WO2019021964A1 - 流体分離用炭素膜およびその製造方法 - Google Patents
流体分離用炭素膜およびその製造方法 Download PDFInfo
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- WO2019021964A1 WO2019021964A1 PCT/JP2018/027316 JP2018027316W WO2019021964A1 WO 2019021964 A1 WO2019021964 A1 WO 2019021964A1 JP 2018027316 W JP2018027316 W JP 2018027316W WO 2019021964 A1 WO2019021964 A1 WO 2019021964A1
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- D06M2101/40—Fibres of carbon
Definitions
- the present invention relates to a carbon membrane for fluid separation and a method of manufacturing the same.
- Membrane separation is used as a method for selectively separating and purifying specific components from various mixed gases and mixed liquids. Membrane separation is of interest because of its energy savings compared to other fluid separation methods.
- organic polymer membranes such as polyimide membranes and cellulose acetate membranes
- inorganic membranes such as zeolite membranes, silica membranes and carbon membranes have been proposed.
- a carbon membrane exhibits excellent gas separation performance and pervaporation separation performance, and can be used in an environment where heat resistance and chemical resistance are required, so its practical use is expected.
- a carbon film a tube-like or tube-like combination is in the form of a lotus root, and a resin of a carbon film precursor such as a phenol resin or polyimide is laminated on the surface of a monolithic ceramic porous support.
- a ceramic support type carbon film carbonized in a non-oxidizing atmosphere has been proposed.
- a carbon film having a phenol resin as a precursor it is disclosed that the separation coefficient of water / ethanol is excellent when the R value calculated from the Raman spectrum is in a specific range (Patent Document 1).
- Patent Document 2 a tubular porous carbon support having a phenolic resin powder as a precursor is formed, and a resin such as a phenolic resin is laminated on the surface, and then a carbon support type carbon film carbonized in a non-oxidizing atmosphere is proposed.
- hollow fiber carbon membranes having a fiber diameter of less than 1 mm may be able to be produced by a continuous process, and are expected to be able to be produced inexpensively compared to ceramic support type carbon membranes.
- a carbon membrane in which two layers of membranes having different affinities with the permeation component are laminated has been proposed (Patent Document 3).
- the hollow fiber carbon membrane is highly brittle, and the hollow fiber carbon membrane is broken due to vibration during production or transportation of the separation module, or sudden pressure or temperature change during use. ing.
- Patent Document 4 studies have been made to improve the flexibility and the elongation at break of the carbon membrane.
- the present inventors produced various carbon membrane precursors and hollow fiber carbon membranes for fluid separation composed of various carbonization conditions, and evaluated their gas permeation performance. As a result, it was found that the hollow fiber carbon membrane in the separation module may break and gas leakage may occur and the separation performance may be lost in the vacuum desorption process before the gas permeation measurement or in the gas permeation measurement. Furthermore, it has been found that the hollow fiber carbon membrane may break even when a gas containing water vapor is permeated or when water is permeated by the pervaporation method.
- the present invention has been made in view of the above problems, and provides a carbon membrane for fluid separation that can suppress breakage of a carbon membrane installed in a separation module during reduced pressure desorption process before fluid permeation or fluid permeation. To be an issue.
- the hollow fiber carbon membrane contracts in the process of desorbing the water vapor adsorbed on the carbon film and the support, or the process of water vapor adsorption It has been found that the stretching and the phenomenon occur reversibly. That is, it was estimated that the water vapor adsorption amount of the carbon film and the support changed in various relative humidity atmospheres, and the carbon film was broken due to the change.
- the present inventors examined the carbonization time shortening and improvement in breaking elongation according to the example given in patent documents 4. As a result, although the number of hollow fiber carbon membranes to be broken was reduced, the breakage could not be sufficiently suppressed. This is presumed to be due to the fact that the support had high hydrophilicity and the amount of water vapor adsorbed to the support was large due to insufficient carbonization of the support portion. Therefore, in order to sufficiently suppress the breakage of the carbon membrane for fluid separation in the separation module, it is not sufficient to improve only the breaking elongation of the carbon membrane, and under various conditions of temperature and atmosphere, the carbon for fluid separation is We came to the conclusion that it is necessary to improve the dimensional stability of the membrane support.
- the present invention for solving the above-mentioned problems is a carbon membrane for fluid separation in which a dense carbon layer is formed on a porous carbon support, and the R value calculated from the Raman spectrum of the porous carbon support when D band peak intensity of the peak intensity / G band (1580 cm -1) of (1360 cm -1)) and R s value, a carbon film for a fluid separation R s value of 1.0 or less.
- the present invention it is possible to suppress breakage of the carbon membrane for fluid separation in the fluid separation module at the time of the vacuum desorption process before fluid permeation and the fluid permeation. Therefore, fluid leakage is suppressed, and a fluid separation carbon film with a high separation coefficient can be provided.
- the carbon membrane for fluid separation of the present invention has a structure in which a dense carbon layer 2 is formed on a porous carbon support 1.
- a dense carbon layer 2 is formed on a porous carbon support 1.
- a solid thread or a film may be sufficient.
- the porous carbon support is a base for maintaining the shape of the dense carbon layer having a function as a separation membrane. Since the support is formed of a carbon material, it has high heat resistance and chemical resistance as compared to a support made of an organic polymer. In addition, since the support has a porous structure, it also has a role as a flow path for fluids such as gas and liquid.
- the porous structure is not limited, and various porous structures such as a closed cell structure or a continuous porous structure can be adopted. The closed cell structure improves the cross-sectional compressive strength. On the other hand, in the case of a continuous porous structure, the pressure loss at the time of fluid permeation is reduced, and the fluid permeation rate is improved.
- the porous structure of the porous carbon support is preferably a bicontinuous porous structure which is a form of a continuous porous structure.
- the co-continuous porous structure is a structure in which branches (carbon parts) and pore parts (voids) are continuously and three-dimensionally regularly entangled. Specifically, as illustrated in FIG. 2, when a cross-section obtained by cutting a sufficiently cooled sample in liquid nitrogen with a tweezer or the like is observed on the surface with a scanning electron microscope, the branches and voids are in the depth direction. Each refers to a structure in which a continuous structure is observed.
- the branches have an effect of supporting the structures with one another, and the stress is dispersed throughout the support. Therefore, the cross-sectional compressive strength is improved, and the carbon membrane for fluid separation can be used without breakage even if the supplied fluid is at high pressure.
- the porous structure of the porous carbon support is preferably a highly uniform structure having a periodic structure, and the structural period is preferably 0.002 ⁇ m to 10 ⁇ m. If the structural period is 0.002 ⁇ m or more, the pressure loss when the fluid passes through the gap decreases, so the fluid permeation rate is improved.
- the structural period is more preferably 0.01 ⁇ m or more, further preferably 0.05 ⁇ m or more. On the other hand, when the structural period is 10 ⁇ m or less, the cross-sectional compressive strength is improved.
- the structural period is more preferably 8 ⁇ m or less.
- the structure period of the porous structure is calculated by the following equation based on the value of the scattering angle 2 ⁇ at the position of the peak top of the scattering intensity obtained by injecting X-rays into the carbon film for fluid separation of the present invention and scattering at small angles.
- Ru. P ⁇ / 2 sin ⁇ P: structural period ( ⁇ m), ⁇ : wavelength of incident X-ray ( ⁇ m)
- the structure period is obtained by X-ray computed tomography (X-ray CT). Specifically, after Fourier-transforming a three-dimensional image taken by X-ray CT, an annular average of the two-dimensional spectrum is taken to obtain a one-dimensional spectrum. The characteristic wavelength corresponding to the position of the peak top in the one-dimensional spectrum is determined, and the structural period of the porous carbon support is calculated from the reciprocal thereof.
- the structural period of the porous carbon support is the same as the value of the structural period calculated by measuring the entire fluid separation carbon film.
- the uniformity of the porous structure is evaluated by the half width of the peak of the scattering intensity when X-rays are incident on the carbon film for fluid separation of the present invention. Specifically, in the graph in which the horizontal axis represents the scattering angle 2 ⁇ and the vertical axis represents the scattering intensity, it means that the smaller the half width of the peak of the scattering intensity, the higher the uniformity.
- the half width of the peak is preferably 5 ° or less, more preferably 1 ° or less, and still more preferably 0.1 ° or less.
- the peak of the peak is a point A
- a straight line parallel to the vertical axis of the graph is drawn from the point A, and the intersection of the straight line and the baseline of the spectrum is a point B.
- the width of the peak is the width on a straight line parallel to the base line and passing through the point C.
- the average porosity of the porous structure of the porous carbon support is preferably 10% to 80%.
- the average porosity is the cross section of a porous carbon support on which an embedded sample is precisely formed by the cross section polisher method (CP method) at a magnification of 1 ⁇ 0.1 (nm / pixel). Observe at a resolution of 10,000 pixels or more, and set an area of interest necessary for calculation from the image to 512 pixels square. Subsequently, the cross-sectional area is A, and the sum of the areas of the pore portions is B, calculated by the following equation, and is a value calculated by the arithmetic average value of 20 arbitrary cross sections.
- the fluid separation carbon membrane is a hollow fiber, the hollow portion is not included in the average porosity.
- Average porosity (%) B / A x 100
- the average porosity is lower, the cross-sectional compressive strength is improved, and the fluid can be transmitted under high pressure conditions. Therefore, the average porosity is more preferably 75% or less, and still more preferably 70% or less.
- the average diameter of the pores is preferably 30 nm or more, more preferably 50 nm or more.
- the average diameter of the pores is preferably 3,000 nm or less, and more preferably 2,500 nm or less.
- the average pore diameter of the porous carbon support is a value obtained by analyzing a carbon membrane for fluid separation by mercury porosimetry.
- the pore volume and the specific surface area are first determined from the pressure when mercury is introduced into the pores by applying pressure and the amount of mercury injected. Subsequently, from the relationship between the pore volume and the specific surface area, the pore radius or diameter is calculated assuming that the pore is a cylinder.
- a pore diameter distribution curve of 5 nm or more and several 100 ⁇ m or less can be obtained, and the pore diameter at the peak top is taken as the average diameter of the porous carbon support. Since the dense carbon layer does not have pores of 5 nm or more, the average pore diameter of the fluid separation carbon membrane is substantially the same as the average diameter of the pores of the porous carbon support.
- the form of the porous carbon support is preferably a fiber or a film.
- the fibers are those having a ratio of the fiber length L to the average diameter D of the fibers (aspect ratio L / D) of 100 or more, and from substantially the same diameter continuously formed in the fiber axial direction (longitudinal direction)
- a hollow fiber having a void portion (hollow portion) or a fiber having no hollow portion, that is, a solid thread can be employed. If the porous carbon support is a fiber, the separation module becomes compact because the membrane area per unit volume of the separation module is larger than that of the film. Even when the form of the porous carbon support is a solid yarn, a porous structure is formed on the porous carbon support.
- the porous carbon support is a fiber
- its average diameter can be set arbitrarily.
- the average diameter is large, pressure loss between the upstream side and the downstream side (permeate side) of the membrane is less likely to occur, and it is easy to secure the differential pressure necessary for fluid permeation. Therefore, the average diameter of the fibers is preferably 50 ⁇ m or more.
- the average diameter of the fibers is small, the bending rigidity is improved, and the membrane area per unit volume in the separation module is increased. Therefore, the average diameter is preferably 500 ⁇ m or less.
- the cross-sectional shape of the fiber is arbitrary, and may be a round cross-section, a multi-lobal cross-section such as a triangle, a flat cross-section or a hollow cross-section.
- a round cross section is preferable because the cross-sectional compressive strength is high.
- the area ratio (hollow area ratio: C / A) of the cross sectional area C of the hollow portion to the cross sectional area A of the porous carbon support is preferably 0.001 or more and 0.7 or less.
- the cross-sectional area A includes the cross-sectional area C of the hollow portion.
- the smaller the hollow area ratio the higher the cross-sectional compressive strength. Therefore, the hollow area ratio is more preferably 0.6 or less.
- the porous carbon support of the present invention has a co-continuous porous structure, the pressure loss at the time of passage of the fluid to the porous structure site is small even if the hollow area ratio is reduced to increase the cross-sectional compressive strength. It is difficult to reduce the transmission rate.
- the porous carbon support may have a plurality of hollow portions in order to achieve both the cross-sectional compressive strength and the fluid permeation rate. In that case, the sum of the cross-sectional areas of the hollow portions is taken as the cross-sectional area C of the hollow portions.
- the thickness of the porous carbon support is not limited.
- the thickness of the porous carbon support is large, the handleability is improved. Therefore, the thickness is preferably 0.01 ⁇ m or more.
- the thickness of the porous carbon support is thin, bending rigidity is improved and it becomes difficult to break. Therefore, the thickness is preferably 5,000 ⁇ m or less.
- Porous carbon support of the present invention (peak intensity of D peak intensity of the bands (1360 cm -1) / G band (1580cm -1)) (R s value) R value calculated from the Raman spectra 1.0 The following are preferred.
- the G band indicates a peak derived from the graphite structure
- the D band indicates a peak derived from the disorder of the crystal structure.
- the R value is a parameter used to evaluate the crystallinity degree or carbonization degree (graphitization degree) of the carbon material, and the smaller the R value, the higher the carbonization degree of the carbon material.
- the carbon membrane for fluid separation is cut, and the cross section, the longitudinal section, and the inner surface (in the case of a hollow fiber) are analyzed.
- the moisture absorption dimensional change rate of the porous carbon support decreases. Therefore, the contraction rate of the carbon film for fluid separation becomes small at the time of pressure reduction desorption process before fluid permeation or fluid permeation, and breakage of the carbon film for fluid separation is suppressed.
- the moisture absorption dimensional change rate is smaller. Therefore R s value is preferably 0.98 or less, more preferably 0.96 or less.
- the R s value is preferably 0.82 or more, more preferably 0.85 or more.
- the R s value of the porous carbon support is 1.0 or less, the variation in the fluid permeation rate and the separation coefficient among the plurality of fluid separation carbon membranes or separation modules manufactured under the same conditions is reduced. Also play.
- the reason why the moisture absorption dimensional change rate decreases when the R s value of the porous carbon support is small is not clear, but one of the hypotheses is estimated as follows. That is, when the R s value is high (the degree of carbonization is low), water vapor is adsorbed to the porous carbon support having amorphous carbon as a main component, the volume of the amorphous carbon increases, and the porous carbon support swells. And stretch. On the other hand, if the R s value is small (the degree of carbonization is high), the amount of water vapor adsorption decreases due to the increase in crystallinity and the increase in hydrophobicity due to the decrease in the amount of functional group of amorphous carbon. The volume increase rate decreases. It is estimated that the moisture absorption dimensional change rate decreases accordingly.
- Kaneko et al. Examine the relationship between the relative humidity and the radius of inertia R g (corresponding to the micropore size of carbon) of activated carbon fibers made of cellulose and polyacrylonitrile as raw materials, and R g increases in an atmosphere with high relative humidity
- R g increases in an atmosphere with high relative humidity
- the micropore size of carbon increases (K Kaneko et al., J. Colloid. Interface Sci. 127 (1) (1989) 298-299). That is, the carbon material having a high degree of carbonization has a reduced water vapor adsorption amount, which makes it difficult to cause structural change of the carbon material. As a result, it is estimated that the moisture absorption dimensional change rate decreases.
- the carbon element composition C s when the surface of the porous carbon support of the present invention is measured by X-ray photoelectron spectroscopy is preferably 85 at% or more and 95 at% or less. If the carbon atom element composition C s of the porous carbon support surface is in this range, the moisture absorption dimensional change rate ⁇ L 1 described later tends to be 0% or more and 0.15% or less.
- the X-ray photoelectron spectroscopy wide scan analysis is performed, and the ratio of carbon atoms when the total of the number of atoms of all the elements present on the sample surface is 100 atomic% is defined as the carbon element composition.
- the amount of adsorption of water vapor is correlated with the amount of various functional groups contained in the carbon material, and the amount of adsorption of water vapor tends to decrease as the amount of functional groups decreases. Therefore, the amount of functional groups of the carbon element composition C s of porous carbon support surface is included in the higher porous carbon support is lowered, moisture dimensional change [Delta] L 1 is likely to be within the aforementioned range.
- Carbon elemental composition C s of porous carbon support surface is more preferably at least 87 atomic%.
- a carbon elemental composition C s of porous carbon support surface is high brittleness becomes high, the handling properties and flexibility of the fluid separation carbon film is reduced.
- the carbon elemental composition C s of porous carbon support surface is more preferably 93 atomic% or less.
- the carbon film for fluid separation is cut, and the cross section, the longitudinal section, and the inner surface in the case of a hollow fiber are analyzed.
- the porous carbon support is a substrate that supports the dense carbon layer that functions as a separation membrane. Therefore, as the fluid separation membrane described later, the moisture absorption dimensional change ⁇ L 1 , the moisture absorption dimensional change ⁇ L 2 described later, the hygroscopic dimensional change ⁇ L 3 described later, the toluene adsorption dimensional change ⁇ M described later, and the standard state described later
- the preferred range of the moisture absorption rate can be applied to the porous carbon support as it is. The details will be described later as the physical properties of the carbon membrane for fluid separation, but “carbon membrane for fluid separation” should be read as “porous carbon support” for the measurement method of each value in the porous carbon support .
- various resins can be used as a precursor of the porous carbon support.
- the precursor of the porous carbon support is polyacrylonitrile or aromatic polyimide
- the moisture absorption dimensional change rate ⁇ L 1 , ⁇ L 2 , ⁇ L 3 easily falls within the range of the present invention, and is preferable because the dimensional stability is excellent.
- the precursor of the porous carbon support is polyacrylonitrile, it is more preferable because the breaking elongation is large and the flexibility is excellent.
- the composition of the aromatic polyimide is not particularly limited, and various aromatic polyimides can be used.
- aromatic polyimides include "Matrimid” (registered trademark) and "P84” (registered trademark).
- polyamic acid which is a precursor of aromatic polyimide can also be used.
- Precursor resin is these polyacrylonitrile or aromatic polyimide, for example, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), scanning electron microscope-energy dispersive
- XPS X-ray photoelectron spectroscopy
- TOF-SIMS time-of-flight secondary ion mass spectrometry
- SEM-EDX type X-ray spectroscopy
- the nitrogen concentration (N / C ratio: nitrogen element composition / carbon element composition) is 0.01 in the measurement of the surface of the porous carbon support in X-ray photoelectron spectroscopy (XPS) This can be confirmed from the fact that it is in the range of not less than 0.06.
- XPS X-ray photoelectron spectroscopy
- the dense carbon layer of the present invention is formed on a porous carbon support and has a function as a fluid separation layer.
- the dense carbon layer is a layer which is made of carbon and in which no pore is observed on the surface or cross section by a scanning electron microscope. “No pores are observed with a scanning electron microscope” means that a cross section formed by the cross section polisher method (CP method) is observed at a magnification of 1 ⁇ 0.1 (nm / pixel). Being below the resolution means that no clear pores are observed.
- the dense carbon layer is usually formed on the outer surface side of the porous carbon support, but in the case of a hollow fiber carbon membrane for fluid separation, it may be formed on the inner surface side, that is, the surface side contacting the hollow portion. It may be formed on both the outer surface side and the inner surface side. In the case of a carbon film for fluid separation of a film, the dense carbon layer may be on both sides of the film or only on one side. When the dense carbon layer is on both sides, the fluid can be separated at the dense carbon layer on both sides by supplying the fluid from the film cross section to the porous carbon support.
- the thickness of the dense carbon layer is not particularly limited, and can be appropriately set according to the application and the like. Generally, when the film thickness is large, the transmission rate of the fluid decreases, so 10 ⁇ m or less is preferable, 5 ⁇ m or less is more preferable, and 1 ⁇ m or less is more preferable. Further, when the film thickness is thin, a defect is easily generated, and the fluid leaks to reduce the separation function. Therefore, 1 nm or more is preferable, and 10 nm or more is more preferable.
- the thickness of the dense carbon layer is the porosity when observing the cross section (cross section perpendicular to the fiber axis in the case of fibers, cross section in the thickness direction in the case of films) of a carbon membrane for fluid separation with a scanning electron microscope.
- the carbon element composition C m at the time of measuring the surface of the dense carbon layer by X-ray photoelectron spectroscopy is preferably 75 atomic% or more and 90 atomic% or less.
- the nitrogen element composition N m is preferably 4 atomic% or more and 15 atomic% or less. Within this range, the permeability and separation of the fluid are excellent, and in particular, the permeation rate in the case where acid gas such as carbon dioxide is selectively permeated and separated is excellent.
- the carbon elemental composition C m and the nitrogen elemental composition N m of the surface of the dense carbon layer can be set in a preferable range from the permeability and separability of the fluid.
- the carbon element composition C m on the surface of the dense carbon layer is more preferably 80 atomic% or more. Further, the nitrogen element composition N m on the surface of the dense carbon layer is more preferably 5 atomic% or more, and more preferably 10 atomic% or less.
- the nitrogen concentration (N m / C m : nitrogen element composition / carbon element composition) measured by X-ray photoelectron spectroscopy is preferably 0.05 or more and 0.25 or less. If it is this range, it is excellent in the permeability and separation nature of fluid. In particular, when selectively separating an acid gas such as carbon dioxide, it is preferable because the permeation rate of carbon dioxide is excellent.
- the nitrogen concentration (N m / C m ) of the dense carbon layer is 0.07 or more, and 0.15 or less is more preferable because the balance between the fluid permeability and the separability is excellent.
- the R value (R m value) calculated from the spectrum obtained by measuring the dense carbon layer by Raman spectroscopy is preferably 1.1 or more and 2.4 or less. If it is this range, it is excellent in the permeability and separation nature of fluid.
- the carbon membrane for fluid separation of the present invention is preferably for gas separation, and particularly in hydrogen / carbon dioxide, carbon dioxide / nitrogen, carbon dioxide / methane separation systems, when the R m value is within the above range, high hydrogen Or carbon dioxide permeation rate and high separation factor can be obtained.
- the R m value is 1.1 or more, the gas transmission rates of hydrogen and carbon dioxide tend to be high. Therefore, 1.3 or more is more preferable, and 1.5 or more is further more preferable.
- the R m value is 2.4 or less, the separation factor tends to be high. Therefore, 2.3 or less is more preferable, and 2.2 or less is more preferable.
- the fluid to be permeated contains water or water vapor, it is preferable that the R m value is 2.3 or less because the water vapor adsorption amount of the carbon membrane for fluid separation is reduced and the reduction of the permeation rate over time is suppressed. .
- a polyamic acid which is a precursor of polyacrylonitrile or aromatic polyimide or aromatic polyimide as the above-mentioned porous carbon support as the precursor of the dense carbon layer.
- the precursor of the dense carbon layer is such a resin, it is excellent in fluid permeability and separation.
- the precursor of the dense carbon layer is polyacrylonitrile, it can be manufactured inexpensively, and when the carbon membranes for fluid separation come into contact with each other in the separation module, defects in the dense carbon layer are less likely to occur, and separation is performed when using the separation module. It is more preferable because the reduction of the coefficient can be suppressed.
- the precursor of the dense carbon layer is polyacrylonitrile or aromatic polyimide, which means that X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), scanning electron microscope-energy dispersive type
- XPS X-ray photoelectron spectroscopy
- TOF-SIMS time-of-flight secondary ion mass spectrometry
- SEM-EDX scanning electron microscope-energy dispersive type
- the composition of the precursor is polyacrylonitrile
- the C1s peak is corrected at 284.6 eV in measurement of the surface of the dense carbon layer in X-ray photoelectron spectroscopy (XPS)
- 398.4 eV of the N1s inner shell spectrum Since a peak is observed at an energy position of ( ⁇ 0.5 eV) and the nitrogen concentration (N m / C m : nitrogen element composition / carbon element composition) is in the range of 0.05 or more and 0.25 or less It can confirm.
- the 398.4 eV peak of the N1s core spectrum is a peak attributed to a carbon-nitrogen double bond or triple bond.
- the carbon membrane for fluid separation of the present invention has a structure in which a dense carbon layer is formed on a porous carbon support.
- the ratio (R m / R s ) of the R m value of the dense carbon layer to the R s value of the porous carbon support is preferably 1.1 or more and 3.0 or less.
- R s being 1.0 or less
- the carbon support has a relatively high degree of carbonization, and the carbonization degree of the dense carbon layer is Since the combination is low, the separation membrane is excellent in fluid permeability and separation while suppressing dimensional change and breakage of the support due to moisture absorption. It is more preferable that R m / R s be 1.5 or more and 2.5 or less, because the dimensional stability and the permeability and separation of the fluid are compatible.
- the carbon elemental composition of the porous carbon support surface as measured by X-ray photoelectron spectroscopy C s (atomic%), the ratio (C m / C of the carbon element of the dense carbon layer surface composition C m (atomic%) s) of preferably 0.85 to 0.95.
- C m / C of the carbon element of the dense carbon layer surface composition C m (atomic%) s preferably 0.85 to 0.95.
- the moisture absorption dimensional change rate ⁇ L 1 of the carbon film for fluid separation calculated by the following equation is preferably 0% or more and 0.15% or less.
- ⁇ L 1 ⁇ (L 100% -L 1% ) / L 1% ⁇ ⁇ 100
- L 1% Dry length of carbon film for fluid separation when left to stand in dry air (temperature 20 ° C., relative humidity 1.0%) environment for 3 hours (mm)
- L 100% Length of carbon film for fluid separation (mm) when left to stand for 3 hours in a saturated steam environment (temperature 20 ° C, relative humidity 100%)
- the length of the porous carbon support is the length in the fiber axial direction. The length can be measured by measuring the sample with a length of 100 mm or more with a stainless steel straight length specified in JIS B 7516 (2005) in a thermostat or in a vacuum dryer, or a thermo-mechanical device capable of adjusting the relative humidity. There is a method of measuring with an analysis (humidity control TMA) device.
- the moisture absorption dimensional change rate ⁇ L 1 of the carbon film for fluid separation is 0% or more and 0.15% or less, the contraction and extension of the carbon film for fluid separation are suppressed in an environment of various water vapor-containing atmospheres. Breakage of the fluid separation carbon membrane in the module is significantly suppressed.
- the moisture absorption dimensional change rate ⁇ L 1 is preferably as close to 0% as possible. Therefore, the moisture absorption dimensional change rate ⁇ L 1 is preferably 0.12% or less, and more preferably 0.10% or less.
- the moisture absorption dimensional change rate ⁇ L 2 of the carbon film for fluid separation calculated by the following equation is preferably 0% or more and 0.1% or less.
- ⁇ L 2 ⁇ (L 100% ⁇ L 65% ) / L 65% ⁇ ⁇ 100
- L 65% Length (mm) of carbon film for fluid separation when left to stand in standard condition (temperature 20 ° C, relative humidity 65%) for 3 hours
- L 100% Length of carbon film for fluid separation (mm) when left to stand for 3 hours in a saturated steam environment (temperature 20 ° C, relative humidity 100%)
- the moisture absorption dimensional change rate ⁇ L 2 is preferably as close to 0% as possible. Therefore, the moisture absorption dimensional change rate ⁇ L 2 is preferably as close to 0% as possible. Therefore, the moisture absorption dimensional
- the moisture absorption dimensional change rate ⁇ L 3 of the carbon film for fluid separation calculated by the following equation is preferably ⁇ 0.1% or more and 0% or less.
- ⁇ L 3 ⁇ (L 1% -L 65% ) / L 65% ⁇ ⁇ 100
- L 65% Length of carbon film for fluid separation (mm) when left to stand under environment of standard condition (temperature 20 ° C, relative humidity 65%) for 3 hours
- L 1% Length of carbon film for fluid separation when left to stand in dry air (temperature 20 ° C, relative humidity 1.0%) environment for 3 hours (mm)
- the moisture separation size change rate ⁇ L 3 of the carbon film for fluid separation is -0.1% or more and 0% or less, the contraction of the carbon film for fluid separation is suppressed when the amount of water vapor contained in the fluid is low.
- the moisture absorption dimensional change rate ⁇ L 3 is preferably as close to 0% as possible. Therefore, the moisture absorption dimensional change rate ⁇ L 3 is preferably ⁇ 0.08% or more, and more preferably ⁇ 0.05% or more.
- the carbon film for fluid separation preferably has a dimensional change rate close to 0% when not only water vapor but also various volatile solvents are adsorbed.
- the type of solvent is benzene, toluene, ethylbenzene, n-hexane, n-heptane, o-xylene, m-xylene, p-xylene, cyclohexane, methanol, ethanol, propanol, isopropanol, diethylene glycol, tetrahydrofuran, acetone, N, N -Dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone and the like.
- the toluene adsorption dimensional change rate ⁇ M represented by the following formula of the carbon membrane for fluid separation of the present invention is preferably 0% or more and 0.1% or less.
- ⁇ M ⁇ (M 2 -M 1 ) / M 1 ⁇ ⁇ 100
- M 1 Length (mm) of carbon film for fluid separation when left to stand in a reduced pressure atmosphere (10 Pa) for 3 hours at a temperature of 20 ° C.
- M 2 Length of carbon membrane for fluid separation when left to stand in a toluene atmosphere containing air at a temperature of 20 ° C. for 3 hours (mm)
- the toluene atmosphere is an atmosphere of a toluene-containing vapor obtained by flowing dry air at 20 ° C. while bubbling toluene.
- the toluene adsorption dimensional change rate is preferably as close to 0% as possible. 0.08% or less is preferable and, as for toluene adsorption dimensional-change rate (DELTA) M, 0.06% or less is more preferable.
- DELTA toluene adsorption dimensional-change rate
- the moisture absorption rate in a standard state is preferably 0% by weight or more and 15% by weight or less.
- the moisture absorption rate in the standard state is more preferably 10% by weight or less, further preferably 5% by weight or less.
- the measurement of the moisture absorption rate is calculated by the following equation using a thermogravimetric measurement (TG) apparatus.
- the moisture absorption ratio tends to be small, and it is for fluid separation in various relative humidity atmospheres The dimensional change of the carbon film is reduced.
- Moisture absorption rate [wt%] ⁇ (b-a) / a ⁇ x 100
- the moisture absorption weight is a weight measured by a TG device after standing for 3 hours in a standard state, and a dry weight is from 20 ° C. to 150 ° C. at a heating rate of 10 ° C./min under nitrogen flow with a TG device. It is a weight when the temperature is raised and held for 3 hours.
- a resin layer may be further formed on the dense carbon layer.
- the resin layer is formed for the purpose of protection of the carbon membrane for fluid separation, improvement of pressure resistance, chemical resistance, permeability, separation, suppression of time-lapse changes thereof, and the like.
- the composition of the resin layer may be aromatic polyimide, aromatic polyamide, cellulose acetate, polysulfone, polyetherimide, polyamideimide, polyethersulfone, polyacrylonitrile, polyphenylene sulfide, polyetheretherketone, polytetrafluoroethylene, polyvinylidene fluoride And silicone resins such as polydimethylsiloxane.
- the carbon membrane for fluid separation of the present invention can use a fluid separation module in which a plurality of carbon membranes are bundled and accommodated in a vessel.
- the fluid separation membrane of the present invention is preferably used for gas separation.
- it can be preferably used in applications such as hydrogen production, carbon dioxide separation and recovery, exhaust gas separation and recovery, natural gas separation, gas dehumidification, production of oxygen from air, and the like.
- the gas supplied may contain impurity components such as water vapor and volatile organic solvents, and the composition and the amount of the components may change over time.
- the carbon membrane for fluid separation may break during use, but in the carbon membrane for fluid separation of the present invention, the dimensional change rate at the time of moisture absorption or at the time of adsorption of volatile organic solvent is close to 0%.
- the fluid can be separated stably.
- a step of carbonizing a molded body containing a resin to be a precursor of a porous carbon support at 900 ° C. or more and 1.500 ° C. or less to obtain a porous carbon support (step 1), forming a carbonizable resin layer to be a precursor of a dense carbon layer on the porous carbon support (step 2), carbonizing the carbonizable resin layer to form a dense carbon layer ( It can manufacture by the manufacturing method of the carbon membrane for fluid separation which has process 3).
- Step 1 is porous by carbonizing a molded body containing a resin (hereinafter sometimes referred to as “support precursor resin”) to be a precursor of a porous carbon support at 900 ° C. or more and 1,500 ° C. or less It is a process of obtaining a carbon support.
- thermoplastic resin or a thermosetting resin can be used as a resin to be a precursor of the porous carbon support (hereinafter sometimes referred to as "support precursor resin").
- support precursor resin examples include polyphenylene ether, polyvinyl alcohol, polyacrylonitrile, phenol resin, aromatic polyester, polyamic acid, aromatic polyimide, aromatic polyamide, polyvinylidene fluoride, cellulose acetate, polyetherimide, polyamide imide and the like. And copolymers thereof.
- thermosetting resin unsaturated polyester resin, alkyd resin, melamine resin, urea resin, polyimide resin, diallyl phthalate resin, lignin resin, urethane resin, phenol resin, polyfurfuryl alcohol resin, and their co-weights Coalescence is mentioned. These may be used alone or in combination.
- a solution spinnable thermoplastic resin as the support precursor resin.
- use of polyacrylonitrile or an aromatic polyimide or a polyamic acid is preferable because the moisture absorption dimensional change rate ⁇ L 1 of the porous carbon support becomes small.
- the molecular weight of the support precursor resin is preferably 10,000 or more in weight average molecular weight.
- weight average molecular weight is 10,000 or more, breakage of the yarn in the spinning process and breakage of the film in the film forming process are reduced.
- the weight average molecular weight is 1,000,000 or less because formability such as spinnability and film formability is improved.
- the porous carbon support is a fiber
- a solution spinnable thermoplastic resin as the support precursor resin.
- Solution spinning is a method in which a resin is dissolved in various solvents to prepare a stock spinning solution, and the solution is passed through a bath composed of a solvent that becomes a poor solvent for the resin to coagulate the resin to obtain fibers.
- Known solution spinning such as wet spinning or wet spinning can be employed.
- an elimination component that can be eliminated after the formation. For example, forming a porous structure by keeping it as a resin mixture with a resin that disappears by post-heating such as carbonization, or dispersing particles that disappear by post-heating such as carbonization, etc. And the average diameter of the pores of the porous structure can be controlled.
- a support precursor resin and an elimination resin are mixed to obtain a resin mixture.
- the mixing ratio is preferably 10 to 90% by weight of the disappearance resin with respect to 10 to 90% by weight of the support precursor resin.
- the resin compatible with the carbonizable resin as the lost resin.
- the compatibility method may be a mixture of only resins, or a solvent may be added.
- the combination of such a carbonizable resin and the disappearance resin is not limited, polyacrylonitrile / polyvinyl alcohol, polyacrylonitrile / polyvinylphenol, polyacrylonitrile / polyvinylpyrrolidone, polyacrylonitrile / polylactic acid and the like can be mentioned.
- the obtained resin mixture is preferably phase separated in the molding process.
- the method of phase separation is not limited, and includes thermally induced phase separation and non-solvent induced phase separation.
- the resin mixture prepared as described above is extruded from the outer tube of a hollow fiber spinneret having a double tube structure, and gas such as air or nitrogen, solvent same as the spinning solution, and lost resin are dissolved from the inner tube of the spinnerette.
- a hollow fiber can be obtained by a method of simultaneously discharging the solution and the like.
- the spinning conditions it is possible to suppress the formation of a dense layer on the outer periphery of the fiber, and to open the pores of the porous structure on the surface of the porous carbon support.
- the composition and temperature of the spinning solution and coagulation bath are appropriately controlled, or the spinning solution is discharged from the inner pipe, and the same solvent as the spinning solution from the outer pipe. And a method of simultaneously discharging a solution in which the lost resin is dissolved.
- the fiber spun by the above-mentioned method can be coagulated in a coagulation bath and subsequently washed with water and dried to obtain a precursor of a porous carbon support.
- a coagulation bath water, ethanol, saline, and a mixed solvent of them and the solvent used in step 1 can be mentioned.
- porous carbon support is a film
- a molded body containing a support precursor resin can be produced by a known casting method or spin coating method.
- the precursor of the porous carbon support produced by the above-mentioned method can be infusibilized before being carbonized.
- the method of infusibilization treatment is not limited, and known methods can be adopted. Specific examples of the method include a method of heating in the presence of oxygen to cause oxidative crosslinking, a method of irradiating a high energy ray such as an electron beam or gamma ray to form a crosslinked structure, impregnating a substance having a reactive group, The method of mixing and forming a crosslinked structure etc. are mentioned. Among them, the method of causing oxidative crosslinking by heating in the presence of oxygen is preferable because the process is simple and the manufacturing cost is low. These techniques may be used alone or in combination.
- the precursor of the porous carbon support which has been subjected to the infusibilization treatment if necessary, is finally carbonized to become a porous carbon support.
- Carbonization is preferably performed by heating in an inert gas atmosphere.
- the inert gas includes helium, nitrogen, argon and the like.
- the flow rate of the inert gas may be an amount that can sufficiently reduce the oxygen concentration in the heating device, and it is preferable to select an appropriate value appropriately according to the size of the heating device, the supply amount of raw materials, the carbonization temperature, etc. .
- the lost resin may be removed by thermal decomposition due to heat during carbonization.
- carbonization temperature is preferably performed at 900 ° C. or higher 1,500 ° C. or less.
- the carbonization temperature is the highest temperature reached when carbonization is performed.
- the carbonization temperature is more preferably 950 ° C. or more in order to reduce the moisture absorption dimensional change rate ⁇ L 1 .
- the carbonization temperature is more preferably 1,300 ° C. or less.
- a temperature rising rate and a temperature-fall rate can be set arbitrarily.
- a rate of 1 ° C./min or more is preferable from the viewpoint of productivity.
- the upper limit of the temperature raising rate or the temperature lowering rate is not limited, and can be arbitrarily set in a range in which no defect such as a crack occurs.
- the holding time of the carbonization temperature can be set arbitrarily.
- the holding time can be set within a range in which the porous carbon support does not shrink in the second carbonization treatment (step 3) for forming a dense carbon layer described later, and is preferably 1 minute to 3 hours.
- One preferred method for adjusting the moisture absorption dimensional change rate ⁇ L 1 of the porous carbon support to the above-mentioned range is to add a crosslinking agent to the precursor fiber.
- the crosslinking agent may be added as a mixture to the stock spinning solution, or may be applied as it is immersed in a solution containing the crosslinking agent during or after any of the coagulation bath, water washing and drying steps described later.
- the crosslinking agent may be a compound that reacts with the precursor resin, or may be a crosslinking agent that does not react with the precursor resin and crosslinks between the crosslinking agents.
- As a crosslinking agent various silane coupling agents and polyfunctional epoxy compounds can be used.
- Another preferable method for adjusting the moisture absorption dimensional change rate ⁇ L 1 of the porous carbon support to the above-mentioned range is to draw a precursor fiber. By stretching the precursor fiber and orienting the carbonizable resin in the fiber axis direction, it is possible to suppress the moisture absorption dimensional change of the porous carbon support.
- still another preferable method for adjusting the moisture absorption dimensional change rate ⁇ L 1 of the porous carbon support to the above-mentioned range is to set the carbonization temperature of the precursor fiber to 900 ° C. or more and 1,500 ° C. or less .
- the carbonization temperature is the highest temperature reached when carbonization is performed. Since the moisture absorption dimensional change rate ⁇ L 1 approaches 0% when the carbonization temperature is increased, the carbonization temperature is more preferably 950 ° C. or higher. On the other hand, if the carbonization temperature is too high, the brittleness may increase and the handleability may be reduced. Therefore, the carbonization temperature is more preferably 1,300 ° C. or less.
- the porous carbon support Before forming the carbonizable resin layer on the porous carbon support in Step 2 described later, the porous carbon support may be subjected to surface treatment in order to improve the adhesion to the carbonizable resin layer.
- surface treatment include oxidation treatment and chemical solution coating treatment.
- the oxidation treatment include chemical oxidation using nitric acid and sulfuric acid, electrolytic oxidation, gas phase oxidation, and ultraviolet irradiation.
- medical solution coat process provision of the primer and sizing agent to a porous carbon support is mentioned.
- Step 2 is a step of forming a carbonizable resin layer to be a precursor of the dense carbon layer on the porous carbon support prepared in Step 1 and further subjected to surface treatment as necessary.
- the thickness of the dense carbon layer can be arbitrarily set by preparing the porous carbon support and the dense carbon layer in separate steps. Therefore, for example, the design of the separation membrane structure can be facilitated, for example, the fluid permeation rate can be improved by reducing the thickness of the dense carbon layer.
- the carbonizable resin various resins which exhibit separability of fluid after carbonization can be adopted. Specifically, polyacrylonitrile, aromatic polyimide, polyamic acid, polybenzoxazole, aromatic polyamide, polyphenylene ether, phenol resin, cellulose acetate, polyfurfuryl alcohol, polyvinylidene fluoride, lignin, wood tar, intrinsic porous polymer ( PIM) and the like.
- the resin layer is preferably polyacrylonitrile or aromatic polyimide or polyamic acid.
- the carbonizable resin may be the same as or different from the above-mentioned support precursor resin.
- the method of forming the carbonizable resin layer is not limited, and any known method can be adopted.
- a general formation method is a method of coating a carbonizable resin itself on a porous carbon support, but after a precursor of the resin is coated on a porous carbon support, the precursor is reacted
- a method of forming a carbonizable resin layer or a counter diffusion method in which a reactive gas or solution is allowed to flow and react from the inside and the outside of the porous carbon support can be adopted. Examples of reactions include heat or catalyzed polymerization, cyclization, crosslinking reactions.
- Examples of coating methods for the carbonizable resin layer include dip coating method, nozzle coating method, spray method, vapor deposition method and cast coating method. From the viewpoint of the easiness of the production method, the dip coating method or the nozzle coating method is preferable when the porous carbon support is fibrous, and the dip coating method or the cast coating method is preferable when the porous carbon support is film.
- the dip coating method is a method in which a porous carbon support is dipped in a coating stock solution containing a solution of a carbonizable resin or a precursor thereof and then withdrawn.
- the viscosity of the coating stock solution in the dip coating method is arbitrarily set according to the conditions such as the surface roughness and the pulling rate of the porous carbon support, and the desired film thickness. If the viscosity of the coating stock solution is high, a uniform resin layer can be formed. Therefore, the shear viscosity at a shear rate of 0.1 s ⁇ 1 is preferably 10 mPa ⁇ s or more, and more preferably 50 mPa ⁇ s or more. On the other hand, the lower the viscosity of the coating stock solution, the thinner the film and the permeation rate of the fluid is improved. Therefore, 1,000 mPa ⁇ s or less is preferable, and 800 mPa ⁇ s or less is more preferable.
- the pulling speed of the porous carbon support in the dip coating method is also optionally set depending on the coating conditions.
- the pulling rate is fast, the thickness of the carbonizable resin layer is increased, and defects as a carbon film can be suppressed. Therefore, 1 mm / min or more is preferable and 10 mm / min or more of a pulling speed is more preferable.
- the film thickness of the carbonizable resin layer becomes nonuniform to cause defects, or the film thickness becomes thick to decrease the fluid permeation rate. Therefore, 1,000 mm / min or less is preferable and 800 mm / min or less is more preferable.
- the temperature of the coating stock solution is preferably 20 ° C. or more and 80 ° C. or less. When the temperature of the coating stock solution is high, the surface tension decreases to improve the wettability to the porous carbon support, and the thickness of the carbonizable resin layer becomes uniform.
- the nozzle coating method laminates a resin or resin precursor on a porous carbon support by passing the porous carbon support through a nozzle filled with a coating stock solution which is a solution of a carbonizable resin or a precursor thereof. How to The viscosity and temperature of the undiluted coating solution, the nozzle diameter, and the passing speed of the porous carbon support can be set arbitrarily.
- porous carbon support (hereinafter referred to as “porous carbon support / carbonizable resin layer composite”) having the carbonizable resin layer formed in step 2 is not suitable for the carbonization treatment (step 3).
- the method of the infusibilization process is not limited, and the process is the same as the infusibilization process of the precursor of the porous carbon support described above.
- Step 3 heats the porous carbon support / carbonizable resin layer composite prepared in Step 2 and optionally subjected to infusibilization treatment to carbonize the carbonizable resin layer and form a dense carbon layer It is a process of forming.
- the porous carbon support / carbonizable resin layer composite in an inert gas atmosphere.
- the inert gas helium, nitrogen, argon and the like can be mentioned.
- the flow rate of the inert gas may be an amount that can sufficiently reduce the oxygen concentration in the heating device, and it is preferable to select an appropriate value appropriately according to the size of the heating device, the supply amount of raw materials, the carbonization temperature, etc. .
- the upper limit of the flow rate of the inert gas is not limited either, but it is preferable to set appropriately in accordance with the temperature distribution and the design of the heating device from the viewpoint of economy and reducing the temperature change in the heating device.
- the surface of the porous carbon support is chemically etched by heating in the mixed gas atmosphere of the above-described inert gas and active gas to control the size of the pore diameter on the surface of the porous carbon support.
- the active gas includes oxygen, carbon dioxide, water vapor, air and combustion gas.
- the concentration of the active gas in the inert gas is preferably 0.1 ppm to 100 ppm.
- the carbonization temperature in this step can be optionally set in the range in which the permeability and separability of the carbon membrane for fluid separation improve, but is lower than the carbonization temperature at the time of carbonizing the precursor of the porous carbon support in step 1 Is preferred.
- the moisture absorption dimensional change rate of the porous carbon support and the carbon membrane for fluid separation is reduced to suppress breakage of the carbon membrane for fluid separation in the separation module while improving the fluid permeation rate and separation performance.
- be able to. 500 degreeC or more is preferable and, as for the carbonization temperature in this process, 550 degreeC or more is more preferable.
- 850 degrees C or less is preferable, and 800 degrees C or less is more preferable.
- the carbon membranes for fluid separation produced by the steps 1 to 3 can be subjected to various known post treatments to obtain a desired permeation rate and separation coefficient.
- post-treatment include heat treatment and pore control by chemical vapor deposition (CVD).
- the R value (R m value) of the dense carbon layer measures the outer surface of the carbon membrane for fluid separation, and is porous
- the R value (R s value) of the carbon support was measured by cleaving the fluid separation carbon membrane in liquid nitrogen to expose the surface (hollow part surface) of the porous carbon support.
- the hollow fiber carbon membrane for fluid separation was measured by X-ray photoelectron spectroscopy.
- X-ray photoelectron spectroscopy measurement the carbon film for fluid separation was cut and spread on a stainless steel sample table using Quantera SXM manufactured by PHI, and the cut sample was fixed to the stainless steel table table.
- 45 ° photoelectron escape angle using a monochromatic AlK 1, 2-wire as an X-ray source was measured with the sample chamber with a vacuum of 1 ⁇ 10 -8 Torr.
- the device-specific sensitivity correction values were C1s: 0.314 and N1s: 0.499.
- the binding energy value of the main peak (peak top) of C1s is adjusted to 284.6 eV.
- the C1s peak area was obtained by drawing a linear baseline in the range of 282 eV to 296 eV, and the N1s peak area was obtained by drawing a linear baseline in the range of 395 eV to 406 eV.
- the nitrogen concentration N / C was expressed by an elemental composition ratio calculated by dividing the ratio of the above N1s peak area by the sensitivity correction value specific to the apparatus.
- ⁇ L 1 ⁇ (L 100% -L 1% ) / L 1% ⁇ ⁇ 100
- L 1% Dry length of carbon film for fluid separation when left to stand in dry air (temperature 20 ° C., relative humidity 1.0%) environment for 3 hours (mm)
- L 100% Length of carbon film for fluid separation (mm) when left to stand for 3 hours in a saturated steam environment (temperature 20 ° C, relative humidity 100%) (Measurement of moisture absorption dimensional change rate ⁇ L 2 )
- One end of a carbon film for fluid separation with a fiber length of 250 mm is fixed to a ruler with a stainless steel straight measure (nominal dimension 300 mm, grade 1) defined by JIS B7516 (2005), and suspended in a thermostat with a glass window.
- ⁇ L 2 ⁇ (L 100% ⁇ L 65% ) / L 65% ⁇ ⁇ 100
- L 65% Length (mm) of carbon film for fluid separation when left to stand in standard condition (temperature 20 ° C, relative humidity 65%) for 3 hours
- L 100% Length of carbon film for fluid separation (mm) when left to stand for 3 hours in a saturated steam environment (temperature 20 ° C, relative humidity 100%)
- ⁇ L 3 One end of a carbon film for fluid separation with a fiber length of 250 mm is fixed to a ruler with a stainless steel straight measure (nominal dimension 300 mm, grade 1) defined by JIS B7516 (2005), and suspended in a thermostat with a glass window.
- ⁇ L 3 ⁇ (L 1% -L 65% ) / L 65% ⁇ ⁇ 100
- L 65% Length of carbon film for fluid separation (mm) when left to stand under environment of standard condition (temperature 20 ° C, relative humidity 65%) for 3 hours
- L 1% Length of carbon film for fluid separation when left to stand in dry air (temperature 20 ° C, relative humidity 1.0%) environment for 3 hours (mm)
- the surface of the porous carbon support portion of the section formed by cutting with a pincer is observed with a scanning electron microscope, and the carbon skeleton branches and When the pores (voids) were continuous and three-dimensionally regularly entangled, it was judged to have a bi-continuous porous structure.
- the gas permeation rate was measured using the separation module prepared above.
- the measurement gas is carbon dioxide and methane, and based on the pressure sensor method of JIS K7126-1 (2006), the pressure change on the permeation side per unit time of carbon dioxide and methane is measured by an external pressure at a measurement temperature of 25 ° C. did.
- the pressure difference between the supply side and the permeation side was set to 0.11 MPa.
- the gas transmission rate Q was calculated by the following equation. Further, the ratio of the gas permeation rate of each component was taken as the separation coefficient ⁇ .
- the membrane area was calculated from the outer diameter and the length in the region contributing to gas permeation.
- Permeation rate Q [permeated gas amount (mol)] / [membrane area (m 2 ) ⁇ time (s) ⁇ pressure difference (Pa)] [Preparation Example 1 of Porous Carbon Support] Poly Sciences Inc. polyacrylonitrile (PAN) (M W 15 50,000) and 10 parts by weight, Sigma Aldrich polyvinylpyrrolidone (PVP) (M W 4 50,000) 10 parts by weight, and manufactured by Wako Pure Chemical Industries, Ltd. Dimethyl sulfoxide (DMSO) 80 parts by weight were mixed and stirred at 100 ° C. to prepare a spinning stock solution.
- PAN polyacrylonitrile
- PVP Sigma Aldrich polyvinylpyrrolidone
- DMSO Dimethyl sulfoxide
- the obtained stock solution for spinning is cooled to 25 ° C., and then using a concentric triple-cap nozzle, an aqueous solution containing 80% by weight of DMSO from the inner tube, a solution for the above spinning solution from the middle tube, and a 90% by weight aqueous solution of DMSO from the outer tube After discharging simultaneously, it was led to a coagulation bath consisting of pure water at 25 ° C., and wound around a roller to obtain a raw yarn. The obtained raw yarn was washed with water and then dried at 25 ° C. for 24 hours in a circulating dryer to prepare a hollow fiber porous carbon support precursor.
- the precursor of the porous carbon support was passed through an electric furnace at 250 ° C., and was heated in an air atmosphere for 1 hour to perform infusibilization treatment.
- the infusible fiber was carbonized at a temperature of 950 ° C. to produce a porous carbon support of hollow fiber.
- Both the outer surface and the inner surface (hollow part surface) of the produced porous carbon support were open, and when the cross section of the hollow fiber was observed, a bicontinuous porous structure was observed.
- a porous carbon support of hollow fibers was produced in the same manner as in Production Example 1 of a porous carbon support except that the carbonization treatment was carried out under the conditions of an ultimate temperature of 1,100 ° C.
- the outer surface and the inner surface of the produced porous carbon support were both open, and when the cross section was observed, a bicontinuous porous structure was observed.
- a porous carbon support of a hollow fiber was produced in the same manner as in Production Example 1 of a porous carbon support except that the final temperature of carbonization was 800 ° C.
- the outer surface and the inner surface of the produced porous carbon support were both open, and when the cross section was observed, a bicontinuous porous structure was observed.
- a porous carbon support of a hollow fiber was produced in the same manner as in Production Example 1 of a porous carbon support except that the carbonization treatment was carried out under the conditions of a final temperature of 600 ° C.
- the outer surface and the inner surface of the produced porous carbon support were both open, and when the cross section was observed, a bicontinuous porous structure was observed.
- PVP polyvinylpyrrolidone
- NMP methyl-2-pyrrolidone
- the obtained stock solution for spinning is cooled to 25 ° C. Then, using a concentric triple-die nozzle, NMP 96 wt% aqueous solution from the inner pipe, the above spinning stock solution from the middle pipe, and 94 wt% aqueous solution of NMP from the outer pipe After discharging simultaneously, it was led to a coagulation bath consisting of pure water at 25 ° C., and wound around a roller to obtain a raw yarn. The obtained raw yarn was washed with water and then dried at 25 ° C. for 24 hours in a circulating dryer to prepare a hollow fiber porous carbon support precursor.
- the precursor fiber was carbonized at a temperature of 900 ° C. to produce a hollow fiber porous carbon support.
- Both the outer surface and the inner surface (hollow part surface) of the produced porous carbon support were open, and when the cross section of the hollow fiber was observed, a bicontinuous porous structure was observed.
- Example 1 The porous carbon support (length 100 mm) of the hollow fiber prepared in Preparation Example 1 is immersed in a polyacrylonitrile / DMSO solution (10 wt% polymer), pulled up, immersed in water to remove the solvent, and removed at 100 ° C. The resultant was dried for 24 hours to prepare a porous carbon support / carbonizable resin layer composite in which a resin layer of polyacrylonitrile was formed on the porous carbon support.
- a polyacrylonitrile / DMSO solution 10 wt% polymer
- porous carbon support / resin layer composite was passed through an electric furnace, and was heated at 250 ° C. in an air atmosphere for 1 hour to perform infusibilization treatment. Subsequently, the infusible fiber was carbonized at a carbonization temperature of 600 ° C. to produce a hollow fiber carbon membrane for fluid separation.
- Example 2 A hollow fiber fluid separation carbon membrane was produced in the same manner as in Example 1 except that the hollow fiber porous carbon support produced in Production Example 2 was used.
- Example 3 A hollow carbon fiber separation carbon membrane was produced in the same manner as in Example 1 except that the hollow fiber porous carbon support produced in Production Example 1 was used and the final temperature for carbonization was 800 ° C.
- Example 4 A hollow carbon fiber separation carbon membrane was produced in the same manner as in Example 1 except that the hollow fiber porous carbon support produced in Production Example 5 was used and the final temperature of the carbonization treatment was 600 ° C.
- Comparative Example 1 A hollow fiber fluid separation carbon membrane was produced in the same manner as in Example 1 except that the hollow fiber porous carbon support produced in Production Example 3 was used.
- Comparative Example 2 A hollow carbon fiber separation carbon membrane was produced in the same manner as in Example 1 except that the hollow fiber porous carbon support produced in Production Example 4 was used and the carbonization temperature was 1,000 ° C.
- Comparative Example 3 An aqueous solution of 80 wt% DMSO is simultaneously discharged from the inner tube of the hollow fiber spinning nozzle of the double tube structure and the spinning solution simultaneously from the outer tube using the spinning solution prepared in Preparation Example 1 to coagulate the pure water at 25 ° C. It was introduced into a bath and wound on a roller to obtain a raw yarn. The obtained raw yarn was washed with water and then dried at 25 ° C. for 24 hours in a circulating drier to prepare a porous carbon support precursor.
- the precursor of the porous carbon support was passed through an electric furnace at 250 ° C., and was heated in an air atmosphere for 1 hour to perform infusibilization treatment.
- the infusible fiber was carbonized at a carbonization temperature of 950 ° C. to produce a hollow fiber carbon membrane for fluid separation.
- the inner surface of the produced porous carbon support was open, but no pores were observed on the outer surface. Further, when the cross section was observed, a bicontinuous porous structure was observed.
- Tables 2 and 3 show the configurations and evaluation results of the carbon membranes for fluid separation prepared in each of the examples and the comparative examples.
- Porous carbon support 2 Dense carbon layer
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Abstract
Description
本発明の流体分離用炭素膜は図1に示すように、多孔質炭素支持体1上に緻密炭素層2が形成された構造からなる。なお、図1では中空糸の形態を一例として示すが、これに限定されず、中実糸であっても、フィルムであってもよい。
多孔質炭素支持体は、分離膜としての機能を有する緻密炭素層の形状を保持するための基材である。支持体が炭素材料で形成されているため、有機高分子からなる支持体と比較して耐熱性や耐薬品性が高い。また、支持体が多孔構造であるため、ガスや液体などの流体の流路としての役割も有する。多孔構造は限定されず、独立気泡構造や連続多孔構造など各種多孔構造を採用できる。独立気泡構造であれば断面圧縮強度が向上する。一方、連続多孔構造であれば流体が透過する際の圧力損失が小さくなり、流体の透過速度が向上する。
P=λ/2sinθ
P:構造周期(μm)、λ:入射X線の波長(μm)
ここで多孔質炭素支持体の構造周期が大きくて小角での散乱が観測できない場合は、X線コンピュータ断層撮影(X線CT)によって構造周期を得る。具体的には、X線CTによって撮影した三次元画像をフーリエ変換した後に、その二次元スペクトルの円環平均を取り、一次元スペクトルを得る。その一次元スペクトルにおけるピークトップの位置に対応する特性波長を求め、その逆数より多孔質炭素支持体の構造周期を算出する。
平均空隙率が高いほど流体の流路としての圧力損失が小さくなり、流体の透過速度が向上する。そのため、平均空隙率は15%以上がより好ましく、18%以上がさらに好ましい。一方、平均空隙率が低いほど断面圧縮強度が向上して、高圧条件で流体が透過できる。そのため、平均空隙率は75%以下がより好ましく、70%以下がさらに好ましい。
本発明の緻密炭素層は、多孔質炭素支持体上に形成され、流体の分離層としての機能を有する。緻密炭素層は、炭素からなり、走査型電子顕微鏡で表面や断面に細孔が観察されない層である。「走査型電子顕微鏡で細孔が観察されない」、とは、クロスセクションポリッシャー法(CP法)により形成させた断面を、1±0.1(nm/画素)となる倍率で観察した際に、解像度以下であることにより明確な細孔が観察されないことを意味する。
本発明の流体分離用炭素膜は、多孔質炭素支持体上に緻密炭素層が形成された構造からなる。
ΔL1={(L100%-L1%)/L1%}×100
L1%:乾燥空気(温度20℃、相対湿度1.0%)環境下に3時間静置したときの流体分離用炭素膜の乾燥長さ(mm)
L100%:飽和水蒸気環境下(温度20℃、相対湿度100%)に3時間静置したときの流体分離用炭素膜の長さ(mm)
ここで、多孔質炭素支持体の長さとは、繊維軸方向の長さである。長さの測定は、恒温槽内や真空乾燥機内で、JIS B7516(2005)で規定されるステンレス製直尺にて長さ100mm以上の試料を測定する方法や、相対湿度が調整可能な熱機械分析(調湿TMA)装置にて測定する方法がある。
ΔL2={(L100%-L65%)/L65%}×100
L65%:標準状態(温度20℃、相対湿度65%)に3時間静置したときの流体分離用炭素膜の長さ(mm)
L100%:飽和水蒸気環境下(温度20℃、相対湿度100%)に3時間静置したときの流体分離用炭素膜の長さ(mm)
流体分離用炭素膜の吸湿寸法変化率ΔL2が0%以上0.1%以下だと、流体に含まれる水蒸気量が高い場合において流体分離用炭素膜の伸長が抑制され、流体分離モジュール内での流体分離用炭素膜の破断が抑制される。吸湿寸法変化率ΔL2は0%に近いほど好ましい。そのため吸湿寸法変化率ΔL2は0.08%以下がより好ましく、0.05%以下がさらに好ましい。
ΔL3={(L1%-L65%)/L65%}×100
L65%:標準状態(温度20℃、相対湿度65%)の環境下に3時間静置したときの流体分離用炭素膜の長さ(mm)
L1%:乾燥空気(温度20℃、相対湿度1.0%)環境下に3時間静置したときの流体分離用炭素膜の長さ(mm)
流体分離用炭素膜吸湿寸法変化率ΔL3が-0.1%以上0%以下だと、流体に含まれる水蒸気量が低い場合において流体分離用炭素膜の収縮が抑制されるため、流体分離モジュール内での流体分離用炭素膜の破断が抑制される。吸湿寸法変化率ΔL3は0%に近いほど好ましい。そのため吸湿寸法変化率ΔL3は-0.08%以上が好ましく、-0.05%以上がより好ましい。
ΔM={(M2-M1)/M1}×100
M1:温度20℃で減圧雰囲気(10Pa)に3時間静置したときの流体分離用炭素膜の長さ(mm)
M2:温度20℃で空気を含有するトルエン雰囲気に3時間静置したときの流体分離用炭素膜の長さmm)
ここで、トルエン雰囲気は、乾燥空気を20℃でトルエンにバブリングしながらフローすることで得たトルエン含有蒸気の雰囲気である。
a:流体分離用炭素膜の乾燥重量(mg)、b:流体分離用炭素膜の吸湿重量(mg)
ここで、吸湿重量は標準状態に3時間静置した後にTG装置にて測定した重量であり、乾燥重量はTG装置にて窒素フロー下、昇温速度10℃/分にて20℃から150℃まで昇温し、3時間保持したときの重量である。
本発明の流体分離用炭素膜は、一例として、多孔質炭素支持体の前駆体となる樹脂を含む成形体を900℃以上1.500℃以下で炭化し、多孔質炭素支持体を得る工程(工程1)、緻密炭素層の前駆体となる炭化可能樹脂層を前記多孔質炭素支持体上に形成する工程(工程2)、前記炭化可能樹脂層を炭化し、緻密炭素層を形成する工程(工程3)を有する流体分離用炭素膜の製造方法により製造できる。
工程1は、多孔質炭素支持体の前駆体となる樹脂(以下、「支持体前駆体樹脂」ということがある)を含む成形体を900℃以上1,500℃以下で炭化することで多孔質炭素支持体を得る工程である。
後述する工程2で多孔質炭素支持体に炭化可能樹脂層を形成する前に、炭化可能樹脂層との接着性を向上させるため、多孔質炭素支持体に表面処理を行ってもよい。このような表面処理としては、酸化処理や薬液コート処理が挙げられる。酸化処理としては、硝酸や硫酸などによる薬液酸化法,電解酸化法,気相酸化法、紫外線照射法が挙げられる。また、薬液コート処理としては、多孔質炭素支持体へのプライマーやサイジング剤の付与が挙げられる。
工程2は、工程1で準備し、必要に応じてさらに表面処理を行った多孔質炭素支持体上に緻密炭素層の前駆体となる炭化可能樹脂層を形成する工程である。多孔質炭素支持体と緻密炭素層をそれぞれ別の工程で作製することにより、緻密炭素層の厚みを任意に設定できる。そのため、例えば、緻密炭素層の厚みを薄くすることによって流体の透過速度を向上させることができるなど、分離膜構造の設計が容易になる。
工程2で作製した、炭化可能樹脂層が形成された多孔質炭素支持体(以下、「多孔質炭素支持体/炭化可能樹脂層複合体」という)は、炭化処理(工程3〕の前に不融化処理を行ってもよい。不融化処理の方法は限定されず、前述の多孔質炭素支持体の前駆体の不融化処理に準じる。
工程3は、工程2で作製され、必要に応じてさらに不融化処理を行った多孔質炭素支持体/炭化可能樹脂層複合体を加熱して、炭化可能樹脂層を炭化し、緻密炭素層を形成する工程である。
工程1から工程3により作製した流体分離用炭素膜は、所望の透過速度および分離係数を得るために、公知の各種後処理をすることができる。後処理の例としては、加熱処理や化学気相成長(CVD)法による細孔制御が挙げられる。
(ラマンスペクトルから計算されるR値)
中空糸の流体分離用炭素膜をラマン分光法にて測定した。ラマン測定は、堀場製作所製のレーザーラマン分光装置T-64000を用い、顕微ラマンモード(ビーム径1μm)、Ar+レーザー(514.5nm)にて行った。得られたスペクトルの700から2,000cm-1の領域で直線近似によりベースラインを取得し、ベースラインに対するGバンド(1,580cm-1付近)およびDバンド(1,360cm-1付近)のバンド強度を読み取った。読み取りは、各バンドのピーク付近の10から20データ点について、最小二乗法による二次関数フィッティングを行い、その極大値から算出した。そして、Dバンドのピーク強度をID、Gバンドのピーク強度をIGとするとき、ピーク強度比ID/IGをR値とした。
中空糸の流体分離用炭素膜をX線光電子分光法にて測定した。X線光電子分光測定はPHI社製QuanteraSXMを用い、流体分離用炭素膜をカットしてステンレス製の試料台上に拡げて並べた後、カットした試料をステンレス製の試料台に固定した。続いて光電子脱出角度を45゜とし、X線源としてmonochromatic AlKα1,2線を用いて、試料チャンバー内を1×10-8Torrの真空度にして測定を行った。当該装置固有の感度補正値はC1s:0.314、N1s:0.499であった。
JIS B7516(2005)で規定されるステンレス製直尺(呼び寸法300mm、1級)に繊維長250mmの流体分離用炭素膜の一端をテープで固定し、ガラス窓付きの恒温槽内に吊り下げた。恒温槽の扉を閉じた後、エアコンプレッサーを用いて乾燥空気を恒温槽内にフローさせて室温20℃、相対湿度1.0%に調整した。3時間静置した後、恒温槽内に流体分離用炭素膜を入れたまま、繊維長を0.1mm単位まで測定し、乾燥長さL1%を計測した。
ΔL1={(L100%-L1%)/L1%}×100
L1%:乾燥空気(温度20℃、相対湿度1.0%)環境下に3時間静置したときの流体分離用炭素膜の乾燥長さ(mm)
L100%:飽和水蒸気環境下(温度20℃、相対湿度100%)に3時間静置したときの流体分離用炭素膜の長さ(mm)
(吸湿寸法変化率ΔL2の測定)
JIS B7516(2005)で規定されるステンレス製直尺(呼び寸法300mm、1級)に繊維長250mmの流体分離用炭素膜の一端をテープで定規に固定し、ガラス窓付きの恒温槽内に吊り下げた。恒温槽の扉を開けた状態で、室温20℃、相対湿度65%の実験室内に3時間静置した後、繊維長を0.1mm単位まで測定し、吸湿長さL65%を計測した。
ΔL2={(L100%-L65%)/L65%}×100
L65%:標準状態(温度20℃、相対湿度65%)に3時間静置したときの流体分離用炭素膜の長さ(mm)
L100%:飽和水蒸気環境下(温度20℃、相対湿度100%)に3時間静置したときの流体分離用炭素膜の長さ(mm)
(吸湿寸法変化率ΔL3の測定)
JIS B7516(2005)で規定されるステンレス製直尺(呼び寸法300mm、1級)に繊維長250mmの流体分離用炭素膜の一端をテープで定規に固定し、ガラス窓付きの恒温槽内に吊り下げた。恒温槽の扉を閉じた後、エアコンプレッサーを用いて乾燥空気を恒温槽内にフローさせて室温20℃、相対湿度1.0%に調整した。3時間静置した後、恒温槽内に流体分離用炭素膜を入れたまま、繊維長を0.1mm単位まで測定し、乾燥長さL1%を計測した。
ΔL3={(L1%-L65%)/L65%}×100
L65%:標準状態(温度20℃、相対湿度65%)の環境下に3時間静置したときの流体分離用炭素膜の長さ(mm)
L1%:乾燥空気(温度20℃、相対湿度1.0%)環境下に3時間静置したときの流体分離用炭素膜の長さ(mm)
(共連続多孔構造の有無)
流体分離用炭素膜または多孔質炭素支持体を液体窒素中で冷却後、ピンセットで割断して形成した断面の多孔質炭素支持体部分を走査型電子顕微鏡で表面観察し、炭素骨格の枝部と細孔部(空隙部)がそれぞれ連続しつつ三次元的に規則的に絡み合った構造であった場合、共連続多孔構造を有すると判定した。
中空糸の流体分離用炭素膜100mmを20本束ね、張力をかけて弛みがないように両端をエポキシ樹脂系接着剤でステンレス製のベッセルに固定し、分離モジュールとした。続いて、分離モジュール内を3時間減圧脱着した後、大気圧に戻し、分離モジュール内の流体分離用炭素膜の破断本数を数えた。
上記で作製した分離モジュールを用い、水蒸気を含まない二酸化炭素を流体分離用炭素膜の外表面側に3時間フローした後、分離モジュール内の流体分離用炭素膜の破断本数を数えた。
二酸化炭素ガスを水温90℃の水浴にバブリングさせた後、上記で作製した分離モジュールにフローさせて温度20℃での飽和水蒸気を含む二酸化炭素を流体分離用炭素膜の外表面側に3時間フローした後、モジュール内の流体分離用炭素膜の破断本数を数えた。
炭素膜の柔軟性テストとして、炭素膜を種々の直径の円柱に180°以上巻きつけて、膜が破断するかどうかを観測した。曲げ半径は、膜が破断しない円柱において最小の半径を有する円柱を求め、その円柱の半径の値で示した。
上記で作製した分離モジュールを用い、ガス透過速度を測定した。測定ガスは二酸化炭素およびメタンを用い、JIS K7126-1(2006)の圧力センサ法に準拠して測定温度25℃で外圧式にて二酸化炭素およびメタンの単位時間当たりの透過側の圧力変化を測定した。ここで、供給側と透過側の圧力差を0.11MPaに設定した。
[多孔質炭素支持体の作製例1]
ポリサイエンス社製ポリアクリロニトリル(PAN)(MW15万)10重量部と、シグマ・アルドリッチ社製ポリビニルピロリドン(PVP)(MW4万)10重量部、そして和光純薬製ジメチルスルホキシド(DMSO)80重量部を混合し、100℃で攪拌して紡糸原液を調製した。
炭化処理の到達温度1,100℃の条件で行った以外は、多孔質炭素支持体の作製例1と同様に中空糸の多孔質炭素支持体を作製した。作製した多孔質炭素支持体の外表面および内表面はともに開孔しており、また断面を観察したところ、共連続多孔構造が観察された。
炭化処理の到達温度800℃の条件で行った以外は、多孔質炭素支持体の作製例1と同様に中空糸の多孔質炭素支持体を作製した。作製した多孔質炭素支持体の外表面および内表面はともに開孔しており、また断面を観察したところ、共連続多孔構造が観察された。
炭化処理の到達温度600℃の条件で行った以外は、多孔質炭素支持体の作製例1と同様に中空糸の多孔質炭素支持体を作製した。作製した多孔質炭素支持体の外表面および内表面はともに開孔しており、また断面を観察したところ、共連続多孔構造が観察された。
多孔質炭素支持体の前駆体として芳香族ポリイミドである“Matrimid”(登録商標)5218(3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物と、5(6)-アミノ-1-(4’-アミノフェニル)-1,3,3’-トリメチルインダンの縮合生成物)を12重量部と、シグマ・アルドリッチ社製ポリビニルピロリドン(PVP)(MW4万)12重量部、そして1-メチル-2-ピロリドン(NMP)76重量部を混合し、100℃で攪拌して紡糸原液を調製した。
作製例1で作製した中空糸の多孔質炭素支持体(長さ100mm)をポリアクリロニトリル/DMSO溶液(ポリマー10重量%)に浸漬した後、引き上げ、水中に浸漬して溶媒を除去し、100℃で24時間乾燥して多孔質炭素支持体上にポリアクリロニトリルの樹脂層を形成した多孔質炭素支持体/炭化可能樹脂層複合体を作製した。
作製例2で作製した中空糸の多孔質炭素支持体を用いた以外は、実施例1と同様に中空糸の流体分離用炭素膜を作製した。
作製例1で作製した中空糸の多孔質炭素支持体を用い、炭化処理の到達温度を800℃とした以外は、実施例1と同様に中空糸の流体分離用炭素膜を作製した。
作製例5で作製した中空糸の多孔質炭素支持体を用い、炭化処理の到達温度を600℃とした以外は、実施例1と同様に中空糸の流体分離用炭素膜を作製した。
作製例3で作製した中空糸の多孔質炭素支持体を用いた以外は、実施例1と同様に中空糸の流体分離用炭素膜を作製した。
作製例4で作製した中空糸の多孔質炭素支持体を用い、炭化処理の温度を1,000℃とした以外は、実施例1と同様に中空糸の流体分離用炭素膜を作製した。
作製例1で調製した紡糸原液を用い、二重管構造の中空糸紡糸ノズルの内管からDMSO80重量%水溶液を、外管から紡糸溶液をそれぞれ同時に吐出して、25℃の純水からなる凝固浴へ導き、ローラーに巻き取ることで原糸を得た。得られた原糸は水洗した後、循環式乾燥機にて25℃で24時間乾燥して多孔質炭素支持体の前駆体を作製した。
2:緻密炭素層
Claims (15)
- 多孔質炭素支持体上に緻密炭素層が形成された流体分離用炭素膜であって、前記多孔質炭素支持体のラマンスペクトルから計算されるR値(Dバンド(1360cm-1)のピーク強度/Gバンド(1580cm-1)のピーク強度)をRs値とするとき、Rs値が1.0以下である流体分離用炭素膜。
- 前記Rs値が0.82以上0.98以下である、請求項1に記載の流体分離用炭素膜。
- 前記緻密炭素層のラマンスペクトルから計算したR値をRm値とするとき、Rm値が1.1以上2.4以下である、請求項1または2に記載の流体分離用炭素膜。
- 前記緻密炭素層のRm値と前記多孔質炭素支持体のRs値の比(Rm/Rs)が1.1以上3.0以下である、請求項1~3のいずれかに記載の流体分離用炭素膜。
- 前記多孔質炭素支持体の前駆体がポリアクリロニトリルまたは芳香族ポリイミドである、請求項1~4のいずれかに記載の流体分離用炭素膜。
- X線光電子分光法で測定される前記多孔質炭素支持体表面の炭素元素組成Csが85原子%以上95原子%以下である、請求項1~5のいずれかに記載の流体分離用炭素膜。
- X線光電子分光法で測定される前記多孔質炭素支持体表面の炭素元素組成Cs(原子%)と、前記緻密炭素層表面の炭素元素組成Cm(原子%)の比(Cm/Cs)が0.85以上0.95以下である、請求項1~6のいずれかに記載の流体分離用炭素膜。
- 下記式で算出される吸湿寸法変化率ΔL1が0%以上0.15%以下である、請求項1~7のいずれかに記載の流体分離用炭素膜。
ΔL1={(L100%-L1%)/L1%}×100
L1%:乾燥空気(温度20℃、相対湿度1.0%)環境下に3時間静置したときの流体分離用炭素膜の乾燥長さ(mm)
L100%:飽和水蒸気環境下(温度20℃、相対湿度100%)に3時間静置したときの流体分離用炭素膜の長さ(mm) - 標準状態における吸湿率が0重量%以上10重量%以下である、請求項1~8のいずれかに記載の流体分離用炭素膜。
- X線光電子分光法で測定される前記緻密炭素層表面の窒素元素組成Nmが4原子%以上15原子%以下である、請求項1~9のいずれかに記載の流体分離用炭素膜。
- X線光電子分光法で測定される前記緻密炭素層の窒素濃度(Nm/Cm:窒素元素組成/炭素元素組成)が0.05以上0.25以下である、請求項1~10のいずれかに記載の流体分離用炭素膜。
- 前記緻密炭素層の前駆体がポリアクリロニトリルまたは芳香族ポリイミドである、請求項1~11のいずれかに記載の流体分離用炭素膜。
- 前記多孔質炭素支持体が共連続多孔構造を有する、請求項1~12のいずれかに記載の流体分離用炭素膜。
- 前記共連続多孔構造の構造周期が0.002μm以上10μm以下である、請求項13に記載の流体分離用炭素膜。
- 工程1:多孔質炭素支持体の前駆体となる樹脂を含む成形体を炭化温度900℃以上1,500℃以下で炭化し、多孔質炭素支持体を得る工程;
工程2:緻密炭素層の前駆体となる炭化可能樹脂層を前記多孔質炭素支持体上に形成する工程;
工程3:前記炭化可能樹脂層を炭化し、緻密炭素層を形成する工程;
を有する流体分離用炭素膜の製造方法。
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03161030A (ja) * | 1989-11-21 | 1991-07-11 | Mitsubishi Rayon Co Ltd | 多孔質炭素複合膜の製法 |
EP0474424A2 (en) | 1990-09-01 | 1992-03-11 | The British Petroleum Company P.L.C. | Membranes |
JPH05220360A (ja) | 1992-02-07 | 1993-08-31 | Ube Ind Ltd | 非対称性中空糸炭素膜及びその製法 |
JP2003138431A (ja) * | 2001-11-01 | 2003-05-14 | Mitsubishi Chemicals Corp | カーボンナノファイバー及びその製造方法 |
JP2005138028A (ja) * | 2003-11-06 | 2005-06-02 | Japan Fine Ceramics Center | カーボンナノチューブを用いたガス分離材及びその製造方法 |
WO2011148713A1 (ja) | 2010-05-27 | 2011-12-01 | 京セラ株式会社 | 炭素膜複合体およびその製造方法ならびに分離膜モジュール |
JP2013063409A (ja) | 2011-09-20 | 2013-04-11 | Toyobo Co Ltd | 中空糸炭素膜およびその製造方法 |
JP2013543433A (ja) * | 2010-10-01 | 2013-12-05 | ビーエーエスエフ ソシエタス・ヨーロピア | 炭素膜の製造方法 |
JP2016041656A (ja) * | 2015-10-29 | 2016-03-31 | 東洋炭素株式会社 | 多孔質炭素 |
JP2016047521A (ja) * | 2014-08-08 | 2016-04-07 | 東レ株式会社 | 耐溶剤性分離膜およびその製造方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8617831D0 (en) * | 1986-07-22 | 1986-08-28 | British Petroleum Co Plc | Production of porous shaped articles |
ES2151781B1 (es) * | 1997-05-14 | 2001-08-16 | Consejo Superior Investigacion | Procedimiento para la preparacion de membranas de carbono. |
JP2010510870A (ja) * | 2006-11-29 | 2010-04-08 | 日本碍子株式会社 | 炭素膜積層体及びその製造方法 |
US10011487B2 (en) * | 2013-03-22 | 2018-07-03 | Toray Industries, Inc. | Porous carbon material, precursor for porous carbon material, process for producing precursor for porous carbon material, and process for producing porous carbon material |
US9620788B2 (en) * | 2013-05-07 | 2017-04-11 | Samsung Sdi Co., Ltd. | Electrode catalyst for fuel cell, electrode for fuel cell including the electrode catalyst, and membrane electrode assembly and fuel cell including the same |
WO2015129488A1 (ja) * | 2014-02-26 | 2015-09-03 | 東レ株式会社 | 多孔質炭素材料、炭素材料強化複合材料、多孔質炭素材料プリカーサ、多孔質炭素材料プリカーサの製造方法、及び多孔質炭素材料の製造方法 |
JP6411770B2 (ja) * | 2014-04-15 | 2018-10-24 | トヨタ自動車株式会社 | 燃料電池用電極触媒、及び燃料電池用電極触媒の製造方法 |
CN106573205B (zh) | 2014-08-08 | 2019-10-08 | 东丽株式会社 | 耐溶剂分离膜 |
CN104726967A (zh) * | 2015-03-30 | 2015-06-24 | 北京化工大学 | 一种聚酰胺酸/聚丙烯腈基碳纤维及其制备方法 |
-
2018
- 2018-07-20 EP EP18838869.8A patent/EP3659697A4/en active Pending
- 2018-07-20 US US16/629,629 patent/US11000812B2/en active Active
- 2018-07-20 CN CN201880047643.8A patent/CN110891673B/zh active Active
- 2018-07-20 JP JP2018540502A patent/JP7120016B2/ja active Active
- 2018-07-20 CA CA3064528A patent/CA3064528A1/en active Pending
- 2018-07-20 WO PCT/JP2018/027316 patent/WO2019021964A1/ja unknown
- 2018-07-20 MY MYPI2019007253A patent/MY197959A/en unknown
- 2018-07-20 AU AU2018306010A patent/AU2018306010B2/en active Active
- 2018-07-20 KR KR1020207000807A patent/KR102522838B1/ko active IP Right Grant
- 2018-07-24 TW TW107125407A patent/TWI789408B/zh active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03161030A (ja) * | 1989-11-21 | 1991-07-11 | Mitsubishi Rayon Co Ltd | 多孔質炭素複合膜の製法 |
EP0474424A2 (en) | 1990-09-01 | 1992-03-11 | The British Petroleum Company P.L.C. | Membranes |
JPH05220360A (ja) | 1992-02-07 | 1993-08-31 | Ube Ind Ltd | 非対称性中空糸炭素膜及びその製法 |
JP2003138431A (ja) * | 2001-11-01 | 2003-05-14 | Mitsubishi Chemicals Corp | カーボンナノファイバー及びその製造方法 |
JP2005138028A (ja) * | 2003-11-06 | 2005-06-02 | Japan Fine Ceramics Center | カーボンナノチューブを用いたガス分離材及びその製造方法 |
WO2011148713A1 (ja) | 2010-05-27 | 2011-12-01 | 京セラ株式会社 | 炭素膜複合体およびその製造方法ならびに分離膜モジュール |
JP2013543433A (ja) * | 2010-10-01 | 2013-12-05 | ビーエーエスエフ ソシエタス・ヨーロピア | 炭素膜の製造方法 |
JP2013063409A (ja) | 2011-09-20 | 2013-04-11 | Toyobo Co Ltd | 中空糸炭素膜およびその製造方法 |
JP2016047521A (ja) * | 2014-08-08 | 2016-04-07 | 東レ株式会社 | 耐溶剤性分離膜およびその製造方法 |
JP2016041656A (ja) * | 2015-10-29 | 2016-03-31 | 東洋炭素株式会社 | 多孔質炭素 |
Non-Patent Citations (1)
Title |
---|
K KANEKO ET AL., J. COLLOID. INTERFACE SCI., vol. 127, no. 1, 1989, pages 298 - 299 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113272484A (zh) * | 2019-02-01 | 2021-08-17 | 东丽株式会社 | 多孔质碳纤维和流体分离膜 |
CN113272484B (zh) * | 2019-02-01 | 2023-04-28 | 东丽株式会社 | 多孔质碳纤维和流体分离膜 |
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