WO1994016993A1 - Process and device for producing carbon fullerenes from carbon-containing solid raw materials - Google Patents

Abstract

A process and device are disclosed for producing carbon Buckminster fullerenes from carbon-containing solid raw materials. Fullerenes may be produced by evaporating carbon-containing bulk materials in the form of solid raw materials from dusts, granulates, grained substances or mixtures thereof which have no substantial rod or cubelike form. Expensive, larger rods or blocks need thus no longer be pushed through the focal point of laser radiation, through the system of an inductive high-frequency field or as arc electrodes (17) in order to be evaporated. A continuous, cost-effective large scale production of fullerenes over a long time thus becomes possible at a normal pressure with a relatively simple equipment. In order to evaporate carbon in an inert rare gas atmosphere, the solid carbon-containing raw materials or carbon compounds are directly led into an electric arc, an inductive high-frequency field or an incident laser beam within a crucible (1A) or tubular casing filled from the outside which is refilled with the carbon-containing raw materials. The carbon-containing raw materials or carbon compounds are free from reactive gaseous components or addition products such as nitrogen, oxygen, hydrogen and steam. Evaporation and supply of carbon-containing raw material is carried out in the reactor (1) in a semi-opened, high converter-like crucible (1A) or in a tubular casing for the evaporating carbon, so that the carbon vapours slowly cool down and rise to condense as carbon black onto the reactor cover (3).

Description

Name: Process for the production of carbon

Fullerenes from carbon-containing solid raw materials and device for this.

Technical field

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.

State of the art

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 atoms cool down and condense to form carbon Buckmisterfullerenes and other fullerene structures (Spektrum der Wissenschaft, Dec. 1991, pp. 80-98).

Furthermore, an apparatus according to Krätschmer and Huffmann is known, where fullerenes can be produced in macroscopic amounts by evaporating graphite in an electric arc. Graphite rods, which are provided with a thread mechanism for rod tracking, serve as electrodes. The evaporating carbon is held near the arc, with the atoms forming molecules and forming carbon Buckminsterfullerenes. In contrast to fullerene formation under the evaporation of carbon and subsequent spontaneous condensation, attempts have also been made to form clusters of carbon atoms from sooty hydrocarbon To form flames. However, this process is only suitable for the formation of carbon Buckminster fullerenes as a random product.

In contrast, 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. In the evaporation process, 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 reactors used hitherto are expensive to set up and maintain, since continuous carbon evaporation and condensation for the formation of carbon Buckminsterfullerenes can only be carried out over a longer period of time with a high outlay on equipment. If one also takes into account the need for a vacuum or low pressures, there are further problems.

Task and solution

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. In particular, 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.

This object is achieved by a method according to the main claim. The advantageous embodiment of the method results from the subclaims. The method of the type mentioned at the outset is further developed in such a way that directly in the electric arc, in the focal point of a laser beam or in the inductive high-frequency field within one from the outside Pressing in (by pressing), by blowing in with inert carrier gases, by trickling in or by shaking in with carbon-containing solid raw materials in the form of dusts, granules, granular substances or mixtures of filled crucibles or a tubular casing containing these raw materials by vibrations, shaking, rotating Crucible or the envelope or by blowing inert inert gas into the crucible filling are fed to the evaporation area and evaporate while increasing the residence time and simultaneously cooling the evaporation area. To carry out this method, a device is provided according to claim 37, which is designed according to claims 39-46.

As a reactor for evaporating the carbon and for condensing the vapors containing fullerene, 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.

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.

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. In addition, 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.

In the area of the upper edge, the area of the outlet opening of the crucible, a sight glass is attached to a reactor nozzle. At the same height, on the other, opposite side, there is an assembly socket which, if the reactor is put into operation, is closed with a blind cover. In the lower area of the reactor there is 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. With a rod-shaped, upper electrical pole from an electrode or a plurality of electrodes, preferably from a graphite rod, and with a lower electrical counter pole from the dust and granule-like, carbon-containing raw material received in the crucible or cf. Figure 1

What is important in this method with only one electrode rod as the electrical counter pole is, inter alia,

* that electrode rods do not have to be pushed in for the supply of raw materials, but the dust / granulate supply maintains the arc between the stick electrode and the surface of dust / granulate, preferably

* The end products which do not contain fullerene, after extraction and preparation for drying, are returned to the evaporation process as a carbon-containing raw material in order to achieve a high raw material yield.

b) With a rod-shaped electrical pole from an electrode or a plurality of electrodes, preferably from a graphite rod, and with the electrical opposite pole from one or more rod-shaped electrodes, preferably from a graphite rod. In this case, the carbon-containing raw material is conveyed into the arc between the electrodes, preferably blown in with an inert gas, cf. Figure 2.

It is essential in this method with two rod-shaped electrodes as electrical counterpoles that "'That electrode rods do not have to be pushed in for the supply of raw materials, but rather the dust / granulate supply maintains the arc between the rod electrode and the surface made of dust / granulate and preferably

* The end products which do not contain fullerene are re-fed to the evaporation process as a carbon-containing raw material after the extraction and drying preparation in order to achieve a high raw material yield.

c) where in a) and b) direct current (the material to be evaporated receives the positive pole) or alternating current can be used.

In the crucible, 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 same thing happens when evaporation is carried out using laser technology (FIG. 4). 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.

Finally, evaporation in an inductive high-frequency field is also possible. The 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.

In the above-mentioned processes, a different raw material structure is used for the first time. Instead of carbon-containing rods, cubes or similar the actual raw materials, namely carbon-containing dusts or granules of graphite, coal, etc. are now used. The grain structure can be fine to coarse.

The fullerene-forming evaporation is not only much cheaper, but also easier.

An essential prerequisite is that 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. For this purpose, 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.

About the process, the basic procedure and the preferred embodiment of the process

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.

Then an inert gas pressure of preferably 1 bar is set. However, the pressure can also range from a few mbar to several bar.

The cooling circuits, preferably water circuits, are then started.

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.

After the arc has been ignited, 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.

Then 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:

1. From the bottom outside or from the side (by pushing in). 2. From the side (by pushing in or blowing in).

3. 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.

It turns out that three equilibria have to be considered for a continuous, fullerene-containing soot production:

1. 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.

3. When using the arc technology, 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.

At the same time, 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. When the hot gases rise towards the reactor cover, 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 fullerene-containing and loose carbon blacks that form there fall after reaching a thicker layer together with the non-evaporated raw material particles flying out of the evaporation space into the lower lock hopper.

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. As already known, 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.

The same applies to the techniques of laser beams and inductive high-frequency loops. The devices to be used in these two methods and in arc technology are shown in FIGS. 1, 4 and 5 of the drawings and are described in more detail in the process.

Description of the preferred apparatus for carrying out the above preferred, arc-generated Process using plasma and a specific embodiment thereof

A 600 mm long, double-walled VA steel reactor with an inner diameter of 150 mm was used as the device of the process. Above the reactor was 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.

In 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. At the level of the crucible's outlet opening there was a nozzle with a sight glass on the reactor. 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.

First 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. In order to exclude partial counter gas pressures towards the reactor, 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.

Alternating current with 360 amps and 40 V was selected as the current. After about 5 minutes, 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.

After extraction with benzene, the proportion of fullerenes in the carbon black was up to 10 percent by weight.

The main features and objectives of the process are therefore summarized:

- Novel in this process is the use of a different raw material structure. Instead of carbon-containing rods, cubes, etc. the actual raw materials, namely carbon-containing dusts or granules made of graphite, coal, aromatic compounds, etc. are now used. The grain structure can be fine to coarse.

- After the extraction and drying preparation, 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 fullerene-forming evaporation is not only much cheaper due to the use of carbon-containing dusts or granules, but also easier.

- The electrode wear is significantly lower if the soot is produced exclusively with the raw material dust / granulate.

- Compact, carbon-containing dusts or granules have the decisive advantage as a raw material, the direct one Evaporation process to offer a variety of smallest particles that do not have to be first crushed at the expense of evaporation energy. As a result, less non-evaporated raw material escapes in the actual evaporation space, since explosive volatilization of solid particles which have previously blown out is reduced.

- The surface offered for evaporation in the smallest space is very high due to the large number of tiny particles. The specific energy utilization is partially higher for the evaporation process.

- 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.

- Before the actual evaporation process, the carbon-containing raw material from dust or granulate can slowly heat up, i.e. an explosive heating 0 is avoided.

- With the use of a converter-like crucible, non-evaporated flies out 1 particle reduced. They are fed back into the process when hot.

When the hot gases rise towards the exit, the sublimation in noble gas atmosphere must take place as quickly as possible.

a) The rapid volatilization of the hot gases in cold zones is reduced by the surrounding carbon inside the crucible. The atoms and molecules contained in the vapors are given time in a hot environment to rearrange themselves in a spherical manner. 5 b) When the hot gases rise in the direction of the reactor cover, the cooling in an 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 0 to black carbon vapors to the reactor cover before they deposit as soot on the cooled reactor walls.

- 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

The invention is explained in more detail below with reference to the reactors for carbon vaporization shown in the drawings for the purpose of producing fullerene-containing soot.

The drawings show:

1 and 2: A double-walled reactor incl

Inner life, an electric arc being generated in a crucible.

Fig. 3: The overall procedural process of

Fullerene production and extraction with a soot extraction lock.

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.

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

7: 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. is shown in the operating position, in which it is guided somewhat below the level H and as a vaporization area has produced a goblet-like depression (27) in the carbon-containing raw material, which surrounds its end on the side.

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

(2A) - or through the side, lower tube (7A) into the crucible (1A). Via a connection (5) or through the pipe (2) there is a connection to the supply container of a raw material supply system.

It is important in this method with an electrode that electrode rods do not have to be pushed in for the supply of raw materials, but the dust / granulate feed maintains the arc between the rod electrode and the surface of dust / granulate for carbon vaporization. In Figure 1 are (1, 7, 10) attached to the reactor nozzle. 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 a crucible standing on a sieve-like support (19). The rod-shaped counter electrode (17) protrudes into the crucible (1A), which in turn hangs on a coolable and movable electrode suspension (14). (15, 16) show the inlet and outlet openings of the coolant for the electrode suspension. (3) shows the coolant tank of the reactor cover, wherein a seal, a sliding packing (4), seals the reactor with the movable electrode suspension (14).

(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).

It is essential in this method with two electrodes that electrode rods do not have to be pushed in for the supply of raw materials, but the dust / granulate feed maintains the arc between the rod electrodes for carbon vaporization.

In Figure 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. As in FIG. 1, the crucible is filled with carbon-containing raw material to a level "h". The laser beam (20) incident there again creates an evaporation area in the form of a goblet-like depression (41).

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.

It is essential in this process with laser technology that monolithic solids do not have to be replenished in order to supply raw materials, but only dust / granules as carbon to be evaporated. In Figure 4 there are (7,10) nozzles attached to the reactor. A sight glass is mounted on the nozzle (7). (6,8) are noble gas inlet or outlet openings, whereby a vacuum can also be generated via these. (1A) is the crucible standing on a sieve-like support (19). The laser cannon (40) projects to 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). (18) shows the outlet valve to the lock. The accumulated carbon blacks containing fullerene and the non-evaporated raw material particles collect here and can be removed via a lock.

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).

It is essential in this process with inductive high frequency that it is not necessary to add monolithic solids for the purpose of raw material supply, but only dust / granules as carbon to be evaporated.

In Figure 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).

(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 6 shows the same double-walled reactor (1) and crucible (1A) as Figure 5. In addition, 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.

It is essential in this process that the evaporation product above the crucible is immediately removed with a suction device (23) above the crucible (1A). 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.

In Figure 7 (2,7,10) are in turn attached to the reactor. A sight glass is mounted on the nozzle (7). (6,8) are noble gas inlet or outlet openings, whereby a vacuum can also be generated via these. The suction device (23) is mounted on the nozzle (10). (1A) is the crucible standing in the rotatable holder (24). The energy and raw material supply systems protrude into the crucible (1A) as shown in FIGS. 1, 2, 4, 5 and 6. (25, 26) 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. The. 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.

B e z u g s z i f f e r n l i s t e

1 reactor

1A tubular casing in the form of a converter-like crucible

H, h level of the crucible

2 sockets

2A raw material feed from above, Fig. 1,4,5,6

3 reactor covers with water tank

4 sealing (sliding packing)

5 Connection to raw material supply system from storage container

6 vacuum connection

7 sockets with sight glass

7A raw material feed from below, FIG. 1

8 noble gas supply

9 water inlet to the double-walled reactor (for coolant)

10 assembly sockets with blind covers

11 ^' Water outlet from double-walled reactor (for coolant) 12 Water inlet of the water-cooled cover (for coolant) 13 Water outlet of the water-cooled cover (for coolant)

14 Movable electrode holder

15 Water outlet of the movable electrode holder

16 water inlet of the movable electrode holder 17 graphite electrode (s), FIG. 1

18 Outlet valve to the lock

19 Sieve-like support for the converter-like crucible or alternatively for the tubular casing, not shown 20 - laser beam

21 adapter for reactor extension

22 Inductive high-frequency system around the crucible, Fig. 5,6

23 Suction device of the smoke extraction system 24 Rotatable crucible holder system, Fig. 7

25 drain opening for coolant of the rotatable crucible holder system

26 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

28 graphite electrode (s), Fig. 2

29 Pipe feed from above, Fig. 2

30 arrow, feed device of the raw material in FIG. 2

31 connecting line between the reactor and extraction system from the exit lock

32 extraction system; Fullerenes go into solution

33 Connection line between extraction system and stripper

34 strippers; Fullerenes are separated from the solvent

35 Stripper output line

36 Connection line between stripper and extraction system

37 dryer; Undissolved carbon from the extraction plant is dried and processed for evaporation in the reactor

38 Connection line between extraction system and dryer

39 Connection line between stripper and reactor

40 laser cannon

41 Chalice-shaped evaporation area, Fig. 4 Connection line, FIG. 8 Common connection line of the connection lines from the exit lock and from the suction device

Claims

P a t e n t a n s r u c h e 1. Process for the production of carbon fullerenes by heating and evaporating carbon-containing material under an inert noble gas atmosphere in a reactor which is supplied from outside the reactor and from impermissible nitrogen, oxygen, hydrogen, water vapor or others reactive gas components or deposits is freed and which is heated to the evaporation temperature generated in an electric arc, an inductive high-frequency field or an incident laser beam, and with the formation of carbon clusters and fullerene-containing ones. Carbon black and / or carbon vapors, in particular Buckminster fullerenes, by cooling and condensation of carbon of the carbon plasma formed, characterized in that the carbon to be supplied from the outside as a solid raw material in the electric arc, in the focal point of a laser beam or in the high-frequency field Form of dusts, granules, granular substances and as a mixture in a crucible filled from the outside with these carbon-containing solid raw materials or within a tubular casing of these raw materials leads to evaporation and is brought into this evaporation area in such a way that before the condensation of the evaporated coal ¬ material of this with cooling and increasing the residence time for clustering together in the Is kept near its evaporation area in the envelope or the converter-like crucible in an inert gas atmosphere and that outside of this evaporation area the condensation of the carbon and the carbon clusters takes place with the formation of the carbon fullerenes. 2. A process for the production of carbon fullerenes according to claim 1, characterized in that all or part of the filling of the crucible or the casing by pressing in (pressing), by blowing in with inert carrier gases, by trickling or by shaking in the carbon-containing solid Raw materials are made from the outside. 3. A process for the production of carbon fullerenes according to claim 1 or 2, characterized in that the introduction of the carbon-containing solid raw materials in the evaporation area by vibrations, shaking, rotating the crucible or the envelope or by blowing in inert vortices ¬ gases into the crucible filling. 4. A process for the production of carbon fullerenes according to any one of claims 1-3, d a d u r c h g e k e n n z e i c h n e t that the vaporized carbon is also held in the envelope or the converter-like crucible by a magnetic field. 5. Process for the production of carbon fullerenes according to one of claims 1-4, characterized in that the dust-like, fine to coarse or granular, granular, carbonaceous raw material to be supplied from the outside is continuously metered into the electric arc between the electric opposing poles in such a way that an arc generated with one or more carbon electrodes without Burning of the carbon electrode (s) is maintained, so that the electrode rod (s) do not have to be replenished for the purpose of power supply to generate the evaporation heat. 6. A process for the production of carbon fullerenes according to one of claims 1-5, d a d u r c h g e k e n n e e c h n e t that the carbon-containing raw material is continuously introduced into the Verdampfungs¬ process. 7. A process for the production of carbon fullerenes according to one of claims 1-6, characterized in that the carbon-containing raw material to be fed in from the outside before being fed into the reactor in accordance with the vaporization temperatures of the undesirably contained oxygen, hydrogen, nitrogen or water vapor or other reactive gas components are degassed by them at up to 2,200 C in a noble gas atmosphere or vacuum. Process for the production of carbon f fullerenes according to one of Claims 1-7, characterized in that after ignition of the arc, the distance between the electrical opposing poles is adjusted in such a way that with the formation of a hot, goblet-like depression below the stick electrode (s) in the fine-grained to coarse-grained or granular, carbon-containing raw material within the crucible or coating by the vaporization of the carbon the evaporation area is generated for the carbon-containing raw material to be supplied from the outside. 9. A process for the production of carbon fullerenes according to any one of claims 1-8, d a d u r c h g e k e n n e z e i c h n e t that the evaporation is generated within a tubular casing or a converter-like crucible. 10. A process for the production of carbon fullerenes according to any one of claims 1-9, characterized in that the evaporation energy of the arc is generated within an envelope or a crucible and the formation of the arc immersed therein on the surface of the dust / granules, in the dust / granules or is regulated between two electrodes a) with a rod-shaped, upper electrical pole from one or more electrodes and with a lower electrical counter pole from the dust and granulate-like, carbon-containing raw material taken up in the crucible or casing of the reactor b) with a rod-shaped, electrical pole from one or more electrodes and with an electrical Counter pole also from one or more rod-shaped electrodes, in which case the carbon-containing raw material is conveyed between the electrodes into the arc or is blown in with noble gas and c) either direct current (the material to be evaporated receives the positive pole) or alternating current is used. 11. A process for the production of carbon fullerenes according to claim 10, that the rod-shaped electrodes and the raw materials consist of carbon-containing material. 12. A method for producing carbon fullerenes according to any one of claims 1-11, characterized in that the evaporation energy generated by laser beams within a crucible or envelope and is controlled such that the laser beams therein both on the surface of the dust / granules and in Dust / granules immersed come into effect. 13. A method for producing carbon fullerenes according to any one of claims 1-12, characterized in that the evaporation energy is generated and controlled by inductive high-frequency technology within a crucible or envelope, the arrangement of the Spulen¬ systems on a cooled wall around Crucible is done around. 1 14. A method for producing carbon fullerenes according to any one of claims 1-13, characterized in that by means of the evaporation of the carbon 5 arcs, laser beams or inductive high-frequency fields, a goblet-like depression is produced in the fine to coarse-grained or granular, carbon-containing raw material within the crucible or casing, which serves as an evaporation area for the carbon-containing raw material to be supplied continuously from outside. 15. A process for the production of carbon fullerenes according to any one of claims 1-14, 5 characterized in that the carbon-containing raw material is permanently fed to the crucible or coating from the outside, the supply in the reactor both from the bottom, from the side and done from above. 0 16. A method for producing carbon fullerenes according to any one of claims 1-15, d a d u r c h g e k e n n z e i c h n e t that the permanent supply of the carbonaceous 25 raw material by pressing in (pressing), blowing in with inert noble gases, shaking or by trickling in from above the evaporation area. 30 17. A method for producing carbon fullerenes according to any one of claims 1- 16, characterized in that the crucible or coating from a high temperature solid, temperature change-resistant and electrically conductive refractory material. 18. A method for producing carbon fullerenes according to any one of claims 8-17, d a d u r c h g e k e n n z e i c h n e t that a crucible or an envelope made of graphite is used. 19. A process for the production of carbon fullerenes according to one of claims 8-18, characterized in that the carbon-containing raw material supplied to the outside of the reactor and located in and in particular on the edges of the crucible or in the casing on or in the dust / granulate the way from the edge of the crucible to the evaporation area is preheated in the form of a goblet-like depression, at the same time avoiding overheating of the evaporation area by permanent cooling with new raw material. 20. A process for the production of carbon fullerenes according to one of claims 1-19, so that continuous, fullerene-containing soot production takes place with the following three equilibria: 1. The external, permanent flow of the carbon-containing raw material is formed depending on the flow of carbon into the - in the form of a hot cup-like depression Evaporation area regulated by carbon evaporation. The evaporation area in the chalice-like depression must not become too hot, i.e. it is cooled by the permanent supply with cooler, vaporized carbon-containing raw materials. In addition, there is also substantial cooling through the evaporation of the carbon. 3. When using the arc technology, 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 pushing the electrodes for the purpose of controlling the arc and replenishing raw materials. 21. A method for producing carbon fullerenes according to any one of claims 1-20, d a d u r c h g e k e n n z e i c h n e t that the carbon-containing raw material present in the converter-like crucible is conveyed into the evaporation area in the form of a goblet-like depression by a pulse-like or permanent vibration. 22. A process for the production of carbon fullerenes according to any one of claims 1-21, characterized in that the carbon-containing raw material present in the converter-like crucible by means of a pulsed or permanent vibration and / or rotation of the crucible in Sense of a rotary kiln is transported in and around the evaporation area. 23. A process for the production of carbon fullerenes according to any one of claims 1-22, characterized in that the carbon-containing raw material supplied to the crucible is swirled slightly on the way to the actual evaporation area before being vaporized with preheated noble gas (helium, argon or other) to give each individual dust particle or granulate the possibility of entering the evaporation process surrounded by noble gas, the turbulence being achieved by pulsing noble gases, preferably from below, with helium. 24. A method for producing carbon fullerenes according to any one of claims 1-23, characterized in that an increased residence time of the plasma made of carbon in extremely hot areas of the evaporation area is achieved by surrounding walls of the tubular casing or of the convertible crucible inside the reactor . 25. A process for the production of carbon fullerenes according to any one of claims 1-24, characterized in that a crucible is constructed so that the hot rising vapors can cool as well as possible during the ascent and the raw material coming in countercurrent is preheated , which is made possible with two features: a) The crucible is additionally closed off by a dome-like dome, preferably made of graphite and narrowing upwards, in the middle of which there is a sufficiently large opening in order, in the event of an arc, both the electrode rod or electrodes and the pierced rod for the To be able to move the carbon-containing raw material back and forth in a contact-free manner with the aid of a movement mechanism and to ensure unimpeded radiation entry in the case of laser beams; b) the ascent phase of the hot, blue to black color-containing fullerenes containing carbon vapors and gases from the dome-like cupola or the envelope in the direction of the opening is extended in time by a relatively long ascent path, so that either with the help of a Have the suction device remove the cooled vapors or the fullerene-containing, sooty particles deposit on the cooled walls of the reactor, in particular on the reactor cover. 26. A process for the production of carbon fullerenes according to any one of claims 1-25, that a direct coating of the evaporation space from preheated, carbon-containing raw material is present, so that the following fullerene-forming advantages result: a) The escape of hot plasma gases is below and to the side of the electrodes, the laser beams or inside in the case of high-frequency fields mechanically - by a kind of coating of the same carbon - by surrounding dust or granulate mixtures. b) The carbon-containing raw materials supplied from the outside, including the noble gases, are preheated on the way to the evaporation area in the form of a goblet-like depression and are fed to the evaporation area in an extremely hot state by a vibrating, rotating or other movement system. 27. A process for the production of carbon fullerenes according to any one of claims 1-26, characterized in that the flying, non-evaporated kohlstoff¬-containing dusts / granules the evaporation process in a hot state by bouncing off the walls of the casing or the crucible and the like cathedral-like dome can be made available again. 128. Process for the production of carbon fullerenes according to one of claims 1-27, d a d u r c h g e k e n n z e i c h n e t that preferably noble gas impressions between 20 mbar and 5 several bar overpressure can be applied. 29. A method for producing carbon fullerenes according to claim 28, d a d u r c h g e k e n n z e i c h n e t that 0 the noble gas pressure in the reactor is about 1 bar. 30. A process for the production of carbon fullerenes according to any one of claims 1-29, d a d u r c h g e k e n n z e i c h n e t that 5 the fullerene-containing carbon blacks produced are permanently removed via a lock chamber and then fed to a fullerene extraction process. 31. A process for the production of carbon fullerenes 0 according to any one of claims 1-30, characterized in that the ascending evaporation gases are immediately removed from the crucible via a suction device from the reactor chamber, then a fullerene extraction process 5 and the noble gas to the reactor is returned. 32. A method for producing carbon fullerenes according to claim 31, 0 characterized in that the suction device and the crucible rotation and fastening system are cooled by a coolant circuit. 133. A method for producing carbon fullerenes according to any one of claims 1-32, characterized in that the electrode holder (movement system) by a 5 separate coolant circuits can be cooled. 34. A method for producing carbon fullerenes according to claim 33, d a d u r c h g e k e n n z e i c h n e t that 10 the electrode holder (movement system) are electrically isolated in addition to the reactor. 35. A method for producing carbon fullerenes according to any one of claims 1-34, 15 d a d u r c h g e k e n n z e i c h n e t that the arc with an electrical current between 10 and more than 300 amps is generated at about 20 - 60 volts. 2036. A method for producing carbon fullerenes according to any one of claims 1-35, d a d u r c h g e k e n n z e i c h n e t that several evaporation rooms are installed as a multiplier within an overall reactor to higher To enable 25 raw material throughputs. 37. A process for the production of carbon fullerenes according to any one of claims 1-36, characterized in that the end products not containing fullerene are re-fed to the evaporation process as a carbon-containing raw material after the extraction and drying preparation in order to obtain a high raw material to reach prey. 38. A method for producing carbon fullerenes according to any one of claims 1-37, for the large-scale, continuous production of carbon Buckminsterfullerenes (C ^). 39. Device for carrying out a method according to one of claims 1-38, characterized in that the reactor (1) consists of a chemical and temperature-resistant, electrically conductive material, double-walled tube with various flanges required for assembly and operation and Nozzle (2,7,10) as well as with noble gas (6,8) and coolant inlet and outlet lines (9,11,12,13). 40. Apparatus according to claim 39, d a d u r c h g e k e n n z e i c h n e t that the material of the reactor is electrically conductive, which is in electrical connection with one of the electrodes of the arc for generating the plasma and / or the crucible (1A). 41. Apparatus according to claim 39 or 40, characterized in that the reactor (1) vertically or also in the horizontal or in other positions standing with a lock hopper for collecting the soot formed containing fullerene and the flown out of the crucible or casing, not evaporated, carbonaceous raw material particles is arranged. 42. Apparatus according to claim 39, 40 or 41, characterized in that the reactor (l) is equipped with a suction device (23) for the permanent removal of fullerene-containing evaporation gases and / or fullerene-containing soot. 43. Apparatus according to claim 39, 40, 41 or 42, characterized in that in the reactor (1) one or more tubular casings and or converter-like crucibles (1A) with corresponding movement, loading and Energie¬ supply systems (7 ,, 2A , 5.7A, 17.20, 22.28). 44. Device according to one of claims 39 - 43, so that the crucible or casing (1A) is additionally surrounded with a metal coil for coolant. 45. Apparatus according to claim 44, d a d u r c h g e k e n n z e i c h n e t that attachments of inductive high-frequency loops (22) or of coils for generating a magnetic field system within the reactor (1) are applied to the coolable crucible or casing (1A). 46. Apparatus according to claims 39-45, so that one or more smoke and / or soot extraction systems with lock outlet valve or with a suction device (23, 18) and with corresponding cooling systems are located in the reactor (1).