CN112250061A - Continuous preparation system and preparation method of single-walled carbon nanotubes - Google Patents
Continuous preparation system and preparation method of single-walled carbon nanotubes Download PDFInfo
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Abstract
The invention belongs to the technical field of new materials, and relates to a continuous preparation system and a process method of a single-walled carbon nanotube. The preparation method comprises the steps of utilizing high temperature generated by direct current arc flame to evaporate a metal catalyst serving as a counter electrode to form micro catalyst particles, quickly combining the micro catalyst particles with a high-temperature cracked organic carbon source to catalyze and generate single-walled carbon nanotubes, cooling the single-walled carbon nanotubes, then cooling the single-walled carbon nanotubes, enabling the cooled single-walled carbon nanotubes to enter a gas-solid separator, enriching and separating the obtained single-walled carbon nanotubes by utilizing a magnetic field, and finally adopting an inert gas back-blowing gas-solid separator to obtain a final product. The method can enable the catalyst to exist in ultrafine particles in a high-temperature growth state, really realize strict regulation and control on the purity, the pipe diameter structure and the like of the single-walled carbon nanotube, and continuously prepare the high-quality single-walled carbon nanotube. The device and the process have high production efficiency and important industrial value.
Description
Technical Field
The invention belongs to the technical field of new materials, relates to a nano carbon material, and particularly relates to a continuous preparation system and a preparation method of a single-walled carbon nanotube.
Background
The development in the field of carbon nanotubes has been dedicated to reducing the defect content and improving the structural integrity, and has been developing towards the direction of thin tube diameter, low defect and high graphitization degree, and the development of high-performance electronic devices has further promoted the emergence of semiconductor carbon materials, and the single-walled carbon nanotubes with controllable structure have become the ultimate target. In order to control the size of the catalyst during the growth of the carbon nanotubes, efficiency has to be sacrificed, the catalyst concentration has to be reduced to a low level to reduce the catalyst particle size, and the growth temperature has to be controlled to avoid aggregation growth in high temperature conditions. However, at the same time, the tube diameter of the single-walled carbon nanotube is small, the surface curvature is large, so that a larger activation energy is required for constructing a stable C-C covalent structure, and the high crystallization degree also depends on high temperature conditions. Therefore, the key point of the preparation technology of the high-quality single-walled carbon nanotube is that higher preparation reaction temperature is needed, and meanwhile, the high-activity catalyst in a continuous stable atomic state is obtained, so that efficient and continuous preparation is realized.
At present, the preparation method of the single-walled carbon nanotube mainly comprises the following steps: chemical vapor deposition, arc ablation, laser, plasma, and the like. The chemical vapor deposition method is a common process route, and the defect content of the single-walled carbon nanotube prepared by the chemical vapor deposition method is high due to the defect of low crystallization degree of the carbon nanotube caused by the inherent low reaction temperature. Li Qingwen et al (Li Qingwen, Yan Hao, Cheng Yan, Zhang Jin, Liu Zhongfan, A scalable CVD synthesis of high-purity single-walled carbon nanotubes with MgO as support material, J.Mater. chem.,2002,12, 1179-1183) reported a method for preparing single-walled carbon nanotubes by chemical vapor deposition using magnesium oxide as a carrier and iron as a catalyst. The floating chemical vapor deposition method adopts a carrier-free gaseous reaction process, and the purity and the quality of the single-walled carbon nanotube product are obviously improved. H.M.Cheng et al H.M.Cheng, F.Li, X.Sun, S.D.M.Brown, M.A.Pimenta, A.Marucci, G.Dresselhaus, M.S.Dresselhaus, Bulk morphology and diameter distribution of single-well carbon nanotubes synthesized by catalytic synthesis of hydrocarbons, Chemical Physics Letters 289,1998.602-610, first reported a floating Chemical vapor deposition process with ferrocene and thiophene as catalysts and ethanol as carbon source, which could continuously drift the gelled single-walled carbon nanotube product from the tail end of the tube furnace, and in subsequent studies, the quality of the single-walled carbon nanotubes could be significantly improved by raising the reaction temperature and adjusting the co-catalyst. Chinese patent 202010326890.0 discloses an improved apparatus and process for preparing single-walled carbon nanotubes by floating chemical vapor deposition, which adopts a vertical structure, a bottom-up gas supply reaction mode, and utilizes the upward natural trend of gas flow to realize continuous collection at the upper end. The Chinese patent 201010234322.4 discloses a method for preparing single-walled carbon nanotubes with controllable diameters, which adopts a high-temperature arc ablation method to fill carbon powder and a metal catalyst into a carbon electrode, and prepares the single-walled carbon nanotubes by direct arc ablation.
However, due to the characteristics of the huge surface area of the single-walled carbon nanotubes, the single-walled carbon nanotubes are easy to agglomerate to form a film-shaped substance, and the traditional cyclone separation or filtration mode easily causes the rapid blockage of a filtration device and cannot continuously run. And performing a stable continuous collection without affecting the high temperature reaction remains a challenging task.
Disclosure of Invention
The invention mainly aims to provide a continuous preparation device and a continuous preparation method of single-walled carbon nanotubes, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme of the invention is as follows: a continuous preparation system of single-wall carbon nano tube, the carbon nano tube preparation device comprises;
the high-temperature reaction cavity is used for generating direct-current arc flame, combining the evaporation of a metal catalyst serving as a counter electrode with an organic carbon source subjected to high-temperature cracking, and catalyzing to generate a single-walled carbon nanotube;
the collecting device is used for cooling the generated single-walled carbon nanotubes, separating and enriching the cooled single-walled carbon nanotubes by using a magnetic field separation method, and then carrying out back flushing collection by using gas;
the auxiliary unit is used for assisting the high-temperature reaction cavity and the collecting device to complete the continuous preparation of the single-walled carbon nanotube;
the high-temperature reaction cavity is connected with the collecting device in series, and the auxiliary units are respectively connected with the high-temperature reaction cavity and the collecting device.
Further, the auxiliary unit comprises a vacuum unit, a gas circuit unit, a power supply unit and a feeding unit;
a bottom electrode is arranged at the bottom of the high-temperature reaction cavity, a crucible used for containing a catalyst is arranged on the bottom electrode, and an electric arc gun which is obliquely inserted into the high-temperature reaction cavity is positioned vertically above the bottom electrode;
an organic carbon source mixed gas interface is arranged on the side wall of the high-temperature reaction cavity and extends into the high-temperature reaction cavity along the tangent line of the side wall of the high-temperature reaction cavity; the height of the side wall of the organic carbon source mixed gas interface in the high-temperature reaction cavity is not higher than the height of the crucible,
an opening is formed right above the top of the high-temperature reaction cavity and is connected with the collecting device through a pipeline, and a feeding interface is arranged on one side of the top of the high-temperature reactor which is obliquely above the bottom electrode;
the vacuum unit is connected with a tail gas outlet of the gas-solid separator; the gas path unit is respectively connected with an organic carbon source mixed gas interface and a carrier gas inlet of the high-temperature reaction cavity;
the power supply unit provides power;
and the feeding unit is connected with a feeding interface of the high-temperature reaction cavity.
Further, the number of the collecting devices is one or two;
the collecting device comprises a material conveying pipe, a cooling unit, a gas-solid separator and a powder collecting tank;
one end of the conveying pipe is communicated with the top of the high-temperature reaction cavity, the other end of the conveying pipe is respectively communicated with the gas-solid separator and the powder collecting tank through a tee joint, an intermediate valve is arranged between the gas-solid separator and the powder collecting tank, and the cooling unit is arranged on the conveying pipe to form a cooling cavity in the conveying pipe provided with the cooling unit;
the gas-solid separator is provided with a tail gas outlet and a back-blowing inlet, and the back-blowing inlet is connected with the gas circuit unit.
Further, the high-temperature reaction cavity comprises a lining of high-temperature ceramic and a double-layer water-cooling stainless steel shell of a high-temperature heat insulation layer, the lining is corundum or mullite, and the high-temperature heat insulation layer is porous ceramic, ceramic fiber felt, hollow ceramic beads, graphite or graphite felt.
Furthermore, the separation mode adopted by the gas-solid separator is an electric control magnetic field separation mode, and a magnetic field enrichment area of the gas-solid separator is formed by bundling a plurality of quartz tubes wound with electromagnetic coils.
The invention also aims to provide a method for preparing the single-walled carbon nanotube by adopting the continuous preparation system of the single-walled carbon nanotube, which is characterized in that the method utilizes high temperature generated by direct-current arc flame to evaporate a metal catalyst used as a counter electrode to form micro catalyst particles, combines the micro catalyst particles with an organic carbon source subjected to pyrolysis to catalyze to generate the single-walled carbon nanotube, cools the single-walled carbon nanotube, concentrates and separates the obtained single-walled carbon nanotube powder by utilizing a magnetic field separation method after cooling, and finally obtains the single-walled carbon nanotube with high purity, high yield and uniform structure by adopting a gas back-blowing gas-solid separator.
Further, the method specifically comprises the following steps:
s1) evacuating air in the system, injecting protective gas into the high-temperature reaction cavity, starting the direct-current arc gun to form stable electric arc with the bottom electrode, and gradually lifting the direct-current arc gun to obtain electric arc flame with a specified length;
s2) feeding the catalyst into the crucible of the bottom electrode, evaporating the catalyst under the action of arc flame, introducing organic carbon source mixed gas from the mixed gas inlet, forming spirally rising gas flow by the organic carbon source mixed gas, combining with the evaporated micro catalyst particles, and starting the growth of the carbon nano tube;
s3) adopting a magnetic field separation technology to enrich the cooled carbon nano-tubes on the inner wall of the collection device;
s4), closing a discharge hole of the high-temperature reaction cavity after the reaction is finished, opening a collecting valve, removing the magnetic field, blowing the enriched carbon nano tube product into a powder collecting tank by utilizing inert gas back blowing, and obtaining a final product.
Further, the protective gas in S1) is any one of nitrogen, argon or helium, or a mixture thereof;
the arc striking gas of the direct current arc gun is argon or helium;
the power of the direct current arc gun is more than 10kW, the current is 50-600A, and the flame length of the arc is 2-50 cm.
Further, the catalyst in S2) is a metal catalyst;
the metal catalyst is any one of iron, cobalt and nickel or contains other alloy elements containing iron, cobalt and nickel.
Further, the flow rate of the organic carbon source mixed gas in the S2) is 1-50L/min;
the organic carbon source gas mixed gas comprises an organic carbon source gas, an inert carrier gas and hydrogen;
the volume percentage of the organic carbon source gas is 5-40%; the volume percentage of the hydrogen is 0.1-40%, and the rest is inert carrier gas;
the organic carbon source gas is one or more of methane, ethane, ethylene, acetylene, propylene, propane, ethanol and methanol;
the inert carrier gas is any one of nitrogen, argon and helium.
Further, the cooling chamber in S3) cools the product to a temperature <300 ℃: the inert gas in the S4) is any one of nitrogen, argon or helium or a mixed gas.
The invention has the beneficial effects that: due to the adoption of the technical scheme, the method disclosed by the invention has the characteristics that:
(1) the method has the advantages that the metal catalyst is directly evaporated at high temperature by electric arc, ultrafine catalyst particles can be obtained, the in-situ and the cracking carbon source are quickly combined, the catalyst particles are prevented from being aggregated and grown in the heating and transporting process in the traditional chemical vapor deposition process, the method is an effective means for maintaining the ultrafine particle size and high-activity catalyst, and the single-walled carbon nanotube with high purity, high yield and uniform structure is prepared;
(2) the high-temperature electric arc is used as a heat source for catalyst evaporation and chemical reaction, the flame core of the high-temperature electric arc can reach 20000 ℃ theoretically, the growth of the single-walled carbon nanotube is facilitated to span a huge potential barrier, and the high-quality single-walled carbon nanotube with average Raman I can be preparedG/IDThe ratio is much higher than that of the traditional chemical vapor deposition method.
(3) The gas-solid particle separation is controlled by adopting an electromagnetic principle, the magnetic characteristics of a catalyst in a single-walled carbon nanotube product are utilized, the catalyst is adsorbed on the wall of a quartz tube to achieve the purpose of enrichment and separation, the blocking problem caused by the traditional particle filtration type separation mode can be avoided for the characteristic that the single-walled carbon nanotube is easy to adhere and agglomerate, and the circular operation is further realized by a gas back-flushing mode;
(4) the double systems of the magnetic gas-solid separation device are alternately used, so that the continuous preparation and collection of the whole system can be realized, the efficiency is high, the operation is simple and convenient, and the system reliability is high;
drawings
FIG. 1 is a schematic view of a continuous carbon nanotube preparing apparatus using a single collecting system according to the present invention.
FIG. 2 is a schematic view of a carbon nanotube continuous production apparatus using a bottom feeding and single collecting system according to the present invention.
FIG. 3 is a schematic view of a carbon nanotube continuous production apparatus using a dual collection system according to the present invention.
Fig. 4 is a scanning electron micrograph of the single-walled carbon nanotube prepared in example 1.
Fig. 5 is a transmission electron micrograph of the single-walled carbon nanotube prepared in example 1.
Fig. 6 is a raman spectrum graph of the single-walled carbon nanotube prepared in example 1.
Fig. 7 is a scanning electron micrograph of single-walled carbon nanotubes prepared according to example 2.
Fig. 8 is a transmission electron micrograph of the single-walled carbon nanotube prepared in example 2.
Fig. 9 is a raman spectrum graph of the single-walled carbon nanotube prepared in example 2.
In the figure:
1. an organic carbon source mixed gas inlet; 2. a bottom electrode and a crucible; 3. a high-temperature reaction chamber; 4. a DC arc gun; 5. a feeding interface; 6. a delivery pipe; 7. a tail gas outlet; 8. a back-flushing inlet; 9. a gas-solid separator; 10. an intermediate valve; 11. a powder collecting tank 12, a high-temperature valve; 13. a cooling unit.
Detailed Description
The technical solution of the present invention is further explained with reference to the accompanying drawings and specific embodiments.
As shown in fig. 1, the present invention relates to a continuous preparation system of single-walled carbon nanotubes, wherein the carbon nanotube preparation apparatus comprises;
the high-temperature reaction cavity 3 is used for generating direct-current arc flame, combining the evaporation of a metal catalyst serving as a counter electrode with an organic carbon source subjected to high-temperature cracking, and catalyzing to generate a single-walled carbon nanotube;
the collecting device is used for cooling the generated single-walled carbon nanotubes, separating and enriching the cooled single-walled carbon nanotubes by using a magnetic field separation method, and then carrying out back flushing collection by using gas;
the auxiliary unit (not shown in the figure) is used for assisting the high-temperature reaction cavity and the collecting device to complete the continuous preparation of the single-walled carbon nanotube;
the high-temperature reaction cavity 3 is connected with the collecting device in series, and the auxiliary units are respectively connected with the high-temperature reaction cavity 3 and the collecting device.
The auxiliary unit comprises a vacuum unit, a gas circuit unit, a power supply unit and a feeding unit;
a bottom electrode is arranged at the bottom of the high-temperature reaction cavity 3, a crucible used for containing a catalyst is arranged on the bottom electrode, and a direct current arc gun 4 obliquely inserted into the high-temperature reaction cavity 3 is positioned vertically above the bottom electrode;
an organic carbon source mixed gas interface 1 is arranged on the side wall of the high-temperature reaction cavity 3 and extends into the high-temperature reaction cavity 3 along the tangent line of the side wall of the high-temperature reaction cavity 3; and the height of the side wall of the organic carbon source mixed gas interface 1 in the high-temperature reaction cavity 3 is not higher than the height of the crucible,
an opening is formed right above the top of the high-temperature reaction cavity 3 and is connected with the collecting device through a pipeline, and a feeding interface 5 is arranged on one side of the top of the high-temperature reactor 3 which is obliquely above the bottom electrode;
the vacuum unit is connected with a tail gas outlet 7 of the gas-solid separator 9; the gas path unit is respectively connected with the organic carbon source mixed gas interface 1 and the carrier gas inlet of the high-temperature reaction cavity 3;
the power supply unit provides power;
and the feeding unit is connected with a feeding interface of the high-temperature reaction cavity.
The number of the collecting devices is one or two;
the collecting device comprises a material conveying pipe 6, a cooling unit, a gas-solid separator 9 and a powder collecting tank 11;
one end of the material conveying pipe 6 is communicated with the top of the high-temperature reaction cavity, the other end of the material conveying pipe is respectively communicated with the gas-solid separator 9 and the powder collecting tank 11 through a tee joint, an intermediate valve 10 is arranged between the gas-solid separator 9 and the powder collecting tank 11, and the cooling unit 13 is arranged on the material conveying pipe 6, so that a cooling cavity is formed in the material conveying pipe 6 provided with the cooling unit;
the gas-solid separator 9 is provided with a tail gas outlet 7 and a back-blowing inlet 8, and the back-blowing inlet 8 is connected with the gas circuit unit.
The high-temperature reaction cavity 3 comprises a high-temperature ceramic lining and a double-layer water-cooling stainless steel shell of a high-temperature heat insulation layer, the lining is corundum or mullite, and the high-temperature heat insulation layer is porous ceramic, ceramic fiber felt, hollow ceramic beads, graphite or graphite felt.
The gas-solid separator 9 adopts an electric control magnetic field separation mode, and a magnetic field enrichment area of the gas-solid separator is formed by bundling a plurality of quartz tubes wound with electromagnetic coils.
The method for preparing the single-walled carbon nanotube by adopting the continuous preparation system of the single-walled carbon nanotube comprises the steps of evaporating a metal catalyst serving as a counter electrode to form micro catalyst particles by utilizing high temperature generated by direct current arc flame, combining the micro catalyst particles with an organic carbon source subjected to pyrolysis to catalyze and generate the single-walled carbon nanotube, cooling, enriching and separating the obtained single-walled carbon nanotube powder by utilizing a magnetic field separation method after cooling, and finally obtaining the single-walled carbon nanotube with high purity, high yield and uniform structure by adopting a gas back-blowing gas-solid separator.
The method specifically comprises the following steps:
s1) evacuating air in the system, injecting protective gas into the high-temperature reaction cavity, starting the direct-current arc gun to form stable electric arc with the bottom electrode, and gradually lifting the direct-current arc gun to obtain electric arc flame with a specified length;
s2) feeding the catalyst into the crucible of the bottom electrode, evaporating the catalyst under the action of arc flame, introducing organic carbon source mixed gas from the mixed gas inlet, forming spirally rising gas flow by the organic carbon source mixed gas, combining with the evaporated micro catalyst particles, and starting the growth of the carbon nano tube;
s3) adopting a magnetic field separation technology to enrich the cooled carbon nano-tubes on the inner wall of the collection device;
s4), closing a discharge hole of the high-temperature reaction cavity after the reaction is finished, opening a collecting valve, removing the magnetic field, blowing the enriched carbon nano tube product into a powder collecting tank by utilizing inert gas back blowing, and obtaining a final product.
Further, the protective gas in S1) is any one of nitrogen, argon or helium, or a mixture thereof;
the arc striking gas of the direct current arc gun is argon or helium;
the power of the direct current arc gun is more than 10kW, the current is 50-600A, and the flame length of the arc is 2-50 cm.
Further, the catalyst in S2) is a metal catalyst;
the metal catalyst is any one of iron, cobalt and nickel or contains other alloy elements containing iron, cobalt and nickel.
The flow rate of the organic carbon source mixed gas in the S2) is 1-50L/min;
the organic carbon source gas mixed gas comprises an organic carbon source gas, an inert carrier gas and hydrogen;
the volume percentage of the organic carbon source gas is 5-40%; the volume percentage of the hydrogen is 0.1-40%, and the rest is inert carrier gas;
the organic carbon source gas is one or more of methane, ethane, ethylene, acetylene, propylene, propane, ethanol and methanol;
the inert carrier gas is any one of nitrogen, argon and helium.
The cooling chamber in S3) cools the product to a temperature <300 ℃: the inert gas in the S4) is any one of nitrogen, argon or helium or a mixed gas.
The organic carbon source mixed gas interface can also be arranged at the bottom of the high-temperature reaction cavity and is positioned at one side of the bottom electrode and the crucible 2, as shown in figure 2.
The crucible is made of graphite.
The cooling unit is a water cooler.
Example 1
The schematic diagram of the single-wall carbon nanotube continuous preparation system adopting the single collection system is shown in figure 1, and the single-wall carbon nanotube continuous preparation system is formed by connecting a high-temperature reaction chamber 3, a cooling chamber 6 and a gas-solid separator 9 in series and is provided with a valve control, and an auxiliary system comprises a vacuum system, a gas path system, a control system, a cooling system, a feeding system and the like. Wherein the outer layer of the high-temperature reaction cavity consists of a double-layer water-cooling stainless steel shell lined with a graphite high-temperature heat insulation layer, and the inner wall of the high-temperature reaction cavity is made of corundum. The bottom of the high-temperature reaction cavity is provided with a bottom electrode 2, a crucible is used for containing a catalyst, and the material is graphite material; the electric arc gun which is obliquely inserted into the high-temperature reaction cavity is opposite to the bottom electrode 4; an organic carbon source mixed gas interface 1 is arranged on the side wall of the high-temperature reaction cavity, so that the organic carbon source mixed gas is enabled to form spirally rising air flow to be combined with tiny catalyst particles formed by evaporation; a feeding interface 5 is arranged obliquely above the high-temperature reactor to ensure that the catalyst is fed from the upper end and directly falls on the bottom electrode. The gas-solid separator 9 is divided into two parts, one part is a magnetic field enrichment area, the other part is a powder collecting tank 11 which is connected by an intermediate valve 10, wherein the magnetic field enrichment area is provided with a tail gas outlet 7 and a back flushing inlet 8.
The preparation process comprises the following steps: s1, starting a vacuum system to evacuate air in the whole system, injecting argon protective gas, then starting a direct current arc gun with power of 10kW, forming a stable arc with the bottom electrode, wherein the current is 200A, the voltage is 50V, and gradually lifting the electrode to obtain an arc flame with the length of 30 cm. S2) feeding the iron catalyst into the graphite crucible of the bottom electrode through a feeding system, and simultaneously introducing organic carbon source mixed gas from a mixed gas inlet, wherein the organic carbon source mixed gas is 45% of methane, 50% of helium and 5% of hydrogen, and the growth of the carbon nano tube is started. S3, opening the electromagnetic field of the magnetic field separator, and adopting the magnetic field separation technology to enrich the carbon nano tube cooled by the cooling cavity on the inner wall of the quartz tube. And S4, after the reaction is finished, closing the discharge hole of the high-temperature reaction cavity, opening the valve of the collection tank, removing the magnetic field, blowing the quartz tube back by using inert gas argon, and blowing the enriched carbon nanotube product into the collection tank to obtain the final product.
And (3) product characterization: the scanning electron microscope photograph of the obtained product is shown in FIG. 3, the product is pure, and the tube bundle is slender and straight; the transmission electron micrograph is shown in FIG. 4, and the product is a single-walled carbon nanotube as can be seen from the free single carbon nanotube; the Raman spectrum curve chart is shown in figure 5, the excitation wavelength is 532nm, the product has obvious RBM peak (radial respiration vibration peak) and higher G/D ratio, IG/ID＝52。
Example 2
The schematic diagram of the single-walled carbon nanotube continuous preparation system adopting the double-collection system is shown in fig. 2, and the system is formed by connecting a high-temperature reaction cavity 3 and a collection device in series and is controlled by a high-temperature valve 12, and the auxiliary system comprises a vacuum system, an air path system, a control system, a cooling system, a feeding system and the like. Wherein the outer layer of the high-temperature reaction cavity 3 consists of a double-layer water-cooling stainless steel shell lined with a graphite high-temperature heat insulation layer, and the inner wall is made of mullite. The bottom of the high-temperature reaction cavity is provided with a bottom electrode 12, a crucible is used for containing a catalyst, and the material is graphite material; the electric arc gun which is obliquely inserted into the high-temperature reaction cavity is opposite to the bottom electrode and the crucible 2; the bottom of the high-temperature reaction cavity 3 is provided with an organic carbon source mixed gas interface 1 to ensure that reaction gas enters the high-temperature reaction cavity from the bottom; a feeding interface 5 is arranged obliquely above the high-temperature reactor to ensure that the catalyst is fed from the upper end and directly falls on the bottom electrode. The feed delivery pipe 6 and the high-temperature reaction chamber 3 are respectively provided with 2 high-temperature valves 12. The 2 gas-solid separators 9 are divided into two parts, one part is a magnetic field enrichment area, the other part is a powder collecting tank 11 which is respectively connected by 2 intermediate valves 10, wherein each magnetic field enrichment area is provided with a tail gas outlet 7 and a back flushing inlet 8.
The preparation process comprises the following steps: s1, starting a vacuum system to evacuate air in the whole system, injecting argon protective gas, then starting a direct current arc gun with power of 100kW, forming a stable arc with the bottom electrode, wherein the current is 500A, the voltage is 200V, and gradually lifting the electrode to obtain 50cm long arc flame. S2, feeding the iron catalyst into the graphite crucible of the bottom electrode through a feeding system, and simultaneously introducing organic carbon source mixed gas from a mixed gas inlet, wherein the organic carbon source mixed gas is 5% of ethylene, 85% of argon and 10% of hydrogen, and starting the growth of the carbon nano tube. S3, starting the electromagnetic field of the magnetic field gas-solid separator 9, and adopting the magnetic field separation technology to enrich the carbon nano-tube cooled by the cooling cavity on the inner wall of the quartz tube. And S4, after reacting for a period of time, closing the high-temperature valve 12, opening the middle valve 10, and simultaneously opening the electromagnetic field of the magnetic field gas-solid separator 9 to continuously collect the product. S5, closing the tail gas outlet 7, opening the intermediate valve 314, discharging the electromagnetic field of the gas-solid separator 9, introducing argon gas from the blowback inlet 8, and blowing the product into the powder collecting tank 11 to obtain the final product. S6 circularly and repeatedly utilizes 2 gas-solid separators 11 to collect, and utilizes a feeding system to supplement the catalyst from a feeding interface 5 to enter a high-temperature reaction chamber, thereby realizing continuous production without stopping.
And (3) product characterization: the scanning electron microscope photograph of the obtained product is shown in FIG. 6, the product is pure, and the tube bundle is slender and straight; as shown in fig. 7, the transmission electron micrograph shows that the product is a single-walled carbon nanotube as seen from the free single-walled carbon nanotube; the Raman spectrum graph is shown in figure 8, the excitation wavelength is 532nm, the product has obvious RBM (radial respiration vibration peak), and the G/D ratio, I, is higherG/ID＝61。
Example 3
The schematic diagram of the single-wall carbon nanotube continuous preparation system adopting the single collection system is shown in figure 1, and the single-wall carbon nanotube continuous preparation system is formed by connecting a high-temperature reaction chamber 3 and a gas-solid separator 9 in series and is provided with a valve control, and an auxiliary system comprises a vacuum system, a gas circuit system, a control system, a cooling system, a feeding system and the like. Wherein the outer layer of the high-temperature reaction cavity consists of a double-layer water-cooling stainless steel shell lined with a graphite high-temperature heat insulation layer, and the inner wall of the high-temperature reaction cavity is made of corundum. The bottom of the high-temperature reaction cavity is provided with a bottom electrode 2, a crucible is used for containing a catalyst, and the material is graphite material; the electric arc gun which is obliquely inserted into the high-temperature reaction cavity is opposite to the bottom electrode 4; the bottom of the high-temperature reaction cavity is provided with an organic carbon source mixed gas interface 1, so that reaction gas is ensured to enter the high-temperature reaction cavity from the side wall; a feeding interface 5 is arranged obliquely above the high-temperature reactor to ensure that the catalyst is fed from the upper end and directly falls on the bottom electrode. The gas-solid separator 9 is divided into two parts, one part is a magnetic field enrichment area 9, the other part is a powder collecting tank 11, the middle parts are connected by a valve 10, and the magnetic field enrichment area is provided with a tail gas outlet 7 and a back flushing inlet 8.
The preparation process comprises the following steps: s1, starting a vacuum system to evacuate air in the whole system, injecting argon protective gas, then starting a direct current arc gun with the power of 17.5kW, forming a stable arc with the bottom electrode, wherein the current is 250A, the voltage is 70V, and gradually lifting the electrode to obtain arc flame with the length of 35 cm. S2, feeding the iron catalyst into the graphite crucible of the bottom electrode through a feeding system, and simultaneously introducing organic carbon source mixed gas from a mixed gas inlet, wherein the organic carbon source mixed gas is acetylene 30%, argon 55% and hydrogen 15%, and the growth of the carbon nano tube is started. S3, opening the electromagnetic field of the magnetic field separator, and adopting the magnetic field separation technology to enrich the carbon nano tube cooled by the cooling cavity on the inner wall of the quartz tube. And S4, after the reaction is finished, closing the discharge hole of the high-temperature reaction cavity, opening the valve of the collection tank, removing the magnetic field, blowing the quartz tube back by using inert gas argon, and blowing the enriched carbon nanotube product into the collection tank to obtain the final product.
Example 4
The schematic diagram of the single-walled carbon nanotube continuous preparation system adopting the double-collection system is shown in fig. 3, and the system is formed by connecting a high- temperature reaction chamber 10 and 2 sets of collection devices in series and is controlled by a valve, and an auxiliary system comprises a vacuum system, a gas circuit system, a control system, a cooling system, a feeding system and the like. Wherein the outer layer of the high-temperature reaction cavity consists of a double-layer water-cooling stainless steel shell lined with a graphite high-temperature heat insulation layer, and the inner wall of the high-temperature reaction cavity is made of mullite. The bottom of the high-temperature reaction cavity is provided with a bottom electrode and a crucible 2, the crucible is used for containing a catalyst and is made of graphite materials; the electric arc gun which is obliquely inserted into the high-temperature reaction cavity is opposite to the bottom electrode and the crucible 2; an organic carbon source mixed gas interface 1 is arranged on the side wall of the high-temperature reaction cavity 3, so that reaction gas can enter the high-temperature reaction cavity 3 from the side wall; a feeding interface 5 is arranged at the upper oblique part of the high-temperature reactor 3 to ensure that the catalyst is fed from the upper end and directly falls on the bottom electrode. 2 conveying pipelines 6 are connected with the high- temperature reaction chamber 3, and 2 conveying pipelines 6 are respectively provided with a high-temperature valve 12. The 2 gas-solid separators 9 comprise a part of magnetic field enrichment area and a part of powder collecting tank 11 which are respectively connected by a valve 12 in the middle, wherein the magnetic field enrichment area is provided with a tail gas outlet 7 and a back-blowing inlet 8.
The preparation process comprises the following steps: s1, starting a vacuum system to evacuate air in the whole system, injecting argon protective gas, then starting a direct current arc gun with power of 120kW, forming a stable arc with the bottom electrode, wherein the current is 600A, the voltage is 200V, and gradually lifting the electrode to obtain an arc flame with the length of 47 cm. S2, feeding the iron catalyst into the graphite crucible of the bottom electrode through a feeding system, and simultaneously introducing organic carbon source mixed gas from a mixed gas inlet, wherein the organic carbon source mixed gas is 10% of ethanol, 75% of helium and 15% of hydrogen, and starting the growth of the carbon nano tube. S3, starting the electromagnetic field of the magnetic field gas-solid separator 9, and adopting the magnetic field separation technology to enrich the carbon nano-tube cooled by the cooling cavity on the inner wall of the quartz tube. And S4, after reacting for a period of time, closing the high-temperature valve 12, opening the intermediate valve 10, and simultaneously opening the electromagnetic field of the magnetic field gas-solid separator 9 to continuously collect the product. S5, closing the tail gas outlet 7, opening a back-flushing valve, unloading the electromagnetic field of the gas-solid separator 9, introducing argon gas from the back-flushing inlet 8, and blowing the product into the powder collecting tank 11 to obtain the final product. S6, collecting by the gas-solid separator 11 repeatedly, and feeding the catalyst into the high-temperature reaction chamber from the feeding interface 15 by the feeding system, so as to realize continuous production without stopping.
Example 5
The schematic diagram of the single-wall carbon nanotube continuous preparation system adopting the single collection system is shown in fig. 2, and the single-wall carbon nanotube continuous preparation system is formed by connecting a high-temperature reaction chamber 3, a cooling chamber 6 and a gas-solid separator 9 in series and is provided with a valve control, and an auxiliary system comprises a vacuum system, a gas path system, a control system, a cooling system, a feeding system and the like. Wherein the outer layer of the high-temperature reaction cavity consists of a double-layer water-cooling stainless steel shell lined with a graphite high-temperature heat insulation layer, and the inner wall of the high-temperature reaction cavity is made of corundum. The bottom of the high-temperature reaction cavity is provided with a bottom electrode 2, a crucible is used for containing a catalyst, and the material is graphite material; the electric arc gun which is obliquely inserted into the high-temperature reaction cavity is opposite to the bottom electrode 4; the bottom of the high-temperature reaction cavity is provided with an organic carbon source mixed gas interface 1, so that reaction gas is ensured to enter the high-temperature reaction cavity from the bottom; a feeding interface 5 is arranged obliquely above the high-temperature reactor to ensure that the catalyst is fed from the upper end and directly falls on the bottom electrode. The gas-solid separator 9 is divided into two parts, one part is a magnetic field enrichment area 9, the other part is a powder collecting tank 11, the middle parts are connected by a valve 10, and the magnetic field enrichment area is provided with a tail gas outlet 7 and a back flushing inlet 8.
The preparation process comprises the following steps: s1, starting a vacuum system to evacuate air in the whole system, injecting argon protective gas, then starting a direct current arc gun with power of 48kW, forming a stable arc with the bottom electrode, wherein the current is 400A, the voltage is 120V, and gradually lifting the electrode to obtain arc flame with the length of 40 cm. S2, feeding the iron catalyst into the graphite crucible of the bottom electrode through a feeding system, and simultaneously introducing an organic carbon source mixed gas from a mixed gas inlet, wherein the organic carbon source mixed gas is 38% of methane, 2% of ethylene, 40% of argon and 20% of hydrogen, and the growth of the carbon nano tube is started. S3, opening the electromagnetic field of the magnetic field separator, and adopting the magnetic field separation technology to enrich the carbon nano tube cooled by the cooling cavity on the inner wall of the quartz tube. And S4, after the reaction is finished, closing the discharge hole of the high-temperature reaction cavity, opening the valve of the collection tank, removing the magnetic field, blowing the quartz tube back by using inert gas argon, and blowing the enriched carbon nanotube product into the collection tank to obtain the final product.
Example 6
The schematic diagram of the single-walled carbon nanotube continuous preparation system adopting the double-collection system is shown in fig. 3, and the system is formed by connecting a high- temperature reaction chamber 3 and 2 collection devices in series and is provided with a valve control, and an auxiliary system comprises a vacuum system, a gas path system, a control system, a cooling system, a feeding system and the like. Wherein the outer layer of the high-temperature reaction cavity consists of a double-layer water-cooling stainless steel shell lined with a graphite high-temperature heat insulation layer, and the inner wall of the high-temperature reaction cavity is made of mullite. The bottom of the high-temperature reaction cavity is provided with a bottom electrode and a crucible 2, the crucible is used for containing a catalyst and is made of graphite materials; the electric arc gun which is obliquely inserted into the high-temperature reaction cavity is opposite to the bottom electrode and the crucible 2; an organic carbon source mixed gas interface 1 is arranged on the side wall of the high-temperature reaction cavity, so that reaction gas is ensured to enter the high-temperature reaction cavity from the bottom; a feeding interface 5 is arranged obliquely above the high-temperature reactor to ensure that the catalyst is fed from the upper end and directly falls on the bottom electrode. 2 conveying pipelines 6 are connected with the high- temperature reaction chamber 3, and 2 conveying pipelines 6 are respectively provided with a high-temperature valve 12. The 2 gas-solid separators 9 comprise magnetic field enrichment areas, one part of the magnetic field enrichment areas is a powder collecting tank 11, and the magnetic field enrichment areas are respectively connected by an intermediate valve 10 and are provided with a tail gas outlet 7 and a back flushing inlet 8.
The preparation process comprises the following steps: s1, starting a vacuum system to evacuate air in the whole system, injecting argon protective gas, then starting a direct current arc gun with power of 90kW, forming a stable arc with the bottom electrode, generating current of 500A and voltage of 180V, and gradually lifting the electrode to obtain arc flame with a length of 46 cm. S2, feeding the iron catalyst into the graphite crucible of the bottom electrode through a feeding system, and simultaneously introducing organic carbon source mixed gas from a mixed gas inlet, wherein the organic carbon source mixed gas is 25% of propane, 55% of helium and 20% of hydrogen, and starting the growth of the carbon nano tube. S3, starting the electromagnetic field of the magnetic field gas-solid separator 9, and adopting the magnetic field separation technology to enrich the carbon nano-tube cooled by the cooling cavity on the inner wall of the quartz tube. And S4, after reacting for a period of time, closing the high-temperature valve 12, opening the intermediate valve 10, and simultaneously opening the electromagnetic field of the magnetic field gas-solid separator 9 to continuously collect the product. S5, closing the tail gas outlet 7, opening a back-flushing valve, unloading the electromagnetic field of the gas-solid separator 9, introducing argon gas from the back-flushing inlet 8, and blowing the product into the powder collecting tank 11 to obtain the final product. S6 the gas-solid separator 11 is used to collect the catalyst repeatedly, and the feeding system is used to feed the catalyst into the high temperature reaction chamber from the feeding interface 5, so as to realize continuous production without stopping.
Example 7
The schematic diagram of the single-wall carbon nanotube continuous preparation system adopting the single collection system is shown in fig. 1, and the single-wall carbon nanotube continuous preparation system is formed by connecting a high-temperature reaction cavity 3 and a collection device in series and is provided with a valve control, and an auxiliary system comprises a vacuum system, a gas circuit system, a control system, a cooling system, a feeding system and the like. Wherein the outer layer of the high-temperature reaction cavity consists of a double-layer water-cooling stainless steel shell lined with a graphite high-temperature heat insulation layer, and the inner wall of the high-temperature reaction cavity is made of corundum. The bottom of the high-temperature reaction cavity is provided with a bottom electrode and a crucible 2, and the crucible is used for containing a catalyst and is made of graphite materials; the electric arc gun which is obliquely inserted into the high-temperature reaction cavity is opposite to the bottom electrode 4; the bottom of the high-temperature reaction cavity is provided with an organic carbon source mixed gas interface 1, so that reaction gas is ensured to enter the high-temperature reaction cavity from the bottom; a feeding interface 5 is arranged obliquely above the high-temperature reactor to ensure that the catalyst is fed from the upper end and directly falls on the bottom electrode. The gas-solid separator 9 is divided into two parts, one part is a magnetic field enrichment area 9, the other part is a powder collecting tank 11, the middle parts are connected by a valve 10, and the magnetic field enrichment area is provided with a tail gas outlet 7 and a back flushing inlet 8.
The preparation process comprises the following steps: s1, starting a vacuum system to evacuate air in the whole system, injecting argon protective gas, then starting a direct current arc gun with the power of 80kW, forming a stable arc with the bottom electrode, and gradually raising the electrode to obtain 43 cm long arc flame, wherein the current is 450A, and the voltage is 150V. S2, feeding the iron catalyst into the graphite crucible of the bottom electrode through a feeding system, and simultaneously introducing organic carbon source mixed gas from a mixed gas inlet, wherein the organic carbon source mixed gas is 20% of ethane, 5% of propylene, 50% of argon and 25% of hydrogen, and the growth of the carbon nano tube is started. S3, opening the electromagnetic field of the magnetic field separator, and adopting the magnetic field separation technology to enrich the carbon nano tube cooled by the cooling cavity on the inner wall of the quartz tube. And S4, after the reaction is finished, closing the discharge hole of the high-temperature reaction cavity, opening the valve of the collection tank, removing the magnetic field, blowing the quartz tube back by using inert gas argon, and blowing the enriched carbon nanotube product into the collection tank to obtain the final product.
Example 8
The schematic diagram of the single-walled carbon nanotube continuous preparation system adopting the double-collection system is shown in fig. 3, and the system is formed by connecting a high- temperature reaction chamber 3 and 2 collection devices in series and is controlled by a high-temperature valve 12, and the auxiliary system comprises a vacuum system, an air path system, a control system, a cooling system, a feeding system and the like. Wherein the outer layer of the high-temperature reaction cavity 3 consists of a double-layer water-cooling stainless steel shell lined with a graphite high-temperature heat insulation layer, and the inner wall is made of mullite. The bottom of the high-temperature reaction cavity 3 is provided with a bottom electrode and a crucible 2, and the crucible is filled with a catalyst which is made of graphite material; the electric arc gun which is obliquely inserted into the high-temperature reaction cavity is opposite to the bottom electrode and the crucible 2; the side wall of the high-temperature reaction cavity is provided with an organic carbon source mixed gas interface 1, so that reaction gas enters the high-temperature reaction cavity 3 from the side wall in a spiral manner; a feeding interface 5 is arranged obliquely above the high-temperature reactor to ensure that the catalyst is fed from the upper end and directly falls on the bottom electrode. 2 conveying pipelines 6 are connected with the high- temperature reaction chamber 3, and 2 conveying pipelines 6 are respectively provided with a high-temperature valve 12. The gas-solid separator 9 is divided into a magnetic field enrichment area, one part of the magnetic field enrichment area is a powder collecting tank 11 which is connected by an intermediate valve 10, and the magnetic field enrichment area is provided with a tail gas outlet 7 and a back flushing inlet 8.
The preparation process comprises the following steps: s1, starting a vacuum system to evacuate air in the whole system, injecting argon protective gas, then starting a direct current arc gun with the power of 50kW, forming a stable arc with the bottom electrode, wherein the current is 400A, the voltage is 120V, and gradually lifting the electrode to obtain 38 cm long arc flame. S2, feeding the iron catalyst into the graphite crucible of the bottom electrode through a feeding system, and simultaneously introducing organic carbon source mixed gas from a mixed gas inlet, wherein the organic carbon source mixed gas is acetylene 30%, argon 55% and hydrogen 15%, and the growth of the carbon nano tube is started. S3, starting the electromagnetic field of the magnetic field gas-solid separator 9, and adopting the magnetic field separation technology to enrich the carbon nano-tube cooled by the cooling cavity on the inner wall of the quartz tube. And S4, after reacting for a period of time, closing 210 the high-temperature valve, opening 12 the high-temperature valve, and simultaneously opening the electromagnetic field of the magnetic field gas-solid separator 9 to continue collecting the product. S5, closing the tail gas outlet 7, opening a back-flushing valve, unloading the electromagnetic field of the gas-solid separator 9, introducing argon gas from the back-flushing inlet 8, and blowing the product into the powder collecting tank 11 to obtain the final product. S6, collecting by using the gas-solid separator 9 repeatedly, and supplementing the catalyst from the feeding interface 5 into the high-temperature reaction chamber by using the feeding system, thereby realizing continuous production without stopping.
Example 9
The schematic diagram of the single-walled carbon nanotube continuous preparation system adopting the double-collection system is shown in fig. 3, and the system is formed by connecting a high-temperature reaction chamber 3 and a collection device in series and is provided with a valve control, and an auxiliary system comprises a vacuum system, a gas circuit system, a control system, a cooling system, a feeding system and the like. Wherein the outer layer of the high-temperature reaction cavity consists of a double-layer water-cooling stainless steel shell lined with a graphite high-temperature heat insulation layer, and the inner wall of the high-temperature reaction cavity is made of mullite. The side wall of the high-temperature reaction cavity is provided with a bottom electrode and a crucible 2, and a catalyst is contained in the crucible and is made of graphite material; an electric arc gun obliquely inserted into the high-temperature reaction cavity 3 is opposite to the bottom electrode and the crucible 2; the side wall of the high-temperature reaction cavity is provided with an organic carbon source mixed gas interface 1, so that reaction gas is ensured to enter the high-temperature reaction cavity from the bottom; a feeding interface 5 is arranged obliquely above the high-temperature reactor to ensure that the catalyst is fed from the upper end and directly falls on the bottom electrode. The feed delivery pipe 6 and the high-temperature reaction chamber 3 are respectively provided with a high-temperature valve 12. The gas-solid separators 310 and 320 are divided into two parts, one part is a magnetic field enrichment area, the other part is a powder collecting tank 11 which is connected by an intermediate valve 11, wherein the magnetic field enrichment area is provided with a tail gas outlet 7 and a back flushing inlet 8.
The preparation process comprises the following steps: s1, starting a vacuum system to evacuate air in the whole system, injecting argon protective gas, then starting a direct current arc gun with power of 100kW, forming a stable arc with the bottom electrode, wherein the current is 500A, the voltage is 200V, and gradually lifting the electrode to obtain 50cm long arc flame. S2, feeding the iron catalyst into the graphite crucible of the bottom electrode through a feeding system, and simultaneously introducing organic carbon source mixed gas from a mixed gas inlet, wherein the organic carbon source mixed gas is 40% of methane, 2% of ethylene, 3% of ethanol, 40% of argon and 15% of hydrogen, and the growth of the carbon nano tube is started. S3, starting the electromagnetic field of the magnetic field gas-solid separator 9, and adopting the magnetic field separation technology to enrich the carbon nano-tube cooled by the cooling cavity on the inner wall of the quartz tube. After the reaction is carried out for a period of time at S4, the high temperature valve 12 is closed, the high temperature valve 12 on the left side is opened, and meanwhile, the electromagnetic field of the magnetic field gas-solid separator 9 is opened to continue collecting products. S5, closing the tail gas outlet 7, opening the intermediate valve 11, discharging the electromagnetic field of the gas-solid separator 9, introducing argon gas from the back-blowing inlet 7, and blowing the product into the powder collecting tank 11 to obtain the final product. S6 the gas-solid separator 11 is used to collect the catalyst repeatedly, and the feeding system is used to feed the catalyst into the high temperature reaction chamber from the feeding interface 5, so as to realize continuous production without stopping.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A continuous preparation system of single-wall carbon nano tubes is characterized in that the carbon nano tube preparation device comprises;
the high-temperature reaction cavity is used for generating direct-current arc flame, combining the evaporation of a metal catalyst serving as a counter electrode with an organic carbon source subjected to high-temperature cracking, and catalyzing to generate a single-walled carbon nanotube;
the collecting device is used for cooling the generated single-walled carbon nanotubes, separating and enriching the cooled single-walled carbon nanotubes by using a magnetic field separation method, and then carrying out back flushing collection by using gas;
the auxiliary unit is used for assisting the high-temperature reaction cavity and the collecting device to complete the continuous preparation of the single-walled carbon nanotube;
the high-temperature reaction cavity is connected with the collecting device in series, and the auxiliary units are respectively connected with the high-temperature reaction cavity and the collecting device.
2. The continuous production system of single-walled carbon nanotubes as claimed in claim 1,
the auxiliary unit comprises a vacuum unit, a gas circuit unit, a power supply unit and a feeding unit;
a bottom electrode is arranged at the bottom of the high-temperature reaction cavity, a crucible used for containing a catalyst is arranged on the bottom electrode, and an electric arc gun which is obliquely inserted into the high-temperature reaction cavity is positioned vertically above the bottom electrode;
an organic carbon source mixed gas interface is arranged on the side wall of the high-temperature reaction cavity and extends into the high-temperature reaction cavity along the tangent line of the side wall of the high-temperature reaction cavity; the height of the side wall of the organic carbon source mixed gas interface in the high-temperature reaction cavity is not higher than the height of the crucible,
an opening is formed right above the top of the high-temperature reaction cavity and is connected with the collecting device through a pipeline, and a feeding interface is arranged on one side of the top of the high-temperature reactor which is obliquely above the bottom electrode;
the vacuum unit is connected with a tail gas outlet of the gas-solid separator; the gas path unit is respectively connected with an organic carbon source mixed gas interface and a carrier gas inlet of the high-temperature reaction cavity;
the power supply unit provides power;
and the feeding unit is connected with a feeding interface of the high-temperature reaction cavity.
3. The continuous production system of single-walled carbon nanotubes as claimed in claim 2, wherein the number of said collecting means is one or two;
the collecting device comprises a material conveying pipe, a cooling unit, a gas-solid separator and a powder collecting tank;
one end of the conveying pipe is communicated with the top of the high-temperature reaction cavity, the other end of the conveying pipe is respectively communicated with the gas-solid separator and the powder collecting tank through a tee joint, an intermediate valve is arranged between the gas-solid separator and the powder collecting tank, and the cooling unit is arranged on the conveying pipe to form a cooling cavity in the conveying pipe provided with the cooling unit;
the gas-solid separator is provided with a tail gas outlet and a back-blowing inlet, and the back-blowing inlet is connected with the gas circuit unit.
4. The system for continuously preparing single-walled carbon nanotubes according to claim 2, wherein the high temperature reaction chamber comprises a double-layer water-cooled stainless steel shell of a high temperature ceramic lining and a high temperature thermal insulation layer, the lining is corundum or mullite, and the high temperature thermal insulation layer is porous ceramic, ceramic fiber felt, hollow ceramic beads, graphite or graphite felt.
5. The system of claim 3, wherein the gas-solid separator employs an electrically controlled magnetic field separation, and the magnetic field enrichment zone of the gas-solid separator is formed by a plurality of quartz tubes wound with electromagnetic coils.
6. A method for preparing single-walled carbon nanotubes by using the continuous preparation system of single-walled carbon nanotubes as claimed in any one of claims 1 to 5, characterized in that the method comprises evaporating a metal catalyst used as a counter electrode to form micro catalyst particles by using high temperature generated by direct current arc flame, combining the micro catalyst particles with a high-temperature cracked organic carbon source, catalyzing to generate single-walled carbon nanotubes, cooling, enriching and separating the obtained single-walled carbon nanotube powder by using a magnetic field separation method, and finally obtaining the single-walled carbon nanotubes with high purity, high yield and uniform structure by using a gas back-blowing gas-solid separator.
7. The system for continuously preparing single-walled carbon nanotubes as claimed in claim 5, comprising the following steps:
s1) evacuating air in the system, injecting protective gas into the high-temperature reaction cavity, starting the direct-current arc gun to form stable electric arc with the bottom electrode, and gradually lifting the direct-current arc gun to obtain electric arc flame with a specified length;
s2) feeding the catalyst into the crucible of the bottom electrode, evaporating the catalyst under the action of arc flame, introducing organic carbon source mixed gas from the mixed gas inlet, forming spirally rising gas flow by the organic carbon source mixed gas, combining with the evaporated micro catalyst particles, and starting the growth of the carbon nano tube;
s3) adopting a magnetic field separation technology to enrich the cooled carbon nano-tubes on the inner wall of the collection device;
s4), closing a discharge hole of the high-temperature reaction cavity after the reaction is finished, opening a collecting valve, removing the magnetic field, blowing the enriched carbon nano tube product into a powder collecting tank by utilizing inert gas back blowing, and obtaining a final product.
8. The method as claimed in claim 7, wherein the protective gas in S1) is any one of nitrogen, argon or helium or a mixture thereof;
the arc striking gas of the direct current arc gun is argon or helium;
the power of the direct current arc gun is more than 10kW, the current is 50-600A, and the flame length of the arc is 2-50 cm.
9. The method as claimed in claim 7, wherein the catalyst in S2) is a metal catalyst;
the metal catalyst is any one of iron, cobalt and nickel or contains other alloy elements containing iron, cobalt and nickel;
the flow rate of the organic carbon source mixed gas in the S2) is 1-50L/min;
the organic carbon source gas mixed gas comprises an organic carbon source gas, an inert carrier gas and hydrogen;
the volume percentage of the organic carbon source gas is 5-40%; the volume percentage of the hydrogen is 0.1-40%, and the rest is inert carrier gas;
the organic carbon source gas is one or more of methane, ethane, ethylene, acetylene, propylene, propane, ethanol and methanol;
the inert carrier gas is any one of nitrogen, argon and helium.
10. The method as claimed in claim 7, wherein the cooling chamber in S3) cools the product to a temperature <300 ℃: the inert gas in the S4) is any one of nitrogen, argon or helium or a mixed gas.
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| WO2022062446A1 (en) * | 2020-09-22 | 2022-03-31 | 江西铜业技术研究院有限公司 | Continuous preparation system and preparation method for single-wall carbon nanotubes |
| CN115650210A (en) * | 2022-09-26 | 2023-01-31 | 江门道氏新能源材料有限公司 | Preparation method and application of single/double-wall carbon nano tube |
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| WO2022062446A1 (en) * | 2020-09-22 | 2022-03-31 | 江西铜业技术研究院有限公司 | Continuous preparation system and preparation method for single-wall carbon nanotubes |
| CN113680299A (en) * | 2021-09-02 | 2021-11-23 | 青岛超晟纳米新材料科技有限公司 | Cold wall reactor |
| CN113860287A (en) * | 2021-09-22 | 2021-12-31 | 江西铜业技术研究院有限公司 | System and method for preparing single-walled carbon nanotube by plasma arc method |
| CN113860287B (en) * | 2021-09-22 | 2022-12-27 | 江西铜业技术研究院有限公司 | System and method for preparing single-walled carbon nanotube by plasma arc method |
| CN113929084A (en) * | 2021-11-09 | 2022-01-14 | 江西铜业技术研究院有限公司 | Single-walled carbon nanotube preparation and collection system and single-walled carbon nanotube |
| CN115650210A (en) * | 2022-09-26 | 2023-01-31 | 江门道氏新能源材料有限公司 | Preparation method and application of single/double-wall carbon nano tube |
| CN115650210B (en) * | 2022-09-26 | 2024-03-26 | 江门市昊鑫新能源有限公司 | Preparation method and application of single/double-wall carbon nano tube |
| CN116553527A (en) * | 2023-06-20 | 2023-08-08 | 烯格沃(上海)纳米技术有限公司 | Industrial synthesis device for single-walled carbon nanotubes |
| CN116553527B (en) * | 2023-06-20 | 2023-12-15 | 烯格沃(上海)纳米技术有限公司 | Industrial synthesis device for single-walled carbon nanotubes |
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| Publication number | Publication date |
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| WO2022062446A1 (en) | 2022-03-31 |
| JP2023543207A (en) | 2023-10-13 |
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