CN1209284C - Method and equipment for preparing Nano carbon tube with multiple walls - Google Patents
Method and equipment for preparing Nano carbon tube with multiple walls Download PDFInfo
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- CN1209284C CN1209284C CN 200310108257 CN200310108257A CN1209284C CN 1209284 C CN1209284 C CN 1209284C CN 200310108257 CN200310108257 CN 200310108257 CN 200310108257 A CN200310108257 A CN 200310108257A CN 1209284 C CN1209284 C CN 1209284C
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Abstract
The present invention discloses a method and a device for preparing a multi-wall carbon nanotube. The method comprises the following steps: 1), transition metal salt, carrier salt and a dispersing agent are mixed according to the molar ratio of 0.9 to 1.1/0.9 to 4.1/0.9 to 1.1, deionized water is added to be prepared into water solution, and then, mixed solution is baked, burnt and milled to prepare a catalyst; 2), the catalyst is evenly sent into a reactor of which the temperature is constant within 600 to 800 DEG C from the top part or the bottom of the reactor by a device comprising a tube type temperature control electric furnace, vertical type reactor, a preheater, a catalyst chamber and a collector, and acetylene gas and nitrogen gas which is preheated to 450 to 600 DEG C are communicated to the bottom of the reactor. The flow ratio of the nitrogen gas and the acetylene gas is 3 to 10/1, and acetylene flow capacity is 1 liter / minute. Making catalytic pyrolysis for hydrocarbon gas, carbon is deposited on the surfaces of catalyst granules to generate the multi-wall carbon nanotube.
Description
Technical field
The present invention relates to prepare the method and the device of multi-walled carbon nano-tubes.
Background technology
Multi-walled carbon nano-tubes is found in 1991, is a kind of one dimension tubular nanometer structure that is made of the coaxial seamless graphite flake of multiwalled.Carbon nanotube is all extremely excellent nano material of a kind of physical and chemical performance, all obtained in a lot of fields using widely, but the scale preparation problem of carbon nanotube remains a bottleneck of its application of restriction.
Summary of the invention
The purpose of this invention is to provide a kind of method and device thereof for preparing multi-walled carbon nano-tubes.
The method for preparing multi-walled carbon nano-tubes of the present invention may further comprise the steps:
1) with 0.9～1.1: 0.9～4.1: 0.9～1.1 mixing in molar ratio of transition metal salt, supporting electrolyte and dispersion agent, adds deionized water and be made into the aqueous solution, then with mixed solution oven dry, calcination again, the levigate catalyzer that makes;
2) catalyzer is evenly sent into constant temperature in 600～800 ℃ reactor from reactor head or bottom, and at the bottom of reactor feeding acetylene gas and the nitrogen that is preheating to 450-600 ℃ of temperature, the throughput ratio of nitrogen and acetylene gas is 3～10: 1, the acetylene flow is 1 liter/minute, the catalytic pyrolysis hydrocarbon gas makes carbon laydown generate multi-walled carbon nano-tubes in the granules of catalyst surface.
Said transition metal salt can be an iron nitrate among the present invention, Xiao Suangu or nickelous nitrate, and supporting electrolyte can adopt magnesium nitrate or aluminum nitrate, and dispersion agent can be citric acid or polyoxyethylene glycol.
Adopt the used device of the inventive method to comprise tubular type temperature control electric furnace, vertical reactor, preheater, catalyst chamber and have the air outlet and the collector of discharge port, reactor places the temperature control electric furnace, the tapered opening in its lower end, this end is communicated with the air outlet of preheater, and on connecting tube, offer inlet mouth, and the upper end of reactor links to each other with the opening for feed of collector, and said catalyst chamber is connected with wherein arbitrary end of reactor.
The present invention has the following advantages:
1. preparation process is continuous, is beneficial to large-scale production, and catalyzer is fluidisation in vertical reactor, and the carbon pipe is collected convenient.And Preparation of Catalyst is simple, needn't add dispersion agent and help disperseing the catalyst activity height through the reduction and the activation of hydrogen.
2. relatively inexpensive carbon sources such as acetylene are adopted in reaction, and temperature of reaction is low, and only to need nitrogen be carrier gas, do not need hydrogen, and are comparatively safe.
3. the big nitrogen of preheater preheating flow is beneficial to and keeps reactor temperature, improves the efficient of fluidized-bed.
4. multistage fluidization regions makes the catalyzer with size distribution can be respectively in different regional fluidisations, the utilization ratio of the catalyzer that has improved.
Description of drawings
Fig. 1 is a kind of structural representations of apparatus of the present invention;
Fig. 2 is the another kind of structural representations of apparatus of the present invention;
Fig. 3 is transmission electron microscope (TEM) photo with the multi-walled carbon nano-tubes of the inventive method preparation.
Embodiment
With reference to Fig. 1, the device of preparation multi-walled carbon nano-tubes comprises tubular type temperature control electric furnace 1, vertical reactor 2, preheater 3, catalyst chamber 4 and have venting port 6 and the collector 5 of discharge port 7, reactor 2 is that the lower end is the silica tube of tapered opening, place temperature control electric furnace 1, tapered opening is communicated with the air outlet of the preheater 3 that is used for pre-hot nitrogen, on connecting tube, offer for the inlet mouth 8 that feeds hydrocarbon gas, like this, can make hydrocarbon gas and converge through the nitrogen of preheating after enter reactor again, the upper end of reactor links to each other with the opening for feed of collector 5, in the illustrated example, catalyst chamber 4 is connected with the upper end of reactor 2, perhaps also can be connected with the lower end of reactor 2 as shown in Figure 2.
The inventive method prepares the embodiment of multi-walled carbon nano-tubes:
1: 1: 1 analytical pure Xiao Suangu of mol ratio, analytical pure magnesium nitrate, analytical pure citric acid are added a little deionized water, make its dissolving fully just; Heat 130 ℃ of oven dry solution, 550 ℃ of firing products 15 minutes in air then, levigate telling-200 order powder is stand-by.Above-mentioned powder is added in the catalyst chamber, constant temperature behind the reactor heating to 750 ℃, the nitrogen preheater is heated to 450 ℃ of constant temperature, feed nitrogen and acetylene gas, the throughput ratio of nitrogen and acetylene gas is 6: 1,1 liter/minute of acetylene flow, the vibrations catalyst chamber, make in the even inflow reactor of catalyzer, the catalytic pyrolysis hydrocarbon gas, catalyzer carries out the secondary fluidisation when reaction generates the carbon pipe, the carbon nanotube of Sheng Chenging enters collector with air-flow at last, collects the multi-walled carbon nano-tubes that makes at collector.The multi-wall carbon nano-tube my humble opinion of collecting is shown in Figure 3.
Claims (3)
1. the method for preparing multi-walled carbon nano-tubes is characterized in that may further comprise the steps:
1) with 0.9～1.1: 0.9～4.1: 0.9～1.1 mixing in molar ratio of transition metal salt, supporting electrolyte and dispersion agent, add deionized water and be made into the aqueous solution, then with mixed solution oven dry, calcination again, the levigate catalyzer that makes, above-mentioned supporting electrolyte is magnesium nitrate or aluminum nitrate, and dispersion agent is citric acid or polyoxyethylene glycol;
2) catalyzer is evenly sent into constant temperature in 600～800 ℃ reactor from reactor head or bottom, and at the bottom of reactor feeding acetylene gas and the nitrogen that is preheating to 450-600 ℃ of temperature, the throughput ratio of nitrogen and acetylene gas is 3～10: 1, the acetylene flow is 1 liter/minute, the catalytic pyrolysis hydrocarbon gas makes carbon laydown generate multi-walled carbon nano-tubes in the granules of catalyst surface.
2. by the described method for preparing multi-walled carbon nano-tubes of claim 1, it is characterized in that said transition metal salt is an iron nitrate, Xiao Suangu or nickelous nitrate.
3. the device for preparing multi-walled carbon nano-tubes by the described method of claim 1, it is characterized in that comprising tubular type temperature control electric furnace (1), vertical reactor (2), preheater (3), catalyst chamber (4) and have air outlet (6) and the collector (5) of discharge port (7), reactor (2) places temperature control electric furnace (1), the tapered opening in its lower end, this end is communicated with the air outlet of preheater (3), and on connecting tube, offer inlet mouth (8), the upper end of reactor links to each other with the opening for feed of collector (5), and said catalyst chamber (4) is connected with wherein arbitrary end of reactor (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108257 CN1209284C (en) | 2003-10-28 | 2003-10-28 | Method and equipment for preparing Nano carbon tube with multiple walls |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108257 CN1209284C (en) | 2003-10-28 | 2003-10-28 | Method and equipment for preparing Nano carbon tube with multiple walls |
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| Publication Number | Publication Date |
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| CN1539731A CN1539731A (en) | 2004-10-27 |
| CN1209284C true CN1209284C (en) | 2005-07-06 |
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| CN 200310108257 Expired - Fee Related CN1209284C (en) | 2003-10-28 | 2003-10-28 | Method and equipment for preparing Nano carbon tube with multiple walls |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100515935C (en) * | 2005-09-02 | 2009-07-22 | 鸿富锦精密工业（深圳）有限公司 | Carbon nano-tube growth apparatus and method |
| 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 |
| KR101560483B1 (en) * | 2013-06-18 | 2015-10-14 | 주식회사 엘지화학 | Apparatus for preparing carbon nanotube fiber and process for preparing carbon nanotube fiber using same |
| CN104525210A (en) * | 2014-11-04 | 2015-04-22 | 内蒙古大学 | Method for preparing MWCNTs-supported copper and cerium catalyst by using iron, cobalt and nickel as matrix |
| CN110589763B (en) * | 2019-09-02 | 2023-02-10 | 四川普瑞思达科技服务有限公司 | Method for preparing hydrogen by catalytic cracking of acetylene |
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