CN1657144A - Composite hollow fiber membrane and its preparation and application - Google Patents
Composite hollow fiber membrane and its preparation and application Download PDFInfo
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- CN1657144A CN1657144A CN 200410021149 CN200410021149A CN1657144A CN 1657144 A CN1657144 A CN 1657144A CN 200410021149 CN200410021149 CN 200410021149 CN 200410021149 A CN200410021149 A CN 200410021149A CN 1657144 A CN1657144 A CN 1657144A
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Abstract
A composite hollow fibre membrane based on the composite resistance Henis membrane model (silica rubber/polysulfone membrane) for separating H2 or N2 with high effect is composed of basic membrane, water-soluble high-molecular layer in rubber state at ordinary temp and silica rubber layer. It can be used for the ammonia synthesizing plant or oil refinary to recover N2 or H2. Its preparing process is also disclosed.
Description
Technical field:
The present invention relates to membrane technology, a kind of hollow fiber composite membrane, preparation method and application of secondary coating are provided especially.
Background technology:
Hydrogen will be played the part of more and more important role in the energy of 21 century and petrochemical industry.At present, the main method of acquisition hydrogen source has two classes: a class is to utilize oil or coal to wait to produce (moisture vapor reforming hydrogen manufacturing, gas partial oxidation hydrogen-preparation, Top's rope method hydrogen manufacturing etc.), and cost is very high, produces 1 ton of hydrogen and need consume petroleum 4～5 tons.Another kind of is to utilize new technology recover hydrogen from various hydrogeneous waste gas, embrane method Recovery technology of hydrogen for example, and back one class will be the effective ways that oil refining industry obtains cheap hydrogen source.
Compare with traditional isolation technics, membrane separation technique have no material consumption, reduced investment, occupation of land less, advantage such as energy consumption is low, non-maintaining, easy to operate.The doughnut embrane method is put forward the hydrogen technology and be can be used for carrying dense hydrogen from synthetic ammonia relief gas and petroleum refinery's gas, and the gas treatment amount can reach several ten thousand m
3/ h, hydrogen mole fraction are greater than 95%, and the rate of recovery is greater than 85%, for enterprise has brought considerable economic.The film separating and reclaiming hydrogen is the widest Membrane Gas Separation Processes of current application face.
The sixties in 20th century, Loeb and Sourirajan develop first cellulose acetate anisotropic membrane with commercial value, lay a good foundation for preparing high saturating amount diffusion barrier, have started new era of membrane technology.At the end of the seventies, Henis has invented the resistance composite membrane, has realized that gas film separates the leap of development.U.S. Monsanto company successfully was applied to gas and synthetic ammonia purge with silicon rubber/polysulfones resistance composite membrane in 1979 and reclaims hydrogen, and since then, the gas film separation has entered the stage of industrial applications.
Existing application is in H
2/ N
2The hollow fiber composite membrane coating process that separates is the primary coating process, belongs to Henis resistance composite membrane.Set forth coating process at intermittence as US4214020, but the infiltration rate of the hollow-fibre membrane after the coating is little to the doughnut boundling, relatively poor for the membrane coat effect that saturating amount is big slightly.US4230463 discloses six kinds of coating processes, is the primary coating process, and made film belongs to Henis resistance composite membrane.These methods can access the film of better performances, but still can't reach intrinsic separation, the permeance property of film.US4767422 discloses a kind of method of composite membrane post processing, mainly is to handle the film of coating with volatile solvent, and to repair the defective of separating layer, evaporation removes to desolvate and makes the film drying again.This method is subjected to the influence of solvent big, and the structure that is difficult for accomplishing neither damaging film can significantly improve separation, the permeance property of composite membrane again.
Summary of the invention:
The purpose of this invention is to provide a kind of hollow fiber composite membrane, it has high gas and selects separation property, high separation.
The invention provides a kind of hollow fiber composite membrane, it is characterized in that: this composite membrane is covered with water soluble polymer coating and silicone rubber coating in regular turn outside basement membrane.
In the hollow fiber composite membrane of the present invention, described basal lamina material is chosen as polysulfones, is the spongelike structure supporting layer; Described polymeric coating layer preferably is chosen as polyoxyethylene PEO.
Hollow fiber composite membrane of the present invention is introduced second coating on Henis resistance composite membrane model based, thereby obtain the hollow fiber composite membrane of novel having " sandwich " structure, in the hollow fiber composite membrane of this " sandwich " structure, defective hole in original basement membrane cortex is successively blocked by water soluble polymer and silicon rubber, improve the selection separation property of gas, improved the H of silicon rubber/polysulfones resistance composite membrane
2/ N
2Pure gas ideal separation factor.
In the hollow fiber composite membrane of the present invention, water soluble polymer can at room temperature keep rubbery state, strand to have the pliability and the thermoplasticity of height, generally contains active carbonyl, carboxyl or hydroxy functional group.The adding of water soluble polymer has been played the bridge linking effect of polysulfones and silicon rubber combination because of having brought two new boundaries in the composite membrane of " sandwich " structure, change the state of silicon rubber in the basement membrane hole of single coating composite membrane, improved the isolating construction and the separating property of composite membrane.
Hollow fiber composite membrane of the present invention is for H
2/ N
2Pure gas has very high ideal separation factor α
H2/N2, mean value reaches 75.4; H
2Infiltration rate J
H2Reach 4.36 * 10
-5Cm
3(STP)/cm
2S cmHg.Can be applied to synthetic ammonia relief gas and petroleum refinery's gas and carry dense hydrogen, improve separation α
H2/N2Make film more be applicable to low pressure, low dense refinery gas hydrogen removal process.Its mesolow, low dense refinery gas mainly are meant the mixing dry gas of catalytic cracked dry gas and family's gas thereof.
The invention provides the preparation method of above-mentioned hollow fiber composite membrane, it is characterized in that process is as follows:
Primary coating:
The consisting of 0.001～2wt% macromolecule, 0.1～1mL coupling agent, 0.1～1mL plasticizer all the other be H of coating liquid
2O;
Coating procedure be basement membrane is immersed in soak 10～60 in the coating liquid, air dry solidifies;
Secondary coating:
The curing agent that consists of 0.2～2wt%SR, SR quality 1/5～1/20 of coating liquid, 0.1～1mL coupling agent, all the other are pentane;
Coating procedure is that the film behind the primary coating is immersed in the coating liquid; Suction to-0.075～-0.095Mpa, the time is 2～5 minutes; Macaroni yarn continued to vacuumize 3～8 minutes after shifting out coating liquid, and vacuum reaches-0.098Mpa, stops to vacuumize; Place 50～100 ℃ environment to solidify 24～72 hours.
Among the preparation method of hollow fiber composite membrane of the present invention, macromolecule can be chosen as polyoxyethylene PEO, polyvinylpyrrolidone PVP, PVAC polyvinylalcohol.
Among the preparation method of hollow fiber composite membrane of the present invention, the used coupling agent of primary coating liquid can be chosen as γ-glycidyl ether propyl trimethoxy silicane KH560 or γ-An Jibingjisanyiyangjiguiwan KH550.
Among the preparation method of hollow fiber composite membrane of the present invention, the used plasticizer of primary coating liquid can be chosen as dioctyl phthalate DOP.
Among the preparation method of hollow fiber composite membrane of the present invention, the used coupling agent of secondary coating liquid can be chosen as γ-glycidyl ether propyl trimethoxy silicane KH560 or γ-An Jibingjisanyiyangjiguiwan KH550.
Preparation method's process of the present invention is simple, the whole process of preparation easy operating, and condition is controlled easily, both has been suitable for a small amount of preparation of laboratory research, also is suitable for amplifying producing.
Hollow fiber composite membrane preparation of the present invention can be used for synthetic ammonia relief gas and petroleum refinery's gas is carried dense hydrogen or is used for low pressure, low dense refinery gas hydrogen removal process.In a word,
1, the present invention is basal lamina material with the polysulfones, is coating material with water soluble polymer PEO etc. with SR respectively, utilizes the method for secondary coating, has prepared the hollow fiber composite membrane of novel having " sandwich " structure.This coating formula, structure and method are in the past report of document or patent institute, also do not see that document discusses.
2, PEO coating liquid concentration is when 0.001～2wt% scope, SR coating liquid concentration are in 0.5～2wt% scope, and the prepared secondary coating hollow fiber composite membrane of the present invention is for H
2/ N
2Pure gas has higher ideal separation factor α
H2/N2, mean value reaches 75.4, H
2Average infiltration rate J
H2Reach 4.36 * 10
-5Cm
3(STP)/cm
2S cmHg is suitable for H
2/ N
2Separation.
3, keep rubbery state under the used water soluble polymer room temperature of the present invention, strand has the pliability and the thermoplasticity of height, generally contains active carbonyl, carboxyl or hydroxy functional group.The adding of water soluble polymer has been played the bridge linking effect of polysulfones and silicon rubber combination because of having brought two new boundaries in the composite membrane of " sandwich " structure, change the state of silicon rubber in the basement membrane hole of single coating composite membrane, improved the isolating construction and the separating property of composite membrane.
4, preparation method's process of the present invention is simple, the whole process of preparation easy operating, and condition is controlled easily, both has been suitable for a small amount of preparation of laboratory research, also is suitable for amplifying producing.
Description of drawings:
Fig. 1 α
H2/N2Relation curve with PEO coating liquid concentration;
Fig. 2 J
H2Relation curve with PEO coating liquid concentration.
The specific embodiment:
Monofilament is of a size of the long 700mm of external diameter 450 μ m internal diameters, 150 μ m do-25 collection of polysulfone hollow fibre anisotropic membrane of wet method spinning are a branch of, are converted into " U " shape, openend is made basement membrane with the epoxy resin casting.Earlier tow is immersed in the water soluble polymer coating liquid of 150mL and soaks the primary coating process of finishing in 10～60 minutes, silk takes out a back air dry and solidified 24 hours.Water soluble polymer coating liquid consist of 0.001～2wt% macromolecule, 0.1～1mL organo silane coupling agent γ-An Jibingjisanyiyangjiguiwan KH-550,0.1～1mL polymeric plasticizer dioctyl phthalate DOP, all the other are H
2O.The macaroni yarn that the primary coating that has solidified is crossed carries out secondary SR vacuum coating.The curing agent that consists of 0.5wt%SR, SR quality 1/15 of SR coating liquid, 0.5mL γ-An Jibingjisanyiyangjiguiwan KH-550, all the other are pentane, tested viscosity is about 0.70cp.At first, suction is to-0.085Mpa, and the vacuum coating time is 3 minutes.Macaroni yarn continued to vacuumize 5 minutes after shifting out coating liquid, and vacuum reaches-0.098Mpa, stopped to vacuumize in the environment that is placed on 60 ℃ solidifying 36 hours.Under 300 ℃, unstripped gas 0.5Mpa condition, on the self-control evaluating apparatus, measure pure H
2, pure N
2See through the gas permeation rate J of film
H2, J
N2, and calculate gas ideal separation factor α
H2/N2=J
H2/ J
N2The prepared film of PEO+SR secondary coating is for H
2/ N
2Pure gas has very high ideal separation factor α
H2/N2, mean value reaches 75.4; H
2Infiltration rate J
H2Reach 4.36 * 10
-5Cm
3(STP)/cm
2S cmHg.
Embodiment 1
Monofilament is of a size of the long 700mm of external diameter 450 μ m internal diameters, 150 μ m do-25 collection of the asymmetric basement membrane of polysulfone hollow fibre of wet method spinning are a branch of, are converted into " U " shape, openend is made basement membrane with the epoxy resin casting.Tow is immersed in soaks the primary coating process of finishing in 15 minutes in the PEO coating liquid of 150mL, silk takes out a back air dry and solidified 24 hours.PEO coating liquid consist of 0.1wt%PEO, 0.5mL organo silane coupling agent γ-An Jibingjisanyiyangjiguiwan KH-550,0.4mL polymeric plasticizer dioctyl phthalate DOP, all the other are H
2O.Under 30 ℃, unstripped gas 0.5MPa condition, on the self-control evaluating apparatus, measure pure H
2, pure N
2See through the gas permeation rate J of film
H2, J
N2, and calculate gas ideal separation factor α
H2/N2=J
H2/ J
N2Record J
H2Be 5.57 * 10
-5Cm
3(STP)/cm
2S cmHg, α
H2/N2Be 42.3, with respect to basement membrane α
H2/N2(basement membrane α improves a lot
H2/N2Be 3～7).
Embodiment 2
Basement membrane make and method of testing with embodiment 1, tow is immersed in the polyvinylpyrrolidone PVP coating liquid of 150mL and soaks the primary coating process of finishing in 30 minutes.PVP coating liquid consist of 0.5wt%PVP, 0.5mL γ-An Jibingjisanyiyangjiguiwan KH-550,0.4mL polymeric plasticizer dioctyl phthalate DOP, all the other are H
2O.Silk takes out the back air dry and solidified 24 hours, records J
H2Be 7.85 * 10
-5Cm
3(STP)/cm
2S cmHg, α
H2/N2Be 16.1, with respect to basement membrane α
H2/N2Raising is arranged.
Embodiment 3
Basement membrane make and method of testing with embodiment 1, tow is immersed in the PVAC polyvinylalcohol coating liquid of 150mL and soaks the primary coating process of finishing in 30 minutes.PVA coating liquid consist of 0.5wt%PVA, 0.5mL γ-An Jibingjisanyiyangjiguiwan KH-550,0.4mL polymeric plasticizer dioctyl phthalate DOP, all the other are H
2O.Silk takes out the back air dry and solidified 24 hours, records J
H2Be 6.09 * 10
-5Cm
3(STP)/cm
2S cmHg, α
H2/N2Be 19.9, with respect to basement membrane α
H2/N2Raising is arranged.
Embodiment 4
Basement membrane making and method of testing are with embodiment 1, and the macaroni yarn that the PEO primary coating that has solidified is crossed carries out secondary SR vacuum coating.The curing agent that consists of 0.5wt%SR, SR quality 1/15 of SR coating liquid, 0.5mL γ-An Jibingjisanyiyangjiguiwan KH-550, all the other are pentane, tested viscosity is about 0.70cp.At first, suction is to-0.085Mpa, and the vacuum coating time is 3 minutes.Macaroni yarn continued to vacuumize 5 minutes after shifting out coating liquid, and vacuum reaches-0.098Mpa, stopped to vacuumize in the environment that is placed on 60 ℃ solidifying 36 hours.Record J
H2Be 4.98 * 10
-5Cm
3(STP)/cm
2S cmHg, α
H2/N2Be 77.8, be suitable for H
2/ N
2Separation.
Claims (10)
1, a kind of hollow fiber composite membrane is characterized in that: this composite membrane is covered with water soluble polymer coating and silicone rubber coating in regular turn outside basement membrane.
2, according to the described hollow fiber composite membrane of claim 1, it is characterized in that: described basal lamina material is a polysulfones.
3, according to the described hollow fiber composite membrane of claim 1, it is characterized in that: described polymeric coating layer is polyoxyethylene PEO.
4, the preparation method of the described hollow fiber composite membrane of a kind of claim 1 is characterized in that process is as follows:
Primary coating:
The consisting of 0.001～2wt% macromolecule, 0.1～1mL coupling agent, 0.1～1mL plasticizer all the other be H of coating liquid
2O;
Coating procedure is basement membrane to be immersed in soak 10～60 minutes, air dry curing in the coating liquid;
Secondary coating:
The curing agent that consists of 0.2～2wt% silicon rubber SR, SR quality 1/5～1/20 of coating liquid, 0.1～1mL coupling agent, all the other are pentane;
Coating procedure is that the film behind the primary coating is immersed in the coating liquid; Suction to-0.075～-0.095Mpa, the time is 2～5 minutes; Macaroni yarn continued to vacuumize 3～8 minutes after shifting out coating liquid, and vacuum reaches-0.098Mpa, stops to vacuumize; Place 50～100 ℃ environment to solidify 24～72 hours.
5, according to the preparation method of the described hollow fiber composite membrane of claim 4, it is characterized in that: described basal lamina material is a polysulfones.
6, according to the preparation method of the described hollow fiber composite membrane of claim 4, it is characterized in that: described macromolecule is polyoxyethylene PEO, polyvinylpyrrolidone PVP, PVAC polyvinylalcohol.
7, according to the preparation method of the described hollow fiber composite membrane of claim 4, it is characterized in that: the used coupling agent of described primary coating liquid is γ-glycidyl ether propyl trimethoxy silicane KH560 or γ-An Jibingjisanyiyangjiguiwan KH550.
8, according to the preparation method of the described hollow fiber composite membrane of claim 4, it is characterized in that: the used plasticizer of described primary coating liquid is dioctyl phthalate DOP.
9, according to the preparation method of the described hollow fiber composite membrane of claim 4, it is characterized in that: the used coupling agent of described secondary coating liquid is γ-glycidyl ether propyl trimethoxy silicane KH560 or γ-An Jibingjisanyiyangjiguiwan KH550.
10, the preparation of the described hollow fiber composite membrane of claim 1 is used for synthetic ammonia relief gas and petroleum refinery's gas is carried dense hydrogen or is used for low pressure, low dense refinery gas hydrogen removal process.
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| CN102565282A (en) * | 2011-12-14 | 2012-07-11 | 天邦膜技术国家工程研究中心有限责任公司 | Sample evaluation method for hollow fiber membrane silk |
| CN103028536A (en) * | 2012-12-20 | 2013-04-10 | 天邦膜技术国家工程研究中心有限责任公司 | Vacuum coating technology of hollow fiber hydrogen nitrogen membrane component |
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| CN105195026A (en) * | 2015-07-17 | 2015-12-30 | 南京佳乐净膜科技有限公司 | Organic/inorganic hybrid hydrophilic modified hollow fiber polymer film and preparation method thereof |
| CN107735165A (en) * | 2015-05-30 | 2018-02-23 | 迪博因特技术公司 | The water vapor transport membrane of support comprising polyethylene oxide copolymer |
| CN108525524A (en) * | 2018-04-17 | 2018-09-14 | 上海穗杉实业股份有限公司 | A kind of prosthetic device of Ho llow fiber membrane for gas separation |
| CN109806779A (en) * | 2019-03-07 | 2019-05-28 | 道和矿冶科技（北京）有限公司 | A kind of preparation method of Polyethersulfone Hollow Fiber Plasma gas separation membrane |
| CN111589299A (en) * | 2020-05-14 | 2020-08-28 | 中冶南方工程技术有限公司 | Nitrogen-hydrogen protective gas separation system and method for steel rolling annealing furnace |
Families Citing this family (1)
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| CN101269301B (en) * | 2008-05-09 | 2010-07-28 | 天津膜天膜工程技术有限公司 | Method for preparing internal air pressure type hollow fiber compound film component |
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| JPS621404A (en) * | 1985-06-27 | 1987-01-07 | Mitsubishi Rayon Co Ltd | Poly-composite hollow fiber membrane and its manufacturing process |
| US5156888A (en) * | 1990-09-14 | 1992-10-20 | Hoechst Celanese Corp. | Method and apparatus for applying polymeric coating |
| CN1130543A (en) * | 1994-12-28 | 1996-09-11 | 普拉塞尔技术有限公司 | Improved production of multilayer composite membranes |
| CN1073877C (en) * | 1997-05-17 | 2001-10-31 | 中国科学院大连化学物理研究所 | Preparation of hollow-fibre composite film |
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2004
- 2004-02-16 CN CNB2004100211494A patent/CN1318127C/en not_active Expired - Fee Related
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| CN102565282B (en) * | 2011-12-14 | 2015-07-22 | 天邦膜技术国家工程研究中心有限责任公司 | Sample evaluation method for hollow fiber membrane silk |
| CN103028536A (en) * | 2012-12-20 | 2013-04-10 | 天邦膜技术国家工程研究中心有限责任公司 | Vacuum coating technology of hollow fiber hydrogen nitrogen membrane component |
| CN107735165A (en) * | 2015-05-30 | 2018-02-23 | 迪博因特技术公司 | The water vapor transport membrane of support comprising polyethylene oxide copolymer |
| CN105005647A (en) * | 2015-07-02 | 2015-10-28 | 哈尔滨工程大学 | Topological optimization method of composite sandwich plate shell structure based on damping maximization |
| CN105005647B (en) * | 2015-07-02 | 2018-01-19 | 哈尔滨工程大学 | One kind is based on the maximized compound sandwich boards shell structure Topology Optimization Method of damping |
| CN105195026A (en) * | 2015-07-17 | 2015-12-30 | 南京佳乐净膜科技有限公司 | Organic/inorganic hybrid hydrophilic modified hollow fiber polymer film and preparation method thereof |
| CN105195026B (en) * | 2015-07-17 | 2017-10-27 | 南京佳乐净膜科技有限公司 | Hybrid hydrophilic modifying hollow fibre polymeric membranes and preparation method thereof |
| CN108525524A (en) * | 2018-04-17 | 2018-09-14 | 上海穗杉实业股份有限公司 | A kind of prosthetic device of Ho llow fiber membrane for gas separation |
| CN108525524B (en) * | 2018-04-17 | 2021-05-14 | 上海穗杉实业股份有限公司 | Repairing device for hollow fiber gas separation membrane |
| CN109806779A (en) * | 2019-03-07 | 2019-05-28 | 道和矿冶科技（北京）有限公司 | A kind of preparation method of Polyethersulfone Hollow Fiber Plasma gas separation membrane |
| CN111589299A (en) * | 2020-05-14 | 2020-08-28 | 中冶南方工程技术有限公司 | Nitrogen-hydrogen protective gas separation system and method for steel rolling annealing furnace |
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