution, the mixture of one or more in the N-methyl pyrrolidone aqueous solution, described outer gel media is a deionized water.
As shown in Figure 1, interior pipe 2 diameters of described system film shower nozzle 5 are 0.2～0.6mm, and outer tube 3 diameters of described system film shower nozzle 5 are 0.5～1.0mm, and described system film shower nozzle 5 is 0～30mm with the liquid level distance L of coagulation bath 6.For the PES doughnut asymmetric membrane for preparing can be preserved under drying regime, the reply film is protected processing.The protection processing method that adopts among the present invention is that single exodermis polyether sulfone hollow-fibre membrane that step b makes was further soaked into 3 hours in methyl alcohol, ethanol or hexane solution.Through after such processing, the PES doughnut asymmetric membrane that makes can not shrink in the kept dry process, keeps its high osmosis energy fully, and when assembling doughnut gas separator, guarantees that hollow-fibre membrane and epoxy resin glue bond are good.
Embodiment 1
Press column weight amount percentage and take by weighing raw material, mean molecule quantity is 135000 PES:35%; NMP:57% and Ethanol:8% are mixed with preparation liquid, and its process is: earlier 8%Ethanol is added stirring and dissolving among 57% the DMAC, to be mixed evenly after, add 35% PES stirring and dissolving again.Placed 72 hours, temperature is 25 ℃.The preparation liquid for preparing is poured in the batch can, leaves standstill deaeration in 24 hours.Shower nozzle is of a size of d
In=0.8mm, d
The hole=0.5mm, preparation liquid is from the ejection of shower nozzle annular space, and temperature is controlled at 24 ℃, injects outer coagulation bath then and solidifies, and again through rinsing bowl, becomes silk with 7 meters/bundling speed coiling boundling.Inner gel medium (core liquid) is gone into nascent state doughnut center to form hollow with the metering infusion, and inner gel medium (core liquid) is the 86%NMP aqueous solution, and outer coagulation bath is an ionized water, and inside and outside coagulation bath temperature all is 24 ℃, and the rinsing bowl temperature also is 24 ℃.The hollow-fibre membrane that spinning forms is assembled into PES doughnut gas separation membrane assembly GS1 in the time of can be in dry state after protection is handled.
Press example 1 described preparation process and condition, mean molecule quantity is 135000 PES:35%; NMP:57% and Ethano l:8% are mixed with preparation liquid.Press example 1 described preparation process.Except inside and outside coagulation bath temperature all is 20 ℃, other process conditions and the example 1 identical hollow-fibre membrane that makes adopt same protection to handle and be assembled into PES doughnut gas separation membrane assembly GS2.
Press example 1 described preparation process and condition, mean molecule quantity is 135000 PES:35%; NMP:57% and Ethanol:8% are mixed with preparation liquid.Press example 1 described preparation process.Except inside and outside coagulation bath temperature all is 17 ℃, other process conditions and the example 1 identical hollow-fibre membrane that makes adopt same protection to handle and be assembled into PES doughnut gas separation membrane assembly GS3.
Embodiment 4
Press example 1 described preparation process and condition, mean molecule quantity is 135000 PES:35%; NMP:57% and Ethanol:8% are mixed with preparation liquid.Press example 1 described preparation process.Except inside and outside coagulation bath temperature all is 13 ℃, other process conditions and the example 1 identical hollow-fibre membrane that makes adopt same protection to handle and be assembled into PES doughnut gas separation membrane assembly GS4.
Press example 1 described preparation process and condition, mean molecule quantity is 135000 PES:35%; NMP:57% and Ethanol:8% are mixed with preparation liquid.Press example 1 described preparation process.Except the inner gel medium was pure water, other process conditions were identical with example 1, make hollow-fibre membrane, adopted same protection to handle and be assembled into PES doughnut gas separation membrane assembly GS5.
Press example 1 described preparation process and condition, mean molecule quantity is 135000 PES:35%; NMP:57% and Ethanol:8% are mixed with preparation liquid.Press example 1 described preparation process.Except the inner gel medium was the 50%NMP aqueous solution, other process conditions were identical with example 1, make the doughnut gas separation membrane, adopted same protection to handle and be assembled into PES doughnut gas separation membrane assembly GS6.
Embodiment 7
Press example 1 described preparation process and condition, mean molecule quantity is 135000 PES:35%; NMP:57% and Ethanol:8% are mixed with preparation liquid.Press example 1 described preparation process.Except the inner gel medium was the 92%NMP aqueous solution, other process conditions were identical with example 1, make hollow-fibre membrane, adopted same protection to handle and be assembled into PES doughnut gas separation membrane assembly GS7.
5～10 of the doughnut gas separation membranes that above-mentioned example 1～7 is made are packed in Φ 8 * 230mm stainless steel tube, and two ends seal with epoxide-resin glue, are assembled into small hollow fiber gas separation membrane assembly GS1, GS2, GS3, GS4, GS5, GS6, GS7.At room temperature assembly is put into 3% silicon rubber and is soaked 3-5min, place 1-3 days then after, under 20 ℃ and 0.5MPa condition, use pure O
2And N
2Measure their gas permeability Ji respectively:
Subscript i refers to O respectively in the formula
2And N
2, Q
iBe the volume flow of gas i under the standard state, cm
3/ s; Δ P is a permeable pressure head, and Pa, A are membrane area, cm
2J
iBe gas permeability, GPU; 1GPU=7.501 * 10
-10Cm
3/ cm
2.Pa.s.
Ideal separation factor α
I/j:
Subscript i and j refer to O respectively in the formula
2And N
2
The performance of table 1PES doughnut gas separation membrane assembly
By table 1 result as can be seen, the prepared a series of PES doughnut gas separation membrane assemblies of the present invention have different O
2And N
2Separating property.Utilize ESEM further to study the structure of hollow-fibre membrane, see Fig. 2 a, Fig. 2 b, Fig. 2 c, Fig. 2 d, Fig. 2 e can find that polyether sulfone (PES) doughnut gas separation membrane section has finger-like pore and spongiform asymmetric membrane (Fig. 2 A, B and C), the film outer surface atresia of multiplication factor 10000 (Fig. 2 D), and the film inner surface of multiplication factor 2000 has the hole (Fig. 2 E) of about 2 μ m, and this polyether sulfone (PES) doughnut gas separation membrane that shows preparation is single exodermis PES asymmetric membrane.Simultaneously, behind silicone rubber coating, can obtain higher optionally gas separation membrane, its hot strength has mechanical strength preferably at 7.9～9.3Mpa.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (2)
1. the preparation method of a single exodermis polyether sulfone doughnut gas separation membrane comprises the following steps:
(a) preparation casting solution
With mass percent be 29%～35%, mean molecule quantity is 50000～150000 polyether sulfone, with mass percent be that 57% the solvent and the additive of surplus join in the container respectively, through dissolving, stir with general mixer and to obtain casting solution after mixing at least three hours, described solvent is selected from one or more the mixture in dimethyl formamide, dimethylacetylamide, the N-methyl pyrrolidone, and described additive is selected from one or more the mixture in methyl alcohol, ethanol, propyl alcohol, the glycerine;
(b) preparation doughnut asymmetric membrane
The casting solution that step a makes is squeezed into outer tube (3) between the annulus of making film shower nozzle (5) by Compressed Gas, interior pipe (2) at system film shower nozzle (5) injects the inner gel medium simultaneously, be outer gel media in the coagulation bath (6), in, the temperature of outer gel media is 0～30 ℃, described casting solution and inner gel medium are injected in the coagulation bath (6) simultaneously, casting solution is frozen into single exodermis polyether sulfone hollow-fibre membrane in coagulation bath (6), described inner gel medium is selected from 50～98% the dimethyl formamide aqueous solution, the dimethylacetylamide aqueous solution, the mixture of one or more in the N-methyl pyrrolidone aqueous solution, described outer gel media is a deionized water.
2. according to the preparation method of the described a kind of single exodermis polyether sulfone doughnut gas separation membrane of claim 1, it is characterized in that: single exodermis polyether sulfone hollow-fibre membrane that step b is made further soaked into 3 hours in methyl alcohol, ethanol or hexane solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101121428A CN100427191C (en) | 2005-12-28 | 2005-12-28 | Production of hollow fibrous air single external skin separating film with polyether sulphone |
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|---|---|---|---|
| CNB2005101121428A CN100427191C (en) | 2005-12-28 | 2005-12-28 | Production of hollow fibrous air single external skin separating film with polyether sulphone |
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| CN1817426A CN1817426A (en) | 2006-08-16 |
| CN100427191C true CN100427191C (en) | 2008-10-22 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101185848B (en) * | 2007-08-29 | 2010-12-01 | 江南大学 | Unsymmetrical network shape pore structure hollow fiber film and preparation method thereof |
| CN103861483A (en) * | 2014-03-21 | 2014-06-18 | 华东理工大学 | Preparation method for low-pressure sulfonated polymer hollow fiber nano-filtration membrane |
| CN105435654B (en) * | 2014-07-02 | 2019-05-31 | 博天（北京）环境设计研究院有限公司 | The preparation method of single skin hollow-fibre membrane |
| CN107626187A (en) * | 2017-11-13 | 2018-01-26 | 安徽名创新材料科技有限公司 | A kind of preparation method of single exodermis PES Ho llow fiber membrane for gas separation |
| CN109174017B (en) * | 2018-10-18 | 2021-08-13 | 天津工业大学 | Solid amine adsorbent, preparation method thereof and CO containing solid amine adsorbent2Adsorption component |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317345A (en) * | 2001-05-17 | 2001-10-17 | 东华大学 | Material of artificial kidney for hemodialysis and its preparing process |
| CN1076630C (en) * | 1997-12-17 | 2001-12-26 | 四川联合大学 | Polyether sulphone hollow fibre film and its manufacturing method and use |
| CN1415407A (en) * | 2002-11-19 | 2003-05-07 | 华东理工大学 | Method for preparing ultra filtration membrane in hollow fiber made from PVC with high flux |
| CN1173772C (en) * | 2001-05-17 | 2004-11-03 | 东华大学 | New material for ascites ultrafiltering, concentrating and back-infusing device and producing method |
-
2005
- 2005-12-28 CN CNB2005101121428A patent/CN100427191C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076630C (en) * | 1997-12-17 | 2001-12-26 | 四川联合大学 | Polyether sulphone hollow fibre film and its manufacturing method and use |
| CN1317345A (en) * | 2001-05-17 | 2001-10-17 | 东华大学 | Material of artificial kidney for hemodialysis and its preparing process |
| CN1173772C (en) * | 2001-05-17 | 2004-11-03 | 东华大学 | New material for ascites ultrafiltering, concentrating and back-infusing device and producing method |
| CN1415407A (en) * | 2002-11-19 | 2003-05-07 | 华东理工大学 | Method for preparing ultra filtration membrane in hollow fiber made from PVC with high flux |
Non-Patent Citations (2)
| Title |
|---|
| Polyethersulfone hollow fiber gas separation membranesprepared from NMP/alcohol solvent systems. Dongliang Wang,K.Li,W.K.Teo.Journal of Membrane Science,Vol.115 . 1996 |
| Polyethersulfone hollow fiber gas separation membranesprepared from NMP/alcohol solvent systems. Dongliang Wang,K.Li,W.K.Teo.Journal of Membrane Science,Vol.115 . 1996 * |
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