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WO2018151175A1 - Membrane de séparation de gaz - Google Patents

Membrane de séparation de gaz Download PDF

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Publication number
WO2018151175A1
WO2018151175A1 PCT/JP2018/005134 JP2018005134W WO2018151175A1 WO 2018151175 A1 WO2018151175 A1 WO 2018151175A1 JP 2018005134 W JP2018005134 W JP 2018005134W WO 2018151175 A1 WO2018151175 A1 WO 2018151175A1
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WO
WIPO (PCT)
Prior art keywords
gas separation
gas
separation membrane
porous support
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/005134
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English (en)
Japanese (ja)
Inventor
泰孝 栗下
美河　正人
諒 黒木
ひとみ 大橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Corp, Asahi Chemical Industry Co Ltd filed Critical Asahi Kasei Corp
Priority to JP2018568581A priority Critical patent/JP6806809B2/ja
Publication of WO2018151175A1 publication Critical patent/WO2018151175A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B01D69/107—Organic support material
    • 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
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/08—Polysaccharides

Definitions

  • the present invention relates to a gas separation membrane that exhibits excellent practicality in the long term.
  • the gas separation membrane of the present invention exhibits particularly excellent performance for olefin separation.
  • Gas separation / concentration using a gas separation membrane is superior in energy efficiency, energy saving, and high safety compared to distillation, high pressure adsorption, and the like.
  • Examples of pioneering practical applications in this field include separation and concentration of gas using a gas separation membrane, hydrogen separation in an ammonia production process, and the like.
  • Recently, studies on gas separation membranes targeting hydrocarbon gases such as separation of olefin gas and paraffin gas have been actively conducted.
  • the gas separation membrane generally has a form in which a gas separation active layer is formed on the surface of a porous support (Patent Documents 1 and 2). This configuration is effective for increasing the amount of gas permeation while giving a certain degree of strength to the membrane.
  • the gas separation active layer is, for example, a layer composed only of a gas separation polymer.
  • the performance of a gas separation membrane is expressed using a permeation rate and a separation coefficient as indices.
  • the transmission speed is expressed by the following formula: (Permeability coefficient of gas separating polymer) / (Thickness of separation layer) Represented by
  • the separation factor is expressed as a ratio of the permeation speeds of the two gases to be separated, and is an amount depending on the material of the gas separating polymer. In order to obtain practical performance as a gas separation membrane, it is necessary to have high gas separation performance and high gas permeability, and to maintain these performances during the use period of the gas separation membrane.
  • the gas separation membrane module for separating hydrocarbon-based gas includes, for example, a porous support, a gas separation active layer, a housing, and an adhesive.
  • the gas separation active layer may optionally contain a metal species (for example, a metal salt) (Patent Documents 3 and 4).
  • the separation target gas causes the gas separation active layer to swell, deteriorate, etc., and the gas separation active layer has defects, peeling from the porous support, etc. There may be a problem that the long-term stability is not good.
  • porous support There are various materials having chemical resistance as the porous support, gas separation active layer, housing, and adhesive of the membrane module for gas separation, and these can be used.
  • gas separation active layer used in the membrane module for gas separation
  • many materials having excellent gas separation performance that is, permeation performance and separation performance have been reported so far.
  • polysaccharides such as cellulose and chitosan are frequently used as a gas separation active layer because of excellent gas separation performance derived from their structural characteristics and availability.
  • polysaccharides are easily decomposed by hydrolysis or the like, and there is a potential danger for carrying out stable long-term operation.
  • an object of the present invention is to provide a gas separation membrane having a gas separation membrane active layer having high gas separation performance and high gas permeability and capable of performing stable long-term operation.
  • the present inventors have intensively studied in order to achieve the above object. As a result, it has been found that the above object can be achieved by adjusting at least one of the crystallinity and crystallite size of the gas separation active layer provided in the produced gas separation membrane, preferably both in an optimum range. It was.
  • a gas separation membrane having a porous support and a gas separation active layer formed on the porous support
  • the gas separation active layer contains a gas separation polymer, and the gas separation polymer is selected from an amino group, a pyridyl group, a group having an imidazole skeleton, a group having an indole skeleton, an amide group, and a sulfonamide group.
  • the degree of crystallinity of the gas-separable polymer represented by the formula (18) is from 46% to 46%, and (B) ⁇
  • K is the Scherrer constant
  • ⁇ is the X-ray wavelength
  • ⁇ is the half-width of the X-ray diffraction peak
  • b is the half-width of the spread of the incident beam
  • ⁇ is the Bragg angle
  • the Scherrer constant K is set to 0.9.
  • the crystallite size on either side of the gas-separable polymer is 3.3 nm or more and 4.0 nm or less, A gas separation membrane satisfying at least one of the above.
  • a gas separation membrane that exhibits excellent practicality in the long term, particularly in the separation of hydrocarbon gases such as olefins.
  • the gas separation membrane in this embodiment has a porous support body and the polysaccharide layer arrange
  • the porous support of the gas separation membrane in the present embodiment is a membrane having a large number of fine holes penetrating the front and back of the membrane.
  • the surface average pore diameter measured with a scanning electron microscope (SEM) is preferably 0.05 ⁇ m or more and 0.5 ⁇ m or less.
  • the material of the porous support is not limited. From the viewpoint of chemical resistance and solvent resistance, polysulfone, polyethersulfone, fluorine-based resin, etc. are preferable, and from the viewpoint of heat resistance, homopolymers or copolymers such as polyimide, polybenzoxazole, polybenzimidazole, etc. Preferably, any of these alone or a mixture thereof is preferable.
  • the fluororesin include polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • the shape of the porous support can be, for example, a hollow fiber shape, a flat membrane shape, or a pleated shape.
  • the film thickness of the porous support having a flat membrane shape or a pleated shape is preferably 1 ⁇ m or more and 1,000 ⁇ m or less from the viewpoint of ensuring sufficiently high gas separation ability and sufficiently high gas permeability.
  • the outer diameter is preferably 0.1 mm or more and 20 mm or less;
  • the inner diameter is preferably 0.1 mm or more and 20 mm or less.
  • the film thickness of the hollow fiber-like porous support is preferably 0.1 mm or more and 20 mm or less from the viewpoint of ensuring sufficiently high gas separation performance and sufficiently high gas permeability.
  • the gas separation active layer is disposed on the above porous support in order to improve the gas separation performance.
  • the gas separation active layer contains at least a gas separation polymer.
  • ⁇ Is 18% or more and 46% or less
  • the degree of crystallinity (%) represented by the formula (1) is 18% or more, the degree of crystallinity is considered to be sufficiently high, and the crystallite size represented by the formula (2) is 3.3 nm or more. The crystal size is considered sufficiently large. In any of these cases, it is presumed that the effect of suppressing swelling and deterioration due to the separation target gas, metal salt, and the like is exhibited by increasing the cohesive force between the polymer chains of the gas-separable polymer. Further, gas does not pass through the crystal part of the gas separating polymer.
  • the degree of crystallinity (%) represented by the mathematical formula (1) is 18% or more and 46% or less, preferably 18% or more and 34% or less, more preferably 18% or more and 31% or less, and 20 It is more preferable that it is not less than 30% and not more than 30%.
  • the crystallite size on either surface represented by the formula (2) is 3.3 nm to 4.0 nm, preferably 3.3 nm to 3.8 nm, and preferably 3.4 nm to 3.8 nm. It is more preferable that
  • the X-ray having a beam diameter of 1 ⁇ m is incident on the gas separation active layer in the cut section from the normal direction of the section of the section, and the transmission method XRD measurement is performed using a two-dimensional detector to perform two-dimensional XRD.
  • a scattering pattern is obtained as a pattern.
  • the porous support is included in the X-ray beam, and the scattering from the porous support is subtracted from the obtained scattering pattern to obtain only the gas separation active layer.
  • the diffraction profile of only the gas separation active layer is obtained by performing annular averaging after removing the diffraction by masking or the like.
  • the background derived from thermal diffuse scattering or the like is removed from the obtained scattering profile assuming a straight line.
  • the gas separation membrane is immersed in a solvent to dissolve the porous support to obtain only the gas separation active layer.
  • the solvent include alcohols such as methanol, ethanol and propanol; polar solvents such as acetonitrile, acetone, dioxane, tetrahydrofuran, chloroform, dichloromethane, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and toluene.
  • the porous support is polyethersulfone, chloroform is preferably used, and when the porous support is PVDF, N-methylpyrrolidone is preferably used.
  • the gas separating polymer in this embodiment is a polysaccharide containing at least one functional group selected from an amino group, a pyridyl group, a group having an imidazole skeleton, a group having an indole skeleton, an amide group, and a sulfonamide group. is there. This is because the excellent gas separation performance derived from the structural characteristics of such a polymer and the availability are considered.
  • a polysaccharide means a polymer having a structure in which monosaccharides are linked by glycosidic bonds, and is a concept including oligosaccharides.
  • the number of repeating units of the polysaccharide is preferably 100 to 10,000, more preferably 300 to 7,000, and still more preferably 500 to 4,000.
  • the polysaccharide in the present embodiment preferably, chitosan, chondroitin, hyaluronic acid, cellulose, chitin, oligoglucosamine and the like, and derivatives thereof are exemplified. These polysaccharides may be used alone or as a mixture. Among these, chitosan is preferably used because of its excellent gas separation performance.
  • chitosan is composed of ⁇ -1,4-N-glucosamine alone or ⁇ -1,4-N-glucosamine and ⁇ -1,4-N-acetylglucosamine as a repeating unit.
  • the ratio of ⁇ -1,4-N-glucosamine in the repeating unit is 70 mol% or more.
  • the ratio of ⁇ -1,4-N-glucosamine in this repeating unit is referred to as the deacetylation rate of the polysaccharide.
  • the gas-separable polymer in the present embodiment has at least one of an amino group, a pyridyl group, a group having an imidazole skeleton, a group having an indole skeleton, an amide group, and a sulfonamide group as repeating units in the molecule. It consists of a gas-separable polymer containing the functional groups of It can be assumed that the gas separation active layer has a repeating unit containing such a group, so that the metal species (particularly metal salt) optionally contained in the gas separation active layer can be highly dispersed and contained.
  • the gas separation membrane can be suitably applied to, for example, separation of olefin and paraffin.
  • a gas-separable polymer containing an amino group is preferable.
  • the amino group has a relatively weak interaction with the metal species (especially metal salts) optionally contained in the gas separation active layer, and thus the mutual interaction between the metal species and the gas to be separated (especially olefins). This is because it is expected that the decrease in action can be suppressed.
  • the presence or absence of the polysaccharide and the presence or absence of a functional group are, for example, elemental analysis, time-of-flight secondary ion mass spectrometry (TOF-SIMS), solid nuclear magnetic resonance analysis (solid NMR), X-ray photoelectron spectroscopy (XPS), argon It can be confirmed by X-ray photoelectron spectroscopy (GCIB-XPS) mounted on a gas cluster ion gun.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • solid NMR solid nuclear magnetic resonance analysis
  • XPS X-ray photoelectron spectroscopy
  • GCIB-XPS X-ray photoelectron spectroscopy
  • the gas separation active layer in the gas separation membrane of the present embodiment may contain a substance having affinity for the separation target gas (particularly olefin).
  • the obtained gas separation membrane can be applied to, for example, separation of olefin and paraffin.
  • a substance having affinity for the separation target gas may also be included in the porous support.
  • the substance having affinity for olefins include metal salts.
  • the metal salt is preferably a metal ion selected from the group consisting of monovalent silver ions (Ag + ) and monovalent copper ions (Cu + ), or metal salts containing complex ions thereof.
  • Ag + or Cu + or a complex ion thereof and F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , CN ⁇ , NO 3 ⁇ , SCN ⁇ , ClO 4 ⁇ , CF 3 SO 3 ⁇ , BF 4 ⁇ , and PF 6 - is comprised metal salt and an anion selected from the group consisting of.
  • the concentration of the metal salt in the gas separation active layer is preferably 10% by mass to 70% by mass, more preferably 30% by mass to 70% by mass, and still more preferably 50% by mass to 70% by mass.
  • the gas separation active layer may be on both sides of the porous support or only on one side.
  • the gas separation active layer may be only on the outer surface of the hollow fiber, may be only on the inner surface, or both the outer surface and the inner surface. It may be on the surface.
  • the gas separation membrane of this embodiment as described above can be suitably used for separation of olefin and paraffin, for example.
  • the side gas flow rate is 50 cc / min
  • the permeation rate of propylene gas measured at 30 ° C. by a constant pressure system in a humidified atmosphere is 10 GPU to 3,000 GPU
  • the propylene / propane separation factor is 50 to 3,000. be able to.
  • the permeation rate of propylene gas is preferably 50 GPU to 2,000 GPU, more preferably 100 GPU to 2,000 GPU.
  • the separation factor of propylene / propane is preferably 100 or more and 1,000 or less, and more preferably 150 or more and 1,000 or less. These values should be measured under conditions of a propylene partial pressure of 1 atm or less, specifically 0.6 atm.
  • the gas separation membrane of the present embodiment has at least the following steps: A process of producing a coating liquid by dissolving the polymer in a solvent (coating liquid manufacturing process), A step of applying the obtained coating solution to the surface of the porous support (application step), A step of drying the coating surface at a temperature lower than the melting point of the porous support to form a gas separation active layer (drying step), and a step of immersing in water of 40 ° C. or more and 100 ° C. or less (dipping step), It is characterized by including.
  • the coating liquid of this embodiment can be produced by dissolving or dispersing a desired gas separating polymer in an aqueous solvent.
  • concentration of the gas separating polymer in the coating liquid is preferably 0.2% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less.
  • the coating solution may contain an organic solvent in a range of 80% by mass or less with respect to the total amount of the solvent.
  • organic solvent used here examples include alcohols such as methanol, ethanol and propanol; polar solvents such as acetonitrile, acetone, dioxane and tetrahydrofuran; These organic solvents may be used alone or in combination of two or more.
  • the coating liquid may contain a surfactant.
  • the surfactant should be a nonionic surfactant from the standpoint of not electrostatically repelling with the gas-separable polymer and being uniformly dissolved in any of acidic, neutral, and basic aqueous solutions. Is preferred.
  • the nonionic surfactant include a long-chain fatty acid ester of polyoxyethylene, a fluorine surfactant having a perfluoro group, and the like. Specific examples thereof include polyoxyethylene long-chain fatty acid esters such as Tween 20 (polyoxyethylene sorbitan monolaurate), Tween 40 (polyoxyethylene sorbitan monopalmitate), Tween 60 (polyoxyethylene sorbitan monostearate).
  • fluorine surfactants having a perfluoro group include fluorine-based compounds Surfactants FC-4430, FC-4432 (above 3M), S-241, S-242, S-243 (above AGC Seimi Chemical), F-444, F-477 (above, DIC) Etc.); It can be mentioned are.
  • the concentration of the surfactant in the coating liquid is preferably 0.001% by mass or more and 1% by mass or less, and 0.01% by mass or more and 0.5% by mass or less with respect to the total amount of the coating liquid. More preferably. This may cause problems such as difficulty in dissolving the surfactant in the coating solution if the concentration of the surfactant is too high; conversely, if the concentration of the surfactant is too low, it is obtained. This is because problems such as a decrease in gas separation performance may occur in the gas separation membrane.
  • the porous support is brought into contact with the coating liquid as described above.
  • the contact method at this time include coating by a dip coating method (dipping method), gravure coating method, die coating method, spray coating method, etc., or coating by a method of depositing on a porous support by filtration Is preferred.
  • the temperature of the coating liquid in contact with the porous support is preferably 0 ° C. or higher and 100 ° C. or lower, and more preferably 20 ° C. or higher and 80 ° C. or lower.
  • the contact temperature is too low, the coating solution may not be applied uniformly on the porous support; conversely, if the contact temperature is too high, the solvent of the coating solution during contact (for example, water) may volatilize excessively.
  • the contact time (immersion time) in the case of contact by the immersion method is preferably 15 minutes or more and 5 hours or less, and more preferably 30 minutes or more and 3 hours or less. If the contact time is too short, it may cause problems such as insufficient coating on the porous support; conversely, if the contact time is too long, the production efficiency of the gas separation membrane will decrease. May occur.
  • a drying step (solvent removal step) is performed.
  • the porous support after the coating process is heated at a temperature lower than the melting point of the porous support to dry the coating film, thereby forming a gas separation active layer on the porous support. It is a process to do.
  • the drying step is preferably performed in an environment of 40 ° C. or more and 160 ° C. or less, more preferably 40 ° C. or more and 120 ° C. or less, preferably 5 minutes or more and 5 hours or less, more preferably 10 minutes or more and 3 hours or less, for example, standing. It can be done by a method.
  • the obtained gas separation membrane is immersed in water at 40 ° C. or higher and 100 ° C. or lower. This step is performed for the purpose of increasing the crystallinity of the gas separating polymer constituting the gas separation membrane and increasing the chemical resistance of the gas separation membrane. This process is presumed to improve the crystallinity of the gas-separable polymer and increase the chemical resistance.
  • the water used for the immersion may contain an organic solvent in a range of 80% by mass or less with respect to the total amount.
  • organic solvent used here examples include alcohols such as methanol, ethanol and propanol; polar solvents such as acetonitrile, acetone, dioxane and tetrahydrofuran; These organic solvents may be used alone or in combination of two or more.
  • the temperature of the water contacted with the gas separation membrane is 40 ° C. or higher and 100 ° C. or lower, preferably 40 ° C. or higher and 80 ° C. or lower, and more preferably 40 ° C. or higher and 60 ° C. or lower. If the temperature is too low, the degree of crystallinity does not increase and the desired chemical resistance cannot be imparted, so that there is a possibility that stable gas separation performance cannot be maintained over a long period of time. On the other hand, if the temperature is too high, peeling of the porous support and the gas separation active layer may occur, which may cause defects in the gas separation membrane.
  • the pressure when immersing the gas separation membrane in water is preferably 0 to 10 atm.
  • the time for immersing the gas separation membrane in water is preferably 1 minute or more and 5 hours or less, and more preferably 1 minute or more and 3 hours or less.
  • the contact time is too short, the degree of crystallinity does not increase, and the desired chemical resistance cannot be imparted. Therefore, there is a possibility that stable gas separation performance cannot be maintained for a long time. Conversely, if the contact time is too long, there is a possibility that problems such as a decrease in the production efficiency of the gas separation membrane may occur.
  • Metal salt impregnation process The gas separation membrane in which the gas separating polymer layer contains a metal salt is further subjected to a metal salt impregnation step in which the gas separation membrane obtained as described above is brought into contact with a metal salt aqueous solution containing a desired metal salt. Can be manufactured. Thereafter, a drying step may optionally be performed.
  • the concentration of the metal salt in the metal salt aqueous solution is preferably 0.1 M or more and 50 M or less.
  • concentration of the metal salt in the aqueous metal salt solution is 0.1 M or less, when the obtained gas separation membrane is used for separation of olefin and paraffin, separation performance with high practicality may not be exhibited. When this concentration exceeds 50M, inconveniences such as an increase in raw material cost occur.
  • the contact treatment of the gas separation membrane with the aqueous metal salt solution is preferably performed by an immersion method.
  • the aqueous solution temperature during immersion is preferably 10 ° C. or higher and 90 ° C. or lower, and more preferably 20 ° C. or higher and 80 ° C. or lower.
  • this immersion temperature is too low, problems such as insufficient impregnation of the metal salt into the gas-separable polymer layer may occur; conversely, if the immersion temperature is too high, an aqueous solution of metal salt during the immersion may occur. May cause problems such as excessive volatilization of the solvent (water).
  • X-ray diffractometer “NanoViewer” manufactured by Rigaku Corporation X-ray wavelength ⁇ : 0.154 nm
  • Optical system Point collimation (1st slit: 0.4 mm ⁇ , 2nd slit: 0.2 mm ⁇ , and guard slit: 0.8 mm ⁇ )
  • Detector Imaging plate (IP) Sample-detector distance: 75.3 mm Environment around the sample: Vacuum Exposure time: 12 hours
  • the peak separation and the full width at half maximum of the amorphous peak were fixed to the above values, and the peak separation was performed. If there is a peak whose peak position is significantly different from the initial value as a result of peak separation, or there is a peak with a negative peak value, the peak separation is performed again without considering that peak. did.
  • the degree of crystallinity was calculated by substituting the area of each peak obtained as a result of peak separation into the above formula (1).
  • the isobutyl modification rate was calculated by proton nuclear magnetic resonance spectroscopy ( 1 H-NMR) measurement.
  • the 1 H-NMR measurement was performed by dissolving the obtained isobutyl-modified chitosan in a mixed solvent of heavy water: heavy trifluoroacetic acid (10: 1) so as to be 10 mg / mL, and using deuterated chloroform as a standard substance.
  • the isobutyl modification rate was 4.2 mol%.
  • 1 H-NMR measurement was performed under the following conditions. Device name: JEOL Ltd., model “JNM-GSX400G” (400 MHz) Measurement temperature: 25 ° C Integration count: 16 times
  • Example 1 Production of gas separation membrane As the porous support, a hollow fiber membrane made of polyvinylidene fluoride (PVDF) having an inner diameter of 0.7 mm, an outer diameter of 1.2 mm, and a length of 7.1 cm was used. A gas separation active layer made of chitosan was formed on the outer surface of the hollow fiber membrane-shaped porous support as described below. To a plastic bottle containing 2 g of acetic acid and 94 g of distilled water, 4 g of chitosan having a deacetylation rate of 100% as raw material chitosan was added and stirred overnight to dissolve.
  • PVDF polyvinylidene fluoride
  • the resulting aqueous solution was filtered under pressure with a filter having a pore size of 5 ⁇ m to remove insoluble impurities.
  • the aqueous solution after filtration was left to stand for 24 hours for degassing.
  • the porous support in the form of a hollow fiber membrane was immersed in the above aqueous solution and then heated at 100 ° C. for 3 hours to perform a drying step, thereby forming a coating film on the outer surface of the hollow fiber.
  • a gas separation membrane was obtained by forming a gas separation active layer made of a polymer.
  • the thickness of the gas separation active layer in the obtained gas separation membrane was 0.5 ⁇ m.
  • the method for forming a gas separation active layer in Example 1 is substantially the same as the method for forming a film of a gas separation polymer in Analysis Example 1 above, except that the drying temperature in the drying step is different.
  • Examples 2 to 5 and Comparative Example 3 A gas separation membrane was prepared in the same manner as in Example 1 except that the conditions of the dipping process were changed as shown in Table 1, and the performance was evaluated.
  • the film thicknesses of the gas separation active layers in the gas separation membranes obtained in these examples and comparative examples were both 0.5 ⁇ m. The results are shown in Tables 2 and 3.
  • Example 6 (1) Production of gas separation membrane A flat membrane made of polyvinylidene fluoride (PVDF) is used as a porous support, and a gas separation active layer made of a gas separation polymer is formed on one side in the same manner as in Analysis Example 3. As a result, a gas separation membrane was obtained. The film thickness of the gas separation active layer in the obtained gas separation membrane was 50 ⁇ m.
  • Performance Evaluation of Gas Separation Membrane Using the gas separation membrane, the supply gas is circulated on the gas separation active layer forming surface side, and the permeated gas is circulated on the surface opposite to the gas separation active layer formation surface. The measurement was carried out by the same method as in Example 1 except that the measurement was performed. The results are shown in Table 2.
  • Example 1 A gas separation membrane was prepared in the same manner as in Example 1 except that the type of raw material chitosan and the conditions of the drying step were as shown in Table 3 and the immersion step was not performed, and the performance was evaluated.
  • the thicknesses of the gas separation active layers in the gas separation membranes obtained in these comparative examples were all 0.5 ⁇ m. The results are shown in Table 3.
  • the gas separation weight was controlled such that the crystallinity was controlled to 18% to 46% and / or the crystallite size was controlled to 3.3 nm to 4.0 nm.
  • a gas separation membrane having a gas separation active layer formed of a coalescence was used, it was verified that it had excellent separation performance stably over the long term.
  • the crystallinity is 18% or more and / or the crystallite size is 3.3 nm or more, it is considered that the crystallinity is sufficiently high and / or the crystal size is sufficiently large.
  • the gas separation membrane of the present embodiment When the gas separation membrane of the present embodiment is used, a method for separating olefin gas or the like that exhibits excellent practicality over the long term is provided.

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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)
  • Biological Depolymerization Polymers (AREA)

Abstract

Une membrane de séparation de gaz qui comprend un support poreux et une couche active de séparation de gaz formée sur le support poreux : la couche active de séparation de gaz contient un polymère de séparation de gaz; le polymère de séparation de gaz est un polysaccharide contenant au moins un type de groupe fonctionnel choisi parmi un groupe aminé, un groupe pyridyle, un groupe ayant un squelette imidazole, un groupe ayant un squelette indole, un groupe amide et un groupe sulfamide; et la cristallinité du polymère de séparation de gaz, ladite cristallinité étant représentée par la formule : cristallinité(%)=[Ic/(Ic+Ia)]×100 {où Ic représente la somme des intégrales des intensités de diffusion de pics cristallins obtenus à partir d'une analyse de diffraction des rayons X de la membrane de séparation de gaz, et Ia représente la somme des intégrales des intensités de diffusion du halo amorphe}, est de 18-46 % inclus.
PCT/JP2018/005134 2017-02-15 2018-02-14 Membrane de séparation de gaz Ceased WO2018151175A1 (fr)

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WO2016194711A1 (fr) * 2015-05-29 2016-12-08 旭化成株式会社 Membrane de séparation de gaz
WO2017026456A1 (fr) * 2015-08-13 2017-02-16 旭化成株式会社 Membrane de séparation de gaz

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