CN112357908A - Continuous preparation device and process for single-walled carbon nanotubes - Google Patents
Continuous preparation device and process for single-walled carbon nanotubes Download PDFInfo
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- 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
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/159—Carbon nanotubes single-walled
Abstract
The invention discloses a continuous preparation device and a process of a single-walled carbon nanotube. The preparation device comprises a liquid injection unit, a growth unit and a collection box, wherein the growth unit comprises a high-temperature furnace body, a growth tube and a conical liner tube nested in the growth tube, the diameter of the upper end opening of the liner tube of the conical liner tube is smaller and is equal to the end part of the growth tube, and the diameter of the lower end opening of the liner tube is larger and is in a high-temperature area. The conical liner tube covers the temperature transition area, so that the airflow rapidly passes through the non-high temperature area, and the problem that the intermediate product is adhered to the furnace tube is avoided. Meanwhile, the uniform transition of the diameter of the conical liner tube avoids the eddy generated when the tube diameter of the airflow is suddenly changed, and further inhibits the problem that the intermediate product is adhered to the furnace tube. The invention improves the continuity and uniformity of the product preparation and eliminates obstacles for the continuous production of single-walled carbon nanotubes. Through the optimization of the process, the prepared single-walled carbon nanotube has the average Raman spectrum IG/ID> 50, has extremely high graphitization degreeHas strong market competitiveness.
Description
Technical Field
The invention relates to the field of carbon nano material manufacturing, in particular to a continuous preparation device and process of a single-walled carbon nanotube.
Technical Field
The carbon nanotube material is a one-dimensional carbon material with a super-large length-diameter ratio, has great advantages in the aspects of electronic transmission, heat transmission and mechanical properties, and has wide application prospect. For example, in the aspect of heat generation, heat-generating films prepared using carbon nanotubes have been already well-established for commercial use; in the aspect of mechanical performance, the wear resistance of the tire can be greatly improved by doping a very small amount of carbon nanotubes; the material is used as an electromagnetic wave absorption material and also has important application in the military field; as chip fabrication approaches the limits of silicon materials, chips of all-carbon materials may be the next generation of promise, where carbon nanotubes play a very important role.
Carbon nano materials have outstanding performance in many fields, but the macro preparation process of the carbon nano materials needs further exploration, and particularly for high-quality single-wall carbon nanotubes or few-wall carbon nanotubes, the macro preparation process is only mastered in extremely individual foreign enterprises, and is not favorable for domestic application research and development. In the existing process, a high-quality single-wall or few-wall carbon nanotube is difficult to obtain by a fluidized bed method, the process is usually used for preparing the multi-wall carbon nanotube, if the single-wall carbon nanotube is prepared by reducing the proportion of an effective catalyst, the multiplying power is low, a product contains a large amount of catalyst impurities, and the catalyst impurities are difficult to remove (Rabinovich et al.chemical engineering journal 2017); the energy concentration of electric arc, laser ablation and high-temperature plasma methods, but the energy is high, which is not beneficial to the control of the reaction process, and the products are doped with a large amount of carbon materials such as fullerene, graphite flake and the like and are difficult to separate (Fan et al. carbon 2016); the floating catalytic chemical vapor deposition method has good prospect.
The floating catalytic chemical vapor deposition method is a process in which a reaction source material is injected into a reactor, and the reaction is completed in the process of conveying the raw material in the reactor under the action of a carrier gas, and the raw material and a product are in a floating state in the reactor, so the floating catalytic chemical vapor deposition method is called. The existing floating chemical vapor deposition method for preparing carbon nanotubes is mainly used for preparing multi-walled carbon nanotubes (for example, the Chinese patent with the application number of 201710679729X). The synthesis of high-purity, high-quality single-walled carbon nanotubes is still more difficult to control, while single-walled carbon nanotubes have superior properties compared to multi-walled carbon nanotubes. Therefore, a perfect single-walled carbon nanotube preparation process is urgently needed to be explored. Because of the characteristics of the process, the single-walled carbon nanotube is prepared by using a floating chemical vapor deposition method, and the product is thinner. In the reaction process, when airflow enters the growth tube from the air inlet tube, the change of the tube diameter can generate vortex, and meanwhile, due to the sealing requirement, the airflow and the product can reach a high-temperature region only after entering the furnace tube through the temperature transition region, and the vortex in the temperature transition region can cause the product to be adhered to the upper part of the furnace tube, so that the product is blocked; the same temperature transition zone and low temperature zone are arranged at the outlet of the furnace tube, and the adhesion problem in the zone can not lead the product to be discharged out of the growth tube and enter the collecting box. Therefore, it is urgently needed to improve the structure of the feed inlet and the discharge outlet of the growth tube to prevent the product from adhering to the tube wall, so that the growth of the single-walled carbon nanotube can be smoothly and continuously carried out.
Disclosure of Invention
The present invention discloses a continuous preparation system and a preparation method of single-walled carbon nanotubes, which solve any of the above problems or other potential problems of the prior art.
In order to solve the problems, the technical scheme of the invention is as follows: a continuous preparation system of single-walled carbon nanotubes comprises a liquid injection unit, a growth unit and a collection box; the liquid injection unit is connected with the top of the growth unit, and the collection box is arranged at the bottom of the growth unit;
the growth unit includes: a high-temperature furnace body, a growth tube and a conical liner tube;
the growth tube is arranged in the center of the interior of the high-temperature furnace body, the growth upper port of the growth tube extends out of the top of the high-temperature furnace body, and the growth lower port of the growth tube is positioned at the discharge port of the high-temperature furnace body;
the conical liner tube is arranged in the growth tube and covers the temperature transition area of the high-temperature furnace body, so that airflow can quickly pass through the non-high-temperature area, the eddy generated when the pipe diameter of the high-temperature furnace body suddenly changes is avoided, and the adhesion of an intermediate product is inhibited.
Furthermore, the upper port of the liner tube of the conical liner tube is an air inlet, the air inlet is flush with the end part of the upper growth port of the growth tube, and the lower end opening of the liner tube of the conical liner tube extends to the high-temperature zone of the high-temperature furnace body.
Further, the diameter of the ports on the liner of the conical liner is smaller than 1/2 of the inner diameter of the growth tube, and the diameter of the ports on the liner is larger than 3/4 of the inner diameter of the growth tube.
Further, the diameter of the upper end opening of the conical liner is smaller than 1/2 of the inner diameter of the growth tube, and the diameter of the lower end opening of the conical liner is larger than 3/4 of the inner diameter of the growth tube.
Further, the taper C of the tapered liner tube ranges from: d is more than or equal to L and less than or equal to C and d is L800,
wherein d is the inner diameter of the growth tube, L is the length of the growth tube, and L800 is the distance from the top end of the growth tube to the 800 ℃ position in the high-temperature furnace body.
Furthermore, the growth unit also comprises a heating unit, and the heating unit is arranged in the high-temperature furnace body and positioned at two sides of the heating pipe.
Another object of the present invention is to provide a method for preparing single-walled carbon nanotubes using the above continuous preparation system, which specifically comprises the steps of:
s1) starting a heating unit to heat the high-temperature furnace body, so that the temperature of the furnace tube is 1200-1600 ℃;
s2) introducing carrier gas into the high-temperature furnace body, starting a liquid injection pump at the same time, and injecting the reaction raw materials into the growth unit through a liquid conveying pipe;
s3) allowing the carrier gas and the reaction raw materials to reach a high-temperature region of the furnace tube through the conical liner tube to generate the carbon nanotube aerogel;
s4), smoothly discharging the generated carbon nanotube aerogel from the lower end opening of the furnace tube in the high-temperature region, entering a collecting box, and cooling to obtain the single-walled carbon nanotube.
Further, the carrier gas in S2) is a mixed gas of hydrogen and an inert gas, and the inert gas is argon, nitrogen or helium.
Further, the reaction raw material is a mixed solution of a carbon source, a catalyst and an auxiliary agent;
wherein the carbon source is ethanol, toluene, cyclohexane or other liquid carbon-containing organic matters;
the catalyst is a compound of iron, cobalt or nickel;
the auxiliary agent is a sulfur simple substance or a sulfur-containing compound.
Further, the Raman spectrum of the single-walled carbon nanotube is averaged to be IG/IDIs greater than 50 and is between 50 and 300cm-1In the interval, the intensity of the RBM peak exceeds 10% of the G peak.
The single-walled carbon nanotube is prepared by adopting the method or the device.
The growth tube and the conical lining tube are made of high-temperature resistant materials such as corundum, mullite, graphite and the like.
The invention has the beneficial effects that: the upstream part of the growth pipe is improved by the invention, and the conical liner pipe covers the low-temperature area and the temperature transition area at the upper part of the furnace pipe and reaches the high-temperature area, so that the airflow quickly passes through the non-high-temperature area, and the problem of sticking of a product at the non-high-temperature area at the upper end of the furnace pipe is avoided. The uniform transition of the diameter of the conical liner tube avoids the eddy generated when the air flow has sudden change in different tube diameters, and further avoids the problem that the product is adhered to the upper end of the furnace tube; the lower end of the furnace tube is positioned in the high-temperature area, and the problem that the generated products are sticky at the lower end of the furnace tube can be avoided by the arrangement. The problem of blockage caused by adhesion of products on the tube wall of the furnace tube in the experimental process is solved, the continuous production time of the single-walled carbon nanotube is greatly prolonged, and the method has very important significance for practical application.
Drawings
FIG. 1 is a schematic view showing the structure of an apparatus for continuously preparing single-walled carbon nanotubes according to the present invention.
Fig. 2 is a raman spectrum curve of the single-walled carbon nanotube prepared in example 1.
FIG. 3 is a scanning electron micrograph of single-walled carbon nanotubes prepared according to example 1.
Fig. 4 is a raman spectrum curve of the single-walled carbon nanotube prepared in example 2.
FIG. 5 is a scanning electron micrograph of single-walled carbon nanotubes prepared according to example 2.
Fig. 6 is a raman spectrum curve of the single-walled carbon nanotube prepared in example 3.
FIG. 7 is a scanning electron micrograph of single-walled carbon nanotubes prepared according to example 3.
In the figure:
10. the device comprises an injection unit, 11, an injection pump, 12, a liquid conveying pipe, 20, a growth unit, 21, a conical liner pipe, 211, an upper port of the liner pipe, 212, a lower port of the liner pipe, 22, a growth pipe, 221, a temperature transition area, 222, a high-temperature area, 223, a lower port of the growth pipe, 224, an upper port of the growth pipe, 23, a high-temperature furnace body, 24, a heating device and 30, and a collection box.
Detailed Description
The following describes embodiments of the present invention with reference to the drawings.
As shown in fig. 1, the present invention relates to a continuous preparation system of single-walled carbon nanotubes, which comprises a liquid injection unit 10, a growth unit 20 and a collection box 30; the liquid injection unit 10 is connected with the top of the growth unit 20, and the collection box 30 is arranged at the bottom of the growth unit 20;
the growth unit 20 includes: a high-temperature furnace body 23, a growth tube 22 and a conical liner tube 21;
the growth tube 22 is arranged at the center position inside the high-temperature furnace body 23, the growth upper port 224 of the growth tube 22 extends out of the top of the high-temperature furnace body 23, and the growth lower port 223 of the growth tube 22 is positioned at the discharge port of the high-temperature furnace body 22;
the conical liner tube 21 is arranged inside the growth tube 22, and the conical liner tube 21 covers the temperature transition zone 221 of the high-temperature furnace body 23, so that the airflow rapidly passes through the non-high-temperature zone, the eddy generated when the pipe diameter of the high-temperature furnace body 22 suddenly changes is avoided, and the adhesion of intermediate products is inhibited.
The upper end 211 of the conical liner tube 21 is an air inlet, the air inlet is flush with the end of the upper growth end 224 of the growth tube 22, and the lower end 212 of the conical liner tube 21 extends to the high temperature zone of the high temperature furnace body.
The diameter of the liner upper port 211 of the tapered liner 21 is less than 1/2 of the inner diameter of the growth tube 22 and the diameter of the liner upper port 212 is greater than 3/4 of the inner diameter of the growth tube 22.
The range of the taper C of the tapered liner 21 is: d is more than or equal to L, C is less than or equal to d and L800，
Wherein d is the inner diameter of the growth tube 22, L is the length of the growth tube 22, L800The distance from the top end of the growth tube to the 800 ℃ position in the high-temperature furnace body 23.
The growth unit 20 further comprises a heating unit 24, and the heating unit 24 is arranged inside the high-temperature furnace body 23 and is positioned at two sides of the growth tube 22.
A method for preparing single-walled carbon nanotubes by adopting the continuous preparation system comprises the following steps:
s1) starting a heating unit to heat the high-temperature furnace body, so that the temperature of the furnace tube is 1200-1600 ℃;
s2) introducing carrier gas into the high-temperature furnace body 23, starting an injection pump at the same time, and injecting the reaction raw materials into the growth unit through an infusion tube;
s3) allowing the carrier gas and the reaction raw materials to reach a high-temperature region of the furnace tube through the conical liner tube to generate the carbon nanotube aerogel;
s4), smoothly discharging the generated carbon nanotube aerogel from the lower end opening of the furnace tube in the high-temperature region, entering a collecting box, and cooling to obtain the single-walled carbon nanotube.
The carrier gas in the S2) is a mixed gas of hydrogen and inert gas, and the inert gas is argon, nitrogen or helium.
The reaction raw material is a mixed solution of a carbon source, a catalyst and an auxiliary agent;
wherein the carbon source is ethanol, toluene, cyclohexane or other liquid carbon-containing organic matters;
the catalyst is a compound of iron, cobalt or nickel;
the auxiliary agent is a sulfur simple substance or a sulfur-containing compound.
Raman spectrum average I of the single-walled carbon nanotubeG/IDIs more than 50 and has obvious RBM peak.
The single-walled carbon nanotube is prepared by adopting the method or the device.
The material of the growth tube 22 and the conical lining tube 21 is usually high temperature resistant material such as corundum, mullite and graphite.
Example (b):
the continuous preparation device of the single-walled carbon nanotube in the embodiment of the invention comprises a liquid injection unit 10, a growth unit 20 and a collection box 30.
In this embodiment, the infusion unit 10 includes an infusion pump 11 and an infusion tube 12. Wherein, the infusion tube 12 is used for conveying the liquid raw material in the infusion pump 11 to the growth tube 22, and the connection of the infusion tube 12 and the infusion pump 11 and the upper port 211 of the conical liner tube is sealed connection.
Further, the carrier gas also enters the growth unit 20 from the upper port 211 of the conical lining tube, under the carrying action of the carrier gas, the raw material flows downwards along with the gas flow, and because the diameter of the upper port 211 of the lining tube is smaller, the mixture of the raw material and the gas flow rapidly passes through the temperature transition zone 221 at the upper end of the growth tube 22 and uniformly diffuses transversely under the action of the conical lining tube 21, and finally reaches the lower port 212 of the lining tube, the diameter of the gas flow is basically equivalent to that of the growth tube 22, so that the gas flow smoothly enters the high-temperature zone 222 of the growth tube.
Further, the intermediate product and the gas flow pass through the high temperature zone 222 of the growth tube to the lower growth port 223 of the growth tube 22, where the temperature is above 900 ℃. Because the temperature of the furnace tube wall is higher, the air flow has stress flowing towards the center of the furnace tube, so that the product is not easy to adhere to the tube wall at the position and can be smoothly discharged and enter the collecting box 30.
Specifically, the reactant solution in the liquid injection pump 11 is a mixed solution of a carbon source, a catalyst and an auxiliary agent. Wherein the carbon source is liquid organic matters such as ethanol, toluene and cyclohexane; the catalyst is a compound of iron and cobalt; the auxiliary agent is sulfur or a sulfur compound.
Further, the carrier gas entering from the upper port 211 of the conical lining tube is a mixed gas of hydrogen and inert gas, and the inert gas is argon, nitrogen or helium.
Example 1
And (3) heating the furnace to 1200 ℃ and keeping the temperature stable, introducing a mixed gas of hydrogen and nitrogen into the reaction device, and injecting the mixed gas into the reaction device by taking a mixture of ethanol, ferrocene and thiophene as a reactant. The reactant and the carrier gas enter from the upper end of the conical liner tube, are transversely and uniformly diffused in the downward transmission process, finally smoothly enter the high-temperature area of the furnace tube from the lower end of the conical liner tube, react, are finally and smoothly discharged from the lower end of the furnace tube with the temperature higher than 900 ℃, grow into single-walled carbon nanotube aerogel and enter the collection device.
The Raman spectrum of the product obtained is shown in FIG. 2, IG/ID53, and has obvious RBM peak, which indicates that the product is high-quality single-wall carbon nano-tube; the scanning electron micrograph of the product is shown in figure 3, and the product is slender and pure and is uniformly distributed.
Example 2
And (3) heating the furnace to 1300 ℃ and keeping the temperature stable, introducing a mixed gas of hydrogen and argon into the reaction device, and injecting a mixture of toluene, ferrocene and sulfur serving as a reactant into the reaction device. The reactant and the carrier gas enter from the upper end of the conical liner tube, are transversely and uniformly diffused in the downward transmission process, finally smoothly enter the high-temperature area of the furnace tube from the lower end of the conical liner tube, react, are finally and smoothly discharged from the lower end of the furnace tube with the temperature higher than 900 ℃, grow into single-walled carbon nanotube aerogel and enter the collection device.
The Raman spectrum of the obtained product is shown in FIG. 4, IG/ID68 and has a distinct RBM peak, indicating that the product is a high quality single-walled carbon nanotube; the scanning electron micrograph of the product is shown in fig. 5, and the product is slender and pure and is uniformly distributed.
Example 3
And (3) heating the furnace to 1600 ℃ and keeping the temperature stable, introducing a mixed gas of hydrogen and helium into the reaction device, and injecting a mixture of cyclohexane, cobaltocene and carbon disulfide into the reaction device. The reactant and the carrier gas enter from the upper end of the conical liner tube, are transversely and uniformly diffused in the downward transmission process, finally smoothly enter the high-temperature area of the furnace tube from the lower end of the conical liner tube, react, are finally and smoothly discharged from the lower end of the furnace tube with the temperature higher than 900 ℃, grow into single-walled carbon nanotube aerogel and enter the collection device.
The Raman spectrum of the product obtained is shown in FIG. 6, IG/ID61, and has obvious RBM peak, which indicates that the product is high-quality single-wall carbon nano-tube; the scanning electron micrograph of the product is shown in FIG. 7, and the product is slender and pure and is uniformly distributed.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto. Any person skilled in the art should be able to substitute or change the technical solution of the present invention and its inventive concept within the scope of the present invention.
Claims (10)
1. A continuous preparation system of single-walled carbon nanotubes comprises a liquid injection unit, a growth unit and a collection box; the liquid injection unit is connected with the top of the growth unit, and the collection box is arranged at the bottom of the growth unit; characterized in that the growth unit comprises: a high-temperature furnace body, a growth tube and a conical liner tube;
the growth tube is arranged in the center of the interior of the high-temperature furnace body, the growth upper port of the growth tube extends out of the top of the high-temperature furnace body, and the growth lower port of the growth tube is positioned at the discharge port of the high-temperature furnace body;
the conical liner tube is arranged inside the growth tube, and the conical liner tube covers the temperature transition area of the high-temperature furnace body.
2. The continuous preparation system according to claim 1, wherein the upper end of the liner tube of the conical liner tube is an air inlet, the air inlet is flush with the end of the upper growth end of the growth tube, and the lower end opening of the liner tube of the conical liner tube extends to the high-temperature zone of the high-temperature furnace body.
3. The continuous production system of claim 2, wherein the tapered liner has an upper liner port diameter less than 1/2 and a lower liner port diameter greater than 3/4 of the inner diameter of the growth tube.
4. The continuous production system of claim 3, wherein the taper C of the tapered liner ranges from: d is more than or equal to L and less than or equal to C and d is L800,
wherein d is the inner diameter of the growth tube, L is the length of the growth tube, and L800 is the distance from the top end of the growth tube to the 800 ℃ position in the high-temperature furnace body.
5. The continuous production system of claim 1, wherein the growth unit further comprises a heating unit disposed inside the high temperature furnace body and located at both sides of the growth tube.
6. A method for preparing single-walled carbon nanotubes using the continuous preparation system according to any one of claims 1 to 5, comprising the steps of:
s1) starting a system to heat the high-temperature furnace body, so that the temperature in the high-temperature furnace body is kept between 1200 and 1600 ℃;
s2) introducing carrier gas into the high-temperature furnace body, and injecting reaction raw materials into the high-temperature furnace body of the growth unit;
s3) the carrier gas and the reaction raw material directly reach a high-temperature area of the high-temperature furnace body through a conical liner tube through a non-high-temperature area to generate the carbon nano tube aerogel;
s4), smoothly discharging the generated carbon nanotube aerogel from the lower port of the growth tube under the action of air flow from the high-temperature area of the high-temperature furnace body, and cooling the carbon nanotube aerogel to obtain the single-walled carbon nanotube.
7. The method as claimed in claim 6, wherein the carrier gas in S2) is a mixed gas of hydrogen and an inert gas, and the inert gas is argon, nitrogen or helium.
8. The method according to claim 6, wherein the reaction raw material is a mixed solution of a carbon source, a catalyst and an auxiliary agent;
wherein the carbon source is ethanol, toluene, cyclohexane or other liquid carbon-containing organic matters;
the catalyst is a compound of iron, cobalt or nickel;
the auxiliary agent is a sulfur simple substance or a sulfur-containing compound.
9. The method of claim 6, wherein the single-walled carbon nanotubes have a Raman spectrum average IG/IDIs greater than 50 and is between 50 and 300cm-1In the interval, the intensity of the RBM peak exceeds 10% of the G peak.
10. A single-walled carbon nanotube produced by the method according to any one of claims 1 to 9.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008157521A1 (en) * | 2007-06-15 | 2008-12-24 | Nanocomp Technologies, Inc. | Injector apparatus and method for production of nanostructures |
| CN102339745A (en) * | 2008-03-27 | 2012-02-01 | 东京毅力科创株式会社 | Gas supply device, processing apparatus and processing method |
| CN103071430A (en) * | 2013-01-30 | 2013-05-01 | 中国石油化工股份有限公司 | Radial fixed bed reactor for oxydehydrogenation of butylene |
| CN103071429A (en) * | 2013-01-30 | 2013-05-01 | 中国石油化工股份有限公司 | Radial fixed bed reactor for oxy-dehydrogenation of butylene |
| CN105366352A (en) * | 2015-12-23 | 2016-03-02 | 盐城市富仕环保科技有限公司 | Sticky material feeding device |
| CN105439119A (en) * | 2015-12-02 | 2016-03-30 | 苏州捷迪纳米科技有限公司 | Vertical continuous preparing device for carbon nano tube fibers and preparing method |
| CN106563286A (en) * | 2016-11-03 | 2017-04-19 | 中北大学 | Crystallization hanging basket used for preparing nanometer and micrometer particles through supercritical atomization and crystallization process |
| CN108715445A (en) * | 2018-07-14 | 2018-10-30 | 深圳市星聚工业自动化有限公司 | A kind of microwave gas diffusion method expanded graphite expanding apparatus |
| CN109754692A (en) * | 2019-03-11 | 2019-05-14 | 北京大学 | One kind being used for the photochemically reactive device of simulated atmosphere pollutant |
| CN111020747A (en) * | 2019-12-25 | 2020-04-17 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | System and method for continuously preparing carbon nanotube fibers based on floating catalytic CVD method |
-
2020
- 2020-11-12 CN CN202011262907.7A patent/CN112357908A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008157521A1 (en) * | 2007-06-15 | 2008-12-24 | Nanocomp Technologies, Inc. | Injector apparatus and method for production of nanostructures |
| CN102339745A (en) * | 2008-03-27 | 2012-02-01 | 东京毅力科创株式会社 | Gas supply device, processing apparatus and processing method |
| CN103071430A (en) * | 2013-01-30 | 2013-05-01 | 中国石油化工股份有限公司 | Radial fixed bed reactor for oxydehydrogenation of butylene |
| CN103071429A (en) * | 2013-01-30 | 2013-05-01 | 中国石油化工股份有限公司 | Radial fixed bed reactor for oxy-dehydrogenation of butylene |
| CN105439119A (en) * | 2015-12-02 | 2016-03-30 | 苏州捷迪纳米科技有限公司 | Vertical continuous preparing device for carbon nano tube fibers and preparing method |
| CN105366352A (en) * | 2015-12-23 | 2016-03-02 | 盐城市富仕环保科技有限公司 | Sticky material feeding device |
| CN106563286A (en) * | 2016-11-03 | 2017-04-19 | 中北大学 | Crystallization hanging basket used for preparing nanometer and micrometer particles through supercritical atomization and crystallization process |
| CN108715445A (en) * | 2018-07-14 | 2018-10-30 | 深圳市星聚工业自动化有限公司 | A kind of microwave gas diffusion method expanded graphite expanding apparatus |
| CN109754692A (en) * | 2019-03-11 | 2019-05-14 | 北京大学 | One kind being used for the photochemically reactive device of simulated atmosphere pollutant |
| CN111020747A (en) * | 2019-12-25 | 2020-04-17 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | System and method for continuously preparing carbon nanotube fibers based on floating catalytic CVD method |
Non-Patent Citations (1)
| Title |
|---|
| 雅科夫•伊西达洛维奇•别莱利曼: "《写给孩子的趣味物理学》", 31 July 2019, 武汉大学出版社 * |
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