CN101734641A - Heater and synthesis method for synthesizing carbon nano tubes by pyrolysis - Google Patents
Heater and synthesis method for synthesizing carbon nano tubes by pyrolysis Download PDFInfo
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- CN101734641A CN101734641A CN200810171823A CN200810171823A CN101734641A CN 101734641 A CN101734641 A CN 101734641A CN 200810171823 A CN200810171823 A CN 200810171823A CN 200810171823 A CN200810171823 A CN 200810171823A CN 101734641 A CN101734641 A CN 101734641A
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- carbon nanotubes
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Abstract
The invention discloses a heater and synthesis method for synthesizing carbon nano tubes by pyrolysis, belonging to the technical field of synthesis of carbon nano tubes. The method comprises the concrete steps of: introducing reaction gas mixture, metallic catalyst nano particles and inert gases in a heating section of the heater, heating the heating section, and collecting carbon nano tubes at the outlet of the heater. The heating section is heated so that the reaction gas mixture in the heating section reaches a temperature required for synthesizing the carbon nano tubes to provide heat sources used as a first element for synthesizing the carbon nano tubes; the reaction gas mixture provides carbon sources used as a second element for synthesizing the carbon nano tubes; and the metallic catalyst nano particles provide catalysts used as a third element for synthesizing the carbon nano tubes. The heater has three elements for synthesizing the carbon nano tubes, and the carbon nano tubes can be synthesized in the heating section. The invention has the advantage that by using a continuous conveying belt sampling mechanism, the carbon nano tubes can be prepared controllably with low cost and high quality in continuous batch, large size, and large scale.
Description
Technical field
The invention belongs to the carbon nanotube synthesis technical field, the well heater and the synthetic method of pyrolysis synthesizing carbon nanotubes particularly is provided.
Background technology
1991 Japanese scholar's Iijima (Iijima) at first found carbon nanotube (Carbon nanotubes, CNTs).Carbon current nanotube synthetic method mainly contains four kinds: (chemieal vapor deposition is CVD) with flame synthesis method (flamesynthesis) for arc discharge method (arc discharge), laser evaporation method (laservaporization), chemical Vapor deposition process.First three plants synthetic method equipment complexity, and the cost height is fit to small-scale, small size, interval type operation.The flame synthesis method has preparation continuously under atmospheric condition, and equipment is simple, and is energy-conservation, low cost, the potentiality of large size, extensive batch preparations.But, also be in the fundamental research stage at present.
Belgian Ivanov in 1994 etc. grow the carbon nanotube of diameter tens nanometers on catalyst particles such as cobalt and iron by pyrolysis with acetylene in document " Ivanov V; Nagy J B et; al.The Study of Carbonnanotubes Produced by Catalytic Method.Chem Phys Lett.1994,223:329-335 ".Use in document " Vander wal RL; Ticich TM; Curtis VE.Diffusion Flame Synthesisof Single-walled Carbon Nanotubes.Chem Phys Lett.2000,354 (1-2): 20-4 " such as the Vander wal of NASA in 2000 is called " pyrolysis flame " and comes synthesizing carbon nanotubes.Grandson protected the people, Zhao Huifu in the Chinese invention patent (patent No.: the burner and the synthetic method that have proposed V-type and pyramid type pyrolysis flame synthesizing carbon nanotubes PNCN1830770-A) in 2006.
Summary of the invention
The object of the present invention is to provide the well heater and the synthetic method of pyrolysis synthesizing carbon nanotubes.It is characterized in that: the heating zone that described pyrolysis synthesize nano carbon pipe heater is a well heater inner logical reaction mixture gas, metal-catalyst nanoparticles and rare gas element, the heating heating zone that ins all sorts of ways is collected carbon nanotube at heater outlet.
The concrete grammar of described pyrolysis synthesizing carbon nanotubes is: feed reaction mixture gas, metal-catalyst nanoparticles and rare gas element from the heating zone of well heater (heating zone be various cross-sectional shapes as: circle, rectangle, square, rhombus, Polygons etc. and various materials are as metal and nonmetallic pipeline) import, in all sorts of ways, as: flame, electricity or electromagnetic induction etc., the heating heating zone, make heating zone internal-response mixed airflow reach the required temperature of synthesizing carbon nanotubes, and keep temperature-stable, even.Heating zone provides the first element of synthesizing carbon nanotubes for the reaction mixture gas stream of its inside: hot environment-thermal source.Reaction mixture gas provides necessary second key element of synthesizing carbon nanotubes-carbon source.The metal-catalyst nanoparticles that adds provides necessary the three elements of synthesizing carbon nanotubes-catalyzer.So this well heater has possessed the three elements of synthesizing carbon nanotubes: thermal source, carbon source and catalyzer, just can be in heating zone synthesizing carbon nanotubes, collect carbon nanotube at heater outlet.Adopt electricity or electromagnetic induction heating heating zone and the sampling substrate that electromagnetic field effect is arranged, regulate electromagnetic field and can make carbon nanotube marshalling, orderly, and can obtain long carbon nanotube.
Beneficial effect of the present invention is to adopt the continuous conveyor sampling mechanism, can accomplish controlled, continuous batch, large size, extensive, high quality, prepare carbon nanotube at low cost.The synthetic method simple possible, and it is convenient, simple and easy to regulate control.
Description of drawings
The well heater synoptic diagram of electricity consumption of Fig. 1 heating zone or electromagnetic induction heating.Wherein 1 the expression reaction mixture gas, metal-catalyst nanoparticles and rare gas element mixed airflow.2 expression electricity or electromagnetic induction heating elements.3 expression heating zones.Heat insulation and the anti-tampering dividing plate of 4 expressions.Heat insulation and anti-tampering dividing plate guarantees that the sampling environment is not heated, the interference of air-flow, electromagnetic induction etc.
Fig. 2 heating zone well heater synoptic diagram of flame heating.Wherein 1 the expression reaction mixture gas, metal-catalyst nanoparticles and rare gas element mixed airflow.2 expression flame-thrower nozzles.3 expression heating zones.Heat insulation and the anti-tampering dividing plate of 4 expressions.
Embodiment
The invention reside in well heater and synthetic method that the pyrolysis synthesizing carbon nanotubes is provided, the present invention is illustrated below in conjunction with Fig. 1.
Following elder generation is example explanation the present invention with the concrete grammar of single-wall carbon nanotube synthesizing.The heating heating zone that ins all sorts of ways as flame, electricity or electromagnetic induction etc., makes heating zone internal-response mixed airflow reach the required temperature of synthesizing carbon nanotubes (600 ℃～1300 ℃), and keeps temperature-stable, evenly.Mix the sufficiently high reaction mixture gas of purity, metal-catalyst nanoparticles and rare gas element from heating zone import feeding.Described reaction mixture gas is meant and can reacts the reactant gases that produces carbon source and help synthesizing carbon nanotubes, as carbon monoxide CO, hydrogen H
2In the liquid fuel of gas mixture or combustiblematerials gas mixture such as geseous fuel or atomizing, wherein geseous fuel is good with acetylene.To carbon monoxide CO, hydrogen H
2Deng gas mixture, the CO in the reaction mixture gas separates out carbon by hydrogenization and hydrogen atom commentaries on classics shape carbon source is provided.To adopting iron is the situation of catalyzer, and CO can cause the fragmentation of macrobead iron, and reaction surface is increased.The concentration of carbon monoxide is suitable, if too big, will produce excessive carbon atom, granules of catalyst is coated by carbon atom lost efficacy; If too little, then do not provide competent carbon atom synthesizing carbon nanotubes, catalyst surface more may be covered by other material and lose efficacy simultaneously.Hydrogen can impel carbon monoxide to decompose in the absorption of catalyst surface, makes CO hydrogenation separate out carbon, and Hydrogen Energy promotion dissociative carbon is absorbed the growth of promotion carbon nanotube by the iron particle.The torpescence carbide that hydrogen can also the decomposition catalyst particle surface covers makes catalyzer keep active, but its required carbon atom of synthesizing carbon nanotubes that also gasified simultaneously, carbon nano tube growth is slowed down even stops.So the ratio of control carbon monoxide/hydrogen is extremely important.Catalyzer is the vital factor of preparation carbon nanotube.Metal-catalyst nanoparticles is the key factor of carbon nano tube growth, and they not only promote the formation of carbon nanotube, but also is to form the requisite seed of carbon nanotube.Diameter of single-wall carbon nano tube is in 1 to 3 nanometer, diameter during greater than 3 nanometers Single Walled Carbon Nanotube just unstable, do not form.The diameter of the size decision carbon nanotube of granules of catalyst, the size that therefore prepares the metal-catalyst nanoparticles of Single Walled Carbon Nanotube must be the 1-3 nanometer scale, otherwise does not form Single Walled Carbon Nanotube.Metal catalyst is commonly used nickel, iron Fe, cobalt Co etc.Several different methods able to produce metal catalyst nano particle is arranged, scribble metallic particles filter paper as pure metal high temperature evaporation (cost is too high), the controlled sublimating technologe of organometallics (as the nitrate solution of catalyst metal), spray technique and burning and produce particulate (only being used for basic test) etc.The spray pyrolysis technology is generation aerosol that use always, lower-cost (aerosol particle) technology, uses very extensively.The Supersonic cavitation erosion that superonic flow nozzzle or piezoquartz and electric drive plate cause, able to produce metal nano particle from metal nitrate or ferrous solution.Ferruginous catalyzer 1 to 3 nano-sized particles is more suitable for the synthetic of Single Walled Carbon Nanotube.Iron Fe has more activity to catalysis CO.Easy and the CO/H of Fe
2The mixed gas reaction of/He produces Single Walled Carbon Nanotube.Adopt pentacarbonyl iron Fe (CO)
5Be catalyzer, the CO after the thermolysis can also be as reaction raw materials.Catalyst concentration is between 200～10000ppm.Rare gas element, as argon Ar, helium He, nitrogen N
2Deng, as thinner, can regulate mixture temperature and reach carbon nanotube synthetic temperature range.Temperature is too low to be not enough to the enough carbon sources of cracking, and too high temperature will be destroyed the carbon nanotube of generation and cause carbon black and a large amount of growths fast of polycyclic aromatic hydrocarbons.Lacking of rare gas element can cause soot formation and noncrystal carbon coated metal particle, and metal catalyst particles was lost efficacy.Yet too much thinner may reduce reaction density, also will cause the minimizing of carbon nanotube.In addition, rare gas element also works to keep catalyst activity.Described reaction mixture gas carbon monoxide CO, hydrogen H
2Can be 0.5～1.5/0.5～1.5/0.5～1.5 with the throughput ratio of rare gas element.If reaction mixture gas is the combustiblematerials gas mixture, so, the temperature of heating combustiblematerials gas mixture is the highest can only to arrive pyrolysis temperature, never can be high to kindling temperature, otherwise will cause the combustiblematerials gas mixture in the heating zone internal combustion, this is unallowed.
Concrete grammar with the synthesizing multi-wall carbon nanotube is example explanation the present invention again.Mix the sufficiently high reaction mixture gas of purity, metal-catalyst nanoparticles and rare gas element from heating zone import feeding.The multi-walled carbon nano-tubes diameter is usually in the scope of tens nanometers.The synthetic of multi-walled carbon nano-tubes can have dual mode in the present invention, the one, can be in the mixed airflow without metal-catalyst nanoparticles, but the sampling substrate must contain metallic catalyst material, as nickel, iron, cobalt etc., or sampling substrate plate carried catalyst, promptly be coated with one deck catalyzer at substrate surface.Fe-series catalyst mainly is molysite such as iron nitrate, ferrocene, pentacarbonyl iron.Nickel catalyst mainly is nickel salts such as nickelous nitrate.The 2nd, metal-catalyst nanoparticles is arranged in the mixed airflow.The multi-walled carbon nano-tubes granules of catalyst can be bigger, can be in tens nanometer range.All the other processes are the same with above-mentioned Single Walled Carbon Nanotube building-up process.
Adopt the heating zone and the sampling substrate that electromagnetic field effect is arranged of electricity or electromagnetic induction heating, regulate electromagnetic field and can make carbon nanotube marshalling, orderly, and can obtain long carbon nanotube.
Claims (9)
1. the well heater of pyrolysis synthesizing carbon nanotubes, it is characterized in that: the well heater of described pyrolysis synthesizing carbon nanotubes is inner logical reaction mixture gas, metal-catalyst nanoparticles and a rare gas element of a kind of heating zone, ining all sorts of ways adds the heating zone of hot heater, collects the well heater of carbon nanotube at heater outlet.
2. according to the well heater of the described pyrolysis synthesizing carbon nanotubes of claim 1, it is characterized in that: the structure of described well heater be heating zone be various cross-sectional shapes as: circle, rectangle, square, rhombus, Polygons etc. and various materials are as metal and nonmetallic pipeline.The heating zone import feeds reaction mixture gas, metal-catalyst nanoparticles and rare gas element.The heating zone outlet has heat insulation and anti-tampering dividing plate.
3. according to the method for the well heater synthesizing carbon nanotubes of the described pyrolysis synthesizing carbon nanotubes of claim 1, it is characterized in that: the concrete grammar of described pyrolysis synthesizing carbon nanotubes is: the heating zone of well heater inner logical reaction mixture gas, metal-catalyst nanoparticles and rare gas element.(as flame, electricity or electromagnetic induction etc.) heating heating zone that ins all sorts of ways makes the heating zone temperature inside reach the required temperature of reaction mixture gas stream synthesizing carbon nanotubes.Heating zone provides the first element of synthesizing carbon nanotubes for the reaction mixture gas stream of its inside: hot environment-thermal source.Reaction mixture gas provides necessary second key element of synthesizing carbon nanotubes-carbon source.The metal-catalyst nanoparticles that adds provides necessary the three elements of synthesizing carbon nanotubes-catalyzer.Rare gas element is as thinner, and the conditioned reaction mixture temperature reaches carbon nanotube synthetic temperature range, and rare gas element also works to keep catalyst activity.This well heater has possessed the three elements of synthesizing carbon nanotubes: thermal source, carbon source and catalyzer, just can be in heating zone synthesizing carbon nanotubes, collect carbon nanotube at heater outlet." pyrolysis " mode is like this separated heating and carbon nanotube building-up process, helps the control of building-up process.
4. according to the well heater of the described pyrolysis synthesizing carbon nanotubes of claim 1, it is characterized in that: heating such as the heating zone electricity consumption of described well heater or electromagnetic induction, reach with the sampling substrate that electromagnetic field effect is arranged, regulate electromagnetic field and can make carbon nanotube marshalling, orderly, and can obtain long carbon nanotube.
5. according to the well heater of the described pyrolysis synthesizing carbon nanotubes of claim 1, it is characterized in that: the sampling substrate of described well heater adopts the continuous conveyor sampling mechanism, can accomplish controlled, continuous batch, large size, extensive, high quality, prepare carbon nanotube at low cost.
6. according to the method for the well heater synthesizing carbon nanotubes of the described pyrolysis synthesizing carbon nanotubes of claim 1, it is characterized in that: described reaction mixture gas is meant and can reacts the reactant gases that produces carbon source and help synthesizing carbon nanotubes, as carbon monoxide CO, hydrogen H
2, additive, or as liquid fuel, additive and the rare gas element etc. of geseous fuel, atomizing.
7. according to the method for the well heater synthesizing carbon nanotubes of the described pyrolysis synthesizing carbon nanotubes of claim 1, it is characterized in that: described metal-catalyst nanoparticles is nickel, iron Fe or cobalt Co etc.
8. according to the method for the well heater synthesizing carbon nanotubes of the described pyrolysis synthesizing carbon nanotubes of claim 1, it is characterized in that: described rare gas element is argon Ar, helium He or nitrogen N
2Deng.
9. according to the well heater of the described pyrolysis synthesizing carbon nanotubes of claim 1, it is characterized in that: described well heater has heat insulation and anti-tampering dividing plate.Heat insulation and anti-tampering dividing plate guarantees that the sampling environment is not heated, the interference of air-flow, electromagnetic induction etc.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107720725A (en) * | 2017-11-22 | 2018-02-23 | 江西悦安超细金属有限公司 | A kind of method and device for preparing CNT |
| CN108314010A (en) * | 2018-03-14 | 2018-07-24 | 暨南大学 | A kind of carbon nanotube and its preparation method and application of flame method modification |
| CN108883938A (en) * | 2016-02-15 | 2018-11-23 | 布莱恩·劳布切尔 | The growth of free atom nanotube |
| CN108892122B (en) * | 2018-08-31 | 2020-10-27 | 北京化工大学 | Method for preparing carbon nano tube by solution combustion |
| CN112909259A (en) * | 2021-02-04 | 2021-06-04 | 陕西科技大学 | Method for preparing carbon nanotube material catalytically grown from FeNi alloy by electromagnetic induction heating method |
| CN113181856A (en) * | 2021-05-08 | 2021-07-30 | 东南大学 | Device and method for synthesizing nano particles by simulating zero-microgravity flame with assistance of magnetic field |
| US11247901B2 (en) | 2012-10-29 | 2022-02-15 | Odysseus Technologies, Inc. | Free atom nanotube growth |
| CN115744877A (en) * | 2022-10-24 | 2023-03-07 | 国家能源集团新能源技术研究院有限公司 | Preparation device of carbon nano material |
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2008
- 2008-11-14 CN CN200810171823A patent/CN101734641A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11247901B2 (en) | 2012-10-29 | 2022-02-15 | Odysseus Technologies, Inc. | Free atom nanotube growth |
| CN108883938A (en) * | 2016-02-15 | 2018-11-23 | 布莱恩·劳布切尔 | The growth of free atom nanotube |
| CN108883938B (en) * | 2016-02-15 | 2023-06-23 | 奥德修斯技术公司 | Free atomic nanotube growth |
| CN107720725A (en) * | 2017-11-22 | 2018-02-23 | 江西悦安超细金属有限公司 | A kind of method and device for preparing CNT |
| CN108314010A (en) * | 2018-03-14 | 2018-07-24 | 暨南大学 | A kind of carbon nanotube and its preparation method and application of flame method modification |
| CN108892122B (en) * | 2018-08-31 | 2020-10-27 | 北京化工大学 | Method for preparing carbon nano tube by solution combustion |
| CN112909259A (en) * | 2021-02-04 | 2021-06-04 | 陕西科技大学 | Method for preparing carbon nanotube material catalytically grown from FeNi alloy by electromagnetic induction heating method |
| CN113181856A (en) * | 2021-05-08 | 2021-07-30 | 东南大学 | Device and method for synthesizing nano particles by simulating zero-microgravity flame with assistance of magnetic field |
| CN113181856B (en) * | 2021-05-08 | 2022-04-29 | 东南大学 | Device and method for synthesizing nano particles by simulating zero-microgravity flame with assistance of magnetic field |
| US11786882B2 (en) | 2021-05-08 | 2023-10-17 | Southeast University | Device and method for magnetic field-assisted simulation of zero-microgravity fame synthesis of nanoparticles |
| CN115744877A (en) * | 2022-10-24 | 2023-03-07 | 国家能源集团新能源技术研究院有限公司 | Preparation device of carbon nano material |
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Inventor after: Sun Baomin Inventor after: Zhao Huifu Inventor after: Guo Yonghong Inventor after: Liu Yuanchao Inventor before: Sun Baomin Inventor before: Zhao Huifu Inventor before: Liu Yuanchao |
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Application publication date: 20100616 |