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WO1994016993A1 - Procede et dispostif permettant de produire des fullerenes de carbone a partir de matieres premieres solides contenant du carbone - Google Patents

Procede et dispostif permettant de produire des fullerenes de carbone a partir de matieres premieres solides contenant du carbone Download PDF

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Publication number
WO1994016993A1
WO1994016993A1 PCT/DE1994/000084 DE9400084W WO9416993A1 WO 1994016993 A1 WO1994016993 A1 WO 1994016993A1 DE 9400084 W DE9400084 W DE 9400084W WO 9416993 A1 WO9416993 A1 WO 9416993A1
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WO
WIPO (PCT)
Prior art keywords
carbon
crucible
reactor
raw material
evaporation
Prior art date
Application number
PCT/DE1994/000084
Other languages
German (de)
English (en)
Inventor
Christoph Becke
Karl-Heinz Roggenkamp
Original Assignee
Lipprandt, Michael
Behrens, Manfred
Glück, Ralf
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lipprandt, Michael, Behrens, Manfred, Glück, Ralf filed Critical Lipprandt, Michael
Publication of WO1994016993A1 publication Critical patent/WO1994016993A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/152—Fullerenes
    • C01B32/154—Preparation
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B6/00—Heating by electric, magnetic or electromagnetic fields
    • H05B6/02—Induction heating
    • H05B6/10—Induction heating apparatus, other than furnaces, for specific applications
    • H05B6/105—Induction heating apparatus, other than furnaces, for specific applications using a susceptor
    • H05B6/108—Induction heating apparatus, other than furnaces, for specific applications using a susceptor for heating a fluid
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B7/00—Heating by electric discharge
    • H05B7/18—Heating by arc discharge

Definitions

  • the present invention relates to a process for the production of carbon fullerenes by heating and evaporating carbon-containing material under an inert inert gas atmosphere in a reactor which is supplied from outside the reactor and from inadmissible nitrogen, oxygen, hydrogen, water vapor - or other reactive gas components or deposits are exempted and which is heated to the vaporization temperature generated in an electric arc, an inductive high-frequency field or an incident laser beam, and with the formation of carbon clusters and soot and / or carbon vapors containing fullerenes, in particular Buckminster fullerenes, by cooling and condensing carbon of the carbon plasma formed.
  • the invention further relates to a device for performing this method.
  • Such a method using a pulsed laser for the vaporization of graphite is known from Smalley.
  • a cluster beam generator is used, in which a rotating graphite disc is placed, onto which a focused laser beam is guided.
  • the carbon vapor that is formed is entrained by a helium stream that passes by and forms a particle beam when expanded into a vacuum.
  • the Krätschmer and Huffmann apparatus is suitable for the formation of fullerenes in macroscopic amounts.
  • These known methods and apparatuses are expensive overall for the production of carbon Buckminster fullerenes, a high electrical output being required to form the smallest macroscopic amounts of fullerene. Since a high evaporation temperature must be reached, the evaporation process takes place directly in an electric arc by evaporation of the carbon electrodes used themselves. Also in the known methods for generating the evaporation energy of the carbon by focusing a laser beam or by irradiating an inductive high-frequency field, the Carbon is introduced into the reactor in the form of carbon-containing rods and cubes made of graphite and the like.
  • Such rod-like and cube-like materials as well as the graphite electrodes to be used for arcing are expensive raw materials due to their production, since these have to be pressed in a special process with the addition of suitable amounts of binders and then tempered.
  • the rods, cubes, plates etc. must each be guided under the focal point of the laser radiation, shifted through the inductive high-frequency field or pushed in as electrodes to form an arc. Evaporation of the electrode tips within an arc requires one to maintain the arc Electrode guide with the help of a screw or slide mechanism, which allows a suitable adjustment of the electrode distance.
  • the present invention is therefore based on the object of improving a method of the type mentioned at the outset and the devices known thereafter for the production of carbon Buckminsterfullerenes and other fullerenes in such a way that the disadvantages mentioned are largely avoided.
  • continuous production of carbon blacks or vapors containing fullerenes in large quantities should be possible with a proportion of Buckminster fullerenes. In terms of process technology, this should be as simple and cheap as possible.
  • a double-walled steel tube made of a temperature-resistant material, preferably a VA steel, with various flanges and nozzles required for assembly is used.
  • the double-walled reactor is necessary for reasons of cooling.
  • the reactor is preferably upright, but can also be installed and operated in the horizontal position or in all other positions with nozzles arranged differently. See Figures 1,2,4,5 and 6.
  • a holder In the interior of the reactor, a holder is mounted in the lower area for the purpose of fastening a crucible or casing in which the carbon vaporization takes place.
  • the crucible consists of a highly refractory, temperature change-resistant and electrically conductive material, preferably of graphite, and can both with carbon-containing (coal, coking coal, graphite, wood and brown coal coke, waste products from ethylene production, graphitized carbon black, especially those after fullerene extraction etc.) dusts, granules as well as with a mixture thereof, preferably with the same carbon-containing material, which also as a raw material to be continuously supplied and evaporated.
  • carbon-containing coal, coking coal, graphite, wood and brown coal coke, waste products from ethylene production, graphitized carbon black, especially those after fullerene extraction etc.
  • the crucible is preferably closed at the top like a dome-like dome. There is a sufficiently large hole in the middle of the dome. In the event of an arc, the bore has the task of being able to move both several and only one electrode rod back and forth without contact using a movement mechanism. In the case of laser beams, the unimpeded entry of the beam must be ensured.
  • a feed pipe for the raw material supply preferably made of graphite, is installed through the bore. The raw material is supplied from the outside by means of a commercially available loading system from a storage vessel.
  • a sight glass is attached to a reactor nozzle.
  • an assembly socket which, if the reactor is put into operation, is closed with a blind cover.
  • a funnel-shaped sluice for collecting and removing the soot.
  • the movement system on which the electrode rods or the one electrode rod are attached is preferably included equipped with a separate cooling system to avoid heat problems in the area of the seal.
  • the motion system is installed in an electrically insulated manner in addition to the reactor.
  • the movement system is state of the art.
  • the crucible can optionally be encased with a coolable device, preferably with a water-cooled stainless steel tubular coil, in order to be able to install a magnetic field system on the outside of the encasement.
  • the magnetic field system has the task of additionally preventing the ionized, hot plasma from escaping from the crucible. Furthermore, it is assumed that the magnetic field system has not yet explainable, fullerene-forming properties.
  • the principle of the method shown here can be implemented as often as a multiplier within an overall reactor with several crucibles or casings in order to enable corresponding raw material throughputs.
  • the evaporation process can be between 50 mbar and several bar overpressure, preferably under normal pressure (1 bar), both on the surface of the carbon-containing crucible filling and deep in the carbon-containing crucible filling by means of laser beams, inductive high-frequency heating or preferably by means of an inert arc Noble gas atmosphere can be carried out.
  • the evaporation can take place in an arc (FIG. 1, 2) by immersing the arc in the crucible both on the surface of the dust / granulate and in the dust / granulate or between two electrode rods as follows.
  • Figure 1
  • a goblet-like depression forms in the area of the arc on the dust / granulate surface, which is permanently supplied with new carbon-containing raw material from dust / granulate through a tube coming from the outside into the crucible.
  • the laser beams evaporate the particles present in the crucible on the surface and go deeper and deeper, so that a goblet-like depression is also formed here. It is important in this process with laser technology, among other things, that monolithic solids do not have to be replenished in order to supply raw materials, but only dust / granules.
  • inductive high-frequency technology evaporates the particles present in the crucible from the center to the outside.
  • the amount missing in the crucible is permanently supplied with new raw material from dust / granulate through a pipe coming from the outside into the crucible. It is important in this process with an inductive high-frequency field that, among other things, it is not monolithic solids which have to be replenished in order to supply raw materials, but only dust / granules.
  • the fullerene-forming evaporation is not only much cheaper, but also easier.
  • the raw materials are free of adsorbed nitrogen, oxygen, hydrogen and in particular free of water vapor, so as not to prevent or hinder fullerene formation in the reactor space due to the presence of these gases.
  • the carbonaceous raw materials from dust or granulate must first be degassed at approximately 2,200 ° C. Oxygen escapes up to approx. 1,700 C, hydrogen up to approx. 2,000 ° C and nitrogen up to approx. 2,150 ° C.
  • the interior of the leak-tested reactor is evacuated several times using a vacuum pump and gases, preferably flushed with helium or argon, in order to eliminate unwanted residual gases such as oxygen, water vapor etc.
  • an inert gas pressure of preferably 1 bar is set.
  • the pressure can also range from a few mbar to several bar.
  • the cooling circuits preferably water circuits, are then started.
  • the electrodes When using the arc technology, after switching on the current of preferably more than 200 amperes and 20-60 volts, the electrodes are moved in the direction of the electrical opposite pole with the aid of the movement mechanisms in order to ignite the arc. Both AC and DC can be used.
  • the arc length can be corrected using the motion echanism.
  • the arc is preferably left to stand for a few minutes until, with the formation of a hot, goblet-like depression in the carbon-containing material of the crucible around the electrodes, an arc lengthening occurs automatically.
  • the raw material supply of the carbon is started.
  • the raw material to be evaporated is replenished from the outside from a storage vessel with a corresponding device and a charging system:
  • the introduction of the raw material preferably takes place from above by trickling in or blowing in within the electrode rods, but preferably by means of a separate graphite tube to the side of one electrode rod or the electrode rods through the bore of the dome-like dome of the crucible or the opening of the casing.
  • the still cold particles initially land on or in the hot dust / granulate. There they can warm up.
  • Pulse-like or permanent shaking of the reactor with a conventional vibration system ensures that raw materials are transported from the edge of the crucible to the evaporation area inside the crucible. During the transport until it is brought into the chalice-like depression, to the actual evaporation area, the raw material is further preheated considerably.
  • the now hot raw material thus falls permanently from all sides into the goblet-like depression of the evaporation area which is produced by the heat.
  • the external, permanent quantity inflow of the carbon-containing raw material is regulated depending on the outflow quantity of carbon into the evaporation area, which is formed in the form of a hot cup-like depression, by the carbon evaporation.
  • the evaporation area in the goblet-like depression must not become too hot, ie it is cooled by the permanent supply with cooler carbonaceous raw materials to be evaporated. In addition, there is also substantial cooling through the evaporation of the carbon.
  • the metered, permanent supply of newly evaporated carbons not only supplies the arc, but is kept stable with a constant arc length and a constant electrode spacing, without having to re-insert the electrodes for the purpose of arc control and raw material replenishment.
  • the crucible walls including the dome-like dome also have the task of reducing the flying out of hot, non-evaporated particles by bouncing off the walls. The hot, rebounded particles are again available to the evaporation process.
  • the interior of the crucible gives the hot, cluster-forming gases the opportunity to stay hot longer or to cool down more slowly before they leave the crucible through the bore.
  • cooling in the inert gas atmosphere must continue to take place as slowly as possible. This is made possible by a relatively long ascent path from the blue to black carbon vapors to the reactor cover before the vapors become fullerene. soot on the cooled reactor walls or be sucked off directly.
  • the product that is taken out of the lower lock hopper or directly extracted is then sent to a Soxhlet extraction.
  • the detached fullerenes are present as a red liquid.
  • the fullerene-containing liquid is evaporated to obtain the fullerene crystals.
  • the evaporated solvent is also reused as condensate.
  • the remaining soot can be used again for evaporation after drying.
  • FIGS. 1, 4 and 5 of the drawings are shown in FIGS. 1, 4 and 5 of the drawings and are described in more detail in the process.
  • a 600 mm long, double-walled VA steel reactor with an inner diameter of 150 mm was used as the device of the process.
  • a water-cooled cover which contained both a water-cooled and movable stick electrode holding system and a raw material feed pipe which is connected to a raw material silo located outside the reactor.
  • a free-flowing, grit-like bulk material was used as the raw material, a grain mixture of discharge soot and graphite between 20 mm and 3 mm in diameter.
  • the raw material was continuously fed into the crucible of the reactor by vibrations. The vibrations also ensured that raw materials were distributed within the crucible in the direction of the goblet-like evaporation zone.
  • a funnel-shaped exit lock was located below the reactor.
  • the reactor itself was a graphite crucible, 170 mm high and 110 mm outside diameter.
  • the inside height was 130 mm, the inside diameter was 80 mm.
  • the crucible was filled to the last 20 mm with the semolina-like bulk material.
  • the height from the crucible outlet opening to the reactor cover was 300 mm.
  • the reactor including the crucible with raw material was the one electrode.
  • the counter electrode consisted of one Graphite rod with a diameter of 15 mm and a length of 350 m.
  • the graphite rod was attached to the water-cooled and vertically movable rod electrode holding system.
  • the reactor including the raw material silo was pumped empty several times with a vacuum pump to 1 mbar and then refilled with helium gas.
  • a cold trap with a carbon filter was installed between the pump and the reactor.
  • Helium was used as the inert gas. Pressures between 0.4 and 1 bar, preferably 1 bar, were chosen as the working pressure in the reactor.
  • the arc burned a "goblet" below the graphite rod in the granular raw material lying in the crucible.
  • the arc was then extended at the same time by pulling out the electrode.
  • the raw material supply then started to vibrate at approx. 30-100 grams / hour in the crucible - and there directly into the "chalice".
  • a comparator kept the electrical arc conditions, including the quantity of raw materials to be evaporated, constant.
  • the resulting smoke must begin bluish within the smoke trail and pass black at the top if you want to get plenty of fullerenes.
  • the soot already shows whether more or less fullerenes are present.
  • the soot must look pitch black and adhere very loosely to the vessel walls.
  • the end products which do not contain fullerene can be returned to the evaporation process as a carbon-containing raw material, which means a high level of raw material utilization.
  • the electrode wear is significantly lower if the soot is produced exclusively with the raw material dust / granulate.
  • the fullerene-forming evaporation can take place under normal pressure 5 in an inert gas atmosphere.
  • a higher gas pressure means the presence of a higher number of noble gas molecules.
  • the evaporation process is carried out by means of an electric arc, laser radiation or inductive heating in an inert atmosphere.
  • the evaporation process takes place in a semi-open, high converter-like crucible, that is, within a 5 raw-like envelope.
  • the carbon-containing raw material from dust or granulate can slowly heat up, i.e. an explosive heating 0 is avoided.
  • the envelope 5 of the evaporation region, the crucible, located inside the reactor can additionally be surrounded by a corresponding magnetic field.
  • the magnetic field system has the task of preventing the ionized, hot plasma from escaping from the envelope, ie the dwell time in a hot environment can be determined. 0 Furthermore, it is assumed that a magnetic field system has fullerene-forming properties. Drawing description
  • Fig. 4 An arrangement with a double-walled reactor according to Fig. 1 and 2, wherein instead of an arc in the crucible, a plasma is generated by a laser.
  • FIG. 5 An arrangement according to FIG. 4, wherein instead of a laser an inductive HF system is used, in the coils of which the crucible is arranged on the inside.
  • Fig. 6 shows in addition to the arrangement of Fig. 1, 2, 4 or 5, the principle of using a Adapters for extending a reactor
  • FIGS. 1, 2, 4, 5 and 6 A modification of the arrangement according to FIGS. 1, 2, 4, 5 and 6, wherein a crucible rotating in the sense of a rotary kiln is used, above which a suction device for removing the vaporized carbon is arranged.
  • Raw material supply and evaporation system and the upper part of the reactor are otherwise to be designed analogously to FIGS. 1, 2, 4, 5 and 6.
  • Figure 7 further shows a smoke extraction system, i.e. The smoke does not deposit on the reactor walls, but can be suctioned off in the reactor due to the process pressures which are substantially higher here and can be fed immediately to the extraction process.
  • Fig. 8 The overall procedural process of fullerene production when using the arrangement according to FIG. 7 with a smoke extraction device additionally arranged to the soot removal lock, the supply of the carbon materials, the removal of the fullerene-containing vapors and carbon blacks and the extraction of the fullerenes according to FIG. 3 as self-contained process sequence takes place.
  • Figure 1 shows the reactor (1) and the arc to be ignited there between dust / granules in the crucible (1A) and represents a counter electrode formed from a graphite rod (17).
  • the crucible is filled up to level H with a carbon-containing dust / granulate mixture, the graphite rod (17) forming the counter electrode to the crucible (1A), which is not electrically insulated from the reactor housing.
  • the arc is located between the end of the rod-shaped counterelectrode (17) and the dust / granulate located in the crucible (1A).
  • the arc is permanently filled with new raw material from dust / granulate through an upper tube coming from outside
  • (12,13) are the inlet and outlet openings of the coolant for the reactor lid tank. (18) shows the outlet valve to the lock.
  • the accumulated soot containing fullerene and the non-evaporated raw material particles collect here and can be removed via a lock.
  • FIG. 2 shows the basic method of arc technology between two electrodes (28, 2B) formed from graphite rods.
  • the arc is located between the end of the electrode (28) projecting through an opening in a dome-like dome of the crucible (1A) and the counter electrodes (2B) located in the crucible (1A).
  • the arc is permanently supplied by the supply of new raw material from dust / granulate through an upper tube (29) coming from outside into the crucible (1A), the raw material trickling between the opposite ends of these electrodes according to arrow (30).
  • the structure of the reactor (1) and the crucible (1A) otherwise corresponds to that of FIG. 1, with no line for a lower raw material supply to the crucible according to line (7A) of FIG. 1.
  • a connection to the reservoir of a raw material supply system is provided via the connection (5).
  • FIG 2 there are (7,10) nozzles attached to the reactor.
  • a sight glass is mounted on the nozzle (7).
  • (6,8) are noble gas inlet and outlet openings, whereby a vacuum can also be generated via these.
  • (1A) is the crucible standing on the sieve-like support (19).
  • the rod-shaped electrode (28) protruding into the crucible (1A), which in turn hangs on the coolable and movable electrode suspension (14) and is fastened in the crucible (1A) and opposite it electrically non-insulated counter electrode (2B).
  • (3) shows the coolant tank of the reactor cover, where (12,13) are the inlet and outlet openings of the coolant for the reactor cover tank (3).
  • (15, 16) show the inflow and outflow openings of the coolant for the electrode suspension.
  • the reactor is sealed against the movable electrode suspension (14) by a seal, a sliding packing (4).
  • (18) shows the outlet valve to the lock.
  • the accumulated soot containing fullerene and the non-evaporated raw material particles collect here and can be removed via a lock.
  • Figure 3 shows the overall procedural process as a closed process.
  • (1) is the double-walled reactor in which the evaporation device with a crucible (1A) shown in FIGS. 1, 2, 4, 5 and 6 is located. Carbon-containing dusts / granules are evaporated in the crucible (1A) depending on the evaporation process and refilled from the outside in accordance with each consumption quantity, see FIGS. 1, 2, 4, 5 and 6.
  • the resulting product is fed from the reactor (1) to the extraction system (32) via a connecting line (31).
  • the extraction process dissolves the fullerenes formed and leads the solution to the stripper (34) via line (33).
  • the solution is evaporated there.
  • the end products of the stripper (34), the fullerenes, leave the system via the outlet line (35), while the re-liquefied solvent, preferably benzene, is fed again to the extraction system (32) via a connecting line (36).
  • the products not dissolved in the extraction process go to the dryer (37) in order to make them available again as raw material for the evaporation process after drying via the line (39) leading to the reactor (1) and the connection (5).
  • the solvent which has been taken out in the dryer (37) is likewise returned in the liquefied state to the extraction system (32) via the line (38) returned there for reuse.
  • FIG. 4 shows the reactor (1) and crucible (1A) according to FIG. 1, where the method of laser technology using a laser cannon (40), the end of which is located above the dome-like opening of the crucible (1A), is shown.
  • the crucible is filled with carbon-containing raw material to a level "h”.
  • the energy of the laser beam evaporates dust / granules in the crucible (1A).
  • the focal point of the laser cannon (40) is aimed at the carbon-containing raw material lying in the crucible (1A).
  • the crucible filling is permanently supplied with new raw material from dust / granulate through the upper tube (2A) coming from outside into the crucible (1A).
  • Via connection (5) there is a connection to the storage container of a raw material supply system.
  • FIG. 5 shows the reactor (1) and crucible (1A) according to FIG. 4, but now an inductive high-frequency evaporation takes place in the crucible (1A) by means of an inductive high-frequency system (22), which is external to the crucible (1A ) is laid out around.
  • the crucible is again filled to a certain level with carbon-containing raw material.
  • the crucible filling is permanently supplied with new raw material from dust / granulate through the upper tube (2A) coming into the crucible (1A) from the outside.
  • a connection to the reservoir of a raw material supply system is provided via the connection (5).
  • FIG. 5 there are (7,10) nozzles attached to the reactor.
  • At the Socket (7) is fitted with a sight glass.
  • (6,8) are noble gas inlet and outlet openings, whereby a vacuum can also be generated via these.
  • (1A) is the crucible standing on a sieve-like support (19).
  • the inductive high-frequency system is located around the crucible (1A).
  • (3) shows the coolant tank of the reactor cover, where (12,13) are the inlet and outlet openings of the coolant for the reactor cover tank (3).
  • Figure 6 shows the same double-walled reactor (1) and crucible (1A) as Figure 5.
  • the principle of the adapter (21) for the extension of the reactor (1) is shown, so that a sufficiently dimensioned path for the carbon-containing vapors and soot can be specified until these are deposited on the reactor cover.
  • FIG. 7 shows a modification of the reactor (1) and arrangement of the crucible (1A) according to the previous exemplary embodiments.
  • the energy and raw material feeds are carried out analogously to those of FIGS. 1, 2, 4, 5 and 6.
  • the crucible (1A) is rotatably supported relative to the housing of the reactor (1) by means of a crucible holder system (24). During the evaporation of the raw material, it can thus be either standing, that is stationary, or rotating as shown in the drawing in the three evaporation methods described his.
  • Fallen soot that has fallen down and raw material particles that have not evaporated collect additionally in the lock (18) and can be removed here.
  • FIGS. 1, 2, 4, 5 and 6. show the inlet and outlet openings of the coolant for the rotatable crucible holder system (24).
  • FIG. 8 shows, like FIG. 3, the overall procedural process as a closed process when using the device according to FIG. 7.
  • (1) is the double-walled reactor in which the evaporation device with a crucible (1A) shown in FIGS. 1, 2, 4, 5, 6 and 7 is located. Carbon-containing dusts / granules are evaporated in the crucible (1A) depending on the evaporation method and refilled from the outside in accordance with the amount consumed (see FIGS. 1, 2, 4, 5 and 6). The fullerene-containing components are now discharged at two different points via the suction device (23) and the lock outlet valve (18). Connecting lines (31, 42) to the extraction system (32) are connected to the side and below the reactor.
  • the connecting lines (31, 42) open into a common seed connecting line (43), with which the resulting product from the reactor (1) is fed to the extraction system (32) according to FIG. 3.
  • the extraction process dissolves the fullerenes formed and leads the solution to the stripper (34) via line (33).
  • the solution is evaporated there.
  • End products of the stripper (34), the fullerenes leave the system via the outlet line (35), while the liquefied solvent, preferably benzene, is fed again to the extraction system (32) via a connecting line (36).
  • the products not dissolved in the extraction process go to the dryer (37) in order to make them available again as raw material for the evaporation process after drying via the line (39) leading to the reactor (1).
  • the solvent which has been taken out in the dryer (37) is likewise returned in the liquefied state to the extraction system (32) via the line (38) returned there for reuse.
  • FIG. 1 7A raw material feed from below, FIG. 1
  • FIG. 16 water inlet of the movable electrode holder 17 graphite electrode (s), FIG. 1
  • FIG. 1 Inflow opening for coolant of the rotatable crucible holder system 27 Cup-shaped depression in the carbon-containing raw material of the crucible, FIG. 1

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  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne un procédé et un dispositif permettant de produire des Buckminster-fullerènes de carbone à partir de matières premières solides contenant du carbone. Les fullerènes sont obtenus par évaporation de matériaux en vrac carbonés se présentant sous forme de matières premières composées de poussières, de granulats, de substances granuleuses ou de leurs mélanges, qui n'ont pas de forme allongée ou cuboïde marquée. Pour l'opération d'évaporation, il n'est donc plus nécessaire de faire passer des tiges ou des blocs de dimensions plus importantes, et coûteux à travers le point focal du rayonnement laser, à travers le système d'un champ inductif de haute fréquence ou comme électrodes d'arc électrique (17). L'invention permet de produire, en continu, à une échelle industrielle sur une longue période, et de manière économique, des fullèrenes, avec un équipement relativement simple, à une pression atmosphérique normalisée. Pour évaporer le carbone dans une atmosphère inerte de gaz rare, les matières premières solides contenant le carbone ou les composés carbonés sont acheminés directement dans un arc électrique, un champ inductif à haute fréquence ou bien un faisceau laser incident à l'intérieur d'un creuset (1A) ou une gaine tubulaire rempli(e) depuis l'extérieur et à remplir à nouveau avec les matières brutes contenant du carbone. Les matières premières solides contenant le carbone ou les composés carbonés sont exempts de gaz réactifs ou d'additifs comme de l'azote, de l'oxygène, de l'hydrogène ou de la vapeur d'eau. L'évaporation et l'acheminement des matières premières contenant du carbone s'opèrent dans le réacteur (1) dans un creuset (1A) semi-ouvert, haut, de type convertisseur, ou dans une gaine tubulaire destinée au carbone qui s'évapore, de manière que le refroidissement des vapeurs de carbone s'effectue lentement et que ces vapeurs se condensent sous forme de noir de carbone sur le couvercle (3) refroidi du réacteur dans un mouvement ascensionnel.
PCT/DE1994/000084 1993-01-27 1994-01-27 Procede et dispostif permettant de produire des fullerenes de carbone a partir de matieres premieres solides contenant du carbone WO1994016993A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4302144.1 1993-01-27
DE4302144A DE4302144C2 (de) 1993-01-27 1993-01-27 Verfahren zur Erzeugung von Kohlenstoff-Fullerenen aus kohlenstoffhaltigen festen Rohstoffen und Vorrichtung dazu

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WO1994016993A1 true WO1994016993A1 (fr) 1994-08-04

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WO (1) WO1994016993A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2187456C2 (ru) * 2000-04-25 2002-08-20 Плугин Александр Илларионович Технический комплекс для производства фуллеритов
RU2203852C2 (ru) * 1997-06-18 2003-05-10 Турышев Борис Иванович Установка для производства фуллеренов
US20240228299A1 (en) * 2022-07-25 2024-07-11 Urbix Resources, Llc. Graphite Purification System and Method

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2764280B1 (fr) 1997-06-06 1999-07-16 Yvan Alfred Schwob Procede pour la fabrication de carbone 60

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992004279A1 (fr) * 1990-08-30 1992-03-19 Research Corporation Technologies, Inc. Nouvelle forme de carbone
WO1993001128A1 (fr) * 1991-07-10 1993-01-21 Commonwealth Scientific And Industrial Research Organisation Preparation et separation de fullerenes
EP0527035A1 (fr) * 1991-08-07 1993-02-10 Mitsubishi Chemical Corporation Procédé de préparation de fullerène
WO1993023331A1 (fr) * 1992-05-15 1993-11-25 Lane David R Iii Procede de production de fullerenes utilisant du plasma

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992004279A1 (fr) * 1990-08-30 1992-03-19 Research Corporation Technologies, Inc. Nouvelle forme de carbone
WO1993001128A1 (fr) * 1991-07-10 1993-01-21 Commonwealth Scientific And Industrial Research Organisation Preparation et separation de fullerenes
EP0527035A1 (fr) * 1991-08-07 1993-02-10 Mitsubishi Chemical Corporation Procédé de préparation de fullerène
WO1993023331A1 (fr) * 1992-05-15 1993-11-25 Lane David R Iii Procede de production de fullerenes utilisant du plasma

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
R.F. CURL ET AL., SPEKTRUM DER WISSENSCHAFT, December 1991 (1991-12-01), pages 88 - 98 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2203852C2 (ru) * 1997-06-18 2003-05-10 Турышев Борис Иванович Установка для производства фуллеренов
RU2187456C2 (ru) * 2000-04-25 2002-08-20 Плугин Александр Илларионович Технический комплекс для производства фуллеритов
US20240228299A1 (en) * 2022-07-25 2024-07-11 Urbix Resources, Llc. Graphite Purification System and Method
US12215029B2 (en) * 2022-07-25 2025-02-04 Urbix, Inc. Graphite purification system and method

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DE4302144C2 (de) 1996-01-25
DE4302144A1 (de) 1994-07-28

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