Mesoporous carbon production apparatus and mesoporous carbon production method

Abstract

Provided is a mesoporous carbon production device and a mesoporous carbon production method. The mesoporous carbon production device includes: a furnace capable of heating zinc organic acid disposed inside to a temperature of the boiling point of zinc or higher; and an exhaust pipe disposed from the inside of the furnace toward the outside, guiding exhaust gas containing zinc vapor as a thermal decomposition product of zinc organic acid from the inside of the furnace to the outside of the furnace. The exhaust pipe has: an exhaust path guiding the exhaust gas from the inside of the furnace to the outside of the furnace, causing zinc vapor contained in the exhaust gas to condense and be exhausted to the outside of the furnace; and a cooling gas path sending cooling gas from the outside of the furnace into the inside of the exhaust path, removing elements other than carbon from zinc organic acid, and generating mesoporous carbon having mesopores derived from zinc oxide generated in the thermal decomposition process of zinc organic acid.

Description

Technical Field

[0001] This invention relates to an apparatus for manufacturing mesoporous carbon having mesopores. Background Technology

[0002] To achieve a sustainable society, efforts are underway to expand the adoption of fuel cell vehicles and electric vehicles, and to develop next-generation high-performance energy devices that support the construction of a hydrogen supply chain. In this ongoing trend of developing electrochemical devices capable of high-level energy storage and generation, it is no exaggeration to say that electrode material generation processes and electrode interface control technologies hold the key to improving device performance.

[0003] Activated carbon, as a classic type of porous carbon, is widely used as an electrode in electrochemical devices due to its large specific surface area and economic viability (see, for example, non-patent literature 1).

[0004] On the other hand, in recent years, porous carbon with highly controlled microstructures such as pore size and specific surface area, which are difficult to control in activated carbon, has been developed. For example, nanoparticles of alumina (Al2O3) and alkaline earth metal oxides (MgO, CaO) are used in molding. It is known to have a method for manufacturing porous carbon called graphene mesoporous sponge, in which several layers of graphene are formed on the molded nanoparticles by chemical vapor deposition (CVD) with methane gas, and then the molded nanoparticles are removed by acid etching (for example, see Patent Document 1, Patent Document 2).

[0005] In addition, there is a known method for manufacturing porous carbon by etching away the molded metal oxide (MgO) nanoparticles after mixing and sintering organic materials such as polyvinyl alcohol (PVA) with metal oxide (MgO) nanoparticles (for example, see Patent Document 3).

[0006] Existing technical documents Non-patent literature Non-patent literature 1: I. Mochida, S.-I. Lee, S. Mitani, S.-H. Yoon and Y. Korai, Tanso 2003 [No. 210] 250-257 [in Japanese] Patent documents Patent Document 1: Japanese Patent No. 6460448 Patent Document 2: Japanese Patent No. 7407393 Patent Document 3: Japanese Patent No. 6677863 Summary of the Invention

[0007] The mesoporous carbon manufacturing apparatus disclosed herein includes: a furnace capable of heating organic zinc acid disposed inside to a temperature above the boiling point of zinc; and an exhaust pipe disposed from the inside of the furnace toward the outside, guiding waste gas containing zinc vapor, which is a thermal decomposition product of organic zinc acid, from the inside of the furnace to the outside of the furnace. The exhaust pipe has: a discharge path that guides the waste gas from the inside of the furnace to the outside of the furnace, causing the zinc vapor contained in the waste gas to condense and be discharged to the outside of the furnace; and a cooling gas path that introduces cooling gas from the outside of the furnace into the interior of the discharge path, removing elements other than carbon from the organic zinc acid, and generating mesoporous carbon having mesopores derived from zinc oxide generated during the thermal decomposition of organic zinc acid.

[0008] The method for manufacturing mesoporous carbon disclosed herein includes: a step of heating organic zinc acid to a temperature above the boiling point of zinc inside a furnace; a step of taking waste gas containing zinc vapor, which is a thermal decomposition product of organic zinc acid, into an exhaust path disposed from the inside of the furnace toward the outside; and a step of introducing cooling gas from the outside of the furnace into the inside of the exhaust path, causing the zinc vapor contained in the waste gas to condense, and guiding the condensed zinc from the inside of the furnace to the outside of the furnace, thereby removing elements other than carbon from organic zinc acid and generating mesoporous carbon having mesopores derived from zinc oxide generated during the thermal decomposition of organic zinc acid. Attached Figure Description

[0009] Figure 1 This is a schematic cross-sectional view showing the schematic cross-sectional structure of the mesoporous carbon manufacturing apparatus of Embodiment 1.

[0010] Figure 2 This is a detailed cross-sectional view showing the detailed cross-sectional structure of the mesoporous carbon manufacturing apparatus of Embodiment 1.

[0011] Figure 3 It means along Figure 2 A schematic cross-sectional view of the exhaust pipe 20 of line AA.

[0012] Figure 4A (a) is Figure 2 (a) is an enlarged view of part A of the cooling gas path, and (b) is a schematic diagram showing the angle between the normal vector of the opening surface of the first opening in (a) and the central axis vector of the discharge path from the outside to the inside of the furnace.

[0013] Figure 4B It means in Figure 2 A plan view of the second opening in a mesoporous carbon manufacturing apparatus, viewed vertically above the cooling gas path located below the inner side of the exhaust pipe.

[0014] Figure 5 It means Figure 2 A partial cross-sectional view of the mesoporous carbon extraction section and zinc recovery section in a mesoporous carbon manufacturing apparatus.

[0015] Figure 6 This is a detailed cross-sectional view showing the detailed cross-sectional structure of the mesoporous carbon manufacturing apparatus of Embodiment 2.

[0016] Figure 7 This is a flowchart illustrating each step of the mesoporous carbon manufacturing method according to Embodiment 3.

[0017] Figure 8A It means Figure 7 A graph showing the firing temperatures for mesoporous carbon manufacturing methods.

[0018] Figure 8B It means Figure 7 A schematic diagram illustrating the changes in raw materials from organic acid zinc to mesoporous carbon during the thermal decomposition process in the method for manufacturing mesoporous carbon.

[0019] Figure 9 This is a graph showing the in-situ XRD measurement data of the thermal decomposition products of zinc citrate (one of the organic zinc acids) during calcination at 100℃, 200℃, 300℃, and 400℃, and the original XRD measurement data of zinc citrate and zinc oxide.

[0020] Figure 10 This is a schematic cross-sectional view showing the macropores, mesopores, and micropores of the mesoporous carbon obtained in the mesoporous carbon manufacturing method of Embodiment 3.

[0021] Symbol Explanation 1. Organic acid zinc (raw material) 2 Cooling gas 3. Inactive gases 4 Exhaust gas 5 Zinc 6 Intermediate thermal decomposition products 7 Mesoporous Carbon 10 furnaces 12 heaters 20, 20a exhaust pipes 22 Drainage path Cooling gas paths 24, 24a, 24b 26 First opening 27 Normal Vector 28. Central axis vector 30. Inactive Gas Supply Department 32 Second opening 34 Thermal insulation materials 36 Coating 38 Sealing materials 40 Raw Material Supply Department 42. Agitator fins 50 Mesoporous Carbon Extraction Section 60 Zinc Recycling Department 70 Inactive gas exhaust section 100, 100a Mesoporous Carbon Manufacturing Apparatus Detailed Implementation

[0022] For example, when activated carbon is used as an electrode in an electric double-layer capacitor (EDLC), the following problems exist: Under high voltage operation, oxygen-containing surface functional groups and crystal defects on the activated carbon surface induce and promote electrolysis of the electrode and electrolyte. Due to the large amount of functional groups present on the surface of activated carbon, a large number of byproducts are generated under high voltage. However, because there are few mesopores (pore size 2nm~50nm) capable of capturing these byproducts as impurities, the cycling characteristics of the EDLC decrease under high voltage. Furthermore, even if oxygen-containing functional groups and end-capped hydrogen are removed from the activated carbon surface through high-temperature heat treatment (above 1000℃), the blockage of the activated carbon's micropores (pore size less than 2nm) causes significant structural changes and shrinkage in the material, thus reducing the specific surface area. Therefore, in activated carbon, there is a trade-off between simultaneously achieving functional group removal and maintaining specific surface area.

[0023] Previous porous carbon manufacturing processes, using alumina (Al₂O₃) and alkaline earth metal oxide nanoparticles (MgO, CaO) as molds and employing CVD and etching, utilized nanoparticles with a diameter of at least 10 nm. This resulted in a limited number of micropores (pore size less than 2 nm). Furthermore, strong acids such as hydrofluoric acid, sulfuric acid, and hydrochloric acid were required to remove the metal oxide nanoparticles from the molds. Therefore, the manufacture of porous carbon necessitates not only calcination equipment but also cleaning and drying equipment, and the large amounts of acid waste generated increase manufacturing costs and environmental impact. In short, the increased manufacturing costs and environmental impact caused by the large amounts of acid waste generated in previous porous carbon manufacturing processes have become a significant challenge.

[0024] Therefore, the purpose of this disclosure is to provide a mesoporous carbon manufacturing apparatus that does not require acid washing.

[0025] The mesoporous carbon manufacturing apparatus according to the first method includes: a furnace capable of heating organic zinc acid disposed inside to a temperature above the boiling point of zinc; and an exhaust pipe disposed from the inside of the furnace toward the outside, guiding waste gas containing zinc vapor, which is a thermal decomposition product of organic zinc acid, from the inside of the furnace to the outside of the furnace. The exhaust pipe has: an exhaust path that guides the waste gas from the inside of the furnace to the outside of the furnace, causing the zinc vapor contained in the waste gas to condense and be discharged to the outside of the furnace; and a cooling gas path that introduces cooling gas from the outside of the furnace into the interior of the exhaust path, removing elements other than carbon from the organic zinc acid, and generating mesoporous carbon having mesopores derived from zinc oxide generated during the thermal decomposition of organic zinc acid.

[0026] The mesoporous carbon manufacturing apparatus involved in the second method can be in the first method described above, wherein the cooling gas path extends from the outside of the furnace to the end of the inlet of the exhaust pipe that draws in the exhaust gas inside the furnace, the cooling gas path has a first opening that feeds cooling gas from the outside of the furnace to the inside of the discharge path, and the normal vector of the opening surface of the first opening forms an angle of 0 degrees or more and less than 90 degrees with respect to the central axis vector of the discharge path from the inside to the outside of the furnace.

[0027] The mesoporous carbon manufacturing apparatus involved in the third method can be in the first or second method described above, wherein the cooling gas path has a plurality of second openings on the pipe wall of the cooling gas path for sending cooling gas into the inner side of the discharge path.

[0028] The mesoporous carbon manufacturing apparatus involved in the fourth method can be in any of the first to third methods described above, with at least a portion of the cooling gas path disposed inside the exhaust pipe.

[0029] In the fifth method, the mesoporous carbon manufacturing apparatus may have an insulation layer on the pipe wall in any of the first to fourth methods described above.

[0030] In the sixth method, the mesoporous carbon manufacturing apparatus, in any of the first to fifth methods described above, allows the inner surface of the exhaust pipe to be coated.

[0031] The mesoporous carbon manufacturing apparatus involved in the seventh method may also be, in any of the first to sixth methods mentioned above, provided with stirring fins on the outer periphery of the exhaust pipe.

[0032] The mesoporous carbon manufacturing apparatus involved in the eighth method may include an inactive gas supply unit that introduces inactive gas from the outside to the inside of the furnace in any of the first to seventh methods described above.

[0033] In any of the first to eighth methods of the mesoporous carbon manufacturing apparatus involved in the ninth method, the exhaust pipe may have a length of more than half the length of the furnace in the longitudinal direction.

[0034] Regarding the mesoporous carbon manufacturing apparatus involved in the tenth method, in any of the first to ninth methods described above, it may have a raw material inlet for supplying organic zinc acid as a raw material from the outside to the inside of the furnace.

[0035] Regarding the mesoporous carbon manufacturing apparatus involved in the eleventh method, in any of the first to tenth methods described above, there may be a mesoporous carbon extraction section for extracting the generated mesoporous carbon to the outside of the furnace.

[0036] Regarding the mesoporous carbon manufacturing apparatus involved in the twelfth method, in any of the first to eleventh methods described above, a zinc recovery section may be provided to extract zinc and zinc oxide discharged from the exhaust pipe to the outside of the furnace.

[0037] The method for manufacturing mesoporous carbon according to the thirteenth method includes: a step of heating organic zinc acid to a temperature above the boiling point of zinc inside a furnace; a step of taking waste gas containing zinc vapor, which is a thermal decomposition product of organic zinc acid, into an exhaust path disposed from the inside of the furnace toward the outside; and a step of introducing cooling gas from the outside of the furnace into the inside of the exhaust path, causing the zinc vapor contained in the waste gas to condense, and guiding the condensed zinc and zinc oxide from the inside of the furnace to the outside of the furnace, thereby removing elements other than carbon from organic zinc acid and generating mesoporous carbon having mesopores derived from zinc oxide generated during the thermal decomposition of organic zinc acid.

[0038] Regarding the mesoporous carbon manufacturing method involved in the fourteenth method, the thirteenth method mentioned above may also include a step of feeding organic zinc acid as a raw material from the outside of the furnace into the furnace.

[0039] In the mesoporous carbon manufacturing method involved in the fifteenth method, the flow rate of the cooling gas can be 0.02 m / s or more and 1.0 m / s or less than the thirteenth method mentioned above.

[0040] Hereinafter, the mesoporous carbon manufacturing apparatus and mesoporous carbon manufacturing method of the present disclosure will be described with reference to the accompanying drawings.

[0041] (Implementation Method 1) Mesoporous Carbon Manufacturing Device Figure 1 This is a schematic cross-sectional view showing the schematic cross-sectional structure of the mesoporous carbon manufacturing apparatus 100 of Embodiment 1. Figure 2 This is a detailed cross-sectional view showing the detailed cross-sectional structure of the mesoporous carbon manufacturing apparatus 100 according to Embodiment 1. It should be noted that, for convenience, in the accompanying drawings, the direction of feeding the raw material zinc organic acid is represented as the X direction, and the vertically upward direction as the Z direction, but this is not a limitation. Furthermore, the furnace 10 is arranged at a slight inclination from the horizontal.

[0042] The mesoporous carbon manufacturing apparatus 100 of Embodiment 1 includes a furnace 10 and an exhaust pipe 20. The furnace 10 is capable of heating the organic zinc acid 1 disposed inside to a temperature above the boiling point of zinc. The exhaust pipe 20 is disposed from the inside of the furnace 10 toward the outside, guiding waste gas 4 containing zinc vapor, which is a thermal decomposition product of the organic zinc acid, from the inside of the furnace 10 to the outside. The exhaust pipe 20 has: an exhaust path 22, which guides the waste gas 4 from the inside of the furnace 10 to the outside, causing the zinc vapor contained in the waste gas 4 to condense and be discharged to the outside of the furnace 10; and a cooling gas path 24, which introduces cooling gas 2 from the outside of the furnace 10 into the exhaust path 22. According to this mesoporous carbon manufacturing apparatus 100, elements other than carbon are removed from the organic zinc acid 1 to generate mesoporous carbon 7 having mesopores originating from zinc oxide generated during the thermal decomposition of the organic zinc acid 1. In addition, zinc 5 and zinc oxide contained in the waste gas 4 can be recovered simultaneously.

[0043] The elements constituting the mesoporous carbon manufacturing apparatus 100 of Embodiment 1 will be described below.

[0044] Furnace Furnace 10 can be any furnace capable of heating the organic acid zinc 1 to a temperature above the boiling point of zinc (907°C), for example, it can be either batch or continuous. Specifically, it can be as follows: Figure 1 and Figure 2 The rotary kiln, core tube furnace, box furnace, and conveyor furnace shown are examples. In intermittent operation, the raw materials are placed in a crucible for firing. The type of crucible can be alumina, quartz, carbon, etc., with no particular restrictions.

[0045] In addition, such as Figure 1 As shown, the furnace 10 can also be configured slightly inclined from horizontal so that the raw material supply section 40, which supplies zinc organic acid as a raw material, is positioned vertically. Thus, by rotating the furnace 10, the raw material zinc organic acid can be conveyed along the X direction.

[0046] Furthermore, the furnace is not limited to an inclined configuration. For example, a spiral groove can be provided on the inner wall of the furnace from the raw material supply section to the downstream side, and the furnace can be rotated to transport the raw material from the upstream side to the downstream side.

[0047] Raw Material Supply Department The mesoporous carbon manufacturing apparatus 100 may be equipped with a raw material supply section 40 for supplying the raw material zinc organic acid 1 into the interior of the furnace 10. This allows for continuous supply of raw material into the interior of the furnace 10 without stopping operation. Furthermore, the raw material supply section is not a necessary component.

[0048] <Exhaust pipe (cooling pipe)> Figure 3 To indicate along Figure 2 A schematic cross-sectional view of the exhaust pipe 20 of line AA.

[0049] The exhaust pipe 20 is configured from the inside of the furnace 10 toward the outside, guiding the exhaust gas 4, which contains zinc vapor as a thermal decomposition product of zinc organic acid, from the inside of the furnace to the outside. The exhaust pipe 20 has an exhaust path 22 that guides the exhaust gas 4 from the inside of the furnace 10 to the outside and a cooling gas path 24 (24a, 24b) that feeds cooling gas from the outside of the furnace 10 into the exhaust path 22.

[0050] The exhaust pipe 20 can also be made of stainless steel, chromium-nickel-iron alloy, ceramic, special nickel alloy, etc.

[0051] A heat-insulating material 34 can also be provided on the wall of the exhaust pipe 20. Examples of heat-insulating materials include silicon dioxide, alumina, and calcium silicate. The exterior of the exhaust pipe 20 is heated by the furnace 10 to above the boiling point of Zn (907°C). Conversely, inside the exhaust pipe 20, cooling gas 2 flows to condense the zinc contained in the incoming waste gas 4. Therefore, by using the heat-insulating material 34 to insulate the interior of the exhaust pipe 20 from the interior of the furnace 10, the temperature drop inside the furnace 10 can be suppressed.

[0052] Alternatively, the axis of the exhaust pipe 20 can be aligned with the axis of the furnace 10, but this is not a limitation; the axes can also be offset. For example, the exhaust pipe 20 can be offset vertically downward (in the -Z direction) from the center of the furnace 10. This allows high-concentration exhaust gas 4 to be drawn into the exhaust pipe 20.

[0053] The length of the exhaust pipe 20 can also be more than half the length of the furnace 10 in the longitudinal direction. In order to take in the zinc-containing waste gas 4, the exhaust pipe needs to be installed in the area inside the furnace 10 where the temperature reaches above the boiling point of zinc.

[0054] In addition, the exhaust pipe 20 can also rotate simultaneously with the furnace 10.

[0055] <Drainage Pathway> The exhaust path 22 is inside the exhaust pipe 20, which draws the exhaust gas 4 from inside the furnace 10 and guides it to the outside.

[0056] Alternatively, a coating 36 can be provided on the inner wall of the exhaust path 22. The coating can be formed, for example, from a material with good peelability to zinc, which is a metal, such as a glass coating (quartz) or ceramic. In this way, condensed zinc can be discharged without being trapped in the exhaust path 22 of the exhaust pipe 20.

[0057] Cooling Gas Path Figure 4A (a) is Figure 2 An enlarged view of section A of the cooling gas path 24. Figure 4A (b) is a schematic diagram showing the angle between the normal vector 27 of the opening surface of the first opening 26 in (a) and the central axis vector 28 of the discharge path 22 from the inside to the outside of the furnace. Figure 4B It means in Figure 2 A plan view of the second opening 32 in the mesoporous carbon manufacturing apparatus, viewed vertically above the cooling gas passage 24 located below the inner side of the exhaust pipe 20.

[0058] like Figure 2 and Figure 3 As shown, cooling gas passages 24 (24a, 24b) are located inside the exhaust pipe 20. Furthermore, in Figure 2 and Figure 3These are respectively installed on the upper and lower sides of the inner side of the exhaust pipe 20, but not limited to the upper and lower sides; they can also be installed on the left and right sides. In addition, more than three can be installed, or only one can be installed.

[0059] Cooling gas, such as room temperature gas, flows from cooling gas path 24 to discharge path 22 inside exhaust pipe 20, causing the zinc contained in the incoming waste gas 4 to condense. That is, by controlling the temperature inside exhaust pipe 20 to below the boiling point of Zn (907°C), the zinc in the waste gas 4 can be condensed to obtain solid zinc and zinc oxide. The cooling gas flowing in cooling gas paths 24 (24a, 24b) can be, for example, carbon dioxide gas in addition to nitrogen and argon. By reacting organic zinc acid with carbon dioxide gas, nano-sized zinc oxide can be generated.

[0060] Furthermore, in order to prevent the temperature inside the furnace 10 from decreasing, the cooling gas 2 needs to be prevented from flowing out of the exhaust pipe 20 into the inside of the furnace 10. Therefore, the cooling gas passages 24 (24a, 24b) provided in the exhaust pipe 20 are shaped such that they fold back at the first opening 26 at the front end. By folding back the front end, the flow direction of the cooling gas 2 flowing out of the cooling gas passages 24 (24a, 24b) can be set to a direction from the inside of the furnace 10 towards the outside (X direction). Specifically, as follows... Figure 4A As shown in the enlarged view of part A in (a), the cooling gas passages 24 (24a, 24b) extend from the outside of the furnace 10 toward the inside, folding back the first opening 26 at the front end by 180 degrees. In this case, as... Figure 4A As shown in (b), the normal vector 27 of the opening surface of the first opening 26 can form an angle of 0 degrees or more and less than 90 degrees with respect to the central axis vector 28 of the discharge path 22 from the inside to the outside of the furnace 10, or an angle of 0 degrees or more and less than 45 degrees. This allows waste gas 4 to be drawn in from the inside of the furnace 10, and zinc condensed by the cooling gas 2 to be conveyed to the downstream zinc recovery section 60. It should be noted that by making the angle between the normal vector 27 of the opening surface of the first opening 26 and the central axis vector 28 of the discharge path 22 from the inside to the outside of the furnace 10 less than 90 degrees, the cooling gas 2 can be prevented from flowing out of the furnace 10.

[0061] like Figure 4B As shown, the cooling gas path 24 (24a, 24b) not only has a first opening 26 at the front end, but also has a second opening 32 at the middle part to supply cooling gas to the discharge path 22.

[0062] <Inactive gas supply pipe> As an example of an inactive gas supply section, the inactive gas supply pipe 30 introduces inactive gas 3 from the outside to the inside of the furnace 10. Specifically, for example, the inactive gas 3, preheated by the heater 12 of the furnace 10, can also be supplied into the furnace 10. This prevents the temperature inside the furnace 10 from decreasing. Furthermore, by adjusting the flow of the inactive gas 3, the flow of exhaust gas 4 entering the exhaust pipe 20 can be divided. Figure 2 As shown, the inactive gas supply pipes 30 can be respectively installed above and below, or to the left and right of the exhaust pipe 20, or only at the lower part. Furthermore, when the inactive gas supply pipes 30 are installed above and below, the supply volume of inactive gas from the above and below the exhaust pipe 20 can be adjusted to increase the flow rate of the inactive gas at the lower part of the exhaust pipe 20. It should be noted that the purpose of increasing the flow rate of the inactive gas at the lower part of the exhaust pipe 20 is to prevent the retention of volatilized CO2, ZnO, etc., during the heating process and at the highest temperature, thereby suppressing excessive carbon volatilization.

[0063] The flow rate of the inactive gas supplied into furnace 10 is, for example, 0.02 m / s or more and 1.0 m / s or less. By setting the flow rate of the inactive gas within the above range, it is possible to suppress the recombining of zinc with oxygen after the thermal decomposition of zinc citrate, which is one of the organic zinc acids. By suppressing the flow rate of the inactive gas to 1.0 m / s or less, it is possible to suppress the dispersion of the organic zinc acid 1, intermediate thermal decomposition products 6, and mesoporous carbon 7 from the raw material during the thermal decomposition process.

[0064] The inactive gas supply pipe 30 can be made of materials such as quartz, stainless steel, chromium-nickel-iron alloy, ceramic, or special nickel alloy.

[0065] Figure 5 It means Figure 2 A partial cross-sectional view of the mesoporous carbon extraction section 50 and the zinc recovery section 60 in the mesoporous carbon manufacturing apparatus.

[0066] <Mesoporous Carbon Extraction Section> The mesoporous carbon extraction section 50 is externally connected to the furnace 10 to extract the transported mesoporous carbon 7. It should be noted that the interior of the furnace 10 is maintained in an inert atmosphere. Therefore, the furnace 10 and the mesoporous carbon extraction section 50 can be connected via a sealing material 38 to maintain the inert atmosphere inside the furnace 10.

[0067] Zinc Recycling Department The zinc recovery unit 60 only needs to be configured to receive zinc 5 and zinc oxide transported in the exhaust pipe 20. Additionally, an inactive gas discharge unit 70 can be provided downstream to discharge inactive gases.

[0068] Furthermore, no piping is provided to connect the exhaust pipe 20 to the zinc recovery unit 60. The zinc 5 and zinc oxide transported in the exhaust pipe 20 can also be recovered by falling directly from the end of the exhaust pipe 20 into the zinc recovery unit 60. In the mesoporous carbon manufacturing apparatus of this embodiment, the zinc 5 and zinc oxide condense into a solid in the exhaust pipe 20, therefore, it is not necessary to provide piping connecting to the exhaust pipe 20.

[0069] (Implementation Method 2) Figure 6 This is a detailed cross-sectional view showing the detailed cross-sectional structure of the mesoporous carbon manufacturing apparatus 100a according to Embodiment 2.

[0070] The mesoporous carbon manufacturing apparatus 100a of Embodiment 2 differs from that of Embodiment 1 in that it has stirring fins 42 provided on the outer periphery of the exhaust pipe 20a. These stirring fins 42 are spirally arranged on the outer periphery of the exhaust pipe 20a, and by the relative rotation between the exhaust pipe 20a and the furnace 10, the organic acid zinc 1, intermediate pyrolysis product 6, and mesoporous carbon 7 can be stirred and transported. Furthermore, by rotating either or both of the exhaust pipe 20a and the furnace 10, relative rotation between them can be achieved.

[0071] (Implementation Method 3) <Mesoporous Carbon Manufacturing Methods> Figure 7 This is a flowchart illustrating each step of the mesoporous carbon manufacturing method according to Embodiment 3.

[0072] (1) Organic acid zinc 1 is fed into the furnace 10 from the outside in as a raw material (S01). Figure 1 and Figure 2 The mesoporous carbon manufacturing apparatus 100 shown supplies zinc organic acid 1, which is used as a raw material, into the interior of the furnace 10 via the raw material supply unit 40. As a result, zinc organic acid 1, which is used as a raw material, can be continuously supplied into the interior of the furnace 10 without stopping operation.

[0073] It should be noted that this process is not necessary in the mesoporous carbon manufacturing method, and can be started in the state where organic zinc acid as raw material is supplied into the furnace 10 in advance.

[0074] <Ingredients> As the raw material for the mesoporous carbon in Embodiment 1, any organic zinc acid raw material containing zinc atoms in its molecular structure is acceptable, preferably selected from one or more of the following: zinc citrate, zinc hydrogen citrate, zinc oxalate, zinc fumarate, zinc succinate, zinc caffeate, zinc chlorogenic acid, zinc ferulic acid, zinc quinic acid, zinc lactate, zinc malonate, zinc gluconate, zinc tartrate, zinc malate, zinc benzoate, zinc pyridinecarboxylate, and zinc octanoate. Two or more organic zinc acid raw materials may also be used in combination. It should be noted that the aforementioned organic zinc acid raw materials can be hydrates or anhydrides.

[0075] Organic acid zinc in Figure 8B In the example shown, citric acid can be mixed with zinc acetate to obtain zinc citrate. However, the above is merely one example and is not a limitation.

[0076] The organic zinc acid raw material can be granulated to an appropriate size by means of appropriate handling within furnace 10.

[0077] <Raw Material Proportions> Two or more zinc organic acids can be mixed, but the ratio of the organic acids to zinc is not particularly limited. On the other hand, from the viewpoint of complex formation between organic acids and zinc, the molar ratio of organic acid to zinc precursor relative to 1.0 of organic acid is preferably 0.8 to 2.2 of zinc precursor, and more preferably 1.0 to 2.0 of zinc precursor. The mixing method of organic acid and zinc precursor can be either wet or dry, without particular limitation.

[0078] (2) The organic acid zinc 1 is heated inside the furnace 10 to a temperature above the boiling point of zinc (SO2).

[0079] Figure 8A It means Figure 7 A graph showing the firing temperatures for mesoporous carbon manufacturing methods. Figure 8B It means Figure 7 A schematic diagram illustrating the changes in raw materials from organic acid zinc to mesoporous carbon during the thermal decomposition process in the method for manufacturing mesoporous carbon. Figure 9 This graph shows the in-situ XRD data of the thermal decomposition products of zinc citrate (one of the organic zinc acids) during calcination at 100℃, 200℃, 300℃, and 400℃, as well as the original XRD data of zinc citrate and zinc oxide.

[0080] Since zinc has a boiling point of 907℃, therefore... Figure 8A As shown, for example, by heating to 950°C and maintaining at 950°C for 6 hours, elements other than carbon can be removed from the organic acid zinc 1 of the raw material, generating mesoporous carbon 7 with mesopores originating from zinc oxide generated during the thermal decomposition of organic acid zinc 1. To avoid oxidation of carbon, the atmosphere at this time is set to, for example, an inert atmosphere.

[0081] like Figure 9 As shown, zinc citrate, as one of the organic zinc acids, maintains its peak value before the firing temperature of 200°C and does not undergo thermal decomposition. On the other hand, it is believed that from the firing temperature of 300°C to 400°C, the peak value of zinc citrate disappears, and a peak value of zinc oxide is generated, resulting in the thermal decomposition of zinc citrate and the formation of a carbon skeleton and zinc oxide.

[0082] (3) The exhaust gas 4 containing zinc vapor, which is a thermal decomposition product of organic acid zinc 1, is taken into the discharge path 22 of the exhaust pipe 20 arranged from the inside of the furnace 10 toward the outside (S03).

[0083] like Figure 1 and Figure 2 As shown, the waste gas 4 is drawn in from the top and bottom of the exhaust pipe 20 through the intake port at the front end of the exhaust pipe 20 by the flow of inactive gas 3 introduced from the outside of the furnace 10 into the interior.

[0084] (4) Cooling gas 2 is introduced from the outside of furnace 10 into the inside of exhaust path 22, so that the zinc vapor contained in the waste gas 4 condenses and the condensed zinc 5 is guided from the inside of furnace 10 to the outside (S04).

[0085] Specifically, such as Figure 2 , Figure 3 , Figure 4A , Figure 4B As shown, cooling gas 2 is introduced into the discharge path 22 from the cooling gas path 24 (24a, 24b) located inside the exhaust pipe 20, causing the zinc vapor contained in the waste gas 4 to condense. The condensed zinc 5 and zinc oxide are transported downstream along the flow of cooling gas 2 and waste gas 4 and recovered to the outside of the furnace 10. It should be noted that since the waste gas 4 produced by thermal decomposition also contains oxygen, sometimes a portion of the condensed zinc 5 becomes zinc oxide.

[0086] According to this mesoporous carbon manufacturing method, elements other than carbon are removed from organic zinc acid 1 to generate mesoporous carbon 7 having mesopores derived from zinc oxide generated during the thermal decomposition of organic zinc acid. Furthermore, zinc 5 and zinc oxide contained in waste gas 4 can be recovered simultaneously.

[0087] Mesoporous carbon Figure 10 This is a schematic cross-sectional view showing the macropores, mesopores, and micropores of the mesoporous carbon 7 obtained in the mesoporous carbon manufacturing method of Embodiment 3.

[0088] The obtained mesoporous carbon is porous carbon particles with mesopores having a pore size of 2nm to 50nm.

[0089] According to the mesoporous carbon manufacturing apparatus of the present invention, heating can be performed at a temperature above the boiling point of zinc, so that elements other than carbon can be removed from organic zinc acid by a firing process without pickling, thereby generating mesoporous carbon having mesopores derived from zinc oxide generated during the thermal decomposition of organic zinc acid.

[0090] [Industrial Applicability] According to the mesoporous carbon manufacturing apparatus disclosed herein, heating can be performed at a temperature above the boiling point of zinc. Therefore, without pickling, elements other than carbon can be removed from organic zinc acid through a calcination process, thereby generating mesoporous carbon having mesopores derived from zinc oxide generated during the thermal decomposition of organic zinc acid.

Claims

1. An apparatus for manufacturing mesoporous carbon, comprising: A furnace capable of heating zinc organic acid contained within to a temperature above the boiling point of zinc; and An exhaust pipe, configured from the inside of the furnace outwards, guides exhaust gas containing zinc vapor, which is a thermal decomposition product of the organic acid zinc, from the inside of the furnace to the outside of the furnace. The exhaust pipe has: An exhaust path guides the exhaust gas from inside the furnace to the outside of the furnace, causing zinc vapor contained in the exhaust gas to condense and be discharged outside the furnace; and A cooling gas path is provided to introduce cooling gas from outside the furnace into the interior of the discharge path. The mesoporous carbon manufacturing apparatus removes elements other than carbon from the organic zinc acid to generate mesoporous carbon having mesopores derived from zinc oxide generated during the thermal decomposition of the organic zinc acid.

2. The mesoporous carbon manufacturing apparatus according to claim 1, wherein, The cooling gas path extends from the outside of the furnace to the end of the intake port inside the furnace that draws in the exhaust gas from the exhaust pipe. The cooling gas path has a first opening for feeding cooling gas from the outside of the furnace to the inside of the discharge path, wherein the normal vector of the opening surface of the first opening forms an angle of 0 degrees or more and less than 90 degrees with respect to the central axis vector of the discharge path from the inside to the outside of the furnace.

3. The mesoporous carbon manufacturing apparatus according to claim 1, wherein, The cooling gas path has multiple second openings on its pipe wall to deliver the cooling gas into the inner side of the discharge path.

4. The mesoporous carbon manufacturing apparatus according to claim 1, wherein, At least a portion of the cooling gas path is located inside the exhaust pipe.

5. The mesoporous carbon manufacturing apparatus according to claim 1, wherein, The exhaust pipe has a heat insulation layer on its wall.

6. The mesoporous carbon manufacturing apparatus according to claim 1, wherein, The inner surface of the exhaust pipe is coated.

7. The mesoporous carbon manufacturing apparatus according to claim 1, wherein, Agitator fins are provided on the outer periphery of the exhaust pipe.

8. The mesoporous carbon manufacturing apparatus according to claim 1, comprising: The inactive gas supply unit introduces inactive gas from the outside of the furnace into the furnace.

9. The mesoporous carbon manufacturing apparatus according to claim 1, wherein, The length of the exhaust pipe relative to the length of the furnace is more than half.

10. The mesoporous carbon manufacturing apparatus according to claim 1, comprising: The raw material inlet allows organic zinc acid to be fed into the furnace from the outside.

11. The mesoporous carbon manufacturing apparatus according to claim 1, comprising: The mesoporous carbon extraction section extracts the generated mesoporous carbon to the outside of the furnace.

12. The mesoporous carbon manufacturing apparatus according to claim 1, comprising: The zinc recovery section removes the zinc and zinc oxide discharged from the exhaust pipe to the outside of the furnace.

13. A method for manufacturing mesoporous carbon, comprising the following steps: The process of heating the organic zinc acid to a temperature above the boiling point of zinc inside the furnace; The process of taking waste gas containing zinc vapor, which is a thermal decomposition product of the organic acid zinc, into an exhaust path through an exhaust pipe arranged from the inside of the furnace toward the outside; and The process involves introducing cooling gas from the outside of the furnace into the inside of the exhaust path, causing the zinc vapor contained in the exhaust gas to condense, and then guiding the condensed zinc from the inside of the furnace to the outside of the furnace. The mesoporous carbon manufacturing method removes elements other than carbon from zinc organic acid to generate mesoporous carbon having mesopores derived from zinc oxide generated during the thermal decomposition of said zinc organic acid.

14. The method for manufacturing mesoporous carbon according to claim 13, further comprising: The process of feeding organic zinc acid as a raw material from the outside of the furnace into the furnace.

15. The method for manufacturing mesoporous carbon according to claim 13, wherein, The flow rate of the cooling gas is above 0.02 m / s and below 1.0 m / s.

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