CN103781536B - Manufacture the method for the PBI doughnut asymmetric membrane being used for gas separaion and fluid separation applications - Google Patents

Manufacture the method for the PBI doughnut asymmetric membrane being used for gas separaion and fluid separation applications Download PDF

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CN103781536B
CN103781536B CN201280043088.4A CN201280043088A CN103781536B CN 103781536 B CN103781536 B CN 103781536B CN 201280043088 A CN201280043088 A CN 201280043088A CN 103781536 B CN103781536 B CN 103781536B
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layer
hole
ground floor
solvent
doughnut
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CN103781536A (en
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I·贾亚维拉
戈帕拉·N·克里希南
安杰尔·桑贾乔
帕利塔·贾亚维拉
斯里尼瓦斯·巴米迪
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SRI International Inc
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Stanford Research Institute
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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
    • 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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

The invention provides the purposes for the preparation of the method for asymmetric doughnut, the asymmetric doughnut prepared by this method and asymmetric doughnut.A kind of method relates to the outer annular hole making polymeric solution intubatton type spinning head in via hole, make hole fluid through the inner tube of spinning head, by atmosphere drippage polymeric solution and hole fluid in drippage distance, and make polymeric solution and hole fluid in bath quenching to form asymmetric doughnut.

Description

Manufacture the method for the PBI doughnut asymmetric membrane being used for gas separaion and fluid separation applications
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
This application claims the priority of the United States serial 61/531,448 that on September 6th, 2011 submits to, its disclosure is incorporated herein by reference in full.
Statement of government interest
The present invention is undertaken by the support of U.S. government under the DE-FC26-07NT43090 authorized at the naval research N00014-10-C-0059 that authorizes of office and Ministry of Energy.U.S. government has some right to the present invention.
Introduce
Many industries from water treatment to gas separaion use for separating of the film method with purifying.These methods usually use the polymeric membrane of plain film or hollow fiber form.Hollow-fibre membrane more widely uses 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) makes the outer annular hole of polymeric solution intubatton type (tube-in-orifice) spinning head in via hole, and described polymeric solution comprises: the polybenzimidazoles of (i) 15 to 25wt%; (ii) pore-forming material of the polymerization of 1 to 5wt%; (iii) for the solvent of this polybenzimidazoles; B () makes hole fluid (borefluid) through the inner tube of spinning head, described hole fluid comprises: the non-solvent for this polybenzimidazoles of (i) 65 to 99wt%; (ii) solvent for this polybenzimidazoles of 1 to 35wt%, wherein this hole fluid makes polymeric solution maintain annular; C () drips polymeric solution and hole fluid by gap (gap), wherein this gap comprises the drippage distance of atmosphere (atmosphere) and 0.3 to 20cm; D () makes polymeric solution and hole fluid quenching in bath (quenching) have annular and the asymmetric doughnut comprising the first concentric layer and the second concentric layer to be formed, wherein ground floor contacts the second layer and is atresia, and wherein this second layer has the hole of aperture in 5 to 250nm scope.
In embodiments:
The method also comprises, with the speed of 1 to 100 m/min, fiber roll (takeup) is become fibre bundle.Fibre bundle can be used as hollow-fibre membrane in such as those suitable film application described herein.
Polymeric solution is stablized at least 6 months chemical degradation in the temperature range of 15 to 25 DEG C.
Wash after the method also comprises spinning and draw this fiber.Such as, after this spinning, operation increases the mechanical strength of fiber.
This polybenzimidazoles is the polybenzimidazoles of sulfonation.
Ground floor forms the inner surface that outer surface and the second layer form asymmetric doughnut.
Ground floor forms the outer surface that inner surface and the second layer form asymmetric doughnut.
By dripping the length of distance and being controlled 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 μm, and wherein the thickness of the second layer within the scope of 10 to 500 μm.
The chemical composition of ground floor and the chemical composition of the second layer are identical.
Partially hardened during polymer is deposited in drippage and hardening completely between cold snap.
In hole, the external diameter in the outer annular hole of intubatton type spinning head is within the scope of 100 to 2000 μm.
By dripping the length of distance and being controlled the thickness of ground floor and the second layer by the relative polarity of solvent and non-solvent, and wherein polybenzimidazoles is the polybenzimidazoles of sulfonation.
The thickness of ground floor within the scope of 0.1 to 10 μm, and wherein the thickness of the second layer within the scope of 10 to 500 μm, and partially hardened and hardening completely between cold snap during wherein polymer is deposited in drippage.
On the other hand, provide a kind of asymmetric doughnut, it comprises the first concentric layer and second concentric layer of the wall forming fiber, wherein: this asymmetric doughnut comprises polybenzimidazole material; Ground floor be atresia and the second layer has the hole of aperture in 5 to 250nm scope; And the external diameter of this asymmetric doughnut is within the scope of 100 to 2000 μm.
In embodiments:
This polybenzimidazoles is the polybenzimidazoles of sulfonation.
Asymmetric doughnut is stablized chemical degradation at up to 400 DEG C.
The thickness of ground floor within the scope of 0.1 to 10 μm, and wherein the thickness of the second layer within the scope of 10 to 500 μm.
Ground floor forms the inner surface that outer surface and the second layer form asymmetric doughnut.
On the other hand, provide a kind of film comprising asymmetric doughnut, described doughnut comprises: polybenzimidazoles; With the first concentric layer and the second concentric layer, wherein ground floor be atresia and the second layer has the hole of aperture in 5 to 250nm scope, wherein the external diameter of fiber is within the scope of 100 to 2000 μm.
In embodiments:
This film is used in one be used for from comprising H 2, CO 2, CO is separated H with in the admixture of gas of methane 2method in, the method comprises makes admixture of gas through this film.
Be used in by this film in a kind of method for removal of impurity from the aqueous solution, 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) makes the outer annular hole of polymeric solution intubatton type spinning head in via hole, and described polymeric solution comprises: the polybenzimidazoles of (i) 15 to 25wt%; (ii) pore-forming material of the polymerization of 1 to 5wt%; (iii) for the solvent of this polybenzimidazoles; B () makes hole fluid through the inner tube of spinning head, described hole fluid comprises: the non-solvent for this polybenzimidazoles of (i) 65 to 99wt%; (ii) solvent for this polybenzimidazoles of 1 to 35wt%, wherein this hole fluid makes polymeric solution maintain annular; C () drips polymeric solution and hole fluid by atmosphere in the drippage distance of 0.3 to 20cm; D () makes the quenching in bath of polymeric solution and hole fluid comprise the asymmetric doughnut of the first concentric layer and the second concentric layer to be formed, wherein ground floor be atresia and the second layer has the hole of aperture in 5 to 250nm scope.
Polymeric solution carries the polymeric material forming asymmetric doughnut, and carries one or more additional component such as pore-forming material, salt, pH-conditioning agent, viscosity modifier and one or more solvents in certain embodiments.
Polymeric solution comprises polybenzimidazoles (PBI).In certain embodiments, PBI is sulfonated.Sulfonation can use any method easily to carry out.Such as, the sulfonation modification of PBI can easily be prepared as follows: 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 chlorine-resistant power, water flux and salt discharge rate.PBI can to produce the amount existence of asymmetric doughnut effectively according to the inventive method.In embodiments, PBI is with 10 to 30wt% or 15 to 25wt% or 15 to 20wt% or to be greater than 10wt%, 15wt%, 17wt%, 20wt% or 25wt% or to be less than the amount existence in the scope of 30wt%, 25wt%, 22wt%, 20wt% or 18wt%.Can there is the PBI of a more than type, precondition is that the gross weight of existence is in given range.
In embodiments, polymeric solution comprises pore-forming material.Pore-forming material is cause or assist the material forming hole in material of the present invention.Such as, the exchange of solvent mechanism of pore-forming material via hole formation.Any suitable pore-forming material can be used.The example of pore-forming material is the compound containing multiple hydroxyl, such as 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 cause required porous amount to be present in polymeric solution in the asymmetric doughnut of gained.In embodiments, pore-forming material is present in polymeric solution 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%.
Polymeric solution comprises the solvent for PBI.That this solvent can exist in solvent soln completely and PBI in the methods of the invention under condition used.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, such as LiCl (e.g., as the stabilizing agent of PBI).
At ambient conditions, such as, in the temperature range of 15 to 25 DEG C, 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 (particularly PBI component) of polymeric solution within stationary phase.Such as, within stationary phase, be less than the PBI component degradation of 10%, 8%, 5%, 3%, 2% or 1% in polymeric solution, precondition is that this solution maintains in the temperature range of 15 to 25 DEG C.
The inventive method relates to the outer annular hole making polymeric solution intubatton type spinning head in via hole.This process can be carried out at an elevated pressure (that is, can force polymeric solution by described hole), or can this solution be made under the influence of gravity and under ambient pressure to ooze this hole.Being oriented in below outer annular hole is a gap, and it can be divided into the extended region below next-door neighbour outer annular hole and the elongated region below extended region easily.After occurring from the external holes of spinning head, 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 by this extended area and enters elongated region subsequently, and girth reduces wherein.In certain embodiments, when polymeric solution is 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 by the elongated region in gap and enters the bath be positioned at below gap.The PI of this bath for condensing in polymeric solution, makes PBI harden completely in bath.In addition, there is exchange of solvent (that is, from the solvent of polymeric solution and from the exchange of solvent of bathing) in this bath.Exchange of solvent causes forming hole in the PBI of sclerosis.
Method of the present invention also relates to the inner tube making hole fluid intubatton type spinning head in via hole.Inner tube is positioned the central authorities' (central shaft relative to spinning head) in outer annular hole.Hole fluid is used for, during polymeric solution to be dripped by gap and enters described bath, polymeric solution being maintained annular.Therefore, to come across time of inner tube identical with the time that polymeric solution comes across outer annular hole for hole fluid.
Hole fluid comprises the mixture of the solvent for PBI and the non-solvent for PBI.In embodiments, hole fluid comprises 65 to 99wt% or is greater than 65wt%, 70wt%, 75wt%, 80wt%, 85wt% or 90wt% or is less than the non-solvent of 99wt%, 95wt%, 90wt%, 85wt%, 80wt%, 75wt% or 70wt%.In embodiments, hole fluid comprises 1 to 35wt% or is greater than 5wt%, 10wt%, 15wt%, 20wt%, 25wt% or 30wt% or is less than the solvent for polybenzimidazoles of 35wt%, 30wt%, 25wt%, 20wt%, 15wt%, 10wt% or 5wt%.
For the solvent that the non-solvent of PBI is not obvious dissolving PBI under a kind of temperature and pressure used in the methods of the invention.Such as, the PBI weight that the solvent that non-solvent can dissolve the similar volume being 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 hole fluid, can phase in version be caused and can transfer by contrary the fibre morphology controlled near inner surface.
The non-solvent of described bath for PBI is filled.Non-solvent in described bath can be identical from the non-solvent existed in the fluid of hole or can be different with it.The precipitation of the PBI that polymeric solution enters caused by described bath is referred to herein as quenching.The quenching of polymeric solution and hole fluid generates has annular and the asymmetric doughnut with the first concentric layer described herein and the second concentric layer.In certain embodiments, the annular of doughnut is equal with the annular (that is, surrounding hole fluid) of the polymeric solution through gap.In certain embodiments, expanding or shrinking other little change causes the annular of polymeric solution in the annular of doughnut and gap unequal, although hollow fibre shape still can 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 in 0.3 to 20cm scope, such as, 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, such as, in solution parameter, gap atmosphere etc.
The inventive method causes being formed the asymmetric doughnut comprising PBI material.The method operates after can also comprising spinning.Such as, 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, such as water, alcohol, glycol or polyol solvent.Draw and can comprise any method for drawing of fiber, such as, stretch by two roller or use any suitable method longitudinal stretching.In certain embodiments, after this spinning, operation increases the mechanical strength of fiber.This increase of mechanical strength may be at least 100%, 150% or 200%, and other that may refer to tensile strength or fibre strength is measured.
Asymmetric doughnut has " baked donut " shape on cross section.Therefore, this fiber comprises the wall that (in cross-section) has annular, and wherein this wall comprises concentric (and contact) layer of ground floor and 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 be atresia and contact the second layer, and the second layer is porose.In some embodiments, ground floor forms the inner surface that outer surface and the second layer form asymmetric doughnut.In other embodiments, ground floor forms the outer surface that inner surface and the second layer form asymmetric doughnut.Due to the porous of the second layer, ground floor is usually finer and close than the second layer.In embodiments, ground floor than second layer densification at least 1.1,1.3,1.5,2,3,4 or 5 times.
By dripping the length of distance and being controlled 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 μm, such as at least 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 5 μm or 8 μm, or be less than 10 μm, 8 μm, 5 μm, 3 μm, 2 μm, 1 μm or 0.5 μm.In certain embodiments, the thickness of the second layer is in the scope of 10 to 500 μm, such as at least 10 μm, 25 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm or 300 μm, or be less than 500 μm, 300 μm, 250 μm, 200 μm, 150 μm, 100 μm, 50 μm or 25 μm.In certain embodiments, the thickness of relatively unsound second layer is at least 10,20,50,100 or 500 times of the thickness of relatively finer and close ground floor.The thickness of each layer is measured by the cross section of fiber.
Transition region between ground floor and the second layer very sharply, such as, may be less than 0.5,0.1,0.05 or 0.01 times of ground floor thickness.In this transition region, fibrous material changes atresia (namely comparatively low-density to higher density) into from porose.In certain embodiments, transition region is thicker, and porous is reduce gradually in the region of at least 0.5,0.8 or 1 times of the thickness of ground floor at thickness.
In embodiments, the porose second layer has the nano grade pore of interconnection.Such as, the average diameter in described hole is in the scope of 5 to 250nm 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-spherical or irregularly shaped.The degree of second layer mesopore and sized fraction ground determined by the polarity (it affects the exchange of solvent mechanism that hole is formed) of solvent used and non-solvent.Other factors comprises bath solvent temperature and pressure, and the speed of gap internal solvent evaporation and degree.
Shear stress in the size of ring-type spinneret orifice, doughnut size, spinning head, doping flow velocity, polymer-to-hole volume flow rate ratio and batch-with-initial velocity ratio (take-up-to-initialvelocityratio) (draw ratio) be the principal element determining final fibre structure.
In embodiments, the chemical composition of ground floor and the chemical composition of the second layer are identical.Therefore, such as, ground floor is made by the identical PBI material being selected from material described herein with the second layer.
In embodiments, asymmetric doughnut is stablized at up to 400 DEG C.Therefore, up at 400 DEG C, there is minimum or not degraded (that is, 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 μm.Therefore, the external diameter of final asymmetric doughnut can within the scope of 100 to 2000 μm, such as be greater than 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 1000 μm or 1500 μm, or be less than 2000 μm, 1500 μm, 1000 μm, 500 μm, 400 μm, 300 μm or 200 μm.Internal diameter (that is, 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 such as 90 to 1990 μm).
Asymmetric doughnut of the present invention may be used for forming hollow-fibre membrane (HFM).Such as, spinning operation as herein described can also comprise with the speed reeling fiber of 1 to 100 m/min to form HFM.
This film can be used in a kind of for from comprising H 2, CO 2, CO is separated H with in the admixture of gas of methane 2method in, the method comprises makes admixture of gas through this film.
This film can be used in a kind of method for removal of impurity from the aqueous solution, and the method comprises makes the aqueous solution through this film.
Can manufacture after doughnut, by the sulfonation of PBI film such as using impregnation drying to operate.
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 be only describe specific embodiments object and and not intended to be limit.
As used in description and the claims of enclosing, singulative " ", " one " and " described " comprise and multiplely refer to thing, indicate unless context is known in addition.Therefore, such as, when mentioning " a kind of solvent ", not only comprise single solvent, and comprise combination or the mixture of two or more different solvents.
The present invention contain draw all combinations of the concrete and preferred embodiment mentioned.Should understand, example as herein described and embodiment are only for illustration of property object, and various amendment thus or change can have suggested to those skilled in the art and should be included within the spirit and scope of the application and the scope of appended claims.The all publications quoted herein, patent and patent application (comprise wherein quote) are incorporated herein by reference in full for all objects.
Embodiment
Following preparation doped solution: 18wt%PBI alloy and 2wt%PVP (K16 – 18, AcrosOrganics, NewJersey) (the daltonian HMW pore-forming agent of molecular weight 8000) in DMAc.
Following preparation hole fluid: 75 to 90wt%IPA and 5 to 25wt%DMAc.
The coagulation bath of preparation containing 100%IPA.
Be selected from water, isopropyl alcohol, methyl alcohol and combination thereof strong non-solvent be used as hole fluid and coagulation bath.Strong non-solvent has the ability to make polymer solution coagulates in the exit of spinning head; Therefore, thin layer can be formed between outside polymer solution, otherwise fiber easily breaks and polymer solution can under gravity as droplets fall.Internal holes fluid is that the mixture of non-solvent and solvent is to avoid the formation of rete.Spinning head is manufactured into 1.2mm external diameter and 0.4mm internal diameter.This doped solution contains 26wt%PBI and 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 in shell side, H 2permeability is 300GPU.
Obtain the magnification at high multiple picture with the fiber of the cross section of 0.5mm external diameter.Similarly, the magnification at high multiple picture with the fiber of the cross section of 0.8mm external diameter is obtained.Described image illustrates porous and the atresia dense outer layer of internal layer.
Compacted zone is at high osmosis H 2with hypotonicity CO 2between separation is provided, and the process having aperture layer to reduce to penetrating gases with low pressure provides mechanical strength.The test of manufactured fiber shows, H 2compare CO 2more permeate readily through film.H 2permeability increase with temperature and increase, and CO 2permeability to temperature relative insensitivity.
The performance of the prepared fiber of the assessment more than 50 days, the performance of representative more than 1000 hours.H 2/ CO 2be selectively increased to 50 from 35 in time, the design object more than 40.Obtain long-term behaviour assessment data.H 2permeability value maintains about 80GPU (gas infiltration unit) in whole test phase.At the end of 1000 hours test phases, the H measured at 250 DEG C 2permeability is 130GPU.
At 150 DEG C, 200 DEG C, 225 DEG C and 250 DEG C 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 DEG C, H 2/ CO 2selective and H 2permeability all increases.At 250 DEG C, H 2/ CO 2ratio increase, and H2 permeability reduction.This shows that the thickness of compacted zone slightly increases.Along with selective reduction, permeability increases.Dense layer thickness is tested between 1 and 10 μm, and can low reach 0.1 μm under test.
Macroporous existence is that high doped is specific and be strongly depend on non-solvent and the exchange of solvent speed of duration of coagulation.Measure containing the H2 permeability of macroporous fiber at room temperature in the scope of 100 to 200GPU, but H2/CO2 is selective is only 5.Low-fiber mechanical strength also falls in macroporous existence.

Claims (7)

1., for the preparation of a method for asymmetric doughnut, described method comprises:
A () makes the outer annular hole of polymeric solution intubatton type spinning head in via hole, described polymeric solution comprises: the polybenzimidazoles of (i) 15 to 25wt%; (ii) pore-forming material of the polymerization of 1 to 5wt%; (iii) for the solvent of described polybenzimidazoles; Wherein said polymeric solution stablizes at least 6 months to chemical degradation in the temperature range of 15 to 25 DEG C and wherein said polybenzimidazoles is the polybenzimidazoles of sulfonation;
B () makes hole fluid through the inner tube of described spinning head, described hole fluid comprises: the non-solvent for described polybenzimidazoles of (i) 65 to 99wt%; (ii) solvent for described polybenzimidazoles of 1 to 35wt%, wherein said hole fluid makes described polymeric solution maintain annular;
C () drips described polymeric solution and hole fluid by gap, wherein said gap comprises the drippage distance of atmosphere and 0.3 to 20cm;
D () makes the quenching in bath of described polymeric solution and hole fluid have annular and the asymmetric doughnut comprising the first concentric layer and the second concentric layer to be formed, wherein said ground floor contacts the described second layer and for atresia, and the wherein said second layer has the hole of aperture in 5 to 250nm scope
Wherein said ground floor is finer and close than the described second layer;
Wherein said ground floor forms outer surface and the described second layer forms the inner surface of described asymmetric doughnut,
The thickness of wherein said ground floor is within the scope of 0.1 to 10 μm, and the thickness of the wherein said second layer is within the scope of 10 to 500 μm,
The chemical composition of wherein said ground floor and the chemical composition of the described second layer are identical,
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 μm,
Wherein by the length of described drippage distance and the thickness being controlled described ground floor and the second layer by the relative polarity of described solvent and non-solvent, and
Partially hardened during wherein said polymer is deposited in drippage and hardening completely between cold snap.
2. method according to claim 1, washs after wherein said method also comprises (e) spinning and draws described fiber.
3. the method described in claim 1 or 2, wherein said method also comprises (f) and becomes fibre bundle to form hollow-fibre membrane described fiber roll with the speed of 1 to 100 m/min.
4. an asymmetric doughnut, it comprises the first concentric layer and second concentric layer of the wall forming described fiber, wherein:
Described asymmetric doughnut comprises polybenzimidazole material;
Described ground floor be atresia and the described second layer has the hole of aperture in 5 to 250nm scope;
Described ground floor is finer and close than the described second layer;
Described polybenzimidazoles is the polybenzimidazoles of sulfonation,
Described asymmetric doughnut is stablized chemical degradation at up to 400 DEG C;
The thickness of described ground floor is within the scope of 0.1 to 10 μm, and the thickness of the wherein said second layer is within the scope of 10 to 500 μm;
Described ground floor forms outer surface and the described second layer forms the inner surface of described asymmetric doughnut; With
The external diameter of described asymmetric doughnut is within the scope of 100 to 2000 μm.
5. a film, it comprises the described asymmetric doughnut of claim 4.
6. one kind for from comprising H 2, CO 2, CO is separated H with in the admixture of gas of methane 2method, described method comprises makes described admixture of gas through film according to claim 5.
7., for a method for removal of impurity from the aqueous solution, described method comprises makes the described aqueous solution through film according to claim 5.
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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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