US20100304141A1 - Carbon microparticle having lignin as raw material and preparation method therefor - Google Patents

Carbon microparticle having lignin as raw material and preparation method therefor Download PDF

Info

Publication number
US20100304141A1
US20100304141A1 US12/745,148 US74514808A US2010304141A1 US 20100304141 A1 US20100304141 A1 US 20100304141A1 US 74514808 A US74514808 A US 74514808A US 2010304141 A1 US2010304141 A1 US 2010304141A1
Authority
US
United States
Prior art keywords
microparticle
carbon
lignin
micro
droplet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/745,148
Other languages
English (en)
Inventor
Katsumi Kamegawa
Tsuyoshi Sakaki
Kinya Sakanishi
Masaya Kodama
Keiko Nishikubo
Yoshio Adachi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Institute of Advanced Industrial Science and Technology AIST
Original Assignee
National Institute of Advanced Industrial Science and Technology AIST
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 National Institute of Advanced Industrial Science and Technology AIST filed Critical National Institute of Advanced Industrial Science and Technology AIST
Assigned to NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY reassignment NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NISHIKUBO, KEIKO, SAKANISHI, KINYA, KODAMA, MASAYA, ADACHI, YOSHIO, KAMEGAWA, KATSUMI, SAKAKI, TSUYOSHI
Publication of US20100304141A1 publication Critical patent/US20100304141A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • C01B32/348—Metallic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to a method for preparing a carbon microparticle. More particularly, it relates to a method for preparing a carbon microparticle from various organic raw materials having lignin as main constituent, and to carbon microparticles obtained thereby.
  • thermal decomposition of a spherical organic macromolecule containing lignin as shown in Patent Reference 1 grinding of a thermosetting resin carbon as shown in Patent Reference 2
  • thermal decomposition of a thermoplastic resin microparticles having activated charcoal powder attached on the surface as shown in Patent Reference 3 deposition of non-graphite structure hollow micro-carbon vaporized by thermal plasma as shown in Patent Reference 4
  • grinding of a carbon material in a solvent as shown in Patent Reference 6 laser illumination of a hydrocarbon compound particle as shown in Patent Reference 7, heat treatment of specially shaped carbon black at 2000° C.
  • Non-Patent References 1 to 4 are reported as scientific articles related to hollow carbon microparticles.
  • Patent Reference 1 Japanese Patent Application Laid-open No. H01-207719
  • Patent Reference 2 Japanese Patent Application Laid-open No. H03-164416
  • Patent Reference 3 Japanese Patent Application Laid-open No. H07-187849
  • Patent Reference 4 Japanese Patent Application Laid-open No. H07-267618
  • the present invention was devised in view of such issues, and an object thereof is to provide a method for preparing a carbon microparticle from an organic raw material having lignin as a main constituent, and in particular, to provide a preparation method for a carbon microparticle having high strength, light weight and high specific surface area. It is another object of the present invention to provide a method for preparing a carbon microparticle from organic raw materials having lignin as a main constituent which saves energy.
  • the present invention adopts the following means.
  • the carbon microparticle preparation method according to the present invention 1 is characterized in that a solution of organic raw material having lignin as a main constituent is turned into a micro-droplet, the micro-droplet is dried to prepare a microparticle, and the microparticle is thermally decomposed in a range of 300° C. to 1200° C. to prepare a carbon microparticle.
  • the carbon microparticle preparation method according to the present invention 2 is characterized in that a mixed solution of an organic raw material having lignin as a main constituent and an inorganic substance is turned into a micro-droplet, the micro-droplet is dried to prepare a microparticle, and the microparticle is thermally decomposed in a range of 300° C. to 1200° C. to prepare a carbon microparticle.
  • the carbon microparticle preparation method according to the present invention 3 is characterized in that, in the carbon microparticle preparation method described in the present invention 2, the inorganic substance is a metal compound constituted by one or more species selected from the group consisting of an oxide, a hydroxide, a carbonate and a halide of a metal, and, based on the property that a carbon wall thickness of the carbon microparticle (portion of the shell that forms a hollow carbon microparticle) becomes thinner as the proportion of the metal compound added increases, the proportion of the metal compound added is adjusted to control the carbon wall thickness of the microparticle.
  • the inorganic substance is a metal compound constituted by one or more species selected from the group consisting of an oxide, a hydroxide, a carbonate and a halide of a metal, and, based on the property that a carbon wall thickness of the carbon microparticle (portion of the shell that forms a hollow carbon microparticle) becomes thinner as the proportion of the metal compound added increases, the proportion of the metal compound added is adjusted to
  • the carbon microparticle preparation method according to the present invention 4 is characterized in that, in the carbon microparticle preparation method described in the present invention 2, prior to being taken out into the air, the carbon microparticle obtained during the thermal decomposition or after the thermal decomposition is brought into contact beforehand with a gas having low reactivity, thereby inactivating the surface of the carbon microparticle by reaction with the gas and inhibiting a rapid heat generation occurring when the carbon microparticle is taken out into the air.
  • the carbon microparticle preparation method according to the present invention 5 is characterized in that a mixed solution of organic raw materials having lignin as a main constituent and a basic compound is turned into a micro-droplet, the micro-droplet is dried to prepare a microparticle, and the microparticle is thermally decomposed in a range of 300° C. to 1200° C. and the specific surface area is increased to prepare a carbon microparticle. This specific surface area is approximately 900 m 2 /g or greater.
  • the carbon microparticle preparation method according to the present invention 6 is characterized in that preprocessing to raise the constituent ratio of lignin is carried out on a pulp waste solution, the pulp waste solution after the preprocessing is turned into a micro-droplet, the micro-droplet is dried to prepare a microparticle, and the microparticle is thermally decomposed in a range of 300° C. to 1200° C. to prepare a carbon microparticle.
  • the carbon microparticle preparation method according to the present invention 7 is characterized in that preprocessing to raise the constituent ratio of lignin is carried out on a pulp waste solution, a solution comprising the pulp waste solution after the preprocessing added with an inorganic substance is turned into a micro-droplet, the micro-droplet is dried to prepare a microparticle, and the microparticle is thermally decomposed in a range of 300° C. to 1200° C. to prepare a carbon microparticle.
  • the carbon microparticle preparation method according to the present invention 8 is the carbon microparticle preparation method described in the present invention 6 or 7, characterized in that separation-collection of high molecular weight lignin is carried out by ultrafiltration as the preprocessing.
  • the carbon microparticle preparation method according to the present invention 9 is the carbon microparticle preparation method described in the present invention 6 or 7, characterized in that a process is carried out as the preprocessing, in which carbon dioxide is absorbed by the pulp waste solution to thereby decrease a hydrogen ion index and deposit a portion of an organic constituent, and the organic constituent is separated.
  • the carbon microparticle according to the present invention 10 is a hollow carbon microparticle characterized in that it is obtained by turning a solution of lignin, or lignin and an inorganic substance into a micro-droplet, drying the micro-droplet is to prepare a microparticle, and thermally decomposing the microparticle in a range of 300° C. to 1200° C.
  • the carbon microparticle according to the present invention 11 is a hollow carbon microcell, characterized in that it is obtained by turning a solution of lignin, or lignin and a basic compound into a micro-droplet, drying the micro-droplet to prepare a microparticle, and thermally decomposing the microparticle in a range of 300° C. to 1200° C., and in that it has an external diameter of 0.2 to 50 ⁇ m and a carbon wall thickness of 0.05 to 20 ⁇ m.
  • the carbon microparticle according to the present invention 12 is the hollow carbon microcell described in the present invention 11, characterized in that the proportion in mass of the lignin and the basic compound is 1:0.5 to 1:2, and the carbon microparticle is hollow and has a high specific surface area. From the fact that the carbon wall becomes thin when the proportion in mass of the basic compound is larger, the carbon wall thickness can be controlled by adjusting the proportion in mass thereof within the range given above. Then, the specific surface area increases remarkably along with increasing proportion in mass of the basic compound. However, when the basic compound was added with a proportion that exceeded 1:2, melting of microparticles was triggered.
  • the carbon microparticle according to the present invention 13 is a hollow carbon microballoon characterized in that it is obtained by turning a solution of lignin as well as a metal compound constituted by one or more species selected from the group consisting of an oxide, a hydroxide, a carbonate and a halide of a metal into a micro-droplet, drying the micro-droplet to prepare a microparticle, and thermally decomposing the microparticle in a range of 300° C. to 1200° C., and in that it has an external diameter of 0.2 to 50 ⁇ m, a carbon wall thickness of 5 to 200 nm and a bulk density of 3 to 20 g/L.
  • the carbon microparticle according to the present invention 14 is the carbon microballoon described in the present invention 13, characterized in that the proportion in mass of the lignin and the metal compound is 1:3 to 1:20. From the fact that the carbon wall becomes thin when the proportion in mass of the metal compound is larger, the carbon wall thickness can be controlled by adjusting the proportion in mass thereof within the range given above. However, when the metal compound was added with a proportion of less than 1:3, no carbon microballoon was generated, and when added with a proportion exceeding 1:20, the microballoons broke up without becoming hollow, and only aggregated products could be obtained.
  • the carbon microparticle according to the present invention 15 is a hollow carbon nanopipe cell characterized in that it is a hollow carbon microparticle obtained by turning a solution of lignin and metasilicate into a micro-droplet, drying the micro-droplet to prepare a microparticle, and thermally decomposing the microparticle in a range of 300° C. to 1200° C., and in that it has an external diameter of 0.2 to 50 ⁇ m and a carbon wall thickness of 0.05 to 20 ⁇ m, and furthermore, the carbon wall thereof is constituted by a carbon nanopipe having an external diameter of 5 to 50 nm and a carbon wall thickness of 1 to 5 nm.
  • the carbon microparticle according to the present invention 16 is the carbon nanopipe cell described in the present invention 15, characterized in that the proportion in mass of the lignin and the metasilicate is 1:3 to 1:20. From the fact that the carbon wall becomes thin when the proportion in mass of metasilicate is increased, the carbon wall thickness can be controlled by adjusting the proportion in mass thereof within the range given above. However, when metasilicate was added with a proportion of less than 1:3 or exceeding 1:20, no carbon nanopipe cell was generated.
  • the carbon microparticle according to the present invention 17 is a hollow, non-graphite carbon nanocell, characterized in that it is obtained by turning a solution of lignin and orthosilicate into a micro-droplet, drying the micro-droplet to prepare a microparticle, and thermally decomposing the microparticle in a range of 300° C. to 1200° C., and in that it has an external diameter of 3 to 30 nm, a carbon wall thickness of 1 to 5 nm and a specific surface area of 1400 to 1600 m 2 /g.
  • the carbon microparticle according to the present invention 18 is the carbon nanocell described in the present invention 17, characterized in that the proportion in mass of the lignin and the orthosilicate is 1:5 to 1:20. From the fact that the carbon wall becomes thin when the proportion in mass of orthosilicate is increased, the carbon wall thickness can be controlled by adjusting the proportion in mass thereof within the range given above. However, when orthosilicate was added with a proportion of less than 1:5 or exceeding 1:20, no carbon nanocell was generated.
  • organic raw materials having lignin as a main constituent include, in addition to lignin, organic compounds in waste solutions discarded in the manufacturing process of paper pulp or waste solutions from the preprocessing thereof, and further, those from the preprocessing of plant raw materials containing lignin such as wood and plants.
  • Lignin is, for instance, a high molecular weight aromatic polymer compound present for instance in wood at 20 to 30 mass %, constituting the intermediate layer between a cell membranes, a portion being considered to be present in a cell membrane.
  • lignin as referred to in the present invention means alkaline lignin, hydrolyzed lignin, lignin sulfonic acid and the like.
  • preprocessing refers to a process for raising the constituent ratio of lignin from [that in] an organic raw material containing lignin, or a process for improving lignin into a structure suitable for the preparation of carbon microparticles. That is to say, it is a process prior to turning an organic raw material containing lignin into a micro-droplet. For instance, when a pulp waste solution is used as an organic raw material, although it is not necessarily a mandatory process, it is desirable to perform preprocessing for raising the constituent proportion of lignin.
  • processes such as (1) absorption of acidic gas to precipitate and separate lignin; (2) addition of an inorganic acid, a multivalent cation or an organic amine to precipitate and separate lignin; (3) fermentation and removal by degradation of sugars in the pulp waste solution; and (4) separation and collection of high molecular weight lignin by ultrafiltration can be considered.
  • Filtration is a general method for separating water and lignin with a filter.
  • the ultrafiltration membranes used in the present invention refer to porous membranes with pore diameters ranging from 1 nm to 100 nm (0.1 ⁇ m).
  • lignin separation-concentration method for preprocessing when using wood, plants and the like as organic raw materials, for instance, well known methods such as alkaline decomposition used in pulp manufacturing or the like can be used.
  • constituent ratio of lignin can be raised by using the lignin separation-concentration method described above, or the like, as necessary.
  • thermal decomposition refers to heating and carbonizing an organic raw materials containing lignin at 300° C. to 1200° C. In general, thermal decomposition is performed at 500° C. to 800° C.
  • inorganic substances used in the present invention are used to control various characteristics such as carbon wall thickness of carbon microparticle, thermoplasticity of lignin, pore structure of carbon wall and conductivity of carbon microparticle.
  • inorganic substances include, in addition to single body carbons, water soluble salts such as an oxide, a hydroxide, a carbonate, a halide, a sulfate, a nitrate, a silicate, a phosphate and a borate of a metal, as well as these microparticles thereof and micro-fibers thereof.
  • inactivation refers to bringing a carbon microparticle obtained during thermal decomposition or after thermal decomposition into contact with a gas having low reactivity to inactivate the surface of the carbon microparticle.
  • Gas with low reactivity means water vapor gas, nitrogen gas containing low concentration of oxygen, and the like. Then, since generation of a gentle reaction with the carbon microparticle surface is required, totally inactive gas such as pure nitrogen is not applicable.
  • turning into a micro-droplet refers to turning for instance a pulp waste solution after preprocessing into micro-droplets with diameters on the order of few tens of ⁇ m or less by methods such as spraying and ultrasonic nebulization.
  • a carbon microparticle refers to a particle comprising thermally decomposed or carbonized lignin in the organic compound.
  • Carbon microparticles have various sizes (diameters on the order of few nm to 50 ⁇ m) and morphologies. In addition, it is characterized by a bulk density of 3 to 300 g/L, and a light weight.
  • carbon microparticles can be prepared from a solution of organic raw materials having lignin as a main constituent, which is a regenerable biological resource. This contributes greatly in the transition from fossil resources to biological resources for preparing carbon microparticles.
  • various characteristics of the carbon microparticle such as carbon wall thickness can be controlled simply by adjusting the proportions of the added inorganic substances.
  • the carbon microparticle obtained by thermal decomposition into contact with a gas having low reactivity, the rapid heat generation occurring when [the particle is] taken out into the air can be suppressed.
  • the carbon microparticle preparation method of the present invention allows a carbon microparticle to be prepared also from a mixed solution of organic raw materials having lignin as a main constituent and a basic compound, and a carbon microparticle obtained thereby is suited to a variety of applications as the specific surface area is equivalent to commercially available activated charcoal. From the fact that it is hollow, the carbon microparticle obtained by the preparation method of the present invention has the property of being extremely light in volume ratio compared to a conventional carbon microparticle, which is filled with carbon or the like all the way inside. Consequently, it is suited in particular to applications that require light weight.
  • the carbon microparticle preparation method of the present invention allows carbon microparticles to be prepared also from pulp waste solutions, and pulp waste solutions can be used actively as biomass resources to prepare carbon microparticles. Furthermore, since the carbon microparticle preparation method of the present invention allows carbon microparticles to be prepared at lower heat treatment temperature than prior art, it also contributes to energy saving.
  • FIG. 1 ( a ) is a photograph of hollow carbon microparticles prepared from lignin sulfonic acid only
  • FIG. 1 ( b ) is a magnified photograph of a fracture cross section of a hollow carbon microparticle thereof;
  • FIG. 2 ( a ) is a magnified photograph of a fracture cross section of a carbon microparticle when the proportion in mass of lignin and sodium hydroxide is 1:0.25
  • FIG. 2 ( b ) is a magnified photograph of a fracture cross section of a carbon microparticle when the proportion in mass of lignin and sodium hydroxide is 1:0.5
  • FIG. 2 ( c ) is a magnified photograph of a fracture cross section of a carbon microparticle when the proportion in mass of lignin and sodium hydroxide is 1:1;
  • FIG. 4 ( b ) is a high magnification photograph of a carbon nanoparticle thereof;
  • FIG. 5 ( a ) is a photograph of carbon prepared from a pulp waste solution which has not been preprocessed
  • FIG. 5 ( b ) is a photograph of carbon microparticles when ultrafiltration processing was performed on a pulp waste solution and high molecular weight constituents served as raw materials
  • FIG. 5 ( c ) is a magnified photograph of a fracture cross section of a carbon microparticle thereof;
  • FIG. 6 ( a ) is a photograph of carbon microcells prepared by ultrasonic nebulization and FIG. 6 ( b ) is a magnified photograph of a carbon wall portion in the fracture cross section of a carbon microcell thereof;
  • FIG. 7 is a photograph of carbon microballoons
  • FIG. 8 ( a ) is a photograph of a carbon nanopipe cell and FIG. 8 ( b ) is a magnified photograph of a carbon wall portion in the fracture cross section of a carbon nanopipe cell thereof;
  • FIG. 9 is a photograph of carbon nanocells.
  • an organic raw material having lignin as a main constituent, which is a biological resource, or a solution of a mixture of this organic raw material and an inorganic substance is turned into a micro-droplet and dried to prepare an organic compound microparticle or a complex microparticle of an organic raw material and an inorganic substance.
  • This organic compound microparticle or complex microparticle is thermally decomposed in a range of 300° C. to 1200° C. and left to cool to prepare a carbon microparticle.
  • the product after thermal decomposition is high, the product is inactivated by being brought into contact with a gas having a low reactivity.
  • the product is washed with water or the like to remove inorganic substances and then dried.
  • the carbon microparticles prepared in this way have a variety of sizes (diameters on the order of few nm to 50 ⁇ m) and morphologies. In addition, they are characterized by bulk densities of 3 to 300 g/L and a light weight.
  • microparticles of lignin sulfonic acid An aqueous solution with 5% total concentration of lignin sulfonic acid was spray-dried to prepare microparticles of lignin sulfonic acid. This was heat-processed under nitrogen atmosphere at 600° C. for one hour and let to cool to prepare hollow carbon microparticles such as those shown in FIGS. 1 ( a ) and ( b ).
  • the hollow carbon microparticles had diameters on the order of few ⁇ m to 10 ⁇ m.
  • aqueous solution with 5% total concentration of lignin and sodium hydroxide (proportion in mass was 1:0.25) was spray-dried to prepare complex microparticles. This was heat-processed under nitrogen atmosphere at 600° C. for one hour and let to cool. Thereafter, this was washed with water and further dried to prepare hollow carbon microparticles such as those shown in FIG. 2 ( a ). In addition, a similar process was performed on an aqueous solution with 1:0.5 as the proportion in mass of lignin and sodium hydroxide and 5% total concentration to prepare hollow carbon microparticles such as those shown in FIG. 2 ( b ).
  • An actual pulp waste solution (total concentration: 23%) was simply diluted to prepare an aqueous solution with 5% total concentration. This aqueous solution was spray-dried to prepare microparticles. This was heat-processed under nitrogen atmosphere at 600° C. for one hour and let to cool, then, washed with water and further dried; the result was that the particles were fused to one another and no carbon microparticle could be obtained as shown in FIG. 5 ( a ). This is due to heat-melting of carbohydrate decomposition products or the like contained in the pulp waste solution in addition to lignin.
  • a. precipitation-separation of lignin by absorption of acidic gas, b. precipitation-separation of lignin by addition of an inorganic acid, a multivalent cation, or an organic amine, c. decomposition-elimination by fermentation of sugar in pulp waste solution, d. separation-collection of high molecular weight lignin by ultrafiltration, and the like may be considered. It is believed that the constituent ratio of lignin can be raised by any methods.
  • this hollow carbon microparticle was on the order of few ⁇ m to 10 ⁇ m. From this, it was demonstrated that by raising the constituent ratio of lignin, carbon microparticles could be prepared also from raw materials containing various organic compounds and inorganic substances other than lignin, such as a pulp waste solution.
  • Example 2 As in the case of Example 2, an aqueous solution of lignin and alkali hydroxide or an aqueous solution of lignin and alkali carboxylate was spray-dried, to prepare a complex microparticle having a diameter on the order of few microns. This was heat-processed under nitrogen atmosphere at 600° C., let to cool to room temperature, then, when the product containing the generated carbon microparticles was taken out into the air, a phenomenon of strong heat generation was observed. Then, such heat generation was pronounced in the case where, lignin sulfonic acid was the raw material. The cause of the heat generation is due to the carbon microparticles and alkaline metals generated by the heat treatment react violently with oxygen or the like in the air.
  • an organic compound microparticle or a complex microparticle of organic raw materials and inorganic substance is prepared by turning into micro-droplets and drying a solution of organic raw materials having lignin as a main constituent, which is a biological resource, as in Example 1, or a solution of a mixture of organic raw materials having lignin as a main constituent and an inorganic substance, as in Examples 2 to 7.
  • a solution in addition to aqueous solutions, organic solutions containing an organic compound other than lignin, and furthermore, a suspension are included.
  • inorganic substance as indicated in Examples 3 to 5, mixtures of inorganic substances are included.
  • spray-drying is carried out in the examples as means for turning [a solution] into micro-droplets; however, without limiting to this, other means may be used, such as ultrasonic nebulization, as indicated in Example 8 described below.
  • carbon microparticles are prepared in the present invention by thermally decomposing organic compound microparticles or complex microparticles in a range of 300° C. to 1200° C. and letting to cool.
  • heat processing temperature was 600° C. in the examples
  • heat processing temperature in the present invention may be in the range of 300° C. to 1200° C.
  • drying of the micro-droplets described above and thermal decomposition of microparticles may be carried out simultaneously inside the same reactor.
  • the product is inactivated by being in contact with a “gas having low reactivity”; this gas is not limited to nitrogen gas pre-saturated with moisture as in Example 7, and may be an inert gas or the like with similarly adjusted moisture. This inactivation processing of the product may be carried out as necessary.
  • washing and drying of the product after thermal decomposition may be carried out as necessary as well.
  • carbon microparticles have been prepared with fossil resources such as oil as raw materials, at high temperatures of 1400° C. or higher.
  • the fossil resource can be substituted with a biological resource such as a pulp waste solution containing lignin.
  • the preparation temperature is on the order of 300° C. to 1200° C. and can be lowered significantly compared to prior art technique, there is contribution to energy saving.
  • the present invention is expected to contribute to a decrease in costs and energy saving also from such a context.
  • carbon microparticles of which carbon black is a representative, are used in majority as tire reinforcing agent.
  • the carbon microparticle generated by the preparation method of the present invention is light weight, and some also exist with an equivalent specific surface area to commercially available activated charcoal, such that, in addition to utilization as rubber reinforcing agent such as for tires, utilization is anticipated as activated charcoal, controlled release material, black pigment, toner, color filter, conductive material, electrostatic prevention agent, battery electrode material, viscous fluid and the like.
  • Carbon microparticles suited to specific applications were prepared by the preparation methods of Example 8 to 11 shown in the following.
  • FIG. 6 ( a ) shows a portion of the fracture cross section of a microparticle thereof. It is clear with this photograph that these are hollow microparticles with a compact carbon structure and a carbon wall thickness of approximately 0.3 ⁇ m.
  • the carbon microcells prepared in this way have external diameters of 0.2 to 50 ⁇ m, carbon wall thicknesses of 0.05 to 20 ⁇ m, and a carbon wall with a compact structure, they are high strength, light weight hollow carbon materials.
  • the carbon microcell of the present invention has a pore structure, which is a compact structure as shown in FIG. 6 ( b ) with micropores as the main body, thus has the characteristic of high physical strength.
  • the carbon microcell obtained in the present Example 8 is hollow carbon, and thus is light weight. Then, it has high strength, since the mesopores and the macropores, which are present in the carbon wall of prior art hollow carbon microparticle and provoke a decrease in strength, are almost inexistent. From this, [the microcell] can be used as a high strength, light weight filling material.
  • the carbon microballoon obtained in the present Example 9 is an ultra-light weight hollow carbon material having an external diameter of 0.2 to 50 ⁇ m, a carbon wall thickness of approximately 5 to 200 nm and a bulk density of 3 to 20 g/L. From this, [the microballoon] can be used as an ultra-light filling material.
  • the carbon nanopipe cells obtained in the present example can be considered as one species of the carbon microcell obtained in Example 8.
  • the external diameter of this carbon nanopipe cell was 0.2 to 50 ⁇ m, and the carbon wall thickness was 0.05 to 20 ⁇ m.
  • it can be considered to be a light-weight hollow carbon material with the carbon wall thereof having a special shape comprising a carbon nanopipe with irregularly curved and crossing structure, as shown in FIG. 8 ( b ), having an external diameter of 5 to 50 nm and a carbon wall thickness of 1 to 5 nm.
  • the carbon nanopipe cell obtained in the present example is a micron-size carbon microparticle, and at the same time, the carbon wall has a structure comprising a nanopipe with numerous voids, thus, the strength is low, which can be used as specially shaped light-weight filling materials, the particles disintegrating by mixing with a resin or rubber and being dispersed in the matrix at the nanopipe level.
  • the carbon wall has a structure comprising a nanopipe with numerous voids, it can also be used as controlled-release materials for substances such as agricultural chemicals and medicinal drugs.
  • the carbon nanocell obtained in the present example has large voids within the particle, an external diameter of 3 to 30 nm and a carbon wall thickness of 1 to 5 nm, it can be considered to be an ultra-fine light-weight hollow carbon material.
  • it has the characteristics of having irregular shape and being of non-graphite quality.
  • the specific surface area is 1400 to 1600 m 2 /g, it has the characteristics of being ultra-fine and having a large specific surface area. That is to say, from the facts that the particle size is even smaller than prior art carbon black, and furthermore, improvement of reinforcement or the like can be expected with the addition of tiny amount, it can be used as an ultra-fine light-weight filler.
  • the specific surface area is extremely large, it can be used as an ultra-fine highly surface adsorbing material.
  • the carbon microparticles obtained by the preparation method of present invention being light-weight and some having an equivalent specific surface area to commercially available activated charcoal, in addition to uses as reinforcing agent for rubber such as of a tire, they can be used as activated charcoal, controlled release material, black pigment, toner, color filter, conductive material, electrostatic prevention agent, battery electrode material, viscous fluid and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
US12/745,148 2007-12-03 2008-11-18 Carbon microparticle having lignin as raw material and preparation method therefor Abandoned US20100304141A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2007311918 2007-12-03
JP2007-311918 2007-12-03
JP2008186135A JP5062593B2 (ja) 2007-12-03 2008-07-17 リグニンを原料とする炭素微粒子及びその製造方法
JP2008-186135 2008-07-17
PCT/JP2008/070961 WO2009072393A1 (ja) 2007-12-03 2008-11-18 リグニンを原料とする炭素微粒子及びその製造方法

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2008/070961 A-371-Of-International WO2009072393A1 (ja) 2007-12-03 2008-11-18 リグニンを原料とする炭素微粒子及びその製造方法

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/536,053 Division US9321649B2 (en) 2007-12-03 2012-06-28 Carbon microparticle having lignin as raw material and preparation method therefor

Publications (1)

Publication Number Publication Date
US20100304141A1 true US20100304141A1 (en) 2010-12-02

Family

ID=40717574

Family Applications (2)

Application Number Title Priority Date Filing Date
US12/745,148 Abandoned US20100304141A1 (en) 2007-12-03 2008-11-18 Carbon microparticle having lignin as raw material and preparation method therefor
US13/536,053 Active 2029-10-30 US9321649B2 (en) 2007-12-03 2012-06-28 Carbon microparticle having lignin as raw material and preparation method therefor

Family Applications After (1)

Application Number Title Priority Date Filing Date
US13/536,053 Active 2029-10-30 US9321649B2 (en) 2007-12-03 2012-06-28 Carbon microparticle having lignin as raw material and preparation method therefor

Country Status (5)

Country Link
US (2) US20100304141A1 (ja)
EP (1) EP2218683A4 (ja)
JP (1) JP5062593B2 (ja)
CN (1) CN101910060B (ja)
WO (1) WO2009072393A1 (ja)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120208103A1 (en) * 2004-11-02 2012-08-16 Samsung Sdi Co., Ltd. Carbon nanosphere with at least one opening, method for preparing the same, carbon nanosphere-impregnated catalyst using the carbon nanosphere, and fuel cell using the catalyst
US8986838B2 (en) 2009-01-22 2015-03-24 National Institute Of Advanced Industrial Science And Technology Hollow carbon microparticle and method for producing same
US20150183813A1 (en) * 2012-06-06 2015-07-02 Upm-Kymmene Corporation Method for fractionating lignin
JP2016023115A (ja) * 2014-07-23 2016-02-08 大王製紙株式会社 炭素微粒子の製造方法
US20160332882A1 (en) * 2013-12-23 2016-11-17 Stora Enso Oyj A conductive carbon powder, a method for the manufacturing thereof and use thereof
US20170073495A1 (en) * 2014-05-12 2017-03-16 Stora Enso Oyj Electrically dissipative polymer composition comprising conductive carbon powder emanating from lignin, a method for the manufacturing thereof and use thereof
US20170313585A1 (en) * 2014-12-11 2017-11-02 Stora Enso Oyj A novel method for carbonizing lignocelluosic material as a powder
US10199177B2 (en) * 2014-07-15 2019-02-05 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method for the synthesis of nanocomposites based on TiO2 and carbonated nanostructures
US10821687B2 (en) 2014-09-30 2020-11-03 Lg Chem, Ltd. Method for producing hollow carbon capsules
CN113698798A (zh) * 2021-08-27 2021-11-26 昆明理工大学 一种橡胶籽壳基导电炭黑的制备方法
US11306209B2 (en) 2015-11-21 2022-04-19 Suncoal Industries Gmbh Particulate carbon material producible from renewable raw materials and method for its production
US11332371B2 (en) 2016-11-08 2022-05-17 University Of Guelph Methods for creation of sub-micron biocarbon materials from biomass and their fields of application
CN115445588A (zh) * 2022-08-15 2022-12-09 东南大学 生物质基多孔碳复合材料及制备与在co2吸附中的应用

Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5062593B2 (ja) 2007-12-03 2012-10-31 独立行政法人産業技術総合研究所 リグニンを原料とする炭素微粒子及びその製造方法
CN102179217B (zh) * 2011-03-10 2013-06-05 江苏国正新材料科技有限公司 一种超能活性电碳中空微球的制备方法
KR101281766B1 (ko) * 2011-04-14 2013-07-02 재단법인 포항산업과학연구원 다공성 탄소재 및 그 제조방법
JP5926169B2 (ja) * 2011-11-29 2016-05-25 京セラ株式会社 セラミックス顆粒およびセラミック焼結体ならびに防護部材
WO2013108061A1 (en) * 2012-01-20 2013-07-25 NATUR FEED S.r.l. Technological adjuvant for fodders and supplements of zootechnical breeding and farming
CN102633252A (zh) * 2012-04-26 2012-08-15 合肥工业大学 一种利用木质素磺酸盐制备超级电容器用多孔炭的方法
JP2014080327A (ja) * 2012-10-16 2014-05-08 National Institute Of Advanced Industrial & Technology ナノ構造から成る炭素微粒子の製造方法
JP6103523B2 (ja) * 2013-01-24 2017-03-29 大王製紙株式会社 炭素微粒子の製造方法及び製造設備
CN103107319B (zh) * 2013-02-19 2015-07-01 中国科学院过程工程研究所 一种锂离子电池碳微球负极材料及其制备方法
WO2014143753A1 (en) 2013-03-15 2014-09-18 Sweetwater Energy, Inc. Carbon purification of concentrated sugar streams derived from pretreated biomass
JP6181461B2 (ja) * 2013-08-12 2017-08-16 花王株式会社 静電荷像現像用トナーの製造方法
CN103588190B (zh) * 2013-10-31 2016-04-06 中国科学院过程工程研究所 一种由木质纤维素制备碳微球的方法
CN103663410B (zh) * 2013-11-25 2016-04-13 陕西煤业化工技术研究院有限责任公司 一种制备中间相炭微球的超声雾化方法及装置
CN104043469B (zh) * 2014-01-06 2017-10-27 北京化工大学 一种掺氮炭黑催化剂及其制备方法和应用
JP6331995B2 (ja) * 2014-03-11 2018-05-30 新日鐵住金株式会社 炭酸化物からの遊離炭素製造方法
JP6384775B2 (ja) * 2014-03-31 2018-09-05 大王製紙株式会社 電子写真トナー用炭素微粒子の製造方法
JP6333025B2 (ja) * 2014-03-31 2018-05-30 大王製紙株式会社 顔料分散液用の炭素微粒子の製造方法、顔料分散液の製造方法、及びインクジェット用インクの製造方法
EP3143077A4 (en) * 2014-05-12 2017-11-01 Stora Enso Oyj Electrically dissipative foamable composition comprising conductive carbon powder emanating from lignin, a method for the manufacturing thereof and use thereof
WO2015173722A1 (en) * 2014-05-12 2015-11-19 Stora Enso Oyj Electrically dissipative elastomer composition comprising conductive carbon powder emanating from lignin, a method for the manufacturing thereof and use thereof
CN104386691B (zh) * 2014-10-21 2016-02-03 北京科技大学 一种制备超级电容器用中空管状活性炭电极材料的方法
WO2016094594A1 (en) 2014-12-09 2016-06-16 Sweetwater Energy, Inc. Rapid pretreatment
JP6552633B2 (ja) * 2015-03-24 2019-07-31 国立大学法人九州大学 ハロゲン化カーボン及びその製造方法
JP6504392B2 (ja) * 2015-04-23 2019-04-24 大王製紙株式会社 炭素微粒子の製造方法
JP6588276B2 (ja) * 2015-08-31 2019-10-09 富士フイルム株式会社 硬化性組成物、カラーフィルタ、遮光膜、固体撮像素子および画像表示装置
JP6547633B2 (ja) * 2015-09-04 2019-07-24 日本製鉄株式会社 炭酸化物からの膜状遊離炭素製造方法
JP2018534233A (ja) * 2015-09-16 2018-11-22 スウィートウォーター・エナジー・インコーポレイテッド 前処理されたバイオマス由来の特殊活性炭
CN105806674A (zh) * 2016-03-08 2016-07-27 武汉水天成环保科技有限公司 一种用于标定的酸纳米性颗粒的制备方法
JP2018035035A (ja) * 2016-08-31 2018-03-08 学校法人 関西大学 炭素量子ドットの製造方法及びその方法で得られる炭素量子ドット
CA3053773A1 (en) 2017-02-16 2018-08-23 Sweetwater Energy, Inc. High pressure zone formation for pretreatment
CN107742586B (zh) * 2017-11-20 2020-07-31 宁波中车新能源科技有限公司 一种微米级球形多孔碳的制备方法及用其制备超级电容器的方法
CN108217625B (zh) 2018-03-16 2020-01-24 伍鹏 纳米碳微粒子的制造方法
CN108511204B (zh) * 2018-04-02 2020-06-16 张家港博威新能源材料研究所有限公司 一种氧氮共掺杂多孔中空碳微球的制备方法
JP7132832B2 (ja) * 2018-11-26 2022-09-07 Ｔｏｙｏ Ｔｉｒｅ株式会社 ゴムウエットマスターバッチを含有するゴム組成物、およびその製造方法
CN109659151B (zh) * 2019-01-17 2020-11-27 中南大学 一种通过调控木质素分子量制备不同碳基超级电容器用电极材料的方法
EP4077490A1 (en) 2019-12-22 2022-10-26 Sweetwater Energy, Inc. Methods of making specialized lignin and lignin products from biomass
CN111252763B (zh) * 2020-03-15 2022-03-15 福州大学 一种含磺酸基的木质素基高物化双性型生物炭及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3775344A (en) * 1970-11-14 1973-11-27 Kureha Chemical Ind Co Ltd Active carbon having a hollow microspherical structure
JPH07267618A (ja) * 1994-03-23 1995-10-17 Mitsubishi Chem Corp 新規な炭素微粒子
WO2006046656A1 (ja) * 2004-10-28 2006-05-04 Mitsubishi Chemical Corporation 球状炭素粒子およびその集合体

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3886093A (en) * 1973-12-14 1975-05-27 Westvaco Corp Activated carbon with active metal sites and process for producing same
US4768469A (en) * 1985-07-31 1988-09-06 Kabushiki Kaisha Toshiba Operation control apparatus for recovery boilers
CA1287459C (en) * 1986-10-01 1991-08-13 Mukesh Jain Process for the preparation of hollow microspheres
JPH01207719A (ja) 1988-02-15 1989-08-21 Toray Ind Inc 液晶素子用スペーサ
JP2788513B2 (ja) 1989-11-20 1998-08-20 昭和電工株式会社 ガラス状カーボン粉末及びその製造方法
JP3326942B2 (ja) 1993-12-27 2002-09-24 ぺんてる株式会社 中空状活性炭成形物の製造方法
US5492870A (en) 1994-04-13 1996-02-20 The Board Of Trustees Of The University Of Illinois Hollow ceramic microspheres by sol-gel dehydration with improved control over size and morphology
JP3633091B2 (ja) 1996-04-09 2005-03-30 旭硝子株式会社 微小無機質球状中実体の製造方法
US5972537A (en) * 1997-09-02 1999-10-26 Motorola, Inc. Carbon electrode material for electrochemical cells and method of making same
JPH11268907A (ja) 1998-03-23 1999-10-05 Nikkiso Co Ltd 空洞炭素およびその製造方法
JP2001220114A (ja) 2000-02-14 2001-08-14 Tokai Carbon Co Ltd 球状炭素微粒子
CN1093581C (zh) * 2000-09-25 2002-10-30 孙连超 亚铵法造纸制浆废液资源化生产多种木素产品的方法
KR100385574B1 (ko) 2001-02-10 2003-05-27 최만수 쉘 형상의 탄소 미세입자 제조방법
JP2002241116A (ja) 2001-02-13 2002-08-28 Akiya Kozawa 超微粒炭素の製造法
JP4386400B2 (ja) * 2001-05-17 2009-12-16 独立行政法人科学技術振興機構 電磁波シールド材料及びその製法
JP4452773B2 (ja) 2003-08-05 2010-04-21 株式会社ナノクリエイツ 炭素微粒子の製造方法及び製造装置
JP4012516B2 (ja) 2004-03-30 2007-11-21 浩史 滝川 カーボンナノバルーン構造体の製造方法
JP2005289666A (ja) * 2004-03-31 2005-10-20 Toyota Boshoku Corp 炭化物の製造方法
JP4762517B2 (ja) 2004-09-09 2011-08-31 株式会社オプトニクス精密 プリンター用トナーの製造方法
CN1314584C (zh) * 2005-06-17 2007-05-09 华东师范大学 一种制备纳米碳微粒的方法
JP4740659B2 (ja) * 2005-06-23 2011-08-03 機能性木質新素材技術研究組合 炭素材料の製造方法
JP4887489B2 (ja) 2006-03-25 2012-02-29 国立大学法人 宮崎大学 レゾルシノール系ポリマーを前駆体とした中空状炭素粒子の製造方法
JP5062593B2 (ja) 2007-12-03 2012-10-31 独立行政法人産業技術総合研究所 リグニンを原料とする炭素微粒子及びその製造方法
JP5288408B2 (ja) 2009-01-22 2013-09-11 独立行政法人産業技術総合研究所 中空炭素微粒子およびその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3775344A (en) * 1970-11-14 1973-11-27 Kureha Chemical Ind Co Ltd Active carbon having a hollow microspherical structure
JPH07267618A (ja) * 1994-03-23 1995-10-17 Mitsubishi Chem Corp 新規な炭素微粒子
WO2006046656A1 (ja) * 2004-10-28 2006-05-04 Mitsubishi Chemical Corporation 球状炭素粒子およびその集合体

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Hou et al. (Carbon Nanotubes and Spheres Produced by Modified Ferrocene Pyrolysis, Chem. Mater. 2002, 14, 3990-3994) *
Machine Translation of JP07-267618 *
Paunov et al. (Fabrication of carbon nanotube-based microcapsules by a colloid templating technique, Nanotechnology 16 (2005) 1522-1525). *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8603934B2 (en) * 2004-11-02 2013-12-10 Samsung Sdi Co., Ltd. Carbon nanosphere with at least one opening, method for preparing the same, carbon nanosphere-impregnated catalyst using the carbon nanosphere, and fuel cell using the catalyst
US20120208103A1 (en) * 2004-11-02 2012-08-16 Samsung Sdi Co., Ltd. Carbon nanosphere with at least one opening, method for preparing the same, carbon nanosphere-impregnated catalyst using the carbon nanosphere, and fuel cell using the catalyst
US8986838B2 (en) 2009-01-22 2015-03-24 National Institute Of Advanced Industrial Science And Technology Hollow carbon microparticle and method for producing same
US20150183813A1 (en) * 2012-06-06 2015-07-02 Upm-Kymmene Corporation Method for fractionating lignin
US9896469B2 (en) * 2012-06-06 2018-02-20 Upm-Kymmene Corporation Method for fractionating lignin
US20160332882A1 (en) * 2013-12-23 2016-11-17 Stora Enso Oyj A conductive carbon powder, a method for the manufacturing thereof and use thereof
US10689256B2 (en) 2013-12-23 2020-06-23 Stora Enso Oyj Conductive carbon powder, a method for the manufacturing thereof and use thereof
US20170073495A1 (en) * 2014-05-12 2017-03-16 Stora Enso Oyj Electrically dissipative polymer composition comprising conductive carbon powder emanating from lignin, a method for the manufacturing thereof and use thereof
US10199177B2 (en) * 2014-07-15 2019-02-05 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method for the synthesis of nanocomposites based on TiO2 and carbonated nanostructures
JP2016023115A (ja) * 2014-07-23 2016-02-08 大王製紙株式会社 炭素微粒子の製造方法
US10821687B2 (en) 2014-09-30 2020-11-03 Lg Chem, Ltd. Method for producing hollow carbon capsules
US10532931B2 (en) * 2014-12-11 2020-01-14 Stora Enso Oyj Method for carbonizing lignocelluosic material as a powder
US20170313585A1 (en) * 2014-12-11 2017-11-02 Stora Enso Oyj A novel method for carbonizing lignocelluosic material as a powder
US11306209B2 (en) 2015-11-21 2022-04-19 Suncoal Industries Gmbh Particulate carbon material producible from renewable raw materials and method for its production
US11312864B2 (en) * 2015-11-21 2022-04-26 Suncoal Industries Gmbh Particulate carbon material producible from renewable raw materials and method for its production
US11639444B2 (en) 2015-11-21 2023-05-02 Suncoal Industries Gmbh Hydrothermal treatment of renewable raw material
US11332371B2 (en) 2016-11-08 2022-05-17 University Of Guelph Methods for creation of sub-micron biocarbon materials from biomass and their fields of application
CN113698798A (zh) * 2021-08-27 2021-11-26 昆明理工大学 一种橡胶籽壳基导电炭黑的制备方法
CN115445588A (zh) * 2022-08-15 2022-12-09 东南大学 生物质基多孔碳复合材料及制备与在co2吸附中的应用

Also Published As

Publication number Publication date
WO2009072393A1 (ja) 2009-06-11
EP2218683A4 (en) 2013-11-06
US20120269715A1 (en) 2012-10-25
US9321649B2 (en) 2016-04-26
JP2009155199A (ja) 2009-07-16
JP5062593B2 (ja) 2012-10-31
CN101910060A (zh) 2010-12-08
EP2218683A1 (en) 2010-08-18
CN101910060B (zh) 2014-12-10

Similar Documents

Publication Publication Date Title
US9321649B2 (en) Carbon microparticle having lignin as raw material and preparation method therefor
Chakraborty et al. Recent advancement of biomass-derived porous carbon based materials for energy and environmental remediation applications
Cao et al. Controllable synthesis of spherical carbon particles transition from dense to hollow structure derived from Kraft lignin
Xin et al. Mesoporous carbons: recent advances in synthesis and typical applications
Nassar et al. A review on the current research on graphene-based aerogels and their applications
Sui et al. Preparation of three-dimensional graphene oxide–polyethylenimine porous materials as dye and gas adsorbents
Xie et al. Porous carbons synthesized by templating approach from fluid precursors and their applications in environment and energy storage: A review
CN104722281B (zh) 一种纳米二氧化钛/壳聚糖三维多孔复合材料及其制备方法
CN103482597B (zh) 一种中大孔炭的制备方法
Sivaranjanee et al. A review on cleaner approach for effective separation of toxic pollutants from wastewater using carbon Sphere’s as adsorbent: Preparation, activation and applications
Gai et al. N-Doped biochar derived from co-hydrothermal carbonization of rice husk and Chlorella pyrenoidosa for enhancing copper ion adsorption
CN1986401A (zh) 一种改进方法制备的多孔微球活性炭
Xu et al. Halloysite nanotubes sponges with skeletons made of electrospun nanofibers as innovative dye adsorbent and catalyst support
CN105621384B (zh) 一种碳材料的合成方法
Rey-Raap et al. Carbon gels and their applications: a review of patents
CN114146679A (zh) 一种毫米级氮掺杂多孔碳球及其制备和应用
Zhou et al. Synthesis and CO2 adsorption performance of TEPA-loaded cellulose whisker/silica composite aerogel
Yao et al. Carbonized lignosulfonate-based porous nanocomposites for adsorption of environmental contaminants
CN105621383B (zh) 一种大孔碳的制备方法
JP6997299B2 (ja) メタハロイサイト粉末およびその製造方法
Li et al. Renewable lignosulfonate-assisted synthesis of hierarchical nanoflake-array-flower ZnO nanomaterials in mixed solvents and their photocatalytic performance
Vinayakumar et al. Processing of aerogels and their applications toward CO2 adsorption and electrochemical reduction: a review
CN105621385B (zh) 一种多孔碳材料的制备方法
Wang et al. Carbon materials from various sources for composite materials
CN109928379A (zh) 两级孔道碳材料及其制备方法

Legal Events

Date Code Title Description
AS Assignment

Owner name: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KAMEGAWA, KATSUMI;SAKAKI, TSUYOSHI;SAKANISHI, KINYA;AND OTHERS;SIGNING DATES FROM 20100421 TO 20100430;REEL/FRAME:024461/0436

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION