CN116692834B - Single-wall carbon nano tube reaction device and preparation method - Google Patents
Single-wall carbon nano tube reaction device and preparation method Download PDFInfo
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- CN116692834B CN116692834B CN202310925061.8A CN202310925061A CN116692834B CN 116692834 B CN116692834 B CN 116692834B CN 202310925061 A CN202310925061 A CN 202310925061A CN 116692834 B CN116692834 B CN 116692834B
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- 239000002243 precursor Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- YNVZDODIHZTHOZ-UHFFFAOYSA-K 2-hydroxypropanoate;iron(3+) Chemical compound [Fe+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O YNVZDODIHZTHOZ-UHFFFAOYSA-K 0.000 description 1
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/159—Carbon nanotubes single-walled
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/02—Single-walled nanotubes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a single-walled carbon nanotube reaction device and a preparation method thereof, and relates to the field of single-walled carbon nanotube production; the high-temperature furnace comprises a high-temperature furnace tube, wherein a low-temperature region and a high-temperature region intermediate-frequency heating device are sequentially arranged on the outer side of the high-temperature furnace tube, and a graphite unit is arranged in the high-temperature furnace tube and positioned at the position of the high-temperature region intermediate-frequency heating device; the original floating catalytic cracking method is creatively broken through, and a medium-frequency heating device is introduced into a low-temperature area, so that single catalyst metal nano particles can be heated to ultrahigh temperature in a microscopic manner, and the activity and carbon dissolving capacity of the catalyst are greatly improved. Meanwhile, in a high-temperature area, the porous graphite unit is subjected to induction heating through the medium-frequency induction device, so that the heat capacity of the high-temperature area in the hearth is increased, catalyst particles are in more full contact with a carbon source, and the reaction efficiency is improved. Overcomes the defect that the traditional floating catalytic cracking method simply realizes high yield by enlarging the size of the cavity, and has important value for the growth of single-wall carbon nano tube powder.
Description
Technical Field
The invention relates to the field of single-walled carbon nanotube production, in particular to a single-walled carbon nanotube reaction device and a preparation method thereof.
Background
Single-walled carbon nanotubes (SWCNT) are widely used as a novel one-dimensional nanomaterial in the fields of new energy, transparent display, antistatic, semiconductors, engineering plastics, etc., due to their excellent electrical conductivity, thermal conductivity, temperature resistance, chemical resistance, mechanical properties, etc. However, the batch preparation technology of SWCNT has restricted its application in various fields, so how to realize low-cost and large-scale preparation is a problem to be solved.
Currently, there are three main ways to prepare single-walled carbon nanotubes: arc methods, laser ablation methods, and chemical vapor deposition methods. The existing arc method and laser ablation method have low yield and high energy consumption, and are difficult to realize large-scale production. The floating catalytic chemical vapor deposition method is the most batched technical scheme at present due to the continuity of raw material supply and product collection. However, the prior art is limited by the limitations of the size of the synthesis equipment cavity, and the yield is not high (less than 1 gram per hour). The yield can be further improved by increasing the number of the reaction pipelines, but the equipment structure is complex because of excessive number of the pipelines, the consistency of the products is difficult to control, and the mass production is difficult. The method is a mode for improving productivity by increasing the size of the cavity, but because the reaction condition of the single-walled carbon nanotube is harsh, the temperature field distribution of the furnace body is changed after the size of the cavity is enlarged, vortex is formed in the cavity by air flow, the heat capacity of carrier gas is small, the temperature in the middle and at the tube wall is uneven after cold air flow is introduced, the carbon nanotube grows along the tube wall more easily, and the volume growth is not realized, so that the yield and the purity are lower.
For the floating catalytic cracking method in the prior art, how to optimize the reaction cavity structure from the angle of the growth mechanism of the single-walled carbon nanotubes, fully realize the dynamic process of gasification-cracking-carbon melting-precipitation of the organic precursor, and further improve the yield of the single-walled carbon nanotubes is a problem to be solved.
Disclosure of Invention
Compared with the traditional floating catalytic cracking device, the device solves the defects of uneven catalyst particle temperature, low utilization rate, large temperature difference of a large-size reaction cavity and the like in the growth principle, has the advantages of simple equipment structure, higher efficiency, higher controllability and the like, and has important value for batch production of single-walled carbon nanotubes.
The invention can be realized by the following technical scheme: a single-wall carbon nanotube reaction device comprises a high-temperature furnace tube, a gas-liquid supply device and a product collection device, wherein the gas-liquid supply device and the product collection device are respectively and hermetically connected with two ends of the high-temperature furnace tube, a low-temperature area and a high-temperature area intermediate-frequency heating device are sequentially arranged on the outer side of the high-temperature furnace tube, graphite units are arranged at positions of the high-temperature area intermediate-frequency heating device in the high-temperature furnace tube, and at least one randomly distributed porous structure formed by through holes is arranged on the graphite units.
The invention further technically improves that: the gas-liquid supply device comprises a gas pipeline and a capillary liquid pipeline coaxially arranged in the gas pipeline, and the gas pipeline and the capillary liquid pipeline are both connected with an ultrasonic atomization device.
The invention further technically improves that: the high-temperature furnace tube adopts a quartz tube or a corundum tube.
The invention further technically improves that: the intermediate frequency heating device comprises an intermediate frequency heating power supply and a water cooling heating coil, wherein the water cooling heating coil is wound on the periphery of the high-temperature furnace tube.
The invention further technically improves that: the water-cooling heating coil is a copper coil pipe with circulating cooling water inside.
The invention further technically improves that: the aperture range of the through hole on the graphite unit is 5 mm-50 mm.
The method for preparing the single-walled carbon nanotubes by the reaction device comprises the following steps:
step one, connecting a gas-liquid pipeline, and placing a graphite unit in a high-temperature region of a high-temperature furnace tube;
step two, introducing air in the inert gas evacuating device, setting power parameters of the two sections of temperature areas, and starting an intermediate frequency heating device of the two sections of temperature areas;
step three, after the temperature in the high-temperature furnace tube in the high-temperature area reaches a set temperature, opening an airflow pipeline and a capillary liquid pipeline, feeding gas and liquid according to a certain airflow speed and a certain liquid feeding speed, and starting an ultrasonic atomization device to synthesize the single-walled carbon nanotube;
and step four, the atomized fluid enters a high-temperature furnace tube to undergo a catalytic cracking reaction, carbon-containing free radicals are melted on the surface of the catalyst and enter a product collecting device along with air flow, and carbon atoms are separated out to form flocculent single-walled carbon nanotubes.
The invention further technically improves that: the gas flow rate of the gas-liquid supply device is 5L/min-100L/min, and the liquid flow rate is 0.5 ml/min-20 ml/min.
The invention further technically improves that: the power of the medium-frequency heating device in the low temperature area is 5 KVA-50 KVA, and the output oscillation frequency is 5 KHz-20 KHz; the power of the intermediate frequency heating device in the high temperature area is 30 KVA-100 KVA, and the output oscillation frequency is 5 KHz-20 KHz.
Compared with the prior art, the invention has the following beneficial effects:
1. the medium-frequency heating device is introduced into the medium-low temperature area, so that catalyst particles formed after ultrasonic atomization can be rapidly heated to high temperature in an induction manner from a microscopic angle, and the method is essentially different from the prior art by means of temperature radiation in the high temperature area.
2. According to the invention, the medium-frequency heating porous graphite unit structure is innovatively introduced in the high-temperature area, the inert atmosphere of the closed space can be utilized to protect the graphite heating unit from being damaged under the long-term high-temperature condition, meanwhile, catalyst particles and a carbon source are more fully contacted in the porous structure after cracking, the carbon dissolving process is easier to realize, and the problem of carbon source waste caused by insufficient contact between the carbon source and the catalyst in the traditional floating catalytic cracking method is solved. Meanwhile, as the graphite unit has higher specific heat capacity compared with gas, the instantaneous microscopic temperature change of the gas flow flowing through the microspheres is smaller, the volume growth of the single-wall carbon nano tube is facilitated, and the mass preparation is realized. The reaction device is simple, has high temperature rising rate and is easy for large-scale production.
Drawings
The present invention is further described below with reference to the accompanying drawings for the convenience of understanding by those skilled in the art.
FIG. 1 is a schematic view showing the overall structure of a reaction apparatus of the present invention;
FIG. 2 is a schematic diagram of the graphite unit structure of the present invention;
FIG. 3 is a schematic diagram of the low temperature zone induction heated catalyst of the present invention;
FIG. 4 is a TEM image of a carbon nanotube according to an embodiment of the present invention;
fig. 5 is a TEM photograph of a carbon nanotube according to the fourth embodiment of the present invention.
In the figure: 1. a gas-liquid supply device; 2. a high temperature furnace tube; 3. a low-temperature area medium-frequency heating device; 4. a high-temperature area medium-frequency heating device; 5. a graphite unit; 6. a product collection device; 7. catalyst metal particles; 11. a gas conduit; 12. a capillary liquid conduit; 13. an ultrasonic atomizing device; 14. sealing the flange plate; 31. a low-temperature area water-cooled heating coil; 32. a low-temperature area medium-frequency heating power supply; 41. a high temperature region water-cooled heating coil; 42. and a high-temperature area medium-frequency heating power supply.
Detailed Description
In order to further describe the technical means and effects adopted by the invention for achieving the preset aim, the following detailed description is given below of the specific implementation, structure, characteristics and effects according to the invention with reference to the attached drawings and the preferred embodiment.
Referring to fig. 1-3, a single-walled carbon nanotube reaction apparatus includes a gas-liquid supply apparatus 1, a high-temperature furnace tube 2, and a product collecting apparatus 6, wherein the gas-liquid supply apparatus 1 and the product collecting apparatus 6 are respectively connected to an inlet and an outlet of the high-temperature furnace tube 2 in a sealing manner; the high-temperature furnace tube 2 is sequentially provided with a low-temperature area intermediate-frequency heating device and a high-temperature area intermediate-frequency heating device along the air flow direction; a graphite unit 5 is arranged in the high-temperature furnace tube 2 in the area where the intermediate-frequency heating device in the high-temperature area is positioned;
specifically, the gas-liquid supply device 1 comprises a gas pipeline 11 and a capillary liquid pipeline 12, wherein the capillary liquid pipeline 12 is coaxially arranged in the gas pipeline 11, and the outlet end of the capillary liquid pipeline 12 extends out of the gas pipeline 11 by a distance of 5-20 mm; the capillary liquid pipeline 12 and the gas pipeline 11 are arranged in the ultrasonic atomization device 13, so that a nano-scale spraying effect can be generated during gas-liquid supply; the gas pipeline 11 and the capillary liquid pipeline 12 are in sealing connection through the sealing flange 14, and the sealing flange 14 is connected with the high-temperature furnace tube 2 through a high-temperature sealing ring;
more, the inner diameter of the capillary liquid pipeline 12 is set to be 0.3-1.5 mm, and the material is stainless steel;
further, the gas-liquid supply apparatus further includes a flow meter and a liquid supply pump connected to the capillary liquid tube 12;
specifically, a quartz tube is adopted as the high-temperature furnace tube 2, and the long-time temperature resistance limit is 1200 ℃; or a corundum tube is adopted, and the long-time temperature resistance limit is 1650 ℃; no matter what material is adopted, the pipe diameter is set to be 100-500 mm, the length is set to be 1000-50000 mm, and the wall thickness is set to be 5-15 mm;
the low-temperature area medium-frequency heating device comprises a low-temperature area water-cooling heating coil 31 and a low-temperature area medium-frequency heating power supply 32, wherein the low-temperature area water-cooling heating coil 31 is a copper coil pipe internally provided with circulating cooling water, the copper coil pipe is wound on the periphery of a high-temperature furnace tube 2, the length of the low-temperature heating area is 300-1500 mm, the output power of the low-temperature area heating power supply is 5-50 KVA, the output oscillating frequency is 1 KHz-20 KHz, and the cooling water flow rate is 5-10L/min;
the action principle of the low-temperature area medium-frequency heating device is as follows: the catalyst metal precursor and the metal nano particles formed by the gas-liquid supply of the gas-liquid supply device 1 and the spraying of the ultrasonic atomization device 13 pass through a low-temperature medium-frequency heating zone, and a low-temperature zone water-cooling heating coil 31 enables induced current to be formed on the surfaces of the catalyst particles through an insulated high-temperature furnace tube 2 to instantly heat up and reach a high-temperature state, so that the reactivity and the carbon dissolving capacity of the catalyst are greatly improved.
The high-temperature area medium-frequency heating device comprises a high-temperature area water-cooling heating coil 41 and a high-temperature area medium-frequency heating power supply 42, wherein the high-temperature area water-cooling heating coil 41 is a copper coil pipe internally provided with circulating cooling water, the copper coil pipe is wound on the periphery of a high-temperature furnace tube 2, the length of the high-temperature heating area is 300-2000 mm, the output power of the high-temperature area heating power supply is 30-110 KVA, the output oscillating frequency is 1 KHz-20 KHz, the cooling water flow rate is 10-20L/min, and the temperature is controlled by a temperature sensor;
principle of action of medium-frequency heating device in high temperature region: after the medium-frequency heating device in the high-temperature area is started, the water-cooling heating coil 41 in the high-temperature area carries out induction heating on the graphite unit 5 through the high-temperature furnace tube 2, the outermost layer of the graphite unit 6 is heated to a set temperature under the action of skin effect, and the whole graphite unit is quickly heated to the set temperature through the excellent heat conducting property of graphite. By "skin effect", it is meant that when an alternating current is passed through a conductor, the current will tend to flow through the surface of the conductor.
Specifically, at least one through hole is arranged in the graphite unit 5 to form a randomly distributed hole-shaped structure, and the aperture is 5 mm-50 mm;
the density of the through holes in the graphite unit 5 has a determining effect on the catalytic cracking synthesis effect of the single-walled carbon nanotubes, namely, the temperature uniformity is high in the dense through holes, and the carbon source is more fully contacted with the catalyst particles; the structural design fundamentally improves the defects that the carrier gas heat capacity of the central point is low and the reaction temperature fluctuation is large due to the influence of air flow because the traditional large-pipe-diameter pipe furnace conducts heat by contact.
Specifically, the product collecting device 6 is a stainless steel tank, and the outlet of the product collecting device is connected to the waste treatment system.
The preparation method of the single-walled carbon nanotube by using the device comprises the following steps:
step one, connecting a gas-liquid pipeline, and placing a graphite unit 5 in a high-temperature region of a high-temperature furnace tube 2;
step two, introducing air in the inert gas evacuating device, respectively setting power parameters of the two sections of temperature areas according to process requirements, and starting an intermediate frequency heating device of the two sections of temperature areas;
step three, after a temperature sensor in the high-temperature section shows that the temperature in the high-temperature furnace tube 2 reaches a set temperature, opening an airflow pipeline 11 and a capillary liquid pipeline 12 for conveying an organic liquid carbon source precursor, feeding gas and liquid according to a certain airflow speed and a liquid feeding speed, and opening an ultrasonic atomization device 13 to synthesize the single-walled carbon nanotube;
step four, atomized fluid enters a high-temperature furnace tube 2, each reaction component is subjected to catalytic cracking reaction under the action of high temperature, carbon-containing free radicals are melted on the surface of a catalyst and enter a product collecting device 6 along with air flow, and carbon atoms are separated out to form flocculent single-wall carbon nanotubes;
it should be noted that:
the gas introduced into the gas pipeline 11 is one or a mixture of more of nitrogen, argon and helium, preferably argon;
in the gas-liquid supply apparatus 1, the flow rate of the gas and the supply amount of the liquid are affected by the formulation and the furnace tube diameter. The gas flow is set to be 5L/min-100L/min; the liquid flow is set to be 0.5 ml/min-20 ml/min;
the organic liquid precursor is a formula for synthesizing the single-walled carbon nanotube and generally comprises a carbon source, a catalyst, an accelerator, an etchant and the like;
the carbon source is ethanol, methanol, toluene, xylene, tetrahydrofuran, benzene, n-hexane, cyclohexane, etc.;
the catalyst is ferrocene, nickel-dicyclopentadienyl, cobalt-dicyclopentadienyl, ferric trichloride, carbonyl iron, ferric lactate and the like;
the accelerator is typically a sulfur-containing compound.
The yield of the single-walled carbon nanotube prepared by the device is 8G/h-60G/h, the TGA analysis purity is 56% -76%, and the Raman G/D is 41-72;
the above data are obtained on the basis of the following examples:
for the size of the device, the high-temperature furnace tube 2 adopts a corundum tube, the outer diameter of the corundum tube is 300mm, the inner diameter of the corundum tube is 285mm, and the length of the corundum tube is 3000mm; the length of the low-temperature heating zone is 800mm, and the length of the high-temperature heating zone is 800mm; the diameter of the graphite unit 5 is 280mm, and the length is 800mm;
organic precursor formula (mass ratio): ethanol/benzene/ferrocene/thiophene = 90/10/5/2;
example 1
Step one, connecting a gas-liquid pipeline, and placing a graphite unit 5 (with 23 circular hole channels with the diameter of 30mm in the inside) in a high-temperature area of a corundum tube;
step two, introducing air in the argon evacuation device, setting the power of a low-temperature area to be 30KVA, outputting oscillation frequency to be 10KHz, and enabling the flow rate of cooling water to be 5L/min; setting the power of a high temperature area as 80KVA, the output oscillation frequency as 5KHz, the flow rate of cooling water as 15L/min and the set temperature as 1600 ℃;
step three, after the set temperature reaches and stabilizes, opening an argon pipeline, setting the flow to be 30L/min, setting the liquid supply speed of an organic liquid carbon source to be 10ml/min, and opening an ultrasonic atomization device 13 to synthesize the single-walled carbon nanotube;
and step four, collecting the product into a cavity of the product collecting device.
The single-walled carbon nanotube powder prepared in the first example had a yield of 32G/h, a purity of 68% and a G/D of 59.
As can be seen from the high-resolution transmission electron microscope picture in FIG. 4, the synthesized single-walled carbon nanotube bundle consists of 1-8 single-walled carbon nanotubes, the tube diameter is 2-3 nm, and a small amount of amorphous carbon is wrapped around the tube wall.
Example two
Step one, connecting a gas-liquid pipeline, and placing a graphite unit 5 (10 round hole channels with the diameter of 50mm are arranged in the inside of a high-temperature area of a corundum tube);
step two, introducing air in the argon evacuation device, setting the power of a low-temperature area to be 50KVA, outputting oscillation frequency to be 5KHz, and enabling the flow rate of cooling water to be 5L/min; setting the power of a high temperature area as 80KVA, the output oscillation frequency as 5KHz, the flow rate of cooling water as 15L/min and the set temperature as 1600 ℃;
step three, after the set temperature reaches and stabilizes, opening an argon pipeline, setting the flow to be 30L/min, setting the liquid supply speed of an organic liquid carbon source to be 10ml/min, and opening an ultrasonic atomization device 13 to synthesize the single-walled carbon nanotube;
step four: the product is collected into the cavity of the product collection device.
The single-walled carbon nanotube powder prepared in the second example had a yield of 15G/h, a purity of 71% and a G/D of 62.
Example III
Step one, connecting a gas-liquid pipeline, and placing a graphite unit 5 (with 23 circular hole channels with the diameter of 30mm in the inside) in a high-temperature area of a corundum tube;
step two, introducing air in the argon evacuation device, setting the power of a low-temperature area to be 30KVA, outputting oscillation frequency to be 10KHz, and enabling the flow rate of cooling water to be 5L/min; setting the power of a high temperature area as 80KVA, the output oscillation frequency as 5KHz, the flow rate of cooling water as 15L/min and the set temperature as 1600 ℃;
step three, after the set temperature reaches and stabilizes, opening an argon pipeline, setting the flow to be 30L/min, setting the liquid supply speed of an organic liquid carbon source to be 10ml/min, and opening an ultrasonic atomization device 13 to synthesize the single-walled carbon nanotube;
and step four, collecting the product into a cavity of the product collecting device.
The single-walled carbon nanotube powder prepared in the third example had a yield of 39G/h, a purity of 69% and a G/D of 57.
Example IV
Step one, connecting a gas-liquid pipeline, and placing a graphite unit 5 (with 23 circular hole channels with the diameter of 30mm in the inside) in a high-temperature area of a corundum tube;
step two, introducing air in the argon evacuation device, setting the power of a low-temperature area to be 5KVA, outputting oscillation frequency to be 20KHz, and cooling water flow rate to be 10L/min; setting the power of a high temperature area as 80KVA, the output oscillation frequency as 5KHz, the flow rate of cooling water as 15L/min and the set temperature as 1600 ℃;
step three, after the set temperature reaches and stabilizes, opening an argon pipeline, setting the flow to be 30L/min, setting the liquid supply speed of an organic liquid carbon source to be 10ml/min, and opening an ultrasonic atomization device 13 to synthesize the single-walled carbon nanotube;
and step four, collecting the product into a cavity of the product collecting device.
The single-walled carbon nanotube powder prepared in the fourth example had a yield of 18G/h, a purity of 64% and a G/D of 51.
As can be seen from the high-resolution transmission electron microscope picture in FIG. 5, the synthesized single-walled carbon nanotube bundle consists of 1-6 single-walled carbon nanotubes, the tube diameter is 2-3 nm, and amorphous carbon wrapped around the tube wall is slightly more than that of the embodiment.
Example five
Step one, connecting a gas-liquid pipeline, and placing a graphite unit 5 (with 23 circular hole channels with the diameter of 30mm in the inside) in a high-temperature area of a corundum tube;
step two, introducing air in the argon evacuation device, setting the power of a low-temperature area to be 30KVA, outputting oscillation frequency to be 10KHz, and enabling the flow rate of cooling water to be 5L/min; setting the power of a high temperature area as 50KVA, the output oscillation frequency as 5KHz, the flow rate of cooling water as 15L/min and the set temperature as 1400 ℃;
step three, after the set temperature reaches and stabilizes, opening an argon pipeline, setting the flow to be 30L/min, setting the liquid supply speed of an organic liquid carbon source to be 10ml/min, and opening an ultrasonic atomization device 13 to synthesize the single-walled carbon nanotube;
and step four, collecting the product into a cavity of the product collecting device.
The single-walled carbon nanotube powder prepared in the fifth example has a yield of 31G/h, a purity of 72% and a G/D of 64.
Example six
Step one, connecting a gas-liquid pipeline, and placing a graphite unit 5 (with 23 circular hole channels with the diameter of 30mm in the inside) in a high-temperature area of a corundum tube;
step two, introducing air in the argon evacuation device, setting the power of a low-temperature area to be 30KVA, outputting oscillation frequency to be 10KHz, and enabling the flow rate of cooling water to be 5L/min; setting the power of a high temperature area as 100KVA, the output oscillation frequency as 20KHz, the flow rate of cooling water as 25L/min and the set temperature as 1600 ℃;
step three, after the set temperature reaches and stabilizes, opening an argon pipeline, setting the flow to be 30L/min, setting the liquid supply speed of an organic liquid carbon source to be 10ml/min, and opening an ultrasonic atomization device 13 to synthesize the single-walled carbon nanotube;
and step four, collecting the product into a cavity of the product collecting device.
The single-walled carbon nanotube powder prepared in the sixth example had a yield of 38G/h, a purity of 70% and a G/D of 66.
Example seven
Step one, connecting a gas-liquid pipeline, and placing a graphite unit 5 (50 round hole channels with the diameter of 20mm are arranged in the inside of a high-temperature area of a corundum tube);
step two, introducing air in the argon evacuation device, setting the power of a low-temperature area to be 30KVA, outputting oscillation frequency to be 10KHz, and enabling the flow rate of cooling water to be 5L/min; setting the power of a high temperature area as 80KVA, the output oscillation frequency as 5KHz, the flow rate of cooling water as 15L/min and the set temperature as 1600 ℃;
step three, after the set temperature reaches and stabilizes, opening an argon pipeline, setting the flow to be 30L/min, setting the liquid supply speed of an organic liquid carbon source to be 10ml/min, and opening an ultrasonic atomization device 13 to synthesize the single-walled carbon nanotube;
and step four, collecting the product into a cavity of the product collecting device.
The single-walled carbon nanotube powder prepared in the seventh example had a yield of 41G/h, a purity of 72% and a G/D of 63.
Example eight
Step one, connecting a gas-liquid pipeline, and placing a graphite unit 5 (with 23 circular hole channels with the diameter of 30mm in the inside) in a high-temperature area of a corundum tube;
step two, introducing air in the argon evacuation device, setting the power of a low-temperature area to be 30KVA, outputting oscillation frequency to be 10KHz, and enabling the flow rate of cooling water to be 5L/min; setting the power of a high temperature area as 30KVA, the output oscillation frequency as 5KHz, the flow rate of cooling water as 15L/min and the set temperature as 1200 ℃;
step three, after the set temperature reaches and stabilizes, opening an argon pipeline, setting the flow to be 30L/min, setting the liquid supply speed of an organic liquid carbon source to be 10ml/min, and opening an ultrasonic atomization device 13 to synthesize the single-walled carbon nanotube;
and step four, collecting the product into a cavity of the product collecting device.
The single-walled carbon nanotube powder prepared in this example had a yield of 14G/h, a purity of 73% and a G/D of 68.
Comparative example one
This comparative example one corresponds to the first step of the embodiment, except that the intermediate frequency heating power supply 32 is turned off in the low temperature region;
the result was that the single-walled carbon nanotube powder prepared in this comparative example had a yield of 5.7G/h, a purity of 67% and a G/D of 59.
The comparative example was analyzed to have a much lower yield than example one, mainly because of the lower catalyst activity in the low temperature zone, which resulted in an affected carbon dissolution process.
Comparative example two
The second comparative example is identical to the first example in that the high temperature area is not provided with a graphite unit 5, and is replaced by a silicon-molybdenum rod resistance heating unit matched with an insulating layer, and the temperature in the high temperature furnace tube 2 is still 1600 ℃;
the single-walled carbon nanotube powder prepared in this comparative example had a yield of 2.9G/h, a purity of 53% and a G/D of 52.
According to analysis, the yield of the comparative example is much lower than that of the example, mainly because the heat capacity in a hearth of a high-temperature area is small, the actual reflected temperature is insufficient in the air flow process, and the contact between a carbon source and a catalyst is insufficient.
Comparative example three
The third comparative example is identical to the first example in that the heating mode is replaced by a silicon-molybdenum rod resistance heating unit matched with an insulating layer, and the temperature in the furnace tube is 1600 ℃;
the single-walled carbon nanotube powder prepared in this comparative example had a yield of 13G/h, a purity of 42% and a G/D of 34.
According to analysis, the yield of the comparative example is lower than that of the example 1, mainly because of the influence of the heat insulation material of the silicon-molybdenum rod high-temperature furnace, the temperature distribution in the hearth is changed, and the carbon dissolving-carbon separating process is influenced.
In summary, the medium-frequency induction heating device with the low-temperature area introduced into the two-stage temperature area can rapidly heat the catalyst particles formed after ultrasonic atomization to high temperature in an induction manner from a microscopic angle, which is essentially different from the temperature radiation in the high-temperature area, and the method improves the activity and the carbon dissolving capacity of the catalyst;
in addition, the porous graphite unit structure is adopted, the inert atmosphere of the closed space can be utilized to protect the graphite heating unit from being damaged under the condition of long-term high temperature, and meanwhile, catalyst particles and a carbon source can be more fully contacted in the porous structure after cracking, so that the carbon dissolving process is easier to realize.
The present invention is not limited to the above embodiments, but is capable of modification and variation in all aspects, including those of ordinary skill in the art, without departing from the spirit and scope of the present invention.
Claims (9)
1. The utility model provides a single-walled carbon nanotube reaction unit, includes high temperature furnace tube (2) and gas-liquid feeding device (1) and product collection device (6) of sealing connection respectively with high temperature furnace tube (2) both ends, its characterized in that, the outside of high temperature furnace tube (2) is equipped with low temperature region and high temperature region intermediate frequency heating device in proper order, is located high temperature region intermediate frequency heating device place in high temperature furnace tube (2) and is equipped with graphite unit (5), be provided with the porous structure of random distribution that at least one through-hole constitutes on graphite unit (5).
2. A single-walled carbon nanotube reactor according to claim 1, characterized in that the gas-liquid supply device (1) comprises a gas pipe (11) and a capillary liquid pipe (12) coaxially arranged inside the gas pipe (11), both of which are connected with an ultrasonic atomizing device (13).
3. The single-walled carbon nanotube reactor according to claim 1, wherein the high-temperature furnace tube (2) is a quartz tube or a corundum tube.
4. The single-walled carbon nanotube reaction apparatus of claim 1 wherein the intermediate frequency heating apparatus comprises an intermediate frequency heating power supply and a water-cooled heating coil, wherein the water-cooled heating coil is wound around the outer periphery of the high temperature furnace tube (2).
5. The single-walled carbon nanotube reactor of claim 4 wherein the water-cooled heating coil is a copper coil with circulating cooling water inside.
6. The single-walled carbon nanotube reaction apparatus of claim 1, wherein the pore diameter of the through-hole on the graphite unit (5) is in the range of 5mm to 50mm.
7. A method for producing single-walled carbon nanotubes using the reaction apparatus of any of claims 1 to 6, comprising the steps of:
step one, connecting a gas-liquid pipeline, and placing a graphite unit (5) in a high-temperature area of a high-temperature furnace tube (2);
step two, introducing air in the inert gas evacuating device, setting power parameters of the two sections of temperature areas, and starting an intermediate frequency heating device of the two sections of temperature areas;
step three, after the temperature in the high-temperature furnace tube (2) in the high-temperature area reaches a set temperature, opening a gas pipeline (11) and a capillary liquid pipeline (12), feeding gas and liquid according to a certain gas flow speed and a certain liquid feeding speed, and starting an ultrasonic atomization device (13) to synthesize the single-walled carbon nanotube;
and step four, the atomized fluid enters a high-temperature furnace tube (2) to undergo a catalytic cracking reaction, carbon-containing free radicals are melted on the surface of the catalyst, and enter a product collecting device (6) along with air flow, and carbon atoms are separated out to form flocculent single-wall carbon nanotubes.
8. The method according to claim 7, characterized in that the gas flow of the gas-liquid supply device (1) is set to 5L/min-100L/min and the liquid flow is set to 0.5 ml/min-20 ml/min.
9. The method of claim 7, wherein the power of the medium frequency heating device in the low temperature region is 5kva to 50kva, and the output oscillation frequency is 5khz to 20khz; the power of the medium-frequency heating device in the high temperature area is 30 KVA-100 KVA, and the output oscillation frequency is 5 KHz-20 KHz.
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| CN103204492A (en) * | 2013-05-03 | 2013-07-17 | 苏州汉纳材料科技有限公司 | New method for improving yield of single-walled carbon nanotube |
| CN108408716A (en) * | 2018-03-26 | 2018-08-17 | 苏州捷迪纳米科技有限公司 | System for manufacturing carbon nm tube |
| CN110777532A (en) * | 2019-11-29 | 2020-02-11 | 山东大学 | Control method for uniformly growing carbon nanotubes on surface of graphite fiber film cloth |
| CN111943722A (en) * | 2020-07-16 | 2020-11-17 | 广东工业大学 | Controllable method for synthesizing carbon nano tube on surface of foamed ceramic and application thereof |
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| CN103204492A (en) * | 2013-05-03 | 2013-07-17 | 苏州汉纳材料科技有限公司 | New method for improving yield of single-walled carbon nanotube |
| CN108408716A (en) * | 2018-03-26 | 2018-08-17 | 苏州捷迪纳米科技有限公司 | System for manufacturing carbon nm tube |
| CN110777532A (en) * | 2019-11-29 | 2020-02-11 | 山东大学 | Control method for uniformly growing carbon nanotubes on surface of graphite fiber film cloth |
| CN111943722A (en) * | 2020-07-16 | 2020-11-17 | 广东工业大学 | Controllable method for synthesizing carbon nano tube on surface of foamed ceramic and application thereof |
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