CN1597503A - Carbon micron pipe formed by nanometer carbon particles and its preparation method - Google Patents
Carbon micron pipe formed by nanometer carbon particles and its preparation method Download PDFInfo
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- CN1597503A CN1597503A CN 200410012525 CN200410012525A CN1597503A CN 1597503 A CN1597503 A CN 1597503A CN 200410012525 CN200410012525 CN 200410012525 CN 200410012525 A CN200410012525 A CN 200410012525A CN 1597503 A CN1597503 A CN 1597503A
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Abstract
A process for preparing the carbon micron-tubes from carbon nanoparticles includes such steps as heating the precursor of catalyst to gasifying it slowly, using the gas mixture of argon and hydrocarbon to carry the gasified catalyst into high-temp reactor, and thermodecomposing. The resultant micro-tube has long length and unique structure.
Description
Technical field
The present invention relates to a kind of preparation method of tubulose carbon, relate in particular to a kind of method for preparing micron order tubulose carbon by the vapour deposition of hydro carbons catalyse pyrolysis.
Background technology
Tubulose carbon is compared with the carbon material of other patterns, has the character and the application background of many uniquenesses.So-called tubulose carbon is meant the one dimension carbon material of the cylinder type hollow structure with rule.Big I according to the tubulose carbon di is divided into nanotube and micron tube.Carbon nanotube has excellent mechanical property and peculiar electromagnetic performance, therefore all has wide practical use in a lot of fields.For example, carbon nanotube can be used for the toughener of matrix material, template, electronics and nanometer device material, catalytic material and the energy storage material of nano material preparation.Micron tube is owing to have bigger caliber, and the reaction system that some can be difficult to carry out in the popular response device is incorporated in the microtubule, constitutes the microreactor of countless separate units, thereby quickens and realize that those are difficult to the reaction of finishing in the popular response device.Also can utilize the pipeline of carbon micron tube to carry out the orientation transmission of material,, play a multiplier effect as medically drug particles directly being sent to some diseased region.In addition, carbon micron tube absorption with the field such as separate important application prospects also arranged.Therefore carbon micron tube is a kind of very promising new carbon.
The research that the relevant at present method with catalyse pyrolysis prepares the carbon pipe mainly concentrates on the nanotube, and lot of documents and patent report are arranged.Reported that as Chinese patent (application number is 02137403) a kind of catalytic pyrolysis method prepares the continuous production method of Single Walled Carbon Nanotube, it is characterized in that bringing tetraethoxy and ferrocene into high temperature reaction zone continuously with hydrogenous carrier gas, generate the nano-complex particle catalyzer of the iron-silicon-dioxide with catalytic effect through reaction in, raw material decomposes the carbon that obtains and form single-wall continuous nanotube under catalyst action; Described high temperature reaction zone temperature is 900-1200 ℃, and carrier gas is made up of hydrogen and diluent gas, and wherein the shared molar percentage of hydrogen is 5-85; The time length of reaction zone is 20-60 minute, and the total flux of hydrogeneous carrier gas is 800-2400ml/mil, and the tetraethoxy flow is 20-100mg/min, and the flow of ferrocene is 0.3-3mg/min.The diameter of resulting Single Walled Carbon Nanotube exists with the form of restrainting about 2nm, and length is several microns to tens of microns, and yield is up to 8%.But it is that the research of micron order carbon pipe does not appear in the newspapers that relevant catalyse pyrolysis prepares diameter.
Goal of the invention
The purpose of this invention is to provide a kind of diameter and have tubulose carbon material of micro-meter scale and preparation method thereof.
The feature of carbon micron tube of the present invention is that external diameter is 50～200 microns, and thickness of pipe is 10～30 microns, and length is 2～10 centimetres, and wherein the tube wall of carbon micron tube is that the carbon granule that comprises metal of 60～70 nanometers constitutes by the self-assembly form by diameter.
Aforesaid metal comprises iron, cobalt or nickel.
The method feature that the present invention adopts is that catalyzer and organic hydrocarbon are carried out pyrolysis in argon gas stream, promptly earlier the heating of catalyzer precursor is made it slow gasification, the catalyzer that will gasify with the mixed gas of argon gas and hydro carbons is brought into and carries out pyrolysis in the high-temperature reactor then, forms carbon micron tube.
Concrete operation method is as follows:
With argon gas catalyzer and varsol being brought into temperature together is in 900～1200 ℃ the reactor, reacts 3～6 hours, turns off reaction gas, drops to room temperature at protective atmosphere, can obtain carbon micron tube at the end of the tree-shaped carbon of thermopair termination.
Aforesaid catalyzer comprises ferrocene, nickelocene or dicyclopentadienylcobalt, and its amount ranges is 0.01～0.5 milligram of/minute square centimeter.
Aforesaid hydro carbons comprises aliphatic hydrocarbon and aromatic hydrocarbon, and aliphatic hydrocarbon mainly contains pentane, normal hexane, heptane or hexanaphthene, and aromatic hydrocarbon mainly contains benzene, toluene or dimethylbenzene; Its amount ranges is 1～25 milligram of/minute square centimeter.
Aforesaid argon flow amount scope is 30～240 ml/min square centimeters.
Advantage of the present invention:
1, equipment is simple, easy handling.
2, the length of Zhi Bei carbon micron tube is long, structure is unique.
3, good reproducibility.
The drawing explanation
Fig. 1 is the partial sweep Electronic Speculum picture of the carbon micron tube for preparing of the present invention, is known that by Fig. 1 the diameter of carbon pipe has bending slightly in 120～150 micrometer ranges.
Fig. 2 is the fracture scanning electron microscope picture of the carbon micron tube for preparing of the present invention.Can be clear that by Fig. 2 the thickness of pipe of carbon pipe is about 25 microns, about 70 microns of internal diameter, tube wall is vesicular structure.
Fig. 3 is the local high multiple sem photograph sheet that amplifies of carbon micron tube outer wall that the present invention prepares.Can be seen that by this figure the tube wall of this carbon pipe is to be that the carbon granule of tens nanometer forms by the self-organization form by diameter, and some spaces not of uniform size are arranged between the particle, the size range in space is that tens nanometer arrives hundreds of nanometers.
Embodiment
Embodiment 1:
Claim 0.1 gram ferrocene, putting into a width is 3 centimetres, and length is in 6 centimetres the porcelain boat, and is heated to 110 ℃.
Reactor is warmed up to 950 ℃ under argon atmospher, then, the flat-temperature zone that ferrocene after will gasifying with argon gas and hexane are brought reactor into.Wherein, the flow of ferrocene is 0.03 milligram of/minute square centimeter; The flow of hexane is 15 milligrams of/minute square centimeters; The flow of argon gas is 80 ml/min square centimeters.950 ℃ of reactions 3 hours, turn off reaction gas, in argon gas stream, be cooled to room temperature, can obtain about 3 centimetres of length, diameter is 80 microns a carbon micron tube.
Embodiment 2:
Claim 0.5 gram ferrocene, putting into a width is 3 centimetres, and length is in 6 centimetres the porcelain boat, and is heated to 150 ℃.
Reactor is warmed up to 1200 ℃ under argon atmospher, then, the flat-temperature zone that ferrocene after will gasifying with argon gas and benzene are brought reactor into.Wherein, the flow of ferrocene is 0.13 milligram of/minute square centimeter; The flow of benzene is 5 milligrams of/minute square centimeters; The flow of argon gas is 160 ml/min square centimeters.1200 ℃ of reactions 5 hours, turn off reaction gas, in argon gas stream, be cooled to room temperature, can obtain about 6 centimetres of length, diameter is 120 microns a carbon micron tube.
Embodiment 3:
Claim 0.4 gram nickelocene, putting into a width is 3 centimetres, and length is in 6 centimetres the porcelain boat, and is heated to 180 ℃.
Reactor is warmed up to 1100 ℃ under argon atmospher, then, the flat-temperature zone that nickelocene after will gasifying with argon gas and toluene are brought reactor into.Wherein, the flow of nickelocene is 0.12 milligram of/minute square centimeter; The flow of toluene is 5 milligrams of/minute square centimeters: the flow of argon gas is 120 ml/min square centimeters.1100 ℃ of reactions 4 hours, turn off reaction gas, in argon gas stream, be cooled to room temperature, can obtain about 4 centimetres of length, diameter is 80 microns a carbon micron tube.
Embodiment 4:
Claim 0.2 gram dicyclopentadienylcobalt, putting into a width is 3 centimetres, and length is in 6 centimetres the porcelain boat, and is heated to 200 ℃.
Reactor is warmed up to 1200 ℃ under argon atmospher, then, the flat-temperature zone that dicyclopentadienylcobalt after will gasifying with argon gas and dimethylbenzene are brought reactor into.Wherein, the flow of dicyclopentadienylcobalt is 0.08 milligram of/minute square centimeter; The flow of dimethylbenzene is 15 milligrams of/minute square centimeters; The flow of argon gas is 200 ml/min square centimeters.1200 ℃ of reactions 3 hours, turn off reaction gas, in argon gas stream, be cooled to room temperature, can obtain length and be 2 centimetres carbon micron tube.
Embodiment 5:
Claim 0.8 gram ferrocene, putting into a width is 3 centimetres, and length is in 6 centimetres the little porcelain boat, and is heated to 150 ℃.
Reactor is warmed up to 1150 ℃ under argon atmospher, then, the flat-temperature zone that ferrocene after will gasifying with argon gas and hexanaphthene are brought reactor into.Wherein, the flow of dicyclopentadienylcobalt is 0.58 milligram of/minute square centimeter; The flow of hexanaphthene dimethylbenzene is 20 milligrams of/minute square centimeters; The flow of argon gas is 240 ml/min square centimeters.1150 ℃ of reactions 2 hours, turn off reaction gas, in argon gas stream, be cooled to room temperature, can obtain length and be 4 centimetres carbon micron tube.
Claims (7)
1. carbon micron tube that forms by nano carbon particle, the external diameter that it is characterized in that carbon micron tube is 50～200 microns, thickness of pipe is 10～30 microns, length is 2～10 centimetres, and wherein the tube wall of carbon micron tube is that the carbon granule that comprises metal of 60～70 nanometers constitutes by the self-assembly form by diameter.
2, the preparation method of a kind of carbon micron tube that is formed by nano carbon particle as claimed in claim 1 is characterized in that comprising the steps:
With argon gas catalyzer and varsol being brought into temperature together is in 900～1200 ℃ the reactor, reacts 3～6 hours, turns off reaction gas, drops to room temperature at protective atmosphere, can obtain carbon micron tube at the end of the tree-shaped carbon of thermopair termination.
3, the preparation method of a kind of carbon micron tube that is formed by nano carbon particle as claimed in claim 2 is characterized in that described catalyzer comprises ferrocene, nickelocene or dicyclopentadienylcobalt, and its amount ranges is 0.01～0.5 milligram of/minute square centimeter.
4, the preparation method of a kind of carbon micron tube that is formed by nano carbon particle as claimed in claim 2 is characterized in that described hydro carbons comprises aliphatic hydrocarbon and aromatic hydrocarbon.
5, the preparation method of a kind of carbon micron tube that is formed by nano carbon particle as claimed in claim 4 is characterized in that described aliphatic hydrocarbon is pentane, normal hexane, heptane or hexanaphthene.
6, the preparation method of a kind of carbon micron tube that is formed by nano carbon particle as claimed in claim 4 is characterized in that described aromatic hydrocarbon is benzene, toluene or dimethylbenzene; Its amount ranges is 1～25 milligram of/minute square centimeter.
7, the preparation method of a kind of carbon micron tube that is formed by nano carbon particle as claimed in claim 2 is characterized in that described argon flow amount scope is 30～240 ml/min square centimeters.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410012525 CN1275852C (en) | 2004-09-16 | 2004-09-16 | Carbon micron pipe formed by nanometer carbon particles and its preparation method |
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| CN 200410012525 CN1275852C (en) | 2004-09-16 | 2004-09-16 | Carbon micron pipe formed by nanometer carbon particles and its preparation method |
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| CN1597503A true CN1597503A (en) | 2005-03-23 |
| CN1275852C CN1275852C (en) | 2006-09-20 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557026A (en) * | 2011-11-09 | 2012-07-11 | 南京邮电大学 | Method for preparing porous carbon micron tube from catkin, poplar seed or phoenix tree seed as raw material |
| CN103387220A (en) * | 2013-07-24 | 2013-11-13 | 哈尔滨工业大学 | Method for preparing sustainable high-yield carbon microtubes |
| CN103551151A (en) * | 2013-11-06 | 2014-02-05 | 中国矿业大学 | Method for preparing recyclable magnetic solid acid catalyst |
| CN104995134A (en) * | 2013-01-22 | 2015-10-21 | Mcd技术有限公司 | Method for producing carbon nanostructures, and device |
| CN109941984A (en) * | 2019-05-09 | 2019-06-28 | 中国科学院山西煤炭化学研究所 | The preparation method and carbon micron tube of carbon micron tube |
| CN115140723B (en) * | 2021-03-30 | 2023-09-05 | 中国石油化工股份有限公司 | Catalyst and method for preparing carbon micro-tube by using same |
-
2004
- 2004-09-16 CN CN 200410012525 patent/CN1275852C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557026A (en) * | 2011-11-09 | 2012-07-11 | 南京邮电大学 | Method for preparing porous carbon micron tube from catkin, poplar seed or phoenix tree seed as raw material |
| CN104995134A (en) * | 2013-01-22 | 2015-10-21 | Mcd技术有限公司 | Method for producing carbon nanostructures, and device |
| CN104995134B (en) * | 2013-01-22 | 2018-06-05 | Mcd技术有限公司 | Produce carbon nano-structured method and device |
| CN103387220A (en) * | 2013-07-24 | 2013-11-13 | 哈尔滨工业大学 | Method for preparing sustainable high-yield carbon microtubes |
| CN103387220B (en) * | 2013-07-24 | 2014-12-10 | 哈尔滨工业大学 | Method for preparing sustainable high-yield carbon microtubes |
| CN103551151A (en) * | 2013-11-06 | 2014-02-05 | 中国矿业大学 | Method for preparing recyclable magnetic solid acid catalyst |
| CN103551151B (en) * | 2013-11-06 | 2015-07-08 | 中国矿业大学 | Method for preparing recyclable magnetic solid acid catalyst |
| CN109941984A (en) * | 2019-05-09 | 2019-06-28 | 中国科学院山西煤炭化学研究所 | The preparation method and carbon micron tube of carbon micron tube |
| CN115140723B (en) * | 2021-03-30 | 2023-09-05 | 中国石油化工股份有限公司 | Catalyst and method for preparing carbon micro-tube by using same |
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| CN1275852C (en) | 2006-09-20 |
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