JPH07215710A - Method for producing fullerene c60 by heating component b of composition component of petroleum pitch under high pressure and temperature - Google Patents

Abstract

PURPOSE:To reasonably obtain a industrially inexpensive fullerene C60 by using specific four kinds of components as a raw material, pretreating and baking them in a special condition. CONSTITUTION:When a component extracted from 3g sample with 150cc n-heptane at 98.4 deg.C is defined as component A, a component extracted from the insoluble portion obtained by the solvent extraction of the component A with 150cc benzene at 80.1 deg.C is defined as component B, a component extracted from the insoluble portion obtained by the solvent extraction of the component B with 150cc quinoline at 237 deg.C is defined as component C and the insoluble portion obtained by the solvent extraction of the component is defined as component D, a baked pitch is obtained by using the component B (99.0-100%) extracted from the insoluble portion, which is obtained by extracting the 460-560 deg.C fraction of the petroleum pitch by- produced at the time of decomposing a desulfurized evacuated gas oil with 6-8C aliphatic hydrocarbon, with the 6-8C aromatic hydrocarbon as a raw material and preheating at 360-600 deg.C under 20-400kg/cm<2>. The baked pitch is heated with the component (B) individually or a mixture with the component C in an inert gas under 50-600kg/cm<2> at 600-1200 deg.C for 2-20hr to obtain a baked pitch containing 4-20% fullerene C60, which is sublimed under high temp. and high vacuum.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is based on a petroleum pitch specific component which is subjected to severe heat pretreatment to produce a heat-stable benzene nucleus and a heat-stable naphthalene nucleus. Very stable to heat, having a small number of side groups of alkyl groups. The component or B. which is extremely stable to this heat. Ingredients and B. which are extremely stable to this heat Extremely stable Q.I. S. The mixture of the components subjected to heat treatment using an air flow under high pressure, high temperature inert gas or decomposition product gas to produce a calcined pitch containing fullerene C _60, which from the fullerene C ₆₀ was solvent extraction, high temperature and high vacuum this The present invention relates to providing a method for producing fullerene C _60, which is sublimated and purified, at a reasonably low cost.

[0002]

2. Description of the Related Art Fullerene C ₆₀ is composed of 12 pentagonal shapes consisting of 60 carbon atoms and 20 hexagonal shapes in the shape of a soccer ball or a rugby ball. A completely new carbon allotrope of a hollow polyhedron with truncated icosahedral structures that do not adjoin, 1985
It was first discovered by Mr. Claude of England and Mr. Smalley of the United States in 1980, but it was considered very difficult to extract it as a solid despite the efforts of many researchers.

In the process of cooling the soot, however, the carbon rod was energized in 1990 by Kretschmer of Germany and Huffman of the United States to vaporize the carbon of the carbon rod of the electrode by arc discharge. In addition, it was discovered that the fullerene C ₆₀ dissolved in benzene was present in the soot. Since then, various characteristics of the fullerene C ₆₀ have been studied, and the characteristics of the fullerene doped with potassium have been variously studied. Is astonishingly remarkable, and the electric resistance value is almost zero at an absolute body temperature of 20 ° K or less, and fullerene C is also present.
_As a semiconductor _{60, the} conversion efficiency of converting light into electricity is about 53.
There is also a very high report of%, and if fullerene C ₆₀ can be obtained in large quantities at low cost, it is highly expected that its industrial use will be expanded.

Since a technique for producing a large amount of fullerene C ₆₀ at a low cost has not been sufficiently developed, at present, this is used to sufficiently study the characteristics of the fullerene C _{60 and} to utilize the characteristics to develop its application. and the amount of the extent necessary in order to, in the price of the current fullerene C ₆₀ can not be obtained fullerene C ₆₀ is still sufficient, if so this at a low cost large amount of available, also the characteristics future It is fully expected to emerge as a product that is being studied more and more and is in the limelight as a completely new material.

As a method for producing a large amount of fullerene C ₆₀ , in 1990, the carbon of an electrode due to arc discharge was vaporized in helium gas by the development of Kretschmer and Huffman, and the gaseous carbon was cooled. Various methods for producing fullerene C ₆₀ and rationalization of the production method have been studied in the process of producing, but in this purified soot, fullerene having 60 or more carbon atoms other than fullerene C ₆₀ is by-produced. However, there is no report up to now that fullerenes having 60 or more carbon atoms other than fullerene C ₆₀ produced as a by-product can be used as a raw material for producing fullerene C ₆₀ . Furthermore, due to arc discharge, the electrode is highly heated,
Since the carbon of the electrode itself is vaporized and evaporated, its thermal efficiency is extremely poor, and the production yield of fullerene C ₆₀ with respect to vaporized carbon is also extremely poor. Therefore, the method for producing fullerene C _{60 by} this electrode discharge is poor in both thermal efficiency and production efficiency for carbon as a raw material, and this conventional method cannot be considered as an industrial method at all. Therefore, we developed a method to produce fullerene C ₆₀ at low cost industrially, researched and cultivated the characteristics of fullerene C ₆₀ , which has not been researched and developed at all up to now, and combined the results with those characteristics to be developed and studied in the future. We are confident that new products will be commercialized and that such products will contribute greatly to the improvement of world culture and global environment.

[0006]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The object of the present invention is to obtain a heat-resistant B.V. composition of a petroleum pitch composition component containing a large amount of benzene and naphthalene nuclei which are extremely stable to heat. For the rational production of fullerene C ₆₀ using the ingredients as raw materials, the initial distillation 460 is produced by distilling the petroleum pitch produced by thermal catalytic cracking (FCC) of desulfurized vacuum gas oil by pressure distillation and cutting it by 85%. C. to final distillation 560 ° C. (H. component 20.0% to 80.0%, B. component 20.0% to 80.0%, average molecular weight 360 to 410, softening point 46 ° C. to 64 ° C.)
First, the raffinate (insoluble matter) obtained by solvent extraction of an aliphatic hydrocarbon having 6 to 8 carbon atoms was used to obtain B. Component (H. component 0% to 1.0%, B. component 99.0% to 100.
0%, average molecular weight 390 to 440, a ° C. to 96 ° C.) Softening point 76 as a starting material, under pressure target temperature 360 ° C. to 600 ° C. under a stream 20 kg / cm ² to 400 kg / cm ² in an inert gas or decomposition product gas It is heated to the target temperature for 2 to 10 hours, and has a highly stable B.I. having a benzene nucleus and a naphthalene nucleus as main components and a side chain of an alkyl group having a small number of carbon atoms. Component (average molecular weight 362 to 376, softening point 80 ° C to 86 ° C) and B. Extremely stable Q.I. S. Ingredient (average molecular weight 824
To 848, a softening point of 347 ° C. to 357 ° C.) or a heat stable B.I. having a side chain of an alkyl group containing 1 benzene nucleus and 2 naphthalene nuclei as main components and having as few carbon atoms as possible. Component (average molecular weight 412 to 416, softening point 74 ° C to 76 ° C) and B. Extremely stable Q.I.
S. Ingredients (average molecular weight 876 to 900, softening point 368
℃ to 378 ℃) containing 72% yield
.About.77%, and the fired pitches of these are extremely stable to heat obtained by solvent extraction of aromatic hydrocarbons having 6 to 8 carbon atoms. Ingredients are very stable to this heat or B. Ingredients and B. which are extremely stable to this heat Raffinate (insoluble matter) obtained by solvent extraction of the component B. Extremely stable Q.I. S. 50 kg of a mixture of ingredients under a stream of inert gas or decomposition product gas
/ Cm ^{2 to} 600 kg / cm ² under pressure 600 ° C
Fullerene which is heat-treated at 1 to 1,200 ° C for 4 hours to 20 hours to form a fired pitch containing 4% to 20% of fullerene C ₆₀ at a yield of 70% to 84%, and is separated by solvent extraction. Fullerene C ₆₀ can be industrially manufactured at low cost by sublimating and purifying C ₆₀ at high temperature under high vacuum.

[0007] Depending on that the fullerene C ₆₀ to pressure heat treatment of this firing pitch by solvent extraction fullerene C ₆₀ was separated and removed above, for the manufacture of fullerenes C ₆₀ capable of producing a fullerene C ₆₀ It can be used repeatedly as a raw material and can be used more sufficiently. That is, petroleum pitch is obtained by solvent extraction of aliphatic hydrocarbons having 6 to 8 carbon atoms and raffinate (insoluble matter) is obtained by solvent extraction of aromatic hydrocarbons having 6 to 8 carbon atoms. The ingredients are first subjected to a strict heat treatment pretreatment to produce a B. Ingredients or this heat stable B. Ingredients and B. which are extremely stable to this heat Extremely stable to heat forming a three-dimensional structure made from the components Q.
S. The mixture and the fullerene C ₆₀ with the component starting depending on the method repeating the mixture under a stream high pressure heat treatment of the inert gas or decomposition product gas of the firing pitch by solvent extraction to separate and remove the fullerene C ₆₀ fullerene C ₆₀
It has become possible to manufacture the first industrially reasonably inexpensively.

The conventional fullerene C ₆₀ is produced by vaporizing carbon of a carbon rod for discharge by an arc discharge in an inert gas such as helium gas, and heating and vaporizing it to an ultrahigh temperature to form a hexagonal carbon mesh. Fullerene C ₆₀ was manufactured in the process of cooling the gas arranged in the above structure. However, the conventional method has extremely poor thermal efficiency, and in the conventional method for producing fullerene C ₆₀ , many fullerenes having 60 or more carbon atoms are by-produced and the production yield of carbon fullerene C ₆₀ is also extremely poor.

[0009] Act against preparation of conventional fullerene _{C 60} is At a production method of the fullerene _{C 60,} an obstacle to petroleum pitch B. A compound of a 6-carbon hexagonal benzene nucleus in which the side chain alkyl groups of the aromatic compound are removed as much as possible and a 10-carbon hexagonal array of two connected naphthalene nuclei B. The main component, which is extremely stable to heat, Ingredients and B. which are extremely stable to this heat Q. Three components are combined to form a carbon three-dimensional structure that is extremely stable to heat. S.
By using a mixture with the ingredients as the raw material, a firing pitch containing fullerene C ₆₀ having excellent physical properties is made only in the process of heating it under high pressure, and the fullerene C ₆₀ is separated by solvent extraction. The removed firing pitch can be reasonably and sufficiently utilized as a raw material for producing the fullerene C ₆₀ , and thus, the fullerene C ₆₀ having excellent physical properties can be reasonably produced in a large amount at a low cost only by this method. It became possible for the first time.

According to the invention of the fine chemical analysis method for petroleum-based pitch, the following facts have been found out. That is, this method is very stable to the heat of petroleum pitch. The ingredients and this heat stable B.I. Extremely stable to heat forming a three-dimensional structure made from the components Q. S. During the heating process of the components under high pressure, carbon and hydrogen in the side chains of the alkyl group of the benzene nucleus and the alkyl group of the naphthalene nucleus of each component are first decomposed and vaporized together and removed as a compound of carbon and hydrogen. The number of chains is decreasing, and the three-dimensional structure of Q. S. It is considered that even the hydrogen atoms of the benzene and naphthalene nuclei of the component skeleton are vaporized to form a three-dimensional structure of carbon only, which forms the most stable fullerene structure at high temperatures. Based on the petroleum pitch B. The ingredients are first severely pretreated to produce a highly heat-stable B. The ingredients and this heat stable B.I. The three-dimensional Q. S.
This is a characteristic method that makes it possible to produce rational fullerene C ₆₀ for the first time by strictly heat-treating components and the like under high pressure.

The above-mentioned petroleum pitch is obtained by solvent extraction of an aliphatic hydrocarbon having 6 to 8 carbon atoms, and the raffinate (insoluble matter) is further obtained by solvent extraction of an aromatic hydrocarbon having 6 to 8 carbon atoms. B. Ingredients (H. ingredient 0% to 1.0%,
B. Ingredient 99.0% to 100.0%, average molecular weight 39
0 to 440, softening point of 76 ° C to 96 ° C) according to the invention of the fine chemical analysis method of petroleum pitch, the oil type of crude oil and the production method of petroleum pitch according to B. It was also found that the chemical structure and physical properties of the components were quite different. Furthermore, this B. It has been found that the chemical structure of the components and their physical properties are also quite different. Furthermore, B. Clarification of the mechanism of fullerene C ₆₀ formation in the case of producing fullerene C ₆₀ using the above ingredients as a raw material, and further, petroleum pitch B. B. of petroleum pitch by fine chemical analysis method of chemical composition of components The components themselves were subjected to B.I. without being subjected to severe preliminary heat treatment.
When the component is used as a raw material for producing fullerene C ₆₀ , a side chain of an alkyl group having 3 or more carbon atoms, which is linked to a benzene nucleus and a naphthalene nucleus, suddenly induces thermal decomposition, and a product generated by the thermal decomposition Pitch adheres to the inner wall of the upper lid of the reactor, making it impossible to continue the heating reaction and the pitch attached to the inner wall of the upper lid of the reactor falls into the reaction product,
The product cannot be used as a raw material for producing fullerene C ₆₀ at all. Therefore, it is absolutely necessary to take measures to eliminate such obstacles.

The composition of the petroleum-based pitch B. Since the chemical compositions of the components differ from each other, the heat treatment should be strictly performed in advance and the B. The components are homogenized as much as possible, and further transferred to a property that is extremely stable to heat. The three-dimensional structure of the three-dimensional structure produced by combining the benzene nucleus and the naphthalene nucleus, which are extremely stable to heat, from the ingredients S. The ingredients are made first, and B. which is extremely stable to these heats. Ingredients and B. which are extremely stable to this heat Q. With a three-dimensional structure that is extremely stable to the heat produced from the ingredients S. It has been found that using ingredients as raw materials is an essential condition for the production of fullerene C ₆₀ .

Therefore, the petroleum-based pitch, which is produced by thermal catalytic cracking (FCC) of desulfurized vacuum gas oil as described above, is distilled under reduced pressure, and a fraction produced by cutting it by 85% is aliphatic carbonized with 6 to 8 carbon atoms. Raffinate (insoluble matter) obtained by solvent extraction of hydrogen can be obtained by solvent extraction of aromatic hydrocarbon having 6 to 8 carbon atoms. Inert gas or decomposition product gas using components (H. component 0% to 1.0%, B. component 99.0% to 100.0%, average molecular weight 390 to 440, softening point 76 ° C to 96 ° C) as a raw material Under a pressure of 20 kg / cm ^{2 to} 400 kg / cm ² under a target air temperature of 360 ° C. to 60 ° C.
It is heated up to 0 ℃ and heat-treated at that temperature for 2 to 10 hours, and it is extremely stable to heat having 2 side chains of benzene nucleus and 1 naphthalene nucleus as main components and side chain of alkyl group with as few carbon atoms as possible. B. Ingredients (average molecular weight 362 to 37
6, softening point 80 ° C to 86 ° C) and B. which is extremely stable to this heat. Q. The three components are heat-bonded and form a three-dimensional structure. S. Ingredients (average molecular weight 824 to 848,
A softening point of 347 ° C. to 357 ° C.) or a highly stable B.I. having a side chain of an alkyl group containing 1 benzene nucleus and 2 naphthalene nuclei as main components and having as few carbon atoms as possible. Ingredients (average molecular weight 412 to 416, softening point 74 ° C to 7
6 ° C.) and B. Q. The three components are heat-bonded and form a three-dimensional structure. S. Ingredients (average molecular weight 876 to 900, softening point 368 ° C to 3
Yield of 72% to 77
%, And the firing pitch of these is 6 to 8 carbon atoms as described above.
The above-mentioned heat-stable B. Ingredients are very stable to this heat or B. Ingredients and this B. Extraction of raffinate (insoluble matter) obtained by solvent extraction of components with quinoline or the like forms a very stable three-dimensional structure against heat. Q. S. The mixture with the components is heated under a flow of an inert gas or a decomposition product gas under a pressure of 50 kg / cm ^{2 to} 600 kg / cm ^{2 and} a temperature of 600 ° C. to 1,2.
After heat treatment at 00 ° C. for 4 hours to 20 hours, B. The components are Q. S. Reacting with the ingredients Q. i. The skeleton of the hexagonal three-dimensional array of carbon only (hexagonal type) is decomposed and vaporized to hydrogen in the skeletons of the three-dimensional structure of the benzene nucleus and the naphthalene nucleus The hexagonal network is curved due to high-pressure heating, and the pentagonal shape is in the center, and the hexagonal carbon gathered around it is a polygonal carbon skeleton that is extremely stable to heat. Generated in a heat-stable fullerene C ₆₀ form a fired pitch containing 4% to 20% of fullerene C ₆₀ in a yield of 70% to 84%, which is separated by solvent extraction. The fullerene C ₆₀ separated by the above method can be industrially manufactured reasonably.

The firing pitch of the residue obtained by extracting the fullerene C ₆₀ with a solvent is usually used as a raw material in the flow of an inert gas or a decomposition product gas at 50 kg / cm ^{2 to} 600 k.
Heat treatment at g / cm ² at a temperature of 550 ° C. to 1,200 ° C. for 2 hours to 10 hours to give 4% of fullerene C _60.
Yield of 74% to 86%
Can be built. Benzene nucleus that is extremely stable to heat 2
Which has a side chain of an alkyl group having as few carbon atoms as possible and having a naphthalene nucleus and a naphthalene nucleus as main components, and is extremely stable to heat. Ingredients (average molecular weight 362 to 376, softening point 80 ° C
B. which is extremely stable to this heat or to taste. Ingredients and B. which are extremely stable to this heat Q. The three components are heat-bonded and form a three-dimensional structure. S. Ingredients (average molecular weight 824 to 848, softening point 347 ° C to 357
Under a stream of inert gas or decomposition product gas mixture as a raw material for the ℃) 50kg / cm ² to 600 kg / cm ²
At a temperature of 600 ° C to 1,200 ° C for 4 hours to 20
Heat treatment for 4 hours to give fullerene C ₆₀ of 4% to 20%
The contained firing pitch was made with a yield of 70% to 84%, and the above-mentioned fullerene C _{60 was} added to 100 parts of the firing pitch of the residue obtained by solvent-extracting the fullerene C ₆₀ from this firing pitch.
B. which is extremely stable to heat of the manufacturing raw material of B. 60 parts to 1 component
40 parts by addition and mixing, or 100 parts by weight of the firing pitch of the residue obtained by solvent-extracting the fullerene C ₆₀ , the B. Ingredients and this B. Q. The three components are heat-bonded and form a three-dimensional structure. S. 60 parts to 140 parts of a mixture with the components are added and mixed, and these are used as raw materials under an inert gas or decomposition product gas stream of 50 kg /
cm ² to 2 hours to be 20 hours of heat treatment at 600 kg / cm ² at a temperature 600 ° C. to 1,200 ° C., 72% calcined pitch containing fullerene _{C 60} 4% to 20% yield to 84% It is possible to build with. Further, it has an extremely heat-stable benzene nucleus and two naphthalene nuclei as main components and has a side chain of an alkyl group having as few carbon atoms as possible. Ingredients (average molecular weight 412
No. 416 to 416, softening point 74 ° C. to 76 ° C.) B. Ingredients and B. which are extremely stable to this heat Q. The three components are heat-bonded and form a three-dimensional structure. S. Ingredients (average molecular weight 876 to 900,
A mixture with a softening point of 368 ° C to 378 ° C) is used as a raw material under an inert gas or decomposition product gas flow of 50 kg / cm.
2 hours to be 20 hours of heat treatment at ² to 600 kg / cm ² of pressure temperature 600 ° C. to 1,200 ° C., 70% calcined pitch containing fullerene _{C 60} 4% to 20% yield to 84% B., which is extremely stable to the heat of the above-mentioned raw material for producing fullerene C ₆₀ , per 100 parts of the firing pitch of the residue obtained by solvent-extracting fullerene C ₆₀ from this firing pitch. 60 to 140 parts of the ingredients are added and mixed,
Alternatively, with respect to 100 parts of the firing pitch of the residue obtained by solvent-extracting fullerene C ₆₀ , B. Ingredients and this B. Q. The three components are heat-bonded and form a three-dimensional structure. S. Mixture with ingredients 60 parts to 140
Parts are added, and these are used as raw materials in a stream of an inert gas or a decomposition product gas at 50 kg / cm ^{2 to} 600 kg / c.
Heat treatment at m ² at a temperature of 600 ° C. to 1,200 ° C. for 2 hours to 20 hours to give fullerene C ₆₀ of 4% to 2%.
Calcined pitch containing 0% becomes possible to produce in 72% to 84% yield, fullerene C ₆₀ to sublimation purification to this was solvent than the firing pitch containing fullerene C ₆₀ in which like under high temperature and high vacuum Can be industrially manufactured.

The conventional method of vaporizing carbon at an extremely high temperature by arc discharge, cooling the vaporized carbon gas to form soot, and solvent-extracting fullerene C ₆₀ produced in the soot are described below. The yield of fullerene C ₆₀ is extremely poor,
Fullerenes with a large number of carbons other than fullerene C ₆₀ cannot be used as a raw material for fullerene C ₆₀ . Therefore, the conventional method for producing fullerene C ₆₀ , which vaporizes carbon at an ultrahigh temperature and cools it, has extremely poor thermal efficiency,
Further, the production efficiency of fullerene C ₆₀ produced in soot is extremely poor, and the conventional production method is poor in both thermal efficiency and carbon efficiency. Therefore, it cannot be considered as an industrially rational method. A more rational method than this conventional method was devised here. That is, B. of petroleum pitch. B. which has a benzene nucleus and a naphthalene nucleus as main components and has a side chain having as few carbon atoms as possible, which is extremely stable to heat. The component or B. which is extremely stable to this heat. Ingredients and B. which are extremely stable to this heat 3 ingredients
Extremely stable Q.
S. By using the mixture with the components as the raw material, both the thermal efficiency of the production of fullerene C ₆₀ and the yield of carbon are extremely good, and therefore fullerene C ₆₀ can be produced rationally and industrially at low cost for the first time. Tonatsuta.

B. Solvent extraction of petroleum pitch with aliphatic hydrocarbons having 6 to 8 carbon atoms to produce raffinate (insoluble matter) by solvent extraction with aromatic hydrocarbons having 6 to 8 carbon atoms. Using the ingredients as raw materials, preheated heat treatment is performed under pressure to form a fired pitch, which is then extracted with a solvent and is extremely stable to heat. Ingredients are very stable to this heat or B.
Ingredients and B. which are extremely stable to this heat Q. Three components are combined to form a three-dimensional structure. S. B. Producing a fired pitch containing fullerene C ₆₀ by heat-treating a mixture with the ingredients as a raw material under high pressure at high temperature and solvent-extracting petroleum-based pitch B. Inert gas used for heat treatment for pre-treatment of components, other heat treatment reaction, etc., is nitrogen, methane, ethane, propane, etc. or mixed gas thereof, and decomposition produced as a by-product during the production of fired pitch. Product gas (for example, hydrogen 6.0%, methane 74.6%, ethane 13.4%, propane 3.6%, butane 1.3%, pentane 0.9%, olefins 0.1%, etc. ) Can be mentioned.

[0017]

Example 1 A fraction produced by distilling petroleum pitch produced by thermal catalytic cracking (FCC) of desulfurized vacuum gas oil by vacuum distillation and cutting it by 85% (initial distillation 460 ° C. to final distillation 560 ° C., H. Component 71.7%, average molecular weight 342, softening point 46 ° C to 4
9 ° C, B.I. Component 28.1%, average molecular weight 432, softening point 76 ° C. to 96 ° C., benzene insoluble content 0.2% or less) are prepared by solvent extraction with benzene using raffinate obtained by solvent extraction of hexane as a raw material. Component (H. component 0.05% or less, B. component 99.9% average molecular weight 43
2. Using a softening point of 75 ° C to 96 ° C as a raw material, a decomposition product gas (hydrogen 5.0%, by-produced when a fired pitch is produced,
Methane 75.2%, ethane 16.6%, propane 3.2
%) Under a pressure of 100 kg / cm ² under a pressure of 500 ° C.
The mixture was heated and calcined for 5 hours with stirring to give 2 benzene nuclei and 1 naphthalene nuclei having a side chain alkyl group having as few carbon atoms as possible and having extremely stable heat. Component (average molecular weight 368, softening point 82 ° C to 86 ° C) and B. Extremely stable Q.I. S. A baked pitch containing components (average molecular weight 842, softening point 350 ° C. to 355 ° C.) and the like was produced with a yield of 74%, and this baked pitch was extremely stable to the heat of extraction with benzene. Component (average molecular weight 368, softening point 82 ° C to 86 ° C) and rafinate produced by solvent extraction of benzene are very stable to heat produced by solvent extraction of quinoline. S. Ingredients (average molecular weight 842, softening point 350
° C. to 355 ° C.) mixture was used as a raw material under pressure temperature under a stream 300 kg / cm ² of the decomposition product gas of the above with 1,00
It was heated at 0 ° C for 8 hours to make a thermally-formed pitch containing 8% of fullerene C ₆₀ with a yield of 75%, and this fired pitch was subjected to solvent extraction to extract and separate the fullerene C ₆₀ reasonably. Fullerene C ₆₀ sublimated at high temperature under vacuum
Can be reasonably and industrially manufactured.

[0018]

Example 2 A distillate produced by distilling petroleum pitch under reduced pressure is produced by solvent extraction of heptane. A solvent is extracted with benzene using raffinate as a raw material. The components were heated at a temperature of 50 kg under a pressure of 100 kg / cm ² under the gas stream of the decomposition product gas of Example 1.
Benzene nucleus 2
Which has a side chain of an alkyl group having as few carbon atoms as possible, with B.
Component (average molecular weight 368, softening point 82 ° C to 86 ° C) and B. Extremely stable Q.I. S. B. Producing a fired pitch containing components (average molecular weight 842, softening point 350 ° C. to 355 ° C.) and the like, and solvent-extracting the fired pitch with benzene. Ingredient (average molecular weight 368, softening point 82
(100 ° C. to 86 ° C.) 100 parts of the fired pitch containing fullerene C _{60 produced according} to Example 1 was solvent-extracted and 100 parts of the fired pitch of the residue separated by fullerene C ₆₀ extraction was added and mixed, and this mixture was mixed as described above. Decomposition product gas flow 3
Heat treatment at a temperature of 1,000 kg / cm ² and pressure of 1,000 ° C. for 4 hours was performed to make a calcination containing 8% of fullerene C ₆₀ with a yield of 78%, and the calcination pitch was solvent extracted to rationalize fullerene C ₆₀ . Can be extracted reasonably and sublimated at high temperature under high vacuum to purify fullerene C ₆₀ , which can be reasonably and industrially produced.

[0019]

EFFECT OF THE INVENTION Petroleum pitch (a mixture of H. component and B. component) produced by thermal catalytic cracking (FCC) of desulfurized vacuum gas oil is mixed with B. Only the component is separated and extracted, and the B. First, radical heat treatment is performed on the components, and regardless of the type of petroleum oil and the production method of the petroleum-based pitch, it is extremely heat-resistant to have a side chain of an alkyl group containing benzene and naphthalene nuclei as main components and having as few carbon atoms as possible. Stable B. Component, or B. which is extremely stable to this heat. Ingredients and this heat stable B. The benzene nucleus and the naphthalene nucleus formed from the components are very stable to heat and form a three-dimensional structure having a side chain with a small number of carbon atoms. S. A mixture with the components is used as a raw material and heat-treated at a high pressure and a high temperature under a stream of an inert gas or a decomposition product gas to prepare a fired pitch containing fullerene C _60, and the fired pitch is separated by solvent extraction and separated. It became possible for the first time to rationally and industrially produce fullerene C ₆₀ by a method of sublimation and purification at high temperature under high vacuum.

Claims (3)

[Claims] 1. A 1H. Components: Components extracted from 3 gr of sample with 150 cc of n-heptane at a temperature of 98.4 ° C. 2 B. Component: H. H. coli obtained by solvent extraction of the components. Insoluble component (rafuinate) to benzene 150c
Ingredients extracted in c at a temperature of 80.1 ° C. 3 Q. S. Ingredients: B. B. obtained by solvent extraction of the components Quinoline 150 from insoluble ingredients (rafuinate)
Ingredients extracted at a temperature of 237 ° C in cc. 4 Q. i. Ingredient: Q. S. Q. Obtained by solvent extraction of components S. Determined as insoluble component (rafuinate). Desulfurization Vacuum petroleum pitch produced as a by-product by thermal catalytic cracking (FCC) of vacuum gas is distilled at a reduced pressure of 85% to make initial distillation at 460 ° C to final distillation at 560 ° C (H. component 20.0% to 8%).
0.0%, B.I. Ingredient 20.0% to 80.0%, average molecular weight 360 to 410, softening point 46 ° C to 64 ° C) is used to convert raffinate (insoluble matter) obtained by solvent extraction of an aliphatic hydrocarbon having 6 to 8 carbon atoms into carbon. B. obtained by solvent extraction of aromatic hydrocarbons of several 6 to 8 Component (H. component 0% to 1.0%, B. component 99.0% to 100.0%, average molecular weight 390 to 440, softening point 76 ° C to 96 ° C)
As a raw material under a stream of inert gas or decomposition product gas 2
Under a pressure of 0 kg / cm ^{2 to} 400 kg / cm ² , the temperature is raised to a target temperature of 360 ° C. to 600 ° C.
A pre-treatment of heating for 10 to 10 hours is carried out, and B. is extremely stable to heat having 2 side chains of benzene nucleus and 1 naphthalene nucleus as main components and side chains of an alkyl group having as few carbon atoms as possible. Ingredients (average molecular weight 362 to 376, softening point 80 ° C
B. which is extremely stable to this heat. Q. The three components are heat-bonded and form a three-dimensional structure. S.
Component (average molecular weight 824 to 848, softening point 347 ° C to 357 ° C), or heat having 1 heat-stable benzene nucleus and 2 naphthalene nuclei as main components and side chains of alkyl groups having as few carbon atoms as possible Extremely stable to B. Ingredients (average molecular weight 412 to 416, softening point 74 ° C to 7
6 ° C.) and B. Q. The three components are heat-bonded and form a three-dimensional structure. S. Ingredients (average molecular weight 876 to 900, softening point 368 ° C to 3
(78 ° C.) etc. to produce a fired pitch with a yield of 72.0% to 77.0%, and the fired pitch is extracted by the solvent extraction of the above-mentioned aromatic hydrocarbon having 6 to 8 carbon atoms. Extremely stable B. Ingredients are very stable to this heat or B. Ingredients and B. which are extremely stable to this heat Extraction of raffinate (insoluble matter) obtained by solvent extraction of the components with quinoline etc. S. 50 kg / c under a stream of inert gas or decomposition product gas
Heating at a temperature of 600 ° C. to 1,200 ° C. under a pressure of m ^{2 to} 600 kg / cm ² for 2 hours to 20 hours yields a firing pitch containing fullerene C ₆₀ of 4% to 20% at a yield of 7
Build 0.0% to 84.0%, industrial production process of the fullerene _{C 60} purification by sublimation fullerene _{C 60} to separate it from the solvent extraction to under high temperature and high vacuum. 2. A raffinate (insoluble matter) produced by petroleum pitch by solvent extraction of an aliphatic hydrocarbon having 6 to 8 carbon atoms.
B. obtained by solvent extraction of aromatic hydrocarbon having 6 to 8 carbon atoms. Component (H. component 0% to 1.0%, B. component 9
9.0% to 100%, average molecular weight 390 to 440,
Using a softening point of 76 ° C to 96 ° C) as a raw material, first, a strict heat treatment pretreatment is carried out to have two benzene nuclei and one naphthalene nuclei as main components and have an alkyl group side chain with as few carbon atoms as possible. B. which is extremely stable to heat Ingredients (average molecular weight 362 to 376, softening point 80 ° C to 86 ° C) 100 parts flavor, or B. Ingredients and B. which are extremely stable to this heat Q. Three components are heat-bonded to form a three-dimensional structure. S. 100 parts of the mixture with the components (average molecular weight 824 to 848, softening point 347 ° C. to 357 ° C.) is used as a raw material, and these are used as a raw material under an inert gas or decomposition product gas flow of 50 kg / cm ^{2 to} 600 kg / cm ² . build firing pitch containing fullerene _{C 6 0} 4% to 20% and heated for 2 hours to 20 hours under pressure temperature 600 ° C. to 1,200 ° C., fullerene C than the sintering pitch
₆₀ parts with a solvent extraction residue firing pitch 60 parts to 14
Add 0 parts and mix well, and then perform the above-mentioned heat treatment to make it extremely stable to heat having side chains of alkyl groups containing 1 benzene nucleus and 2 naphthalene nucleus as main components and having as few carbon atoms as possible. B. Ingredients (average molecular weight 412 to 416,
Softening point 74 ° C to 76 ° C) 100 parts of taste, or B. which is extremely stable to heat. Ingredients and B. which are extremely stable to this heat Q. The three components are heat-bonded and form a three-dimensional structure. S. Ingredients (average molecular weight 876 to 900, softening point 3
68 ° C. to 378 ° C.) with respect to 100 parts of a mixture, and using these as a raw material, under an inert gas or a decomposition product gas or a stream of a decomposition product gas, 50 kg / cm ^{2 to} 600 kg /
The fullerene C ₆₀ is heated at a temperature of 600 ° C. to 1,200 ° C. under a pressure of cm ² for 2 hours to 20 hours to obtain 4% to 2 of fullerene C _60.
A firing pitch containing 0% was made, and the firing pitch of the residue obtained by solvent-extracting fullerene C ₆₀ from this firing pitch was ₆₀ %.
Part to 140 parts are added and mixed well, and 50 kg / cm ^{2 to} 600 k under a stream of an inert gas or a decomposition product gas.
By heating at a temperature of 600 ° C. to 1,200 ° C. under a pressure of g / cm ² for 2 hours to 20 hours, a firing pitch containing 4% to 20% of fullerene C ₆₀ was produced with a yield of 72% to 84%. Fullerene C _{60 for} solvent extraction
The method according to claim 1, characterized in that it is industrially refined and manufactured at a reasonably low cost by subliming and refining under high temperature vacuum. 3. A firing pitch obtained by solvent-extracting fullerene C ₆₀ from a firing pitch containing fullerene C ₆₀ having 60 carbon atoms to separate and remove fullerene C ₆₀ is used as a raw material. Firing pitch containing fullerene C ₆₀ at 4% to 20% by heat treatment under pressure of 50 kg / cm ^{2 to} 600 kg / cm ^{2 at} a temperature of 550 ° C. to 1,200 ° C. for 2 hours to 10 hours under a flow of generated gas. It is possible to produce fullerene C ₆₀ with a yield of 74% to 86%, which is separated by solvent extraction.
The method according to claim 1, characterized in that it is sublimated under high temperature and high vacuum to purify and produce it at low cost.