CN1793451A - Process for preparing plate type nano carbon fibre - Google Patents
Process for preparing plate type nano carbon fibre Download PDFInfo
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- CN1793451A CN1793451A CN 200610023181 CN200610023181A CN1793451A CN 1793451 A CN1793451 A CN 1793451A CN 200610023181 CN200610023181 CN 200610023181 CN 200610023181 A CN200610023181 A CN 200610023181A CN 1793451 A CN1793451 A CN 1793451A
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Abstract
The invention discloses plate type nanometer carbon fiber manufacturing method. It includes the following steps: contacting the mixture argon and hydrogen with nanometer ferroferric oxide at 500-700 centigrade degree for 0.5-6h; rate of volume flow of argon and hydrogen is 5:1-1:2; leading carbon resources and heat for 4-24h; the rate of volume flow of carbon resources and hydrogen is 10:1-1:1; cooling to gain. The invention has advantages of simple operation, 5g-95g/gcat specific yield, and low cost. It is easy to realize large-scale production, and can be applied to electrode material and catalyst carrier. Thus its application prospect is very extensive.
Description
Technical field
The present invention relates to the preparation method of carbon nano-fiber, especially prepare the method for carbon nanofibers.
Background technology
Carbon nano-fiber is a kind one-dimensional nano material that just begins to have purpose synthetic after nineteen nineties, carbon nano-fiber is except that performances such as the characteristic with common gas-phase growth of carbon fibre such as low-density, high ratio modulus, high specific strength, high conductivity, also have specific area big, conduct electricity very well, advantage such as micro-structural is adjustable, be expected as catalyst carrier, lithium rechargeable battery anode, electrode for capacitors, high-efficiency adsorbent, structural reinforcement material etc., therefore become the research focus in recent years.
Its diameter of carbon nano-fiber is roughly between 50～400nm, belong to same class material with multiple-wall carbon nanotube in essence, be relative multiple-wall carbon nanotube, wall thickness and diameter are bigger, mainly are the fibrous carbon materials that is formed by the orderly stacked arrangement of certain direction by graphene film.The stacked direction of its graphene film can parallel with fibre axis (tubular type carbon nano-fiber or multiple-wall carbon nanotube), vertical (carbon nanofibers), or have a certain degree (herring-bone form carbon nano-fiber).Process conditions that can be by control carbon nano-fiber preparation process such as catalyst composition, structure, carbon source, growth temperature wait the carbon nano-fiber that obtains different micro-structurals.
Produce carbon nano-fiber and can pass through arc process (Iijima S Nature, 352 (1991) 56), laser method Science such as (, 273 (1996) 483) Thess A, catalytic decomposition method Carbon such as (, 27 (1989) 315) Baker RTK etc.But present most promising industrial method is the method for gas phase catalysis pyrolysis carbon compound, the chemical vapour deposition technique that just is widely used, this method uses iron, cobalt, nickel or its mixture to be catalyst, catalytic cracking of hydrocarbon or carbon monoxide under nitrogen atmosphere, and make carbon be deposited on the catalyst granules surface to obtain carbon nano-fiber.
Carbon nano-fiber is applied in catalytic field, existing many reports.Because the high-graphitized and high-specific surface area of carbon nano-fiber, there is strong interaction between the graphene film edge that the metallic crystal of load and itself expose on the carbon nano-fiber simultaneously, the pattern characteristic of the reactive metal of load be may change, special activity and selectivity formed.Simultaneously, when adopting different micro-structurals such as tubular type, fish-bone or board-like carbon nano-fiber, catalytic performance also there is appreciable impact.(J.Phys.Chem.B 102 (1998) in Rodriguez research group, 5168) to the carbon nano-fiber load different activities metal of different shape and micro-structural, respectively to ethene, the 1-butylene, 1, reactivity and selectivity have been investigated in 3-butadiene hydrogenation reaction, and compare with the carrier loaded catalyst of routine.The result shows, is that its activity of catalyst and all more conventional carried catalyst of selectivity of carrier has bigger variation with the carbon nano-fiber, and the catalyst activity after the carbon fiber surface load of different micro-structurals shows different behaviors in different reaction systems.(the J.Phys.Chem.B of Baker research group; 105 (2001); 11994) studied that load rhodium Rh carries out the ethene formylated on the carbon nano-fiber of different micro-structurals; wherein the carbon fiber of " stratiform " form provides higher selectivity than the carbon fiber of " board-like " and " herring-bone form ".The inventor (Zhou Jinghong etc., petrochemical industry, 33 (2004) 987) is to carbon nano-fiber loaded palladium catalyst studies show that in terephthalic acid (TPA) hydrofinishing of different micro-structurals, and carbon nanofibers supported palladium catalyst activity is the highest.
At present more about the preparation and the application study of tubular type carbon nano-fiber and herring-bone form carbon nano-fiber in the world, domestic also existing more relevant patent, as " a kind of method for preparing the herring-bone form carbon nano-fiber " (Chinese patent, application number: 02136034.0), " a kind of method for preparing carbon fiber and CNT (carbon nano-tube) " (Chinese patent, application number: 03110850.4) or the like, but do not see the patent that relevant carbon nanofibers prepares as yet.Therefore, the preparation method of a kind of relevant carbon nanofibers of developmental research will be to make us the very problem of concern.
Summary of the invention
It is simple relatively to the purpose of this invention is to provide a kind of operation, the output height, and the new method of low-cost preparation carbon nanofibers is to satisfy the needs of relevant field development.
Method of the present invention comprises the steps:
The mixture of argon gas and hydrogen is contacted with catalyst, carry out the reduction of catalyst, temperature is 500～700 ℃, and preferred 550～650 ℃, the recovery time is 0.5～6 hour, and the flow of the mixture of argon gas and hydrogen is: 8～80m
3/ hour. the kilogram catalyst is the argon gas of benchmark and the mixture flow rate of hydrogen with the per kilogram catalyst promptly, and the volume ratio of argon gas and hydrogen is 5: 1～1: 2, is preferably 4: 1～3: 1;
According to optimized technical scheme of the present invention, when the mixture of argon gas and hydrogen contacts with catalyst, be warming up to 500～700 ℃ with the speed of 2～4 ℃/min;
Said catalyst is the ferriferrous oxide nano powder, average grain diameter 5～15nm;
Import carbon source insulation 4～24 hours then, the volume ratio of carbon source and hydrogen is 10: 1～1: 1, is preferably 4: 1～3: 1, and the flow of carbon source and hydrogen is: 6～60m
3/ hour. the kilogram catalyst, cooling promptly gets carbon nanofibers, can feed argon gas and cool off;
Said carbon source is a carbon monoxide.
Method of the present invention has following characteristics:
The technology of preparation carbon nano-fiber provided by the invention, its micro-structural of the carbon fiber that obtains is board-like, the graphene film of promptly forming carbon fiber is axial vertical with fiber, compare with other tubular type carbon nano-fiber and fish-bone carbon nano-fiber that adopts chemical vapour deposition technique to prepare, have bigger specific area and graphite marginal texture, can be up to 270m
2/ g.
Technology of the present invention is simple.The present invention is the new method that combines matrix method and mobile catalysis method, with the nano ferriferrous oxide granule of uniform grading as catalyst, pass to after hydrogen and argon gas suitably reduce, feed hydrogen and carbon monoxide as growth promoter and carbon source, can prepare the very high carbon nanofibers of degree of graphitization at a lower temperature.
The output height of carbon nanofibers.The present invention adopts nano ferriferrous oxide granule as catalyst, cost is lower, the productive rate height, productive rate can be up to the 95g/g catalyst under the preparation process condition optimizing, be easy to large-scale preparation, be the preparation method who has the commercial Application potentiality, have broad application prospects, in particular for catalyst carrier and electrode material.
Description of drawings
Fig. 1 is ESEM (SEM) photo of the carbon nanofibers that makes with the inventive method.
Fig. 2 is high-resolution-ration transmission electric-lens (HRTEM) photo of the carbon nanofibers that makes with the inventive method.
Fig. 3 is X-ray diffraction (XRD) collection of illustrative plates of the carbon nanofibers that makes with the inventive method.
Embodiment 1
1.0g the ferriferrous oxide nano powder, average grain diameter 5nm is tiled in the quartz boat, and this quartz boat places reactor middle part constant temperature zone.At Ar: H
2=120: program is warming up to 600 ℃ in the mixed airflow of 40mL/min, and keeps 3 hours.Then gas is switched to reacting gas, CO: H
2=80: 20mL/min, temperature of reactor continue to keep 600 ℃, and growth course continues to switch to the argon gas of 80mL/min after 16 hours, stops heating, makes reactor naturally cool to room temperature, obtains black powder shape product 14.2g.The black powder shape product that obtains is carried out ESEM and high-resolution transmission electron microscope observing respectively, see Fig. 1 and Fig. 2.
The black powder product that obtains as seen from Figure 1 is that diameter is the carbon nano-fiber of 50～200nm, shows that through elementary analysis wherein the content of carbon surpasses 95%, and its XRD figure spectrum (as shown in Figure 3) shows that its degree of graphitization is very high.The high resolution electron microscopy photo of Fig. 2 can clearly be observed the axial vertical of graphene film and carbon fiber, and what promptly prepare is carbon nanofibers.
Embodiment 2
1.0g the ferriferrous oxide nano powder, average grain diameter 15nm is tiled in the quartz boat, and this quartz boat places reactor middle part constant temperature zone, and this reactor is compared with the reactor among the embodiment 1, and diameter is the former twice, and the area of quartz boat also increases 2 times.At Ar: H
2=1000: the speed with 3 ℃/min in the mixed airflow of 200mL/min is warming up to 400 ℃, and keeps 2 hours, is warming up to 600 ℃ with 2 ℃/min then and keeps 0.5 hour, then gas is switched to reacting gas, CO: H
2=800: 200mL/min, temperature of reactor keeps 570 ℃, and growth course continues to switch to the argon gas of 800mL/min after 24 hours, makes reactor naturally cool to room temperature, obtains black powder shape product 95g.
Claims (6)
1. a method for preparing carbon nanofibers is characterized in that, comprises the steps:
The mixture of argon gas and hydrogen is contacted with the nano ferriferrous oxide catalyst, and temperature is 500～700 ℃, and the time is 0.5～6 hour, and the flow of the mixture of argon gas and hydrogen is: 8～80m
3/ hour. the kilogram catalyst, the volume ratio of argon gas and hydrogen is 5: 1～1: 2;
Import carbon source insulation 4～24 hours then, the volume ratio of carbon source and hydrogen is 10: 1～1: 1, and the flow of carbon source and hydrogen mixture is: 6～60m
3/ hour. the kilogram catalyst, cooling promptly gets carbon nanofibers.
2. method according to claim 1 is characterized in that, the mixture of argon gas and hydrogen contacts with catalyst, and temperature is 550～650 ℃.
3. method according to claim 1 is characterized in that, the volume flow ratio of argon gas and hydrogen is 4: 1～3: 1.
4. method according to claim 1 is characterized in that, said catalyst is the ferriferrous oxide nano powder, and average grain diameter is 5～15nm.
5. method according to claim 1 is characterized in that, said carbon source is CO, and the volume flow ratio of CO and hydrogen is 4: 1～3: 1.
6. method according to claim 1 is characterized in that, its graphene film of the carbon nano-fiber that obtains and fiber axis are to vertical.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101912792A (en) * | 2010-08-06 | 2010-12-15 | 华东理工大学 | Catalyst used in preparation of COx-free hydrogen through ammonia decomposition reaction and preparation method thereof |
| CN102026916A (en) * | 2008-02-05 | 2011-04-20 | 普林斯顿大学理事会 | Functionalized graphene sheets having high carbon to oxygen ratios |
| CN102149632A (en) * | 2008-09-09 | 2011-08-10 | 巴特尔纪念研究院 | Mesoporous metal oxide graphene nanocomposite materials |
| CN101550003B (en) * | 2009-04-22 | 2012-10-03 | 湖南大学 | Nano-graphite alkenyl composite wave-absorbing material and method of preparing the same |
| US8450014B2 (en) | 2008-07-28 | 2013-05-28 | Battelle Memorial Institute | Lithium ion batteries with titania/graphene anodes |
| US8557441B2 (en) | 2010-10-09 | 2013-10-15 | Battelle Memorial Institute | Titania-graphene anode electrode paper |
| US8557442B2 (en) | 2008-07-28 | 2013-10-15 | Battelle Memorial Institute | Nanocomposite of graphene and metal oxide materials |
| US8563169B2 (en) | 2009-08-10 | 2013-10-22 | Battelle Memorial Institute | Self assembled multi-layer nanocomposite of graphene and metal oxide materials |
| US8835046B2 (en) | 2009-08-10 | 2014-09-16 | Battelle Memorial Institute | Self assembled multi-layer nanocomposite of graphene and metal oxide materials |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004107118A (en) * | 2002-09-17 | 2004-04-08 | Ulvac Japan Ltd | Method for manufacturing graphite nano-fiber, electron emitting source and display element |
| CN1193931C (en) * | 2003-06-09 | 2005-03-23 | 清华大学 | Synthesis of double walled carbon nano-tubes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102026916A (en) * | 2008-02-05 | 2011-04-20 | 普林斯顿大学理事会 | Functionalized graphene sheets having high carbon to oxygen ratios |
| US10017632B2 (en) | 2008-02-05 | 2018-07-10 | The Trustees Of Princeton University | Functionalized graphene sheets having high carbon to oxygen ratios |
| US9546092B2 (en) | 2008-02-05 | 2017-01-17 | The Trustees Of Princeton University | Functionalized graphene sheets having high carbon to oxygen ratios |
| CN102026916B (en) * | 2008-02-05 | 2014-07-16 | 普林斯顿大学理事会 | Functionalized graphene sheets having high carbon to oxygen ratios |
| US9070942B2 (en) | 2008-07-28 | 2015-06-30 | Battelle Memorial Institute | Nanocomposite of graphene and metal oxide materials |
| US8450014B2 (en) | 2008-07-28 | 2013-05-28 | Battelle Memorial Institute | Lithium ion batteries with titania/graphene anodes |
| US8557442B2 (en) | 2008-07-28 | 2013-10-15 | Battelle Memorial Institute | Nanocomposite of graphene and metal oxide materials |
| CN102149632A (en) * | 2008-09-09 | 2011-08-10 | 巴特尔纪念研究院 | Mesoporous metal oxide graphene nanocomposite materials |
| US9346680B2 (en) | 2008-09-09 | 2016-05-24 | Battelle Memorial Institute | Mesoporous metal oxide graphene nanocomposite materials |
| CN102149632B (en) * | 2008-09-09 | 2014-08-13 | 巴特尔纪念研究院 | Mesoporous metal oxide graphene nanocomposite materials |
| CN101550003B (en) * | 2009-04-22 | 2012-10-03 | 湖南大学 | Nano-graphite alkenyl composite wave-absorbing material and method of preparing the same |
| US9017867B2 (en) | 2009-08-10 | 2015-04-28 | Battelle Memorial Institute | Self assembled multi-layer nanocomposite of graphene and metal oxide materials |
| US8835046B2 (en) | 2009-08-10 | 2014-09-16 | Battelle Memorial Institute | Self assembled multi-layer nanocomposite of graphene and metal oxide materials |
| US8563169B2 (en) | 2009-08-10 | 2013-10-22 | Battelle Memorial Institute | Self assembled multi-layer nanocomposite of graphene and metal oxide materials |
| CN101912792A (en) * | 2010-08-06 | 2010-12-15 | 华东理工大学 | Catalyst used in preparation of COx-free hydrogen through ammonia decomposition reaction and preparation method thereof |
| CN101912792B (en) * | 2010-08-06 | 2013-03-06 | 华东理工大学 | Catalyst used in preparation of COx-free hydrogen through ammonia decomposition reaction and preparation method thereof |
| US9040200B2 (en) | 2010-10-09 | 2015-05-26 | Battelle Memorial Institute | Titania-graphene anode electrode paper |
| US8557441B2 (en) | 2010-10-09 | 2013-10-15 | Battelle Memorial Institute | Titania-graphene anode electrode paper |
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