CN101264882A - Method for preparing carbon nano-tube by using porous Ni3Al alloy as catalyst - Google Patents
Method for preparing carbon nano-tube by using porous Ni3Al alloy as catalyst Download PDFInfo
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- CN101264882A CN101264882A CNA2008100311382A CN200810031138A CN101264882A CN 101264882 A CN101264882 A CN 101264882A CN A2008100311382 A CNA2008100311382 A CN A2008100311382A CN 200810031138 A CN200810031138 A CN 200810031138A CN 101264882 A CN101264882 A CN 101264882A
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Abstract
The invention relates to a carbon nano-tube preparation method via porous Ni<SUB>3</SUB>Al alloy catalysis, which uses porous Ni<SUB>3</SUB>Al alloy as catalyst; methanol steam is used as carbon source; N<SUB>2</SUB> gas is adopted as carrier gas; the carrier gas passes through the pores of the porous Ni<SUB>3</SUB>Al alloy catalyst under the catalysis temperature of 450 DEG C to 650 DEG C and thus mixture of black chips and catalyst fines is obtained; pure black carbon nano-tube chips are obtained after being filtered and dried. The carbon nano-tube preparation method has the advantages that the utilization rate of the carbon source gas is high, the production efficiency is high, the catalyst content contained in the prepared carbon nano-tubes is low and the production cost is low, applicable for industrial production and capable of replacing the prior production technique of carbon nano-tubes.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nanotube, be meant a kind of employing porous Ni especially
3The Al alloy as catalyst prepares the method for carbon nanotube.
Background technology
Since Japanese scientist S.Iijima 1991 find carbon nanometer tubes since, worldwide started the upsurge of one research carbon nanotube.Carbon nanometer tube is owing to have very high mechanical property (Young's modulus can reach 1TPa, and tensile strength can reach 100GPa), good thermal conductivity (for adamantine twice) and fabulous electric current current capacity (for 1000 times of the current capacity of copper conductor) has obtained scientists and payes attention to greatly.Adopt carbon nanotube to come the research that material carries out modification (as the carbon nanotube reinforced epoxy) is just being become the focus in investigation of materials field, have very application prospects as the wild phase of matrix material.
Scientists has been developed a variety of methods that prepare carbon nanotube, as catalytic pyrolysis method, arc process, laser evaporation method etc.Wherein catalytic pyrolysis method is acknowledged as the most potential preparation method, and has become one of the research focus in made of carbon nanotubes field owing to be convenient to control and the energy mass production.Catalytic pyrolysis method is meant to be the method that cracking catalyst carbonaceous gas or liquid prepare carbon nanotube to contain transition metal at a certain temperature.In the method, catalyzer mainly is to adopt the product of transition metal oxide behind hydrogen reducing that contains the alloy or the oxide compound of transition metal or be added with other metal and rare earth, i.e. nano transition metal (as Ni, Fe, Co etc.); Carbon source is the hydro carbons carbonaceous gas.Make carbonaceous gas (as organic gass such as ethene, acetylene, CO, methane, propylene) (be generally 600 ~ 1000 ℃) at a certain temperature, under catalyst actions such as nano transition metal Fe, Co or Ni, carry out catalytic decomposition, obtain carbon nanotube with this, in addition, catalytic pyrolysis method also can be used to prepare carbon nano pipe array, and this also is the big advantage of catalytic pyrolysis method with respect to other several preparation methods.
Ni
3The Al alloy often is used to do superalloy, but because it can generate the Ni particle of nanometer under the situation of low oxygen partial pressure, and the Ni particle of nanometer can be used as the growth catalyst that generates carbon nanotube, can be used as a kind of catalystic material of novel preparation CNT (carbon nano-tube).
At present, adopt porous Ni both at home and abroad
3The Al alloy is made report that the catalyst pyrolysis prepares carbon nanotube seldom.D.H.Chun etc. adopt the Ni of as cast condition first
3The rolling laminar Ni that forms of Al
3The Al alloy is carbon source as catalyzer with methyl alcohol, adopts catalytic pyrolysis method to prepare carbon nanotube, but in this research the growing amount of carbon nanotube seldom, only at Ni
3The top layer of Al thin slice has generated a spot of carbon nanotube because its specific surface area is less, and the contact surface of catalyzer and carbon-source gas is also less, and its activity of such catalysts is also lower simultaneously, thereby the amount of the feasible carbon nanotube that generates is also less.Make carbon-source gas to make full use of, waste greatlyyer, can't realize large batch of production, and the too high levels of catalyzer in the carbon nanotube of preparation.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art and the employing porous Ni that catalyst content is low, production cost is low in the carbon nanotube of a kind of carbon-source gas utilization ratio height, production efficiency height, preparation is provided
3The Al alloy as catalyst prepares the method for carbon nanotube.
The present invention---a kind of employing porous Ni
3The Al alloy as catalyst prepares the method for carbon nanotube, comprises the steps:
1, raw material:
Adopting porosity is 40% ~ 90%, and the aperture is the porous Ni of 80 ~ 100um
3The Al alloy is as catalyzer;
Adopt methanol steam as carbon source;
Adopt N
2Gas is as carrier gas;
2, catalysis:
Speed with 1L/min adds methanol steam the carrier gas N that moves with 2 ~ 8L/min speed
2In the gas, at N
2Under the drive of gas, under 450 ℃ ~ 650 ℃ catalytic temperature, pass porous Ni
3The hole of Al alloy catalyst, carbon source gas carries out catalysis, decomposition on the catalyst pores surface, obtains the mixture of broken end of black and catalyst fines;
The catalysis time is 1 ~ 24 hour.
3, pickling: place chloroazotic acid to soak 0.5 ~ 4 hour at the broken end of black carbon nanotube of gained and the mixture of catalyst fines, subsequently after filtration, be drying to obtain the pure broken end of black carbon nanotube.
The present invention on the one hand, utilizes porous Ni owing to adopt above-mentioned starting material and processing method
3The hole of Al alloy, effectively increased the contact area of carbon source and catalyzer, improved the yield of carbon nanotube greatly, the carbon nanotube after catalysis generates and the mass ratio of catalyst themselves can reach 7: 1, compare with the catalytic efficiency (1: 1 ~ 3: 1) of prior art, much higher; In addition, the present invention adopts methyl alcohol as carbon source raw material, compare as carbon source than employing hydro carbons carbonaceous gas in the preparation method of carbon nano-tube with existing, it is low to have raw materials cost, wide material sources, and the methanol steam of complete reaction can not reclaim by the method for condensation and recycle, thereby can further reduce cost, and can effectively prevent the pollution of the environment; Adopt the N that simply obtains easily
2Gas adopts hydrogen to compare with argon gas as carrier gas with technology is arranged, and cost is relatively low; Simultaneously, catalyzer---porous Ni
3The Al intermetallic compound can adopt the preparation of element powders metallurgical technology, and its technology is simple, flow process short, equipment is conventional equipment, and tooling cost can well be controlled, and is easy to realize producing in batches; Compare with the Preparation of Catalyst cost of prior art, obviously reduce.In sum, the present invention---a kind of employing porous Ni
3The Al alloy as catalyst prepares the method for carbon nanotube, has the advantage that catalyst content is low, production cost is low in the carbon nanotube of carbon-source gas utilization ratio height, production efficiency height, preparation, is suitable for suitability for industrialized production, alternative existing carbon nanotube production technique.
Description of drawings
Accompanying drawing is the electromicroscopic photograph of the pure nano-carbon tube of gained after the pickling of the present invention.
Embodiment
Embodiment 1:
Getting porosity is 40%, and the aperture is the Ni of 80um
3Al alloy porous material; Speed with 1L/min adds methanol steam the carrier gas N that moves with 2L/min speed
2In the gas, under 450 ℃ ~ 650 ℃ catalytic temperature, pass porous Ni
3The hole of Al alloy catalyst, catalyzed reaction 1h obtains the material of the broken powder of black; At last the broken powder material of this black is soaked 0.5 ~ 4h in chloroazotic acid, filtration, drying obtain the broken end of ater, and the broken end of black of this moment is detected through X-ray diffraction and is pure carbon nanotube.Adopting the carbon nanotube that this kind technology makes and the mass ratio of original catalyst is 1: 1.
Embodiment 2:
Getting porosity is 65%, and the aperture is the Ni of 90um
3Al alloy porous material; Speed with 1L/min adds methanol steam the carrier gas N that moves with 5L/min speed
2In the gas, under 450 ℃ ~ 650 ℃ catalytic temperature, pass porous Ni
3The hole of Al alloy catalyst, catalyzed reaction 12h obtains the material of the broken powder of black; At last the broken powder material of this black is soaked 0.5 ~ 4h in chloroazotic acid, filtration, drying obtain the broken end of ater, and the broken end of black of this moment is detected through X-ray diffraction and is pure carbon nanotube.Adopting the carbon nanotube that this kind technology makes and the mass ratio of original catalyst is 3: 1.
Embodiment 3:
Getting porosity is 90%, and the aperture is the Ni of 100um
3Al alloy porous material; Speed with 1L/min adds methanol steam the carrier gas N that moves with 8L/min speed
2In the gas, under 450 ℃ ~ 650 ℃ catalytic temperature, pass porous Ni
3The hole of Al alloy catalyst, catalyzed reaction 24h obtains the material of the broken powder of black; At last the broken powder material of this black is soaked 0.5 ~ 4h in chloroazotic acid, filtration, drying obtain the broken end of ater, and the broken end of black of this moment is detected through X-ray diffraction and is pure carbon nanotube.Adopting the carbon nanotube that this kind technology makes and the mass ratio of original catalyst is 7: 1.
Claims (1)
1, a kind of employing porous Ni
3The Al alloy as catalyst prepares the method for carbon nanotube, comprises the steps:
1), raw material:
Adopting porosity is 40% ~ 90%, and the aperture is the porous Ni of 80 ~ 100um
3The Al alloy is as catalyzer;
Adopt methanol steam as carbon source;
Adopt N
2Gas is as carrier gas;
2), catalysis:
Speed with 1L/min adds methanol steam the carrier gas N that moves with 2 ~ 8L/min speed
2In the gas, at N
2Under the drive of gas, under 450 ℃ ~ 650 ℃ catalytic temperature, pass porous Ni
3The hole of Al alloy catalyst, carbon source gas carries out catalysis, decomposition on the catalyst pores surface, obtains the mixture of broken end of black and catalyst fines;
The catalysis time is 1 ~ 24 hour.
3), pickling: place chloroazotic acid to soak 0.5 ~ 4 hour at the broken end of black carbon nanotube of gained and the mixture of catalyst fines, subsequently after filtration, be drying to obtain the pure broken end of black carbon nanotube.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100311382A CN101264882B (en) | 2008-04-24 | 2008-04-24 | Method for preparing carbon nano-tube by using porous Ni3Al alloy as catalyst |
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| CN2008100311382A CN101264882B (en) | 2008-04-24 | 2008-04-24 | Method for preparing carbon nano-tube by using porous Ni3Al alloy as catalyst |
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| CN101264882A true CN101264882A (en) | 2008-09-17 |
| CN101264882B CN101264882B (en) | 2010-07-14 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108506388A (en) * | 2018-05-02 | 2018-09-07 | 中南大学 | A kind of low noise high metal army Vehicular friction plate and preparation method thereof |
| CN108757784A (en) * | 2018-05-04 | 2018-11-06 | 中南大学 | A kind of weatherability high metal army Vehicular friction plate and preparation method thereof |
| CN112517009A (en) * | 2020-11-03 | 2021-03-19 | 佛山科学技术学院 | Modified porous copper-nickel alloy plate and preparation method and application thereof |
| CN113102755A (en) * | 2021-04-25 | 2021-07-13 | 中国海洋大学 | Intermetallic compound-carbon nanotube porous composite material and preparation method thereof |
-
2008
- 2008-04-24 CN CN2008100311382A patent/CN101264882B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108506388A (en) * | 2018-05-02 | 2018-09-07 | 中南大学 | A kind of low noise high metal army Vehicular friction plate and preparation method thereof |
| CN108757784A (en) * | 2018-05-04 | 2018-11-06 | 中南大学 | A kind of weatherability high metal army Vehicular friction plate and preparation method thereof |
| CN108757784B (en) * | 2018-05-04 | 2020-10-02 | 中南大学 | Weather-resistant high-metal friction plate for military vehicle and preparation method thereof |
| CN112517009A (en) * | 2020-11-03 | 2021-03-19 | 佛山科学技术学院 | Modified porous copper-nickel alloy plate and preparation method and application thereof |
| CN112517009B (en) * | 2020-11-03 | 2023-05-30 | 佛山科学技术学院 | Modified porous copper-nickel alloy plate and preparation method and application thereof |
| CN113102755A (en) * | 2021-04-25 | 2021-07-13 | 中国海洋大学 | Intermetallic compound-carbon nanotube porous composite material and preparation method thereof |
| CN113102755B (en) * | 2021-04-25 | 2022-04-05 | 中国海洋大学 | Intermetallic compound-carbon nanotube porous composite material and preparation method thereof |
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| CN101264882B (en) | 2010-07-14 |
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Effective date of registration: 20210630 Address after: 337000 Industrial Park B, Lianhua County, Pingxiang City, Jiangxi Province Patentee after: Jiangxi Yongtai Powder Metallurgy Co.,Ltd. Address before: Yuelu District City, Hunan province 410082 Changsha Lushan Road No. 2 Patentee before: CENTRAL SOUTH University |
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