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WO2003014018A1 - Matiere carbonee, matiere d'occlusion de gaz renfermant ladite matiere carbonee et procede de stockage de gaz a l'aide de cette matiere d'occlusion de gaz - Google Patents

Matiere carbonee, matiere d'occlusion de gaz renfermant ladite matiere carbonee et procede de stockage de gaz a l'aide de cette matiere d'occlusion de gaz Download PDF

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Publication number
WO2003014018A1
WO2003014018A1 PCT/JP2002/007708 JP0207708W WO03014018A1 WO 2003014018 A1 WO2003014018 A1 WO 2003014018A1 JP 0207708 W JP0207708 W JP 0207708W WO 03014018 A1 WO03014018 A1 WO 03014018A1
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Prior art keywords
carbon
gas
carbon material
hydrogen
adsorption
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PCT/JP2002/007708
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English (en)
Japanese (ja)
Inventor
Yasunori Yokomichi
Hitoshi Nishino
Katsuhiro Sasaki
Ryoichi Nishida
Takeo Matsui
Original Assignee
Osaka Gas Company Limited
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 Osaka Gas Company Limited filed Critical Osaka Gas Company Limited
Publication of WO2003014018A1 publication Critical patent/WO2003014018A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0021—Carbon, e.g. active carbon, carbon nanotubes, fullerenes; Treatment thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Definitions

  • Carbon material comprising the carbon material, and gas storage method using the gas storage material
  • the present invention relates to a carbon material, and more particularly to a carbon material having an amorphous structure, a gas storage material made of the carbon material, and a gas storage method using the gas storage material.
  • Activated carbon is widely known as a carbon-based gas storage material. Activated carbon has many pores during the manufacturing process, which is due to the crystal structure of activated carbon being an amorphous structure. It is thought that gas molecules are adsorbed on such pores. The type of gas that can be absorbed depends mainly on the size of the pore diameter, and the amount of gas adsorbed depends on the surface area or pore volume of the pores. It is considered.
  • Activated carbon has been manufactured under activation conditions that can provide more pores on the tongue carbon surface.
  • halogen gas such as chlorine, fluorine, bromine, iodine, phosgene, etc.
  • chain and formula hydrocarbons halogenated hydrocarbons
  • liquid nitrogen temperature e.g., 196 ° C.
  • an object of the present invention is to provide a carbon material which can store a gas having a very low critical temperature such as hydrogen even at room temperature. Disclosure of the invention
  • the present inventors have conducted intensive studies to produce a carbon material that can occlude a gas having a very low critical temperature such as hydrogen even at room temperature, and as a result, treated a certain raw material under specific conditions. By doing so, it is possible to obtain an amorphous nano-carbon having an amorphous structure, for example, a carbon material containing amorphous carbon particles, an amorphous carbon fiber, and the like. It has been found that it has the ability to occlude gases with low critical temperatures even at room temperature.
  • the present invention has been completed based on the above findings and further studied, and provides the following carbon material, gas storage material and gas storage method.
  • Item 1 True density is 2.1 to 3.1 gZ cm 3 ,
  • the hydrogen / carbon weight ratio by elemental analysis is 0.013 or less
  • the volume of the Ultramiku orifice with a diameter of 0.6 nm or less is 0.05 ml / g or more when measured by the ultrahigh vacuum nitrogen adsorption method at 196 ° C,
  • Item 1 characterized in that the integrated intensity ratio (IaZlb) of the integrated intensity (la) of the peak to the integrated intensity (lb) of the peak having a peak center at 1200 cm- 1 to 1500 cm- 1 is 1 or less.
  • the carbon material according to 1.
  • Item 3 The carbon material according to Item 1 or 2, wherein the specific surface area is 1000 m 2 / g or more.
  • Item 4 In the nitrogen gas adsorption isotherm at liquid nitrogen temperature (-196 ° C), the relative pressure
  • Item 5 A gas P and a storage material comprising the carbon material according to any one of Items 1 to 4 above.
  • Item 6 A hydrogen storage material comprising the carbon material according to any one of Items 1 to 4.
  • Item 7 Gas is stored using the gas P and storage material described in Item 5 above. Gas storage method.
  • Item 8 A hydrogen storage method characterized by storing hydrogen using the hydrogen storage material according to Item 6 above.
  • FIG. 1 is a graph showing the hydrogen storage characteristics of activated carbon (TPD 5 ° C./min temperature rise) in Test Example 2.
  • FIG. 2 is a graph showing hydrogen storage characteristics (TPD 3 ° C./min temperature rise) of activated carbon in Test Example 2.
  • FIG. 3 is a graph showing hydrogen storage characteristics (TPD 5 ° C./min temperature rise) of the amorphous carbon material of the present invention in Test Example 2.
  • FIG. 4 is a graph showing the hydrogen storage characteristics (TPD 3 ° C./min temperature rise) of the amorphous carbon material of the present invention in Test Example 2.
  • FIG. 5 is a graph showing the results of ultrahigh vacuum nitrogen adsorption measurement (SWPA method) in Test Example 3.
  • FIGS. 1 to 4 have the following meanings.
  • SWPA stands for Super Wide Pressure Adsorption.
  • the carbon material of the present invention has a property of absorbing gas and is a carbon material containing a nanoscale carbon having an amorphous structure.
  • the carbon material of the present invention typically contains amorphous carbon such as amorphous carbon particles and amorphous carbon fiber.
  • carbon materials having a tube structure such as carbon nanotubes It has been considered to be useful as a gas storage material because it stores gas in the space (hollow portion) surrounded by the tube wall made of such a material.
  • the present invention provides an excellent gas occlusion that can absorb gas even at room temperature because the nanoscale carbon has a specific amorphous structure regardless of whether it has a tube structure or not. It was completed after finding that it had the ability.
  • the carbon material of the present invention contains a nanoscale force element substantially consisting of an amorphous structure.
  • the nanoscale carbon has only an amorphous structure.
  • the carbon material of the present invention has an amorphous structure, it has many pores that effectively work for hydrogen adsorption at room temperature, particularly pores smaller than 2 nm in diameter (that is, ultra-fine particles having a pore diameter of 0.6 nm or less). It has a large number of edges on the hexagonal mesh of carbon.
  • the edge of the carbon hexagonal plane means the end carbon atom of the carbon hexagonal plane.
  • This carbon atom is chemically very active due to its unsaturated sp 2 electron, and easily reacts with foreign elements such as oxygen to form surface functional groups. It is presumed that effective interaction for hydrogen adsorption at room temperature occurs between these unsaturated sp 2 electrons and surface functional groups and hydrogen.
  • the amorphous carbon particles constituting the carbon material of the present invention are carbon particles consisting of only an amorphous structure having a particle diameter of about 5 nm to 500 nm, especially about 10 to 400 nm, and have a spherical or cubic shape. Shape, rectangular parallelepiped, disk, flake, film or similar shape. Among these shapes, granules represented by a sphere, a cubic shape, and a rectangular parallelepiped shape, in particular, a spherical shape are more preferable than a fibrous shape when a material is formed at a high density.
  • a nanopole in which the shape of the constituent amorphous wall is spherical or closed shell can be exemplified. The average diameter of the nanopoles is of the order of 0.5 to 50 nm, in particular 5 to 30 nm.
  • the amorphous carbon fiber is a carbon fiber having a diameter of 100 nm or less, particularly about 5 to 500 nm, particularly about 10 to 400 nm, and has only an amorphous structure.
  • the ratio (L / D) of the length L of the fiber to the outer diameter D is 2 or more, preferably 5 or more, and more preferably 50 to 500.
  • the particle diameter of the amorphous carbon particles and the diameter of the amorphous fiber are measured by measuring the size of an image observed by a scanning electron microscope or a transmission electron microscope.
  • the carbon material of the present invention may be composed of amorphous carbon particles, amorphous carbon fibers, or the like, or may be composed of a mixture thereof.
  • the carbon material of the present invention has various physical properties. Hereinafter, these physical properties will be described.
  • the carbon material of the present invention has a true density of 2.:! ⁇ 3.1 gZ cm 3 about, is particularly 2.4 ⁇ 2.7.01 3 extent.
  • the true density is usually measured by the same procedure as the weight method used for measuring the amount of stored hydrogen, by measuring the buoyancy of helium exerted on the sample under a pressure of! The volume was determined from the measured buoyancy and calculated from the weight / volume.
  • the hydrogen / carbon weight ratio by elemental analysis is 0.013 or less, preferably 0.011 or less, more preferably 0.0063 or less, and particularly 0.005 to 0.011.
  • Samples of amorphous carbon material of the present invention after holding 0.99 ° C, 2 hours under a reduced pressure of 10 "3 Pa or less, - 196 ° C, and have use gravimetry the adsorption isotherm of nitrogen at 10- 5 Pa By analyzing the obtained adsorption isotherm of nitrogen under ultra-high vacuum, the pore volume of pertramic mixture was determined.
  • SWPA means super wide pressure adsorption.
  • HRA high-resolution adsorption
  • SWPA the apparatus in the pressure (about 1 0- 2 P a) of the HRA measuring device ⁇ 1/1 0 0 0 pressure or lower pressure than, i.e., 1 0- 5 P a or By using a lower pressure, the measurement method is improved so that the measurement of the pores of the Ultramic mouth can be performed.
  • the relative pressure that is, the nitrogen pressure (P), the nitrogen saturated vapor pressure (Po (PZPO) in the range of 0.5 or more shows a hysteresis loop in which the ratio between the adsorption amount on the desorption side and the adsorption amount on the adsorption side is 1.1 or more. This is advantageous because it has the property that it can be stably held.
  • the carbon material of the present invention has a pore volume of 0.2 ml or less for micropores having a pore diameter of 2 nm or less determined by a Dubinin analysis method using a gas adsorption amount of a gas at a boiling point under atmospheric pressure in a gas adsorption method. / g or more.
  • micropore refers to a pore having a pore diameter of 2 nm or less obtained by the Dubinin analysis method using the gas adsorption amount at the boiling point of the gas at atmospheric pressure in the above gas adsorption method. .
  • the Dubinin analysis method is a method of obtaining the pore volume of the pores of the Miku mouth from adsorption isotherms of various gases.
  • the pore volume of the pores in the orifice of Miku was determined by Dubinin-Radushkevich plot.
  • the nitrogen gas adsorption method uses liquid nitrogen temperature (1 196) and various relative pressures of nitrogen (ratio of nitrogen pressure (P) to nitrogen saturated vapor pressure (Po) at 1 196: P / Po).
  • P nitrogen pressure
  • Po nitrogen saturated vapor pressure
  • the measurement of the amount of nitrogen adsorbed on the sample in the present invention is performed by a constant volume method that calculates the amount of nitrogen adsorbed from a change in the nitrogen pressure in a container of known volume filled with the sample.
  • a pore distribution measuring device (ASAP2400, manufactured by Micromeritics Co., Ltd.) was used. Before the nitrogen adsorption measurement, 0.02 g of the sample was heated at 200 ° C while evacuating the sample container, and the process was continued until the degree of vacuum in the sample container reached lOmmTorr.
  • the pore volume of the micropores having a pore diameter of 2 nm or less determined by the above analysis method may be 0.2 ml / g or more, preferably 0.25 ml / g or more, more preferably 0.3mlZg or more.
  • the upper limit of the pore volume is not particularly limited, but is generally about 1.5 ml / g, particularly about 2.0 ral / g.
  • the carbon material of the present invention has two or more (particularly 2 to 4) types of hydrogen adsorption sites. This was demonstrated by the fact that at least two peaks were observed in thermal desorption (TPD) measurement using hydrogen gas (see Test Example 2 below).
  • the carbon material of the present invention is characterized by having an amorphous structure instead of graphite.
  • the amorphous structure in the present invention is an average distance d between carbon hexagonal mesh planes obtained by a diffractometry method in a powder X-ray diffraction method (incident X-ray: CuKQ!).
  • . 2 is 0.43 nm (4.3 A) or more.
  • d. 0 2 particularly preferably 0.43 ⁇ 0.55nm (4.3-5.5A) about.
  • the amorphous carbon material of the present invention has a diffraction angle (2 is 25.1 degrees or less, preferably 24.1 degrees or less) determined by the diffractometry method in powder X-ray diffraction (incident X-ray: CuKQ!). In particular, it is 23.5-24.5 degrees, and the half-width at 2 ⁇ band is 3.2 degrees or more, preferably 7 degrees or more, particularly 5.0 to 8.0 degrees.
  • This integrated intensity ratio has the following significance. That is, of the Raman-active vibrations of the graphite structure, which peak center of the scan Bae spectrum is observed Raman shift 1540cm- 1 ⁇ 1650cm- 1 in the range (especially 1580cm- around 1), E 2 g vibratory And originates from the lattice vibration in the carbon hexagonal plane. On the other hand, in general, the range of 1200 cm- 1 to 1500 cm- 1 The center of the spectrum peak is also observed around (especially around 1360 cm- 1 ). This vibration is an Alg- type vibration, which is thought to be caused by the transition or loss of the local structure from hexagonal symmetry to lower symmetry, reflecting the disorder of the crystal structure. I have.
  • a broad spectrum having a peak center near 1360 cm- 1 is considered to have a diamond-like structure, that is, a property derived from sp 3 bonds.
  • the broad scan Bae spectrum near 1360Cm- 1 but be derived from that L a is small it is thought to be the main, there are cases where both the properties of sp 3 bonds.
  • a case where both the properties of sp 3 bonds is a case where in the structure sp 2 is the main binding, partially sp 3 bond occurs.
  • the part where the sp 3 bond has occurred has a dangling bond of a carbon bond, or an atom other than carbon is bonded to the carbon atom, and is considered to be chemically active. This is presumed to be effective for gas storage at room temperature.
  • the carbon material of the present invention has a specific surface area measured by the BET method of 1000 m 2 / g or more, particularly 1000 to 1500 m 2 / g.
  • the carbon material of the present invention is characterized in that the average area of one carbon hexagonal mesh plane is 0.85 nm 2 or less.
  • the average area of the carbon hexagonal mesh plane is calculated by squaring the length of the crystallite image included in a range of 10 OA squares selected arbitrarily in the observation image of the transmission electron microscope and the area of the carbon hexagonal mesh plane. By defining and summing the area of the carbon hexagonal meshes included in the range of 10 OA square by the number of carbon hexagonal meshes, the area value of each carbon hexagonal mesh is averaged.
  • the carbon material of the present invention has the various physical properties described above and is useful as a gas storage material.
  • the carbon material of the present invention can be obtained by subjecting a fixed power source and a specific catalyst to heat treatment under specific conditions.
  • the carbon source examples include a fluorine-containing polymer or fluorine-containing carbon, and among them, PTFE film, PTTE powder, Freon 116 (C 2 F 6 ) and the like are preferable.
  • polyimide can be used as a source of carbon. Polyimide has a property that the carbon skeleton is easily retained when pyrolyzed and carbonized, and pores are easily formed in the process of removing the desorbed components due to the thermal decomposition.
  • a particularly preferred example is a polyimide film sold by DuPont under the trade name "Kapton".
  • As the catalyst an iron fluoride or iron oxide can be exemplified, inter alia FeF 2 or Fe 2 0 3 is preferred.
  • the particle size of these catalysts is not particularly limited, it is generally preferable to use them in the form of powder having an average particle size of about 0.01 to 50 m, particularly about 0.01 to about 10 m.
  • the carbon source and the catalyst are placed in a reactor separately or in contact with each other.
  • a carbon source in the form of a film a method in which the above powdery catalyst is uniformly sprinkled on a film and put into a reaction furnace can be exemplified, and when a powdery carbon source is used, the powdery catalyst is used.
  • a method in which a carbon source and catalyst particles are previously dry-blended or wet-blended and uniformly mixed and then placed in a reaction furnace can be exemplified.
  • a vacuum furnace using a quartz tube, an alumina tube or the like can be generally used.
  • the reaction conditions are typically such that the carbon source and the catalyst are placed in the furnace as described above, the furnace is set to an inert gas atmosphere, and the pressure in the furnace is set to lPa to 200 kPa, preferably 5 Pa to
  • the carbon material of the present invention is manufactured by setting the furnace temperature to 150 kPa, setting the furnace temperature to 600 to 1500 ° C, preferably 800 to 1200, and heating the furnace for 0.5 hours or more, particularly 0.5 to 5 hours. can do.
  • the product obtained by the above method may contain an iron compound which is a residue derived from the above catalyst, but this iron compound does not significantly impair the gas storage properties of the carbon material of the present invention. Therefore, the product obtained by the above method may be used as it is.
  • Gas storage material and gas storage method comprising carbon material of the present invention
  • the carbon material of the present invention is excellent in gas storage capacity. Therefore, the present invention also provides a gas occluding material comprising the carbon material of the present invention.
  • the carbon material comprising the carbon material of the present invention can stably store various gases at room temperature.
  • the gas that can be stored by the gas storage material of the present invention include hydrogen, methane, argon, nitrogen, neon, and the like.
  • the gas occluding material of the present invention has an advantage that the gas can be stably occluded at room temperature, and therefore has extremely high industrial value.
  • the gas occluding material of the present invention has an occluding ability even at room temperature. For example, at a hydrogen pressure of 10 MPa, at room temperature, 1% or more, particularly 3 to 5% by weight of hydrogen, Indicates the amount of occlusion.
  • the carbon material of the present invention has many structures capable of stably adsorbing various gases, it can occlude various gases stably, and in particular, a gas having a very low critical temperature such as hydrogen. However, it can be stably stored even at a temperature around room temperature (for example, 0 to 40). In particular, the carbon material of the present invention is useful as a hydrogen storage material.
  • the present invention also provides a gas storage method, particularly a hydrogen storage method, using the carbon material of the present invention.
  • a gas occlusion material made of the carbon material of the present invention is used. What is necessary is just to expose to the said gas atmosphere.
  • the pressure of the above gas atmosphere Is not less than 0.03 MPa, preferably from 0.2 MPa to 50 MPa, more preferably from 0.5 MPa to 20 MPa.
  • the gas storage method of the present invention has an advantage that a gas such as hydrogen, which has been difficult to occlude at room temperature with conventional activated carbon, can be occluded well even at room temperature.
  • the gas storage method of the present invention is also advantageous in that gas can be taken in and out only by pressure change. That is, gas can be taken in and out in the same way as a conventional gas cylinder.
  • FeF 2 powder particle diameter: 500 m or less
  • the furnace used was a quartz tube with an inner diameter of 50 mm, a length of 650 mm, and a wall thickness of 2.5 mm. After the inside of the furnace was replaced with nitrogen three times, the pressure was reduced to 5 Pa, and the inside of the furnace was heated at 900 ° C for 1 hour to obtain 0.7 g of a carbon material.
  • the carbonaceous material obtained was composed of amorphous carbon with a diameter of 20 to 500 nm.
  • Table 1 shows the physical properties of the obtained carbon material containing amorphous carbon fibers as a main component.
  • the particle size 10 X m or less of the PTFE powder 10g and the particle size lO U m following Fe 2 0 3 powder 1 g were mixed using a mill, the mixture was placed in an alumina container was placed in a furnace. The same quartz tube as in Example 1 was used for the furnace. After the inside of the furnace was replaced with argon three times, the pressure was reduced to 5 Pa, and the furnace was heated at 1200 ° C for 1 hour to obtain 2.1 g of a carbon material.
  • the carbonaceous material was composed of amorphous carbon particles having a diameter of 20 to 200 nm.
  • Table 1 shows the physical properties of the obtained carbon material mainly composed of amorphous force-pong particles.
  • a 5 m piece of a 100 mX 10 mm X 10 mm polyimide film (manufactured by DuPont, trade name "Rockton Film”) was sprinkled with 1 ⁇ of powder uniformly and placed in a furnace.
  • the same quartz tube as in Example 1 was used for the furnace.
  • the furnace pressure was set to 50 Pa, the temperature was raised to 900 ° C at a heating rate of l ° CZmin, and the furnace was heated at 900 ° C for 1 hour to produce a carbon material.
  • 1.6 g were obtained.
  • the carbonaceous material was composed of amorphous carbon particles having a diameter of 100 to 200 nm.
  • Table 1 shows the physical properties of the carbon material containing the obtained amorphous carbon particles as a main component.
  • “Hydrogen to carbon weight ratio” was calculated from the results of elemental analysis and elemental analysis.
  • the “volume of ultramicropores having a pore diameter of 0.55 nm or less” was measured according to the ultrahigh vacuum nitrogen adsorption method at 196 ° C. described above.
  • D. 2 is determined by the diffractometry method in powder X-ray diffraction (incident X-ray: CuKQ!).
  • Integrated intensity ratio (IaZlb) is the integrated intensity of a peak having a peak centered at l ⁇ Ocm- 1 from 1650Cm- 1 obtained by Raman spectroscopy (la), having a peak center from 1200Cm- 1 to 1500 cm _1 This is the ratio of the integrated intensity to the integrated intensity (lb) of the peak.
  • the presence or absence of a hysteresis loop is defined as the relative pressure (ie, nitrogen pressure (P), — nitrogen saturation vapor pressure (Po) at 196 ° C) in the nitrogen gas adsorption isotherm at liquid nitrogen temperature (1 196 ° C).
  • P nitrogen pressure
  • Po nitrogen saturation vapor pressure
  • the ratio was determined by examining the presence or absence of a hysteresis loop in which the ratio between the adsorption amount on the desorption side and the adsorption amount on the adsorption side was 1.1 or more in the range of 0.5 or more.
  • the measurement method is the same as in Table 1), and the amount of hydrogen storage was similarly evaluated.
  • Table 2 shows the results.
  • the evaluation criteria in Table 2 are as follows:
  • the hydrogen storage amount was 1% by weight or more based on the weight of the storage material even at room temperature.
  • Table 2 shows that conventional activated carbon does not absorb hydrogen at room temperature, but that the carbon material of the present invention has excellent hydrogen storage ability even at room temperature.
  • the hydrogen storage characteristics of the amorphous carbon material of the present invention and the activated carbon (comparative) were evaluated using a thermal desorption apparatus.
  • Example 1 As the amorphous carbon material of the present invention, the one produced in Example 1 was used. A commercial product (trade name “Maxsorb”, manufactured by Kansai Thermal Chemical Co., Ltd.) was used as the activated carbon.
  • the temperature was raised from 1 165 ° C (start temperature) to 50 ° C (end temperature) at a rate of 3 ° CZ, and the amount of desorbed hydrogen was measured.
  • FIGS. 1 to 4 show the hydrogen storage characteristics of each sample using thermal desorption (TPD).
  • TPD thermal desorption
  • 1 and 2 show the hydrogen storage properties of activated carbon
  • FIGS. 3 and 4 show the hydrogen storage properties of the amorphous carbon material of the present invention.
  • activated carbon has a slower heating rate from 57 minutes to 3 ° CZ, and the release of hydrogen is slower, resulting in a lower peak and a broader peak.
  • a single peak was observed at around -178 even under the temperature increasing conditions. Therefore, it is assumed that activated carbon has only one kind of adsorption site.
  • the amorphous carbon material of the present invention has two peaks in a low temperature region of ⁇ 160 ° C. or lower regardless of the heating conditions, and the peak position and the shape of the peaks Showed remarkable changes depending on the heating conditions.
  • the heating rate was 3 Z minutes, a weak broad peak was observed at around -50 ° C.
  • the above-mentioned SPA indicates super wide pressure adsorption.
  • HRA high-resolution adsorption
  • SWPA is 1/1 0 0 0 pressure or lower pressure than that of the device the pressure of the HRA measuring apparatus (about 1 0- 2 P a), i.e., 1 0- 5 P a or
  • the measurement method is improved so that the measurement of the pores of the Ultramic mouth can be performed.
  • Analysis of this graph showed that the volume of ultramicropores of 0.55 nm or less was It was shown to be 0.06 ml / g.
  • Pobs on the horizontal axis indicates the measured nitrogen pressure
  • Pvap indicates the nitrogen vapor pressure at the measurement temperature.
  • the carbon material of the present invention can stably occlude various gases, and in particular, stably occlude gases such as hydrogen having a very low critical temperature even at room temperature. Therefore, the industrial value is extremely high.

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Abstract

L'invention concerne une matière carbonée présentant une masse volumique réelle de 2,1 à 3,1 g/cm3, un rapport C/H en poids inférieur ou égal à 0,013 tel que déterminé par analyse élémentaire, un volume d'ultramicropores qui présentent un diamètre de pores n'excédant pas 0,6 nm supérieur ou égal à 0,05 ml/g tel que mesuré selon le procédé d'adsorption d'azote sous ultravide à 196 °C ainsi que deux ou plusieurs types de sites d'adsorption d'hydrogène. Cette matière carbonée présente également une d002, déterminée selon le procédé de diffraction de rayons X sur poudre (rayon X incident : CuKα), inférieure ou égale à 4,3 Å et contient une matière carbonée nanométrique présentant une structure amorphe, composée de particules de carbone amorphe, de fibres de carbone amorphe ou d'un mélange des deux. Cette invention concerne également une matière d'occlusion de gaz renfermant ladite matière carbonée ainsi qu'un procédé de stockage d'un gaz à l'aide de cette matière d'occlusion de gaz.
PCT/JP2002/007708 2001-08-06 2002-07-29 Matiere carbonee, matiere d'occlusion de gaz renfermant ladite matiere carbonee et procede de stockage de gaz a l'aide de cette matiere d'occlusion de gaz WO2003014018A1 (fr)

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JP2001-238343 2001-08-06
JP2001238343 2001-08-06
JP2002-96408 2002-03-29
JP2002096408 2002-03-29

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US12286540B2 (en) 2015-02-03 2025-04-29 Monolith Materials, Inc. Carbon black generating system
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US11492496B2 (en) 2016-04-29 2022-11-08 Monolith Materials, Inc. Torch stinger method and apparatus
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