CN116902967A - Device and method for preparing high-value carbon material and graphene-mesoporous carbon hybrid - Google Patents
Device and method for preparing high-value carbon material and graphene-mesoporous carbon hybrid Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 265
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 220
- 239000007788 liquid Substances 0.000 claims abstract description 219
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 184
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 143
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 85
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 85
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 62
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 238000007599 discharging Methods 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 80
- 239000007789 gas Substances 0.000 claims description 77
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 62
- 229910052739 hydrogen Inorganic materials 0.000 claims description 60
- 239000001257 hydrogen Substances 0.000 claims description 60
- 239000002994 raw material Substances 0.000 claims description 55
- 238000010521 absorption reaction Methods 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 23
- 238000010574 gas phase reaction Methods 0.000 claims description 21
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 18
- 238000007667 floating Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000013589 supplement Substances 0.000 claims description 11
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000005056 compaction Methods 0.000 claims description 10
- 229910052733 gallium Inorganic materials 0.000 claims description 10
- 230000002035 prolonged effect Effects 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 claims 1
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- 229910052749 magnesium Inorganic materials 0.000 description 9
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/18—Nanoonions; Nanoscrolls; Nanohorns; Nanocones; Nanowalls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
Abstract
The invention provides a device for preparing high-value carbon materials, which mainly comprises a liquid metal melting device, a liquid hydrocarbon tank for recycling volatile metal, and a pipeline for returning the volatile metal and the liquid hydrocarbon to the liquid metal melting device. The invention also provides a preparation method of the high-value carbon material, which is to introduce gaseous alkane into a liquid metal melting device and crack the gaseous alkane at high temperature to generate graphene. And simultaneously, introducing mesoporous carbon above the liquid metal, continuously cracking residual methane at high temperature to generate graphene-mesoporous carbon hybrids, controlling the height of a carbon product above the liquid metal, and discharging periodically. After the volatile metal is absorbed by the liquid hydrocarbon, the volatile metal is periodically returned to the liquid metal melting device. The method has the advantages of low energy consumption, high product purity, continuous operation and low cost. Due to the existence of the graphene-mesoporous carbon, the dispersion of the graphene can be promoted, and pure graphene with high specific surface area and graphene-mesoporous carbon hybrids can be prepared.
Description
Technical Field
The invention relates to the technical field of nano material processing, in particular to a device and a method for preparing a high-value carbon material and a graphene-mesoporous carbon hybrid.
Background
SP with graphene in two-dimensional structure 2 The hybridized carbon material has the advantages of large specific surface area and good conductivity, and can be used as an electrode material of a capacitor or a conductive agent of a lithium ion battery and an environment adsorption material. However, since the bulk density of graphene is small, a large amount of graphene is added, which results in a decrease in the compaction density of the pole pieces of the energy storage device and a decrease in the energy density of the device.
Mesoporous carbon is a special activated carbon, SP 3 The hybrid carbon structure is mainly obtained by an activation and cyclization method of microporous activated carbon, and has the advantage of high bulk density. But SP is 3 Hybrid carbon and SP 2 The hybrid carbon is less conductive than the hybrid carbon. And thus has a tendency to decay in performance at high power when used in electrode materials.
Obviously, if the hybrid of graphene and mesoporous carbon can be prepared and a certain proportion is controlled, the excellent electrode material-graphene-mesoporous carbon hybrid with two properties can be obtained. The graphene-mesoporous carbon hybrid combines the advantages of graphene and mesoporous carbon, and the graphene is used as one of materials with the best electrical conductivity, so that the electrical conductivity and the thermal conductivity of the composite hybrid can be remarkably improved. The graphene-mesoporous carbon hybrid has wide application prospects in the fields of electronic devices, energy storage, sensors and the like. And the mesoporous carbon has rich pore structures and high specific surface area, and can provide more active sites and adsorption spaces. Through the combination with the graphene, the graphene-mesoporous carbon hybrid can show good performance in the fields of catalysts, adsorption materials, separation membranes and the like. In addition, graphene is used as a material with extremely high mechanical strength, so that the mechanical property of the composite hybrid can be improved. The method has potential application prospect in preparing high-performance composite materials and reinforcing materials.
Currently, graphene is mainly deposited by chemical vapor deposition(Chemical Vapor Deposition, CVD) silicon, oxide template method or graphite intercalation stripping. In the CVD method, the conversion rate of the carbon source is very low and the cost is high. Whereas mesoporous carbon is usually activated by water vapor of microporous carbon, CO 2 The preparation method is activated or alkali activated, and the preparation environment of the activated or alkali activated preparation method is greatly different. If the graphene is prepared by adopting an oxide template method, and then is compounded with mesoporous carbon, template and other removal procedures exist, and the purity of the mesoporous carbon is influenced.
At present, a method for preparing graphene by cracking hydrocarbons with methane as a main component by using liquid molten metal is reported, but the method is still in a research stage, further improvement and optimization are needed to improve the quality and yield of graphene, and the specific surface area of the graphene obtained by the method is low, so that improvement is still needed. Meanwhile, the molten metal generally contains a low-melting-point metal, and after volatilization, the melting point is increased, so that the energy consumption is increased.
Therefore, at present, a device and a method for preparing high-value carbon materials (high-purity and high-specific-surface-area graphene, graphene-mesoporous carbon hybrids and the like) by adopting liquid molten metal to crack alkane in a synergic manner are not available.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation device and a preparation method of a high-value carbon material and a graphene-mesoporous carbon hybrid obtained by the method, and the high-purity and high-specific-surface-area carbon material is prepared by adopting a mode of cracking alkane by liquid molten metal and cooperating with mesoporous carbon. The specific invention comprises the following steps:
in a first aspect, the present invention provides an apparatus for producing a high value carbon material, the apparatus comprising:
a liquid molten metal device 1, wherein 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 level 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 state molten metal device 1 is used for converting gaseous alkane entering through the raw material inlet 7 into graphene and hydrogen, and the liquid state molten metal device 1 is used for enabling mesoporous carbon entering through the mesoporous carbon inlet 5 to react with the gaseous alkane to generate graphene-mesoporous carbon hybrid;
a volatile metal absorption device 2, wherein the volatile metal absorption device 2 is provided with a gas product inlet 9 and a liquid hydrocarbon outlet 13; the volatile metal absorbing device 2 is filled with liquid hydrocarbon and is used for absorbing metal vapor volatilized in the liquid molten metal device 1 entering the volatile metal absorbing device through a gas product inlet 9, and circulating the liquid hydrocarbon absorbed with the metal vapor to the raw material inlet 7 through a liquid hydrocarbon outlet 13 to be supplied to the liquid molten metal device 1 so as to realize the addition of volatile metal;
The gas product outlet 8 is communicated with the gas product inlet 9 through a pipeline;
the liquid hydrocarbon outlet 13 is connected to the raw material inlet 7 via a pipe.
Optionally, the liquid molten metal device 1 further comprises a carbon product outlet 6, the carbon product outlet 6 being located above the liquid level, below the mesoporous carbon inlet 5.
Optionally, the volatile metal absorption device 2 further comprises a baffle 11 and a gas outlet 10, wherein the baffle 11 is used for prolonging the residence time of the metal vapor in the liquid hydrocarbon, and the gas outlet 10 is used for discharging the gas without metal.
In a second aspect, the present invention provides a method for preparing a high value carbon material, the method being suitable for use in the apparatus according to the first aspect, the method comprising:
introducing gaseous alkane into the liquid molten metal device 1 through the raw material inlet 7, converting the gaseous alkane into graphene and hydrogen when the gaseous alkane passes through the liquid molten metal section 3 in the form of bubbles, floating the graphene on the liquid surface, introducing mesoporous carbon into the gas-phase reaction section 4 of the liquid molten metal device 1 through the mesoporous carbon inlet 5, and catalyzing residual gaseous alkane to generate graphene on the surface of the mesoporous carbon in the falling process to form the graphene-mesoporous carbon hybrid;
The mesoporous carbon and the graphene-mesoporous carbon hybrid further fall to the liquid level, so that the graphene floating on the liquid level is effectively dispersed, and stacking among the graphene is reduced;
stopping gaseous alkane feeding when the height of the solid carbon product floating on the liquid level reaches 1/2-3/4 of the height between the liquid level and the mesoporous carbon inlet 5, introducing hydrogen into the raw material inlet 7, and blowing the solid carbon product out of the device from the carbon product outlet 6;
a small amount of metal components volatilized along with hydrogen from a gas product outlet 8 enter a volatilized metal absorption device 2 from a gas product inlet 9, stay time is prolonged through a baffle 11, the metal components are absorbed by liquid hydrocarbon, and the hydrogen is discharged from a gas outlet 10 to obtain hydrogen;
recovering the feeding of gaseous alkane and mesoporous carbon to make the preparation process continuous;
the liquid alkane in the volatile metal absorption device 2 is circulated to the raw material inlet 7 of the device 1 through the liquid hydrocarbon outlet 13 at regular intervals, so as to complete the circulation and the supplement of the volatile metal components.
Optionally, the gaseous alkane is methane, and/or ethane;
the molecular weight of the liquid alkane ranges from 160 to 260;
the molten metal is formed by melting mixed metal powder under the condition of applied voltage and current, the temperature of the molten metal is 600-1200 ℃, the mixed metal powder is formed by mixing one or more of copper, nickel, iron, molybdenum and manganese with one or more of aluminum, gallium and tin, and the granularity of the mixed metal powder is 1-10 mu m.
Optionally, the mesoporous carbon has a particle size of 1-50 μm.
Optionally, the gaseous alkane is left in the liquid molten metal section 3 for a time of 1 to 20s;
the residence time of the gaseous alkane in the gas phase reaction section 4 is 1-10s.
In a third aspect, the present invention provides a graphene-mesoporous carbon hybrid obtained by the preparation method described in the second aspect.
Optionally, the specific surface area of the graphene-mesoporous carbon hybrid is 1600-2400m 2 /g；
The compaction density of the graphene-mesoporous carbon hybrid is 300-600kg/m 3 ；
In the graphene-mesoporous carbon hybrid, the mass fraction of the graphene is 0.1% -10%.
Optionally, in the graphene-mesoporous carbon hybrid, the growth height of the graphene is 1-20 μm.
Compared with the prior art, the invention has the following advantages:
the invention provides a device for preparing high-value carbon materials, which mainly comprises a liquid metal melting device, a liquid hydrocarbon tank for recycling volatile metal, and a pipeline for returning the volatile metal and the liquid hydrocarbon to the liquid metal melting device. The invention also provides a preparation method of the high-value carbon material, which is to introduce gaseous alkane into a liquid metal melting device and crack the gaseous alkane at high temperature to generate graphene. And simultaneously, introducing mesoporous carbon above the liquid metal, continuously cracking residual methane at high temperature to generate graphene-mesoporous carbon hybrids, controlling the height of a carbon product above the liquid metal, and discharging periodically. After the volatile metal is absorbed by the liquid hydrocarbon, the volatile metal is periodically returned to the liquid metal melting device. The method has the advantages of low energy consumption, high product purity, continuous operation and low cost. Due to the existence of the graphene-mesoporous carbon, the dispersion of the graphene can be promoted, and pure graphene with high specific surface area and graphene-mesoporous carbon hybrids can be prepared.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a schematic structural diagram of an apparatus for preparing high-value carbon materials according to an embodiment of the present invention;
FIG. 2 shows a flow chart of a method for preparing a high value carbon material according to an embodiment of the present invention.
Wherein reference numerals shown in fig. 1 are as follows:
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 plate and 13-liquid hydrocarbon outlet.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. Any product that is the same as or similar to the present invention, which anyone in the light of the present invention or combines the present invention with other prior art features, falls within the scope of the present invention based on the embodiments of the present invention. And all other embodiments that may be made by those of ordinary skill in the art without undue burden and without departing from the scope of the invention.
Specific experimental steps or conditions are not noted in the examples and may be performed in accordance with the operation or conditions of conventional experimental steps described in the prior art in the field. The reagents used, as well as other instruments, are conventional reagent products available commercially, without the manufacturer's knowledge. Furthermore, the drawings are merely schematic illustrations of embodiments of the invention and are not necessarily drawn to scale. The same reference numerals in the drawings denote the same or similar parts, and thus a repetitive description thereof will be omitted. Some of the block diagrams shown in the figures are functional entities and do not necessarily correspond to physically or logically separate entities.
Techniques, methods, and apparatus known to one of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate.
In the description of the present invention, it should be understood that the terms "first," "second," and the like are used for defining the components, and are merely for convenience in distinguishing the corresponding components, and the terms are not meant to have any special meaning unless otherwise indicated, so that the scope of the present invention is not to be construed as being limited.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Before the detailed description of the graphene-mesoporous carbon hybrid, the preparation method and the device provided by the invention, the following description is necessary:
the existing method for preparing the graphene still needs to solve the problems of low specific surface area and agglomeration of the graphene, and mesoporous carbon has the characteristic of large bulk density, so that the method can improve the agglomeration condition of the graphene to a certain extent and can obtain additional graphene-mesoporous carbon hybrids when used for preparing high-value carbon material graphene. Based on the existing conception, the liquid molten metal device 1 is matched with the volatile metal absorption device 2 to realize the mode of cracking alkane by using liquid molten metal, and the liquid molten metal device is matched with mesoporous carbon to prepare high-purity and high-specific-surface-area graphene and graphene-mesoporous carbon hybrids. In particular to a preparation device and a preparation method of a high-value carbon material and a graphene-mesoporous carbon hybrid obtained by the method. The specific implementation content is as follows:
in a first aspect, the present invention provides an apparatus for preparing a high-value carbon material, and fig. 1 shows a schematic structural diagram of an apparatus for preparing a high-value carbon material according to an embodiment of the present invention, and referring to fig. 1, the apparatus includes:
The liquid metal device 1, the liquid metal device 1 holds liquid metal, the liquid metal device 1 is divided into a liquid metal section 3 and a gas phase reaction section 4 by the liquid level of the liquid metal, the liquid 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-state molten metal device 1 is used for converting gaseous alkane entering through the raw material inlet 7 into graphene and hydrogen, and the liquid-state molten metal device 1 is used for enabling mesoporous carbon entering through the mesoporous carbon inlet 5 to react with the gaseous alkane to generate graphene-mesoporous carbon hybrid;
a volatile metal absorption device 2 connected with the liquid molten metal device 1, wherein the volatile metal absorption device 2 is provided with a gas product inlet 9 and a liquid hydrocarbon outlet 13; the volatile metal absorbing device 2 is filled with liquid hydrocarbon and is used for absorbing metal vapor volatilized in the liquid molten metal device 1 entering the volatile metal absorbing device through the gas product inlet 9, and recycling the liquid hydrocarbon absorbed with the metal vapor to the raw material inlet 7 through the liquid hydrocarbon outlet 13 to be supplied into the liquid molten metal device 1 so as to realize the addition of the volatile metal; the method comprises the steps of carrying out a first treatment on the surface of the Wherein the gas product outlet 8 is communicated with the gas product inlet 9 through a pipeline; the liquid hydrocarbon outlet 13 is connected to the raw material inlet 7 by a pipe.
With continued reference to fig. 1, the liquid molten metal apparatus 1 further includes a carbon product outlet 6, the carbon product outlet 6 being located above the liquid level, below the mesoporous carbon inlet 5. So as to ensure that the product graphene-mesoporous carbon hybrid and graphene can be smoothly blown away from the liquid molten metal device 1 by hydrogen.
The inside of the volatile metal absorption device 2 is also provided with a baffle 11 and a gas outlet 10, wherein the baffle 11 is used for prolonging the residence time of metal vapor in liquid hydrocarbon, so that the metal vapor has enough time to condense, solid metal particles are formed to be recovered, and the purity of the hydrogen discharged from the gas outlet 10 is improved.
In a second aspect, the present invention provides a method for preparing a high-value carbon material, and fig. 2 shows a flowchart of a method for preparing a high-value carbon material according to an embodiment of the present invention, and as shown in fig. 2, the method is applicable to the apparatus of the first aspect, and the method specifically includes the following steps:
s1, introducing alkane into a liquid molten metal device 1 through a raw material inlet 7, converting the alkane into graphene and hydrogen when the alkane passes through a liquid molten metal section 3 in a bubble form, floating the graphene on the liquid surface, introducing mesoporous carbon into a gas-phase reaction section 4 of the liquid molten metal device 1 through a mesoporous carbon inlet 5, and catalyzing residual alkane to generate graphene on the surface of the mesoporous carbon in the falling process to form graphene-mesoporous carbon hybrid;
S2, the graphene-mesoporous carbon hybrid further falls to the liquid level, so that the graphene floating on the liquid level is effectively dispersed, and stacking among the graphene is reduced;
s3, stopping alkane feeding when the height of the solid carbon product floating on the liquid level reaches 1/2-3/4 of the height between the liquid level and the mesoporous carbon inlet 5, introducing hydrogen into the raw material inlet 7, and blowing out the solid carbon product from the carbon product outlet 6;
s4, a small amount of metal components volatilized along with hydrogen from a gas product outlet 8 enter a volatilized metal absorption device 2 from a gas product inlet 9, stay time is prolonged through a baffle 11, the metal components are absorbed by liquid hydrocarbon, and the hydrogen is discharged from a gas outlet 10 to obtain hydrogen;
s5, recovering the feeding of alkane and mesoporous carbon again to enable the preparation process to be continuous;
and S6, periodically circulating 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 circulation and the supplement of the volatile metal components.
In the specific implementation, the mesoporous carbon enters the gas-phase reaction section 4, and as the surface of the mesoporous carbon has a certain activating group, alkane which is not reacted in the liquid molten metal section 3 can be further cracked, and graphene is generated on the surface of the mesoporous carbon, so that a seamless connected graphene-mesoporous carbon hybridization structure is formed, the conversion rate of hydrocarbons is improved, and the additional value of the subsequent hydrogen product is higher. Meanwhile, high-temperature gaseous hydrogen generated by alkane pyrolysis can also perform shaping effect on the structure of mesoporous carbon (including improving graphitization degree and removing metal impurities), so that the dispersing cost and the purifying cost are saved by about 20%.
Further, volatile metal components are added into the gas phase reaction section 4 along with hydrogen and unreacted alkane, and in the reaction of alkane and graphene, the conversion rate of gaseous hydrocarbon is further improved due to high dispersibility of the volatile metal components, and the separation cost of a gas product is reduced by 20% -30%.
In the specific implementation, in the process of preparing graphene by adopting liquid molten metal catalysis, gaseous alkane is catalyzed to react to generate graphene and hydrogen, the generated graphene floats on the liquid surface of the liquid metal, and residual (unreacted) gaseous alkane rising along with the hydrogen further reacts with the added mesoporous carbon to enable hydrocarbons to generate graphene on the surface of the hydrocarbon, so that a seamless hybrid structure-graphene-mesoporous carbon is formed. The generated graphene-mesoporous carbon has larger stacking density than graphene, and under the stirring of molten metal and bubbles, the graphene floating on the liquid surface is further effectively dispersed by the dropped graphene-mesoporous carbon, so that stacking is reduced, and the proportion of the graphene with high specific surface area is improved by about 20-30%. In addition, the existence of mesoporous carbon reduces the splashing degree of molten metal and increases the safety of equipment.
In the concrete implementation, the liquid alkane with high boiling point is used for cooling and collecting the volatile metal, so that the process is safe, the operation is simple, the equipment cost is reduced by 2%, and the management cost is reduced by 5%.
In some embodiments, the alkane introduced at feed inlet 7 may be methane, and/or ethane; the molecular weight of the liquid alkane in the volatile metal absorption device 2 ranges from 160 to 260; the molten metal can be formed by melting mixed metal powder under the condition of applied voltage and current, the temperature of the molten metal is 600-1200 ℃, 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 of aluminum, gallium and tin, and the granularity of the mixed metal powder is 1-10 mu m.
In some embodiments, the mesoporous carbon may have a particle size ranging from 1 to 50 μm.
In a third aspect, the present invention provides a graphene-mesoporous carbon hybrid obtained by the preparation method of the second aspect.
In some embodiments, the specific surface area of the graphene-mesoporous carbon hybrid obtained is 1600-2400m 2 /g；
The compacted density of the graphene-mesoporous carbon hybrid is 300-600kg/m 3 ；
In the graphene-mesoporous carbon hybrid, the mass fraction of the graphene is 0.1% -10%.
In some embodiments, the graphene-mesoporous carbon hybrids obtained have a growth height of graphene ranging from 1 to 20 μm.
In order to make the present invention more clearly understood by those skilled in the art, the following examples will illustrate an apparatus and method for preparing a high-value carbon material and a graphene-mesoporous carbon hybrid according to the present invention.
Example 1
Mixed metal powder (90% copper, 5% aluminum, 5% gallium, particle size range 1-5 μm) was placed in a liquid molten metal liquid metal apparatus 1, voltage and current were applied at 850 ℃, the metal powder was changed to liquid molten metal, and a liquid molten metal segment 3 was formed in the liquid molten metal apparatus 1.
Hydrocarbon (100% methane) is introduced into the liquid molten metal through the bottom raw material inlet 7 at a pressure of 5MPa, and the hydrocarbon reacts with the liquid metal in the form of tiny bubbles for 20 seconds to generate small pieces of graphene and hydrogen.
The small graphene and hydrogen gradually float upwards to reach the upper surface of the liquid molten metal. Introducing mesoporous carbon (particle size of 1-50 μm) into a liquid molten metal device 1 from a mesoporous carbon inlet 5, reacting the mesoporous carbon with rising residual methane in a gas phase reaction section 4 for 10 seconds, continuously cracking the methane, generating graphene (the height of the graphene is 1-20 μm) on the surface of the mesoporous carbon, and forming a hybrid (the graphene almost vertically grows on the surface of mesoporous carbon particles, wherein the specific surface area is 1600-2400 m) 2 Per gram, a compaction density of 300-600kg/m 3 . The mass fraction of the graphene in the hybrid is 0.1% -10%).
Methane is cracked to produce hydrogen gas which exits the reactor at the gas product outlet 8 of the liquid molten metal apparatus 1. The hybrid of the mesoporous carbon and the 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. And the dispersion of graphene is promoted.
The height of the hybrid of the graphene and the mesoporous carbon and the height of the pure graphene are gradually increased, when the height of the hybrid reaches 1/2-3/4 of the height between the liquid molten metal and the feeding hole of the mesoporous carbon, methane and the mesoporous carbon are stopped from entering, only hydrogen is introduced into 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 product is cooled and then used. And the hydrocarbon raw material is introduced into the raw material inlet 7, the mesoporous carbon feeding of the mesoporous carbon inlet 5 is recovered, and the hydrogen feeding of the raw material inlet 7 is gradually closed, so that the process is continuously operated.
A small amount of metal components volatilized with the gas from the gas product outlet 8 enter the volatilized metal absorption unit 2 from the gas product inlet 9, are absorbed into liquid hydrocarbons (hydrocarbons having molecules 160-260), pass through the internal baffles 11 for prolonged residence time, and then get metal-free gas through the gas outlet 10.
The hydrocarbon in the volatile metal absorption device 2 is circulated to the raw material inlet 7 of the liquid molten metal device 1 through the liquid hydrocarbon outlet 13 at regular intervals, so that the circulation and the supplement of volatile metal components are realized, and the volatile components of the liquid molten metal section 3 are kept stable. After entering the liquid molten metal device 1, the liquid hydrocarbon in the volatile metal absorption device 2 is also converted into graphene and hydrogen.
Example 2
Mixed metal powder (70% copper, 5% molybdenum, 5% manganese, 20% gallium, particle size in the range 5-10 μm) was placed in a liquid molten metal apparatus 1, voltage and current were applied at 900 ℃, the metal powder was changed to liquid molten metal, and a liquid molten metal segment 3 was formed in the liquid molten metal apparatus 1.
Hydrocarbons (50% methane, 50% ethane) are introduced into the liquid molten metal through the bottom raw material inlet 7 at a pressure of 1MPa, the hydrocarbons such as methane or ethane react with the liquid metal in the form of tiny bubbles for 10 seconds, and the ethane is completely converted to form small pieces of graphene and hydrogen.
The small graphene and hydrogen gradually float upwards to reach the upper surface of the liquid molten metal. Mesoporous carbon (particle diameter of 50 μm) is introduced into the liquid molten metal device 1 from the mesoporous carbon inlet 5, the mesoporous carbon reacts with rising residual methane for 10 seconds in the gas phase reaction section 4, methane is continuously cracked, graphene (the height of the graphene is 1 μm) is generated on the surface of the mesoporous carbon, and a hybrid is formed (the graphene almost vertically grows on the surface of mesoporous carbon particles, the specific surface area is 2000 m) 2 Per gram, a compaction density of 500kg/m 3 . Graphene hybridThe mass fraction of (2) is 0.1%).
Methane is cracked to produce hydrogen gas which exits the reactor at the gas product outlet 8 of the liquid molten metal apparatus 1. The hybrid of the mesoporous carbon and the 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. And the dispersion of graphene is promoted.
The height of the hybrid of graphene and mesoporous carbon and the height of pure graphene are gradually increased, when the height of the hybrid reaches 75% of the height between the liquid molten metal and the feeding port of the mesoporous carbon, methane and the mesoporous carbon are stopped, only hydrogen is introduced into 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 product is cooled and then used. And the hydrocarbon raw material is introduced into the raw material inlet 7, the mesoporous carbon feeding of the mesoporous carbon inlet 5 is recovered, and the hydrogen feeding of the raw material inlet 7 is gradually closed, so that the process is continuously operated.
A small amount of metal component (gallium) volatilized with the gas from the gas product outlet 8 enters the volatilized metal absorption unit 2 from the gas product inlet 9, is absorbed into liquid hydrocarbons (molecular weight range 160-240), passes through the internal baffles 11 for prolonged residence time, and then gets metal-free gas through the gas outlet 10.
The liquid hydrocarbon in the volatile metal absorption device 2 is circulated to the raw material inlet 8 of the liquid molten metal device 1 through the liquid hydrocarbon outlet 13 at regular intervals, so that the circulation and the supplement of the volatile metal component (gallium) are realized, and the volatile components of the liquid molten metal section 3 are kept stable. After entering the liquid molten metal device 1, the liquid hydrocarbon in the volatile metal absorption device 2 is also converted into graphene and hydrogen.
Example 3
Mixed metal powder (5% copper, 40% aluminum, 30% gallium, 25% nickel, particle size in the range of 1-5 μm) was placed in a liquid molten metal apparatus 1, voltage and current were applied at 600 ℃, the metal powder was changed to liquid molten metal, and a liquid molten metal segment 3 was formed in the liquid molten metal apparatus 1.
Gaseous hydrocarbons (100% ethane) are introduced into the liquid molten metal through the bottom raw material inlet 7 at a pressure of 2MPa, the gaseous hydrocarbons react with the liquid metal in the form of very small bubbles for 20 seconds, and the ethane is completely converted to form small pieces of graphene, methane and hydrogen.
The small pieces of graphene, methane and hydrogen gradually float upwards to reach the upper surface of the liquid molten metal. Mesoporous carbon (particle size of 1 μm) is introduced into the liquid molten metal device 1 from the mesoporous carbon inlet 5, the mesoporous carbon reacts with rising residual methane and ethane in the gas phase reaction section 4 for 15 seconds, methane and ethane are continuously cracked, graphene (the height of the graphene is 1 μm) is generated on the surface of the mesoporous carbon, and hybrids are formed (the graphene almost vertically grows on the surface of mesoporous carbon particles, the specific surface area is 1600 m) 2 Per gram, a compaction density of 300kg/m 3 . The mass fraction of graphene in the hybrid is 8%).
Ethane and methane are cracked to produce hydrogen gas which exits the reactor at the gas product outlet 8 of the liquid molten metal apparatus 1. The hybrid of the mesoporous carbon and the graphene falls on the surface of the liquid molten metal, and is mixed with the graphene floating out of the liquid metal under the stirring of bubbles, so that the dispersion of the graphene is promoted.
The height of the hybrid of graphene and mesoporous carbon and the height of pure graphene are gradually increased, when the height of the hybrid reaches 1/2 of the height between the liquid molten metal and the feeding port of the mesoporous carbon, methane and the mesoporous carbon are stopped, only hydrogen is introduced into 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 product is cooled and then used. And the hydrocarbon raw material is introduced into the raw material inlet 7, the mesoporous carbon feeding of the mesoporous carbon inlet 5 is recovered, and the hydrogen feeding of the raw material inlet 7 is gradually closed, so that the process is continuously operated.
A small amount of metal components (aluminum, gallium) volatilized with the gas from the gas product outlet 8 enters the volatilized metal absorption unit 2 from the gas product inlet 9, is absorbed into liquid hydrocarbons (molecular weight range 2000-260), passes through the internal baffles 11 for a prolonged residence time, and then passes through the gas outlet 10 to obtain a metal-free gas.
The liquid hydrocarbon in the volatile metal absorption device 2 is circulated to the raw material inlet 8 of the liquid molten metal device 1 through the liquid hydrocarbon outlet 13 at regular intervals, so that the circulation and the supplement of volatile metal components (aluminum and gallium) are realized, and the volatile components of the liquid molten metal section 3 are kept stable. After entering the liquid molten metal device 1, the liquid hydrocarbon in the volatile metal absorption device 2 is also converted into graphene and hydrogen.
Example 4
Mixed metal powder (50% copper, 20% nickel, 30% tin, particle size in the range of 1-10 μm) is placed in a liquid molten metal apparatus 1, voltage and current are applied at 1200 ℃, the metal powder is changed to liquid molten metal, and a liquid molten metal segment 3 is formed in the liquid molten metal apparatus 1.
Gaseous hydrocarbons (90% methane, 10% ethane) are introduced into the liquid molten metal through the bottom feed inlet 7 at a pressure of 1MPa, and the gaseous hydrocarbons react with the liquid metal in the form of very small bubbles for 10 seconds, with complete conversion of the ethane to form small pieces of graphene and hydrogen.
The small graphene and hydrogen gradually float upwards to reach the upper surface of the liquid molten metal. Mesoporous carbon (particle diameter of 50 μm) is introduced into the liquid molten metal device 1 from the mesoporous carbon inlet 5, the mesoporous carbon reacts with rising residual methane for 12 seconds in the gas phase reaction section 4, methane is continuously cracked, graphene (the height of the graphene is 20 μm) is generated on the surface of the mesoporous carbon, and a hybrid is formed (the graphene almost vertically grows on the surface of mesoporous carbon particles, the specific surface area is 2400m 2 Per gram, a compaction density of 600kg/m 3 . The mass fraction of graphene in the hybrid is 10%).
Methane is cracked to produce hydrogen gas which exits the reactor at the gas product outlet 8 of the liquid molten metal apparatus 1. The hybrid of the mesoporous carbon and the 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. And the dispersion of graphene is promoted.
The height of the hybrid of graphene and mesoporous carbon and the height of pure graphene are gradually increased, when the height of the hybrid reaches 3/4 of the height between the liquid molten metal and the feeding port of the mesoporous carbon, methane and the mesoporous carbon are stopped, only hydrogen is introduced into 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 product is cooled and then used. And the hydrocarbon raw material is introduced into the raw material inlet 7, the mesoporous carbon feeding of the mesoporous carbon inlet 5 is recovered, and the hydrogen feeding of the raw material inlet 7 is gradually closed, so that the process is continuously operated.
A small amount of metal component (tin) volatilized with the gas from the gas product outlet 8 enters the volatilized metal absorption unit 2 from the gas product inlet 9, is absorbed into liquid hydrocarbon (molecular weight range 160-200), passes through the internal baffle 11 for a prolonged residence time, and then passes through the gas outlet 10 to obtain a metal-free gas.
The hydrocarbon in the volatile metal absorption device 2 is circulated to the raw material inlet 8 of the liquid molten metal device 1 through the liquid hydrocarbon outlet 13 at regular intervals, so that the circulation and the supplement of the volatile metal component (tin) are realized, and the volatile components of the liquid molten metal section 3 are kept stable. After entering the liquid molten metal device 1, the liquid hydrocarbon in the volatile metal absorption device 2 is also converted into graphene and hydrogen.
Example 5
Mixed metal powder (50% iron, 20% aluminum, 30% magnesium, particle size in the range of 2-8 μm) was placed in a liquid molten metal apparatus 1, voltage and current were applied at 1100 ℃, the metal powder was changed to liquid molten metal, and a liquid molten metal segment 3 was formed in the liquid molten metal apparatus 1.
Gaseous hydrocarbons (40% methane, 60% ethane) are introduced into the liquid molten metal through the bottom raw material inlet 7 at a pressure of 4MPa, and the gaseous hydrocarbons react with the liquid metal in the form of very small bubbles for 1 second to generate small pieces of graphene and hydrogen.
The small graphene and hydrogen gradually float upwards to reach the upper surface of the liquid molten metal. Mesoporous carbon (particle size of 10 μm) is introduced into the liquid molten metal device 1 from the mesoporous carbon inlet 5, the mesoporous carbon reacts with rising residual methane for 1 second in the gas phase reaction section 4, methane is continuously cracked, graphene (the height of the graphene is 1 μm) is generated on the surface of the mesoporous carbon, and a hybrid is formed (the graphene almost vertically grows on the surface of mesoporous carbon particles, the specific surface area is 1800 m) 2 Per gram, a compaction density of 450kg/m 3 . The mass fraction of graphene in the hybrid is 2%).
Methane is cracked to produce hydrogen gas which exits the reactor at the gas product outlet 8 of the liquid molten metal apparatus 1. The hybrid of the mesoporous carbon and the 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. And the dispersion of graphene is promoted.
The height of the hybrid of graphene and mesoporous carbon and the height of pure graphene are gradually increased, when the height of the hybrid reaches 3/4 of the height between the liquid molten metal and the feeding port of the mesoporous carbon, methane and the mesoporous carbon are stopped, only hydrogen is introduced into 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 product is cooled and then used. And recovering the hydrocarbon raw material from the inlet 7, recovering the mesoporous carbon feeding from the mesoporous carbon inlet 5, and gradually closing the hydrogen feeding from the inlet 7, so that the process is continuously operated.
A small amount of metal components (aluminum, magnesium) volatilized with the gas from the gas product outlet 8 enters the volatilized metal absorption unit 2 from the gas product inlet 9, is absorbed into liquid hydrocarbons (molecular weight range of 180-200), passes through the internal baffles 11 for a prolonged residence time, and then passes through the gas outlet 10 to obtain a metal-free gas.
The hydrocarbons in the volatile metal absorption device 2 are circulated to the raw material inlet 8 of the liquid molten metal device 1 through the liquid hydrocarbon outlet 13 at regular intervals, so that the circulation and the supplement of volatile metal components (aluminum and magnesium) are realized, and the volatile components of the liquid molten metal section 3 are kept stable. After entering the liquid molten metal device 1, the liquid hydrocarbon in the volatile metal absorption device 2 is also converted into graphene and hydrogen.
Example 6
A mixed metal powder (20% nickel, 80% magnesium, particle size in the range 5-8 μm) is placed in a liquid metal melting apparatus 1, voltage and current are applied at 900 ℃, the metal powder is changed to liquid metal, and a liquid metal segment 3 is formed in the liquid metal melting apparatus 1.
Gaseous hydrocarbons (20% methane, 80% ethane) are introduced into the liquid molten metal through the bottom feed inlet 7 at a pressure of 4MPa, and the gaseous hydrocarbons react with the liquid metal in the form of very small bubbles for 8 seconds, with complete conversion of the ethane to form small pieces of graphene, methane and hydrogen.
The small pieces of graphene, methane and hydrogen gradually float upwards to reach the liquid state meltingThe upper surface of the molten metal. Mesoporous carbon (particle size of 10 μm) is introduced into the liquid molten metal device 1 from the mesoporous carbon inlet 5, the mesoporous carbon reacts with rising residual methane for 15 seconds in the gas phase reaction section 4, methane is continuously cracked, graphene (the height of the graphene is 1 μm) is generated on the surface of the mesoporous carbon, and a hybrid is formed (the graphene almost vertically grows on the surface of mesoporous carbon particles, the specific surface area is 1800 m) 2 Per gram, a compaction density of 450kg/m 3 . The mass fraction of graphene in the hybrid is 2%).
Methane is cracked to produce hydrogen gas which exits the reactor at the gas product outlet 8 of the liquid molten metal apparatus 1. The hybrid of the mesoporous carbon and the 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. And the dispersion of graphene is promoted.
The height of the hybrid of graphene and mesoporous carbon and the height of pure graphene are gradually increased, when the height of the hybrid reaches 3/4 of the height between the liquid molten metal and the feeding port of the mesoporous carbon, methane and the mesoporous carbon are stopped, only hydrogen is introduced into 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 product is cooled and then used. And recovering the hydrocarbon raw material from the inlet 7, recovering the mesoporous carbon feeding from the mesoporous carbon inlet 5, and gradually closing the hydrogen feeding from the inlet 7, so that the process is continuously operated.
A small amount of metal component (magnesium) volatilized with the gas from the gas product outlet 8 enters the volatilized metal absorption unit 2 from the gas product inlet 9, is absorbed into liquid hydrocarbons (molecular weight range of 180-200), passes through the internal baffle 11 for a prolonged residence time, and then passes through the gas outlet 10 to obtain a metal-free gas.
The hydrocarbon in the volatile metal absorption device 2 is circulated to the raw material inlet 8 of the liquid molten metal device 1 through the liquid hydrocarbon outlet 13 at regular intervals, so that the circulation and the supplement of the volatile metal component (magnesium) are realized, and the volatile components of the liquid molten metal section 3 are kept stable. After entering the liquid molten metal device 1, the liquid hydrocarbon in the volatile metal absorption device 2 is also converted into graphene and hydrogen.
Example 7
A mixed metal powder (30% copper, 70% magnesium, particle size in the range of 2-8 μm) was placed in a liquid metal melting apparatus 1, voltage and current were applied at 890 ℃, the metal powder was changed to liquid metal, and a liquid metal segment 3 was formed in the liquid metal melting apparatus 1.
Gaseous hydrocarbons (70% methane, 30% ethane) are introduced into the liquid molten metal through the bottom feed inlet 7 at a pressure of 1.5MPa, the gaseous hydrocarbons react with the liquid metal in the form of very small bubbles for 7 seconds, and the ethane is completely converted to small pieces of graphene, methane and hydrogen.
The small pieces of graphene, methane and hydrogen gradually float upwards to reach the upper surface of the liquid molten metal. Introducing mesoporous carbon (particle size of 5-6 μm) into a liquid molten metal device 1 from a mesoporous carbon inlet 5, reacting the mesoporous carbon with rising residual methane in a gas phase reaction section 4 for 20 seconds, continuously cracking the methane, generating graphene (the height of the graphene is 1-2 μm) on the surface of the mesoporous carbon, and forming a hybrid (the graphene almost vertically grows on the surface of mesoporous carbon particles, wherein the specific surface area is 1890 m) 2 Per gram, a compaction density of 430kg/m 3 . The mass fraction of graphene in the hybrid is 3%).
Methane is cracked to produce hydrogen gas which exits the reactor at the gas product outlet 8 of the liquid molten metal apparatus 1. The hybrid of the mesoporous carbon and the 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. And the dispersion of graphene is promoted.
The height of the hybrid of graphene and mesoporous carbon and the height of pure graphene are gradually increased, when the height of the hybrid reaches 55% of the height between the liquid molten metal and the feeding port of the mesoporous carbon, methane and the mesoporous carbon are stopped, only hydrogen is introduced into 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 product is cooled and then used. And recovering the hydrocarbon raw material from the inlet 7, recovering the mesoporous carbon feeding from the mesoporous carbon inlet 5, and gradually closing the hydrogen feeding from the inlet 7, so that the process is continuously operated.
A small amount of metal component (magnesium) volatilized with the gas from the gas product outlet 8 enters the volatilized metal absorption unit 2 from the gas product inlet 9, is absorbed into liquid hydrocarbons (molecular weight range 180-220), passes through the internal baffles 11 for a prolonged residence time, and then passes through the gas outlet 10 to obtain a metal-free gas.
The hydrocarbon in the volatile metal absorption device 2 is circulated to the raw material inlet 8 of the liquid molten metal device 1 through the liquid hydrocarbon outlet 13 at regular intervals, so that the circulation and the supplement of the volatile metal component (magnesium) are realized, and the volatile components of the liquid molten metal section 3 are kept stable. After entering the liquid molten metal device 1, the liquid hydrocarbon in the volatile metal absorption device 2 is also converted into graphene and hydrogen.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, one skilled in the art can combine and combine the different embodiments or examples described in this specification.
For the purposes of simplicity of explanation, the methodologies are shown as a series of acts, but one of ordinary skill in the art will recognize that the present invention is not limited by the order of acts described, as some acts may, in accordance with the present invention, occur in other orders and concurrently. Further, those skilled in the art will recognize that the embodiments described in the specification are all of the preferred embodiments, and that the acts and components referred to are not necessarily required by the present invention.
The device and the method for preparing the high-value carbon material and the graphene-mesoporous carbon hybrid provided by the invention are described in detail, and specific examples are applied to illustrate the principle and the implementation mode of the invention, and the description of the examples is only used for helping to understand the method and the core idea of the invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (10)
1. An apparatus for producing a high value carbon material, the apparatus comprising:
the liquid molten metal device is divided into a liquid molten metal section and a gas phase reaction section by the liquid level 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 for converting gaseous alkane entering through a raw material inlet into graphene and hydrogen, and is used for enabling mesoporous carbon entering through a mesoporous carbon inlet to react with the gaseous alkane to generate graphene-mesoporous carbon hybrid;
The volatile metal absorption device is provided with a gas product inlet and a liquid hydrocarbon outlet; the volatile metal absorbing device is used for absorbing metal vapor volatilized in the liquid molten metal device entering the volatile metal absorbing device through the gas product inlet, and circulating the liquid hydrocarbon absorbed with the metal vapor to the raw material inlet through the liquid hydrocarbon outlet to be supplied to the liquid molten metal device so as to realize the supplement of volatile metal;
the gas product outlet is communicated with the gas product inlet through a pipeline; the method comprises the steps of carrying out a first treatment on the surface of the
The liquid hydrocarbon outlet is communicated with the raw material inlet through a pipeline.
2. The apparatus of claim 1, wherein the liquid molten metal apparatus further comprises a carbon product outlet located above the liquid level below the mesoporous carbon inlet.
3. The apparatus of claim 1, wherein the volatile metal absorption device further comprises a baffle for extending the residence time of the metal vapor in the liquid hydrocarbon and a gas outlet for discharging the metal-free gas.
4. A method for the production of high value carbon material, characterized in that the method is applied to the apparatus according to any one of the preceding claims 1-3, the method comprising:
Introducing gaseous alkane into a liquid molten metal device through a raw material inlet, converting the gaseous alkane into graphene and hydrogen when the gaseous alkane passes through the liquid molten metal section in a bubble form, floating the graphene on the liquid surface, introducing mesoporous carbon into a gas-phase reaction section of the liquid molten metal device through a mesoporous carbon inlet, and catalyzing residual gaseous alkane to generate graphene on the surface of the mesoporous carbon in the falling process to form the graphene-mesoporous carbon hybrid;
the graphene-mesoporous carbon hybrid further falls to the liquid level, so that the graphene floating on the liquid level is effectively dispersed, and stacking among the graphene is reduced;
stopping feeding gaseous alkane and introducing hydrogen into the raw material inlet when the height of the solid carbon product floating on the liquid level reaches 1/2-3/4 of the height between the liquid level and the mesoporous carbon inlet, and blowing the solid carbon product out of the device from the carbon product outlet;
a small amount of metal components volatilized along with hydrogen from a gas product outlet enter a volatilized metal absorption device from a gas product inlet, stay time is prolonged through a baffle plate, the metal components are absorbed by liquid hydrocarbon, and the hydrogen is discharged from the gas outlet to obtain hydrogen;
Recovering the feeding of gaseous alkane and mesoporous carbon to make the preparation process continuous;
and (3) periodically circulating the liquid alkane in the volatile metal absorption device to a raw material inlet of the device through a liquid hydrocarbon outlet to complete the circulation and the supplement of the volatile metal components.
5. The method of claim 4, wherein the gaseous alkane is methane, and/or ethane;
the molecular weight of the liquid alkane ranges from 160 to 260;
the molten metal is formed by melting mixed metal powder under the condition of applied voltage and current, the temperature of the molten metal is 600-1200 ℃, the mixed metal powder is formed by mixing one or more of copper, nickel, iron, molybdenum and manganese with one or more of aluminum, gallium and tin, and the granularity of the mixed metal powder is 1-10 mu m.
6. The method according to claim 4, wherein the mesoporous carbon has a particle size of 1 to 50. Mu.m.
7. The method of claim 4, wherein the gaseous alkane is present in the liquid molten metal zone for a residence time of 1 to 20 seconds;
the residence time of the gaseous alkane in the gas phase reaction section is 1-10s.
8. A graphene-mesoporous carbon hybrid obtained by the method of any one of claims 4 to 7.
9. The graphene-mesoporous carbon hybrid according to claim 8, wherein the specific surface area of the graphene-mesoporous carbon hybrid is 1600-2400m 2 /g；
The compaction density of the graphene-mesoporous carbon hybrid is 300-600kg/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, wherein the graphene has a growth height of 1-20 μm.
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