Continuous production of carbon nanotubes and fullerenes
A method and a device for production of fullerene-related carbon nanotubes and fullerenes in direct current arc discharge between two graphite electrodes are disclosed. Two features distinctive from conventional arc discharge technique providing remarkably high productivity of the present method are introduced. The first feature comprises means for maintaining an optimal temperature of anode end surface to suppress formation of large carbon clusters and micro-crystallite carbon particles useless for synthesis of carbon nanotubes and fullerenes. The second one comprises means for maintaining an optimal concentration of carbon and catalyst vapor in vapor generation zone to ensure optimal yields of carbon nanotubes and fullerenes. Airtight plug-in cartridges are used to supply consumable electrodes and catalyst material inside closed-loop device without process being stopped. The means to perform automatic continuous feeding of consumable electrodes and catalyst, pneumatic transportation of condensables and their automatic continuous discharge are also described.
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BACKGROUND OF THE INVENTIONThe present invention relates to such nanostructures as carbon nanotubes and fullerenes and a continuous method of their production. Fullerene C.sub.60, C.sub.70 and higher fullerenes were first produced in gram quantities in arc discharge between two graphite electrodes in 1990 [W. Kreatschmer et. al. “Solid C60: A new form of carbon”, Nature, 347, 354-357 (1990)]. It is still the major technique in commercial production of fullerenes, which is though characterized by limited productivity.
Carbon nanotubes is a tubular form of carbon closely related to the C.sub.60 molecule, which can be also produced by the mentioned above arc discharge technique with addition of metal catalyst. Carbon nanotubes produced in arc discharge are called fullerene-related nanotubes. They have much less structure defects and possess superior properties in comparison with nanotubes produced by alternative methods like, for example, carbon vapor deposition (CVD) method. Carbon nanotubes production by arc discharge technique possesses the same disadvantages as fullerene production—limited productivity and high final product cost. Numerous optimization efforts have demonstrated that reasonable yields of said carbon nanostructures can be produced by arc discharge technique in a very narrow area of process parameters comprising usage of graphite electrodes 4-10 mm in diameter, electric current 50-100 A and reactor pressure 30-200 Torr [Bogdanov, A. A., Deininger, D., Dyuzhev, G. A. Development Prospects of the Commercial Production of Fullerenes, Zhurnal Tekhnicheskoi Fiziki, 45(5), 521-527 (2000)]. At the same time productivity of a single arc could not exceed the limit of a few grams of carbon nanotubes or fullerenes per hour.
We believe there are two major reasons accounting for the mentioned productivity limitation of arc discharge technique. The first one represents the fact that carbon vapor concentration in vapor generation zone is a function of anode evaporation rate. Formation of carbon nanotubes and fullerenes is a polyatomic process, which is quite sensitive to concentration of reaction components. That means that nanotube and fullerene yields are also functions of anode evaporation rate and productivity of existing arc discharge technique can't be scaled up in principle because any attempt to increase evaporation rate would increase carbon vapor concentration and promote primary formation of carbon black particles, which will dramatically reduce yield of the desired nanostructures. In order to scale up productivity of arc discharge technique it is necessary to make anode evaporation rate and carbon vapor concentration mutually independent.
The second reason of limited productivity of arc discharge technique constitutes the fact that temperature of anode surface rises with increase of electric current, which causes excessive formation of large carbon clusters and micro-crystallite carbon particles useless for synthesis of carbon nanotubes and fullerenes. Thus, fine micro-crystallite carbon particles were discovered in graphite vapor at temperatures above 2900 K [Wachi, F. M., Gilmartin D. E. High-temperature mass spectrometry —I. Free vaporization studies of graphites. Carbon, 8, 141-154 (1970)]. Another study of carbon clusters C1-C7 at equilibrium conditions showed that partial vapor pressure of larger carbon clusters grows faster with temperature then partial vapor pressure of smaller clusters [Gingerich, K. A., Finkbeiner, H. C., Schmude, R. W. Enthalpies of formation of small linear carbon clusters. J. Am. Chem. Soc. 116, 3884-3888 (1994)]. Both examples demonstrate that rise of anode surface temperature negatively affects carbon vapor composition and reduces yield of desired carbon nanostructures.
A method of the present invention eliminates both mentioned above negative phenomena and enables remarkably high productivity and reasonable yields of both fullerene-related nanotubes and fullerenes produced by arc discharge technique. Since the method is easily scalable only economical considerations of the most appropriate scale and the largest size of graphite electrodes readily available could limit its utmost productivity.
Commercially suitable process necessarily requires continuous type of production. There are a number of publications where authors disclose one or several aspects of continuous fullerene production. Thus, in the work [Smalley R. E., Haufler R. E. Electric arc process for making fullerenes. U.S. Pat. No. 5,227,038; 1993] authors described a closed-loop device for fullerene generation comprising means for filtration of condensables. The work [Lorents D. C., Malhotra R. Process and apparatus for producing and separating fullerenes. U.S. Pat. No. 5,304,366; 1994] also presents a closed-loop reactor for fullerene synthesis comprising means to separate different types of fullerenes in temperature gradient. The work [Duzhev G. A., Basargin I. V., Filippov B. M., Alekseev N. I., Afanasiev D. V., Bogdanov A. A. Method for producing fullerene-contained carbon and device for carrying out said method. WO 02/096800, 2002] introduced inert gas circulating system and considered continuous movement of graphite electrode inside the electric arc zone. Since carbon nanotubes are less mature then fullerenes we were not able to find out any explicit descriptions of their continuous production by arc discharge technique.
Present invention bridges this gap and introduces detailed description of a closed-loop device for continuous production of carbon nanotubes and fullerenes comprising continuous automated feeding of graphite electrodes and catalyst into vapor generation zone, usage of airtight interchangeable plug-in cartridges providing uninterruptible source of fresh carbon and catalyst, pneumatic transportation of condensables and their automated discharge outside of said closed-loop device.
BRIEF SUMMARY OF THE INVENTIONThis invention provides a method and a device for continuous production of fullerene-related carbon nanotubes and fullerenes in arc discharge between two graphite electrodes, one of which is a movable consumable anode and another one is a motionless non-consumable cathode. Vapor generation zone is maintained between said graphite electrodes. Catalyst in a form of metal wire or fine metal powder is fed into vapor generation zone through perforation in cathode body. Since the invention presents continuously working closed-loop device uninterruptible supply of fresh portions of catalyst is provided by means of interchangeable airtight plug-in cartridges. Consumable graphite electrodes are also delivered inside the closed-loop device by means of interchangeable airtight plug-in cartridges, equipped with mechanisms for electrode automatic jointing. Jointed graphite electrodes are continuously fed into vapor generation zone by conveyor transporters equipped with spring clamps. Injection of a noble gas flow parallel to anode end surface maintains its optimal temperature and suppresses formation of large carbon clusters and micro-crystallite carbon particles in vapor generation zone. Noble gas flow coaxial to graphite electrodes maintains an optimal concentration of carbon vapor in vapor generation zone to ensure optimal yields of carbon nanotubes and fullerenes. Condensables containing fullerene-related carbon nanotubes and fullerenes are pneumatically transported by a noble gas flow outside of vapor generation zone, cooled down, filtered, collected in a storage bin and automatically discharged out of closed-loop device. Carbon nanotubes and fullerenes are recovered from discharged condensables. These and other features of the invention will become clear from the following detailed description.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
A method and a device for continuous production of fullerene-related carbon nanotubes and fullerenes are disclosed.
Referring to
Functioning of arc discharge section 6 is more specifically demonstrated in
Referring to
Catalyst suitable for synthesis of carbon nanotubes mainly comprises transition metals from the forth and the fifth periods of the periodic system of elements, preferably Fe, Co, Ni and Y or their alloys. Referring to
Claims
1. A method for continuous production of carbon nanotubes and fullerenes comprising:
- a. establishing vapor generation zone in an atmosphere of a noble gas by starting and maintaining direct current arc discharge between two graphite electrodes, one of which is a movable consumable anode and another one is a motionless non-consumable cathode;
- b. providing means for maintaining an optimal temperature of anode end surface to suppress formation of large carbon clusters and micro-crystallite carbon particles in vapor generation zone;
- c. providing means for maintaining an optimal concentration of carbon and catalyst vapor in vapor generation zone to ensure optimal yields of carbon nanotubes and fullerenes;
- d. continuous automated feeding of a movable anode into vapor generation zone;
- e. continuous automated feeding of a catalyst for carbon nanotube synthesis in a form of a metal wire or a fine metal powder into vapor generation zone through central perforation in cathode body;
- f. formation of condensables outside of vapor generation zone containing fullerene-related carbon nanotubes and fullerenes;
- g. pneumatic transportation of condensables by a noble gas flow, their cooling, filtration and collection in a storage bin and a noble gas flow re-circulation;
- h. automated discharge of condensables from the storage bin and recovery of carbon nanotubes and fullerenes.
2. The method as set forth in claim 1 wherein the means for maintaining optimal temperature of anode end surface comprise jet flow of a noble gas parallel to anode end surface providing effective removal of just evaporated carbon clusters and facilitating effective evaporation of new clusters.
3. The method as set forth in claim 1 wherein the means for maintaining an optimal concentration of carbon and catalyst vapor in vapor generation zone comprise an admixture of carbon vapor with a noble gas flow coaxial with electrodes and directed from cathode to anode.
4. The method as set forth in claim 1 wherein the means for maintaining an optimal concentration of carbon vapor in vapor generation zone also serve for pneumatic transportation of condensables.
5. The method as set forth in claim 1 wherein precautions are taken to prevent melting of catalyst material inside the cathode body while catalyst is fed into vapor generation zone through perforation in cathode body.
6. A device for continuous production of carbon nanotubes and fullerenes, which represents closed-loop system and includes:
- a. an airtight water-cooled chamber comprising an arc discharge section containing vapor generation zone between two graphite electrodes, an anode feeding section containing means to provide automated jointing of separate graphite electrodes and their gradual transportation into vapor generation zone and a catalyst feeding section containing means to provide continuous supply of catalyst through central perforation in cathode body into vapor generation zone;
- b. an interchangeable airtight plug-in cartridge containing multiple graphite electrodes for non-stop device operation;
- c. an interchangeable airtight plug-in cartridge containing catalyst in a form of metal wire or a fine metal powder for non-stop device operation;
- d. means for maintaining an optimal temperature of anode surface and an optimal concentration of carbon vapor in vapor generation zone comprising at least one gas nozzle and at least one gas distributor placed within arc discharge section of the airtight chamber;
- e. means for pneumatic transporting of the condensables and noble gas flow re-circulation;
- f. a heat-exchanger to maintain constant temperature of the re-circulating noble gas flow comprising means for continuous cleaning heat exchanger inner walls from the condensables;
- g. a filter to separate the condensables from a noble gas flow comprising means for filter automatic self-cleaning;
- h. a storage bin for filtered condensables comprising means for automated discharge of said condensables outside of a storage bin.
7. The device as set forth in claim 6 wherein automated jointing of separate graphite electrodes is accomplished by at least two mechanisms installed in plug-in cartridge —pushing mechanism providing coaxial position of two electrodes and revolving mechanism jointing said electrodes by the means of female threads on both electrode ends and jointing nipple.
8. The device as set forth in claim 6 wherein gradual transportation of graphite electrodes into vapor generation zone is accomplished by two conveyor transporters equipped with spring clamps tightly embracing said electrodes from the two opposite sides.
9. The device as set forth in claim 6 wherein the means for graphite electrodes gradual transportation into vapor generation zone are used to supply electric current to said electrodes.
10. The device as set forth in claim 6 wherein said catalyst for carbon nanotubes synthesis is supplied in a form of a metal wire or a fine metal powder and the means for its continuous supply into vapor generation zone are presented by any standard or customized wire or powder feeder suitable for the purposes of the present invention.
11. The device as set forth in claim 6 wherein said cathode body has a central perforation for a catalyst feeding ending in a widening and several side perforations ending in the same widening to create protective gas shield and prevent catalyst vapor deposition on the inner sidewalls of the widening.
12. The device as set forth in claim 6 wherein maintaining an optimal temperature of anode end surface comprises two gas nozzles creating two jet counter-flows with their collision point located outside of vapor generation zone.
13. The device as set forth in claim 6 wherein re-circulation of a noble gas flow is accomplished by oil-less gas pump, oil-less gas compressor or other similar means.
14. The device as set forth in claim 6 wherein re-circulating noble gas is separated into at least three flows supplied to arc discharge section, anode feeding section and catalyst feeding section of the airtight chamber.
15. The device as set forth in claim 6 wherein screw conveyer accomplishes continuous cleaning of condensables from the heat exchanger inner walls.
16. The device as set forth in claim 6 wherein deposited on filter surface condensables are cleaned by periodic pulses of reversed gas flow, vibration or any other effective means for filter cleaning.
17. The device as set forth in claim 6 wherein condensables from filter and heat exchanger are collected at the same storage bin to simplify procedure of their discharge.
Type: Application
Filed: Jul 21, 2003
Publication Date: Jan 27, 2005
Inventor: Dmitri Koulikov (Jersey City, NJ)
Application Number: 10/623,871