A device and method for preparing carbon material and graphene-mesoporous carbon hybrid

Abstract

The present invention provides a device for preparing carbon materials, which mainly includes a liquid metal melting device and a liquid hydrocarbon tank for recovering volatile metals, and a pipeline for returning volatile metals and liquid hydrocarbons to the liquid molten metal device. The present invention also provides a method for preparing carbon materials, wherein gaseous alkanes are passed into the liquid metal melting device, and graphene is generated by cracking at high temperature. At the same time, mesoporous carbon is passed above the liquid metal, and the remaining methane is continuously cracked at high temperature to generate graphene-mesoporous carbon hybrids, and the height of the carbon product above the liquid metal is controlled, and the material is discharged regularly. After the volatile metal is absorbed by the liquid hydrocarbon, it is regularly returned to the liquid molten metal device. This method has the advantages of low energy consumption, high product purity, continuous operation, and low cost. Due to the presence of graphene-mesoporous carbon, the dispersion of graphene can be promoted, and pure graphene and graphene-mesoporous carbon hybrids with high specific surface area can be prepared.

Description

Technical Field

[0001] The present invention relates to the technical field of nano material processing, and in particular to a device and method for preparing carbon materials and a graphene-mesoporous carbon hybrid. Background Art

[0002] Graphene is a two-dimensional SP2 hybrid carbon material with the advantages of large specific surface area and good conductivity. It can be used as an electrode material for capacitors or a conductive agent for lithium-ion batteries and an environmental adsorption material. However, since the stacking density of graphene is very small, adding a large amount of it will lead to a decrease in the compaction density of the pole piece of the energy storage device and a decrease in the energy density of the device.

[0003] Mesoporous carbon is a special type of activated carbon with an SP3 hybrid carbon structure. It is mainly obtained by the activation method of microporous activated carbon and has the advantage of high bulk density. However, compared with SP2 hybrid carbon, SP3 hybrid carbon has insufficient conductivity. Therefore, when used as an electrode material, it has a tendency to attenuate performance under high power.

[0004] Obviously, if a hybrid of graphene and mesoporous carbon can be prepared and a certain ratio can be controlled, an excellent electrode material with two properties can be obtained - graphene-mesoporous carbon hybrid. Graphene-mesoporous carbon hybrid combines the advantages of graphene and mesoporous carbon. As one of the materials with the best conductivity, graphene can significantly improve the conductivity and thermal conductivity of the composite hybrid. This makes graphene-mesoporous carbon hybrids have broad application prospects in electronic devices, energy storage, and sensors. In addition, mesoporous carbon has rich pore structure and high specific surface area, which can provide more active sites and adsorption space. Through the combination with graphene, graphene-mesoporous carbon hybrids can show good performance in the fields of catalysts, adsorption materials, and separation membranes. In addition, graphene, as a material with extremely high mechanical strength, can improve the mechanical properties of composite hybrids. This has potential application prospects in the preparation of high-performance composite materials and reinforced materials.

[0005] At present, graphene is mainly produced by chemical vapor deposition (CVD)-silicon, oxide template method or graphite intercalation exfoliation. In the CVD method, the conversion rate of the carbon source is very low and the cost is high. Mesoporous carbon is often produced by water vapor activation, CO2 activation or alkali activation of microporous carbon, and the preparation environment of the two is quite different. If graphene is prepared by the oxide template method and then compounded with mesoporous carbon, there is a template removal process, which will affect the purity of the mesoporous carbon.

[0006] At present, there are also reports on the method of preparing graphene by cracking hydrocarbons with methane as the main component in liquid molten metal, but this method is still in the research stage and needs further improvement and optimization to improve the quality and yield of graphene. In addition, the specific surface area of ​​graphene obtained by this method is low and still needs to be improved. At the same time, molten metal generally contains low melting point metals, which will cause the melting point to rise after volatilization, and increase energy consumption.

[0007] Therefore, there is currently no device or method for using liquid molten metal to crack alkanes to synergistically prepare carbon materials (high-purity, high specific surface area graphene, graphene-mesoporous carbon hybrids, etc.). Summary of the invention

[0008] In view of the above problems existing in the prior art, the present invention provides a carbon material preparation device, a preparation method and a graphene-mesoporous carbon hybrid obtained by the method, and adopts a liquid molten metal to crack alkanes and cooperate with mesoporous carbon to prepare a high-purity, high specific surface area carbon material. The specific content of the invention is as follows:

[0009] In a first aspect, the present invention provides a device for preparing a carbon material, the device comprising:

[0010] A liquid molten metal device 1, wherein the liquid molten metal is contained in the liquid molten metal device 1, the liquid molten metal device 1 is divided into a liquid molten metal section 3 and a gas phase reaction section 4 by the liquid surface of the liquid molten metal, the liquid molten metal section 3 is provided with a raw material inlet 7, and the gas phase reaction section 4 is provided with a mesoporous carbon inlet 5 and a gas product outlet 8; the liquid molten metal device 1 is used to convert gaseous alkanes entering through the raw material inlet 7 into graphene and hydrogen, and the liquid molten metal device 1 is used to react the mesoporous carbon entering through the mesoporous carbon inlet 5 with the gaseous alkanes to generate graphene-mesoporous carbon hybrids;

[0011] The volatile metal absorption device 2 is provided with a gas product inlet 9 and a liquid hydrocarbon outlet 13; the volatile metal absorption device 2 contains liquid hydrocarbons for absorbing the metal vapor volatilized from the liquid molten metal device 1 entering the volatile metal absorption device 2 through the gas product inlet 9, and circulates the liquid hydrocarbons absorbing the metal vapor to the raw material inlet 7 through the liquid hydrocarbon outlet 13 to be supplied to the liquid molten metal device 1, thereby realizing the addition of volatile metals;

[0012] The gas product outlet 8 is connected to the gas product inlet 9 through a pipeline;

[0013] The liquid hydrocarbon outlet 13 is connected to the raw material inlet 7 through a pipeline.

[0014] Optionally, the liquid molten metal device 1 further comprises a carbon product outlet 6 , and the carbon product outlet 6 is located above the liquid surface and below the mesoporous carbon inlet 5 .

[0015] Optionally, the volatilized metal absorption device 2 further comprises a baffle 11 and a gas outlet 10, wherein the baffle 11 is used to prolong the residence time of the metal vapor in the liquid hydrocarbon, and the gas outlet 10 is used to discharge the gas without metal.

[0016] In a second aspect, the present invention provides a method for preparing a carbon material, the method being applicable to the device described in the first aspect, the method comprising:

[0017] The gaseous alkane is introduced into the liquid molten metal device 1 through the raw material inlet 7. When the gaseous alkane passes through the liquid molten metal section 3 in the form of bubbles, it is converted into graphene and hydrogen. The graphene floats on the liquid surface. The mesoporous carbon is introduced into the gas phase reaction section 4 of the liquid molten metal device 1 through the mesoporous carbon inlet 5. During the falling process, the residual gaseous alkane is catalyzed to generate graphene on the surface of the mesoporous carbon, thereby forming the graphene-mesoporous carbon hybrid.

[0018] The mesoporous carbon and the graphene-mesoporous carbon hybrid further fall to the liquid surface, effectively dispersing the graphene floating on the liquid surface and reducing the stacking of the graphenes;

[0019] When the height of the solid carbon product floating on the liquid surface reaches 1 / 2-3 / 4 of the height between the liquid surface and the mesoporous carbon inlet 5, the gaseous alkane feed is stopped, and hydrogen is introduced into the raw material inlet 7 to blow the solid carbon product out of the device from the carbon product outlet 6;

[0020] A small amount of metal components volatilized from the gas product outlet 8 along with hydrogen enter the volatilized metal absorption device 2 from the gas product inlet 9, pass through the baffle 11 to extend the residence time, are absorbed by the liquid hydrocarbon, and hydrogen is discharged from the gas outlet 10 to obtain hydrogen;

[0021] The feed of gaseous alkane and mesoporous carbon is restored to make the preparation process continuous;

[0022] The liquid alkane in the volatile metal absorption device 2 is periodically circulated to the raw material inlet 7 of the device 1 through the liquid hydrocarbon outlet 13 to complete the cyclic replenishment of the volatile metal component.

[0023] Optionally, the gaseous alkane is methane and / or ethane;

[0024] The molecular weight range of the liquid alkane is 160-260;

[0025] The molten metal is formed by melting mixed metal powder under conditions of applied voltage and current, the temperature of the molten metal is 600-1200 oC, the mixed metal powder is mixed with one or more of copper, nickel, iron, molybdenum and manganese and one or more of aluminum, gallium and tin, and the particle size of the mixed metal powder is 1-10 μm.

[0026] Optionally, the particle size of the mesoporous carbon is 1-50 μm.

[0027] Optionally, the residence time of the gaseous alkane in the liquid molten metal section 3 is 1-20 s;

[0028] The residence time of the gaseous alkane in the gas phase reaction section 4 is 1-10 s.

[0029] In a third aspect, the present invention provides a graphene-mesoporous carbon hybrid obtained by the preparation method described in the second aspect.

[0030] Optionally, the specific surface area of ​​the graphene-mesoporous carbon hybrid is 1600-2400 m2 / g;

[0031] The compacted density of the graphene-mesoporous carbon hybrid is 300-600 kg / m3;

[0032] In the graphene-mesoporous carbon hybrid, the mass fraction of the graphene is 0.1%-10%.

[0033] Optionally, in the graphene-mesoporous carbon hybrid, the growth height of the graphene is 1-20 μm.

[0034] Compared with the prior art, the present invention has the following advantages:

[0035] The present invention provides a device for preparing carbon materials, which mainly includes a liquid metal melting device, a liquid hydrocarbon tank for recovering volatile metals, and a pipeline for returning volatile metals and liquid hydrocarbons to the liquid molten metal device. The present invention also provides a method for preparing carbon materials, wherein gaseous alkanes are introduced into the liquid metal melting device, and are cracked at high temperature to generate graphene. At the same time, mesoporous carbon is introduced above the liquid metal, and the remaining methane is continuously cracked at high temperature to generate graphene-mesoporous carbon hybrids, and the height of the carbon product above the liquid metal is controlled, and the material is discharged regularly. After the volatile metals are absorbed by the liquid hydrocarbons, they are regularly returned to the liquid molten metal device. The method has the advantages of low energy consumption, high product purity, continuous operation, and low cost. Due to the presence of graphene-mesoporous carbon, the dispersion of graphene can be promoted, and pure graphene and graphene-mesoporous carbon hybrids with high specific surface area can be prepared. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0037] Figure 1 A schematic diagram of the structure of a carbon material preparation device provided in an embodiment of the present invention is shown;

[0038] Figure 2 A flow chart of a method for preparing carbon material provided by an embodiment of the present invention is shown.

[0039] Among them, the attached Figure 1 The reference numerals shown are explained as follows:

[0040] 1-liquid molten metal device, 2-volatile metal absorption device, 3-liquid molten metal section, 4-gas phase reaction section, 5-mesoporous carbon inlet, 6-carbon product outlet, 7-raw material inlet, 8-gas product outlet, 9-gas product inlet, 10-gas outlet, 11-baffle, 13-liquid hydrocarbon outlet. DETAILED DESCRIPTION

[0041] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means a limitation on the present invention and its application or use. Based on the embodiments of the present invention, any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts falls within the scope of protection of the present invention. In addition, all other embodiments obtained by ordinary technicians in this field without carrying out creative work belong to the scope of protection of the present invention.

[0042] In the embodiment, no specific experimental steps or conditions are indicated, and the operation or conditions of the conventional experimental steps described in the prior art in this field can be carried out. The reagents used and other instruments that do not indicate the manufacturer are conventional reagent products that can be obtained commercially. In addition, the accompanying drawings are only schematic diagrams of the embodiments of the present invention and are not necessarily drawn to scale. The same reference numerals in the figures represent the same or similar parts, and thus their repeated description will be omitted. Some block diagrams shown in the accompanying drawings are functional entities and do not necessarily correspond to physically or logically independent entities.

[0043] Technologies, methods, and equipment known to ordinary technicians in the relevant field may not be discussed in detail, but where appropriate, the technologies, methods, and equipment should be considered as part of the description of the present invention.

[0044] In the description of the present invention, it should be understood that the use of terms such as "first" and "second" to limit components is only for the convenience of distinguishing the corresponding components. Unless otherwise stated, the above terms have no special meaning and therefore cannot be understood as limiting the scope of protection of the present invention.

[0045] In addition, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0046] Before describing in detail the graphene-mesoporous carbon hybrid, preparation method and device provided by the present invention, it is necessary to make the following explanations:

[0047] The existing methods for preparing graphene still need to focus on solving the problems of low specific surface area and agglomeration of graphene, while mesoporous carbon has the characteristics of high stacking density. Using it in the preparation of carbon material graphene can not only improve the agglomeration of graphene to a certain extent, but also obtain additional graphene-mesoporous carbon hybrids. Based on this existing concept, the present invention adopts a liquid molten metal device 1 in conjunction with a volatile metal absorption device 2 to achieve the method of cracking alkanes with liquid molten metal, and cooperates with mesoporous carbon to prepare high-purity, high specific surface area graphene, and graphene-mesoporous carbon hybrids. Specifically, a carbon material preparation device, a preparation method, and a graphene-mesoporous carbon hybrid obtained by the method are provided. The specific implementation content is as follows:

[0048] In a first aspect, the present invention provides a device for preparing a carbon material. Figure 1 The schematic diagram of the structure of the device for preparing carbon material provided by the embodiment of the present invention is shown. Referring to 1, the device comprises:

[0049] A liquid molten metal device 1, wherein the liquid molten metal is contained in the liquid molten metal device 1, the liquid molten metal device 1 is divided into a liquid molten metal section 3 and a gas phase reaction section 4 by the liquid surface of the liquid molten metal, the liquid molten metal section 3 is provided with a raw material inlet 7, and the gas phase reaction section 4 is provided with a mesoporous carbon inlet 5 and a gas product outlet 8; the liquid molten metal device 1 is used to convert gaseous alkanes entering through the raw material inlet 7 into graphene and hydrogen, and the liquid molten metal device 1 is used to react mesoporous carbon entering through the mesoporous carbon inlet 5 with gaseous alkanes to generate graphene-mesoporous carbon hybrids;

[0050] The volatile metal absorption device 2 is connected to the liquid molten metal device 1, and is provided with a gas product inlet 9 and a liquid hydrocarbon outlet 13; the volatile metal absorption device 2 contains liquid hydrocarbons for absorbing the metal vapor volatilized from the liquid molten metal device 1 entering therein through the gas product inlet 9, and circulates the liquid hydrocarbons absorbing the metal vapor to the raw material inlet 7 through the liquid hydrocarbon outlet 13 to be supplied to the liquid molten metal device 1, thereby realizing the replenishment of the volatile metal; wherein the gas product outlet 8 and the gas product inlet 9 are connected through a pipeline; and the liquid hydrocarbon outlet 13 and the raw material inlet 7 are connected through a pipeline.

[0051] Continue to see Figure 1 The liquid molten metal device 1 further comprises a carbon product outlet 6, which is located above the liquid surface and below the mesoporous carbon inlet 5. This ensures that the product graphene-mesoporous carbon hybrid and graphene can be smoothly blown away from the liquid molten metal device 1 by hydrogen.

[0052] A baffle 11 and a gas outlet 10 are also provided inside the volatile metal absorption device 2. The baffle 11 is used to prolong the residence time of the metal vapor in the liquid hydrocarbon so that the metal vapor has enough time to condense and form solid metal particles to be recovered, thereby improving the purity of the hydrogen discharged from the gas outlet 10.

[0053] In a second aspect, the present invention provides a method for preparing a carbon material. Figure 2 The flowchart of the method for preparing carbon material provided by the embodiment of the present invention is shown as follows: Figure 2 As shown, the method is applicable to the device of the first aspect above, and the method specifically comprises the following steps:

[0054] S1, introducing alkane into the liquid molten metal device 1 through the raw material inlet 7, and converting the alkane into graphene and hydrogen when passing through the liquid molten metal section 3 in the form of bubbles, and the graphene floats on the liquid surface, and then introducing the mesoporous carbon into the gas phase reaction section 4 of the liquid molten metal device 1 through the mesoporous carbon inlet 5, and in the process of falling, catalyzing the residual alkane to generate graphene on the surface of the mesoporous carbon, forming a graphene-mesoporous carbon hybrid;

[0055] S2, the graphene-mesoporous carbon hybrid further falls to the liquid surface, effectively dispersing the graphene floating on the liquid surface and reducing the stacking of graphene;

[0056] S3, when the height of the solid carbon product floating on the liquid surface reaches 1 / 2-3 / 4 of the height between the liquid surface and the mesoporous carbon inlet 5, the alkane feed is stopped, and hydrogen is introduced into the raw material inlet 7 to blow the solid carbon product out of the device from the carbon product outlet 6;

[0057] S4, a small amount of metal components volatilized from the gas product outlet 8 along with hydrogen enter the volatilized metal absorption device 2 from the gas product inlet 9, pass through the baffle 11 to extend the residence time, are absorbed by the liquid hydrocarbon, and hydrogen is discharged from the gas outlet 10 to obtain hydrogen;

[0058] S5, resuming the feeding of alkane and mesoporous carbon to make the preparation process continuous;

[0059] S6. Regularly circulate the liquid alkane in the volatile metal absorption device 2 to the raw material inlet 7 of the device 1 through the liquid hydrocarbon outlet 13 to complete the cyclic replenishment of the volatile metal component.

[0060] In specific implementation, the mesoporous carbon enters the gas phase reaction section 4. Since the mesoporous carbon surface has certain activation groups, the alkanes that have not reacted in the liquid molten metal section 3 can be further cracked to generate graphene on its surface, thereby forming a seamless graphene-mesoporous carbon hybrid structure, which improves the conversion rate of hydrocarbons and makes the subsequent hydrogen products more valuable. At the same time, the high-temperature gaseous hydrogen generated by the cracking of alkanes will also play a shaping role in the structure of the mesoporous carbon (including increasing the degree of graphitization and removing metal impurities), saving about 20% of the dispersion and purification costs.

[0061] Furthermore, volatile metal components also enter the gas phase reaction section 4 together with hydrogen and unreacted alkanes. In the reaction between alkanes and graphene, due to the high dispersibility of volatile metal components, the conversion rate of gaseous hydrocarbons is further improved, and the separation cost of gas products is reduced by 20%-30%.

[0062] In the specific implementation, in the process of preparing graphene by catalysis of liquid molten metal, gaseous alkanes are catalytically reacted to generate graphene and hydrogen. The generated graphene floats on the surface of the liquid metal, and the residual (unreacted) gaseous alkanes rising with the hydrogen further react with the added mesoporous carbon, so that hydrocarbons generate graphene on its surface, thereby forming a seamless hybrid structure - graphene-mesoporous carbon. The generated graphene-mesoporous carbon has a higher packing density than graphene. Under the agitation of molten metal and bubbles, the graphene floating on the liquid surface is further effectively dispersed by the falling graphene-mesoporous carbon, reducing stacking, thereby increasing the proportion of high specific surface area graphene by about 20-30%. In addition, the presence of mesoporous carbon reduces the splashing degree of molten metal and increases equipment safety.

[0063] In specific implementation, since chemically stable, high-boiling-point liquid alkanes are used to cool and collect volatile metals, the process is highly safe and easy to operate, reducing equipment costs by 2% and management costs by 5%.

[0064] In some embodiments, the alkane introduced into the raw material inlet 7 may be methane and / or ethane; the molecular weight of the liquid alkane in the volatile metal absorption device 2 may be in the range of 160-260; the molten metal may be formed by melting a mixed metal powder under the conditions of applying voltage and current, and the temperature of the molten metal may be in the range of 600-1200 o C, the mixed metal powder is formed by mixing one or more of copper, nickel, iron, molybdenum and manganese with one or more of low melting point metals such as aluminum, gallium and tin, and the particle size of the mixed metal powder is 1-10 μm.

[0065] In some embodiments, the particle size of the mesoporous carbon may be 1-50 μm.

[0066] In a third aspect, the present invention provides a graphene-mesoporous carbon hybrid obtained by the preparation method of the second aspect.

[0067] In some embodiments, the specific surface area of ​​the obtained graphene-mesoporous carbon hybrid is 1600-2400 m 2 / g;

[0068] The compacted density of graphene-mesoporous carbon hybrids is 300-600 kg / m 3 ;

[0069] In the graphene-mesoporous carbon hybrid, the mass fraction of graphene is 0.1%-10%.

[0070] In some embodiments, in the obtained graphene-mesoporous carbon hybrid, the growth height of graphene is 1-20 μm.

[0071] In order to enable those skilled in the art to more clearly understand the present invention, the device and method for preparing carbon materials and the graphene-mesoporous carbon hybrid of the present invention are now described in detail through the following examples.

[0072] Example 1

[0073] Mixed metal powder (90% copper, 5% aluminum, 5% gallium, particle size range 1-5 μm) was placed in a liquid molten metal device 1, voltage and current were applied, and the temperature was 850 o C, the metal powder becomes liquid molten metal, and forms a liquid molten metal section 3 in the liquid molten metal device 1.

[0074] Hydrocarbons (100% methane) are introduced into the liquid molten metal through the bottom raw material inlet 7 at a pressure of 5 MPa. The hydrocarbons react with the liquid metal in the form of tiny bubbles for 20 seconds to generate small pieces of graphene and hydrogen.

[0075] The small pieces of graphene and hydrogen gradually float up and reach the upper surface of the liquid molten metal. Mesoporous carbon (particle size 1-50 μm) is introduced into the liquid molten metal device 1 from the mesoporous carbon inlet 5. The mesoporous carbon reacts with the rising residual methane in the gas phase reaction section 4 for 10 seconds, continues to crack the methane, and generates graphene on the surface of the mesoporous carbon (the height of the graphene is 1-20 μm), forming a hybrid (graphene grows almost vertically on the surface of the mesoporous carbon particles. The specific surface area is 1600-2400 m 2 / g, compacted density is 300-600 kg / m 3 . The mass fraction of graphene in the hybrid is 0.1%-10%).

[0076] Methane is cracked to generate hydrogen, which leaves the reactor from the gas product outlet 8 of the liquid molten metal device 1. The hybrid of mesoporous carbon and graphene falls to the surface of the liquid molten metal, and is mixed with the graphene floating out of the liquid metal under the stirring of bubbles, promoting the dispersion of graphene.

[0077] The height of the hybrid of graphene and mesoporous carbon and pure graphene gradually increases. When the height reaches 1 / 2-3 / 4 of the height between the liquid molten metal and the mesoporous carbon feed port, the methane and mesoporous carbon are stopped, and only hydrogen is passed through the raw material inlet 7, and all carbon products are blown out of the liquid molten metal device 1 from the solid outlet 6. The carbon products are cooled and used for other purposes. The hydrocarbon raw material is resumed to the raw material inlet 7, the mesoporous carbon feed of the mesoporous carbon inlet 5 is resumed, and the hydrogen feed of the raw material inlet 7 is gradually closed, so that the process is operated continuously.

[0078] A small amount of metal components volatilized with the gas from the gas product outlet 8 enter the volatilized metal absorption device 2 from the gas product inlet 9, are absorbed into the liquid hydrocarbons (hydrocarbons with a molecular weight of 160-260), pass through the internal baffle 11 to extend the residence time, and then obtain metal-free gas through the gas outlet 10.

[0079] The hydrocarbons in the volatile metal absorption device 2 are regularly circulated to the raw material inlet 7 of the liquid molten metal device 1 through the liquid hydrocarbon outlet 13, so as to realize the cyclic replenishment of the volatile metal components, so that the volatile components of the liquid molten metal section 3 remain stable. After the liquid hydrocarbons in the volatile metal absorption device 2 enter the liquid molten metal device 1, they are also converted into graphene and hydrogen.

[0080] Example 2

[0081] Mixed metal powder (70% copper, 5% molybdenum, 5% manganese, 20% gallium, with a particle size range of 5-10 μm) was placed in a liquid molten metal device 1, and voltage and current were applied at a temperature of 900 o C, the metal powder becomes liquid molten metal, and forms a liquid molten metal section 3 in the liquid molten metal device 1.

[0082] Hydrocarbons (50% methane, 50% ethane) are introduced into the liquid molten metal through the bottom raw material inlet 7 at a pressure of 1 MPa. Hydrocarbons such as methane or ethane react with the liquid metal in the form of tiny bubbles for 10 seconds. Ethane is completely converted to generate small pieces of graphene and hydrogen.

[0083] The small pieces of graphene and hydrogen gradually float up and reach the upper surface of the liquid molten metal. Mesoporous carbon (particle size 50 μm) is introduced into the liquid molten metal device 1 from the mesoporous carbon inlet 5. The mesoporous carbon reacts with the rising residual methane in the gas phase reaction section 4 for 10 seconds, continues to crack the methane, and generates graphene on the surface of the mesoporous carbon (the height of the graphene is 1 μm), forming a hybrid (graphene grows almost vertically on the surface of the mesoporous carbon particles. The specific surface area is 2000 m 2 / g, compacted density is 500 kg / m 3 . The mass fraction of graphene in the hybrid is 0.1%).

[0084] Methane is cracked to generate hydrogen, which leaves the reactor from the gas product outlet 8 of the liquid molten metal device 1. The hybrid of mesoporous carbon and graphene falls to the surface of the liquid molten metal, and is mixed with the graphene floating out of the liquid metal under the stirring of bubbles, promoting the dispersion of graphene.

[0085] The height of the hybrid of graphene and mesoporous carbon and pure graphene gradually increases. When the height reaches 75% of the height between the liquid molten metal and the mesoporous carbon feed port, the methane and mesoporous carbon are stopped, and only hydrogen is passed through the raw material inlet 7, and all carbon products are blown out of the liquid molten metal device 1 from the solid outlet 6. The carbon products are cooled and used for other purposes. The hydrocarbon raw material is resumed to the raw material inlet 7, the mesoporous carbon feed of the mesoporous carbon inlet 5 is resumed, and the hydrogen feed of the raw material inlet 7 is gradually closed, so that the process is operated continuously.

[0086] A small amount of metal component (gallium) volatilized with the gas from the gas product outlet 8 enters the volatilized metal absorption device 2 from the gas product inlet 9, is absorbed into the liquid hydrocarbon (molecular weight range 160-240), passes through the internal baffle 11 to extend the residence time, and then obtains the metal-free gas through the gas outlet 10.

[0087] The liquid hydrocarbons in the volatile metal absorption device 2 are regularly circulated to the raw material inlet 8 of the liquid molten metal device 1 through the liquid hydrocarbon outlet 13, so as to realize the cyclic replenishment of the volatile metal component (gallium) and keep the volatile components of the liquid molten metal section 3 stable. After the liquid hydrocarbons in the volatile metal absorption device 2 enter the liquid molten metal device 1, they are also converted into graphene and hydrogen.

[0088] Example 3

[0089] Mixed metal powder (5% copper, 40% aluminum, 30% gallium, 25% nickel, particle size range 1-5 μm) was placed in a liquid molten metal device 1, and voltage and current were applied at a temperature of 600 o C, the metal powder becomes liquid molten metal, and forms a liquid molten metal section 3 in the liquid molten metal device 1.

[0090] Gaseous hydrocarbons (100% ethane) are introduced into the liquid molten metal through the bottom raw material inlet 7 at a pressure of 2 MPa. The gaseous hydrocarbons react with the liquid metal in the form of tiny bubbles for 20 seconds, and the ethane is completely converted to generate small pieces of graphene, methane and hydrogen.

[0091] Small pieces of graphene, methane and hydrogen gradually float up and reach the upper surface of the liquid molten metal. Mesoporous carbon (particle size 1 μm) is introduced into the liquid molten metal device 1 from the mesoporous carbon inlet 5. The mesoporous carbon reacts with the rising residual methane and ethane in the gas phase reaction section 4 for 15 seconds, and continues to crack methane and ethane, and generates graphene on the surface of the mesoporous carbon (the height of the graphene is 1 μm), forming a hybrid (graphene grows almost vertically on the surface of the mesoporous carbon particles. The specific surface area is 1600 m 2 / g, compacted density is 300 kg / m 3 . The mass fraction of graphene in the hybrid is 8%).

[0092] Ethane and methane are cracked to generate hydrogen, which leaves the reactor from the gas product outlet 8 of the liquid molten metal device 1. The hybrid of mesoporous carbon and graphene falls to the surface of the liquid molten metal, and under the stirring of bubbles, mixes with the graphene floating out of the liquid metal, promoting the dispersion of the graphene.

[0093] The height of the hybrid of graphene and mesoporous carbon and pure graphene gradually increases. When the height reaches 1 / 2 of the height between the liquid molten metal and the mesoporous carbon feed port, the feeding of methane and mesoporous carbon is stopped, and only hydrogen is passed through the raw material inlet 7, and all carbon products are blown out of the liquid molten metal device 1 from the solid outlet 6. The carbon products are cooled and used for other purposes. The hydrocarbon raw material is resumed to the raw material inlet 7, the mesoporous carbon feed of the mesoporous carbon inlet 5 is resumed, and the hydrogen feed of the raw material inlet 7 is gradually closed, so that the process is operated continuously.

[0094] A small amount of metal components (aluminum, gallium) volatilized with the gas from the gas product outlet 8 enters the volatilized metal absorption device 2 from the gas product inlet 9, is absorbed into the liquid hydrocarbon (molecular weight range 2000-260), passes through the internal baffle 11 to extend the residence time, and then obtains the metal-free gas through the gas outlet 10.

[0095] The liquid hydrocarbons in the volatile metal absorption device 2 are regularly circulated to the raw material inlet 8 of the liquid molten metal device 1 through the liquid hydrocarbon outlet 13, so as to realize the cyclic replenishment of the volatile metal components (aluminum, gallium), so that the volatile components of the liquid molten metal section 3 remain stable. After the liquid hydrocarbons in the volatile metal absorption device 2 enter the liquid molten metal device 1, they are also converted into graphene and hydrogen.

[0096] Example 4

[0097] Mixed metal powder (50% copper, 20% nickel, 30% tin, particle size range 1-10 μm) was placed in a liquid molten metal device 1, voltage and current were applied, and the temperature was 1200 o C, the metal powder becomes liquid molten metal, and forms a liquid molten metal section 3 in the liquid molten metal device 1.

[0098] Gaseous hydrocarbons (90% methane, 10% ethane) are introduced into the liquid molten metal through the bottom raw material inlet 7 at a pressure of 1 MPa. The gaseous hydrocarbons react with the liquid metal in the form of tiny bubbles for 10 seconds, and the ethane is completely converted to generate small pieces of graphene and hydrogen.

[0099] The small pieces of graphene and hydrogen gradually float up and reach the upper surface of the liquid molten metal. Mesoporous carbon (particle size 50 μm) is introduced into the liquid molten metal device 1 from the mesoporous carbon inlet 5. The mesoporous carbon reacts with the rising residual methane in the gas phase reaction section 4 for 12 seconds, continues to crack the methane, and generates graphene on the surface of the mesoporous carbon (the height of the graphene is 20 μm), forming a hybrid (graphene grows almost vertically on the surface of the mesoporous carbon particles. The specific surface area is 2400 m 2 / g, compacted density is 600 kg / m 3 . The mass fraction of graphene in the hybrid is 10%).

[0100] Methane is cracked to generate hydrogen, which leaves the reactor from the gas product outlet 8 of the liquid molten metal device 1. The hybrid of mesoporous carbon and graphene falls to the surface of the liquid molten metal, and is mixed with the graphene floating out of the liquid metal under the stirring of bubbles, promoting the dispersion of graphene.

[0101] The height of the hybrid of graphene and mesoporous carbon and pure graphene gradually increases. When the height reaches 3 / 4 of the height between the liquid molten metal and the mesoporous carbon feed port, the methane and mesoporous carbon are stopped, and only hydrogen is passed through the raw material inlet 7, and all carbon products are blown out of the liquid molten metal device 1 from the solid outlet 6. The carbon products are cooled and used for other purposes. The hydrocarbon raw material is resumed to the raw material inlet 7, the mesoporous carbon feed of the mesoporous carbon inlet 5 is resumed, and the hydrogen feed of the raw material inlet 7 is gradually closed, so that the process is operated continuously.

[0102] A small amount of metal component (tin) volatilized with the gas from the gas product outlet 8 enters the volatilized metal absorption device 2 from the gas product inlet 9, is absorbed into the liquid hydrocarbon (molecular weight range is 160-200), passes through the internal baffle 11 to extend the residence time, and then obtains the metal-free gas through the gas outlet 10.

[0103] The hydrocarbons in the volatile metal absorption device 2 are regularly circulated to the raw material inlet 8 of the liquid molten metal device 1 through the liquid hydrocarbon outlet 13, so as to realize the cyclic replenishment of the volatile metal component (tin) and keep the volatile components of the liquid molten metal section 3 stable. After the liquid hydrocarbons in the volatile metal absorption device 2 enter the liquid molten metal device 1, they are also converted into graphene and hydrogen.

[0104] Example 5

[0105] Mixed metal powder (50% iron, 20% aluminum, 30% magnesium, particle size range 2-8 μm) was placed in a liquid molten metal device 1, voltage and current were applied, and the temperature was 1100 o C, the metal powder becomes liquid molten metal, and forms a liquid molten metal section 3 in the liquid molten metal device 1.

[0106] Gaseous hydrocarbons (40% methane, 60% ethane) are introduced into the liquid molten metal through the bottom raw material inlet 7 at a pressure of 4 MPa. The gaseous hydrocarbons react with the liquid metal in the form of tiny bubbles for 1 second to generate small pieces of graphene and hydrogen.

[0107] The small pieces of graphene and hydrogen gradually float up and reach the upper surface of the liquid molten metal. Mesoporous carbon (particle size 10 μm) is introduced into the liquid molten metal device 1 from the mesoporous carbon inlet 5. The mesoporous carbon reacts with the rising residual methane in the gas phase reaction section 4 for 1 second, continues to crack the methane, and generates graphene on the surface of the mesoporous carbon (the height of the graphene is 1 μm), forming a hybrid (graphene grows almost vertically on the surface of the mesoporous carbon particles. The specific surface area is 1800 m 2 / g, compacted density is 450 kg / m 3 . The mass fraction of graphene in the hybrid is 2%).

[0108] Methane is cracked to generate hydrogen, which leaves the reactor from the gas product outlet 8 of the liquid molten metal device 1. The hybrid of mesoporous carbon and graphene falls to the surface of the liquid molten metal, and is mixed with the graphene floating out of the liquid metal under the stirring of bubbles, promoting the dispersion of graphene.

[0109] The height of the hybrid of graphene and mesoporous carbon and pure graphene gradually increases. When the height reaches 3 / 4 of the height between the liquid molten metal and the mesoporous carbon feed port, the methane and mesoporous carbon are stopped, and only hydrogen is passed through the raw material inlet 7, and all carbon products are blown out of the liquid molten metal device 1 from the solid outlet 6. The carbon products are cooled and used for other purposes. The hydrocarbon raw material is resumed to the inlet 7, the mesoporous carbon feed of the mesoporous carbon inlet 5 is resumed, and the hydrogen feed of the inlet 7 is gradually closed, so that the process is operated continuously.

[0110] A small amount of metal components (aluminum, magnesium) volatilized with the gas from the gas product outlet 8 enters the volatilized metal absorption device 2 from the gas product inlet 9, is absorbed into the liquid hydrocarbon (molecular weight range is 180-200), passes through the internal baffle 11 to extend the residence time, and then obtains the metal-free gas through the gas outlet 10.

[0111] The hydrocarbons in the volatile metal absorption device 2 are regularly circulated to the raw material inlet 8 of the liquid molten metal device 1 through the liquid hydrocarbon outlet 13, so as to realize the cyclic replenishment of the volatile metal components (aluminum, magnesium), so that the volatile components of the liquid molten metal section 3 remain stable. After the liquid hydrocarbons in the volatile metal absorption device 2 enter the liquid molten metal device 1, they are also converted into graphene and hydrogen.

[0112] Example 6

[0113] The mixed metal powder (20% nickel, 80% magnesium, particle size range 5-8 μm) was placed in a liquid molten metal device 1, and voltage and current were applied at a temperature of 900 o C, the metal powder becomes liquid molten metal, and forms a liquid molten metal section 3 in the liquid molten metal device 1.

[0114] Gaseous hydrocarbons (20% methane, 80% ethane) are introduced into the liquid molten metal through the bottom raw material inlet 7 at a pressure of 4 MPa. The gaseous hydrocarbons react with the liquid metal in the form of tiny bubbles for 8 seconds, and the ethane is completely converted to generate small pieces of graphene, methane and hydrogen.

[0115] Small pieces of graphene, methane and hydrogen gradually float up and reach the upper surface of the liquid molten metal. Mesoporous carbon (particle size 10 μm) is introduced into the liquid molten metal device 1 from the mesoporous carbon inlet 5. The mesoporous carbon reacts with the rising residual methane in the gas phase reaction section 4 for 15 seconds, continues to crack the methane, and generates graphene on the surface of the mesoporous carbon (the height of the graphene is 1 μm), forming a hybrid (graphene grows almost vertically on the surface of the mesoporous carbon particles. The specific surface area is 1800 m 2 / g, compacted density is 450 kg / m 3 . The mass fraction of graphene in the hybrid is 2%).

[0116] Methane is cracked to generate hydrogen, which leaves the reactor from the gas product outlet 8 of the liquid molten metal device 1. The hybrid of mesoporous carbon and graphene falls to the surface of the liquid molten metal, and is mixed with the graphene floating out of the liquid metal under the stirring of bubbles, promoting the dispersion of graphene.

[0117] The height of the hybrid of graphene and mesoporous carbon and pure graphene gradually increases. When the height reaches 3 / 4 of the height between the liquid molten metal and the mesoporous carbon feed port, the methane and mesoporous carbon are stopped, and only hydrogen is passed through the raw material inlet 7, and all carbon products are blown out of the liquid molten metal device 1 from the solid outlet 6. The carbon products are cooled and used for other purposes. The hydrocarbon raw material is resumed to the inlet 7, the mesoporous carbon feed of the mesoporous carbon inlet 5 is resumed, and the hydrogen feed of the inlet 7 is gradually closed, so that the process is operated continuously.

[0118] A small amount of metal component (magnesium) volatilized with the gas from the gas product outlet 8 enters the volatilized metal absorption device 2 from the gas product inlet 9, is absorbed into the liquid hydrocarbon (molecular weight range is 180-200), passes through the internal baffle 11 to extend the residence time, and then obtains the metal-free gas through the gas outlet 10.

[0119] The hydrocarbons in the volatile metal absorption device 2 are regularly circulated to the raw material inlet 8 of the liquid molten metal device 1 through the liquid hydrocarbon outlet 13, so as to realize the cyclic replenishment of the volatile metal component (magnesium) and keep the volatile components of the liquid molten metal section 3 stable. After the liquid hydrocarbons in the volatile metal absorption device 2 enter the liquid molten metal device 1, they are also converted into graphene and hydrogen.

[0120] Example 7

[0121] The mixed metal powder (30% copper, 70% magnesium, particle size range 2-8 μm) was placed in a liquid molten metal device 1, and voltage and current were applied at a temperature of 890 o C, the metal powder becomes liquid molten metal, and forms a liquid molten metal section 3 in the liquid molten metal device 1.

[0122] Gaseous hydrocarbons (70% methane, 30% ethane) are introduced into the liquid molten metal through the bottom raw material inlet 7 at a pressure of 1.5 MPa. The gaseous hydrocarbons react with the liquid metal in the form of tiny bubbles for 7 seconds, and the ethane is completely converted to generate small pieces of graphene, methane and hydrogen.

[0123] Small pieces of graphene, methane and hydrogen gradually float up and reach the upper surface of the liquid molten metal. Mesoporous carbon (particle size 5-6 μm) is introduced into the liquid molten metal device 1 from the mesoporous carbon inlet 5. The mesoporous carbon reacts with the rising residual methane in the gas phase reaction section 4 for 20 seconds, continues to crack the methane, and generates graphene on the surface of the mesoporous carbon (the height of the graphene is 1-2 μm), forming a hybrid (graphene grows almost vertically on the surface of the mesoporous carbon particles. The specific surface area is 1890 m 2 / g, compacted density is 430kg / m 3 . The mass fraction of graphene in the hybrid is 3%).

[0124] Methane is cracked to generate hydrogen, which leaves the reactor from the gas product outlet 8 of the liquid molten metal device 1. The hybrid of mesoporous carbon and graphene falls to the surface of the liquid molten metal, and is mixed with the graphene floating out of the liquid metal under the stirring of bubbles, promoting the dispersion of graphene.

[0125] The height of the hybrid of graphene and mesoporous carbon and pure graphene gradually increases. When the height reaches 55% of the height between the liquid molten metal and the mesoporous carbon feed port, the feeding of methane and mesoporous carbon is stopped, and only hydrogen is passed through the raw material inlet 7, and all carbon products are blown out of the liquid molten metal device 1 from the solid outlet 6. The carbon products are cooled and used for other purposes. The hydrocarbon raw material is resumed to the inlet 7, the mesoporous carbon feed of the mesoporous carbon inlet 5 is resumed, and the hydrogen feed of the inlet 7 is gradually closed, so that the process is operated continuously.

[0126] A small amount of metal component (magnesium) volatilized with the gas from the gas product outlet 8 enters the volatilized metal absorption device 2 from the gas product inlet 9, is absorbed into the liquid hydrocarbon (molecular weight range is 180-220), passes through the internal baffle 11 to extend the residence time, and then obtains the metal-free gas through the gas outlet 10.

[0127] The hydrocarbons in the volatile metal absorption device 2 are regularly circulated to the raw material inlet 8 of the liquid molten metal device 1 through the liquid hydrocarbon outlet 13, so as to realize the cyclic replenishment of the volatile metal component (magnesium) and keep the volatile components of the liquid molten metal section 3 stable. After the liquid hydrocarbons in the volatile metal absorption device 2 enter the liquid molten metal device 1, they are also converted into graphene and hydrogen.

[0128] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification.

[0129] For the method embodiments, for the sake of simplicity, they are all described as a series of action combinations, but those skilled in the art should know that the present invention is not limited by the order of the actions described, because according to the present invention, some steps can be performed in other orders or simultaneously. Secondly, those skilled in the art should also know that the embodiments described in the specification are all preferred embodiments, and the actions and components involved are not necessarily required by the present invention.

[0130] The above is a detailed introduction to a device, method and graphene-mesoporous carbon hybrid for preparing carbon materials provided by the present invention. Specific examples are used in this article to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core idea; at the same time, for those skilled in the art, according to the idea of ​​the present invention, there will be changes in the specific implementation method and application scope. In summary, the content of this specification should not be understood as a limitation on the present invention.

Claims

1. A device for preparing carbon material, characterized in that: The device comprises: A liquid molten metal device, wherein the liquid molten metal is contained in the liquid molten metal device, the liquid molten metal device is divided into a liquid molten metal section and a gas phase reaction section by the liquid surface of the liquid molten metal, the liquid molten metal section is provided with a raw material inlet, and the gas phase reaction section is provided with a mesoporous carbon inlet and a gas product outlet; the liquid molten metal device is used to convert gaseous alkanes entering through the raw material inlet into graphene and hydrogen, and the liquid molten metal device is used to react the mesoporous carbon entering through the mesoporous carbon inlet with the gaseous alkanes to generate graphene-mesoporous carbon hybrids; A volatile metal absorption device, wherein the volatile metal absorption device is provided with a gas product inlet and a liquid hydrocarbon outlet; the volatile metal absorption device contains liquid hydrocarbons for absorbing metal vapor volatilized from the liquid molten metal device entering the volatile metal absorption device through the gas product inlet, and circulates the liquid hydrocarbons absorbing the metal vapor to the raw material inlet through the liquid hydrocarbon outlet to be supplied to the liquid molten metal device, thereby realizing the addition of volatile metals; The gas product outlet and the gas product inlet are connected through a pipeline; The liquid hydrocarbon outlet and the raw material inlet are connected through a pipeline.

2. The device according to claim 1, characterized in that The liquid molten metal device also includes a carbon product outlet, which is located above the liquid level and below the mesoporous carbon inlet.

3. The device according to claim 1, characterized in that The volatilized metal absorption device further comprises a baffle and a gas outlet, wherein the baffle is used to prolong the residence time of the metal vapor in the liquid hydrocarbon, and the gas outlet is used to discharge the gas without metal.

4. A method for preparing a carbon material, characterized in that: The method is applicable to the device described in any one of claims 1 to 3 above, and the method comprises: Passing gaseous alkanes into a liquid molten metal device through a raw material inlet, the gaseous alkanes are converted into graphene and hydrogen when passing through the liquid molten metal section in the form of bubbles, and the graphene floats on the liquid surface, passing mesoporous carbon into a gas phase reaction section of the liquid molten metal device through a mesoporous carbon inlet, and during the falling process, the residual gaseous alkanes are catalyzed to generate graphene on the surface of the mesoporous carbon, thereby forming the graphene-mesoporous carbon hybrid; The graphene-mesoporous carbon hybrid further falls to reach the liquid surface, effectively dispersing the graphene floating on the liquid surface and reducing the stacking of the graphenes; When the height of the solid carbon product floating on the liquid surface reaches 1 / 2-3 / 4 of the height between the liquid surface and the mesoporous carbon inlet, the gaseous alkane feed is stopped, and hydrogen is introduced into the raw material inlet to blow the solid carbon product out of the device from the carbon product outlet; A small amount of metal components volatilized from the gas product outlet along with hydrogen enter the volatilized metal absorption device from the gas product inlet, pass through the baffle to extend the residence time, are absorbed by the liquid hydrocarbon, and hydrogen is discharged from the gas outlet to obtain hydrogen; The feed of gaseous alkane and mesoporous carbon is restored to make the preparation process continuous; The liquid alkane in the volatile metal absorption device is regularly circulated to the raw material inlet of the device through the liquid hydrocarbon outlet to complete the cyclic replenishment of the volatile metal component.

5. The preparation method according to claim 4, characterized in that: The gaseous alkane is methane and / or ethane; The molecular weight range of the liquid alkane is 160-260; The molten metal is formed by melting mixed metal powder under conditions of applied voltage and current, the temperature of the molten metal is 600-1200°C, the mixed metal powder is mixed with one or more of copper, nickel, iron, molybdenum and manganese and one or more of aluminum, gallium and tin, and the particle size of the mixed metal powder is 1-10 μm.

6. The preparation method according to claim 4, characterized in that: The particle size of the mesoporous carbon is 1-50 μm.

7. The preparation method according to claim 4, characterized in that: The residence time of the gaseous alkane in the liquid molten metal section is 1-20 s; The residence time of the gaseous alkane in the gas phase reaction section is 1-10 s.

8. A graphene-mesoporous carbon hybrid obtained according to the preparation method described in any one of claims 4 to 7 above.

9. The graphene-mesoporous carbon hybrid according to claim 8, characterized in that: The specific surface area of ​​the graphene-mesoporous carbon hybrid is 1600-2400 m 2 / g; The compacted density of the graphene-mesoporous carbon hybrid is 300-600 kg / m 3 ; In the graphene-mesoporous carbon hybrid, the mass fraction of the graphene is 0.1%-10%.

10. The graphene-mesoporous carbon hybrid according to claim 8, characterized in that: In the graphene-mesoporous carbon hybrid, the growth height of the graphene is 1-20 μm.

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