CN1539731A - 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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- CN1539731A CN1539731A CNA2003101082570A CN200310108257A CN1539731A CN 1539731 A CN1539731 A CN 1539731A CN A2003101082570 A CNA2003101082570 A CN A2003101082570A CN 200310108257 A CN200310108257 A CN 200310108257A CN 1539731 A CN1539731 A CN 1539731A
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Abstract
A process for preparing multi-wall carbon nanotubes includes proportionally mixing salt of transition metal, carrier salt and disperser, adding deionized water to obtain aqueous solution, baking, calcining, grinding to obtain catalyst, using an equipment consisting of temp-controllable tubular electric furnace, vertical reactor, preheater, catalyst chamber and collector to feed the catalyst in the reactor at 600-800 deg.C from its top or bottom, feeding acetylene gas and preheated N2 at 450-600 deg.C from its bottom, and catalytic cracking of carbon-hydrogen gas to deposit carbon on the surface of catalyst particle to obtain target product.
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 (5)
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, 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.
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. by the described method for preparing multi-walled carbon nano-tubes of claim 1, it is characterized in that said supporting electrolyte is magnesium nitrate or aluminum nitrate.
4. by the described method for preparing multi-walled carbon nano-tubes of claim 1, it is characterized in that said dispersion agent is citric acid or polyoxyethylene glycol.
5. 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).
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| Application Number | Priority Date | Filing Date | Title |
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| 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 |
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| 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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| CN1539731A true CN1539731A (en) | 2004-10-27 |
| CN1209284C 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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| CN104641028A (en) * | 2013-06-18 | 2015-05-20 | Lg化学株式会社 | Device for manufacturing carbon nanotube fibers and method for manufacturing carbon nanotube fibers using same |
| CN110589763A (en) * | 2019-09-02 | 2019-12-20 | 四川普瑞思达科技服务有限公司 | Method for preparing hydrogen by catalytic cracking of acetylene |
-
2003
- 2003-10-28 CN CN 200310108257 patent/CN1209284C/en not_active Expired - Fee Related
Cited By (7)
| 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 |
| CN104641028A (en) * | 2013-06-18 | 2015-05-20 | Lg化学株式会社 | Device for manufacturing carbon nanotube fibers and method for manufacturing carbon nanotube fibers using same |
| US9556542B2 (en) | 2013-06-18 | 2017-01-31 | Lg Chem, Ltd. | Device for manufacturing carbon nanotube fibers and method for manufacturing carbon nanotube fibers 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 |
| CN110589763A (en) * | 2019-09-02 | 2019-12-20 | 四川普瑞思达科技服务有限公司 | Method for preparing hydrogen by catalytic cracking of acetylene |
| 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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| CN1209284C (en) | 2005-07-06 |
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Owner name: NINGBO HUASHI NANO-MATERIAL CO., LTD. Free format text: FORMER OWNER: HUANG DEHUAN; ZHANG XIAOBIN; CHENG JIPENG; TU JIANGPING Effective date: 20070119 |
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Effective date of registration: 20070119 Address after: 315040 Ningbo city science and Technology Park Yang Mu Qi Lane 226 No. 17 Room 302 Patentee after: Ningbo Huashi Nanomaterials Co., Ltd. Address before: 200060, room 13, No. 288, Lane 301, Macao Road, Shanghai, Putuo District Co-patentee before: Zhang Xiaobin Patentee before: Huang Dehuan Co-patentee before: Cheng Jipeng Co-patentee before: Tu Jiangping |
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Owner name: SHANGHAI HUASHI NANO MATERIALS CO., LTD. Free format text: FORMER OWNER: NINGBO HUASHI NANO-MATERIAL CO., LTD. Effective date: 20080425 |
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Effective date of registration: 20080425 Address after: A building, Xin Mei Industrial Zone, No. 260 Lian Cao Road, Shanghai, Minhang District Patentee after: Shanghai Huashi Nano Material Co., Ltd. Address before: Ningbo city science and Technology Park Yang Mu Qi Lane 226 No. 17 Room 302 Patentee before: Ningbo Huashi Nanomaterials Co., Ltd. |
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