KR102011690B1 - Manufacturing method of fullerene - Google Patents

Abstract

The present invention comprises steps of: (a) pulverizing a natural mineral to prepare a mineral powder; (b) adding an organic mixed solvent to the mineral powder and heat treating the same; (c) adding a basic solution to the mineral powder, which is heat-treated in the step (b) to extract and separate a carbon component; and (d) washing the carbon component with water and then drying the same. According to the present invention, by conducting adding the organic mixed solvent and heat treating the same before the step of extracting and separating the carbon component from the mineral powder, an inorganic material except silicon is almost eliminated, thereby being able to more effectively remove silicon from the mineral powder. Therefore, it is possible to obtain fullerene with high purity, thereby having very excellent physical and chemical properties.

Description

Fullerene manufacturing method {MANUFACTURING METHOD OF FULLERENE}

The present invention relates to a method for producing fullerene which can obtain a high purity fullerene from natural minerals at a higher yield.

Fullerenes generally refer to C ₆₀ , in which ₆₀ carbons are combined into a soccer ball or spherical shape, but in small quantities there are also higher order fullerines such as C ₇₀ , C ₇₆ , C ₇₈ , C ₈₂ , C ₉₀ , C ₉₄ , C ₉₆ do. Fullerene has very hard properties due to its unique structure, and has excellent anti-oxidation, antibacterial and physicochemical properties, and thus is being applied industrially in various fields such as electrodes and cosmetics of batteries.

An example of the technique related to this is disclosed in Patent Documents 1 and 2 below. The following Patent Document 1 relates to a device including a fullerene thin film layer and a method of manufacturing the same, discloses a technology in which a fullerene derivative is applied to the thin film layer, Patent Document 2 relates to a light emitting display device using a fullerene-based carbon compound and a method of manufacturing the same A technique applied to a hole transport layer of a light emitting display device is disclosed.

On the other hand, fullerene can be extracted from natural minerals using an electrochemical method or a polar solvent extraction method, and natural minerals include inorganic materials such as silicon, nickel and iron in addition to organic substances such as carbon, carbon allotrope, and fullerene. When some of these minerals are extracted with the fullerene, there is a problem that the purity of the fullerene falls. Therefore, the research on the manufacturing method for obtaining a high-purity fullerene is ongoing.

Republic of Korea Patent No. 10-0992475 Republic of Korea Patent No. 10-0622229

It is an object of the present invention to provide a method for producing fullerene which can obtain high purity fullerene from natural minerals in high yield in a relatively simple manner without expensive production facilities.

The object of the invention is not limited to the above-mentioned object. The object of the present invention will become more apparent from the following description, and will be realized by the means described in the claims and combinations thereof.

Method for producing a fullerene according to an embodiment of the present invention to achieve the above object is (a) pulverizing the natural mineral to prepare a mineral powder, (b) adding a heat treatment by adding an organic mixed solvent to the mineral powder (c) extracting and separating a carbon component by adding a basic solution to the mineral powder having been heat-treated in step (b), and (d) washing the carbon component with water and drying the same.

At this time, the natural mineral in the step (a) may be? Hite (shungite).

In addition, the particle size of the mineral powder in step (a) may be 1 ~ 50um.

Here, the heat treatment in step (b) may be carried out for 6 to 18 hours at a temperature of 50 ~ 500 ℃.

In addition, in step (b), the organic mixed solvent may be blended with a nonpolar organic solvent and alcohol in a weight ratio of 2 to 6: 1.

Herein, the nonpolar organic solvent may be one selected from toluene, cyclohexane, heptane, benzene, and a combination thereof, and the alcohol may be one selected from ethanol, methanol, and a combination thereof.

And, the extraction and separation in step (c) may be carried out for 10 to 300 hours at a temperature of 50 ~ 500 ℃.

In addition, in step (c), the basic solution may be added in an amount of 100 to 1000 parts by weight based on 100 parts by weight of the mineral powder, and the basic solution may include potassium hydroxide.

And, in the step (d) may be carried out at a temperature of 60 ~ 300 ℃.

In addition, the step (c) may further comprise the step of acid treatment of the carbon component.

And, the acid treatment may be carried out until the pH of the carbon component is 4 ~ 10.

Here, the acid treatment is acetic acid, citric acid, citrate, sodium peroxide, disodium phosphate, diammonium phosphate, sodium citrate (sodium citrate), triethanolamine (triethanolamine), potassium phosphate (potassium phosphate) may be carried out using one acid selected from a combination thereof.

According to the method for producing fullerene of the present invention, there is an advantage that a high yield of high purity fullerene can be obtained from natural minerals by a relatively simple method.

In addition, according to the method for preparing fullerene of the present invention, the inorganic material except silicon is almost removed by performing heat treatment by adding an organic mixed solvent prior to the step of extracting and separating the carbon component from the mineral powder. Si) can be more effectively removed, and thus, a high purity fullerene can be obtained, which has very good physical and chemical properties.

1 is a process chart for explaining a method for producing a fullerene according to an embodiment of the present invention.
2 is a SEM photograph of? Guit and fullerene prepared according to Example 1 of the present invention.
3 to 5 are graphs showing the composition of the fullerene prepared according to? Guide, Example 1 and Comparative Example 1.
6 to 8 are malditope graphs of fullerenes prepared according to? Guide, Example 1 and Comparative Example 1. FIG.

Hereinafter, the present invention will be described in detail with reference to the embodiments shown in the accompanying drawings, but the present invention is not limited to the illustrated embodiments.

The above and other objects and novel features of the present invention will become more apparent from the description of the specification and the accompanying drawings.

EMBODIMENT OF THE INVENTION Hereinafter, the manufacturing method of manufacturing the fullerene of this invention is demonstrated in detail according to drawing.

1 is a process chart for explaining a method for producing a fullerene according to an embodiment of the present invention.

Referring to FIG. 1, first, natural minerals are ground to prepare mineral powders (S10).

Natural minerals, which are the main raw materials of the present invention, collectively refer to minerals containing carbon components, that is, carbon atoms, and in addition to carbon atoms, oxygen (O), silicon (Si), aluminum (Al), iron (Fe), calcium (Ca), sodium Inorganic materials such as (Na), nickel (Ni), potassium (K), sulfur (S), magnesium (Mg), titanium (Ti), and halogen elements. The natural mineral is not limited to its use as long as it contains a carbon component. Preferably, the natural mineral is selected from a variety of minerals including a carbon component, which is a naturally occurring, homogeneous crystalline solid phase having a regular atomic arrangement. It may be, but the type is not limited. In the present invention, the carbon component includes carbon molecules composed only of carbon atoms, allotropes thereof, compounds including at least one carbon atom, and the like, and may preferably include fullerenes. That is, the natural mineral of the present invention may be a mineral containing a fullerene, and may be a mineral including a compound and a carbon-containing compound in addition to the fullerene.

Fullerene, on the other hand, is a hollow spherical compound in which carbon atoms are arranged in a spherical shape like a soccer ball or a cut icosahedron. For example, C ₆₀ , which is a general form, is composed of 12 pentagons and 20 hexagons, and hollows may be formed by combining carbon rings of pentagons and hexagons. Such fullerenes include general fullerenes having a carbon number of C ₆₀ to C ₈₀ , as well as carbon allotropes such as C ₂₀ , C ₇₀ , C ₇₆ , C _84, etc., which have smaller or larger carbon numbers, and preferably C ₂₀ It may have a carbon number of ~ C ₁₅₀ , more preferably C ₆₀ ~ C ₈₀ , but is not limited to this, fullerene is a special limitation to the number of carbon because the structure and the number of carbon may vary depending on the type of natural mineral Do not put

The natural mineral is not particularly limited as long as it contains a carbon component as described above, but it is preferable to select one having a high content of the carbon component, preferably 20 to 90% by weight can be selected and applied. If the content of the carbon component is less than 20% by weight, less carbon component is obtained compared to the process, the efficiency is lowered, the manufacturing cost may be expensive.

Such natural minerals may be, for example, coal, clay minerals, and swungite, preferably swungite. Sungite is a black, soft mineral like pitch, rich in silicon dioxide (SiO ₂ ), silicon compounds such as silicates, and carbonaceous materials such as anthracite, and especially 25% to 50% by weight of fullerene. Suitable. ? Shungite can be purchased and used in Karelia, India, China, Tibet, Russia.

The natural mineral is a ball mill, attrition mill, jet mill, rotary mill to facilitate the extraction of carbon components in the extraction and separation steps described below. And it can be milled with any one of the equipment selected from the vibration mill (Vibration mill). The pulverized mineral powder may have a particle size of 1 ~ 50um, preferably 10 ~ 20um. If the particle size of the mineral powder is less than 1um, it may be difficult to handle and may be dispersed in the air, thereby increasing the amount of loss. If the particle size is more than 50um, the natural mineral may have a low surface area in contact with the basic solution, thereby lowering the carbon content extraction rate. Therefore, it is preferable to grind the natural mineral to a particle size of 1 ~ 50um so that the carbon component can be extracted more efficiently from the natural mineral.

After pulverizing natural minerals, the step of screening only the mineral powder having a particle size range of 1 to 50 μm may be further performed using a sieve, and the mineral powder having a particle size exceeding the range of 50 μm may further have a particle size range of 1 to 50 μm. Grinding can be performed. As the selection step is further carried out, the yield of the carbon component in the extraction step may be higher.

Next, an organic mixed solvent is added to the mineral powder and subjected to heat treatment (S20).

1 to 5 times (V / W), preferably 1 to 2 times (V / W) volume of the organic mixed solvent is added to the total weight of the mineral powder crushed in step S10 and then 20 to 40 using a stirrer Minutes, preferably 30 minutes, and then heat treated for 6-18 hours, preferably 10-14 hours at a temperature of 50-500 ° C., preferably 90-150 ° C. Oxygen (O), aluminum (Al), iron (Fe), calcium (Ca), sodium (Na), nickel (Ni), potassium (K), sulfur (S), magnesium (Mg), titanium, except Si Inorganic substances or ash components such as (Ti) and halogen elements can be removed. If the heat treatment temperature is less than 50 ° C, it may be difficult to remove the ash component present in and on the surface of the mineral powder, and if it exceeds 500 ° C, it may be higher than the boiling point of the fullerene and the fullerene structure may be destroyed. The organic mixed solvent may be mixed with a nonpolar organic solvent and an alcohol in a weight ratio of 2 to 6: 1, preferably 2: 4. If the ratio of the non-polar organic solvent is less than 2, it may be difficult to dissolve the ash component present in and on the surface of the mineral powder, and if it exceeds 6, the organic mixed solvent remaining on the surface of the mineral powder may not be completely evaporated through ultra sonic. Problems may arise. The nonpolar organic solvent may be one selected from toluene, cyclohexane, heptane, benzene and combinations thereof, preferably toluene, and the alcohol is one selected from ethanol, methanol and combinations thereof, preferably Ethanol.

The heat treatment can be carried out using a facility equipped with a condenser, and may be carried out in the presence of an inert gas such as nitrogen (N ₂ ), argon (Ar), and helium (He) gas, if necessary. It is not. In addition, after the heat treatment is completed, one of the methods of rapid filtration, slow filtration, sterile gauze, filtration using a paper or glass filter, high speed rotary separation using a centrifugal separator, etc. is selected. Filtering may be carried out.

Oxygen (O), aluminum (Al), iron (Fe), calcium (Ca), sodium (Na), nickel (Ni), potassium (K), excluding silicon present in the mineral powder, by the heat treatment as described above Since inorganic or ash components such as sulfur (S), magnesium (Mg), titanium (Ti), and halogen elements may be removed, high purity carbon components may be extracted in an extraction step to be described later, thereby physically and chemically Properties can be further improved.

Thereafter, a basic solution is added to the mineral powder after the heat treatment is completed, and the carbon component is extracted and separated (S30).

After adding the basic solution to 100 parts by weight of the mineral powder, 100 to 1000 parts by weight, preferably 100 to 500 parts by weight of the mineral powder, the heat treatment is completed in step S20, any one selected from a heating stirrer or a high temperature pressurizer The apparatus may be heated and extracted for 10 to 300 hours, preferably 20 to 200 hours, at a temperature of 50 to 500 ° C, preferably 100 to 200 ° C. Heat extraction can be carried out under conditions equipped with a steam condenser. If the extraction temperature is less than 50 ℃, the silicon compound is not dissolved in the basic solution can be difficult to extract the carbon component, if it exceeds 500 ℃, the crystals are broken and the yield of fullerene of the C ₆₀ structure may be low. Therefore, the above temperature and time ranges are favorable conditions for carbon component yield and energy efficiency. If the basic solution is added in less than 100 parts by weight, the extraction rate or yield of the carbon component may be lowered, and if more than 1000 parts by weight, the synergistic effect is not so great due to the addition of more than necessary, there is a problem that only the manufacturing cost rises Can be. The basic solution may include 10 to 100% by weight of the basic material with respect to the total weight of the basic solution, but is not limited thereto, and may be appropriately adjusted according to the type or amount of natural minerals, silicon or residual minerals. In this case, the basic material may include Group 3 to Group 12 elements and their hydroxides, preferably potassium hydroxide (KOH), and when the potassium compound is used alone as the basic material, the silicon compound may be formed by the strong base potassium hydroxide. Since it can be easily dissolved and separated in a short time, manufacturing time can be shortened.

The natural mineral can be separated into a carbon component and a silicon compound by the heat extraction as described above. For example, when referring to shungite,? Gite is a silicon compound such as silicon dioxide (SiO ₂ ), silicate and anthracite coal; The same carbon component, wherein the silicon compound can be dissolved in a basic solution. Thus, the liquid layer of the silicon compound and the basic solution and the solid layer of the carbon component can be separated, the solid layer by any one of the method of filtration separation through a filter, or high-speed rotary separation using a centrifugal separator or the like. Can be separated. At this time, the carbon component, which is a solid layer obtained separately, is not only silicon (Si) but also oxygen (O), aluminum (Al), iron (Fe), calcium (Ca), sodium (Na), nickel (Ni), and potassium (K). ), High purity fullerene containing almost no inorganic or ash components such as sulfur (S), magnesium (Mg), titanium (Ti), and halogen elements.

In addition, when fullerene is applied to electric and electronic fields such as fuel cells, solar cells, secondary batteries, and the like, the boron (B) component may be 0.01 to 20 parts by weight, preferably 100 parts by weight, based on 100 parts by weight of natural minerals. It can carry out by adding 0.1-10 weight part further. If the boron component is less than 0.01 parts by weight, it may be difficult to implement the electrical properties of the fullerene because there is no improvement effect of the hollow structure, if it exceeds 20 parts by weight, the synergistic effect is not large due to the use more than necessary, the manufacturing cost may be increased have. The boron component may be selected from boron compounds. For example, the boron-based compound is H ₃ BO ₃ , B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₆ H ₁₀ , BI ₃ , NaBO ₂ , NaBH ₄ , Na ₂ B ₄ O ₇ and these It may comprise at least one selected from the hydrate of, wherein the hydrate is NaBO ₂ 4H ₂ O (meta-borate hydrate), NaBH ₄ 4H ₂ O (boro-hydrate) and Na ₂ B ₄ O _{It may be 7} 10H ₂ O (borax, tetra-borate hydrate). As described above, by further adding a boron component to maximize the hollow structure, the porosity of the fullerene may be improved, and thus the electrical characteristics may be improved.

Then, the carbon component is acid treated (S40).

The acid extracted or separated in step S30 may be immersed in an acid solution or sprayed with an acid solution on the carbon component to perform acid treatment several times until the pH of the carbon component reaches 4 to 10. It can be carried out under high temperature conditions so that it can be made more quickly. More specifically, the carbon component and the acid solution may be put in a weight ratio of 1: 8 to 20 so that the carbon component may be immersed in the acid solution in the heating reactor, and may be heated at a temperature condition of 40 to 90 ° C.

When the acid treatment is appropriately adjusted according to the application field, when applied to the cosmetic composition, the pH can be adjusted to 4 ~ 6, when applied to the fertilizer pH can be adjusted to 8 ~ 10.

The acid solution is acetic acid, citric acid, citrate, sodium peroxide, disodium phosphate, diammonium phosphate, sodium citrate one selected from citrate, triethanolamine, potassium phosphate and combinations thereof, preferably one selected from acetic acid, citric acid, and combinations thereof. More preferably, acetic acid and citric acid may be a mixed acid in a range of 1: 1 to 10. In addition, the acid solution may be an aqueous solution containing 10 to 80% by weight, and in detail, 10 to 60% by weight of acetic acid solution and 10 to 60% by weight of citric acid solution, and a combination thereof, preferably Preferably, 10 to 60% by weight of acetic acid solution and 10 to 60% by weight of citric acid solution may be a mixed aqueous solution of 1: 1-10. In the present invention, by performing the acid treatment using a weak acid such as acetic acid and citric acid, it is possible to precisely adjust the acidity, it is possible to shorten the washing process to be described later, as well as the generation of contaminants, there is an environmentally friendly advantage.

Although this acid treatment is an omittable process, it may be carried out to save the time required for the step of washing with water, if necessary.

Finally, the carbon component is washed with water and dried (S50).

After washing several times until the water, which is the washing liquid, is neutralized using any one of methods such as flowing water, spraying and immersing the carbon component in which the acid treatment is completed in step S40, hot air drying, heating drying, and natural drying (room temperature Drying) or drying equipment can be carried out at a temperature of 50 ~ 200 ℃, preferably 100 ~ 150 ℃ using equipment such as a dryer. Here, the water may be purified water or distilled water that does not affect the pH of the carbon component because it does not contain mineral components and other ions other than water molecules, it may be used by heating to a temperature of 50 ~ 100 ℃. By this washing, the acid solution and impurities remaining on the surface of the carbon component can be completely removed to obtain a higher purity carbon component.

If the drying temperature is less than 50 ℃, the time required for drying may be low, the work efficiency may be low, and if the drying temperature exceeds 200 ℃, the manufacturing cost may be increased due to more than necessary temperature conditions, the temperature conditions in the above range It is not limited, It can carry out by changing temperature conditions and time suitably according to a desired formulation, such as powder or a paste.

When the drying step as described above is completed, a high purity fullerene (S60) having almost no minerals is obtained, the extraction rate may be 95% or more. The fullerene prepared by the above method is subjected to a heat treatment by adding an organic mixed solvent prior to the step of extracting and separating the carbon component from the mineral powder, thereby removing almost all inorganic matters except silicon, thereby removing silicon (Si) from the mineral powder. It can be removed more effectively, and thus it is possible to obtain high purity fullerene. These fullerenes have various fields such as cosmetics, pharmaceuticals, medical devices, plastics processing, agriculture, electrical / electronics, optics, fuel cells, solar cells, energy devices such as secondary cells, and purification fields. Can be applied to

Example 1. Fullerene Preparation

1 kg of natural minerals were pulverized to a particle size of 10 μm, an organic mixed solvent obtained by mixing 40 ml of toluene and 10 ml of ethanol was added to the mineral powder, stirred with a stirrer for 30 minutes, and heat-treated at 110 ° C. for 12 hours. Thereafter, 5 kg of sodium hydroxide and 20 L of purified water were added to the filtered mineral powder using a filter, and extracted at 130 ° C. for 150 hours, washed 7 to 10 times with water, and dried at 150 ° C. to prepare the fullerene of Example 1. It was.

Comparative Example 1. Fullerene Preparation

Fullerene of Comparative Example 1 was prepared in the same manner as in Example 1, except that the full mineral was extracted without pulverizing the natural mineral.

Experimental Example 1. Composition Analysis

(1) SEM picture

In order to analyze the geometry of the fullerene molecular aggregates,? Guit and the fullerene prepared according to Example 1 were dispersed in water, dropped on a glass substrate, dried, and observed in a scanning electron microscope (SEM).

2 is a SEM photograph of? Guit and fullerene prepared according to Example 1 of the present invention.

As a result, referring to Figure 2,? Guide and the fullerene of Example 1, it was confirmed that the particles of various sizes from a few um to several tens of um connected to each other and agglomerated to have an aggregate shape, in particular, the fullerene of Example 1? The particles were found to be finer than the guides.

(2) EDS analysis

An energy dispersive spectrometer (EDS) was used to observe the composition of? Guit, the fullerene prepared according to Example 1 and Comparative Example 1.

Table 1 is a table showing the composition of the fullerene prepared according to? Guide, Example 1 and Comparative Example 1, Figures 3 to 5 is a graph showing the composition of the fullerene prepared according to? Guide, Example 1 and Comparative Example 1. .

wt% C O Si Al S K Ca Ti Zn Na Mg Cu Fe Cl ? Guide 18.72 37.44 14.88 1.36 8.85 5.80 5.18 1.37 2.77 1.51 2.11 Example 1 92.72 5.76 1.73 0.86 0.23 0.76 Comparative Example 1 86.43 3.17 1.09 0.95 5.33 0.18 1.33 0.24 1.06 0.22 The ratio of Si and O is measured relatively high on glass substrate.

As a result, referring to Table 1 and FIGS. 3 to 5, in Comparative Example 1, not only carbon, but also other elements such as silicon, sulfur, potassium, calcium, sodium, magnesium, copper, iron, chlorine, etc. While trace elements were identified, in the fullerene of Example 1, trace elements other than carbon were not identified, and other elements were found to have been reduced or removed. In addition, the carbon element of Example 1 was 92.72%, which was higher in purity than Comparative Example 1, which is 86.43%, and may be estimated to be about 97% or more in view of the measurement on the glass substrate. Therefore, the fullerene of the present invention was confirmed that the high purity of the inorganic material or almost no impurities.

(3) Malditope analysis (MALDI-TOF)

The Malditops mass spectrometer analyzed the phases of? Guit, the fullerenes prepared according to Example 1 and Comparative Example 1.

6 to 8 are malditope graphs of fullerenes prepared according to? Guide, Example 1 and Comparative Example 1. FIG.

As a result, referring to Figures 6 to 8, the fullerene of Example 1 was confirmed that a variety of peaks, such as C ₅₅ , C ₅₆ , C ₆₀ , C ₆₆ , C ₇₀ , unlike the fullerene of Comparative Example 1 was observed. . Accordingly, it was found that the fullerene of Example 1 contains Buckminsterfullerene, such as C ₆₀ and C ₇₀ , which are representative fullerenes.

Although the invention made by the present inventors has been described in detail according to the above embodiments, the present invention is not limited to the above embodiments and can be variously modified without departing from the gist thereof.

Claims (12)

(a) milling natural minerals to produce mineral powders;
(b) heat-treating the mixture for 6 to 18 hours at a temperature of 50 to 500 ° C. by adding an organic mixed solvent to the mineral powder;
(c) extracting and separating carbon components by adding a basic solution to the mineral powder in which heat treatment is completed in step (b); And
(d) washing the carbon component with water and then drying it;
A method of producing a fullerene further comprising the step of acidifying the carbon component between (c) and (d) with one selected from acetic acid, citric acid, and combinations thereof.
The method of claim 1,
The natural mineral in step (a) is? Manufacturing method of fullerene (shungite).
The method of claim 1,
The particle size of the mineral powder in the step (a) is 1 ~ 50um method of producing a fullerene.
delete The method of claim 1,
In the step (b), the organic mixed solvent is a non-polar organic solvent and alcohol is a method of producing a fullerene blended in a weight ratio of 2 to 6: 1.
The method of claim 5,
The nonpolar organic solvent is one kind selected from toluene, cyclohexane, heptane, benzene, and a combination thereof, and the alcohol is one kind selected from ethanol, methanol, and a combination thereof.
The method of claim 1,
Extraction and separation in step (c) is a method for producing a fullerene is carried out for 10 to 300 hours at a temperature of 50 ~ 500 ℃.
The method of claim 1,
In the step (c), the basic solution is added to 100 to 1000 parts by weight with respect to 100 parts by weight of the mineral powder, the basic solution is a method for producing fullerene containing potassium hydroxide.
The method of claim 1,
Drying in the step (d) is a method for producing fullerene is carried out at a temperature of 60 ~ 300 ℃.
delete The method of claim 10,
The acid treatment is a method of producing a fullerene is carried out until the pH of the carbon component is 4 ~ 10.
delete

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