CN100447076C - Method of preparing multi-wall carbon nano-tube from coal - Google Patents
Method of preparing multi-wall carbon nano-tube from coal Download PDFInfo
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- CN100447076C CN100447076C CNB2007100985499A CN200710098549A CN100447076C CN 100447076 C CN100447076 C CN 100447076C CN B2007100985499 A CNB2007100985499 A CN B2007100985499A CN 200710098549 A CN200710098549 A CN 200710098549A CN 100447076 C CN100447076 C CN 100447076C
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Abstract
This invention relates to a method for preparing multi-wall carbon nm tubes with coal as the raw material, which applies a chemical gaseous phase deposition method to prepare them by pyrogenating coal powder mixed with a catalyst under high temperature to get multi-wall carbon nm tubes with uniform-distributed walls and productivity at gram level/h.
Description
Technical field
The present invention relates to a kind of method for preparing multi-walled carbon nano-tubes, particularly relating to the cleaned coal is the method for feedstock production multi-walled carbon nano-tubes.
Background technology
Since 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.Through the high resolving power microtechnique observation of carbon nanotube is found that carbon nanotube has the cylindrical structural of the sexangle lattice that forms based on carbon atom.What have multilayered structure is called multi-walled carbon nano-tubes (Multi-walled carbonnanotubes abbreviates MWNTs as), and the caliber of MWNTs is generally 20～200nm.A large amount of studies show that, MWNTs has great application prospect at aspects such as electron device, an emission, hydrogen storage material, reinforced composite and support of the catalyst.
Up to the present, the preparation method of MWNTs is broadly divided into three classes: arc process, laser evaporation method and chemical Vapor deposition process.Wherein, chemical Vapor deposition process has can prepare the advantage of carbon nanotube on a large scale continuously, thereby is subjected to domestic and international investigator's favor.At present, chemical Vapor deposition process is the feedstock production carbon nanotube with hydrocarbon gas such as methane, ethene, benzene mainly, causes the cost of carbon nanotube high.With material preparation carbon nanotube cheap and easy to get is to reduce one of its cost techniques approach.
Rich coal resources in China, low price contain the macromole weak bond and as the mineral substance of catalyzer etc., these characteristics have determined coal to can be used as the carbon source material of preparation carbon nanotube.In early 1990s, Pang etc. have synthesized soccerballene with coke, and this is to prepare carbon nanomaterial with coal as carbon source first.Afterwards, a large amount of bibliographical informations prepare carbon nanotube with coal or coke, mainly adopt arc process.And be carbon source with the coal, the open both at home and abroad report and the document that adopt chemical Vapor deposition process to prepare carbon nanotube still do not have.
Summary of the invention
The object of the present invention is to provide a kind of is the method for feedstock production multi-walled carbon nano-tubes with the coal.This method is is raw material with the coal, simply adopt chemical Vapor deposition process to prepare multi-walled carbon nano-tubes in a large number, and preparation process is to realize by the coal dust that pyrolysis at high temperature is mixed with catalyzer.
Above-mentioned purpose of the present invention reaches by the following technical programs:
A kind of is the method for feedstock production multi-walled carbon nano-tubes with the coal, and its step is as follows:
(1) feed coal is pulverized, screening and mixes with metal catalyst, evenly spread after with agate mortar the mixture mill being spared and be loaded in the porcelain boat, again porcelain boat is put into silica tube.
Feed coal is cleaned coal or low ash coal, and granularity is 100～200 orders.
Metal catalyst is a ferrocene, and granularity is 100～200 orders.
The mass ratio of feed coal and metal catalyst is 1: 1～1: 3.
(2) silica tube in the step (1) is put into the tube type resistance furnace that contains the temperature programming device, after the logical rare gas element 15min emptying of flow velocity with 50～100ml/min, open the temperature programming device and heat.It is 1h～3h that reaction times is set, and temperature of reaction is 900 ℃～1100 ℃; Heating finishes the back and reduces to 10～40 ℃ naturally, and whole process is carried out under protection of inert gas.The multi-walled carbon nano-tubes of gained is deposited on porcelain boat and the silica tube tube wall.
Rare gas element is nitrogen or argon gas or helium.
Effect of the present invention and benefit are as follows:
1. be carbon source with coal cheap and easy to get, greatly reduce the cost of preparation MWNTs, simplified preparation process condition.
2. adopt the MWNTs output of present method preparation higher, productive rate can reach 0.5～1.0g/h, and device is expected to reach a kilogram magnitude after amplifying improvement.
3. Zhi Bei MWNTs purity is higher, can reach 40～60%.
4. few and mechanics of Zhi Bei MWNTs uniform diameter, textural defect and Electronic Performance are good, can be used as hydrogen storage material, matrix material or support of the catalyst etc.
Description of drawings
Fig. 1 is that the present invention utilizes chemical Vapor deposition process to be prepared the device synoptic diagram of multi-walled carbon nano-tubes by coal.
Fig. 2 is the photo of the transmission electron microscope of the prepared multi-walled carbon nano-tubes of the embodiment of the invention 1.
Fig. 3 is the photo of the scanning electronic microscope of the prepared multi-walled carbon nano-tubes of the embodiment of the invention 1.
Fig. 4 is the photo of the transmission electron microscope of the prepared multi-walled carbon nano-tubes of the embodiment of the invention 2.
Fig. 5 is the photo of the transmission electron microscope of the prepared multi-walled carbon nano-tubes of the embodiment of the invention 3.
Embodiment
The present invention will be further described below by specific embodiment.
Embodiment 1:
As shown in Figure 1: be that the present invention utilizes chemical Vapor deposition process to prepare the device synoptic diagram of multi-walled carbon nano-tubes with coal.Wherein 1 represents thermopair; 2 are the temperature programming instrument; 3 is porcelain boat; 4 is water; 5 is under meter; 6 is silica tube; 7 is rare gas element.Is to mix at 1: 2 100 purpose cleaned coal and 100 purpose catalyzer ferrocene by mass ratio, evenly spreads after even with the agate mortar mill to be loaded in the porcelain boat, porcelain boat is put into the silica tube that places the electric tube furnace middle part again.After the logical nitrogen 50ml/min emptying in 15 minutes, open the temperature programming device and heat.It is 2h that reaction times is set, and temperature of reaction is 1000 ℃.Reaction finishes the back and reduces to 40 ℃ naturally, and whole process is carried out under nitrogen protection.Products therefrom is collected in porcelain boat He on the silica tube tube wall.Under these conditions, the yield of MWNTs is 0.8g/h.Characterize with transmission electron microscope (TEM) and scanning electronic microscope (SEM) MWNTs product, see Fig. 2 and Fig. 3 respectively gained.As can be seen from Figure 2, the MWNTs of generation twines mutually, uniform diameter, and caliber is 50～80nm.The MWNTs majority of Sheng Chenging is a blank pipe as can see from Figure 3, and the impurity that contains is less.The MWNTs content that this method is produced is about 40%.
Embodiment 2
Is to mix at 1: 3 200 order cleaned coal and 200 order catalyzer ferrocene by mass ratio, evenly spreads after even with the agate mortar mill to be loaded in the porcelain boat, puts into the silica tube that places the electric tube furnace middle part.Electric tube furnace is controlled by the temperature programming instrument.After the helium injection gas 100ml/min emptying in 15 minutes, open the temperature programming device and heat.It is 2h that reaction times is set, and temperature of reaction is 900 ℃.Reaction finishes the back and reduces to 10 ℃ naturally.Entire reaction course is carried out under the helium protection.Products therefrom is collected on porcelain boat bottom and silica tube tube wall.Under these conditions, the yield of MWNTs is 0.5g/h.Characterize with the MWNTs product of transmission electron microscope (TEM), as shown in Figure 4 gained.Can find out that the caliber of MWNTs is 70～80nm.The MWNTs content that this method is produced is about 50%.
Embodiment 3
Is to mix at 1: 2 150 purpose cleaned coal and 150 purpose catalyzer ferrocene by mass ratio, evenly spreads after even with the agate mortar mill and is loaded on the porcelain boat bottom, puts into the silica tube that places the electric tube furnace middle part.After the logical argon gas 70ml/min emptying in 15 minutes, open the temperature programming device and heat.It is 1h that reaction times is set, and temperature of reaction is 900 ℃.Reaction finishes the back and reduces to 30 ℃ naturally.Entire reaction course is carried out under argon gas atmosphere.Products therefrom is collected on porcelain boat bottom and silica tube tube wall.Under these conditions, the yield of MWNTs is 0.5g/h.Characterize with the MWNTs product of transmission electron microscope (TEM), as shown in Figure 5 gained.Can find out that the caliber of MWNTs is 20～40nm.The MWNTs content that this method is produced is about 50%.
Embodiment 4
Is to mix at 1: 3 100 order cleaned coal and 200 order catalyzer ferrocene by mass ratio, evenly spreads after even with the agate mortar mill and is loaded on the porcelain boat bottom, puts into the silica tube that places the electric tube furnace middle part.After the logical nitrogen 50ml/min emptying in 15 minutes, open the temperature programming device and heat.It is 1h that reaction times is set, and temperature of reaction is 1100 ℃.Reaction finishes the back and reduces to 15 ℃ naturally.Entire reaction course is carried out under nitrogen protection.Products therefrom is collected on porcelain boat bottom and silica tube tube wall.
Embodiment 5
Is to mix at 1: 2 200 order low ash coals and 100 order catalyzer ferrocene by mass ratio, evenly removes after even with the agate mortar mill and is loaded on the porcelain boat bottom, puts into the silica tube that places the electric tube furnace middle part.After the logical nitrogen 50ml/min emptying in 15 minutes, open the temperature programming device and heat.It is 3h that reaction times is set, and temperature of reaction is 1000 ℃.Reaction finishes the back and reduces to 40 ℃ naturally.Entire reaction course is carried out under nitrogen protection.Products therefrom is collected on porcelain boat bottom and silica tube tube wall.
Claims (3)
1, a kind of is the method for feedstock production multi-walled carbon nano-tubes with the coal, it is characterized in that:
(1) feed coal is pulverized, sieved and mixes with the metal catalyst ferrocene, the mass ratio of described feed coal and metal catalyst ferrocene is 1: 1～1: 3;
With agate mortar mixture mill is evenly spread after even and to be loaded in the porcelain boat, again porcelain boat is put into silica tube;
(2) silica tube in the step (1) is put into the tube type resistance furnace that contains the temperature programming device, after the logical rare gas element 15min emptying of flow velocity with 50～100ml/min, open the temperature programming device and heat; It is 1h～3h that reaction times is set, and temperature of reaction is 900 ℃～1100 ℃; Heating finishes the back and reduces to 10～40 ℃ naturally, and whole process is carried out under protection of inert gas, and the multi-walled carbon nano-tubes of gained is deposited on porcelain boat and the silica tube tube wall.
2, according to claim 1 is the method for feedstock production multi-walled carbon nano-tubes with the coal, it is characterized in that:
Described feed coal is cleaned coal or low ash coal, and granularity is 100～200 orders;
Described metal catalyst ferrocene, granularity are 100～200 orders.
3, according to claim 1 is the method for feedstock production multi-walled carbon nano-tubes with the coal, it is characterized in that:
Described rare gas element is nitrogen or argon gas or helium.
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| CN100447076C true CN100447076C (en) | 2008-12-31 |
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| CN102432002A (en) * | 2011-09-28 | 2012-05-02 | 南昌大学 | Graphene-based clad pipe and its preparation technology |
| CN105731423B (en) * | 2016-01-29 | 2017-10-24 | 太原理工大学 | The integrated apparatus and method of a kind of pyrolysis of coal generation CNT |
| CN107311146A (en) * | 2016-04-25 | 2017-11-03 | 山西中兴环能科技有限公司 | A kind of serialization prepares the device and method of nano-carbon material |
| CN106006604B (en) * | 2016-05-31 | 2017-12-08 | 太原理工大学 | The method of catalysis pyrolysis solid carbon materials CNT |
| CN110745809B8 (en) * | 2019-10-29 | 2021-07-02 | 西安交通大学 | Method for preparing carbon nanotubes from coal |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1541938A (en) * | 2003-11-06 | 2004-11-03 | 大连理工大学 | Method and apparatus for continuous preparation of carbon nanometer tube material from coal |
| US20060121279A1 (en) * | 2004-12-07 | 2006-06-08 | Petrik Viktor I | Mass production of carbon nanostructures |
| CN1857998A (en) * | 2006-01-10 | 2006-11-08 | 梁逵 | Method for preparing carbon nano material by micro wave radiation of coal |
| WO2006135253A1 (en) * | 2005-06-16 | 2006-12-21 | Sinvent As | Method and reactor for producing carbon nanotubes |
| CN1944244A (en) * | 2006-08-11 | 2007-04-11 | 中国科学院等离子体物理研究所 | Method for preparing carbon nano tube using high power plasma generator |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1541938A (en) * | 2003-11-06 | 2004-11-03 | 大连理工大学 | Method and apparatus for continuous preparation of carbon nanometer tube material from coal |
| US20060121279A1 (en) * | 2004-12-07 | 2006-06-08 | Petrik Viktor I | Mass production of carbon nanostructures |
| WO2006135253A1 (en) * | 2005-06-16 | 2006-12-21 | Sinvent As | Method and reactor for producing carbon nanotubes |
| CN1857998A (en) * | 2006-01-10 | 2006-11-08 | 梁逵 | Method for preparing carbon nano material by micro wave radiation of coal |
| CN1944244A (en) * | 2006-08-11 | 2007-04-11 | 中国科学院等离子体物理研究所 | Method for preparing carbon nano tube using high power plasma generator |
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