WO2004007820A1 - 微細炭素繊維の製造方法 - Google Patents
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- WO2004007820A1 WO2004007820A1 PCT/JP2003/009027 JP0309027W WO2004007820A1 WO 2004007820 A1 WO2004007820 A1 WO 2004007820A1 JP 0309027 W JP0309027 W JP 0309027W WO 2004007820 A1 WO2004007820 A1 WO 2004007820A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
Definitions
- the present invention relates to a method for producing fine carbon fibers such as vapor-grown carbon fibers and carbon nanotubes, and more particularly, to a technique for continuously and stably producing fine carbon fibers at low cost.
- Carbon nanotubes are a type of vapor-grown carbon fiber (VGCF) that has been studied for a long time, and have various names depending on the thickness of the fiber. In general, those with a fiber diameter of 1 or more are vapor-grown carbon fiber (VGCF), those with a fiber diameter of 50 nm or less are carbon nanotubes (CNT), and those with a fiber diameter of 50 nm between them. Larger and smaller than 1 m are called carbon nanofibers (CNF).
- VGCF vapor-grown carbon fiber
- CNT carbon nanotubes
- CNF carbon nanofibers
- the crystal structure of these fine carbon materials takes a variety of forms, including single-walled carbon nanotubes (SWNTs), each of which is made up of a single layer of graphene sheet made of carbon, and multiple layers of graphene. Sheets are laminated and have a concentric laminated structure (or an annual ring-shaped structure) as a multi-walled carbon nanotube (MWNT), and further, a crystal structure intermediate between the two, that is, a crystal plane is formed. There is a nano-cone having a cone-shaped crystal structure that spreads at a certain angle with respect to its central axis.
- SWNTs single-walled carbon nanotubes
- MWNT multi-walled carbon nanotube
- the fine carbon material having a shape other than the tube shape examples include a ribbon-like fine carbon material having a structure in which graph ensheets are laminated so as to be orthogonal to the fiber direction, and a coil-like material having an amorphous structure which does not exhibit crystallinity.
- carbon nanotubes can be used as electron beam sources used in image display devices and semiconductor manufacturing devices and as filler materials for composite materials. It is preferable that the fibers have high crystallinity and are straight, and that the fiber diameter is small and uniform. If the carbon nanotubes are not straight and are forced, the carbon fibers are likely to be entangled with each other and easily become flocked. When it becomes a floc, it is difficult to grind and it is difficult to arrange carbon fibers when used. In addition, even when added to a resin or the like as a filler material, it is difficult to uniformly disperse, and it is difficult to obtain a composite material having desired characteristics.
- the arc method and the laser method have a low productivity because it is difficult to scale up the manufacturing equipment, and it is also difficult to make the manufacturing process continuous.
- the arc method and the laser method have a low productivity because it is difficult to scale up the manufacturing equipment, and it is also difficult to make the manufacturing process continuous.
- non-fibrous carbon is easily generated at the same time, so the production efficiency is low, and it is also difficult to separate and collect carbon nanotubes and non-fibrous carbon. Therefore, it is difficult to produce high quality carbon nanotubes suitable for industrial products using the arc method or the laser method.
- the CVD method is the most preferable method for mass production, but it is difficult to reduce the fiber diameter by the CVD method, and the fiber diameter tends to be uneven. Furthermore, even if the fiber diameter can be reduced according to the manufacturing conditions, there is a problem that curled carbon nanotubes are easily generated.
- the CCVD method which uses a fixed layer carrying a catalyst to produce carbon nanotubes with a small fiber diameter, has attracted attention.
- the production of carbon nanotubes by the CCVD method is almost the same as the CC VD method studied in the early stage of the development of the VGCF, except that a porous material having fine pores such as zeolite as a carrier is used. It differs in that it is used.
- fine catalyst particles can be produced using these pores, and it has become possible to produce extremely fine carbon nanotubes.
- FIG. 5 is a schematic configuration diagram of a production process for producing fine carbon fibers by a conventional batch-type CCVD method.
- the manufacturing apparatus 200 shown in this figure includes a cylindrical reactor 201 arranged horizontally, a heater 202 disposed around the outer periphery of the reactor 201 to heat the reactor 201 from outside, and
- the reactor 201 includes a source gas supply unit 203 and a carrier gas supply unit 204 connected to the right end of the reactor 201 in the figure, and a supported catalyst supply unit 205 connected to the left end of the reactor 201 in the figure.
- a first carbon fiber recovery section 206 for recovering the supported catalyst introduced into the reaction furnace from the supported catalyst supply section 205 and subjected to the reaction together with the fine carbon fibers generated on the supported catalyst is provided in the reaction furnace.
- a bag filter 208 is connected to the right end of the reactor 201 to derive the post-reaction gas from the reactor 201 and separate the post-reaction gas into fine carbon fibers and exhaust gas. Connected to the side.
- the bagfill 208 has a gas discharge section 208a and a solid discharge section 208b.
- An exhaust gas treatment device 210 is connected to the gas discharge portion 208a, and a second carbon fiber recovery portion 209 is connected to the solid discharge portion 208b.
- the fine carbon fibers which are discharged to 210 and are solid are collected by the second carbon fiber collecting section 209.
- a supported catalyst such as zeolite supporting a catalyst is introduced from a supported catalyst supply unit 205 into a reaction furnace 201 into which a raw material gas and a carrier gas have been charged, and a chemical thermal decomposition reaction is performed.
- a chemical thermal decomposition reaction is performed.
- fine carbon fibers are grown on the supported catalyst.
- the supported catalyst holding the fine carbon fibers on the surface is recovered to the first carbon fiber recovery unit 206.
- the reaction After the reaction, the post-reaction gas is discharged from the reactor 201 to the bag filter 208, and separated into fine carbon fibers and exhaust gas by the bag filter 208.
- fine carbon fibers separated by the bag filter 208 are collected in the carbon fiber collection unit 209, and the exhaust gas is sent to the exhaust gas treatment device 210.
- fine carbon fibers can be produced by the CC VD method using the production apparatus shown in FIG.
- the unreacted raw material gas and low- and high-boiling components of by-products are contained in the gas after being subjected to the reaction.
- exhaust gas treatment such as combustion treatment or adsorption treatment is required.
- a large amount of carrier gas is used as described above, so that the amount of exhaust gas itself increases and the cost of exhaust gas treatment increases.
- sulfuric acid such as hydrogen sulfide and thiophene
- sulfuric acid such as hydrogen sulfide and thiophene
- the sulfur compound is contained in the exhaust gas after the reaction, so it is necessary to remove the sulfur compound.
- the treatment cost becomes extremely large due to the large amount of the exhaust gas itself.
- the present invention is intended to continuously and stably produce fine carbon fibers such as vapor-grown carbon fibers and carbon nanotubes having an arbitrary fiber diameter, particularly a fine fiber diameter, at a low cost. It is an object of the present invention to provide a method for producing fine carbon fibers that can be used. Disclosure of the invention
- the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, using ultra-fine particles composed of transition metal as a catalyst, a chemical pyrolysis method of CO and organic compounds (C VD method and CC VD method).
- C VD method and CC VD method a chemical pyrolysis method of CO and organic compounds
- high-quality fine carbon fibers with extremely small fiber diameters are obtained by using at least one organic compound containing a Group VIB element of the periodic table of elements in the molecule as a raw material. Fibers are produced, and when such an organic compound is used as a raw material, reaction by-products and undecomposed raw materials can be easily separated and recovered from the gas after the reaction, and the carrier gas and the carrier gas can be recycled by recycling the gas after the reaction to the reaction furnace. It has been found that the amount of exhaust gas can be reduced.
- a raw material gas composed of an organic compound, a carrier gas composed of hydrogen and Z or an inert gas, and an ultrafine catalyst containing at least one transition metal are introduced into a reaction furnace.
- a chemical pyrolysis reaction in the reaction furnace wherein an organic compound containing a Group III element of the Periodic Table of Elements in the molecule is used as a raw material organic compound.
- the reaction is carried out in 2 X 1 0 5 P a pressure below.
- the post-reaction gas preferably a gas obtained by removing by-products and undecomposed gas from the post-reaction gas, is re-introduced into the reaction furnace by a recycle means connected to the reaction furnace and used.
- Examples of the organic compound containing a Group VIB element in a molecule used in the present invention include, as compounds containing oxygen, alcohols, ketones, phenols, ethers, aldehydes, organic acids, and esters. .
- sulfur compound examples include thiols, thioethers, and thiophenes, and thiophene is particularly preferably used.
- These starting organic compounds can be supplied to a reaction furnace by spraying a liquid, a solution or a solid even in a gaseous state.
- a fine carbon fiber is produced by a CVD method or a CCVD method, and ultrafine particles made of a transition metal are used as a catalyst.
- Transition metals include, for example, iron, connort, nickel, yttrium, titanium
- Vanadium, manganese, chromium, copper, niobium, molybdenum, palladium, tungsten, platinum, and the like can also be used as a catalyst. Further, these may be used alone or in combination of two or more selected from them. Depending on the combination, a greater catalytic effect can be obtained.
- the form of the compound may be an organic compound, an inorganic compound, or a combination thereof. Can be used.
- the organic compound Hua-Sen, nickel sen, cobalt sen and the like can be used.
- the inorganic compound may be in any form such as an oxide, a nitrate, a sulfate, and a chloride.
- sulfur, H 2 S, CS 2, S 0 2 it may be added to the sulfur compound such Chiofen.
- the starting organic compound is an organic compound such as a hydrocarbon containing no Group VIB element in the molecule.
- the catalyst may be the metal or compound fine particles as they are (CVD method), or the metal or compound may be supported on the inorganic carrier of the fine particles (CCVD method).
- the inorganic carrier for example, alumina, zeolite, carbon, magnesium, calcium and the like can be used.
- any method such as a method of gasifying alone, a method of mixing with a carbon raw material and then gasifying, a method of diluting with a carrier gas, and a method of dissolving in a carbon raw material and charging it in a liquid state are used. Good.
- the post-reaction gas used for producing the fine carbon fibers is re-introduced into the reaction furnace by the recycling means, so that the post-reaction gas, which has been conventionally exhausted as exhaust gas, is discharged to the outside. Can be used effectively.
- the amount of carrier gas used can be reduced and the amount of exhaust gas can also be reduced, so that both the cost of carrier gas and the cost of exhaust gas treatment can be reduced. Therefore, it is possible to reduce the cost related to the production of fine carbon fibers as compared with the related art.
- the production of the fine carbon fiber of the present invention is a method of producing a fine carbon fiber by a chemical pyrolysis method using an organic compound containing a Group VIB element as a raw material and using ultrafine particles composed of a transition metal as a catalyst.
- Carrier gas supply unit carbon fiber separation device for separating and recovering the fine carbon fibers generated inside the reactor from the gas after the reaction, and recycling for cooling the gas after the reaction and introducing it into the reactor again It is carried out by a process comprising means and preferably a device for condensing and separating condensed components in the gas after the reaction.
- the separation device is connected to a carbon fiber recovery device, and the fine carbon fiber separated from the gas after the reaction by the separation device is recovered to the fine carbon fiber recovery device.
- the cooling gas is passed through another separation device to further collect fine carbon fibers.
- the gas that has exited the fine carbon fiber recovery apparatus can be discharged as it is after exhaust gas treatment.
- the gas from which the fine carbon fiber has been recovered is recycled to the reaction furnace by the recycling means.
- the gas is further cooled to condense condensed components such as water generated by the reaction in the gas and unreacted raw materials, and then separated and introduced into a reaction furnace.
- the separated condensate is discharged after drainage treatment.
- unreacted raw materials can be separated from condensate and recycled as raw materials.
- unreacted raw material compounds, generated water, and high-boiling by-products may also adhere to the fine carbon fiber that is the product obtained from the separation and recovery device, so the product is once heated and vaporized.
- a method combining one or two or more of distillation, PJ: deposition, and membrane separation can be used.
- the fine carbon fiber is separated from the post-reaction gas, and the fine carbon fiber is also recovered from the cooled post-reaction gas. It is possible to prevent an increase in production cost due to a decrease in recovery rate.
- the fine carbon fibers produced by the chemical pyrolysis reaction have extremely low bulk density and are light, so that all or those separated from the catalyst float in the reactor. Therefore, these fine carbon fibers and reaction by-products accompany the post-reaction gas discharged from the reactor. Then, when the fine carbon fibers are mixed with the gas to be recycled and re-introduced into the reaction furnace and subjected to the reaction, the carbon further grows on the fine carbon fibers, and the fiber diameter becomes coarse ( There is a possibility that the desired fiber diameter may not be obtained. Therefore, in the present invention, by providing the separation means, the fine carbon fibers in the gas after the reaction are removed, so that only the gas components are re-introduced into the reaction furnace, and the fiber diameter is prevented from being increased. ing. Thus, fine carbon fibers having a desired fiber diameter can be stably manufactured.
- a filter / cyclone having a function of efficiently separating a solid from a gas, or a combination thereof is preferably used as a separating means.
- the selection of these filters and cyclones may be appropriately selected according to the amount of gas, the temperature, and the like. For example, if the amount of post-reaction gas is large, the amount of fine carbon fibers recovered by the separation means also increases, so it is necessary to prevent the load on one filter from increasing. In this case, a combination of a large-filled filter and a fine-filled bag filter or a combination of a cyclone and a bag filter may be used.
- the gas discharged from the reactor has a high temperature of about 600 ° C or more, depending on the temperature of the reactor.
- a cooling means such as a water cooling jacket is provided in the path from the reaction furnace or the carbon fiber recovery section to the separation device to cool the post-reaction gas. Then, after cooling to 40 ° C. or more and 150 ° C. or less (preferably 100 ° C. or less) by this cooling, separation by a bag filter may be performed.
- a filter that can withstand as high a temperature as possible, since a solid product that is difficult to cool may be mixed in the gas after the reaction.
- the gas after separating the fine carbon fibers is further cooled to collect unreacted raw material organic compounds and condensates such as generated water and separate them.
- the separation can be an apparatus combining at least one of distillation, adsorption and membrane separation.
- the temperature of the gas re-introduced into the reaction furnace is preferably set to 40 ° C. or higher.
- the post-reaction gas discharged from the reactor includes unreacted hydrocarbons and organic compounds with low and high boiling components. Included as a by-product.
- these organic compounds adhere to the inner surface of the manufacturing apparatus, there is a possibility that the pipes constituting the manufacturing apparatus may be blocked. In order to manufacture safely, it is necessary to take measures to prevent these pipes from clogging.
- the present inventor has conducted various studies on the manufacturing conditions for the purpose, and as a result, if at least the temperature of the gas passed through the recycling means and re-introduced into the reactor is set to 40 ° C. or more, It has been found that the precipitation of such organic compounds can be almost completely prevented, and as a result, clogging of the piping can be prevented.
- the gas temperature by setting the gas temperature to 40 ° C or higher when passing through the recycling means where the temperature of the gas is the lowest in the entire manufacturing equipment, the raw material gas in the equipment, the post-reaction gas, or the recycled gas Gas power and organic compounds can be prevented from precipitating. Therefore, if the temperature of the gas is less than 40 ° C at the position where the temperature of the gas is the lowest, the temperature may be maintained at 40 ° C or more by keeping or heating by means such as coating as necessary. To do.
- the temperature of the gas that passes through the inside of the recycling means and is re-introduced into the reaction furnace is 60 ° C. or higher. That is, if the temperature of the gas is set to 60 ° C. or higher, the precipitation of the organic compound from the gas can be more effectively suppressed, so that more stable production is possible.
- the position where the reaction gas is reintroduced into the reaction furnace may be directly returned to the reaction furnace, or may be reintroduced into the reaction furnace after being mixed with the raw material gas and Z or the carrier gas. In the latter case, for example, when a liquid raw material is gasified and used, it is preferable to raise the temperature of the reacted gas in advance to a predetermined temperature so that the raw material gas and the mixed gas after the reaction do not liquefy. .
- the post-reaction gas is re-introduced into a reaction furnace by a recycling means and used.
- the concentration is preferably 50% or more.
- the amount of gas re-introduced into the reactor for recycling is at most the same as the amount of carrier gas introduced into the reactor.
- the pressure is positive with respect to the atmospheric pressure.
- the gas after the reaction when the gas after the reaction is circulated and reused, the gas after the reaction always contains hydrogen gas and raw material organic compounds. If oxygen is mixed into this hydrogen gas or organic compound, a fire or a large explosion may occur. In order to prevent this, it is necessary to maintain the inside of the system including the piping at positive pressure instead of negative pressure. In particular, since the suction side of the gas circulating means for circulating gas in the device is most likely to be under negative pressure, it is preferable to take measures to prevent this part from being under negative pressure.
- the following measures can be taken to prevent negative pressure.
- a safety gas for example, an inert gas such as N 2 or A 1-
- an inert gas such as N 2 or A 1-
- a circulation system for adjusting pressure is added before and after the gas circulation means.
- the raw material gas supplied from the raw material gas supplied from the raw material gas
- a reaction gas may be generated by separately or mixing with a carrier gas supplied from a carrier gas supply source, and the reaction gas may be supplied to a reaction furnace. In the latter case, a raw material gas and a carrier gas are mixed to generate a reactive gas, and this reactive gas is introduced into a reactor.
- the recycled gas is mixed with the carrier gas and introduced into the reactor.
- FIG. 1 is a configuration diagram schematically showing a manufacturing process according to an embodiment of the reference example.
- FIG. 2 is a configuration diagram schematically showing the manufacturing process of the first embodiment.
- FIG. 3 is a configuration diagram schematically showing the manufacturing process of the second embodiment.
- FIG. 4 is a configuration diagram schematically showing the manufacturing process of the third embodiment.
- FIG. 5 is a diagram schematically showing a conventional production process by a batch CCVD method.
- FIG. 1 is a configuration diagram schematically showing a process for producing fine carbon fibers which is an embodiment of a reference example serving as a reference of the present invention.
- the manufacturing process of the present invention shown in this figure is a manufacturing process for manufacturing fine carbon fibers by the CC VD method, and includes a cylindrical reactor 3 and a raw material gas supply unit connected to the inlet end of the reactor. 2.Carrier gas supply unit 1 and catalyst input device 20; Fine carbon fiber separation and recovery device 4 connected to the outlet end of reactor 3; Fine carbon connected to the bottom of fine carbon fiber separation and recovery device 4 Fiber recovery tank 8, post-reaction gas cooling device 6 connected to the upper part, second fine carbon fiber separation and recovery device 5 for further separating fine carbon fibers from the cooling gas, and exhaust gas treatment device 1 and 2.
- the reactor 3 is heated to 600 ° C or higher and 125 ° C or lower by a heater provided in the reactor 3. .
- the temperature of the above-mentioned reactor is an example of the production conditions. Actually, the temperature of the carbon source (oxygen-containing organic compound, etc.) used as a raw material, the type of catalyst, the type of carrier gas, etc. The optimum condition is set by the combination of.
- a raw material gas composed of an organic compound containing a Group VIB element in a molecule is introduced into the reaction furnace 3 from the raw material supply unit 2, and hydrogen, methane, or an inert gas is introduced.
- the carrier gas composed of the above is introduced from the carrier gas supply unit 1 into the reaction furnace 3.
- a catalyst for causing a reaction to convert carbon into fibers in the reactor 3 is introduced into the reactor 3.
- the raw material gas is decomposed by heat in the reaction furnace 3, and fine carbon fibers are generated by the action of the catalyst.
- the generated fine carbon fibers are sent to the fine carbon fiber separation / recovery device 4 together with the gas in the reaction furnace.
- the fine carbon fiber is separated from the post-reaction gas by the fine carbon fiber separation / recovery device 4 and sent to the fine carbon fiber tank 8.
- the gas that has exited the fine carbon fiber separation / recovery device 4 is cooled by the cooling device 6 to 40 ° C. or higher and 150 ° C. or lower, and enters the second fine carbon separation / recovery device 5.
- fine carbon fibers are further recovered by a separation device that can be used for low-temperature gas such as a bag filter and stored in the recovery tank 8.
- the gas that has exited the second fine carbon fiber separation / recovery device 5 is treated by an exhaust gas treatment device and then discharged out of the system.
- FIG. 2 is a schematic diagram illustrating a process for producing fine carbon fibers according to the first embodiment of the present invention.
- FIG. The production process of the present invention shown in this figure is a production process for producing fine carbon fibers by the CC VD method, and is a process provided with a recycling device. That is, in the embodiment of the above reference example, the gas discharged from the second fine carbon fiber separation / recovery device 5 was exhausted out of the system after being treated by the exhaust gas treatment device. Is a process of circulating a part of it to the reactor. In this process, the circulating gas and the exhaust gas can be freely controlled, and therefore, the gas circulation amount in the reaction system can be easily controlled.
- FIG. 3 is a configuration diagram schematically showing a process for producing fine carbon fibers according to a second embodiment of the present invention.
- a part of the gas exiting the second fine carbon fiber separation / recovery device 5 is circulated to the reaction furnace by the gas circulation blower 9.
- the temperature of the gas is further reduced by a cooling device 7 separate from the cooling device 6, and reaction by-products such as water contained in the gas and undecomposed raw material organic matter are condensed from the gas. It is a process of separating and removing gas and circulating gas.
- the separated condensate passes through a condensate tank 10 and is sent to a moisture separator 11 where condensates such as water and organic gas are recovered, and this gas is also circulated to the reactor 3.
- the condensate accumulated in the water separator 11 is discharged out of the system after being treated by the wastewater treatment device 15.
- the circulating gas does not contain water or organic compounds with relatively high boiling points As a result, the water concentration can be kept low, so that the condensation of water can be suppressed, and clogging of piping and the like can be prevented.
- FIG. 4 is a configuration diagram schematically showing a process for producing fine carbon fibers according to a third embodiment of the present invention.
- the gas circulated to the reaction furnace by the circulation blower 9 out of the gas exiting the second fine carbon fiber separation / recovery device 5 is described in the second embodiment.
- This is a process in which the gas is cooled by the cooling device 7 to further reduce the temperature of the gas, condensing reaction by-products such as water contained in the gas, and undecomposed raw material organic matter, and separating and removing it from the gas for circulation.
- this is a process in which the gas discharged from the second fine carbon fiber separation / recovery device 5 is cooled by the total amount cooling device 7 and the condensate in the gas is separated.
- Part of the gas from which the condensate has been separated is circulated to the reaction furnace by the blower 9, and the remaining gas is sent to the exhaust gas treatment device 12, where it is discharged out of the system after treatment.
- the separated condensate passes through the condensate tank 10 and is sent to the moisture separator 11 to collect condensate such as water and organic matter, and this gas is also circulated to the reaction furnace 3.
- the condensate accumulated in the gas-liquid separator 11 is treated by the wastewater treatment device 15 and then discharged out of the system.
- the process was performed as shown in FIG.
- the reactor used was a one-piece, one-piece reactor with a structure that heats a 200-diameter SiC reaction tube from the outside and can rotate the reaction tube at a constant speed.
- Ethyl alcohol was used as a raw material carbon source, and was continuously charged at a flow rate of 7.4 NL / min.
- Argon gas was used as the carrier gas, and the flow rate was 5 NL / min.
- the catalyst used was a two-component system consisting of molybdenum and cobalt.
- the catalyst was supported on magnesium oxide with an average particle size of 0.1 im or less according to a conventional method, and then concentrated in an inert gas at a rate of 15 g / min. It was put in.
- the reaction temperature was 810 ° C
- the reaction pressure was normal pressure
- the reaction was continuously performed at a rotation speed of 3 rpm.
- crude CNTs of 1 S gZmin were obtained by adding volatile components to the catalyst recovered in the CNT recovery tank.
- the CNT content in the crude CNT was 3.8 gmin.
- the reaction furnace is a rotary type reaction tube which heats a reaction tube made of SiC having an inner diameter of 200 ⁇ similar to that of the reference example from the outside and which can rotate the reaction tube at a constant speed.
- Ethyl alcohol was used as the carbon source of the raw material in the same manner as in the Reference Example, and was continuously charged at a flow rate of 7.4 NLZmin.
- Molybdenum and cobalt catalysts were used, supported on magnesium oxide with an average particle size of 0.1 zm or less, and then charged in an inert gas at a rate of 15 g / min.
- the reaction temperature was 805, the reaction pressure was normal pressure, and the reaction was continuously performed at a rotation speed of 2 rpm.
- the reacted gas (including unreacted ethyl alcohol and decomposition products) equivalent to 20% of the argon gas in the outlet reaction gas was recycled, and the remainder was sent to an exhaust gas treatment system. Therefore, the carrier gas in the furnace was adjusted so that the newly introduced argon gas was 4 NL / min.
- the amount of the catalyst and crude CNT recovered in the CNT recovery tank was 19.3 gZ min.
- the CNT content in the crude CNT is 4.OgZmin.
- the CNT yield was improved by 0.2 gZmin over the case without recycling, and the amount of argon input was reduced by 20%.
- This example was implemented by the process shown in FIG.
- the reaction furnace used in this reaction was to heat a reaction tube made of SiC having an inner diameter of 200 ⁇ from the outside, and a rotary reaction tube having a structure capable of rotating the reaction tube at a constant speed was used.
- Ethyl alcohol was used as a raw material carbon source in the same manner as in the Reference Example, and was continuously charged at a flow rate of 7.4 NL / min.
- Molybdenum and cobalt catalysts were used, supported on magnesium oxide with an average particle size of 0.1 m or less, and then charged in an inert gas at a rate of 15 g / min.
- the reaction temperature was 815 ° C
- the reaction pressure was normal pressure
- the reaction was continuously performed at a rotation speed of 1 rpm.
- the gas after the reaction corresponding to 50% of the outlet reaction gas argon gas was cooled by the cooler 7, water was removed by the water separator, and then recycled to the reaction system.
- the residue was sent to an exhaust gas treatment system.
- Carrier gas in the furnace is 3 NL / min for newly charged gas and 3 NL / min for recycled gas.
- the amount of the catalyst and crude CNT recovered in the CNT recovery tank was 19.6 g / min.
- the CNT content in the crude CNT was 4.2 g / min.
- the CNT yield improved by 0.4 g / min compared to the case without recycling, and the amount of argon input was reduced by 50%.
- the reaction furnace used in this reaction was to heat a reaction tube made of SiC with an inner diameter of 200 ⁇ from the outside, and a mouth-to-mouth type reaction tube capable of rotating the reaction tube at a constant speed was used.
- Ethyl alcohol was used as the raw material carbon source in the same manner as in the Reference Example, and was continuously charged at a flow rate of 7.4 N I / min.
- Molybdenum and cobalt catalysts are used, and the average particle size is 0.1 After that, what was condensed in an inert gas was introduced at a rate of 15 g / min.
- the reaction temperature was 800 ° C
- the reaction pressure was normal pressure
- the reaction was continuously performed at a rotation speed of 1 rpm.
- the outlet reaction gas was cooled in its entirety by the cooler 7 to recover unreacted components and carbon containing an oxygen-containing hydrid, and then water was removed by the separator 11 before being recycled to the reaction system.
- the gas after the reaction corresponding to 50% of the argon gas after the reaction at the outlet of the cooler 7 was recycled, and the remainder was sent to an exhaust gas treatment system.
- the amount of carrier gas in the furnace is 3 NL / min for new input and 3 NLZ min for recycle.
- the amount of the catalyst and crude CNT recovered in the CNT recovery tank was 19.6 g / min.
- the CNT content in the crude CNT was 4.7 g / min.
- the CNT yield was improved by 0.7 g / min compared to the case without recycling, and the amount of argon input was reduced by 50%.
- the present invention is a method capable of continuously and stably producing fine carbon fibers at a high yield at a low cost, and is suitable for producing high-quality carbon nanotubes and the like.
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AU2003252658A AU2003252658A1 (en) | 2002-07-17 | 2003-07-16 | Method for producing fine carbon fiber |
JP2004521220A JP4388890B2 (ja) | 2002-07-17 | 2003-07-16 | 微細炭素繊維の製造方法 |
US10/521,453 US20060099134A1 (en) | 2002-07-17 | 2003-07-16 | Method for producing fine carbon fiber |
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US (1) | US20060099134A1 (ja) |
JP (1) | JP4388890B2 (ja) |
AU (1) | AU2003252658A1 (ja) |
WO (1) | WO2004007820A1 (ja) |
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JP2004155628A (ja) * | 2002-11-08 | 2004-06-03 | Japan Science & Technology Agency | 原料循環カーボン構造物製造方法および装置 |
JP2006290682A (ja) * | 2005-04-12 | 2006-10-26 | Kitami Institute Of Technology | ナノ炭素の製造方法およびナノ炭素製造用触媒反応装置 |
WO2006117924A1 (ja) * | 2005-04-28 | 2006-11-09 | Bussan Nanotech Research Institute Inc. | 透明導電膜および透明導電膜用コーティング組成物 |
JP2006315891A (ja) * | 2005-05-11 | 2006-11-24 | Japan Steel Works Ltd:The | 低級炭化水素の直接分解による機能性ナノ炭素及び水素の製造方法 |
WO2008149792A1 (ja) * | 2007-05-31 | 2008-12-11 | Showa Denko K. K. | カーボンナノファイバー、その製造方法及び用途 |
JP2009161426A (ja) * | 2007-12-31 | 2009-07-23 | Semes Co Ltd | 流動層炭素ナノチューブの生成装置並びにそれを使用した炭素ナノチューブの生成設備及び方法 |
US7879261B2 (en) | 2007-03-26 | 2011-02-01 | Showa Denko K.K. | Carbon nanofiber, production process and use |
JP2015520104A (ja) * | 2012-04-23 | 2015-07-16 | シーアストーン リミテッド ライアビリティ カンパニー | バイモーダルサイズ分布を有するカーボンナノチューブ |
JP2016516158A (ja) * | 2013-02-26 | 2016-06-02 | ブリローイン エナジー コーポレイション | 水素化物における低エネルギー核反応の制御および自律制御熱発生モジュール |
US9896341B2 (en) | 2012-04-23 | 2018-02-20 | Seerstone Llc | Methods of forming carbon nanotubes having a bimodal size distribution |
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EP1445236A1 (fr) | 2003-02-05 | 2004-08-11 | Université de Liège | Procédé et installation pour la fabrication de nanotubes de carbone |
JP4129459B2 (ja) * | 2005-02-10 | 2008-08-06 | 有限会社末富エンジニアリング | 改質触媒用不織布および織布 |
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- 2003-07-16 JP JP2004521220A patent/JP4388890B2/ja not_active Expired - Fee Related
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JP2004155628A (ja) * | 2002-11-08 | 2004-06-03 | Japan Science & Technology Agency | 原料循環カーボン構造物製造方法および装置 |
JP2006290682A (ja) * | 2005-04-12 | 2006-10-26 | Kitami Institute Of Technology | ナノ炭素の製造方法およびナノ炭素製造用触媒反応装置 |
US9403682B2 (en) | 2005-04-12 | 2016-08-02 | National University Corporation Kitami Institute Of Technology | Method for producing nanocarbon and catalytic reaction device for producing nanocarbon |
US7947245B2 (en) | 2005-04-12 | 2011-05-24 | National University Corporation Kitami Institute Of Technology | Method for producing nanocarbon and catalytic reaction device for producing nanocarbon |
WO2006117924A1 (ja) * | 2005-04-28 | 2006-11-09 | Bussan Nanotech Research Institute Inc. | 透明導電膜および透明導電膜用コーティング組成物 |
JP4697941B2 (ja) * | 2005-05-11 | 2011-06-08 | 株式会社日本製鋼所 | 低級炭化水素の直接分解による機能性ナノ炭素及び水素の製造方法 |
JP2006315891A (ja) * | 2005-05-11 | 2006-11-24 | Japan Steel Works Ltd:The | 低級炭化水素の直接分解による機能性ナノ炭素及び水素の製造方法 |
US7879261B2 (en) | 2007-03-26 | 2011-02-01 | Showa Denko K.K. | Carbon nanofiber, production process and use |
WO2008149792A1 (ja) * | 2007-05-31 | 2008-12-11 | Showa Denko K. K. | カーボンナノファイバー、その製造方法及び用途 |
US8308990B2 (en) | 2007-05-31 | 2012-11-13 | Showa Denko K.K. | Carbon nanofiber, production process and use |
JP5242563B2 (ja) * | 2007-05-31 | 2013-07-24 | 昭和電工株式会社 | カーボンナノファイバー、その製造方法及び用途 |
JP2009161426A (ja) * | 2007-12-31 | 2009-07-23 | Semes Co Ltd | 流動層炭素ナノチューブの生成装置並びにそれを使用した炭素ナノチューブの生成設備及び方法 |
JP2015520104A (ja) * | 2012-04-23 | 2015-07-16 | シーアストーン リミテッド ライアビリティ カンパニー | バイモーダルサイズ分布を有するカーボンナノチューブ |
US9896341B2 (en) | 2012-04-23 | 2018-02-20 | Seerstone Llc | Methods of forming carbon nanotubes having a bimodal size distribution |
JP2018095552A (ja) * | 2012-04-23 | 2018-06-21 | シーアストーン リミテッド ライアビリティ カンパニー | バイモーダルサイズ分布を有するカーボンナノチューブ |
JP2016516158A (ja) * | 2013-02-26 | 2016-06-02 | ブリローイン エナジー コーポレイション | 水素化物における低エネルギー核反応の制御および自律制御熱発生モジュール |
US11752459B2 (en) | 2016-07-28 | 2023-09-12 | Seerstone Llc | Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same |
US11951428B2 (en) | 2016-07-28 | 2024-04-09 | Seerstone, Llc | Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same |
JP2018035368A (ja) * | 2017-10-27 | 2018-03-08 | 住友大阪セメント株式会社 | 樹脂廃棄物の処理方法、及び樹脂廃棄物の処理システム |
Also Published As
Publication number | Publication date |
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JP4388890B2 (ja) | 2009-12-24 |
JPWO2004007820A1 (ja) | 2005-11-10 |
US20060099134A1 (en) | 2006-05-11 |
AU2003252658A1 (en) | 2004-02-02 |
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