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WO2007119698A1 - Charbon actif, procédé de fabrication de celui-ci, et appareil de production - Google Patents

Charbon actif, procédé de fabrication de celui-ci, et appareil de production Download PDF

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Publication number
WO2007119698A1
WO2007119698A1 PCT/JP2007/057759 JP2007057759W WO2007119698A1 WO 2007119698 A1 WO2007119698 A1 WO 2007119698A1 JP 2007057759 W JP2007057759 W JP 2007057759W WO 2007119698 A1 WO2007119698 A1 WO 2007119698A1
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WO
WIPO (PCT)
Prior art keywords
carbonization
activated carbon
superheated steam
activation
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2007/057759
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English (en)
Japanese (ja)
Inventor
Tadashi Yokoi
Ikuyoshi Kohchi
Michio Inagaki
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.)
Intellectual Property Bank Corp
Original Assignee
Intellectual Property Bank Corp
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 Intellectual Property Bank Corp filed Critical Intellectual Property Bank Corp
Publication of WO2007119698A1 publication Critical patent/WO2007119698A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B7/00—Coke ovens with mechanical conveying means for the raw material inside the oven
    • C10B7/10—Coke ovens with mechanical conveying means for the raw material inside the oven with conveyor-screws
    • 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
    • C01B32/336—Preparation characterised by gaseous activating agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • 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
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to activated carbon obtained by performing carbonization treatment such as drying, dry distillation, activation, etc. using a woody material as a raw material, a method for producing the same, and a production apparatus.
  • Patent Document 1 discloses activated carbon using an organic electrolytic solution as an electrolytic solution, in which particles of a metal compound having a predetermined particle size are mixed with a petroleum-based carbon precursor, and argon is added.
  • a method for producing activated carbon by heating in an oxidizing gas such as water vapor or carbon dioxide after maintaining the temperature at 700 to 2000 ° C for a long time in a non-oxidizing atmosphere such as nitrogen or nitrogen Has been.
  • the obtained activated carbon is shown to have a force S that the specific surface area based on micropores calculated from the nitrogen adsorption isotherm by the t_plot method is 70% or less of the total specific surface area.
  • Patent Document 2 a primary air activation treatment is performed on a carbonized material at 450 ° C. to 550 ° C.:! To 10 hours, and then at 350 to 430 ° C. for 10 hours.
  • a method for producing activated carbon characterized by performing a secondary air activation treatment for ⁇ 60 hours is disclosed. It is shown that the mesopore volume is relatively large and activated carbon is obtained.
  • an alkaline earth metal compound powder is added to a carbonized material such as coatas obtained by heat-treating (sintering) synthetic resin, petroleum-based pitch, or petroleum-based pitch (raw material).
  • a technique for producing a predetermined activated carbon by high-temperature heat treatment is disclosed.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2000-340470
  • Patent Document 2 JP 2005-286170 A Patent Document 3: Japanese Patent Laid-Open No. 2004-175660
  • the present invention uses a wood material as a raw material, activated carbon having a large specific surface area and a pore structure suitable for an electric double layer capacitor of an aqueous electrolyte, and a method for producing the same The purpose is to provide.
  • the activated carbon of the present invention is manufactured by continuously performing a carbonization treatment and an activation treatment in a superheated steam atmosphere on a treatment object mainly composed of a wood material.
  • the total specific surface area is 600 m 2 / g or more, and the outer specific surface area has a pore distribution structure occupying 20% to 75% of the total specific surface area.
  • the total specific surface area was calculated using the ⁇ plot method from the amount of nitrogen gas adsorbed on the activated carbon.
  • the method for producing activated carbon according to the present invention includes a step of drying a treatment object mainly composed of a wood material, and a treatment object dried in the drying step at a temperature of 400 ° C to 950 ° C.
  • Carbonization and activation treatment are continuously performed by retaining in a hot steam atmosphere for a predetermined period of time. * In the carbonization * activation treatment step, the average of superheated steam for performing the activation treatment The temperature is 750 ° C to 900 ° C.
  • the activated carbon production method of the present invention is the above-described production method, wherein the carbonization 'activation treatment step is performed when the temperature of the superheated steam at the start of the carbonization activation treatment is 400 ° C to 700 ° C and the carbonization' activation treatment is terminated.
  • the temperature of the superheated steam is 750 ° C to 950 ° C, and the temperature of the superheated steam is increased from the start of the carbonization activation process.
  • the activated carbon production apparatus of the present invention includes a carbonization furnace that includes a water vapor introduction port for introducing superheated water vapor, and performs carbonization treatment and activation treatment on a processing object mainly composed of a wood material.
  • the carbonization furnace is located on the supply port side of a processing object mainly composed of a wood material, and the carbonization part carbonizes the processing object by contacting with the superheated steam;
  • An activation part that is located on the discharge port side of the object to be treated and performs an activation treatment by continuously contacting the object to be treated carbonized in the carbonization part with superheated steam, and the steam inlet is It is characterized in that at least two or more activation parts are provided.
  • the activated carbon production apparatus is characterized in that a flow rate control valve for controlling the flow rate of superheated steam is provided at any one or more of the steam inlets.
  • the carbonization section is provided with a low-temperature gas inlet for additionally introducing a gas of 150 to 300 ° C.
  • the carbonization furnace is arranged so as to be inclined downward by 0.1 to 10 degrees from the carbonization part toward the activation part.
  • an inclination angle control device for adjusting the inclination angle of the carbonization furnace is provided.
  • a processing object mainly composed of a wood material is used as a raw material, and it has a large specific surface area, and further has a high ratio of the external specific surface area to the total specific surface area.
  • the size of the outer specific surface area greatly contributes to the improvement of the electrostatic capacity of the electric double layer capacitor, and can be suitably used for the electric double layer capacitor.
  • woody materials are used as starting materials, in recent years they have been released in large quantities in forests, and it is possible to use thinned wood as high-value-added activated carbon such as electrode materials for electric double layer capacitors. It becomes possible.
  • FIG. 1 is an overall configuration diagram of a carbonization device for producing activated carbon for producing activated carbon according to Embodiment (1) of the present invention.
  • FIG. 2 is a diagram showing a carbonization furnace of a carbonization apparatus for producing activated carbon according to Embodiment (1) of the present invention.
  • FIG. 3 is a view showing a temperature distribution in the carbonization furnace according to Embodiment (1) of the present invention.
  • FIG. 4 is a diagram showing a carbonization furnace of a carbonization apparatus for producing activated carbon according to Embodiment (2) of the present invention.
  • FIG. 5 is a view showing a temperature distribution in the carbonization furnace according to Embodiment (2).
  • the activated charcoal of the present invention is manufactured by continuously performing carbonization treatment and activation treatment in a superheated steam atmosphere on a processing object mainly composed of a wood material, and has a total specific surface area of 600 m 2 / g or less. Pores with an outer specific surface area of 20% to 75% of the total specific surface area It has a distribution structure.
  • the activated carbon of the present invention preferably has 1000 m 2 / g or more, preferably having a total specific surface area of 800 m 2 / g or more.
  • the ratio of the outer specific surface area to the total specific surface area is preferably 35% or more and 75% or less, preferably 50% or more75. Particularly preferred is / 0 or less.
  • the present inventors have continuously performed carbonization treatment and activation treatment in a superheated steam atmosphere on an object to be treated mainly composed of a wood material, thereby providing a total specific surface area force S600m 2 /
  • the inventors have found that activated carbon having a pore distribution structure having a surface area of g or more and an outer specific surface area of 20% to 75% of the total specific surface area can be produced, and the present invention has been completed. That is, in the activated carbon of the present invention, the outer specific surface area, which is the specific surface area excluding micropores having a pore diameter of 2 nm or less, occupies 20% or more and 75% or less of the total specific surface area, and most of them have a pore diameter. This is due to 2-50 nm mesopores.
  • the total specific surface area and the external specific surface area of the activated carbon in the present invention were measured by the following method using a nitrogen adsorption measuring apparatus.
  • the ⁇ plot method proposed by Sing was used to calculate the total specific surface area. Specifically, nitrogen gas adsorption at low relative pressure
  • the ⁇ value is the amount of adsorption W at each relative pressure expressed as ⁇ / ⁇ on the adsorption isotherm.
  • the total specific surface area S is the origin in the a plot.
  • the outer specific surface area S is a micropore.
  • micropore specific surface area S was determined from the total specific surface area S.
  • the activated carbon in the present invention has a specific surface area of 550 m 2 / g or more when expressed using BET specific surface area SBET calculated by the BET method.
  • the BET specific surface area was calculated from the amount of nitrogen gas adsorbed on the activated carbon using the BET equation.
  • FIG. 1 is an overall configuration diagram of a carbonization apparatus for producing activated carbon according to Embodiment (1) of the present invention.
  • FIG. 2 is a view showing a carbonization furnace used in a carbonization apparatus for producing activated carbon.
  • the carbonization apparatus 10 for producing activated carbon introduces the processing object supply means 20 for supplying raw materials such as wood chips to the drying furnace 30, and the steam discharged from the carbonization furnace 40 to introduce the processing object. Is heated by a drying furnace 30 that performs a drying process for discharging the dried processing target and used steam, and the processing target dried in the drying furnace 30 is supplied and heated from the high-temperature steam generator 60.
  • Carbonization is performed by introducing steam and carbonizing and activating the processing target to discharge carbonized carbon and used water vapor. * Carbonization furnace 40 that performs the activation process and activated carbon carbonized in the carbonization furnace 40 are cooled. And a discharge device 50 for storage.
  • the carbonization apparatus 10 for producing activated carbon is discharged from the high-temperature steam generator 60 for generating high-temperature superheated steam supplied from the waste heat boiler 80 and supplied to the carbonization furnace 40, and the drying furnace 30.
  • the deodorizing furnace 70 that heats the impurities contained in the used steam and deodorizes and burns it to discharge high-temperature exhaust, and the high-temperature exhaust gas discharged from the deodorizing furnace 70 heats the water to the high-temperature steam generator 60.
  • Waste heat boiler 80 that generates steam for supply, water supply device 90 that supplies water to the waste heat boiler 80, and exhaust gas after heat exchange in the waste heat boiler 80 after being discharged from the deodorizing furnace 70
  • a dust collector 96 that collects the dust and moisture contained in the dust using a cyclone, etc., and makes it odorless and smoke-free, and an exhaust pipe 98 that releases the exhausted air after dust collection to the atmosphere,
  • the processing object supply means 20 includes a hopper 22 that stores a raw material processing object such as wood chips, a conveyor 24 that supplies the processing object stored in the hopper 22 to a feeder 26, and a drying furnace. 30 is provided with a feeder 26 for weighing and processing objects.
  • a processing object supply port 32 for supplying the processing object weighed by the feeder 26, a cylindrical part 33 for moving the stirring object while stirring and dry-drying the processing object, Stirring blades 34 such as multiple propeller feeders that can be rotated while stirring and moving the processing object in the cylindrical shell 31 while drying and dry distillation, and an outlet for discharging the dried and dry-distilled processing target 35, a steam inlet 36 for introducing the used steam discharged from the carbonization furnace 40 from the outside of the cylindrical portion 33 in the tangential direction (tangential direction) of the cylinder inner surface in the same direction as the rotation direction of the stirring blade 34, Used steam after heating the processing object in the cylindrical shell 31 from the inner surface of the cylindrical portion 33 to the outer side of the cylindrical portion 33 Water vapor outlet 37 is provided to discharge in the direction (tangential direction).
  • a treatment object supply port 42 for supplying the dried treatment object discharged from the discharge port 35 of the drying furnace 30, and the treatment object are carbonized and activated.
  • Rotating stirring blade 44 from the outside of cylindrical part 43 The steam inlet 46 to be introduced in the same direction as the cylinder inner surface tangential direction (tangential direction) and the used steam after heating the processing object in the cylindrical shell 41 from the inner surface of the cylindrical portion 43 to the outer side of the cylindrical portion Tangent direction of inner surface of cylindrical part 43
  • a water vapor outlet 47 is provided to discharge in the (tangential direction).
  • the rotating shaft of the stirring blade configured to be rotatable is provided so as to be parallel to the cylindrical portion 43.
  • the carbonization furnace 40 is arranged so as to be inclined downward from the processing object supply port 42 toward the discharge port 45, and the inclination angle is preferably 0.1 ° to: 10 °. 0.5. It is particularly preferred that the angle be ⁇ 2 °. Since the carbonization furnace 40 is inclined downward from the treatment object supply port 42 toward the discharge port 45, it is possible to move the treatment object reliably and stably in combination with the movement by the stirring blade 44. It becomes.
  • An angle control device for tilting the carbonization furnace 40 is preferably provided.
  • the cylindrical shell 41 of the carbonization furnace 40 continuously includes a carbonization part that carbonizes a processing object mainly composed of a wood material by contacting with superheated steam, and a processing object carbonized in the carbonization part. In this way, it is classified into an activation part that performs activation treatment by contacting with superheated steam.
  • the temperature of the superheated steam at the treatment object supply port 42 is the carbonization start temperature when the carbonization process is started 400.
  • C force is preferred, 500.
  • Ability to be C S Exit 45 The temperature of the superheated steam at the end of the activation process is the end temperature of the activation process at the end of the activation process.
  • the flow rate of superheated steam or used steam supplied to the carbonization furnace 40 is preferably 5 (m / s) or more in order to promote heat transfer to the object to be treated. However, if it is 20 (m / s) or more, problems such as erosion occur in the parts used in the carbonization furnace 40, so there is an appropriate flow velocity range.
  • the steam inlet 46 is preferably provided with a flow rate control valve that controls the flow rate of superheated steam by adjusting the opening area or the like of the steam inlet by a pressure adjusting mechanism or a throttle.
  • the discharge device 50 includes a cooling jacket 52 that cools the activated carbon that has been carbonized and activated in the carbonization furnace 40 with water, and a water-cooled jacket that sends the finished activated carbon to the product tank 54 while cooling the activated carbon.
  • a screw conveyor 56 is provided.
  • the high-temperature steam generator 60 introduces steam from the waste heat boiler 80 into an atmosphere in which LPG or the like is burned by a panner to generate superheated steam.
  • the superheated steam generated by the high-temperature steam generator 60 is supplied to the carbonization furnace 40, and activated carbon is generated by dry distillation, carbonization, and activation of the object to be treated.
  • the deodorization furnace 70 supplies used steam discharged from the carbonization furnace 40 into a combustion atmosphere such as petroleum parner, and includes ammonia, mercabtan, hydrogen sulfide, methyl sulfide contained in the used steam. Deodorizing and burning impurities such as methyl disulfide, trimethylamine, acetoaldehyde, and styrene, and exhausting high-temperature exhaust.
  • the waste heat boiler 80 heats water in multiple stages using the high-temperature exhaust discharged from the deodorization furnace 70 to generate steam (dry steam), and supplies the steam to the high-temperature steam generator 60.
  • the dust collector 96 collects dust (solid matter, etc.) and water contained in the exhaust gas after being exchanged in the waste heat boiler 80 after being discharged from the deodorizing furnace 70 using a cyclone or the like. At the same time, the smoke-free process is performed. In addition, the exhaust pipe 98 discharges clean exhaust air after dust collection to the atmosphere.
  • the deodorizing furnace blower 72 is operated to supply combustion air to the deodorizing furnace 70.
  • Kerosene is supplied from the kerosene tank 74 to the deodorizing furnace 70 using the kerosene pump 76, and combustion is started.
  • 800 to 1200 (° C) exhaust is discharged, and this high-temperature exhaust is supplied to the waste heat boiler 80.
  • the soft water stored in the soft water tank 94 is pumped by the feed water pump 95 via the water softener 92 of the water supply device 90 and supplied to the waste heat boiler 80.
  • the In the latter stage of the waste heat boiler 80 the supplied soft water is heated to a high temperature. Further, it is supplied to the front stage of the waste heat boiler 80 to generate 150 to 300 (° C.) superheated steam (dry steam) and supply it to the high temperature steam generator 60.
  • the blower 62 is operated to supply combustion air to the high temperature water steam generator 60.
  • LPG is supplied from the LPG cylinder 64 through the governor 66 to the panner 68 and ignited.
  • the steam of 150 ° C to 300 ° C introduced from the waste heat boiler 80 is further heated to produce superheated steam of 750 ° C to 950 ° C, more preferably 880 ° C to 920 ° C. And then supplied to the carbonization furnace 40.
  • a processing object such as a wood material that is a source of activated carbon is put in the hopper 22 of the processing object supply means 20 and stored in advance.
  • the processing object stored in the hopper 22 is supplied to the feeder 26 by the conveyor 24 provided in the processing object supply means 20.
  • the feeder 26 measures and supplies a predetermined amount of processing object to the drying furnace 30 as appropriate.
  • the processing object is supplied into the processing object supply port 32 force cylindrical shell 31 provided in the cylindrical shell 31 of the drying furnace 30. Since the stirring blade 34 is rotating inside the cylindrical shell 31, the processing object is gradually moved toward the discharge port 35 while being stirred in the cylindrical portion 33 in the cylindrical shell 31.
  • the used superheated steam of 750 ° C to 950 ° C discharged from the carbonization furnace 40 from the steam inlet 36 is in the same direction as the rotation direction of the stirring blade 34 from the outside of the cylindrical portion 33.
  • Cylindrical Introduced in the inner tangential direction (tangential direction) generating strong vortices. Therefore, the superheated steam undergoes a reaction such as heat decomposition or hydrolysis without being mixed well with the object to be treated which is stirred and moved by the stirring blade 34.
  • the object to be treated is heated, dried, and dry-distilled by the superheated steam, and proceeds through the cylindrical part 33 toward the water vapor outlet 37, and the used superheated steam is circular from the inner surface of the cylindrical part 33.
  • the cylinder part 33 is discharged in the tangential direction (tangential direction) of the inner surface.
  • the steam outlet 37 is provided so that the used superheated steam is discharged in the tangential direction of the inner surface of the cylindrical part 33, the swirling flow of the superheated steam in the cylindrical part 33 is maintained, and Keeping the relative flow rate high, promote heat transfer.
  • the superheated steam is introduced from the outside of the cylindrical portion 33 at a flow rate of 5 to 20 (m / s) in the tangential direction of the inner surface of the cylinder in the same direction as the rotation direction of the stirring blade 34. Try to generate a vortex.
  • the superheated steam is sprayed from the side surface of the cylindrical portion 33 near the product outlet 35 at a flow rate of 5 to 20 (mZs) in the circumferential tangential direction, and the steam outlet provided near the inlet of the processing object supply port 32 is used. From the outlet 37, it discharges toward the circumferential tangential direction in the same rotational direction as the stirring blade 34.
  • This structure facilitates the transfer of heat to the object to be processed because the steam moves in the reactor while maintaining a large relative velocity with the object to be processed to some extent with a swirling flow.
  • the temperature of the water approaches that of water vapor, and various reactions such as drying and dry distillation are promoted.
  • the used superheated steam near the processing object supply port 32 or the steam discharge port 37 has a temperature of 250 ° C to 600 ° C. 300 ° C to 500 ° Especially preferred to have a temperature of C.
  • This used water vapor contains harmful substances such as nitrogen compounds and odors.
  • the deodorizing furnace 70 the harmful water contained in the used water vapor is burned together with kerosene, etc. 800 Upon heating to a temperature of ° C to 1200 ° C, harmful substances are decomposed.
  • the processing object dried in the drying furnace 30 is discharged from the discharge port 35 and supplied to the carbonization furnace 40 of the next processing step.
  • the object to be processed discharged from the drying furnace 30 is provided in the cylindrical shell 41 of the drying furnace 40 and supplied to the inside of the cylindrical shell 41 through the processing object supply port 42 force. Since the stirring blades 44 are rotating inside the cylindrical shell 41, the processing object is gradually moved toward the discharge port 45 while being stirred in the cylindrical portion 43 in the cylindrical shell 41.
  • the superheated steam supplied from the high-temperature steam generator 60 is introduced from the steam inlet 46 into the cylinder inner surface tangential direction (tangential direction) in the same direction as the rotation direction of the stirring blade 44 from the outer side of the cylindrical portion 43.
  • a strong swirl flow of water vapor is generated. Therefore, the superheated steam is well mixed with the object to be treated that is being stirred and moved by the stirring blade 44.
  • the cylindrical part 43 advances toward the water vapor outlet 47, and the used water vapor moves from the inner surface of the cylindrical part 34 to the outer side of the cylindrical part.
  • the steam outlet 47 is provided so that the used steam is discharged in the tangential direction of the inner surface of the cylindrical part 43, so that a reaction such as thermal decomposition or hydrolysis is promoted while being well mixed with the object to be treated.
  • FIG. 3 shows a temperature distribution in the carbonization furnace according to Embodiment (1) of the present invention.
  • the temperature distribution in the furnace is such that the temperature rises from the treatment object supply port 42 to the discharge port 45 of the carbonization furnace 40 and the temperature of the superheated steam rises from the start to the end of the carbonization activation process.
  • the temperature of the superheated steam is set so that Specifically, the temperature of superheated steam is 400 ° C to 700 ° C in the carbonization part that carbonizes the processing object mainly composed of wood material, and the processing object carbonized in the carbonization part is continuous. It is particularly preferable to set the average temperature of the superheated steam in the activation part to be 750 ° C to 900 ° C, particularly preferably 750 ° C to 850 ° C.
  • the temperature of the superheated steam at the processing object supply port 42 when starting the carbonization process is set to 400 ° C to 700 ° C. It is particularly preferable that the temperature of the superheated steam at the outlet 45 at the end of the activation process at 800 ° C to 920 ° C is 800 ° C to 880 ° C. preferable.
  • the residence time in the activation part which is carried out after the carbonization of the object to be treated in the apparatus, is preferably about 10 to 30 minutes. If the residence time is insufficient, the generation of pores is insufficient, and if the residence time is too long, the pore size develops too much and the specific surface area may decrease.
  • activated carbon generated as a result of carbonization and activation in the carbonization furnace 40 is discharged from the discharge port 45 and supplied to the discharge device 50. If high-temperature activated carbon discharged from the carbonization furnace 40 is placed in an oxygen atmosphere, it may be recombusted. Therefore, it is cooled by a cooling jacket 52 provided in the discharge device 50. Further, the activated carbon is cooled and stored in the product tank 54 by a screw conveyor 56 with a water cooling jacket.
  • the present invention uses two types of reactors to carbonize. It is not limited to the example of processing.
  • high-temperature superheated steam is generated by using superheated steam that has been heat-recovered from the high-temperature exhaust discharged from the deodorizing furnace 70 in accordance with the type and amount of the object to be treated. Even if superheated steam is introduced into a dry carbonization furnace (first reactor) to dry the object to be treated, it is carbonized and used steam is discharged to achieve the object of the present invention. It is possible.
  • a carbonization promotion furnace (third reaction furnace) that introduces superheated steam to promote carbonization of the object to be processed and discharges used steam, and steam discharged from the carbonization promotion furnace is introduced.
  • Carbonization furnace (second reactor) that discharges used steam by carbonizing the object to be processed, and drying that discharges used steam by introducing the steam discharged from the carbonization furnace power and drying the object to be processed
  • the furnace first reactor
  • high-temperature steam generator that generates high-temperature superheated steam to introduce steam into the carbonization furnace
  • a deodorizing furnace that heats impurities to deodorize and burn high-temperature exhaust, and a waste that generates water to heat and supply steam to the high-temperature steam generator using the high-temperature exhaust discharged from the deodorizing furnace.
  • a multi-stage reactor is cascaded with a thermal boiler Also it is possible to achieve the purposes of the present invention as active carbon for producing carbide device for carbonizing the treated object by use.
  • FIG. 4 shows a carbonizing furnace of the carbonizing apparatus for producing activated carbon according to the embodiment (2) of the present invention.
  • FIG. 5 shows the furnace temperature distribution in the carbonization furnace according to Embodiment (2).
  • the carbonization furnace 40 is provided with one steam inlet 46 as shown in Fig. 2, but as shown in Fig. 4, the activation part of the carbonization furnace 40 is provided. It is also possible to provide a plurality of steam inlets 46, 46A, 46B only on the side. By providing a plurality of water vapor inlets 46, 46A, 46B in the carbonization furnace 40, it becomes possible to increase the force S to heat the object to be processed to a high temperature in the activation part. In this case, the average superheated steam in the activation part of the carbonization furnace 40 The temperature is preferably 750 ° C to 900 ° C, particularly preferably 750 ° C to 850 ° C.
  • a low temperature gas introduction port 48 for additionally introducing a low temperature gas of 150 to 300 ° C. is provided near the processing object supply port 42 of the carbonization section.
  • each of these steam inlets 46, 46A, 46B allows superheated steam discharged from the high-temperature steam generator 60 to be tangential to the inner surface of the cylinder in the same direction as the rotation direction of the stirring blade 44 from the outer side of the cylindrical part 43 ( In the tangential direction). If the number of steam inlets is increased more than necessary, the superheated steam flow per steam inlet may be weakened and the swirling flow of superheated steam may be weakened.
  • the thinned wood chips that have been processed to a size that can be processed are put into the hopper 22 of the processing object supply means 20 and stored in advance.
  • the processing object stored in the hopper 22 is supplied to the feeder 26 by the conveyor 24 provided in the processing object supply means 20.
  • the object to be treated supplied to the drying furnace 30 is gradually moved in the direction of the discharge port 35 while being agitated by the stirring blade 34 inside the cylindrical shell 31 and dried.
  • the processing object dried in the drying furnace 30 is discharged from the discharge port 35 and supplied to the carbonization furnace 40 of the next processing step, and carbonization and activation are performed.
  • the inside of the carbonization furnace 40 is 80 from the steam inlet 36. Superheated steam at 0 ° C.
  • the introduced superheated steam was set so that the average temperature of the superheated steam in the activation process in the carbonization furnace 40 was 760 ° C.
  • the activated carbon produced as a result of carbonization and activation in the carbonization furnace 40 was discharged from the discharge port 45, and the specific surface area, pore structure evaluation, and electric double layer capacitor capacity of the obtained activated carbon were measured.
  • Example 2 The same procedure as in Example 1 was performed except that the temperature of the superheated steam introduced from the steam inlet was set to 874 ° C and the average temperature of the superheated steam in the activation process in the carbonization furnace 40 was set to 840 ° C. It was.
  • Example 3 the temperature of the superheated steam introduced from the steam inlet is set to 828 ° C, and a reaction such as carbonization or activation is performed while being well mixed with the processing target being stirred and moved by the stirring blade 34. It is a ⁇ row.
  • Example 4 the temperature of the superheated steam introduced from the steam inlet is set to 832 ° C, and the reaction such as carbonization or activation is performed while being well mixed with the processing target being stirred and moved by the stirring blade 34. It is a ⁇ row.
  • Example 5 the temperature of superheated steam introduced from the steam inlet is set to 849 ° C., and the reaction such as carbonization or activation is performed while being well mixed with the object to be stirred and moved by the stirring blade 34. It is a ⁇ row.
  • Example 2 The same procedure as in Example 1 was performed except that the temperature of the superheated steam introduced from the steam inlet was set to 780 ° C and the average temperature of the superheated steam in the activation process in the carbonization furnace 40 was set to 745 ° C. It was.
  • the temperature of superheated steam introduced from the steam inlet is set to 940 ° C, and the temperature inside the carbonization furnace 40 is increased.
  • the same procedure as in Example 1 was performed except that the average temperature of superheated steam in the active process was 905 ° C.
  • the activated carbon produced in each Example and Comparative Example is pulverized in an agate mortar to obtain an activated carbon powder, and the obtained activated carbon powder is heat-treated at 900 ° C. for 1 hour in a nitrogen stream. After that, it was dried in a gas adsorption measurement cylinder at 300 ° C for several hours in a vacuum, and the activated carbon powder was weighed. The activated carbon powder was placed in an aluminum foil container to prevent scattering in a vacuum. And the adsorption curve of high purity nitrogen gas was measured at 77K. Then, the adsorption of nitrogen gas at the nitrogen gas relative pressure PZP ⁇ 0.3 in the obtained nitrogen gas adsorption curve.
  • the BET specific surface area SBET was measured by a multipoint method.
  • the specific surface area of the micropore was calculated by the Hi-Plot method proposed by Sing. Low relative
  • the total specific surface area S, the outer specific surface area S, and the micropore specific surface area S were determined.
  • Table 1 shows data on the specific surface area of the activated carbon obtained in (Examples:! To 5) and (Comparative Examples 1 and 2).
  • the activated carbons obtained in Examples 1 and 2 have not only a large BET specific surface area and a large total specific surface area, but also the ratio of the external specific surface area to the total specific surface area. 0. 49, 0. 46 and ⁇ ⁇ always large for 0.12, 0.17 respectively I understand.
  • the electric double layer capacitor was measured for the activated carbon.
  • the current density was changed from 50 mA to 1000 mA in 1 MH SO electrolyte, and the current was changed.
  • Table 2 shows the measurement results for the activated carbon obtained in Examples 1 and 2.
  • Table 2 also shows the results of measurements on commercially available coconut shell activated carbon for capacitors as Reference Example 1.
  • the sample for measurement was obtained by mixing activated carbon powder obtained by pulverizing activated carbon in an agate mortar, acetylene black, and PTFE powder at a ratio of 80:10:10 and forming into a film shape.
  • the film thickness used was about 100 mm.
  • the activated carbons obtained in Examples 1 and 2 and Examples 6 to 9 have a rate performance of 0.63 to 0.77 which is larger than that of commercially available activated carbon. It can be seen that it can be suitably used as an electrode of an electric double layer capacitor. Also, the steam inlet temperature is large (0.71 or more) when the temperature is 800 ° C (Example 1), 874 ° C (Example 2), 887 ° C (Example 8), and 937 ° C (Example 9). ) Activated carbon with Rate Performance is obtained.
  • This invention uses a wood-based material as a raw material to perform carbonization treatment such as drying, dry distillation, activation, etc.
  • carbonization treatment such as drying, dry distillation, activation, etc.
  • it can be used for the purpose of producing activated carbon having a large specific surface area and a pore structure suitable for an electric double layer capacitor of an aqueous electrolyte.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Coke Industry (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

L'invention concerne un charbon actif fabriqué à partir d'une matière première organique, telle qu'un matériau ligneux, qui présente une grande surface spécifique et une structure de pores appropriée pour un condensateur électrique à double couche, et un procédé de fabrication de celui-ci. Le charbon actif décrit est fabriqué en soumettant la matière première principalement composée d'un matériau ligneux à un traitement de carbonisation et un traitement d'activation réalisés en continu sous une atmosphère de vapeur surchauffée, lequel charbon actif présente une surface spécifique totale de 600 m²/g ou plus et une structure de distribution des pores telle que la surface spécifique externe occupe 20 à 75 % de la surface spécifique totale.
PCT/JP2007/057759 2006-04-10 2007-04-06 Charbon actif, procédé de fabrication de celui-ci, et appareil de production Ceased WO2007119698A1 (fr)

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WO2011003434A1 (fr) * 2009-07-10 2011-01-13 BLüCHER GMBH Installation et procédé de production de charbon actif
WO2012060159A1 (fr) * 2010-11-04 2012-05-10 新熱工業株式会社 Dispositif et procédé de traitement de carbonisation d'un matériau de résine
CN104609419A (zh) * 2015-02-13 2015-05-13 洛阳月星新能源科技有限公司 一种活性炭材料、制备方法和超级电容器
CN105618025A (zh) * 2016-01-14 2016-06-01 北京道顺国际技术开发有限责任公司 一种磺化炭低温催化有机废弃物制备生物质炭的方法
CN115244230A (zh) * 2020-03-13 2022-10-25 帝人株式会社 碳纤维电极基体材料的制造方法及制造装置

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JP5935039B2 (ja) * 2012-02-23 2016-06-15 地方独立行政法人青森県産業技術センター 活性炭製造方法
JP5099939B1 (ja) * 2012-05-02 2012-12-19 春男 上原 活性炭製造システム
CN103851633A (zh) * 2014-02-20 2014-06-11 煤炭科学研究总院 一种多膛炉尾气净化处理及余热利用方法
WO2016208669A1 (fr) * 2015-06-26 2016-12-29 サンコール株式会社 Dispositif de carbonisation
JP6815763B2 (ja) * 2015-06-26 2021-01-20 サンコール株式会社 炭化装置
MA49239A (fr) * 2017-03-23 2021-04-28 Act&Sorb Carbonisation et activation d'un matériau contenant du carbone
WO2025216133A1 (fr) * 2024-04-10 2025-10-16 パナソニックＩｐマネジメント株式会社 Condensateur électrochimique

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WO2011003434A1 (fr) * 2009-07-10 2011-01-13 BLüCHER GMBH Installation et procédé de production de charbon actif
KR101436864B1 (ko) 2009-07-10 2014-09-02 블뤼허 게엠베하 활성탄을 제조하기 위한 장치 및 방법
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WO2012060159A1 (fr) * 2010-11-04 2012-05-10 新熱工業株式会社 Dispositif et procédé de traitement de carbonisation d'un matériau de résine
CN104609419A (zh) * 2015-02-13 2015-05-13 洛阳月星新能源科技有限公司 一种活性炭材料、制备方法和超级电容器
CN104609419B (zh) * 2015-02-13 2016-10-05 洛阳月星新能源科技有限公司 一种活性炭材料、制备方法和超级电容器
CN105618025A (zh) * 2016-01-14 2016-06-01 北京道顺国际技术开发有限责任公司 一种磺化炭低温催化有机废弃物制备生物质炭的方法
CN105618025B (zh) * 2016-01-14 2018-04-17 北京道顺国际技术开发有限责任公司 一种磺化炭低温催化有机废弃物制备生物质炭的方法
CN115244230A (zh) * 2020-03-13 2022-10-25 帝人株式会社 碳纤维电极基体材料的制造方法及制造装置

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