CN1696052A - Method for preparing Nano carbon tubes - Google Patents
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- CN1696052A CN1696052A CN 200410018203 CN200410018203A CN1696052A CN 1696052 A CN1696052 A CN 1696052A CN 200410018203 CN200410018203 CN 200410018203 CN 200410018203 A CN200410018203 A CN 200410018203A CN 1696052 A CN1696052 A CN 1696052A
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Abstract
A process for preparing carbon nanotubes by chemical vapor deposition method features that the metallic catalyst (Fe, Co, or Ni) is carried by SiO2 as carrier, and the acetylene, propene, or methane is used as carbon source.
Description
Technical field
The invention belongs to the synthetic field of inorganic functional material, more specifically to the Preparation of catalysts method and at high temperature be that raw material (methane, ethene or propylene etc.) cracking prepares the method for carbon nanotube with the carbon-source gas.
Background technology
Since Japanese scientist Iijiam in 1991 finds carbon nanotube (CNTs), owing to it has the very big concern that peculiar physics, chemical property and good application prospects have caused the various countries scientific and technical personnel.The scientists prediction, carbon nanotube will become the most promising monodimension nanometer material of 21 century.Carbon nanotube is the cylindrical structural of the sexangle lattice that forms based on carbon atom, and what have single layer structure is called Single Walled Carbon Nanotube (SWNT), and what have multilayered structure is called multi-walled carbon nano-tubes (MWNTs).Theoretical prediction and experimental studies have found that carbon nanotube has very peculiar electrical properties, closely related with its structure, can be used for making nano electron devices such as transistor.Carbon nanotube is a kind of good thermally conductive material, relies on the ultrasonic wave transferring heat energy.Carbon nanotube has very high intensity and toughness, and the Young's modulus of elasticity of carbon nanotube reaches as high as 3.7Tpa, and the density of carbon nanotube only is 1/7 of steel, but its tensile strength is 100 times of steel.Carbon nanotube has very big specific surface area, is the ideal hydrogen storage material.In addition, carbon nanotube acid and alkali-resistance, high temperature resistant, but the materialization of can deriving because of having good physical strength and excellent electroconductibility, therefore can be used to prepare matrix material, chemical sensing material and artificial-muscle again.
Carbon nanotube is since being found, and its preparation technology has obtained broad research.Now existing multiple preparation method is as arc discharge method, laser ablation, electrolysis, cryogenic solid cracking, hydrocarbon oxidation catalyst decomposition or chemical Vapor deposition process etc.Wherein, chemical Vapor deposition process is present a kind of comparatively widely method for preparing carbon nanotube.Generally select for use Fe, Co, Ni and alloy thereof as catalyzer, clay, silicon-dioxide, diatomite, aluminum oxide and magnesium oxide etc. are as carrier, acetylene, propylene and methane etc. are as carbon source, hydrogen, nitrogen, helium, argon gas or ammonia are as carrier gas, in 530 ℃～1130 ℃ scopes, the free carbon ion that the hydrocarbon polymer cracking produces can generate single wall or multi-walled carbon nano-tubes under catalyst action.Its required equipment is all relative with processing condition simple, is applicable to the mass preparation of carbon nanotube.But its size is uneven, different in size, defectiveness, and its key is catalytic preparation and dispersion.Contain impurity such as a large amount of amorphous carbons, nanocarbon particle and catalyst particle in the thick product of unordered, the nondirectional multi-walled carbon nano-tubes of preparation at present, there is more crystal defect, be difficult for disperseing, usually bend and be out of shape, degree of graphitization is relatively poor, and these shortcomings have bad influence to the mechanical property and the physical and chemical performance of carbon nanotube.In the preparation technology of carbon nanotube, the composition of catalyzer, the kind of unstripped gas, temperature of reaction etc. all influence output, quality and the microtexture of carbon nanotube to some extent.Therefore, develop a kind of carbon nanotube output height, quality is good, result of use is good preparation method has become in the development of hydro carbons catalytic decomposition method needs one of gordian technique that solves.
Summary of the invention
The objective of the invention is to propose a kind of with low cost, simple, the quality of carbon nanotube is good, the preparation method that output is high.
Technical scheme is as follows:
Select for use Fe, Co, Ni and alloy thereof as catalyzer, clay, silicon-dioxide, diatomite, aluminum oxide and magnesium oxide etc. are as carrier, acetylene, propylene and methane etc. are as carbon source, hydrogen, nitrogen, helium, argon gas or ammonia are as carrier gas, in 530 ℃～1130 ℃ scopes, the free carbon ion that the hydrocarbon polymer cracking produces can generate single wall or multi-walled carbon nano-tubes under catalyst action;
(1) prepares catalyzer with sol-gel method: silicon ester (AR), ethanol ((AR) and (0.5-2M) nitrate (AR) aqueous solution mix with 1: 1: 1 (volume ratio), stir, add several acid or alkali as a catalyst then and accelerate hydrolysis reaction, promote the formation of gel; Dry under 40～60 ℃ constant temperature wet gel, obtain xerogel; Then xerogel is ground to form particle as catalyzer;
(2) prepared powder catalyst is tiled on the quartz boat; put into the flat-temperature zone of tubular oven; under nitrogen protection, be warming up to 400～800 ℃, fed hydrogen 20～40 minutes; reducing catalyst; be heated to 600～1000 ℃ then, feed acetylene, reacted 30～120 minutes; under the atmosphere of nitrogen, be cooled to normal temperature, promptly prepared carbon nanotube.
Described silicon ester is methyl silicate Si (OCH
3)
4(TMOS) or tetraethoxy Si (OC
2H
5)
4(TEOS).
Described nitrate is iron nitrate, Xiao Suangu and nickelous nitrate.
Described acid catalyst is a protonic acid, and alkaline catalysts is the buffered soln of ammoniacal liquor or ammoniacal liquor and Neutral ammonium fluoride.
It is simple, easy to operate to utilize experimental technique of the present invention to prepare the process of carbon nanotube, and cost is lower, and productive rate is big; Made the carbon nanotube of a large amount of uniform diameter, internal diameter 5～20nm, external diameter is at 20～50nm.
Adopt the foreign matter content in the carbon nano tube products of this law preparation few, the degree of graphitization height, the caliber of carbon nanotube is more even, surperficial smoother, the carbon nanotube after purified can directly be used for developing matrix material or as gas storage material.
Description of drawings
Fig. 1 is a transmission electron microscope photo of implementing the carbon nanotube of employing the present invention preparation;
Fig. 2 is a stereoscan photograph of implementing the carbon nanotube of employing the present invention preparation;
Fig. 3 is a transmission electron microscope photo of implementing the carbon nanotube of four employing the present invention preparations;
Fig. 4 is a local transmission electron microscope photo of implementing the carbon nanotube of four employing the present invention preparations.
Embodiment
Content of the present invention is further elaborated by following embodiment and accompanying drawing, but does not limit the scope of the invention.
Embodiment one
2M iron nitrate 10ml (AR) mixes with tetraethoxy (AR) 10ml and ethanol (AR) 10ml, and fully stir about is 30 minutes.Slowly add the hydrofluoric acid (AR) of about 0.3ml then, further stir.Make wet gel, wet gel was descended dry 7 days 60 ℃ of constant temperature, grind to form single-size as catalyzer.Powder catalyst 100mg is tiled on the quartz boat, be put in the flat-temperature zone of tube furnace, (flow is 500ml/min) is warmed up to 400 ℃ under nitrogen atmosphere, feeds hydrogen, and flow is 300ml/min, reductase 12 5min, be warming up to 600 ℃, feed acetylene, flow is 50ml/min, reaction 60min cools off under the atmosphere of nitrogen.Promptly prepared carbon nanotube, the product production that obtains is 133mg.
Embodiment two
Identical with step with embodiment one other conditions, the temperature of reaction that changes acetylene is 800 ℃, and the output that obtains carbon nanotube is 156mg.
Embodiment three
Identical with step with embodiment one other conditions, the temperature of reaction that changes acetylene is 1000 ℃, and the output of the carbon nanotube that obtains is 189mg.
Embodiment four
Identical with step with embodiment one other conditions, changing the hydrogen reaction temperature is 750 ℃, and the time that acetylene feeds is 30min.The output of the carbon nanotube that obtains is 76.6mg.
Embodiment five
Identical with step with embodiment one other conditions, the flow that changes hydrogen is 100ml/min.The output of the carbon nanotube that obtains is 162mg.
Embodiment six
Identical with step with embodiment one other conditions, the flow that changes hydrogen is 100ml/min, and the temperature that acetylene feeds is 800 ℃.The output of the carbon nanotube that obtains is 171.1mg.
Embodiment seven
Identical with embodiment one other conditions with step, adopt 0.5M iron nitrate 10ml (AR) to mix with tetraethoxy (AR) 10ml ethanol (AR) 10ml.The output that obtains carbon nanotube is 156mg.
Embodiment eight
Identical with embodiment one other conditions with step, adopt 0.5M Xiao Suangu 10ml (AR) to prepare catalyzer, the output of the carbon nanotube that obtains is 178.5mg.
Claims (4)
1. method for preparing carbon nanotube, select for use Fe, Co, Ni and alloy thereof as catalyzer, clay, silicon-dioxide, diatomite, aluminum oxide and magnesium oxide etc. are as carrier, acetylene, propylene and methane etc. are as carbon source, hydrogen, nitrogen, helium, argon gas or ammonia are as carrier gas, in 530 ℃～1130 ℃ scopes, the free carbon ion that the hydrocarbon polymer cracking produces can generate single wall or multi-walled carbon nano-tubes under catalyst action; It is characterized in that:
(1) prepares catalyzer with sol-gel method: silicon ester (AR), ethanol ((AR) and (0.5-2M) nitrate (AR) aqueous solution mix with 1: 1: 1 (volume ratio), stir, add several acid or alkali as a catalyst then and accelerate hydrolysis reaction, promote the formation of gel; Dry under 40～60 ℃ constant temperature wet gel, obtain xerogel; Then xerogel is ground to form particle as catalyzer;
(2) prepared powder catalyst is tiled on the quartz boat; put into the flat-temperature zone of tubular oven; under nitrogen protection, be warming up to 400～800 ℃, fed hydrogen 20～40 minutes; reducing catalyst; be heated to 600～1000 ℃ then, feed acetylene, reacted 30～120 minutes; under the atmosphere of nitrogen, be cooled to normal temperature, promptly prepared carbon nanotube.
2. the method for preparing carbon nanotube as claimed in claim 1 is characterized in that described silicon ester is methyl silicate Si (OCH
3)
4(TMOS) or tetraethoxy Si (OC
2H
5)
4(TEOS).
3. the method for preparing carbon nanotube as claimed in claim 1 is characterized in that described nitrate is iron nitrate, Xiao Suangu and nickelous nitrate.
4. the method for preparing carbon nanotube as claimed in claim 1 is characterized in that described acid catalyst is a protonic acid, and alkaline catalysts is the buffered soln of ammoniacal liquor or ammoniacal liquor and Neutral ammonium fluoride.
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Cited By (25)
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| CN100402420C (en) * | 2006-09-18 | 2008-07-16 | 北京大学 | Preparation method of reducing single-wall carbon nano-tube |
| CN100411742C (en) * | 2006-10-26 | 2008-08-20 | 上海交通大学 | Mechanically shearing process of preparing one-dimensional nanometer material |
| CN100443402C (en) * | 2006-01-26 | 2008-12-17 | 上海交通大学 | Chemical shearing method for preparing high dispersion short carbon nanometer tube |
| CN101437755B (en) * | 2006-04-24 | 2011-04-20 | 独立行政法人产业技术综合研究所 | Single-walled carbon nanotube, carbon fiber aggregate containing the single-walled carbon nanotube, and method for production of the single-walled carbon nanotube or the carbon fiber aggregate |
| CN102161481A (en) * | 2011-05-18 | 2011-08-24 | 浙江大学 | Preparation method for synthesizing carbon nanotubes in quantity and with low cost |
| CN102249216A (en) * | 2011-06-10 | 2011-11-23 | 电子科技大学 | Method for affecting growth morphology of carbon nanotubes by controlling hydrolysis degree |
| WO2012174679A1 (en) * | 2011-06-23 | 2012-12-27 | 山东大展纳米材料有限公司 | Preparation method of nano carbon material by using clay catalytic material |
| WO2014071693A1 (en) * | 2012-11-08 | 2014-05-15 | 北京大学 | Single-walled carbon nanotube positioning and growing method |
| CN103803522A (en) * | 2012-11-08 | 2014-05-21 | 北京大学 | Preparation method of semiconductor single-walled carbon nanotubes |
| CN103935993A (en) * | 2014-04-25 | 2014-07-23 | 南京邮电大学 | Method for improving graphitization degree of carbon nano tube |
| CN105152129A (en) * | 2015-09-23 | 2015-12-16 | 厦门理工学院 | Method for preparing tungsten-carbon nano composite particle material |
| CN105543804A (en) * | 2015-12-23 | 2016-05-04 | 北京控制工程研究所 | Uniformity control method for growing carbon nano tubes in titanium alloy shading cover |
| CN106435210A (en) * | 2016-09-27 | 2017-02-22 | 宁波大地化工环保有限公司 | Preparation method of trapping agent special for precious metal |
| CN106517146A (en) * | 2016-11-11 | 2017-03-22 | 苏州赛福德备贸易有限公司 | Method for preparing composite nanocarbon material |
| CN107570160A (en) * | 2017-10-18 | 2018-01-12 | 哈尔滨金纳科技有限公司 | A kind of medical stone is method for preparing catalyst, catalyst and the application that carrier is used for CNT production |
| CN107601458A (en) * | 2017-09-12 | 2018-01-19 | 刘云芳 | A kind of preparation method of single-walled carbon nanotube |
| CN108654961A (en) * | 2018-05-16 | 2018-10-16 | 安徽三环水泵有限责任公司 | A kind of method for repairing and mending of flow passage component of slurry pump |
| CN110422838A (en) * | 2019-09-11 | 2019-11-08 | 广州方中化工有限公司 | A kind of preparation of carbon nanotube and separation method |
| CN110479310A (en) * | 2019-09-04 | 2019-11-22 | 西南石油大学 | The preparation and application of supported sulfided Co catalysts for selectivity synthesis carbon nanotube |
| CN111362253A (en) * | 2020-03-13 | 2020-07-03 | 内蒙古骏成新能源科技有限公司 | Carbon nano tube prepared by catalytic cracking of hydrocarbon by gas-phase damping method, device and method |
| CN112290021A (en) * | 2020-09-28 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Preparation method of carbon nano tube conductive agent for lithium ion battery |
| CN112850688A (en) * | 2021-02-03 | 2021-05-28 | 成都市丽睿科技有限公司 | Preparation method of nanoscale carbon material |
| CN113644267A (en) * | 2021-08-03 | 2021-11-12 | 西北工业大学 | Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof |
| CN115532268A (en) * | 2022-09-24 | 2022-12-30 | 山东碳峰新材料科技有限公司 | Preparation and application of iron-based carbon nanotube catalyst |
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| JP4404961B2 (en) * | 2002-01-08 | 2010-01-27 | 双葉電子工業株式会社 | A method for producing carbon nanofibers. |
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| CN100443402C (en) * | 2006-01-26 | 2008-12-17 | 上海交通大学 | Chemical shearing method for preparing high dispersion short carbon nanometer tube |
| CN101437755B (en) * | 2006-04-24 | 2011-04-20 | 独立行政法人产业技术综合研究所 | Single-walled carbon nanotube, carbon fiber aggregate containing the single-walled carbon nanotube, and method for production of the single-walled carbon nanotube or the carbon fiber aggregate |
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| CN100411742C (en) * | 2006-10-26 | 2008-08-20 | 上海交通大学 | Mechanically shearing process of preparing one-dimensional nanometer material |
| CN102161481B (en) * | 2011-05-18 | 2012-11-28 | 浙江大学 | Preparation method for synthesizing carbon nanotubes in quantity and with low cost |
| CN102161481A (en) * | 2011-05-18 | 2011-08-24 | 浙江大学 | Preparation method for synthesizing carbon nanotubes in quantity and with low cost |
| CN102249216A (en) * | 2011-06-10 | 2011-11-23 | 电子科技大学 | Method for affecting growth morphology of carbon nanotubes by controlling hydrolysis degree |
| WO2012174679A1 (en) * | 2011-06-23 | 2012-12-27 | 山东大展纳米材料有限公司 | Preparation method of nano carbon material by using clay catalytic material |
| WO2014071693A1 (en) * | 2012-11-08 | 2014-05-15 | 北京大学 | Single-walled carbon nanotube positioning and growing method |
| CN103803522A (en) * | 2012-11-08 | 2014-05-21 | 北京大学 | Preparation method of semiconductor single-walled carbon nanotubes |
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| CN105543804B (en) * | 2015-12-23 | 2017-11-28 | 北京控制工程研究所 | A kind of uniformity control method in titanium alloy light shield growth inside CNT |
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| CN111362253A (en) * | 2020-03-13 | 2020-07-03 | 内蒙古骏成新能源科技有限公司 | Carbon nano tube prepared by catalytic cracking of hydrocarbon by gas-phase damping method, device and method |
| CN111362253B (en) * | 2020-03-13 | 2021-09-21 | 成都科汇机电技术有限公司 | Carbon nano tube prepared by catalytic cracking of hydrocarbon by gas-phase damping method, device and method |
| CN112290021A (en) * | 2020-09-28 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Preparation method of carbon nano tube conductive agent for lithium ion battery |
| CN112290021B (en) * | 2020-09-28 | 2022-09-06 | 合肥国轩高科动力能源有限公司 | Preparation method of carbon nano tube conductive agent for lithium ion battery |
| CN112850688A (en) * | 2021-02-03 | 2021-05-28 | 成都市丽睿科技有限公司 | Preparation method of nanoscale carbon material |
| CN113644267A (en) * | 2021-08-03 | 2021-11-12 | 西北工业大学 | Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof |
| CN113644267B (en) * | 2021-08-03 | 2023-09-29 | 西北工业大学 | Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof |
| CN115532268A (en) * | 2022-09-24 | 2022-12-30 | 山东碳峰新材料科技有限公司 | Preparation and application of iron-based carbon nanotube catalyst |
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