KR20160148909A - Fluorine-containing polybenzimidazole asymmetric hollow fiber membrane for gas separation and preparation method thereof - Google Patents
Fluorine-containing polybenzimidazole asymmetric hollow fiber membrane for gas separation and preparation method thereof Download PDFInfo
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- KR20160148909A KR20160148909A KR1020150085695A KR20150085695A KR20160148909A KR 20160148909 A KR20160148909 A KR 20160148909A KR 1020150085695 A KR1020150085695 A KR 1020150085695A KR 20150085695 A KR20150085695 A KR 20150085695A KR 20160148909 A KR20160148909 A KR 20160148909A
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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
- B01D71/58—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
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/021—Manufacturing thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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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
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
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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
- B01D69/10—Supported membranes; Membrane supports
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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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
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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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Abstract
The present invention relates to a fluorine-containing polybenzimidazole asymmetric liquid containing a fluorine-containing polybenzimidazole spinning liquid obtained by spinning the fluorine-containing polybenzimidazole spinning solution through a dry-wet phase transformation process and then solvent-replacing the residual solvent with methanol, The present invention relates to a technique for preparing a hollow fiber membrane and applying it to gas separation.
According to the present invention, it is possible to provide a fluorine-containing polybenzimidazole asymmetric hollow fiber membrane excellent in thermal, mechanical and chemical stability as well as gas permeability for gas separation, and also to provide a fluorine-containing polybenzimide A disazo hollow fiber membrane may be used as the porous support of the composite membrane.
Description
The present invention relates to a fluorine-containing polybenzimidazole asymmetric hollow fiber membrane for gas separation and a method for producing the same. More particularly, the present invention relates to a fluorine-containing polybenzimidazole spinning solution having a high concentration, And then subjecting the residual solvent to solvent substitution with methanol, hexane or the like, and then applying the same to gas separation. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing polybenzimidazole asymmetric hollow fiber membrane.
The use of polymer membranes for gas separation is rapidly growing due to its innovative design and process development, not only in terms of production cost, but also in terms of volume reduction of equipment, efficiency of energy utilization, and ease of recovery of byproducts. Among these materials for polymer gas separation membranes, those that are thermally, mechanically, and chemically stable at high temperature and high pressure are being researched and developed. Typical examples thereof include polybenzothiazole, polybenzoxazole, and polybenzimidazole. In particular, polybenzimidazole (PBI) -based polymers have a higher density than other aromatic polymers, exhibit a pyrolysis temperature of 500 ° C or higher, and are known to exhibit glass transition temperatures of 400 ° C or higher. Such PBI thermally, Has recently attracted a great deal of attention in the gas separator market due to its chemical stability (Patent Document 1).
However, since PBI generally has high crystallinity and is excellent in mechanical strength, solubility in a conventional organic solvent is low, and it is not easy to obtain a high-concentration polymer solution. Therefore, it is not easy to produce a defect-free hollow-fiber type gas separation membrane It is known. Recently, a method of separating a hollow fiber membrane for gas separation from a spinning solution in which a polymer selected from polysulfone, polyether sulfone, polyimide, polyetherimide, polyamide and PBI is dissolved in N-methylpyrrolidone (NMP) However, a specific method for producing PBI at a high concentration as a spinning solution for producing a hollow fiber membrane has not been disclosed (Patent Document 2).
In addition, studies on PBI hollow fiber membranes for hydrogen separation and carbon dioxide capture from syngas have been carried out. Conventional meta-PBI (m-1) produced by the polymerization reaction of 3,3'-diaminobenzidine and isophthalic acid, Discloses a PBI hollow fiber membrane produced from a PBI system spinning solution. However, the method of obtaining a PBI spinning solution at a high concentration and the change of a bubble roll after a spin washing process have not been specifically known One).
Therefore, the present inventors have paid attention to the fact that PBI containing fluorine atoms are more chemically stable, and if PBI containing a fluorine atom can be prepared as a high-concentration spinning solution, an asymmetric hollow fiber membrane can be obtained through a normal dry-wet phase transformation process The present invention has been completed based on the fact that the defect-free PBI asymmetric hollow fiber membrane prepared by controlling the solvent substitution process after spinning can be applied for gas separation.
SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a fluorine-containing polybenzimidazole spinning solution for forming a hollow fiber at a high concentration, Containing polybenzimidazole hollow fiber membrane excellent in gas permeability and capable of obtaining an asymmetric hollow fiber membrane containing polybenzimidazole and a method for producing the same.
In order to accomplish the above object, the present invention provides a fluorine-containing polybenzimidazole asymmetric hollow fiber membrane for gas separation having a repeating unit represented by the following formula (1).
≪ Formula 1 >
In addition, the fluorine-containing polybenzimidazole asymmetric hollow fiber membrane is used as a porous support of a composite membrane.
The present invention also relates to a process for preparing a fluorine-containing polybenzimide (hereinafter, referred to as " fluorine-containing polybenzimidazole ") from a polymer solution obtained by condensation polymerization of I) 3,3'-diaminobenzidine and 4,4'- (hexafluoro- isopropylidene) Obtaining a solution of the azole; II) dissolving the fluorine-containing polybenzimidazole powder in an organic solvent containing lithium chloride to obtain a spinning solution; III) supplying and discharging the spinning solution together with a bore solution to a double spinning nozzle to form a hollow fiber; And IV) obtaining an asymmetric hollow fiber membrane through a series of steps of external coagulation, washing, winding, solvent substitution and drying of the hollow fiber, and a process for producing an asymmetric hollow fiber membrane containing fluorine-containing polybenzimidazole to provide.
The polymerization solvent in the step I) is a polyphosphoric acid or a mixed solvent of phosphorus pentoxide and methanesulfonic acid.
The fluorine-containing polybenzimidazole powder in the step I) is characterized in that the polymer solution is precipitated in deionized water to remove residual phosphoric acid, followed by drying in a vacuum oven at 60 to 100 ° C.
And then washed with 12% ammonia water at 40 to 50 DEG C for 2 to 3 days to remove the remaining phosphoric acid, and then washed with deionized water to neutral pH.
The organic solvent in the step II) is any one selected from the group consisting of N-methylpyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide, and mixtures thereof.
The spinning solution has a concentration of 12 to 15% by weight.
The bore solution is characterized by at least one selected from the group consisting of water, isopropanol, ethylene glycol, polyethylene glycol, glycerol, dimethoxy ethanol, diethoxy ethanol, butoxy methanol, dimethoxybutylene oxide and diglycidyl dimethyl ether .
In the step III), the discharging rate of the spinning solution is 1.0 to 3.0 cc / min, and the discharging rate of the bore solution is 0.5 to 2.0 cc / min.
The solvent substitution in the step IV) is performed by treating with hot water, and then using methanol and hexane sequentially to remove the residual solvent for 5 to 12 hours.
And further coating the surface of the asymmetric hollow fiber membrane obtained in the step IV) with polydimethylsiloxane.
The present invention also provides a membrane module comprising the asymmetric hollow fiber membrane containing fluorine-containing polybenzimidazole for gas separation.
According to the present invention, it is possible to obtain a fluorine-containing polybenzimidazole spinning solution for forming a hollow fiber at a high concentration and to control the solvent substitution process after spinning to obtain a defect-free fluorine-containing polybenzimidazole asymmetric hollow fiber membrane, , It is possible to provide a fluorine-containing polybenzimidazole asymmetric hollow fiber membrane excellent in mechanical and chemical stability as well as gas permeability for gas separation, and also to provide a fluorine-containing polybenzimidazole hollow fiber membrane produced from the present invention as a composite membrane It can also be used as a porous support.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the 1 H-NMR spectra of PBI-HFA, (b) PBI-IPA of the fluorine-containing polybenzimidazole powder obtained from the synthesis example of the present invention,
2 is a schematic view of a conventional hollow fiber membrane manufacturing apparatus.
FIG. 3 is a photograph of the appearance of the fluorine-containing polybenzimidazole asymmetric hollow fiber membrane according to the concentration of the spinning solution according to the present invention. FIG.
Fig. 4 is a graph showing the surface and cross-section (a) of the hollow fluorine-containing polybenzimidazole asymmetric hollow fiber membrane after washing the hollow fiber with water only, and the fluorine-containing polybenzimidazole Scanning electron microscope (SEM) images of the asymmetric hollow fiber membrane surface and cross section (b).
5 is a scanning electron microscope (SEM) image of the surface and cross section of a fluorine-containing polybenzimidazole asymmetric hollow fiber membrane produced from an embodiment of the present invention.
6 is a gas permeation test module for fluorine-containing polybenzimidazole asymmetric hollow fiber membranes according to the present invention.
Hereinafter, the fluorine-containing polybenzimidazole asymmetric hollow fiber membrane for gas separation according to the present invention will be described in detail.
Generally, a hollow fiber membrane of a polymer material for gas separation is produced by wet spinning or dry-wet spinning of a polymer solution (spinning solution) of a desired material. At this time, the main factors affecting the structure of the hollow fiber membrane are the concentration and composition of the polymer solution, the kind of the organic solvent for obtaining the polymer solution, the kind and composition of the external coagulant and the bore solution, the air gap, And a discharge speed. Accordingly, in the production of the hollow fiber membrane, the hollow fiber membrane having the desired structure can be produced by suitably controlling such factors. Since the hollow fiber membrane usually has a thin skin layer, it has a high gas permeability as compared with the single material membrane and maintains the mechanical strength due to the porous support at the bottom. In particular, the hollow fiber membrane can form a porous structure, which can be used as a support for a composite membrane formed by coating a porous membrane with a highly selective layer on a porous support, thereby improving the gas permeability and selectivity of the composite membrane .
Therefore, the present invention provides a fluorine-containing polybenzimidazole asymmetric hollow fiber membrane for gas separation having a repeating unit represented by the following formula (1).
≪ Formula 1 >
The fluorine-containing polybenzimidazole asymmetric hollow fiber membrane having a repeating unit represented by the above-mentioned formula (1) is basically a polybenzimidazole film as a film material, and not only has excellent thermal and mechanical properties, but also contains fluorine atoms And has excellent chemical stability.
In addition, the fluorine-containing polybenzimidazole asymmetric hollow fiber membrane has a porous structure and a high gas permeability, so that it can be used as a porous support of a composite membrane.
Accordingly, in order to obtain a fluorine-containing polybenzimidazole hollow fiber membrane for gas separation having a repeating unit represented by the above-mentioned formula (1), in the present invention, I) 3,3'-diaminobenzidine and 4,4'- (hexafluoro To obtain a fluorine-containing polybenzimidazole powder from a polymer solution obtained by condensation polymerization of bis (benzoic acid) in a polymerization solvent; II) dissolving the fluorine-containing polybenzimidazole powder in an organic solvent containing lithium chloride to obtain a spinning solution; III) supplying and discharging the spinning solution together with a bore solution to a double spinning nozzle to form a hollow fiber; And IV) obtaining an asymmetric hollow fiber membrane through a series of steps of external coagulation, washing, winding, solvent substitution and drying of the hollow fiber, and a process for producing an asymmetric hollow fiber membrane containing fluorine-containing polybenzimidazole to provide.
First, in the present invention, in order to synthesize a fluorine-containing polybenzimidazole, 3,3'-diaminobenzidine represented by the following formula (I) as a tetraamine monomer is reacted with an aromatic dicarboxylic acid monomer represented by the following
(I)
≪
That is, in the step I), the condensation polymerization reaction of the two monomers 3,3'-diaminobenzidine and 4,4 '- (hexafluoro-isopropylidene) bis (benzoic acid) It is preferable to use polyphosphoric acid, but a mixture for phosphorus pentoxide and methanesulfonic acid may also be used.
The polycondensation reaction is carried out by dissolving 3,3'-diaminobenzidine and 4,4 '- (hexafluoro-isopropylidene) bis (benzoic acid) in the polymerization solvent and stirring at 130 to 150 ° C for 2 to 5 hours Then, the temperature is raised to 170 to 180 ° C and the reaction is carried out for 12 to 15 hours to obtain a polymer solution. Subsequently, the polymer solution is precipitated in deionized water, and then the remaining phosphoric acid is removed and dried in a vacuum oven at 60 to 100 DEG C to obtain a fluorine-containing polybenzimidazole polymer powder. At this time, in order to remove the remaining phosphoric acid, it is washed with 12% ammonia water at 40 ~ 50 ° C for 2 ~ 3 days, repeatedly washed with deionized water to neutral pH.
Next, the fluorine-containing polybenzimidazole powder obtained in the step I) is dissolved in an organic solvent containing lithium chloride to obtain a spinning liquid. In general, polybenzimidazole has high crystallinity and hydrogen bonds between imidazole rings in the polymer chains cause hydrogen bonding between the chains, so that the solubility of the polymer in the organic solvent is very low. It is known that it is difficult to obtain a polymer solution.
Therefore, in the present invention, it has been found that a high-concentration polymer solution can be obtained by using a mixed solvent obtained by mixing lithium chloride in an organic solvent. However, when a fluorine-containing polybenzimidazole powder is added to a mixed solvent of an organic solvent and lithium chloride, The solution may be obtained by dissolving the fluorine-containing polybenzimidazole powder in an organic solvent, adding lithium chloride, or dissolving the organic solvent, lithium chloride and fluorine-containing polybenzimidazole powder simultaneously in an organic solvent, A high concentration solution can not be obtained.
In addition, it is preferable to use a solvent having a relatively high boiling point (150 DEG C or higher) as the organic solvent. If the boiling point is low, defects may be generated in the hollow fiber selected layer due to rapid evaporation of the organic solvent during the hollow fiber spinning process. If the boiling point is too high, evaporation of the organic solvent does not occur while the spinning solution passes through the air, I can not get it. Therefore, as the organic solvent, any one selected from the group consisting of N-methylpyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide and mixtures thereof may be used. Among them, N-methylpyrrolidone is more preferable desirable.
If the concentration of the spinning solution is less than 12% by weight, it is difficult to obtain a desired type of hollow fiber. When the concentration of the spinning solution exceeds 15% by weight, uniformity A skin layer is not easily formed and the selectivity may be deteriorated.
Subsequently, the spinning solution is fed and discharged into a double spinning nozzle together with a bore solution to form a hollow fiber. The bore solution, which acts as an internal coagulant, is selected from the group consisting of water, isopropanol, ethylene glycol, polyethylene glycol, glycerol, dimethoxy ethanol, At least one selected from the group consisting of ethanol, butoxyethanol, butoxymethanol, dimethoxybutylene oxide and diglycidyl dimethyl ether can be used, and it is more preferable to use water.
Also, the discharging speed of the spinning solution is adjusted to 1.0 to 3.0 cc / min, and the discharging speed of the bore solution is adjusted to 0.5 to 2.0 cc / min to prevent secondary elongation.
Finally, the hollow fiber formed in the step (III) is subjected to a series of processes such as external coagulation, washing, winding, solvent replacement and drying to obtain an asymmetric hollow fiber membrane. The hollow fiber is injected into the primary coagulation bath filled with tap water, , The hollow fiber finished with phase transformation in the primary coagulation bath removes the residual solvent from the secondary coagulation bath and is wound at a constant speed. In particular, if the hollow fiber membrane is washed only with water and then dried at room temperature, the water in the hollow fiber membrane having a porous support structure is dried and twisted. Therefore, after the wound hollow fiber membrane is treated with hot water, methanol and hexane are sequentially used And the solvent is completely replaced by a solvent for 5 to 12 hours to completely remove the residual solvent, followed by drying at room temperature to produce a defect-free asymmetric hollow fiber membrane.
In addition, the present invention may further include a step of coating the surface of the asymmetric hollow fiber membrane obtained in the step IV) with polydimethylsiloxane to remove defects of the asymmetric hollow fiber membrane and improve permeability of the gas.
The present invention also provides a membrane module comprising the asymmetric hollow fiber membrane containing fluorine-containing polybenzimidazole for gas separation.
Hereinafter, specific examples and comparative examples will be described in detail with reference to the accompanying drawings.
[Synthesis Example] Synthesis of fluorine-containing polybenzimidazole powder
(14 mmol) of 3,3'-diaminobenzidine, 5.5 g (14 mmol) of 4,4 '- (hexafluoro-isopropylidene) bis (benzoic acid) and 125 g of polyphosphoric acid as a polymerization solvent And the mixture was stirred in an argon gas atmosphere at 150 DEG C for 5 hours. After sufficiently dissolving the monomers, the reaction temperature was gradually raised to 180 ° C and reaction was carried out for 15 hours. The polymer solution was then precipitated in deionized water and washed with 12% ammonia water at 50 < 0 > C for 3 days to remove residual phosphoric acid. Finally, fluorine-containing polybenzimidazole powder (PBI-HFA) was prepared by washing with deionized water to a neutral acidity and then drying in a vacuum oven at 60 ° C. For comparison, 2.3 g of isophthalic acid as an aromatic dicarboxylic acid (PBI-IPA) was also synthesized in the same manner as in Example 1, except that the fluorine-free polybenzimidazole powder (14 mmol) was used.
[Examples] Preparation of fluorine-containing polybenzimidazole asymmetric hollow fiber membrane
In a 1 L round bottom flask equipped with a stirrer, 1.2 g of lithium chloride was added to 86.8 g of N-methylpyrrolidone to obtain a mixed solvent. After the mixed solvent was heated to 150 ° C, 12 g of polybenzimidazole powder (PBI-HFA) synthesized from the above Synthesis Example was added to obtain a spinning solution. At this time, the spinning solution was left under reduced pressure overnight to completely remove the bubbles, and the impurities were filtered using a 120 mesh porous metal filter. The spinning solution was supplied to the double spinning nozzle through a gear pump and discharged through the outer nozzle of the spinning nozzle (discharge rate of the spinning solution: 2.0 cc / min). Water inside the double spinning nozzle, the bore solution, (Bore solution discharge rate of 1.0 cc / min) was supplied through a pump to form a hollow fiber between the bore solution and the dope solution (air gap 30 cm). The hollow fiber thus formed was poured into a primary coagulation bath filled with tap water. The hollow fiber finished with phase transformation in the primary coagulation bath removed the residual solvent from the secondary coagulation bath and was wound at a constant speed. Subsequently, the hollow fiber was treated with hot water for 2 hours, and then methanol and hexane were successively used for solvent replacement for 5 hours each time to completely remove the residual solvent. The resultant was dried at room temperature for 48 hours to obtain a fluorine-containing polybenzimidazole asymmetric hollow The desert was prepared.
[Comparative Example] Production of fluorine-free polybenzimidazole asymmetric hollow fiber membrane
A polybenzimidazole asymmetric hollow fiber membrane containing no fluorine was prepared in the same manner as in Example except for using a fluorine-free polybenzimidazole powder (PBI-IPA) synthesized for comparison in the above Synthesis Example Respectively.
Figure 1 shows 1 H-NMR spectrum of the fluorine-containing polybenzimidazole powder (PBI-HFA) and polybenzimidazole powder containing no fluorine (PBI-IPA) obtained from Synthesis Example of the present invention [(a) PBI -HFA, (b) PBI-IPA]. 1, PBI-HFA and PBI-IPA were synthesized by confirming the hydrogen of the imidazole ring NH, which is a characteristic peak of the polybenzimidazole chain, in the range of δ 13.2 and the aromatic group of the benzene ring in the range of
FIG. 2 is a schematic view of a conventional hollow fiber membrane production apparatus. The polybenzimidazole asymmetric hollow fiber membranes according to Examples and Comparative Examples of the present invention were produced using the hollow fiber membrane production apparatus shown in FIG.
FIG. 3 is a photograph of the external shape of the fluorine-containing polybenzimidazole asymmetric hollow fiber membrane according to the concentration of the spinning solution according to the present invention. The polybenzimidazole asymmetric hollow fiber membrane having a fluorine-containing polybenzimidazole structure has a hollow fiber shape in its outer shape, but it can be seen that a hollow fiber of a desired shape can not be formed if the concentration of the spinning solution is less than 12% by weight. Therefore, it has been confirmed that the critical concentration of the spinning solution for obtaining a homogeneous polybenzimidazole asymmetric hollow fiber membrane is 12 wt%, and when the concentration of the spinning solution is more than 15 wt%, a uniform skin layer is not easily formed .
4 shows the surface and cross-section (a) of the fluorine-containing polybenzimidazole asymmetric hollow fiber membrane which is washed with water only after the hollow fiber membrane is washed with water only, and the fluorine- As shown in FIG. 4 (a), the hollow fiber finished with phase transformation by external solidification was treated with water alone as shown in FIG. 4 (a). As a result, the surface of the imidazole asymmetric hollow fiber membrane and the cross- When washed and dried at room temperature, the water in the hollow fiber membrane having the porous support structure was dried to cause twisting phenomenon. On the other hand, after the hollow fiber was treated with hot water as shown in FIG. 4 (b), methanol and hexane were sequentially used It was found that the asymmetric hollow fiber membrane without defects was obtained by completely removing the residual solvent by drying the solvent at room temperature for 5 hours.
5 shows a scanning electron microscope (SEM) image of a fluorine-containing polybenzimidazole asymmetric hollow fiber membrane prepared from an embodiment of the present invention, It can be confirmed that the desert is made.
[Test example] Gas permeability measurement test
In order to measure the gas permeability of the polybenzimidazole asymmetric hollow fiber membranes prepared in Examples and Comparative Examples of the present invention, a gas permeation test module as shown in Fig. 6 was fabricated [5 strands of hollow fiber membrane, 9.5 cm, effective membrane area 5.97 cm 2 (outer diameter 400 μm),
As shown in Table 1 above, the fluorine-containing polybenzimidazole (PBI-HFA) asymmetric hollow fiber membrane prepared from the examples of the present invention is a fluorine-free conventional polybenzimidazole (PBI-IPA ) Permeability of nitrogen, oxygen, and carbon dioxide is much higher than that of the asymmetric hollow fiber membrane, and the selectivity is not significantly lowered in consideration of the normal trade-off relationship between gas permeability and selectivity. In addition, by coating the surface of the fluorine-containing polybenzimidazole (PBI-HFA) asymmetric hollow fiber membrane prepared from the embodiment of the present invention with polydimethylsiloxane, it is possible to improve the permeation selectivity by supplementing the selective layer.
Therefore, according to the present invention, a fluorine-containing polybenzimidazole spinning solution for forming a hollow fiber can be obtained at a high concentration, and a defect-free fluorine-containing polybenzimidazole asymmetric hollow fiber membrane can be obtained by controlling the solvent- It is possible to provide a fluorine-containing polybenzimidazole asymmetric hollow fiber membrane excellent in thermal, mechanical and chemical stability as well as gas permeability for gas separation and also to provide a fluorine-containing polybenzimidazole hollow fiber membrane produced from the present invention as a composite It may also be used as a porous support of membranes.
Claims (13)
≪ Formula 1 >
II) dissolving the fluorine-containing polybenzimidazole powder in an organic solvent containing lithium chloride to obtain a spinning solution;
III) supplying and discharging the spinning solution together with a bore solution to a double spinning nozzle to form a hollow fiber; And
IV) A process for producing an asymmetric hollow fiber membrane for gas separation, comprising the step of external coagulation, washing, winding, solvent replacement and drying of the hollow fiber.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100644366B1 (en) | 2005-11-08 | 2006-11-10 | 한국화학연구원 | New spinning processes for asymmetric gas separation hollow fiber membranes |
| KR101389543B1 (en) | 2009-05-15 | 2014-04-28 | 한양대학교 산학협력단 | Preparation method of polybenzimidazole |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100644366B1 (en) | 2005-11-08 | 2006-11-10 | 한국화학연구원 | New spinning processes for asymmetric gas separation hollow fiber membranes |
| KR101389543B1 (en) | 2009-05-15 | 2014-04-28 | 한양대학교 산학협력단 | Preparation method of polybenzimidazole |
Non-Patent Citations (1)
| Title |
|---|
| 비특허문헌 1 Rajinder P. Singh et al., Energy Procedia 63, 153-159(2014) |
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