CN108946710B - Method for preparing graphene based on detonation process and device for preparing graphene - Google Patents
Method for preparing graphene based on detonation process and device for preparing graphene Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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Abstract
The invention discloses a method for industrially producing graphene based on a detonation process and a device for preparing large-size graphene. The raw materials used in the invention are low in price, the prepared graphene has no surface functional groups, and the number of layers and the area are controllable, the yield of the graphene is up to 30-60%, and the method is extremely suitable for industrial scale production and application.
Description
Technical Field
The present invention relates to a method for preparing graphene, and more particularly, to a method and an apparatus for preparing large-sized graphene based on a detonation technology.
Background
In recent years, graphene materials have been the leading field of technological innovation. Because of the advantages of excellent electric conductivity, ultrahigh electron mobility, specific surface area, high heat conductivity, high light transmission, high fracture strength, good chemical stability and the like, the material is known as a miraculous material in the 21 st century, and has wide application prospect in various technical fields.
At present, the main preparation methods of graphene are as follows: mechanical lift-off, chemical lift-off, redox, SiC epitaxy, chemical vapor deposition, and the like. The mechanical stripping method is simple and easy to operate, and the prepared graphene is high in quality, but the graphene prepared by the method is usually small in area and extremely low in efficiency. Uncontrollable property exists in the process of preparing graphene by a chemical stripping method, and the addition of strong acid, strong base and other substances in the preparation process destroys the structure of graphene sp 2. The cost for preparing graphene by the redox method is low, but the prepared graphene has a lot of defects, and the performance of the prepared graphene is seriously influenced. The SiC epitaxy method can prepare single-layer graphene with a large area, but the industrial popularization of the method is limited by the factors of severe preparation process conditions, complex equipment, expensive monocrystal SiC substrate and the like. The chemical vapor deposition method has the advantages of high quality of the prepared graphene film, controllable layer number, large size and the like, but the development of the graphene material is still restricted by the problem of high cost.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method and equipment of graphene, wherein in the preparation process, gaseous hydrocarbon is used as a carbon source, oxygen in a certain proportion is mixed, a proper amount of solid metal or nonmetal compound is added as a catalyst, the mixture is ignited and detonated by a high-energy ignition device under proper pressure and temperature, and condensed carbon and free carbon decomposed from the hydrocarbon are self-assembled into the graphene under the action of high temperature and high pressure generated by detonation. The preparation process of the method is rapidly completed, no oxidation reaction is involved, the prepared graphene sp2 crystal face structure is complete, the preparation process is simple, the cost is low, the preparation equipment can be modularly expanded, and the method is suitable for industrial mass production of graphene.
The invention discloses a method for industrially producing graphene based on a detonation process, which comprises the industrial production steps of preparing an air source, vacuumizing, filling the air source, heating the air source and preparing the graphene by detonation self-assembly;
the method is characterized in that: a catalyst preparation step is carried out before vacuumizing; after the graphene is prepared by detonation self-assembly, a step of pressure relief, material collection and catalyst removal is carried out;
the catalyst preparation step refers to catalyst selection and catalyst adding;
and removing the catalyst in the graphene mixed powder prepared by the step of preparing the graphene through detonation self-assembly by adopting a screening method or a magnetic separation method.
The invention discloses a method for industrially producing graphene based on a detonation process, which is characterized by comprising the following steps of:
step one, preparing an air source;
selecting gaseous hydrocarbon as a carbon source and selecting oxygen as a deflagration auxiliary agent;
opening a carbon source gas valve (1) and an oxygen valve (2); adjusting the flow rate of the carbon source gas flow meter (3) and the flow rate of the oxygen flow meter (4);
closing the material valve (6);
monitoring the air pressure of the mixing chamber (5) to be not lower than 1MPa through a first air pressure gauge (15);
controlling the molar volume ratio of the hydrogen component to the oxygen in the carbon source gas to be 2: 1-5: 1, and flowing into the mixing chamber (5);
step two, adding a catalyst;
opening a top cover of the detonation synthesis chamber (7), selecting a solid metal or nonmetal compound as a catalyst (8), uniformly scattering the solid metal or nonmetal compound at the bottom of the detonation synthesis chamber (7), and closing and locking the top cover of the detonation synthesis chamber (7);
the catalyst (8) is uniformly paved at the bottom of the detonation synthesis chamber (7) and has the thickness of 0.3-15 mm;
step three, emptying the detonation synthesis chamber;
closing the feeding valve (6) and the air release valve (13); opening a vacuumizing unit (14) and a pipeline valve (12), and exhausting gas in the detonation synthesis chamber (7) to enable the air pressure value displayed by a second barometer (16) on the detonation synthesis chamber (7) to be not lower than 5 Pa;
filling detonation gas;
closing the vacuum-pumping pipeline valve (12) and the vacuum-pumping unit (14);
opening a feeding valve (6);
controlling the time for the gas source of the mixing chamber (5) to enter the detonation synthesis chamber (7), wherein the gas source filling time is 10-30 min, and the pressure value of the second barometer (16) is monitored to be 0.02-1.0 MPa;
after the mixed gas is filled, closing the feeding valve (6);
preheating detonation gas;
starting a preheating system (9), heating the mixed gas in the detonation synthesis chamber (7), collecting the temperature of the detonation synthesis chamber (7) to 60-120 ℃ through a temperature measuring instrument (17), wherein the air pressure of a second barometer (16) is not lower than 0.8 MPa;
igniting and detonating;
starting the high-energy ignition and detonation device (11) to enable the mixed gas in the detonation synthesis chamber (7) to explode instantly, and enabling condensed carbon and free carbon decomposed from hydrocarbon to be self-assembled into graphene under the action of high temperature and high pressure generated by detonation;
step seven, forcibly cooling the detonation synthesis chamber;
starting a cooling system (10) to cool the detonation synthesis chamber (7) to 50-25 ℃;
step eight, collecting graphene and removing catalyst residues;
opening a gas release valve (13) to release pressure of the detonation synthesis chamber (7);
opening a top cover of the detonation synthesis chamber (7) after pressure relief, and collecting the graphene mixed powder;
and removing the catalyst in the graphene mixed powder by adopting a screening method or a magnetic separation method.
The invention has the beneficial effects that: the invention provides a novel method and equipment for preparing graphene, wherein the preparation method has the advantages of stable process, good consistency, controllable number of prepared graphene layers, no surface functional group and higher crystal quality of finished products; the preparation equipment has a simple structure, does not need a high-temperature heating system, has low energy consumption, can modularly expand the capacity, and realizes the industrial large-scale production of the graphene.
Drawings
Fig. 1 is a process flow diagram for preparing large-size graphene based on a detonation process.
Fig. 2 is a structural diagram of an apparatus for preparing large-sized graphene based on a detonation process according to the present invention.
FIG. 2A is a schematic diagram of a detonation synthesis chamber and heating and cooling system according to the present invention.
FIG. 2B is a schematic view of the pressure control of the second pressure gauge during the process from vacuum pumping to pressure relief.
Fig. 3 is an X-ray photoelectron spectrum of the graphene powder obtained in example 1 of the present invention.
Fig. 3A is a raman spectrum of the graphene powder obtained in example 1 of the present invention.
Fig. 3B is an atomic force microscope topography of the graphene powder obtained in example 1 of the present invention and a thickness profile line diagram of a graphene microchip.
Fig. 4 is an atomic force microscope morphology diagram of the graphene powder prepared in comparative example 1 and a thickness profile diagram of the graphene nanoplatelets.
Fig. 5 is an atomic force microscope topography of the graphene powder obtained in example 2 of the present invention and a thickness profile line diagram of a graphene microchip.
| 1. Carbon |
2. |
3. Carbon |
| 4. Oxygen flow meter | 5. Mixing |
6. Feeding |
| 7. |
8. Catalyst and process for preparing same | 9. |
| 10. |
11. High- |
12. Vacuum-pumping pipeline valve |
| 13. Air release valve | 14. |
15. |
| 16. |
17. Temperature measuring instrument |
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Referring to fig. 1, the method for preparing large-size graphene based on a detonation process of the invention includes the industrial production steps of gas source preparation, catalyst preparation, vacuumizing, gas source filling, gas source heating, detonation self-assembly graphene preparation, and pressure relief material receiving; the method is an improvement of the existing technology for preparing graphene by adopting a detonation technology, and the improvement is that a catalyst of a solid metal or nonmetal compound exists in mixed gas during detonation, and conventional treatment technical means are adopted for vacuumizing, gas source heating, pressure relief and material collection. The specific detailed steps are shown in fig. 2:
step one, preparing an air source;
selecting gaseous hydrocarbon as a carbon source and selecting oxygen as a deflagration auxiliary agent; the dosage is as follows: the molar volume ratio of the hydrogen component to the oxygen in the carbon source gas is 2: 1-5: 1.
Opening a carbon source gas valve 1 and an oxygen valve 2; adjusting the flow rate of the carbon source gas flow meter 3 and the flow rate of the oxygen flow meter 4;
closing the material valve 6;
monitoring the air pressure of the mixing chamber 5 to be not lower than 1MPa through a first air pressure gauge 15;
controlling the molar volume ratio of the hydrogen component to the oxygen in the carbon source gas to be 2: 1-5: 1, and flowing the mixture into the mixing chamber 5. The carbon source gas and the oxygen gas flow into the mixing chamber according to a certain molar volume ratio to be mixed. The proportion is selected according to the principle that the detonation reaction process is always in a hydrogen-passing and oxygen-deficient state, and the prepared graphene is guaranteed to have no surface functional groups.
In the invention, the carbon source gas and the oxygen gas flow into the mixing chamber for mixing according to a certain proportion by controlling the flow rate of the flow meters (3 and 4), and the proportion is selected according to the principle that the molar volume ratio of the hydrogen component in the carbon source gas is larger than that of the oxygen gas, so that the detonation reaction process is always in a hydrogen-passing and oxygen-lacking state, and the prepared graphene has no surface functional groups.
In the first step of the present invention, the carbon source gas may be a gaseous hydrocarbon, which includes one or more of alkane materials such as methane, ethane, propane and butane, olefin materials such as ethylene, propylene and butylene, and alkyne materials such as acetylene and propyne;
in the first step of the present invention, the carbon source gas may also be some normally liquid hydrocarbons, such as benzene, xylene, cyclohexane, etc. in aromatic hydrocarbons, and when the liquid hydrocarbons are used as the carbon source, an auxiliary heating vaporization device is required to make the liquid hydrocarbons in a gaseous state for use.
In the invention, on one hand, a carbon source gas valve 1 is opened and a carbon source gas flow meter 3 is adjusted, on the other hand, an oxygen valve 2 is opened and an oxygen flow meter 4 is adjusted to control the molar ratio of carbon source and oxygen to be filled into a mixing chamber 5, so that the mixing chamber 5 is always kept in an over-hydrogen and under-oxygen environment; the pressure of the hydrogen-rich oxygen-poor environment in the mixing chamber 5 is monitored by a first pressure gauge 15.
In the first step of the method, oxygen is selected as an explosion auxiliary agent, and the oxygen component and the hydrogen component in the hydrocarbon are combined into water vapor after detonation, so that the prepared graphene is high in purity and free of other surface functional groups.
Step two, adding a catalyst;
opening the top cover of the detonation synthesis chamber 7, selecting a certain amount of solid metal or nonmetal compound as a catalyst 8 and uniformly scattering the catalyst 8 at the bottom of the detonation synthesis chamber 7, and closing and locking the top cover of the detonation synthesis chamber 7; the catalyst 8 is generally uniformly spread on the bottom of the detonation synthesis chamber 7, and has a thickness of 0.3-15 mm.
In the present invention, the catalyst 8 may be a solid metal such as gold, platinum, nickel, iron, copper, aluminum, etc., a solid non-metal compound such as alumina, magnesia, titania, etc., or a mixture of the above metals and non-metal compounds.
In the second step of the invention, a certain amount of solid metal or nonmetal compound is selected as the catalyst, so that on one hand, the yield of the graphene can be improved, and on the other hand, the size of the product graphene prepared by the method is larger.
In the present invention, the advantage of using the catalyst 8 is that the catalyst can provide more active surface for the condensed carbon and free carbon decomposed by the detonation reaction, which is beneficial to the nucleation and crystallization of carbon atoms and the growth of graphene. Without the catalyst 8, the size of the graphene synthesized by the detonation reaction is 300 nm or less, and it is difficult to sufficiently exhibit the inherent characteristics of the graphene material. Under the condition of using the catalyst 8, the size of the prepared graphene is increased by 10-80 times, the size is 4-20 micrometers, the defect density is lower, and the service performance is more excellent.
Step three, emptying the detonation synthesis chamber;
closing the feed valve 6 and the bleed valve 13; and opening the vacuumizing unit 14 and the pipeline valve 12, and exhausting the gas in the detonation synthesis chamber 7 to enable the gas pressure value displayed by the second gas pressure gauge 16 on the detonation synthesis chamber 7 to be not lower than 5 Pa.
Filling detonation gas;
closing the vacuum pumping pipeline valve 12 and the vacuum pumping unit 14;
opening the feeding valve 6;
controlling the time for the mixed gas in the mixing chamber 5 to enter the detonation synthesis chamber 7, generally 10-30 min, and monitoring the air pressure value of the second air pressure gauge 16 to be 0.02-1.0 MPa;
after the mixed gas is filled, closing the feeding valve 6;
in the fourth step of the present invention, the pressure of the mixed gas filled in the detonation synthesis chamber 7 is slightly lower than that of the mixing chamber 5, which is beneficial to the manufacture of large-sized graphene.
Preheating detonation gas;
starting the preheating system 9, heating the mixed gas in the detonation synthesis chamber 7, collecting the temperature of the detonation synthesis chamber 7 to 60-120 ℃ through a temperature measuring instrument 17, and the air pressure of a second air pressure gauge 16 is not lower than 0.8 MPa;
the temperature acquisition of the detonation synthesis chamber 7 is displayed by a temperature measuring instrument.
In step five of the present invention, the preheating system 9 may be a conventional resistance wire heating, or because the detonation synthesis chamber 7 is provided in a hollow sandwich structure (as shown in fig. 2A), and high-temperature and pressurized hot air is charged into the heating channel. The mixed gas in the detonation synthesis chamber 7 is preheated to 60-120 ℃. The effect is that on one hand, the activity of the mixed gas is improved, so that the mixed gas is easier to detonate; on the other hand, the whole system is in a higher energy state due to preheating, and growth of large-size graphene is facilitated.
Igniting and detonating;
starting the high-energy ignition and detonation device 11 to enable the mixed gas in the detonation synthesis chamber 7 to explode instantly, and enabling condensed carbon and free carbon decomposed from hydrocarbon to be self-assembled into graphene under the action of high temperature and high pressure generated by detonation;
in the sixth step of the present invention, the high-energy ignition and detonation device 11 may be initiated by explosive, by an electric detonator, or by other means such as high-voltage discharge.
In the invention, carbon source gas and oxygen are ignited and detonated by a high-energy ignition device under proper pressure and temperature, and condensed carbon and free carbon decomposed from hydrocarbon are self-assembled into a graphene product under the action of high temperature and high pressure generated by detonation.
Step seven, forcibly cooling the detonation synthesis chamber;
starting the cooling system 10 to cool the detonation synthesis chamber 7;
in the seventh step of the present invention, the detonation synthesis chamber 7 after the detonation reaction needs to be forcibly cooled to reduce the temperature thereof to 50 ℃ to 25 ℃, which is beneficial to the subsequent collection of graphene. The cooling system 10 may be a conventional water cooling method, or may be a method of filling liquid nitrogen into a cooling channel as shown in fig. 2A to rapidly cool the graphene mixed powder.
Step eight, collecting graphene and removing catalyst residues;
opening the air release valve 13 to release the pressure of the detonation synthesis chamber 7;
opening a top cover of the detonation synthesis chamber 7 after pressure relief, and collecting the graphene mixed powder;
and removing the catalyst in the graphene mixed powder by adopting a screening method or a magnetic separation method. In the invention, the prepared graphene powder is subjected to detection on indexes such as purity, carbon atom layer number, area size, electrical property and thermal property, and is subpackaged and identified according to different grades.
Referring to fig. 2, an apparatus for preparing large-sized graphene based on a detonation process according to the present invention is designed according to the industrial production steps of fig. 1, and includes an air source system, a detonation self-assembled graphene system, a vacuum pumping system, a preheating system, and a cooling system;
the gas source system is used for providing raw materials for preparing graphene by detonation; the gas source system comprises a container for storing carbon source gas, a container for storing oxygen, a mixing chamber 5, a gas source pipeline, a valve, a flowmeter and a pressure gauge, wherein the valve, the flowmeter and the pressure gauge are arranged on the gas source pipeline;
the vacuumizing system is used for providing an oxygen-free environment for the detonation synthesis chamber 7; the vacuumizing system is arranged behind the detonation synthesizing chamber 7 and comprises a vacuum unit 14, a vacuum pipeline for communicating the vacuum unit 14 with the detonation synthesizing chamber 7 and a valve arranged on the vacuum pipeline;
the preheating system is used for heating the detonation synthesis chamber 7; the preheating system can be a conventional resistance wire heating system or a pressurized high-temperature gas;
the cooling system is used for cooling the detonation synthesis chamber 7; the cooling system can be water-cooled or liquid nitrogen.
The detonation self-assembly graphene system completes the explosion of the raw materials under the high-energy ignition detonation to obtain graphene; the detonation self-assembly graphene system comprises a detonation synthesis chamber 7, a preheating system 9, a cooling system 10, a high-energy ignition and detonation device 11 and a feeding pipeline; the detonation synthesis chamber 7 is communicated with the mixing chamber 5 through a feeding pipeline; the high-energy ignition and detonation device 11 is arranged above the detonation synthesis chamber 7; the outer wall of the detonation synthesis chamber 7 is, from inside to outside, a preheating system 9 and a cooling system 10. The detonation synthesis chamber 7 may be a structure having two hollow layers as shown in fig. 2A.
Example 1
Referring to fig. 1, 2A, and 2B, graphene is prepared using acetylene gas as a carbon source gas
Step one, preparing an air source;
selecting acetylene gas with the purity of more than or equal to 99.99 percent as a carbon source, and selecting oxygen with the purity of more than or equal to 99.99 percent as a deflagration auxiliary agent;
opening a carbon source gas valve 1 and an oxygen valve 2; adjusting the flow rate of the carbon source gas flow meter 3 and the flow rate of the oxygen flow meter 4;
closing the material valve 6;
monitoring the air pressure of the mixing chamber 5 to be 1MPa through a first air pressure gauge 15;
controlling acetylene and oxygen to flow into the mixing chamber 5 in a molar volume ratio of 2: 1; the mixing chamber 5 had a volume of 50 liters;
step two, adding a catalyst;
selecting a detonation synthesis chamber 7 with the volume of 20 liters; opening a top cover of the detonation synthesis chamber 7, weighing 20 g of nickel powder with the purity of 99.5% and the particle size of 30-50 microns as a catalyst 8, uniformly scattering the nickel powder at the bottom of the detonation synthesis chamber 7, wherein the spreading thickness is 1mm, and closing and locking the top cover of the detonation synthesis chamber 7;
step three, emptying the detonation synthesis chamber;
closing the feeding valve 6 and the air release valve 13, opening the vacuumizing unit 14 and the pipeline valve 12, and pumping out the gas in the detonation synthesis chamber 7, so that the gas pressure displayed by a second gas pressure gauge 16 on the detonation synthesis chamber 7 is 5Pa (as shown in FIG. 2B);
filling detonation gas;
closing the vacuum pumping pipeline valve 12 and the vacuum pumping unit 14; opening the feeding valve 6; the time for the mixed gas in the mixing chamber 5 to enter the detonation synthesis chamber 7 is 20min, the pressure of the second gas pressure gauge 16 is monitored to be 0.67MPa (as shown in figure 2B), and the feeding valve 6, the carbon source gas valve 1 and the oxygen valve 2 are closed in sequence after the mixed gas is filled;
preheating detonation gas;
the preheating system is a hollow channel arranged on the outer wall of the detonation self-assembly graphene system;
as shown in fig. 2A, the preheating system 9 is started, hot gas with the temperature of 150 ℃ and the pressure of 1MPa is charged into the heating channel 9A, the mixed gas in the detonation synthesis chamber 7 is heated, the temperature of the detonation synthesis chamber 7 is collected by the temperature detector 17 to reach 80 ℃, and the gas pressure of the second gas pressure gauge 16 is 0.8MPa (as shown in fig. 2B);
igniting and detonating;
starting a high-energy ignition and detonation device 11 adopting a high-voltage discharge mode to enable the mixed gas in the detonation synthesis chamber 7 to explode instantly, and enabling condensed carbon and free carbon decomposed from hydrocarbon to be self-assembled into graphene under the action of high temperature and high pressure generated by detonation;
step seven, forcibly cooling the detonation synthesis chamber;
the cooling system is a hollow channel arranged on the outer wall of the preheating system;
as shown in fig. 2A, the cooling system 10 is started, and liquid nitrogen is filled into the cooling channel 10A, so that the temperature of the detonation synthesis chamber 7 is reduced to 45 ℃; the temperature is collected by a temperature measuring instrument 17;
step eight, collecting graphene, screening and removing catalyst residues;
opening the air release valve 13 to release the pressure of the detonation synthesis chamber 7; after the pressure is released, the top cover of the detonation synthesis chamber 7 is opened, and the graphene mixed powder prepared by detonation is collected by using objects such as a brush, a wide-mouth bottle and the like.
And (3) detecting indexes such as purity, carbon atom layer number, area size and electrical property thermal property of the collected graphene mixed powder by adopting a magnetic separation method, and subpackaging and identifying according to different grades.
An X-ray photoelectron spectrum of the graphene powder prepared by the industrial production process of example 1 is shown in fig. 3, a raman spectrum is shown in fig. 3A, and a topographic map of an atomic force microscope and a thickness profile map of a graphene microchip are shown in fig. 3B. The purity of the prepared graphene is more than 99%, the number of carbon atom layers is estimated to be between 4 and 7, the size of the microchip is estimated to be between 4 and 10 micrometers, and the wave number of the sample is 1350.4cm-1、1565.8cm-1、2693.3cm-1Obvious Raman peaks appear at all. The yield of the graphene powder prepared in the example 1 can reach 60%. In the present invention, the yield means a percentage between the mass of the produced graphene and the mass of carbon in the carbon source filled into the detonation synthesis chamber 7.
Comparative example 1
The same industrial production process and materials as those in example 1 were adopted, except that no catalyst was added, i.e., nickel powder having a purity of 99.5% and a particle size of 30 to 50 μm. The topographic map of the prepared graphene in an atomic force microscope and the thickness profile map of the graphene microchip are shown in fig. 4. The size of the microchip is 100-200 nanometers, and the yield of the graphene powder is 37%. By comparing fig. 3B with fig. 4, the size of the graphene prepared by the method of the present invention is much larger than that of the graphene without loading the catalyst, so that the graphene can be referred to as large-sized graphene.
Example 2
Preparation of graphene by using methane gas as carbon source gas
Step one, preparing an air source;
selecting methane gas with the purity of more than or equal to 99.99 percent as a carbon source, and selecting oxygen with the purity of more than or equal to 99.99 percent as a deflagration auxiliary agent;
opening a carbon source gas valve 1 and an oxygen valve 2; adjusting the flow rate of the carbon source gas flow meter 3 and the flow rate of the oxygen flow meter 4;
closing the material valve 6;
monitoring the air pressure of the mixing chamber 5 to be 0.8MPa through a first air pressure gauge 15;
controlling methane and oxygen to flow into the mixing chamber 5 according to a molar volume ratio of 4: 1;
step two, adding a catalyst;
selecting a detonation synthesis chamber 7 with the volume of 20 liters; opening a top cover of the detonation synthesis chamber 7, uniformly scattering 15 g of iron powder with the purity of 99.5% and the particle size of 30-50 microns as a catalyst 8 at the bottom of the detonation synthesis chamber, closing and locking the top cover of the detonation synthesis chamber 7;
step three, emptying the detonation synthesis chamber;
closing the feeding valve 6 and the air release valve 13, opening the vacuumizing unit 14 and the pipeline valve 12, and pumping out the gas in the detonation synthesis chamber 7 to ensure that the pressure value of a second pressure gauge 16 on the detonation synthesis chamber 7 is 5.5 Pa;
filling detonation gas;
closing the vacuum pumping pipeline valve 12 and the vacuum pumping unit 14; opening the feeding valve 6; enabling the mixed gas in the mixing chamber 5 to enter the detonation synthesis chamber 7 for 20min, monitoring the air pressure of the second barometer 16 to be 0.3MPa, and closing the feeding valve 6, the carbon source gas valve 1 and the oxygen valve 2 in sequence after the mixed gas is filled;
preheating detonation gas;
starting the preheating system 9, heating the mixed gas in the detonation synthesis chamber 7 to 90 ℃, wherein the pressure of the second barometer 16 is 0.8 MPa;
igniting and detonating;
starting a high-energy ignition and detonation device 11 adopting a high-voltage discharge mode to enable mixed gas in a detonation synthesis chamber to explode instantly, and enabling condensed carbon and free carbon decomposed from hydrocarbon to be self-assembled into graphene under the action of high temperature and high pressure generated by detonation;
step seven, forcibly cooling the detonation synthesis chamber;
starting the cooling system 10 to reduce the temperature of the detonation synthesis chamber 7 to 40 ℃;
step eight, collecting graphene, screening and removing catalyst residues;
opening the air release valve 13 to release the pressure of the detonation synthesis chamber 7; and opening a top cover of the detonation synthesis chamber 7, and collecting the graphene mixed powder prepared by detonation by using objects such as a brush, a wide-mouth bottle and the like.
And (3) detecting indexes such as purity, carbon atom layer number, area size and electrical property thermal property of the collected graphene mixed powder by adopting a magnetic separation method, and subpackaging and identifying according to different grades.
An atomic force microscope morphology diagram of the graphene powder prepared by the process of example 2 and a thickness profile diagram of the graphene nanoplatelets are shown in fig. 5. The number of carbon atom layers is estimated to be between 5 and 9, the size of the microchip is estimated to be between 6 and 12 micrometers, and the yield of the graphene powder is 40 percent in the embodiment.
Example 3
Preparation of graphene by using cyclohexane as carbon source gas
Step one, preparing an air source;
cyclohexane with the purity of more than or equal to 99.99 percent is selected as a carbon source, the cyclohexane is heated to 95 ℃ at first and is completely vaporized into gas, and the gas pipeline component and the mixing chamber 5 also need to be preheated to 95 ℃ by an electric tracing band auxiliary heating system; selecting oxygen with the purity of more than or equal to 99.99 percent as a deflagration auxiliary agent;
opening a carbon source gas valve 1 and an oxygen valve 2; adjusting the flow rate of the carbon source gas flow meter 3 and the flow rate of the oxygen flow meter 4;
closing the material valve 6;
monitoring the air pressure of the mixing chamber 5 to be 1MPa through a first air pressure gauge 15;
controlling the cyclohexane and oxygen vaporized into gas to flow into the mixing chamber 5 according to the molar volume ratio of 2: 1;
step two, adding a catalyst;
opening a top cover of the detonation synthesis chamber 7, uniformly scattering 20 g of copper powder with the purity of 99.5% and the particle size of 30-50 microns as a catalyst 8 at the bottom of the detonation synthesis chamber, closing and locking the top cover of the detonation synthesis chamber 7;
step three, emptying the detonation synthesis chamber;
closing the feeding valve 6 and the air release valve 13, opening the vacuumizing unit 14 and the pipeline valve 12, and pumping out the gas in the detonation synthesis chamber 7 to ensure that the air pressure of a second barometer 16 on the detonation synthesis chamber 7 is 10 Pa;
filling detonation gas;
closing the vacuumizing pipeline valve 12 and the vacuumizing unit 14, opening the feeding valve 6 to ensure that the time for the mixed gas in the mixing chamber 5 to enter the detonation synthesis chamber 7 is 10min, monitoring the air pressure of the second barometer 16 to be 0.5MPa, and closing the feeding valve 6, the carbon source gas valve 1 and the oxygen valve 2 in sequence after the mixed gas is filled;
preheating detonation gas;
starting the preheating system 9, heating the mixed gas in the detonation synthesis chamber 7 to 120 ℃, wherein the gas pressure of the second barometer 16 is 1 MPa;
igniting and detonating;
starting a high-energy ignition and detonation device 11 adopting an electric detonator mode to enable mixed gas in a detonation synthesis chamber to explode instantly, and enabling condensed carbon and free carbon decomposed from hydrocarbon to be self-assembled into graphene under the action of high temperature and high pressure generated by detonation;
step seven, forcibly cooling the detonation synthesis chamber;
starting the cooling system 10 to reduce the temperature of the detonation synthesis chamber to 40 ℃;
step eight, collecting graphene, screening and removing catalyst residues;
opening the air release valve 13 to release the pressure of the detonation synthesis chamber; and opening a top cover of the detonation synthesis chamber 7, and collecting the graphene mixed powder prepared by detonation by using objects such as a brush, a wide-mouth bottle and the like.
And (3) detecting indexes such as purity, carbon atom layer number, area size and electrical property and thermal property of the collected graphene mixed powder by adopting a screening separation method, and subpackaging and identifying according to different grades.
The number of carbon atom layers of the graphene powder prepared by the process of the embodiment 3 is 7-9, the size of the microchip is 8-20 microns, and the yield of the graphene powder is 55%.
Example 4
Preparation of graphene by using propylene gas as carbon source gas
Step one, preparing an air source;
selecting propylene gas with the purity of more than or equal to 99.99 percent as a carbon source, and selecting oxygen with the purity of more than or equal to 99.99 percent as a deflagration auxiliary agent;
opening a carbon source gas valve 1 and an oxygen valve 2; adjusting the flow rate of the carbon source gas flow meter 3 and the flow rate of the oxygen flow meter 4;
closing the material valve 6;
monitoring the air pressure of the mixing chamber 5 to be 0.8MPa through a first air pressure gauge 15;
controlling the propylene and the oxygen to flow into the mixing chamber 5 according to the molar volume ratio of 3: 1; the mixing chamber 5 had a volume of 50 liters;
step two, adding a catalyst;
opening a top cover of the detonation synthesis chamber 7, 6 g of aluminum powder with the purity of 99.5% and the particle size of 50-100 microns, then weighing 12 g of aluminum oxide powder with the purity of 99.5% and the particle size of 100-200 microns, mixing the two materials to be used as a catalyst 8, uniformly scattering the catalyst at the bottom of the detonation synthesis chamber, and closing and locking the top cover of the detonation synthesis chamber 7;
step three, emptying the detonation synthesis chamber;
closing the feed valve 6 and the bleed valve 13; opening the vacuumizing unit 14 and the pipeline valve 12; pumping out the gas in the detonation synthesizing chamber 7, wherein the pressure of the second barometer 16 is 15 Pa;
filling detonation gas;
closing the vacuumizing pipeline valve 12 and the vacuumizing unit 14, opening the feeding valve 6 to enable the mixed gas in the mixing chamber 5 to enter the detonation synthesis chamber 7 for 30min, controlling the air pressure of the second barometer 16 to be 0.5MPa, and sequentially closing the feeding valve 6, the carbon source gas valve 1 and the oxygen valve 2 after the mixed gas is filled;
preheating detonation gas;
starting the preheating system 9, heating the mixed gas in the detonation synthesis chamber 7 to 100 ℃, wherein the pressure of the second barometer 16 is 1.5 MPa;
igniting and detonating;
starting a high-energy ignition and detonation device 11 adopting a high-voltage discharge mode to enable mixed gas in a detonation synthesis chamber to explode instantly, and enabling condensed carbon and free carbon decomposed from hydrocarbon to be self-assembled into graphene under the action of high temperature and high pressure generated by detonation;
step I, forcibly cooling the detonation synthesis chamber;
starting the cooling system 10 to reduce the temperature of the detonation synthesis chamber to 30 ℃;
step eight, collecting graphene, screening and removing catalyst residues;
opening the air release valve 13 to release the pressure of the detonation synthesis chamber; and opening a top cover of the detonation synthesis chamber 7, and collecting the graphene mixed powder prepared by detonation by using objects such as a brush, a wide-mouth bottle and the like.
And (3) detecting indexes such as purity, carbon atom layer number, area size and electrical property and thermal property of the collected graphene mixed powder by adopting a screening separation method, and subpackaging and identifying according to different grades.
The number of carbon atom layers of the graphene powder prepared by the process of the embodiment 4 is between 4 and 7, the size of the microchip is between 5 and 8 micrometers, and the yield of the graphene powder is 38 percent.
Example 5
Preparation of graphene by using mixed gas of acetylene and propylene as carbon source gas
Step one, preparing an air source;
selecting acetylene gas and propylene gas with the purity of more than or equal to 99.99 percent as carbon sources respectively, and selecting oxygen with the purity of more than or equal to 99.99 percent as a deflagration auxiliary agent;
opening a carbon source gas valve 1 and an oxygen valve 2; adjusting the flow rate of the carbon source gas flow meter 3 and the flow rate of the oxygen flow meter 4;
closing the material valve 6;
monitoring the air pressure of the mixing chamber 5 to be 1MPa through a first air pressure gauge 15;
controlling acetylene, propylene and oxygen to flow into the mixing chamber 5 according to the molar volume ratio of 3:1: 1; the mixing chamber 5 had a volume of 50 liters;
step two, adding a catalyst;
opening a top cover of the detonation synthesis chamber 7, weighing 5 g of nickel powder with the purity of 99.5% and the particle size of 50-100 microns, weighing 12 g of magnesium oxide powder with the purity of 99.5% and the particle size of 100-200 microns, mixing the two materials to be used as a catalyst 8, uniformly scattering the catalyst at the bottom of the detonation synthesis chamber, and closing and locking the top cover of the detonation synthesis chamber 7;
step three, emptying the detonation synthesis chamber;
closing the feed valve 6 and the bleed valve 13; opening the vacuumizing unit 14 and the pipeline valve 12; pumping out the gas in the detonation synthesis chamber 7 to make the gas pressure of a second gas pressure gauge 16 on the detonation synthesis chamber 7 be 5 Pa;
filling detonation gas;
closing the vacuumizing pipeline valve 12 and the vacuumizing unit 14, opening the feeding valve 6 to ensure that the time for the mixed gas in the mixing chamber 5 to enter the detonation synthesis chamber 7 is 20min, the air pressure of the second barometer 16 is 0.5MPa, and closing the feeding valve 6, the carbon source gas valve 1 and the oxygen valve 2 in sequence after the mixed gas is filled;
preheating detonation gas;
starting the preheating system 9, heating the mixed gas in the detonation synthesis chamber 7 to the temperature of 80 ℃, wherein the air pressure of the second barometer 16 is 1 MPa;
igniting and detonating;
starting a high-energy ignition and detonation device 11 adopting a high-voltage discharge mode to enable mixed gas in a detonation synthesis chamber to explode instantly, and enabling condensed carbon and free carbon decomposed from hydrocarbon to be self-assembled into graphene under the action of high temperature and high pressure generated by detonation;
step seven, forcibly cooling the detonation synthesis chamber;
starting the cooling system 10 to reduce the temperature of the detonation synthesis chamber to 35 ℃;
step eight, collecting graphene, screening and removing catalyst residues;
opening the air release valve 13 to release the pressure of the detonation synthesis chamber; and opening a top cover of the detonation synthesis chamber 7, and collecting the graphene mixed powder prepared by detonation by using objects such as a brush, a wide-mouth bottle and the like.
And (3) detecting indexes such as purity, carbon atom layer number, area size and electrical property and thermal property of the collected graphene mixed powder by adopting a screening separation method, and subpackaging and identifying according to different grades.
The number of carbon atom layers of the graphene powder prepared by the process of the embodiment 5 is 4-7, the size of the microchip is 5-10 microns, and the yield of the graphene powder can reach 45%.
Claims (4)
1. A method for industrially producing graphene based on a detonation process comprises the industrial production steps of gas source preparation, vacuumizing, gas source filling, gas source heating and detonation self-assembly to prepare graphene;
the method is characterized by comprising the following steps:
step one, preparing an air source;
selecting gaseous hydrocarbon as a carbon source and selecting oxygen as a deflagration auxiliary agent;
the carbon source gas is a gaseous hydrocarbon containing one or more of alkane materials of methane, ethane, propane and butane or olefin materials of ethylene, propylene and butylene or alkyne materials of acetylene and propyne;
opening a carbon source gas valve (1) and an oxygen valve (2); adjusting the flow rate of the carbon source gas flow meter (3) and the flow rate of the oxygen flow meter (4);
closing the material valve (6);
monitoring the air pressure of the mixing chamber (5) to be not lower than 1MPa through a first air pressure gauge (15);
controlling the molar volume ratio of the hydrogen component to the oxygen in the carbon source gas to be 2: 1-5: 1, and flowing into the mixing chamber (5);
step two, adding a catalyst;
opening a top cover of the detonation synthesis chamber (7), selecting a solid metal or nonmetal compound as a catalyst (8), uniformly scattering the solid metal or nonmetal compound at the bottom of the detonation synthesis chamber (7), and closing and locking the top cover of the detonation synthesis chamber (7);
the catalyst (8) is uniformly paved at the bottom of the detonation synthesis chamber (7) and has the thickness of 0.3-15 mm;
the catalyst (8) is a solid metal of gold, platinum, nickel, iron, copper or aluminum, or a solid non-metallic compound of aluminum oxide, magnesium oxide or titanium dioxide, or a mixture of a solid metal and a solid non-metallic compound;
step three, emptying the detonation synthesis chamber;
closing the feeding valve (6) and the air release valve (13); opening a vacuumizing unit (14) and a pipeline valve (12), and exhausting gas in the detonation synthesis chamber (7) to enable the air pressure value displayed by a second barometer (16) on the detonation synthesis chamber (7) to be not lower than 5 Pa;
filling detonation gas;
closing the vacuum-pumping pipeline valve (12) and the vacuum-pumping unit (14);
opening a feeding valve (6);
controlling the time for the gas source of the mixing chamber (5) to enter the detonation synthesis chamber (7), wherein the gas source filling time is 10-30 min, and the pressure value of the second barometer (16) is monitored to be 0.02-1.0 MPa;
after the mixed gas is filled, closing the feeding valve (6);
preheating detonation gas;
starting a preheating system (9), heating the mixed gas in the detonation synthesis chamber (7), collecting the temperature of the detonation synthesis chamber (7) to 60-120 ℃ through a temperature measuring instrument (17), wherein the air pressure of a second barometer (16) is not lower than 0.8 MPa;
igniting and detonating;
starting the high-energy ignition and detonation device (11) to enable the mixed gas in the detonation synthesis chamber (7) to explode instantly, and enabling condensed carbon and free carbon decomposed from hydrocarbon to be self-assembled into graphene under the action of high temperature and high pressure generated by detonation;
step seven, forcibly cooling the detonation synthesis chamber;
starting a cooling system (10) to cool the detonation synthesis chamber (7) to 50-25 ℃;
step eight, collecting graphene and removing catalyst residues;
opening a gas release valve (13) to release pressure of the detonation synthesis chamber (7);
opening a top cover of the detonation synthesis chamber (7) after pressure relief, and collecting the graphene mixed powder;
removing the catalyst in the graphene mixed powder by adopting a screening method or a magnetic separation method;
the purity of the prepared graphene is more than 99%; the number of carbon atom layers is 4-9, the size of the microchip is 4-20 microns, and the wave number is 1350.4cm-1、1565.8cm-1、2693.3cm-1Obvious Raman peaks appear at all parts; the yield of the prepared graphene powder is 30-60%.
2. The device for preparing the graphene based on the detonation process, which is designed according to the method for industrially producing the graphene based on the detonation process of claim 1, comprises an air source system, a detonation self-assembly graphene system, a vacuum pumping system, a preheating system and a cooling system; the method is characterized in that:
the gas source system is used for providing raw materials for preparing graphene by detonation; the gas source system comprises a container for storing carbon source gas, a container for storing oxygen, a mixing chamber (5), a gas source pipeline, a valve, a flowmeter and a pressure gauge, wherein the valve, the flowmeter and the pressure gauge are arranged on the gas source pipeline;
the vacuumizing system is used for providing an oxygen-free environment for the detonation synthesis chamber (7); the vacuumizing system is arranged behind the detonation synthesis chamber (7) and comprises a vacuum unit (14), a vacuum pipeline and a valve, wherein the vacuum pipeline is used for communicating the vacuum unit (14) with the detonation synthesis chamber (7);
the preheating system is used for heating the detonation synthesis chamber (7);
the cooling system is used for cooling the detonation synthesis chamber (7);
the detonation self-assembly graphene system completes the explosion of the raw materials under the high-energy ignition detonation to obtain graphene; the detonation self-assembly graphene system comprises a detonation synthesis chamber (7), a preheating system (9), a cooling system (10), a high-energy ignition and detonation device (11) and a feeding pipeline; the detonation synthesis chamber (7) is communicated with the mixing chamber (5) through a feeding pipeline; the high-energy ignition and detonation device (11) is arranged above the detonation synthesis chamber (7); the outer wall of the detonation synthesis chamber (7) is provided with a preheating system (9) and a cooling system (10) from inside to outside.
3. The apparatus of claim 2, wherein: the preheating system is used for charging hot gas with the temperature not lower than 100 ℃ and the pressure of 0.6-1 MPa into the heating channel (9A).
4. The apparatus of claim 2, wherein: the cooling system is used for filling liquid nitrogen into the cooling channel (10A).
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|---|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420361A (en) * | 2012-05-22 | 2013-12-04 | 海洋王照明科技股份有限公司 | A method of preparing graphene by explosion |
| CN105836729A (en) * | 2016-04-11 | 2016-08-10 | 大连理工大学 | Synthesis method of carbon nanotube by using gaseous detonation method |
| CN107324317A (en) * | 2017-07-04 | 2017-11-07 | 刘鹏 | A kind of high pressure prepares the device and method of grapheme material |
| CN107934944A (en) * | 2018-01-11 | 2018-04-20 | 大连理工大学 | A kind of method for preparing graphene quantum dot |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9440857B2 (en) * | 2013-05-10 | 2016-09-13 | Kansas State University Research Foundation | Process for high-yield production of graphene via detonation of carbon-containing material |
-
2018
- 2018-07-12 CN CN201810765580.1A patent/CN108946710B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420361A (en) * | 2012-05-22 | 2013-12-04 | 海洋王照明科技股份有限公司 | A method of preparing graphene by explosion |
| CN105836729A (en) * | 2016-04-11 | 2016-08-10 | 大连理工大学 | Synthesis method of carbon nanotube by using gaseous detonation method |
| CN107324317A (en) * | 2017-07-04 | 2017-11-07 | 刘鹏 | A kind of high pressure prepares the device and method of grapheme material |
| CN107934944A (en) * | 2018-01-11 | 2018-04-20 | 大连理工大学 | A kind of method for preparing graphene quantum dot |
Non-Patent Citations (1)
| Title |
|---|
| "气相爆轰合成碳纳米材料的研究";王帅;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20150715;B020-220页 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022246443A1 (en) * | 2021-05-20 | 2022-11-24 | Nabors Energy Transition Solutions Llc | Graphene synthesis unit |
| US12371326B2 (en) | 2021-12-22 | 2025-07-29 | Nabors Energy Transition Solutions Llc | Sulfur doped carbon-based nanomaterial and methods of forming the same |
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