KR20130128813A - Method for manufacturing fullerene using by combustion - Google Patents
Method for manufacturing fullerene using by combustion Download PDFInfo
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- KR20130128813A KR20130128813A KR1020120052843A KR20120052843A KR20130128813A KR 20130128813 A KR20130128813 A KR 20130128813A KR 1020120052843 A KR1020120052843 A KR 1020120052843A KR 20120052843 A KR20120052843 A KR 20120052843A KR 20130128813 A KR20130128813 A KR 20130128813A
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- transition metal
- fullerene
- combustion
- metal compound
- producing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/128—Mixtures of organometallic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/152—Fullerenes
- C01B32/154—Preparation
Abstract
One or more transition metal compounds selected from the group consisting of transition metal halides, transition metal sulfides, transition metal carbides, organic transition metal compounds, transition metal nitrides and transition metal oxides in the production of fullerenes by incomplete combustion of hydrocarbons By adding as a catalyst has a much higher productivity than the conventional combustion method, it can have the effect of reducing the production cost and the possibility of mass production.
Description
The present invention relates to a method for producing fullerenes by a combustion method that improves the production efficiency of fullerenes by using a transition metal compound as a catalyst when incomplete combustion of hydrocarbons and reduces production costs.
The structure of incomplete combustion products, ie, flaming soot, produced when carbon-containing materials combust has been studied for a long time. However, because of its complicated structure, it was not clearly demonstrated, and its industrial use was almost limited to rubber reinforcements and black pigments. In 1985, fullerene was found from soot, and in 1987, C 60 was detected during combustion, and incomplete combustion was noticed as a fullerene synthesis method.
Fullerenes are generally molecules of carbon only having a spherical, elliptical, tubular, planar shape, etc., one of the carbon allotrope. Spherical fullerenes are called buckyballs, tubular fullerenes are called carbon nanotubes (CNTs), and planar fullerenes are called graphenes. Of these, fullerenes are very small and as strong as diamonds. In addition, since it has a strong bond between the hollow structure and carbon atoms like a soccer ball, it is not toxic to the human body due to its low reactivity. In addition, it absorbs light and receives electrons well.It can be used as a conductor, a superconductor by mixing several metal atoms, or by connecting fullerenes to new fibers, sensors, and catalysts. Attention is being made to substances.
Such a method of producing fullerene includes a laser irradiation method for extracting fullerene from soot produced by irradiating graphite with a laser in an inert gas atmosphere heated to a high temperature of about 1200 ° C., and fullerene from soot produced by heating graphite in an inert gas atmosphere. The resistive heating method to extract, the arc discharge method to extract fullerene from the carbon medium produced | generated by arc discharge between two graphite electrodes, etc. are mentioned.
Japanese Laid-Open Patent Publication No. 1993-186865 describes a method for producing a carbon cluster by arc discharge or resistance heating a pair of electrodes made of a carbon rod and a metal rod inside a container filled with an inert gas. 1994-056414 describes a method of decomposing aromatic carbon compounds using high-temperature plasma and extracting fullerene from the soot produced. However, all of the above methods have problems of high cost and low yield of starting materials and devices used to produce fullerene.
In order to solve the above problems, the present invention relates to a method for producing fullerene by a combustion method in which the fuel in which a transition metal compound is added to a hydrocarbon is incompletely burned to improve the production efficiency of fullerene and reduce the production cost.
The present invention
a) reacting a fuel prepared by adding a transition metal halide, a transition metal sulfide, a transition metal carbide, an organic transition metal compound, a transition metal nitride and a transition metal oxide to the hydrocarbon by adding a catalyst Injecting and igniting the furnace to incomplete combustion;
b) collecting the soot produced in step a);
c) extracting fullerene from the soot;
It relates to a method for producing a fullerene by a combustion method comprising a.
In addition, the present invention is a transition metal element constituting the transition metal compound is titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), Copper (Cu), Yttrium (Y), Zinc (Zn), Niobium (Nb), Molybdenum (Mo), Ruthenium (Ru), Palladium (Pd), Silver (Ag), Tantalum (Ta), Tungsten (W), The present invention relates to a method for producing fullerene by combustion, which is at least one metal element selected from the group consisting of platinum (Pt), iridium (Ir) and gold (Ag).
In another aspect, the present invention is the organic transition metal compound is selected from the group consisting of metallocene (phthalocyanine), phthalocyanine (acetylacetone complex), carbonyl complex (carbonyl complex) and Wilkinson complex (Wilkinson complex) As one or more organic transition metal compounds, in particular, ferrocene (ferrocene), nickellocene (nickelocene), cobaltocene (cobaltocene), osmocene (ruthenocene), nickel phthalocyanine (nickel phthalocyanine), cobalt Phthalocyanine (cobalt phthalocyanine), copper phthalocyanine (copper phthalocyanine), nickel acetylacetonato (cobalt acetylacetonato), iron acetylacetonato (ferric acetylacetonato), copper acetylacetonatodium (atocopper) Iridium acetylacetonato, nickel carbonyl, cobalt carbony l), ferric pentacarbonyl, bis (triphenylphosphine) dicarbonyl (bis- (tripenylphosphine) dicarbonyl), dibromobis (triphenylphosphine) nickel (dibromo-bis- (tripenylphosphine) nickel And chlorotris (triphenylphosphine) rhodium (chloro-tris- (tripenylphosphine) rhodium), and a method for producing fullerene by combustion using at least one organic transition metal compound selected from the group consisting of.
In addition, the present invention is the hydrocarbon, benzene, toluene, xylene, xylene, pitch, pitch coke, petroleum coke, coal tar, fluoranthene (fluoranthene), pyrene, chrysene, phenanthrene, naphthalene, naphthalene, anthracene, methylnaphthalene, fluorene, biphenyl and acenaphthene A method for producing fullerene by combustion using at least one hydrocarbon selected from the group consisting of (acenaphthene). Wherein the hydrocarbon is added 98 to 99.5% by weight of the total 100% by weight of the fuel, 0.5 to 2% by weight of the transition metal compound is added.
The present invention also relates to a method for producing fullerenes by the combustion method in which the temperature of the incomplete combustion is adjusted to 800 to 1500 ° C.
The present invention also relates to a method for producing fullerene by the combustion method using a method of dissolving the soot in a solvent by the extraction method of step c), and then refluxing, centrifugation or filtration. Here, the solvent is toluene, xylene, xylene, benzene, chlorobenzene, dichlorobenzene, 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) , 1-methylnaphthalene, 1-chloronaphthalene, tetralin, anisole, 1,1,2,3-tetrachloroethane (1,1,2 , 3-tetrachloroethane, decaline, 2-methylthiophene, 2-carbon bisulfide, cyclohexane, water, ethylene glycol, diethylene glycol ( One or more solvents selected from the group consisting of diethylene glycol, triethylene glycol, and tetraethylene glycol may be used.
The invention also relates to a C 60 or C 70 fullerene produced by the above process.
Hereinafter, the present invention will be described in more detail.
First, the fuel used in the present invention is prepared by adding a transition metal compound as a catalyst to a hydrocarbon. The hydrocarbon is used as a carbon source of the fullerenes produced, preferably aromatic hydrocarbons. More preferably, benzene, toluene, xylene, pitch, pitch coke, petroleum coke, coal tar, fluoranthene, pyrene, chrysene, phenanthrene, naphthalene, anthracene, methylnaphthalene, fluorene, biphenyl, acenaphthene and the like can be used. Can be. In addition, these materials can be used individually or in combination of 2 or more types.
The transition metal compound generally refers to a compound in which several anions or molecules are coordinated with the transition metal element, and the transition metal compound is not limited to the kind as long as it has the function of the catalyst required by the present invention. Wherein the transition metal element is titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), yttrium (Y) , Zinc (Zn), niobium (Nb), molybdenum (Mo), ruthenium (Ru), palladium (Pd), silver (Ag), tantalum (Ta), tungsten (W), platinum (Pt), iridium (Ir) And gold (Ag), and the like, and may be used in combination of one or more than two.
Examples of the transition metal compound include transition metal halides, transition metal sulfides, transition metal carbides, organic transition metal compounds, transition metal nitrides and transition metal oxides. These transition metal compounds may be used alone or in combination of two or more. Preferred examples of the organic transition metal compound include metallocene, phthalocyanine, acetylacetone complex, carbonyl complex and Wilkinson complex, and more preferably ferrocene, nickellocene, cobaltocene, osmocene, lutenocene and nickel. Phthalocyanine, cobalt phthalocyanine, copper phthalocyanine, nickel acetylacetonato, cobalt acetylacetonato, iron acetylacetonato, copper acetylacetonato, iridium acetylacetonato, nickel carbonyl, cobalt carbonyl, iron pentacarbonyl, bis (triphenyl It is preferable to use phosphine) dicarbonyl, dibromobis (triphenylphosphine) nickel, chlorotris (triphenylphosphine) rhodium, and the like.
The transition metal compound is added 0.5 to 2% by weight of the total 100% by weight of the fuel and the hydrocarbon is preferably added to 98 to 99.5% by weight. When the transition metal compound is added in excess of 2% by weight, the transition metal element may act as an impurity in the over-supplied transition metal compound, which may be a factor to inhibit the characteristics of the fullerene produced.
In addition, in the present invention, a catalyst activator may be further added to activate the reaction of the transition metal compound and the carbon which are catalysts. The catalyst activator is not limited to the type within the range that can achieve the object of the present invention, it is preferable to use a thiophene-based compound. The catalytically active agent may be added in an amount of 0.01 to 0.4 parts by weight based on 100 parts by weight of the fuel.
Fuel produced by the above method is introduced into the reactor to incomplete combustion. Here, the incomplete combustion refers to the generation of soot, carbon monoxide, and the like other than water and carbon dioxide while oxygen and hydrocarbon react by a heat source. The conditions of the incomplete combustion may include an insufficient amount of oxygen supplied at the time of combustion, a high boiling point of the fuel, or a large number of carbon atoms of the hydrocarbon in the fuel component. In the present invention, it is preferable to control the supply of oxygen in order to perform the incomplete combustion. If enough oxygen is supplied, the amount of soot is reduced. If not enough oxygen is supplied, ignition will not occur or combustion will end. Therefore, it is necessary to constantly adjust the supply of oxygen to meet the conditions of incomplete combustion required by the present invention. At this time, the temperature inside the reaction furnace during incomplete combustion in the present invention is preferably 800 to 1500 ℃.
Next, if enough soot is generated by the incomplete combustion, soot is collected. Soot is usually attached to devices such as internal walls of reactors or additional collecting nets. Since the soot usually contains carbon black and fullerene, a step of separating and purifying the fullerene from the soot is further required.
The method for purifying fullerene in the present invention is not limited to a kind, and preferably, after dissolving the soot in a solvent, the fullerene and the soot are separated by a method such as a reflux apparatus, centrifugation or filtration.
The solvent is not limited as long as it is a component capable of dissolving the fullerene in the soot. The solvent is preferably a nonpolar solvent or alcohols, more preferably toluene, xylene, benzene, chlorobenzene, dichlorobenzene, 1,2,4-trichlorobenzene, 1-methylnaphthalene, 1-chloronaphthalene, tetralin, anisole, 1,1,2,3-tetrachloroethane, decalin, 2-methylthiophene, 2-sulfide carbon, cyclohexane and the like can be used. Ethylene glycol, diethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, or tetratethylene glycol may be used as the alcohol. In addition, water may be used for dispersion, and the solvent including water may be used alone or in combination of two or more thereof.
After dissolving the soot in a solvent to make a solution, it can be extracted using a method such as reflux, centrifugation or filtration to separate the fullerene from the solution. In this case, ultrasonic waves may be irradiated before refluxing, centrifugation, or filtration in order to promote dissolution of the fullerene present in the solution. The ultrasonic wave is preferably irradiated for 30 minutes to 1 hour in the wavelength range of 10 to 40 khz.
When the solution is completed, it is extracted in a solid form by refluxing, centrifugation, or filtration to extract soluble components including fullerene dissolved in the solution. When the soluble component is extracted in a solid form, the method may further include heat treating the soluble component or evaporating under reduced pressure to remove residual solvent. It is also possible to use liquid chromatography in this purification process.
The present invention shows a higher production efficiency than the conventional combustion method by adding a transition metal compound to the hydrocarbon as a catalyst in the production of fullerene by incomplete combustion of the hydrocarbon, thereby reducing the production cost and the effect of mass production. In addition, the indirect reduction of carbon dioxide emissions, energy savings due to the lowering of the combustion temperature, etc. can be expected, and thus the life of the combustion device can be extended.
Hereinafter, the present invention will be described in more detail with reference to examples. The following examples are only examples for explaining the present invention more specifically, but the scope of the present invention is not limited by the following examples.
Example 1
Ferrocene (ferrocene, Fe (C 5 H 5 ) 2 ) was added to 99 wt% benzene as a catalyst to prepare a fuel. The fuel produced was put into a stove-type reactor and ignited. After the ignition, the temperature inside the reactor was adjusted to 1150 ° C., and the fuel was incompletely burned by supplying oxygen appropriately so as not to lower the temperature.
The soot generated by the incomplete combustion was collected, added to 100 g of toluene and dissolved. Thereafter, the ultrasonic wave was irradiated for 40 minutes at a wavelength of 30 kHz, and the toluene solution after irradiation was composed of an eluent composed of methanol / toluene = 51/49 volume ratio, analyzed by liquid chromatography (HPLC), and quantified. The amount of fullerene quantified is measured and shown in Table 1.
[Example 2]
Fullerene was prepared under the same conditions as in Example 1 except that cobaltocene (Cobaltocene, Co (C 5 H 5 ) 2 was used as a catalyst), and the amount of the fullerene prepared was shown in Table 1 below.
[Example 3]
Fullerene was prepared under the same conditions as in Example 1 except that 1 wt% of iron pentacarbonyl (Fe (CO) 5 ) was used as a catalyst. The amount of fullerenes prepared is shown in Table 1 below.
Example 4
Fullerene was prepared under the same conditions as in Example 1 except that 1 wt% of iridium acetylacetonato (Ir (acac) 3 ) was used as a catalyst. The amount of fullerenes prepared is shown in Table 1 below.
[Example 5]
Fullerene was prepared under the same conditions as in Example 1 except that 1 wt% of ruthenocene (Ruenocene, Ru (C 5 H 5 ) 2 ) was used as a catalyst. The amount of fullerenes prepared is shown in Table 1 below.
Comparative Example 1
Fuel was prepared using only 100% by weight of benzene (benzene, C 6 H 6 ) without adding a catalyst. The remaining conditions were the same as in Example 1 to prepare a fullerene. The amount of fullerenes prepared is shown in Table 1 below.
[Table 1]
Examples 1 to 5 in which the transition metal compound was added to the hydrocarbon as a catalyst as shown in Table 1, the yield was improved by about 2 to 9 times compared to Comparative Example 1 without the catalyst.
Claims (10)
b) collecting the soot produced in step a);
c) extracting fullerene from the soot;
Method of producing a fullerene by a combustion method comprising a.
The transition metal elements constituting the transition metal compound are titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zinc, niobium, molybdenum, ruthenium, palladium, silver, tantalum, tungsten, platinum, iridium and gold Method for producing fullerene by the combustion method of at least one metal element selected from the group consisting of.
The organic transition metal compound is a method for producing fullerene by the combustion method is at least one organic transition metal compound selected from the group consisting of metallocene, phthalocyanine, acetylacetone complex, carbonyl complex and Wilkinson complex.
The organic transition metal compound may be ferrocene, nickellocene, cobaltocene, osmocene, lutenocene, nickel phthalocyanine, cobalt phthalocyanine, copper phthalocyanine, nickel acetylacetonato, cobalt acetylacetonato, iron acetylacetonato, copper acetylacetonato , Iridium acetylacetonato, nickel carbonyl, cobalt carbonyl, iron pentacarbonyl, bis (triphenylphosphine) dicarbonyl, dibromobis (triphenylphosphine) nickel and chlorotris (triphenylphosphine) rhodium Method for producing fullerene by the combustion method of at least one organic transition metal compound selected from the group consisting of.
The hydrocarbon is from the group consisting of benzene, toluene, xylene, pitch, pitch coke, petroleum coke, coal tar, fluoranthene, pyrene, chrysene, phenanthrene, naphthalene, anthracene, methylnaphthalene, fluorene, biphenyl and acenaphthene A method for producing fullerenes by combustion, which is at least one hydrocarbon selected.
A method for producing fullerene by the combustion method in which 0.5 to 2% by weight of the transition metal compound is added to 98 to 99.5% by weight of the hydrocarbon.
The incomplete combustion is a method for producing fullerene by the combustion method made at 800 to 1500 ℃.
The step c) is a method for producing fullerenes by the combustion method of dissolving the soot in a solvent, followed by reflux, centrifugation or filtration to extract fullerenes.
The solvent is toluene, xylene, benzene, chlorobenzene, dichlorobenzene, 1,2,4-trichlorobenzene, 1-methylnaphthalene, 1-chloronaphthalene, tetralin, anisole, 1,1,2,3- Tetrachloroethane, decalin, 2-methylthiophene, 2-sulfide carbon, cyclohexane, water, ethylene glycol, diethylene glycol, triethylene glycol and a method for producing fullerene by the combustion method of at least one selected from the group consisting of tetraethylene glycol. .
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| KR1020120052843A KR20130128813A (en) | 2012-05-18 | 2012-05-18 | Method for manufacturing fullerene using by combustion |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540565A (en) * | 2016-01-17 | 2016-05-04 | 河南科技学院 | Method for preparing fullerene |
| CN109467075A (en) * | 2018-12-24 | 2019-03-15 | 厦门大学 | A kind of continuous burning production equipment and its synthetic method synthesizing tonne fullerene |
-
2012
- 2012-05-18 KR KR1020120052843A patent/KR20130128813A/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540565A (en) * | 2016-01-17 | 2016-05-04 | 河南科技学院 | Method for preparing fullerene |
| CN109467075A (en) * | 2018-12-24 | 2019-03-15 | 厦门大学 | A kind of continuous burning production equipment and its synthetic method synthesizing tonne fullerene |
| CN109467075B (en) * | 2018-12-24 | 2020-04-24 | 厦门大学 | Continuous combustion production equipment for synthesizing ton-level fullerene and synthesis method thereof |
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