CN103781536A - Process for fabricating PBI hollow fiber asymmetric membranes for gas separation and liquid separation - Google Patents
Process for fabricating PBI hollow fiber asymmetric membranes for gas separation and liquid separation Download PDFInfo
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- CN103781536A CN103781536A CN201280043088.4A CN201280043088A CN103781536A CN 103781536 A CN103781536 A CN 103781536A CN 201280043088 A CN201280043088 A CN 201280043088A CN 103781536 A CN103781536 A CN 103781536A
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- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000012528 membrane Substances 0.000 title claims description 9
- 239000012510 hollow fiber Substances 0.000 title abstract 5
- 238000000926 separation method Methods 0.000 title description 5
- 230000008569 process Effects 0.000 title description 3
- 239000007788 liquid Substances 0.000 title description 2
- 239000012530 fluid Substances 0.000 claims abstract description 34
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000010791 quenching Methods 0.000 claims abstract description 7
- 230000000171 quenching effect Effects 0.000 claims abstract description 7
- 229920002480 polybenzimidazole Polymers 0.000 claims description 61
- 239000002904 solvent Substances 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 55
- 235000012489 doughnuts Nutrition 0.000 claims description 46
- 239000000835 fiber Substances 0.000 claims description 33
- 238000009987 spinning Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 12
- 238000006277 sulfonation reaction Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 208000034189 Sclerosis Diseases 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000002144 chemical decomposition reaction Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004693 Polybenzimidazole Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003287 bathing Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1216—Three or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/085—Details relating to the spinneret
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
- B01D69/088—Co-extrusion; Co-spinning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1218—Layers having the same chemical composition, but different properties, e.g. pore size, molecular weight or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
- B01D2325/0231—Dense layers being placed on the outer side of the cross-section
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2325/04—Characteristic thickness
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2325/30—Chemical resistance
Abstract
The invention provides methods for preparing an asymmetric hollow fiber, the asymmetric hollow fibers prepared by such methods, and uses of the asymmetric hollow fibers. One method involves passing a polymeric solution through an outer annular orifice of a tube-in-orifice spinneret, passing a bore fluid though an inner tube of the spinneret, dropping the polymeric solution and bore fluid through an atmosphere over a dropping distance, and quenching the polymeric solution and bore fluid in a bath to form an asymmetric hollow fiber.
Description
Assignee: SRI International
Inventor: I Jia Ya Wella, Ge Pala N Clichy south, Anjar Sang Jiaqiao, Pa Litajiaya Wella and Si Lini gas Ba meter Di
The cross reference of related application
The application requires the priority of the United States serial 61/531,448 of submitting on September 6th, 2011, and its disclosure is incorporated herein by reference in full.
Statement of government interest
The present invention is that the support of the DE-FC26-07NT43090 Xia Shou U.S. government that authorizes of the N00014-10-C-0059 that authorizes in naval research office and Ministry of Energy is carried out.U.S. government has some right to the present invention.
Introduce
The many industries that separate from water treatment to gas use for separating of with the film method of purifying.These methods are usually used the polymeric membrane of plain film or doughnut form.Hollow-fibre membrane is more widely used than flat sheet membrane, because the ratio of its surface area and volume is high.
Correlation technique comprises US7771518, US5683584 and US2011/0266223.
Summary of the invention
In one aspect, the invention provides a kind of method for the preparation of asymmetric doughnut, described method comprises: (a) make the outer annular hole of polymeric solution intubatton type (tube-in-orifice) spinning head in via hole, described polymeric solution comprises: (i) 15 to 25wt% polybenzimidazoles; (ii) pore-forming material of 1 to 5wt% polymerization; (iii) for the solvent of this polybenzimidazoles; (b) make the inner tube of hole fluid (bore fluid) through spinning head, described hole fluid comprises: (i) 65 to 99wt% the non-solvent for this polybenzimidazoles; (ii) 1 to 35wt% the solvent for this polybenzimidazoles, wherein this hole fluid makes polymeric solution maintain annular; (c) by gap (gap) drippage polymeric solution and hole fluid, the drippage distance that wherein this gap comprises atmosphere (atmosphere) and 0.3 to 20cm; (d) make polymeric solution and hole fluid quenching in bath (quenching) there is annular and comprise the first concentric layer and the asymmetric doughnut of the second concentric layer to form, wherein ground floor contacts the second layer and is atresia, and wherein this second layer has the hole of aperture within the scope of 5 to 250nm.
In embodiments:
The method also comprises with the speed of 1 to 100 m/min fiber roll (take up) is become to fibre bundle.Fibre bundle can be being for example used as hollow-fibre membrane in those suitable film application described herein.
Polymeric solution is stablized at least 6 months chemical degradation in the temperature range of 15 to 25 ℃.
This fiber is washed and drawn to the method after also comprising spinning.For example, the mechanical strength of operation increase fiber after this spinning.
This polybenzimidazoles is the polybenzimidazoles of sulfonation.
Ground floor formation outer surface and the second layer form the inner surface of asymmetric doughnut.
Ground floor formation inner surface and the second layer form the outer surface of asymmetric doughnut.
Length by drippage distance and control the thickness of ground floor and the second layer by the relative polarity of solvent and non-solvent.
The thickness of ground floor within the scope of 0.1 to 10 μ m, and wherein the thickness of the second layer within the scope of 10 to 500 μ m.
The chemical composition of ground floor and the chemical composition of the second layer are identical.
Polymer is deposited in partially hardened and sclerosis completely between cold snap during drippage.
In hole, the external diameter in the outer annular hole of intubatton type spinning head is within the scope of 100 to 2000 μ m.
Length by drippage distance and control the thickness of ground floor and the second layer by the relative polarity of solvent and non-solvent, and the polybenzimidazoles that wherein polybenzimidazoles is sulfonation.
The thickness of ground floor is within the scope of 0.1 to 10 μ m, and wherein the thickness of the second layer is within the scope of 10 to 500 μ m, and wherein polymer is deposited in partially hardened and sclerosis completely between cold snap during drippage.
On the other hand, provide a kind of asymmetric doughnut, the first concentric layer that it comprises the wall that forms fiber and the second concentric layer, wherein: this asymmetric doughnut comprises polybenzimidazole material; Ground floor be atresia and the second layer there is the hole of aperture within the scope of 5 to 250nm; And the external diameter of this asymmetric doughnut is within the scope of 100 to 2000 μ m.
In embodiments:
This polybenzimidazoles is the polybenzimidazoles of sulfonation.
Asymmetric doughnut is stablized chemical degradation at up to 400 ℃.
The thickness of ground floor within the scope of 0.1 to 10 μ m, and wherein the thickness of the second layer within the scope of 10 to 500 μ m.
Ground floor formation outer surface and the second layer form the inner surface of asymmetric doughnut.
On the other hand, provide a kind of film that comprises asymmetric doughnut, described doughnut comprises: polybenzimidazoles; With the first concentric layer and the second concentric layer, wherein ground floor is atresia and the second layer has the hole of aperture within the scope of 5 to 250nm, and wherein the external diameter of fiber is within the scope of 100 to 2000 μ m.
In embodiments:
This film is used in a kind of for from comprising H
2, CO
2, CO and methane admixture of gas in separate H
2method in, the method comprises makes admixture of gas through this film.
This film is used in a kind of for from the method for aqueous solution removal of impurity, the method comprises makes the aqueous solution through this film.
The present invention provides all combinations of cited aspect especially, and each combination is independent seemingly sets forth complicatedly.
The detailed description of specific embodiments
In one aspect, the invention provides a kind of method for the preparation of asymmetric doughnut, described method comprises: (a) make the outer annular hole of polymeric solution intubatton type spinning head in via hole, described polymeric solution comprises: (i) 15 to 25wt% polybenzimidazoles; (ii) pore-forming material of 1 to 5wt% polymerization; (iii) for the solvent of this polybenzimidazoles; (b) make the inner tube of hole fluid through spinning head, described hole fluid comprises: (i) 65 to 99wt% the non-solvent for this polybenzimidazoles; (ii) 1 to 35wt% the solvent for this polybenzimidazoles, wherein this hole fluid makes polymeric solution maintain annular; (c) in 0.3 to 20cm drippage distance, drip polymeric solution and hole fluid by atmosphere; (d) quenching is to form the asymmetric doughnut that comprises the first concentric layer and the second concentric layer in bath to make polymeric solution and hole fluid, and wherein ground floor is atresia and the second layer has the hole of aperture within the scope of 5 to 250nm.
Polymeric solution carries the polymeric material that forms asymmetric doughnut, and carries in certain embodiments one or more additional components for example pore-forming material, salt, pH-conditioning agent, viscosity modifier and one or more solvents.
Polymeric solution comprises polybenzimidazoles (PBI).In certain embodiments, PBI is sulfonated.Sulfonation can be undertaken by any method easily.For example, can easily be prepared as follows the sulfonation modification of PBI: form covalently bound SO by sulfuric acid treatment
3-, and the nitrogen of hydrogen and imidazole ring forms stable key.Sulfonation PBI (SPBI) doughnut provides higher resistance to chlorine power, water flux and salt discharge rate.PBI can exist with the amount that effectively produces asymmetric doughnut according to the inventive method.In embodiments, PBI is with 10 to 30wt% or 15 to 25wt% or 15 to 20wt% or exist with the amount that is greater than 10wt%, 15wt%, 17wt%, 20wt% or 25wt% or be less than in the scope of 30wt%, 25wt%, 22wt%, 20wt% or 18wt%.Can there is the PBI of more than a type, precondition be exist gross weight in given range.
In embodiments, polymeric solution comprises pore-forming material.Pore-forming material is cause or assist the material that forms hole in material of the present invention.For example, the exchange of solvent mechanism that pore-forming material via hole forms.Can use any suitable pore-forming material.The example of pore-forming material is the compound that contains multiple hydroxyls, for example glycol and polyalcohol.Example comprises isopropyl alcohol, ethylene glycol, propane diols, polyvinyl alcohol, carbohydrate and polysaccharide etc.Another example of pore-forming material is PVP.Pore-forming material is to be enough to causing required porous amount to be present in polymeric solution in the asymmetric doughnut of gained.In embodiments, pore-forming material with 1 to 5wt% or 1 to 3wt% or the scope that is less than 5wt%, 4wt%, 3wt% or 2wt% or is greater than 1wt%, 2wt%, 3wt% or 4wt% be present in polymeric solution.
Polymeric solution comprises the solvent for PBI.That this solvent exists in the solvent soln completely and PBI under condition used in the methods of the invention.The example of suitable solvent is DMA (DMAc), dimethyl sulfoxide (DMSO) (DMSO), N-N-dimethyl formamide (DMF), N-methyl-2-pyrrolidines (NMP), pyridine etc.The combination of solvent is also suitable.
This polymeric solution can also comprise one or more additives, for example LiCl (as, as the stabilizing agent of PBI).
Under environmental condition, for example, in the temperature range of 15 to 25 ℃, this polymeric solution is stablized at least 6 months chemical degradation.In certain embodiments, stable at least 9 months or 12 months of polymeric solution.Therefore there is not significant degraded in the component of polymeric solution (particularly PBI component), within stationary phase.For example, within stationary phase, be less than 10%, 8%, 5%, 3%, 2% or 1% PBI component degradation in polymeric solution, precondition is that this solution maintains in the temperature range of 15 to 25 ℃.
The inventive method relates to the outer annular hole that makes polymeric solution intubatton type spinning head in via hole.This process can be carried out (that is, can force polymeric solution to pass through described hole) under the pressure raising, or can under the impact of gravity and under environmental pressure, make this solution ooze this hole.What be oriented in below, outer annular hole is a gap, and it can be divided into the extended region of below, next-door neighbour outer annular hole and the elongated region of extended region below easily.After the external holes of spinning head occurs, polymeric solution (it has the annular of annular aperture) first enters extended area, and its girth in this extended area is slightly expanded.Polymeric solution moves through this extended area and enters subsequently elongated region, and girth reduces therein.In certain embodiments, when polymeric solution is during through gap, a part for solvent is evaporated from polymeric solution.This evaporation increases the concentration of PBI in polymeric solution, and some sclerosis can occur PBI in gap.Polymeric solution is moved and is entered the bath that is positioned at below, gap by the elongated region in gap.The PI of this bath for condensing in polymeric solution, makes PBI sclerosis completely in bathing.In addition, in this bath, there is exchange of solvent (, from the solvent of polymeric solution and from the exchange of solvent of bathing).Exchange of solvent causes forming hole in the PBI of sclerosis.
Method of the present invention also relates to the inner tube that makes hole fluid intubatton type spinning head in via hole.Inner tube is positioned the central authorities' (with respect to central shaft of spinning head) in outer annular hole.Hole fluid, for during polymeric solution drips and enter described bath by gap, is maintained annular by polymeric solution.Therefore it is identical with the time that polymeric solution comes across outer annular hole that, hole fluid comes across time of inner tube.
Hole fluid comprises for the solvent of PBI with for the mixture of the non-solvent of PBI.In embodiments, hole fluid comprises 65 to 99wt% or be greater than 65wt%, 70wt%, 75wt%, 80wt%, 85wt% or 90wt% or be less than the non-solvent of 99wt%, 95wt%, 90wt%, 85wt%, 80wt%, 75wt% or 70wt%.In embodiments, hole fluid comprises 1 to 35wt% or be greater than 5wt%, 10wt%, 15wt%, 20wt%, 25wt% or 30wt% or be less than the solvent for polybenzimidazoles of 35wt%, 30wt%, 25wt%, 20wt%, 15wt%, 10wt% or 5wt%.
It is the solvent of not obvious dissolving PBI under a kind of temperature and pressure used in the methods of the invention for the non-solvent of PBI.For example, non-solvent can dissolve the PBI weight that the solvent of the similar volume that is less than 10%, 5%, 1%, 0.5% or 0.1% can dissolve.The example of the non-solvent of PBI comprises water and alcohol, such as methyl alcohol, ethanol, isopropyl alcohol, normal propyl alcohol etc.
By liquid is used as to hole fluid, can causes and change mutually and can transfer near the fibre morphology of controlling inner surface by contrary.
Described bath is used for the non-solvent of PBI and is filled.Non-solvent in described bath can be identical from the non-solvent existing in the fluid of hole or can be different with it.The precipitation that polymeric solution enters the caused PBI of described bath is referred to herein as quenching.The quenching of polymeric solution and hole fluid generates the asymmetric doughnut that has annular and have the first concentric layer described herein and the second concentric layer.In certain embodiments, the annular of doughnut equates with the annular (, around hole fluid) of the polymeric solution through gap.In certain embodiments, expanding or shrinking other little variation causes the annular of polymeric solution in the annular of doughnut and gap unequal, although doughnut shape can still be derived from the annular of the polymeric solution in gap.
Gap comprises atmosphere.Atmosphere can be air, and pure gas is as nitrogen or argon, or any required composition of gas.Between spinning head and bath, the length in gap is referred to herein as drippage distance.Drippage distance can be any length within the scope of 0.3 to 20cm, for example, be greater than 0.3cm, 0.5cm, 1cm, 3cm, 5cm, 10cm or 15cm, or be less than 20cm, 15cm, 10cm, 5cm, 3cm or 1cm.The relative length of expansion area and elongated region will depend on many factors, for example, in solution parameter, gap atmosphere etc.
The inventive method causes forming the asymmetric doughnut that comprises PBI material.The method operates after can also comprising spinning.For example, after spinning, operation comprises washing and draws this fiber.Washing can be carried out with the mixture of the non-solvent of PBI or non-solvent, for example water, alcohol, glycol or polyol solvent.Draw and can comprise any method for drawing of fiber, for example, stretch by two rollers or use any suitable method longitudinal stretching.In certain embodiments, the mechanical strength of operation increase fiber after this spinning.This increase of mechanical strength may be at least 100%, 150% or 200%, and may refer to tensile strength or fibre strength other measure.
Asymmetric doughnut has " baked donut " shape on cross section.Therefore, this fiber comprises (in cross section) and has annular wall, and wherein this wall comprises ground floor (and contact) layer concentric with the second layer.Difference between the external diameter of ring and the internal diameter of ring represents the twice of the thickness of fibre wall.
Doughnut of the present invention is asymmetric, because they comprise the first concentric layer and the second concentric layer, wherein ground floor is atresia and the contact second layer, and the second layer is porose.In some embodiments, ground floor formation outer surface and the second layer form the inner surface of asymmetric doughnut.In other embodiments, ground floor formation inner surface and the second layer form the outer surface of asymmetric doughnut.Due to the porous of the second layer, ground floor is conventionally finer and close than the second layer.In embodiments, ground floor is than second layer densification at least 1.1,1.3,1.5,2,3,4 or 5 times.
Length by drippage distance and control the thickness of ground floor and the second layer by the relative polarity of solvent and non-solvent.In certain embodiments, the thickness of ground floor in the scope of 0.1 to 10 μ m, for example at least 0.1 μ m, 0.5 μ m, 1 μ m, 2 μ m, 3 μ m, 5 μ m or 8 μ m, or be less than 10 μ m, 8 μ m, 5 μ m, 3 μ m, 2 μ m, 1 μ m or 0.5 μ m.In certain embodiments, the thickness of the second layer is in the scope of 10 to 500 μ m, for example at least 10 μ m, 25 μ m, 50 μ m, 100 μ m, 150 μ m, 200 μ m, 250 μ m or 300 μ m, or be less than 500 μ m, 300 μ m, 250 μ m, 200 μ m, 150 μ m, 100 μ m, 50 μ m or 25 μ m.In certain embodiments, the thickness of relatively unsound second layer is at least 10,20,50,100 or 500 times of thickness of relatively finer and close ground floor.Press the cross section of fiber and measure the thickness of each layer.
Transition region between ground floor and the second layer may be very sharply, for example, be less than 0.5,0.1,0.05 or 0.01 times of ground floor thickness.In this transition region, fibrous material is from the porose atresia (compared with low-density to higher density) that changes into.In certain embodiments, transition region is thicker, and reduces gradually in the region of at least 0.5,0.8 or 1 times of the porous thickness that is ground floor at thickness.
In embodiments, the porose second layer has the nano grade pore of interconnection.For example, the average diameter in described hole is in 5 to 250nm scope or be greater than 5nm, 25nm, 50nm, 100nm, 150nm or 200nm or be less than 250nm, 200nm, 150nm, 100nm, 50nm or 25nm.Described hole can be spherical, part is spherical or irregularly shaped.The degree of second layer mesopore and size are partly determined by the polarity (it affects the exchange of solvent mechanism that hole forms) of solvent and non-solvent used.Other factors comprises bathes solvent temperature and pressure, and speed and the degree of the evaporation of gap internal solvent.
Shear stress in the size of ring-type spinneret orifice, doughnut size, spinning head, doping flow velocity, polymer-to the volume flow rate ratio in-hole and batch-with-initial velocity ratio (take-up-to-initial velocity ratio) (draw ratio) is the principal element of definite final fibre structure.
In embodiments, the chemical composition of ground floor and the chemical composition of the second layer are identical.Therefore, for example, ground floor and the second layer are made by the identical PBI material that is selected from material described herein.
In embodiments, asymmetric doughnut is stablized at up to 400 ℃.Therefore,, at up to 400 ℃, there is minimum or not degraded (, being less than 10wt%, 5wt%, 3wt% or 1wt%) in fibrous material.
In hole, the external diameter in the outer annular hole of intubatton type spinning head is within the scope of 100 to 2000 μ m.Therefore, the external diameter of final asymmetric doughnut can be within the scope of 100 to 2000 μ m, for example be greater than 100 μ m, 200 μ m, 300 μ m, 400 μ m, 500 μ m, 1000 μ m or 1500 μ m, or be less than 2000 μ m, 1500 μ m, 1000 μ m, 500 μ m, 400 μ m, 300 μ m or 200 μ m.Internal diameter (, the diameter of the cavity in doughnut) can be determined by the external diameter of ground floor and the second layer and thickness (and therefore can within the scope of 90 to 1990 μ m for example).
Asymmetric doughnut of the present invention can be used to form hollow-fibre membrane (HFM).For example, spinning operation as herein described can also comprise with the speed of 1 to 100 m/min batch fiber with form HFM.
This film can be used in a kind of for from comprising H
2, CO
2, CO and methane admixture of gas in separate H
2method in, the method comprises makes admixture of gas through this film.
This film can be used in a kind of for from the method for aqueous solution removal of impurity, and the method comprises makes the aqueous solution through this film.
Can be after for example using impregnation drying operation manufacture doughnut, by the sulfonation of PBI film.
Except as otherwise noted, otherwise the disclosure is not limited to specific operation, material etc., because these can change.It is also understood that term used herein is only for the object of describing specific embodiments is not intended to limit.
As used in description and the claims of enclosing, singulative " ", " one " and " described " comprise multiple things that refer to, unless context clear indication in addition.Therefore, for example, while, mentioning " a kind of solvent ", not only comprise single solvent, and comprise combination or the mixture of two or more different solvents.
All combinations of the draw concrete and preferred embodiment of mentioning are contained in the present invention.Should understand, example as herein described and embodiment be only for illustrative object, and various modifications thus or change meeting to those skilled in the art have suggested and should be included in the application's spirit and scope and the scope of appended claims within.All publications, patent and the patent application of quoting herein (comprise wherein quote) are incorporated herein by reference in full for all objects.
Embodiment
Be prepared as follows doped solution: 18wt%PBI alloy and 2wt%PVP in DMAc (K16 – 18, Acros Organics, New Jersey) (the daltonian HMW pore-forming agent of molecular weight 8000).
Be prepared as follows hole fluid: 75 to 90wt%IPA and 5 to 25wt%DMAc.
The coagulation bath that preparation contains 100%IPA.
Be selected from the strong non-solvent of water, isopropyl alcohol, methyl alcohol and combination thereof as hole fluid and coagulation bath.Strong non-solvent has the ability in the exit of spinning head, polymer solution to be condensed; Therefore, can between outside polymer solution, form thin layer, otherwise fiber easily breaks and polymer solution can be under gravity as droplets fall.Internal holes fluid is that the mixture of non-solvent and solvent is to avoid forming rete.Spinning head is manufactured into 1.2mm external diameter and 0.4mm internal diameter.This doped solution contains 26wt%PBI and the 2wt.%LiCl in N-dimethylacetylamide (DMAc).According to the concrete composition of doped solution, hole fluid and coagulation bath are for the manufacture of asymmetric PBI hollow-fibre membrane, and this film has zero defect selective gas separating layer, H in shell side
2permeability is 300GPU.
Obtain the magnification at high multiple picture of the fiber of the cross section with 0.5mm external diameter.Similarly, obtain the magnification at high multiple picture of the fiber of the cross section with 0.8mm external diameter.Described image illustrates porous and the fine and close skin of atresia of internal layer.
Compacted zone is at high osmosis H
2with hypotonicity CO
2between separation is provided, and the process that porose layer is reduced to permeability gas with low pressure provides mechanical strength.The test of manufacturing fiber shows, H
2compare CO
2more promptly permeate by film.H
2permeability increase with temperature, and CO
2permeability to temperature relative insensitivity.
Exceed the performance of assessing prepared fiber for 50 days, representative exceedes the performance of 1000 hours.H
2/ CO
2be selectively increased to 50 from 35 in time, exceed 40 design object.Obtain long-term behaviour assessment data.H
2permeability value maintains about 80GPU (gas permeation unit) in whole test phase.In the time that within 1000 hours, test phase finishes, the H measuring at 250 ℃
2permeability is 130GPU.
At 150 ℃, 200 ℃, 225 ℃ and 250 ℃ with GPU unit with H
2the measure of the change H of permeability
2/ CO
2.Along with temperature is increased to up to 225 ℃, H
2/ CO
2selective and H
2permeability all increases.At 250 ℃, H
2/ CO
2ratio increase, and H2 permeability reduction.This thickness that shows compacted zone slightly increases.Along with elective reduction, permeability increases.Dense layer thickness is tested between 1 and 10 μ m, and can test low reaching under 0.1 μ m.
Macroporous existence is that high doped is specific and strongly depend on non-solvent and the exchange of solvent speed of duration of coagulation.The H2 permeability that contains macroporous fiber of measuring is at room temperature in 100 to 200GPU scope, but H2/CO2 is only selectively 5.Low-fiber mechanical strength also falls in macroporous existence.
Claims (15)
1. for the preparation of a method for asymmetric doughnut, described method comprises:
(a) make the outer annular hole of polymeric solution intubatton type spinning head in via hole, described polymeric solution comprises: (i) 15 to 25wt% polybenzimidazoles; (ii) pore-forming material of 1 to 5wt% polymerization; (iii) for the solvent of described polybenzimidazoles;
(b) make the inner tube of hole fluid through described spinning head, described hole fluid comprises: (i) 65 to 99wt% the non-solvent for described polybenzimidazoles; (ii) 1 to 35wt% the solvent for described polybenzimidazoles, wherein said hole fluid makes described polymeric solution maintain annular;
(c) drip described polymeric solution and hole fluid by gap, the drippage distance that wherein said gap comprises atmosphere and 0.3 to 20cm;
(d) make the quenching in bath of described polymeric solution and hole fluid there is annular and comprise the first concentric layer and the asymmetric doughnut of the second concentric layer to form, wherein said ground floor contacts the described second layer and for atresia, and the wherein said second layer has the hole of aperture within the scope of 5 to 250nm.
2. method according to claim 1:
(a) comprise with the speed of 1 to 100 m/min and become fibre bundle to form hollow-fibre membrane described fiber roll;
(b) wherein said polymeric solution is stablized at least 6 months chemical degradation in the temperature range of 15 to 25 ℃;
(c) comprise after spinning washing and draw described fiber;
(d) polybenzimidazoles that wherein said polybenzimidazoles is sulfonation; Or
(e) comprise (a), (b), (c) and any combination or sub-combination (d).
3. method according to claim 1, wherein said ground floor formation outer surface and the described second layer form the inner surface of described asymmetric doughnut.
4. method according to claim 1, wherein said ground floor formation inner surface and the described second layer form the outer surface of described asymmetric doughnut.
5. method according to claim 1, the thickness of wherein said ground floor is within the scope of 0.1 to 10 μ m, and the thickness of the wherein said second layer is within the scope of 10 to 500 μ m.
6. method according to claim 1, the chemical composition of wherein said ground floor and the chemical composition of the described second layer are identical.
7. method according to claim 1, in wherein said hole, the external diameter in the described outer annular hole of intubatton type spinning head is within the scope of 100 to 2000 μ m.
8. method according to claim 1, wherein by the length of described drippage distance with control the thickness of described ground floor and the second layer by the relative polarity of described solvent and non-solvent, and the wherein said polybenzimidazoles polybenzimidazoles that is sulfonation.
9. method according to claim 1, the thickness of wherein said ground floor is within the scope of 0.1 to 10 μ m, and the thickness of the wherein said second layer is within the scope of 10 to 500 μ m, and wherein said polymer is deposited in partially hardened and sclerosis completely between cold snap during drippage.
10. an asymmetric doughnut, the first concentric layer that it comprises the wall that forms described fiber and the second concentric layer, wherein:
Described asymmetric doughnut comprises polybenzimidazole material;
Described ground floor is that second layer atresia and described has the hole of aperture within the scope of 5 to 250nm; With
The external diameter of described asymmetric doughnut is within the scope of 100 to 2000 μ m.
11. asymmetric doughnuts according to claim 10, wherein:
(a) polybenzimidazoles that described polybenzimidazoles is sulfonation; Or
(b) described asymmetric doughnut is stablized chemical degradation at up to 400 ℃; Or
(c) thickness of described ground floor is within the scope of 0.1 to 10 μ m, and the thickness of the wherein said second layer is within the scope of 10 to 500 μ m.
12. asymmetric doughnuts according to claim 10, wherein said ground floor formation outer surface and the described second layer form the inner surface of described asymmetric doughnut.
13. 1 kinds of films, the described asymmetric doughnut that it comprises claim 10.
14. 1 kinds for separate the method for H2 from the admixture of gas that comprises H2, CO2, CO and methane, and described method comprises makes described admixture of gas through the film described in claim 13.
15. 1 kinds for the method from aqueous solution removal of impurity, and described method comprises makes the described aqueous solution through the film described in claim 13.
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|---|---|---|---|
| US201161531448P | 2011-09-06 | 2011-09-06 | |
| US61/531,448 | 2011-09-06 | ||
| PCT/US2012/054033 WO2013036693A2 (en) | 2011-09-06 | 2012-09-06 | Process for fabricating pbi hollow fiber asymmetric membranes for gas separation and liquid separation |
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| CN103781536B CN103781536B (en) | 2015-12-23 |
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| JP (1) | JP6062945B2 (en) |
| KR (1) | KR101951065B1 (en) |
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| US5683584A (en) * | 1991-04-12 | 1997-11-04 | Minntech Corporation | Hollow fiber membranes and method of manufacture |
| US6015516A (en) * | 1998-06-16 | 2000-01-18 | National University Of Singapore | Ultrathin high-performance hollow fiber membranes |
| US20030159980A1 (en) * | 1999-03-19 | 2003-08-28 | Barss Robert P. | Solvent-resistant microporous polybenzimidazole membranes |
| US20040154986A1 (en) * | 1999-01-29 | 2004-08-12 | Kwok-Shun Cheng | Skinned hollow fiber membrane and method of manufacture |
| KR100644366B1 (en) * | 2005-11-08 | 2006-11-10 | 한국화학연구원 | New spinning processes for asymmetric gas separation hollow fiber membranes |
| CN101642683A (en) * | 2009-09-10 | 2010-02-10 | 杨乾 | Double-layer composite hollow fiber nano-filtration membrane and preparation method and special tool thereof |
| CN101844040A (en) * | 2010-06-07 | 2010-09-29 | 苏州信望膜技术有限公司 | Hollow fiber nanofiltration membrane and preparation method thereof |
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|---|---|---|---|---|
| CA2300519C (en) * | 1999-03-19 | 2008-02-12 | Bend Research, Inc. | Solvent-resistant microporous polybenzimidazole membranes |
| US20110311745A1 (en) * | 2008-12-16 | 2011-12-22 | National University Of Singapore | Chemically-modified polybenzimidazole membranous tubes |
-
2012
- 2012-09-06 JP JP2014528706A patent/JP6062945B2/en active Active
- 2012-09-06 KR KR1020147005734A patent/KR101951065B1/en active IP Right Grant
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|---|---|---|---|---|
| US5683584A (en) * | 1991-04-12 | 1997-11-04 | Minntech Corporation | Hollow fiber membranes and method of manufacture |
| US6015516A (en) * | 1998-06-16 | 2000-01-18 | National University Of Singapore | Ultrathin high-performance hollow fiber membranes |
| US20040154986A1 (en) * | 1999-01-29 | 2004-08-12 | Kwok-Shun Cheng | Skinned hollow fiber membrane and method of manufacture |
| US20030159980A1 (en) * | 1999-03-19 | 2003-08-28 | Barss Robert P. | Solvent-resistant microporous polybenzimidazole membranes |
| KR100644366B1 (en) * | 2005-11-08 | 2006-11-10 | 한국화학연구원 | New spinning processes for asymmetric gas separation hollow fiber membranes |
| CN101642683A (en) * | 2009-09-10 | 2010-02-10 | 杨乾 | Double-layer composite hollow fiber nano-filtration membrane and preparation method and special tool thereof |
| CN101844040A (en) * | 2010-06-07 | 2010-09-29 | 苏州信望膜技术有限公司 | Hollow fiber nanofiltration membrane and preparation method thereof |
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| JP2014527906A (en) | 2014-10-23 |
| JP6062945B2 (en) | 2017-01-18 |
| CN103781536B (en) | 2015-12-23 |
| KR20140070540A (en) | 2014-06-10 |
| KR101951065B1 (en) | 2019-04-22 |
| WO2013036693A3 (en) | 2013-05-02 |
| WO2013036693A2 (en) | 2013-03-14 |
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