CN114832729B - Device and method for simultaneously producing carbon nano tube and graphene - Google Patents

Device and method for simultaneously producing carbon nano tube and graphene Download PDF

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CN114832729B
CN114832729B CN202210319216.9A CN202210319216A CN114832729B CN 114832729 B CN114832729 B CN 114832729B CN 202210319216 A CN202210319216 A CN 202210319216A CN 114832729 B CN114832729 B CN 114832729B
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copper alloy
graphene
reaction zone
carbon
gas
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CN114832729A (en
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骞伟中
崔超婕
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Tsinghua University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/001—Controlling catalytic processes
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    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
    • B01J8/004—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor by means of a nozzle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005—Separating solid material from the gas/liquid stream
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    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818—Feeding of the fluidising gas
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818—Feeding of the fluidising gas
    • B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
    • 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
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
    • B01J2523/84—Metals of the iron group
    • B01J2523/845—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
    • B01J2531/002—Materials
    • B01J2531/004—Ligands

Abstract

The invention provides a device and a method for simultaneously producing carbon nanotubes and graphene, comprising a reaction device and a separation device, wherein the reaction device main body comprises a liquid copper alloy reaction zone and a separation zone, and the liquid copper alloy reaction zone is provided with a dispersion structural member, a solid inlet and a gas inlet; and a separation structural member is arranged in the separation area. Heating in a liquid copper alloy reaction zone to keep the low-melting-point copper alloy in a molten state; nano metal catalyst particles are added into molten copper alloy. The introduced carbon source forms tiny bubbles under the influence of the dispersion structural member, graphene grows in the copper alloy, and carbon nanotubes grow on the nano metal catalyst. The carbon nano tube prevents graphene from being coalesced under the stirring of the structural member and the bubbles; and separating to obtain graphene and carbon nano tube solid products and gas products. The invention can directly produce high-quality carbon nanotubes and graphene, and has the advantages of simple reactor structure, no need of preparing a template agent for graphene growth, convenient control and low cost.

Description

Device and method for simultaneously producing carbon nano tube and graphene
Technical Field
The invention relates to the field of nano material preparation, in particular to a device and a method for simultaneously producing carbon nano tubes and graphene.
Background
The carbon nano tube and the graphene are nano materials formed by SP2 hybridized carbon, and have the excellent characteristics of large specific surface area, adjustable conductivity and semi-conductivity, good thermal conductivity, high mechanical strength, and the like, and can be independently used for adsorption, field emission devices, capacitor electrode materials, compounding with metals, polymers, ceramics and the like, and improving the conductivity, strength, antistatic property and the like of a main material. Mainstream preparation methods of carbon nanotubes include gas-solid phase chemical vapor deposition, laser ablation, and arc methods, which are all usually at temperatures higher than 600 ℃. The preparation method of the graphene comprises high-temperature gas-solid phase chemical vapor deposition, graphite stripping and the like. In general, the smaller the number of graphene layers, the more excellent the performance. However, the graphene layers are easy to accumulate to form multi-layer graphene. The finer the diameter of the carbon nanotube, the more excellent the performance. However, the diameter is generally dependent on the size of the nano metal particles, and the metal is easy to aggregate at high temperature to form large particles, or the activity is too high, and the carbon generated by cracking hydrocarbon is too much, and both the large particles and the large particles easily form multi-wall carbon nano tubes.
At present, copper is reported to be melted into a liquid phase, and hydrocarbon is introduced for cracking to form graphene. The advantage of this method is that the device is relatively simple. The method has the defects that in liquid copper, the contact and cracking process of hydrocarbons and copper are not easy to control, and the generated graphene is in a multi-layer state. And the temperature of the molten copper simple substance is required to be higher than the melting point (1180 ℃), which exceeds the temperature of preparing carbon nanotubes and graphene by most chemical vapor deposition, so that amorphous carbon is easy to generate, and the purity of the graphene is reduced. In addition, because the chemical vapor deposition method for preparing the carbon nano tube is simpler and more convenient, few reports for preparing the carbon nano tube by the high-temperature liquid metal phase exist.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a device and a method for simultaneously producing carbon nanotubes and graphene, so as to solve the problems that in the current process of preparing graphene from liquid molten copper, the contact and cracking process of hydrocarbons and copper are not easy to control, the produced graphene is in a multi-layer state, and the temperature of a molten copper simple substance needs to be higher than a melting point, amorphous carbon is easy to be produced, and the purity of the graphene is reduced.
The invention provides a device for simultaneously producing carbon nanotubes and graphene, which comprises a reaction device and a separation device; wherein, the liquid crystal display device comprises a liquid crystal display device,
the reaction device comprises a reaction device main body, wherein a liquid copper alloy reaction zone is arranged at the lower part of the inside of the reaction device main body, and a separation zone is arranged at the upper part of the inside of the reaction device main body; the lower end of the separation zone is communicated with the upper end of the liquid copper alloy reaction zone, and the diameter of the separation zone is smaller than that of the liquid copper alloy reaction zone;
a gas feed port is arranged on the side wall of the lower part of the liquid copper alloy reaction zone, and a solid feed port is arranged on the side wall of the upper part of the liquid copper alloy reaction zone; a dispersion structural member is arranged in the liquid copper alloy reaction zone; a separation structural member is arranged in the separation region; a gas-solid outlet is arranged on the side wall of the upper part of the separation zone;
The separation device comprises a separator connected with the gas-solid outlet; a gas outlet is arranged at the top end of the separator, and a solid outlet is arranged at the bottom end of the separator.
Furthermore, it is preferable that the diameter of the separation zone is 1/5 to 1/2 of the diameter of the liquid copper alloy reaction zone.
In addition, preferably, the shape of the dispersion structural member is a grid shape, and the void ratio of the grid-shaped dispersion structural member is 50% -90%.
Furthermore, it is preferable that the separation structure member comprises an umbrella-shaped structure member provided in the middle of the separation region, and an end portion of the umbrella-shaped structure member is fixed to the inner side wall of the reaction apparatus main body by a fixing connection member.
Furthermore, it is preferable that the number of umbrella-shaped structural members is at least two.
The method for simultaneously producing the carbon nano tube and the graphene provided by the invention adopts the device for simultaneously producing the carbon nano tube and the graphene to produce the carbon nano tube and the graphene, and comprises the following steps:
adding copper alloy powder into the liquid copper alloy reaction zone through the solid feed port, so that the filling height of the copper alloy powder is lower than the top end of the dispersing structural member;
Heating copper alloy powder in the liquid copper alloy reaction zone to form liquid copper alloy at a preset temperature;
introducing process gas into the liquid copper alloy through the gas charging port, wherein the process gas is dispersed to form small bubbles under the action of the dispersion structural member, and the small bubbles generate graphene in the liquid copper alloy; wherein the process gas comprises a carrier gas and a carbon source;
adding metal nano catalyst particles into a liquid copper alloy reaction zone in which the graphene is generated through the solid charging port, wherein the metal nano catalyst particles are in contact with the carbon source to grow into carbon nanotubes, and the carbon nanotubes prevent the graphene from being coalesced under the stirring action of the dispersing structural member and the small bubbles, so that a primary carbon product is formed in the liquid copper alloy reaction zone;
with the increase of the accumulation amount of the primary carbon products, the primary carbon products are carried into the separation zone by the air flow, in the separation zone, the primary carbon products stained with the copper alloy powder return into the liquid copper alloy reaction zone under the blocking action of the separation structural member, and the primary carbon products not stained with the copper alloy powder enter the separation device through the gas-solid outlet by bypassing the separation structural member under the action of the air flow;
And carrying out gas-solid separation treatment on the primary carbon product in the separation device through the separator, and collecting the gas flowing out of the gas outlet and collecting the carbon product containing carbon nano tubes and graphene, which is discharged from the solid outlet.
In addition, preferably, the copper alloy powder is one of copper-aluminum alloy powder, copper-silver alloy powder, copper-tin alloy powder and copper-zinc alloy powder or at least two of the copper-aluminum alloy powder, copper-silver alloy powder, copper-tin alloy powder and copper-zinc alloy powder mixed according to any proportion; and the copper alloy powder is in a liquid state at the preset temperature under normal pressure.
In addition, preferably, in the process of heating the copper alloy powder in the liquid copper alloy reaction zone to form the liquid copper alloy at a preset temperature,
heating the copper alloy powder in the liquid copper alloy reaction zone in an electric induction heating or gas heating mode; the preset temperature is 600-1000 ℃.
In addition, preferably, in the process gas, the volume of the carbon source and the carrier gas is 1:1 to 1:10; the carrier gas is an inert gas; the carbon source is C 1 -C 12 Hydrocarbon or C of (C) 1 -C 12 Hydrocarbon and H of (2) 2 Mixed gas mixed according to any proportion; the mass airspeed of the carbon source is 0.001-1kg/kg/h; the residence time of the process gas in the liquid copper alloy reaction zone is 0.001-0.1 hours; at the position of In the carbon product containing the carbon nano tube and the graphene, the mass ratio of the carbon nano tube to the graphene is 100:1-1:100; the specific surface area of the carbon product is 200-2000 square meters per gram.
In addition, preferably, metal nano catalyst particles are added into the liquid copper alloy reaction zone in which the graphene is generated through the solid feed inlet, the metal nano catalyst particles are in contact with the carbon source to grow into carbon nanotubes, the carbon nanotubes prevent the graphene from being aggregated under the action of the dispersing structural member and the stirring of the small bubbles, and in the process of forming a primary carbon product in the liquid copper alloy reaction zone,
adding metal nano catalyst particles into a liquid copper alloy reaction zone in which the graphene is generated through the solid feed inlet every 2-4 hours;
the volume ratio of the metal nano catalyst particles added each time to the liquid copper alloy in the liquid copper alloy reaction zone in which the graphene is generated is 1-10%;
the metal nano catalyst particles comprise a metal component and a carrier; wherein, the liquid crystal display device comprises a liquid crystal display device,
the mass percentage of the metal component in the metal nano catalyst particles is 1-20%;
The metal component is any one of iron, cobalt and nickel or at least two of the iron, cobalt and nickel mixed according to a proportion;
the carrier is alumina or silica;
the particle size of the metal nano catalyst particles is 1-20 microns.
According to the technical scheme, the device for simultaneously producing the carbon nano tube and the graphene provided by the invention has the advantages that the liquid copper alloy reaction zone, the separation zone and the design of the reducing structure between the two zones are arranged in the reaction device main body, so that the primary carbon product generated in the reaction zone can stably enter the separation zone under the action of air flow; through the design of the dispersing structural member, the process gas entering the liquid copper alloy reaction zone is dispersed into small bubbles, so that the generated carbon nano tube can prevent graphene from coalescing under the stirring action of the dispersing structural member and the small bubbles, and the quality of the generated carbon product is ensured; the design of the separation structural member prevents the outflow of the carbon product stained with the metal powder, thereby further ensuring the quality of the carbon product; compared with the traditional device structure for generating graphene by gas-solid phase chemical vapor deposition, the device has the advantages of simple structure, reasonable design and low device cost; the method for simultaneously producing the carbon nano tube and the graphene has the advantages similar to the device because the device provided by the invention is adopted, and meanwhile, the method provided by the invention can be used for melting at lower temperature than pure copper by adopting the alloy of copper, so that the activity of copper is reduced, the carbon generated by cracking is reduced, the thin-layer graphene is favorably generated, and the generation probability of the thin-layer graphene is improved by 50% -90%; the energy consumption is reduced by 30% -50% compared with the pure copper liquid method; the nano metal catalyst particles are added, so that carbon nanotubes can be generated, and the generated carbon nanotubes are in a dispersed state due to low cracking rate of a carbon source, so that the aggregation of graphene is ensured, the graphene is not easy to aggregate, the carbon nanotubes in the later stage are easy to disperse and use, and the energy consumption in the dispersing process is reduced by 20% -30%; meanwhile, the control of the number of layers of the graphene is realized by means of the dispersion effect and the carbon source competition effect.
To the accomplishment of the foregoing and related ends, one or more aspects of the invention comprise the features hereinafter fully described. The following description and the annexed drawings set forth in detail certain illustrative aspects of the invention. These aspects are indicative, however, of but a few of the various ways in which the principles of the invention may be employed. Furthermore, the invention is intended to include all such aspects and their equivalents.
Drawings
Other objects and attainments together with a more complete understanding of the invention will become apparent and appreciated by referring to the following description taken in conjunction with the accompanying drawings. In the drawings:
fig. 1 is a schematic structural view of an apparatus for simultaneously producing carbon nanotubes and graphene according to an embodiment of the present invention;
fig. 2 is a process flow diagram of a method for simultaneously producing carbon nanotubes and graphene according to an embodiment of the present invention.
In the drawing, a 1-reaction device main body, a 11-liquid copper alloy reaction zone, a 111-gas feed port, a 112-solid feed port, a 12-separation zone, a 121-gas-solid outlet, a 13-dispersion structure, a 14-separation structure, a 2-separator, a 21-gas outlet and a 22-solid outlet.
The same reference numerals will be used throughout the drawings to refer to similar or corresponding features or functions.
Detailed Description
In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of one or more embodiments. It may be evident, however, that such embodiment(s) may be practiced without these specific details.
Aiming at the problems that in the process of preparing graphene by the liquid molten copper phase, the contact and cracking process of hydrocarbons and copper are not easy to control, the generated graphene is in a multi-layer state, amorphous carbon is easy to generate due to the fact that the temperature of a molten copper simple substance is required to be higher than an alkane point, the purity of the graphene is reduced, and the like, the device and the method for simultaneously producing the carbon nano tube and the graphene are provided.
Specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
In order to illustrate the apparatus for simultaneously producing carbon nanotubes and graphene provided by the present invention, fig. 1 shows a structure of an apparatus for simultaneously producing carbon nanotubes and graphene according to an embodiment of the present invention.
As shown in fig. 1, the device for simultaneously producing carbon nanotubes and graphene provided by the invention comprises a reaction device and a separation device; wherein, the liquid crystal display device comprises a liquid crystal display device,
the reaction device comprises a reaction device main body 1, wherein a liquid copper alloy reaction zone 11 is arranged at the lower part of the inside of the reaction device main body 1, and a separation zone 12 is arranged at the upper part of the inside of the reaction device main body 1; the lower end of the separation zone 12 is communicated with the upper end of the liquid copper alloy reaction zone 11, and the diameter of the separation zone 12 is smaller than that of the liquid copper alloy reaction zone 11; a gas feed port 111 is provided on the side wall of the lower part of the liquid copper alloy reaction zone 11, and a solid feed port 112 is provided on the side wall of the upper part of the liquid copper alloy reaction zone 11; a dispersion structural member 13 is arranged in the liquid copper alloy reaction zone; a separating structure 14 is arranged inside the separating zone 12; a gas-solid outlet 121 is provided on a side wall of an upper portion of the separation zone 12; the separation device comprises a separator 2 connected with the gas-solid outlet 121; a gas outlet 21 is provided at the top end of the separator 2 and a solids outlet 22 is provided at the bottom end of the separator.
Wherein the separator 2 is a cyclone separator, through which the gas and solids in the primary carbon product can be separated, thereby obtaining a carbon product and collecting the gas.
By arranging the liquid copper alloy reaction zone 11 and the separation zone 12 in the reaction device main body 1 and designing the reducing structure between the two zones, the primary carbon product generated in the reaction zone can stably enter the separation zone 12 under the action of air flow; through the design of the dispersing structural member 13, the process gas entering the liquid copper alloy reaction zone 11 is dispersed into small bubbles, so that the generated carbon nano tube can prevent graphene from being aggregated under the stirring action of the dispersing structural member 13 and the small bubbles, and the quality of the generated carbon product is ensured; the design of the separation structural member 14 prevents the outflow of the carbon product stained with the metal powder, thereby further ensuring the quality of the carbon product; compared with the traditional device structure for generating the carbon nano tube by gas-solid phase chemical vapor deposition, the whole device has simple structure, reasonable design and low device cost.
As a preferred embodiment of the present invention, the diameter of separation zone 12 is 1/5 to 1/2 of the diameter of the liquid copper alloy reaction zone.
As a preferred embodiment of the present invention, the dispersion structure 13 is in the shape of a grid, and the void ratio of the grid-shaped dispersion structure 13 is 50% -90%. Wherein, the grid-shaped dispersion structural member 13 can be made of corrosion-resistant materials and is formed by cross connection of at least two cross bars and at least two vertical bars, and the end parts of the cross bars and the vertical bars are fixed on the side wall of the reaction device main body 1.
As a preferred embodiment of the present invention, the separation structure 14 comprises an umbrella-shaped structure provided in the middle of the separation zone, and the end of the umbrella-shaped structure is fixed to the inner side wall of the reaction apparatus main body by a fixing connector. The gas or liquid or solid may be deflected or bypassed as it encounters the separating structure. Small liquids or solids flow upward with the gas. Large or heavy liquids or solids move downward. Has separation effect.
As a preferred embodiment of the invention, the number of umbrella-shaped structures is at least two. The plurality of umbrella-shaped structural members can enable the separation effect to be better.
Fig. 2 shows a process flow of a method for simultaneously producing carbon nanotubes and graphene according to an embodiment of the present invention.
As shown in fig. 2, the method for simultaneously producing carbon nanotubes and graphene provided by the invention adopts the device for simultaneously producing carbon nanotubes and graphene to produce carbon nanotubes and graphene, and comprises the following steps:
s1, adding copper alloy powder into a liquid copper alloy reaction zone 11 through a solid feed port 112, so that the filling height of the copper alloy powder is lower than the top end of a dispersion structural member 13;
s2, carrying out heating treatment on copper alloy powder in the liquid copper alloy reaction zone 11 to enable the copper alloy powder to form liquid copper alloy at a preset temperature;
S3, introducing process gas into the liquid copper alloy through a gas feed port 111, and dispersing the process gas under the action of a dispersion structural member 13 to form small bubbles, wherein the small bubbles generate graphene in the liquid copper alloy; wherein the process gas comprises a carrier gas and a carbon source;
s4, adding metal nano catalyst particles into the liquid copper alloy reaction zone 11 with the graphene through a solid feed inlet 112, enabling the metal nano catalyst particles to contact a carbon source, growing into carbon nanotubes, and preventing the graphene from being aggregated under the action of a dispersing structural member and small bubbles stirring, so as to form a primary carbon product in the liquid copper alloy reaction zone;
s5, carrying the primary carbon products into a separation area 12 by the air flow along with the increase of the accumulation amount of the primary carbon products, returning the primary carbon products stained with copper alloy powder into a liquid copper alloy reaction area 11 under the blocking action of a separation structural member 14 in the separation area 12, and enabling the primary carbon products not stained with copper alloy powder to enter a separation device through a gas-solid outlet 121 by bypassing the separation structural member 14 under the action of the air flow;
s6, carrying out gas-solid separation treatment on the primary carbon product in the separation device through the separator 2, and collecting gas flowing out from the gas outlet 21 and collecting carbon product containing carbon nano tubes and graphene, which is discharged from the solid outlet 22.
The method for simultaneously producing the carbon nano tube and the graphene has the advantages similar to those of the device because the device provided by the invention is adopted, and meanwhile, the method provided by the invention can be used for melting at a lower temperature than pure copper by adopting the copper alloy, so that the activity of copper is reduced, the carbon generated by cracking is reduced, the thin-layer graphene is favorably generated, and the generation probability of the thin-layer graphene is improved by 50% -90%; the energy consumption is reduced by 30% -50% compared with the pure copper liquid method; the nano metal catalyst particles are added, so that carbon nanotubes can be generated, and the generated carbon nanotubes are in a dispersed state due to low cracking rate of a carbon source, so that the aggregation of graphene is ensured, the graphene is not easy to aggregate, the carbon nanotubes in the later stage are easy to disperse and use, and the energy consumption in the dispersing process is reduced by 20% -30%; meanwhile, the control of the number of layers of the graphene is realized by means of the dispersion effect and the carbon source competition effect.
As a preferred embodiment of the present invention, the copper alloy powder is one of copper-aluminum alloy powder, copper-silver alloy powder, copper-tin alloy powder, copper-zinc alloy powder or at least two of them mixed in an arbitrary ratio; and the copper alloy powder is in a liquid state at a preset temperature under normal pressure.
As a preferred embodiment of the present invention, in the process of heating copper alloy powder in a liquid copper alloy reaction zone to form a liquid copper alloy at a preset temperature,
heating copper alloy powder in the liquid copper alloy reaction zone in an electric induction heating or gas heating mode; the preset temperature is 600-1000 ℃.
The melting point of the copper alloy is far lower than that of copper; the quality of the carbon product is not affected. When using electric induction heating, green electricity can be used to reduce CO2 emissions, and the technology has great green potential.
As a preferred embodiment of the invention, the volume of the carbon source and the carrier gas in the process gas is 1:1-1:10; the carrier gas is an inert gas; the carbon source is C 1 -C 12 Hydrocarbon or C of (C) 1 -C 12 Mixed gas of hydrocarbon and H2 according to any proportion; the mass airspeed of the carbon source is 0.001-1kg/kg/h; the residence time of the process gas in the liquid copper alloy reaction zone is 0.001-0.1 hours; in a carbon product containing carbon nanotubes and graphene, the mass ratio of the carbon nanotubes to the graphene is 100:1-1:100; the specific surface area of the carbon product is 200-2000 square meters per gram.
As a preferred embodiment of the present invention, metal nano catalyst particles are added into a liquid copper alloy reaction zone where graphene is generated through a solid feed port, the metal nano catalyst particles are contacted with a carbon source to generate carbon nanotubes, the carbon nanotubes are prevented from being aggregated under the action of a dispersing structural member and small bubble stirring, and in the process of forming a primary carbon product in the liquid copper alloy reaction zone,
Adding metal nano catalyst particles into a liquid copper alloy reaction zone in which graphene is generated through a solid feed inlet every 2-4 hours;
the volume ratio of the metal nano catalyst particles added each time to the liquid copper alloy in the liquid copper alloy reaction zone in which the graphene is generated is 1-10%;
the metal nano catalyst particles comprise a metal component and a carrier; wherein, the mass percentage of the metal component in the metal nano catalyst particles is 1-20%; the metal component is any one of iron, cobalt and nickel or at least two of the iron, cobalt and nickel mixed according to a proportion; the carrier is alumina or silica; the particle size of the metal nano catalyst particles is 1-20 microns.
In order to better illustrate the device and the method for simultaneously producing the carbon nanotubes and the graphene, provided by the invention, the following specific embodiments are provided.
Example 1
And assembling the device for simultaneously producing the carbon nano tube and the graphene. Wherein the diameter of the separation zone 12 is 1/2 of the diameter of the liquid copper alloy reaction zone 11; the void ratio of the dispersion structure 13 was 75%.
Copper alloy powder (copper aluminum powder, which is in a liquid state at 600 ℃ or higher under normal pressure) is charged into the liquid copper alloy reaction zone 11 through the solid charging port 112, and the charging height is controlled to be lower than the upper edge of the dispersion structure 13. Melting copper alloy powder at 600 ℃ by electric induction heating, and keeping the molten state;
Process gas (carrier gas is nitrogen; carbon source is mixed gas of 10% H2 and 90% CH 4. The volume of the carbon source and the carrier gas is 1:1) is introduced through the gas feed port 111, and the mass space velocity of the carbon source is controlled to be 0.001kg/kg/h. The process gas is dispersed by the dispersion structure 13 to form micro bubbles, and graphene grows in the copper alloy. The residence time of the process gas in the liquid copper alloy reaction zone 11 was 0.001 hours. Metal nano-catalyst particles (metal component is iron, carrier is alumina, mass ratio of metal in catalyst is 1%, particle size is 1-10 micrometers) are added into liquid copper alloy with volume ratio of 10% through solid feed inlet 112, and added into liquid copper alloy reaction zone 11. The hydrocarbon gas contacts with the nano metal catalyst particles to grow the carbon nano tubes. The generated carbon nanotubes prevent graphene from coalescing under the agitation of the dispersion structure 13 and bubbles.
When the carbon product becomes more, it automatically floats up to the surface of the liquid copper alloy reaction zone 11 due to the density difference. When accumulated too much, it is carried by the gas stream into the separation zone 12. The small amount of metal-contaminated powder is relatively heavy and encounters the barrier of the separating structure 14 in the separating zone and returns to the liquid copper alloy reaction zone 11. A large amount of powder which is not adhered with metal bypasses the separation structural member 14 under the action of the air flow and enters the cyclone separator through the air-solid outlet 121. The gaseous product is collected through a gas outlet 21. Carbon product is collected through solids outlet 22. The carbon product is a product with the mass ratio of the obtained carbon nano tube to the graphene of 100:1, and the specific surface area of the product is 200 square meters per gram.
Nano metal catalyst particles with a volume proportion of 10% of liquid copper alloy were added through the solid feed port 112 every 2 hours.
Example 2
And assembling the device for simultaneously producing the carbon nano tube and the graphene. Wherein the diameter of the separation zone 12 is 1/3 of the diameter of the liquid copper alloy reaction zone 11; the void ratio of the dispersion structure 13 was 85%.
Copper alloy powder (copper-tin powder, which is liquid at 800 ℃ or higher at normal pressure) is charged into the liquid copper alloy reaction zone 11 through the solid charging port 112, and the charging height is controlled to be lower than the upper edge of the dispersion structure 13. Melting copper alloy powder at 800 ℃ by heating gas, and keeping the molten state;
process gas (carrier gas is argon; carbon source is CH 4; the volume of the carbon source and the carrier gas is 1:10) is introduced through the gas feed port 111, and the mass space velocity of the carbon source is controlled to be 0.001kg/kg/h. The process gas is dispersed by the dispersion structure 13 to form micro bubbles, and graphene grows in the copper alloy. The residence time of the process gas in the liquid copper alloy reaction zone 11 was 0.1 hours. Metal nano-catalyst particles (the metal component is cobalt, the carrier is silicon oxide, the mass ratio of metal in the catalyst is 5%, the particle size is 10-20 microns) are added into the liquid copper alloy through a solid feed inlet 112, and the liquid copper alloy is added into a liquid copper alloy reaction zone 11. The hydrocarbon gas contacts with the nano metal catalyst particles to grow the carbon nano tubes. The generated carbon nanotubes prevent graphene from coalescing under the agitation of the dispersion structure 13 and bubbles.
When the carbon product becomes more, it automatically floats up to the surface of the liquid copper alloy reaction zone 11 due to the density difference. When accumulated too much, it is carried by the gas stream into the separation zone 12. The small amount of metal-contaminated powder is relatively heavy and encounters the barrier of the separating structure 14 in the separating zone and returns to the liquid copper alloy reaction zone 11. A large amount of powder which is not adhered with metal bypasses the separation structural member 14 under the action of the air flow and enters the cyclone separator through the air-solid outlet 121. The gaseous product is collected through a gas outlet 21. Carbon product is collected through solids outlet 22. The carbon product is a product with the mass ratio of the obtained carbon nano tube to the graphene of 1:1, and the specific surface area is 1000 square meters per gram.
Nano metal catalyst particles with a volume proportion of 5% of liquid copper alloy were added through the solid feed port 112 every 3 hours.
Example 3
And assembling the device for simultaneously producing the carbon nano tube and the graphene. Wherein the diameter of the separation zone 12 is 1/4 of the diameter of the liquid copper alloy reaction zone 11; the void ratio of the dispersion structure 13 was 50%.
Copper alloy powder (copper silver powder, which is in a liquid state at 600 ℃ or higher under normal pressure) is charged into the liquid copper alloy reaction zone 11 through the solid charging port 112, and the charging height is controlled to be lower than the upper edge of the dispersion structure 13. Melting copper alloy powder at 900 ℃ by electric induction heating, and keeping a molten state;
Process gas (carrier gas is nitrogen; carbon source is 90% H2 and 10% CH4. Volume of carbon source and carrier gas is 1:2) is introduced through gas feed port 111, and the mass space velocity of the carbon source is controlled to be 0.005kg/kg/h. The process gas is dispersed by the dispersion structure 13 to form micro bubbles, and graphene grows in the copper alloy. The residence time of the process gas in the liquid copper alloy reaction zone 11 is 0.001 to 0.1 hours. Metal nano-catalyst particles (metal component is iron, carrier is silicon oxide, mass ratio of metal in catalyst is 2%, grain size is 1-10 micrometers) are added into liquid copper alloy with volume ratio of 1% through solid feed inlet 112, and added into liquid copper alloy reaction zone 11. The hydrocarbon gas contacts with the nano metal catalyst particles to grow the carbon nano tubes. The generated carbon nanotubes prevent graphene from coalescing under the agitation of the dispersion structure 13 and bubbles.
When the carbon product becomes more, it automatically floats up to the surface of the liquid copper alloy reaction zone 11 due to the density difference. When accumulated too much, it is carried by the gas stream into the separation zone 12. The small amount of metal-contaminated powder is relatively heavy and encounters the barrier of the separating structure 14 in the separating zone and returns to the liquid copper alloy reaction zone 11. A large amount of powder which is not adhered with metal bypasses the separation structural member 14 under the action of the air flow and enters the cyclone separator through the air-solid outlet 121. The gaseous product is collected through a gas outlet 21. Carbon product is collected through solids outlet 22. The carbon product is a product with the mass ratio of the obtained carbon nano tube to the graphene of 1:100, and the specific surface area is 2000 square meters per gram.
Nano metal catalyst particles with a volume ratio of 1% of liquid copper alloy were added through the solid feed port 112 every 4 hours.
Example 4
And assembling the device for simultaneously producing the carbon nano tube and the graphene. Wherein the diameter of the separation zone 12 is 1/4 of the diameter of the liquid copper alloy reaction zone 11; the porosity of the dispersion structure 13 was 70%.
Copper alloy powder (copper zinc powder, which is liquid at 900 ℃ or higher under normal pressure) is charged into the liquid copper alloy reaction zone 11 through the solid charging port 112, and the charging height is controlled to be lower than the upper edge of the dispersion structure 13. Melting copper alloy powder at 950 ℃ by electric induction heating, and keeping the molten state;
process gas (carrier gas is nitrogen; carbon source is C1-C6 hydrocarbon; the volume of carbon source and carrier gas is 1:10) is introduced through the gas feed port 111, and the mass space velocity of the carbon source is controlled to be 0.02kg/kg/h. The process gas is dispersed by the dispersion structure 13 to form micro bubbles, and graphene grows in the copper alloy. The residence time of the process gas in the liquid copper alloy reaction zone 11 was 0.05 hours. Metal nano-catalyst particles (nickel as a metal component, silicon oxide as a carrier, 20% by mass of metal in the catalyst, and 10-20 μm in particle diameter) were added to the liquid copper alloy in a volume ratio of 10% through the solid feed port 112, and added to the liquid copper alloy reaction zone 11. The hydrocarbon gas contacts with the nano metal catalyst particles to grow the carbon nano tubes. The generated carbon nanotubes prevent graphene from coalescing under the agitation of the dispersion structure 13 and bubbles.
When the carbon product becomes more, it automatically floats up to the surface of the liquid copper alloy reaction zone 11 due to the density difference. When accumulated too much, it is carried by the gas stream into the separation zone 12. The small amount of metal-contaminated powder is relatively heavy and encounters the barrier of the separating structure 14 in the separating zone and returns to the liquid copper alloy reaction zone 11. A large amount of powder which is not adhered with metal bypasses the separation structural member 14 under the action of the air flow and enters the cyclone separator through the air-solid outlet 121. The gaseous product is collected through a gas outlet 21. Carbon product is collected through solids outlet 22. The carbon product is a product with the mass ratio of the obtained carbon nano tube to the graphene of 50:1, and the specific surface area is 800 square meters per gram.
Nano metal catalyst particles with a volume proportion of 10% of liquid copper alloy were added through the solid feed port 112 every 2 hours.
Example 5
And assembling the device for simultaneously producing the carbon nano tube and the graphene. Wherein the diameter of the separation zone 12 is 1/3 of the diameter of the liquid copper alloy reaction zone 11; the void ratio of the dispersion structure 13 was 80%.
Copper alloy powder (copper aluminum powder, which is in a liquid state at 600 ℃ or higher under normal pressure) is charged into the liquid copper alloy reaction zone 11 through the solid charging port 112, and the charging height is controlled to be lower than the upper edge of the dispersion structure 13. Melting copper alloy powder at 700 ℃ by electric induction heating, and keeping a molten state;
Process gas (carrier gas is helium; carbon source is C6-C12 hydrocarbon; the volume of carbon source and carrier gas is 1:5) is introduced through gas feed port 111, and the mass space velocity of the carbon source is controlled to be 0.6kg/kg/h. The process gas is dispersed by the dispersion structure 13 to form micro bubbles, and graphene grows in the copper alloy. The residence time of the process gas in the liquid copper alloy reaction zone 11 was 0.08 hours. Metal nano-catalyst particles (metal component 50% cobalt; 30% iron, 20% nickel, carrier alumina: 15% metal in catalyst mass ratio; particle size 20 μm) were added to the liquid copper alloy at a volume ratio of 1% through the solid feed port 112, and added to the liquid copper alloy reaction zone 11. The hydrocarbon gas contacts with the nano metal catalyst particles to grow the carbon nano tubes. The generated carbon nanotubes prevent graphene from coalescing under the agitation of the dispersion structure 13 and bubbles.
When the carbon product becomes more, it automatically floats up to the surface of the liquid copper alloy reaction zone 11 due to the density difference. When accumulated too much, it is carried by the gas stream into the separation zone 12. The small amount of metal-contaminated powder is relatively heavy and encounters the barrier of the separating structure 14 in the separating zone and returns to the liquid copper alloy reaction zone 11. A large amount of powder which is not adhered with metal bypasses the separation structural member 14 under the action of the air flow and enters the cyclone separator through the air-solid outlet 121. The gaseous product is collected through a gas outlet 21. Carbon product is collected through solids outlet 22. The carbon product is a product with the mass ratio of the obtained carbon nano tube to the graphene of 1:50, and the specific surface area is 1800 square meters per gram.
Nano metal catalyst particles with a volume ratio of 1-10% of the liquid copper alloy were added through the solid feed port 112 every 4 hours.
Example 6
And assembling the device for simultaneously producing the carbon nano tube and the graphene. Wherein the diameter of the separation zone 12 is 1/2 of the diameter of the liquid copper alloy reaction zone 11; the void ratio of the dispersion structure 13 was 50%.
Copper alloy powder (copper silver aluminum zinc powder, which is liquid at 600 ℃ or higher under normal pressure) is charged into the liquid copper alloy reaction zone 11 through the solid charging port 112, and the charging height is controlled to be lower than the upper edge of the dispersion structure 13. Melting copper alloy powder at 1200 ℃ by electric induction heating, and keeping a molten state;
and a process gas (argon is used as a carrier gas, a mixed gas of 20% H2,60% CH4 and 20% C6-C7 aromatic hydrocarbon is used as a carbon source) is introduced through a gas feed inlet 111, the volume of the carbon source and the carrier gas is 1:2, and the mass airspeed of the carbon source is controlled to be 0.1kg/kg/h. The process gas is dispersed by the dispersion structure 13 to form micro bubbles, and graphene grows in the copper alloy. The residence time of the process gas in the liquid copper alloy reaction zone 11 was 0.01 hours. Metal nano-catalyst particles (nickel as a metal component, silicon oxide as a carrier, 20% by mass of metal in the catalyst, and 10-20 μm in particle diameter) were added to the liquid copper alloy in a volume ratio of 1.9% through the solid feed port 112, and added to the liquid copper alloy reaction zone 11. The hydrocarbon gas contacts with the nano metal catalyst particles to grow the carbon nano tubes. The generated carbon nanotubes prevent graphene from coalescing under the agitation of the dispersion structure 13 and bubbles.
When the carbon product becomes more, it automatically floats up to the surface of the liquid copper alloy reaction zone 11 due to the density difference. When accumulated too much, it is carried by the gas stream into the separation zone 12. The small amount of metal-contaminated powder is relatively heavy and encounters the barrier of the separating structure 14 in the separating zone and returns to the liquid copper alloy reaction zone 11. A large amount of powder which is not adhered with metal bypasses the separation structural member 14 under the action of the air flow and enters the cyclone separator through the air-solid outlet 121. The gaseous product is collected through a gas outlet 21. Carbon product is collected through solids outlet 22. The carbon product is a product with the mass ratio of the obtained carbon nano tube to the graphene of 2:1, and the specific surface area is 1200 square meters per gram.
Nano metal catalyst particles with a volume ratio of 1.9% of liquid copper alloy were added through the solid feed port 112 every 2.4 hours.
Example 7
And assembling the device for simultaneously producing the carbon nano tube and the graphene. Wherein the diameter of the separation zone 12 is 1/5 of the diameter of the liquid copper alloy reaction zone 11; the void ratio of the dispersion structure 13 was 90%.
Copper alloy powder (copper aluminum zinc powder, which is in a liquid state at a temperature of 700 ℃ or higher than normal pressure) is charged into the liquid copper alloy reaction zone 11 through the solid charging port 112, and the charging height is controlled to be lower than the upper edge of the dispersion structure 13. Melting copper alloy powder at 100 ℃ by electric induction heating, and keeping the molten state;
And process gas (carrier gas is argon, carbon source is C6-C12 aromatic hydrocarbon, the volume of the carbon source and the carrier gas is 1:5) is introduced through the gas feed port 111, and the mass airspeed of the carbon source is controlled to be 0.25kg/kg/h. The process gas is dispersed by the dispersion structure 13 to form micro bubbles, and graphene grows in the copper alloy. The residence time of the process gas in the liquid copper alloy reaction zone 11 was 0.02 hours. Metal nano-catalyst particles (the metal component is cobalt, the carrier is silicon oxide, the mass ratio of metal in the catalyst is 3%, the particle size is 2-12 microns) are added into the liquid copper alloy through a solid feed inlet 112, and the liquid copper alloy is added into a liquid copper alloy reaction zone 11. The hydrocarbon gas contacts with the nano metal catalyst particles to grow the carbon nano tubes. The generated carbon nanotubes prevent graphene from coalescing under the agitation of the dispersion structure 13 and bubbles.
When the carbon product becomes more, it automatically floats up to the surface of the liquid copper alloy reaction zone 11 due to the density difference. When accumulated too much, it is carried by the gas stream into the separation zone 12. The small amount of metal-contaminated powder is relatively heavy and encounters the barrier of the separating structure 14 in the separating zone and returns to the liquid copper alloy reaction zone 11. A large amount of powder which is not adhered with metal bypasses the separation structural member 14 under the action of the air flow and enters the cyclone separator through the air-solid outlet 121. The gaseous product is collected through a gas outlet 21. Carbon product is collected through solids outlet 22. The carbon product is a product with the mass ratio of the obtained carbon nano tube to the graphene of 20:1, and the specific surface area is 1000 square meters per gram.
Nano metal catalyst particles with a volume proportion of 10% of liquid copper alloy were added through the solid feed port 112 every 3.5 hours.
According to the device and the method for simultaneously producing the carbon nano tube and the graphene, the liquid copper alloy reaction zone and the separation zone are arranged in the reaction device main body, and the design of the reducing structure between the two zones can ensure that the primary carbon product generated in the reaction zone stably enters the separation zone under the action of air flow; through the design of the dispersing structural member, the process gas entering the liquid copper alloy reaction zone is dispersed into small bubbles, so that the generated carbon nano tube can prevent graphene from coalescing under the stirring action of the dispersing structural member and the small bubbles, and the quality of the generated carbon product is ensured; the design of the separation structural member prevents the outflow of the carbon product stained with the metal powder, thereby further ensuring the quality of the carbon product; compared with the traditional device structure for generating the carbon nano tube by gas-solid phase chemical vapor deposition, the whole device has simple structure, reasonable design and low device cost; the method for simultaneously producing the carbon nano tube and the graphene has the advantages similar to the device because the device provided by the invention is adopted, and meanwhile, the method provided by the invention can be used for melting at lower temperature than pure copper by adopting the alloy of copper, so that the activity of copper is reduced, the carbon generated by cracking is reduced, the thin-layer graphene is favorably generated, and the generation probability of the thin-layer graphene is improved by 50% -90%; the energy consumption is reduced by 30% -50% compared with the pure copper liquid method; the nano metal catalyst particles are added, so that carbon nanotubes can be generated, and the generated carbon nanotubes are in a dispersed state due to low cracking rate of a carbon source, so that the aggregation of graphene is ensured, the graphene is not easy to aggregate, the carbon nanotubes in the later stage are easy to disperse and use, and the energy consumption in the dispersing process is reduced by 20% -30%; meanwhile, the control of the number of layers of the graphene is realized by means of the dispersion effect and the carbon source competition effect.
The apparatus and method for simultaneously producing carbon nanotubes and graphene according to the present invention are described above by way of example with reference to the accompanying drawings. However, it will be appreciated by those skilled in the art that various modifications may be made to the apparatus and method for simultaneously producing carbon nanotubes and graphene set forth above without departing from the scope of the present invention. Accordingly, the scope of the invention should be determined from the following claims.

Claims (9)

1. The device for simultaneously producing the carbon nano tube and the graphene is characterized by comprising a reaction device and a separation device; wherein, the liquid crystal display device comprises a liquid crystal display device,
the reaction device comprises a reaction device main body, wherein a liquid copper alloy reaction zone is arranged at the lower part of the inside of the reaction device main body, and a separation zone is arranged at the upper part of the inside of the reaction device main body; the lower end of the separation zone is communicated with the upper end of the liquid copper alloy reaction zone, and the diameter of the separation zone is smaller than that of the liquid copper alloy reaction zone;
a gas feed port is arranged on the side wall of the lower part of the liquid copper alloy reaction zone, and a solid feed port is arranged on the side wall of the upper part of the liquid copper alloy reaction zone; a dispersion structural member is arranged in the liquid copper alloy reaction zone; a separation structural member is arranged in the separation region; a gas-solid outlet is arranged on the side wall of the upper part of the separation zone; the separation structural member comprises an umbrella-shaped structural member arranged in the middle of the separation region, and the end part of the umbrella-shaped structural member is fixed on the inner side wall of the reaction device main body through a fixed connecting piece;
The separation device comprises a separator connected with the gas-solid outlet; a gas outlet is arranged at the top end of the separator, and a solid outlet is arranged at the bottom end of the separator.
2. The apparatus for simultaneously producing carbon nanotubes and graphene according to claim 1, wherein the diameter of the separation zone is 1/5-1/2 of the diameter of the liquid copper alloy reaction zone.
3. The apparatus for simultaneously producing carbon nanotubes and graphene according to claim 1, wherein the dispersion structure has a shape of a grid, and the void ratio of the dispersion structure of the grid is 50% -90%.
4. The apparatus for simultaneously producing carbon nanotubes and graphene of claim 1, wherein the number of umbrella-shaped structures is at least two.
5. A method for simultaneously producing carbon nanotubes and graphene, wherein the method adopts the device for simultaneously producing carbon nanotubes and graphene according to any one of claims 1 to 4, and comprises the following steps:
adding copper alloy powder into the liquid copper alloy reaction zone through the solid feed port, so that the filling height of the copper alloy powder is lower than the top end of the dispersing structural member;
Heating copper alloy powder in the liquid copper alloy reaction zone to form liquid copper alloy at a preset temperature;
introducing process gas into the liquid copper alloy through the gas charging port, wherein the process gas is dispersed to form small bubbles under the action of the dispersion structural member, and the small bubbles generate graphene in the liquid copper alloy; wherein the process gas comprises a carrier gas and a carbon source;
adding metal nano catalyst particles into a liquid copper alloy reaction zone in which the graphene is generated through the solid charging port, wherein the metal nano catalyst particles are in contact with the carbon source to grow into carbon nanotubes, and the carbon nanotubes prevent the graphene from being coalesced under the stirring action of the dispersing structural member and the small bubbles, so that a primary carbon product is formed in the liquid copper alloy reaction zone;
with the increase of the accumulation amount of the primary carbon products, the primary carbon products are carried into the separation zone by the air flow, in the separation zone, the primary carbon products stained with the copper alloy powder return into the liquid copper alloy reaction zone under the blocking action of the separation structural member, and the primary carbon products not stained with the copper alloy powder enter the separation device through the gas-solid outlet by bypassing the separation structural member under the action of the air flow;
And carrying out gas-solid separation treatment on the primary carbon product in the separation device through the separator, and collecting the gas flowing out of the gas outlet and collecting the carbon product containing carbon nano tubes and graphene, which is discharged from the solid outlet.
6. The method for simultaneously producing carbon nanotubes and graphene according to claim 5, wherein the copper alloy powder is one of copper-aluminum alloy powder, copper-silver alloy powder, copper-tin alloy powder, copper-zinc alloy powder or at least two of them mixed in an arbitrary ratio; and the copper alloy powder is in a liquid state at the preset temperature under normal pressure.
7. The method for simultaneously producing carbon nanotubes and graphene according to claim 5, wherein, in the process of heating the copper alloy powder in the liquid copper alloy reaction zone to form a liquid copper alloy at a predetermined temperature,
heating the copper alloy powder in the liquid copper alloy reaction zone in an electric induction heating or gas heating mode;
the preset temperature is 600-1000 ℃.
8. The method for simultaneous production of carbon nanotubes and graphene according to claim 5, wherein the volume of the carbon source and the carrier gas in the process gas is 1:1 to 1:10; the carrier gas is an inert gas; the carbon source is C 1 -C 12 Hydrocarbon or C of (C) 1 -C 12 Mixed gas of hydrocarbon and H2 according to any proportion; the mass airspeed of the carbon source is 0.001-1kg/kg/h;
the residence time of the process gas in the liquid copper alloy reaction zone is 0.001-0.1 hours;
in the carbon product containing the carbon nano tube and the graphene, the mass ratio of the carbon nano tube to the graphene is 100:1-1:100; the specific surface area of the carbon product is 200-2000 square meters per gram.
9. The method for simultaneous production of carbon nanotubes and graphene according to claim 5, wherein metal nano-catalyst particles are added into the liquid copper alloy reaction zone in which the graphene is generated through the solid feed port, the metal nano-catalyst particles are in contact with the carbon source to grow into carbon nanotubes, the carbon nanotubes are prevented from coalescing under the action of the dispersion structure and the stirring of the small bubbles, and in the process of forming a primary carbon product in the liquid copper alloy reaction zone,
adding metal nano catalyst particles into a liquid copper alloy reaction zone in which the graphene is generated through the solid feed inlet every 2-4 hours;
the volume ratio of the metal nano catalyst particles added each time to the liquid copper alloy in the liquid copper alloy reaction zone in which the graphene is generated is 1-10%;
The metal nano catalyst particles comprise a metal component and a carrier; wherein, the liquid crystal display device comprises a liquid crystal display device,
the mass percentage of the metal component in the metal nano catalyst particles is 1-20%;
the metal component is any one of iron, cobalt and nickel or at least two of the iron, cobalt and nickel mixed according to a proportion;
the carrier is alumina or silica;
the particle size of the metal nano catalyst particles is 1-20 microns.
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