Method of production of the nanocarbonic material

FIELD: chemical industry; methods of production of the nanocarbonic materials.

SUBSTANCE: the invention is intended for chemical industry and may be used at production of the heterogeneous catalysts for synthesis of the isoalkanes from the methane, the natural gas, the synthesis gas, the catalytic oxidation of carbon monoxide. The source raw is schungite, which is sequentially treated at heating with the melted alkali at the temperature of no more than 500°C; and in the mode of boiling it is treated with the concentrated inorganic acid, in the capacity of which they use НСl or HF; and with the strong oxidant from the row including HClO4 and ВаО2 in the mode of boiling treatment at the temperature of up to 150°С within no more than 2 h. After treatment with each of these reactants the formed intermediate product is flushed and dried. Then conduct the thermal treatment with the high-temperature gaseous oxidation in the oxygen or air medium in the high-temperature furnace at the temperature of 700-1200°С with production of the target product - the nanocarbonic material. The invention allows to produce the nanocarbonic material containing up to 90 mass % of the nanotubes and others nanocarbonic forms, and up to 70 mass % of the open nanocarbonic forms; and also one time to treat of no less than 100 kg of schungite in one apparatus with the volume of no more than 70 l. At that the output of the nanocarbonic material is up to 20 mass % from the initial mass of mass of schungite.

EFFECT: the invention allows to produce up to 20 mass percent of the nanocarbonic material from the initial mass of schungite.

7 cl, 1 dwg, 7 ex

 

The invention relates to chemical technology, more specifically to a method for production of carbon-containing natural mineral shungite nanocarbon material fulleren-like type, containing nanotubes, nanoarray, neolocality, nano-cones, which, in turn, can be used as a heterogeneous catalyst in the industrial synthesis of isoalkanes from methane, natural gas, synthesis gas, the catalytic oxidation of carbon monoxide CO and in several other applications.

When the description of the invention following terms are used.

Nanotechnology - the technology of objects whose size is of the order of 10-9m (BAS): BDT, 1997. S).

Fullerenes are a form of carbon, which represents a closed surface structure, which includes only five - or six-membered ring of carbon atoms. Fullerenes were discovered in the second half of the 80-ies (H.W. Kroto, J.R. Heath, O′'brien, S.C. et al. With60. Bakminsterfullerene // Nature. 1985. V.318. P.162) and was first produced in macroscopic quantities arc method in 1990 (Kratchmar W., L.D. Lamb, Fostiropoutos K., Huffman D.R. Solid C60a new form of carbon // Nature. 1990. V.347. P.354).

Fullerene soot - dispersed product of the combustion of carbon materials, usually of graphite containing fullerenes. Fullerene soot is the main raw material for producing fullerenes.

Nanotubes, nanoarray, manolakou the hospitals, the nano-cones - nanocarbon forms in the structure of natural or synthetic carbon material. Characteristic morphology of nanotubes is the presence in their structure one or several cylindrical surfaces with a diameter of more than 1 nm, nested into each other and identical in its structure of graphene planes of the graphite. Nanotubes as a new form of carbon was first described in the work (Iijima S. Helical microtubules of graphitic carbon // Nature. 1991. V.35. P.56). The structure related to the nanotube nano-forms that arise, usually at the arc method of their production as a byproduct, described in a review paper (T.W. Ebbesen, Carbon nanotubes: preparation and properties. Ed. Ebbesen T.W., CRS Press, Boca Raton, 1997, p.139).

Shungite is a metamorphic rock, a mineral containing cryptocrystalline carbon (from 30%to 90%) (BAS): BDT, 1997. S). Typical carbon content of shungite is the most various nanocarbon forms with a relatively narrow channel with a diameter of about 1 nm, the characteristic size of 10-15 nm and a large number graptopetalum layers: short and at the same time thick nanotubes, and neolocality, nano-cones, nonabusive (Zaidenberg A.Z., Rozhkova N.N., Kovatevsky V.V. et. al. Physical Chemical Model of Fullerene-like Shungite Rocks // Mol. Mat. 1996. V.8. P.107).

Getting nanocarbon material from shungite - removing the carbon component of the carbon-containing p is arodnogo raw materials shungite using the method of selective oxidation, further enrichment of this component of the nanocarbon forms and disclosure of their channels.

Multiwall (MWNT) and single-layer (SWNT) nanotubes, nanoarray, neolocality, nano-cones are an example of artificial nanocarbon forms. There are two main methods of their production. The first method - arc, based on receiving a nanocarbon material of the products thermalpower evaporation of a graphite anode, separated on the walls of the discharge chamber (Mat), the volume of the chamber ("web") or on the cathode in the form of a solid Deposit. The second method is the chemical decomposition of carbon carriers for catalytically processed substrate (CVD methods) or gaseous catalyst (HIPCO method). When implementing the known methods the content of nanotubes in the resulting carbon material can reach 70-90 wt.%, including open channels - up to 50%. SWNT and MWNT-nanotubes have a large specific surface area and sorption capacity, potentially high heterogeneous catalytic activity. Detailed description of the methods of producing nanotubes and more complex nanocarbon forms contained in the monograph (Harris PJ. Carbon Nanotubes and Rotated Structures, Cambridge University Press. 2003. Pp.20-80). The disadvantages of the above methods are high cost and low specific performance.

Known attempt at making heterog the spent metal catalyst carrier in the form of carbon nanotubes. Carbon nanotubes germinated in the pore size range of 1-100 μm specially made of porous substrates by introducing into the pores of nano-sized germ growth of nanotubes (U.S. patent 6713519).

The resulting catalyst was successfully tested in the process of converting natural gas type of Fischer-Tropsch synthesis. Along with the catalytic conversion of methane occurs and the catalytic growth of nanotubes, i.e. the renewal of the carrier metal catalyst. On the one hand, it is an advantage of this technology. However, this process, unfortunately, and unmanaged growth of nanotubes in the pores is able by itself to absorb over time, the metal catalyst and inhibit the conversion process. In addition, the known method is extremely expensive, in particular, for the manufacture of special substrates, and there is no information about the possibility of its implementation on an industrial scale.

Despite the potentially high heterogeneous catalytic activity of carbon materials on the basis of the artificially synthesized nanotubes are not implemented due to the complexity and demands of their receipt.

Performance arc method of synthesis of SWNT does not exceed 50 grams per day from a single reactor with a working volume of not more than 50 l (Harris P.J. Carbon Nanotubes and Related Structures. Cambridge University Press, 2003, Pp.70-72), which is connected with limited performance samog the reactor, and the need for subsequent multistage fine chemical purification of nanotubes from amorphous carbon, graphite components and traces of metal catalyst (Kajiura, H., Tsutsui, S., Huang H., Murakami Y. // Chem. Phys. Lett. 2002. V.364. P.586).

Getting nanocarbon materials SWNT and MWNT CVD methods also does not exceed a few grams per day due to extremely time-consuming process of preparation of the substrate, although the chemical cleaning process in this case is somewhat simpler (Cumar M, Ando J. // Chem. Phys. Lett. 2003. V.374. P.521). The problem of purification of nanotubes inherent and HIPCO method. This determines a very high market value is known nanocarbon materials: $120000-900000/kg for SWNT and $25000-250000/kg for MWNT (see the websites of leading manufacturers: http://www.sesres.com/FullerenesPrices.asp; http://www.mercorp.com/ mercorp/Nanotubes/mer-nanotubes.pdf; as well as an overview: http://www.metodolog.ru/00234/00234 .html).

The high cost of known methods of obtaining nanocarbon materials, including SWNT and MWNT, makes their implementation in industrial production almost unprofitable.

Along with nanotubes (and accompanying the process of their production nanolocalized, nanoarray, nano-cones, etc. in mass applications can be used comparatively cheaper nanocarbon materials in the form of fullerene mobiles or so-called "washed" fullerene soot (Ponomarev A.N., Barchenko V.T., Charykov N.A. et al. 4-th Bien. Inter. W-sh. "Fullerens and AtomicClusters". 1999. St-Petersburg. P.237). The content of nanotubes in them does not exceed 1-2 wt.%. The cost of "laundered" fullerene soot is significantly lower than the cost of nanotubes (not more than $1000 per 1 kg).

The known method of its use in heterogeneous catalytic hydrogenation in organic synthesis (U.S. patent 6653509). However, due to the low content of nanocarbon forms and, consequently, the low specific surface area and sorption capacity of fullerene mobile or "laundered" fullerene soot is not effective as catalysts.

From the above it follows that the search for affordable and effective nanocarbon material, allowing to solve problems of adsorption and heterogeneous catalysis, intractable by other means, was held still among the artificially obtained nanostructures. The latter due to their high cost will not be of practical use, at least in the short term.

The authors of the claimed invention proposes a new technological direction associated with the use of natural carbon material shungite with a high content of nanocarbon forms: allocation of shungite carbon content and the enrichment of these nanocarbon forms. Other natural carbon materials containing nanocarbon forms, is unknown.

Currently shungite is used as fill in the ü for lightweight concrete (so-called changeset), material for water purification from organic and inorganic pollutants, the comprehensive substitute for coke in the production of cast iron, a substitute of white carbon black in the rubber. Natural materials are used in practically without additional processing. Nanocarbon structure of shungite opened relatively recently (Zaidenberg A.Z., Rozhkova N.N., Kovalevsky, V.V. et al. Physical Chemical Model of Fullerene-like Shungite Rocks // Mot. Mat. 1996. V.8. P.107). It was used purely physical methods. The carbon component of shungite as such is not specifically allocated and not used. The methods of removing carbon content of shungite and its enrichment nanocarbon forms, then there are ways of getting nanocarbon material from shungite is not known.

None of these above technologies are not applicable to natural carbon-containing minerals shungite. This is due to the presence of silicates and oxides of silicon, transition and heavy metals (Pb, Zn, Fe, Co, Ni, etc. in the form of free metals, oxides and soluble salts and non-metallic compounds (type S, CS2, SiC and so on), which is not in raw materials for the artificially obtained nanocarbon material. The removal of impurities with the preservation of the structure of the nanotubes in the carbon component of shungite is a separate technological problem.

All known methods are the eyes of the TCI any artificial carbon material are reduced to the oxidation of the chemically more active part of the processed carbon material, non nanotubes and other nano-forms. So, for nanotubes cathodic Deposit produced without the participation of the catalyst, the preferred method of oxidation is the intercalation of foreign atoms between graphene layers in graphite components chopped Deposit, which on subsequent heating goes legarrea thermal expanded fraction (U.S. patent 5695734).

Nanotubes obtained by catalytic cultivation in the conditions of the arc or by chemical synthesis in CVD-installed, cleaned amorphous carbon and traces of catalytic material in the combined gas-phase oxidation (U.S. patent 5346683), graphitization in a high temperature vacuum furnace described, for example, in article (Andrews, R., Jacques, D., D. Qian, E.C. Dickey Purification and structurat anneating of muftiwalled carbon nanotubes at graphitization temperatures // Carbon. 2001. V.39. P.1681), or processing multiple liquid oxidants (U.S. patent 5698175).

As can be seen, the methods of processing the carbon component-specific, depending on the method of allocation of carbon content and ash impurities. So, for example, a method of selective intercalation does not apply to shungite due to the fact that graphite fraction is a relatively small part of its carbon content. Because of the risk of damage and fracture of nanotubes for sungi is not suitable hard technology disclosure nanotubes, used in the aforementioned known methods (arc method in the absence of catalyst, the arc method with the participation of the catalyst, laser synthesis, pyrolysis of hydrocarbons and decomposition, pyrolysis involving volatile catalyst and so on).

Thus, it can be argued that at present the development of an industrial method of production of high-performance nanocarbon material remains relevant.

Closest to the claimed invention is a method of allocating natural fullerenes from shungite described in the article by Kholodkevich SV and others, the Allocation of natural fullerenes from Karelian shungite, reports of the Academy of Sciences, 1993, CH, No. 3, SS-341. In this way shungite rock undergoes a chemical enrichment by treatment with inorganic acids and organic solvents, heat treatment in the range of 100-800°in vacuum, in inert gases or air. At the final stage selected from shungite products were deposited films on the cooled poloski crystalline silicon or fused silica.

However, this method cannot get fulleren-like material - a mixture of carbon single - and multiwall nanotubes, nanoarray, nonholonomic etc. Should be noted that the methods for producing fullerenes and fulleren-like materials have a fundamental R the differences, because of strong oxidants (such as HClO4and molten alkalis destroy fullerenes, but allow fulleren-like structure. And fullerenes, and fulleren-like materials are nanocarbon materials.

The task of the invention is to increase the specific productivity of the method of producing nanocarbon material fulleren-like type, containing nanotubes, nanoarray, neolocality, nano-cones, and the reduction of its cost.

The inventive method is characterized by the following set of essential features.

As a source of raw materials use shungite. Shungite is treated with molten alkali when heated. Processed with alkali shungite washed with water and dried. The obtained intermediate product is treated with concentrated inorganic acid, which use HF or HCl, when heated. The acid-treated product is washed with water and dried. The obtained intermediate product is processed by strong oxidizer from a number of HClO4, BaO2when heated. Processed a strong oxidant product is washed with water and dried. Conduct high-temperature gas-phase oxidation (in air, in the atmosphere O2, Cl2water vapour) are obtained intermediate product in high temperaturey furnace to obtain the desired product.

The processing of raw materials shungite alkali expediently carried out at temperatures above the melting point of the alkali, but not above 500°C.

The processing of the intermediate product a concentrated inorganic acid, which use HF or HCl, is carried out in the mode of boiling at the temperature of boiling concentrated solution of the appropriate acid.

The processing of the intermediate product is a strong oxidant from a number of HClO4, BaO2produce in the mode of boiling fluids at temperatures up to 150°C for no more than 2 hours

Mentioned high-temperature gas-phase oxidation (in air, in the atmosphere O2, Cl2) obtained intermediate product is carried out at a temperature of 700-1200°With, for example, in a high temperature furnace.

Processing of shungite molten alkali spend within 2-24 hours (preferably 4-6 h), concentrated inorganic acid - for 2-20 h (optimally 3-4 h), the final gas-phase oxidation within 2-6 hours (preferably 3-4 hours). Before processing the feedstock shungite may be subjected to grinding.

The set of essential features of the claimed method provides receive the following technical result:

- improving the performance of the method of obtaining highly efficient the CSOs nanocarbon material to processing of at least 10 kg of shungite in one device not more than 7 litres per day, with the yield of the target product 20% by weight of raw materials (for comparison: in arc method of synthesis of SWNT - a few dozen grams of target product per day in a 50-liter reactor);

- reduce the target product through the use of natural raw materials, reduce energy intensity and increase the performance of the process;

- obtaining the target product - nanocarbon material - containing nanotubes and other nano-forms from 20 to 90 wt.%, including the disclosed nano-forms - up to 70 wt.%.

Analysis of the known prior art did not allow to find a solution that exactly matches the set of essential characteristics with declare that confirms the novelty of the method. Only the set of essential features of the proposed method allows to achieve the technical result.

Based on the known literature on inorganic chemistry (see Karapetyants NH, Drakin S.N. General and inorganic chemistry. - M.: Chemistry, 1994. 588 S.; Dibrov N.A. Inorganic chemistry. - S.-Petersburg: DOE, 2001. 431 C.), it can be assumed that:

- processing of shungite raw lye will allow you to clear it from the silicates and oxides of silicon;

treatment of the resulting intermediate product is a concentrated inorganic acid will allow to cleanse it from the metal compounds;

handling strong oxidant from a number of HClO4, BaO2will remove non-metallic impurities, knowledge is sustained fashion part of the amorphous carbon and some of the carbon in the graphite form;

- gas-phase oxidation in a high temperature furnace will allow you to remove the remaining nannotrigona part carbon and expose a significant portion of the cavities in the nanocarbon forms.

However, it was impossible to predict what will happen with natural nanocarbon forms in shungite in the process of its purification from impurities in harsh chemical and thermal processing. The range of the obtained results were totally unexpected. First, the sequence of operations for at least the first five, can not be arbitrary. Secondly, during the processing of a strong oxidant in order to remove amorphous carbon treatment with perchloric acid led to selective preservation of nanocarbon materials for a period of not more than two hours, and further etching caused rapid oxidation and destruction of the nanocarbon material. Obvious are the performance of the process, the yield of the target product and the quality of its structure. Thus, the claimed method satisfies the condition of patentability "inventive step".

The drawing shows obtained using an electron microscope photograph of a sample nanocarbon material obtained using the proposed method. Scale 1:500000 (a real increase of 100,000). In pictures visible partially open layered on which trubka 1.

To confirm the conformity of the invention the condition of "industrial applicability" below are examples of its specific implementation.

To define the structure of nanocarbon material was used electron microscope JEM-100S (JEOL, Japan) at magnification 10000-100000.

Control the removal of impurities from shungite was carried out using x-ray diffraction analysis.

The percentage of nanotubes and other nano-forms with accuracy up to 10% was defined as the average of the five electronic photographs of each of the studied sample.

The percentage of open nanotubes and other nano-forms were determined by direct counting and subsequent averaging of the results.

Example 1

In a graphite crucible were mixed 10 g of crushed stones with molten alkali NaOH and Poplawski mixture at a temperature of 500°C for 4 hours

Obtained after treatment with alkali, the product was washed in 3.5 l of distilled water until a neutral pH, filtered and then dried at a temperature of 80°C for 1 h

The mass remaining in the processing of the product was 3,071 g, i.e. the relative loss of mass (here and everywhere hereinafter in relation to the initial mass of shungite) at this stage of processing amounted to 69.3%.

The obtained intermediate product formation is atively of concentrated hydrochloric acid for 2 h boiling at a temperature of 120° C.

Obtained after treatment with acid, the product was washed with distilled water until neutral pH, filtered and dried at a temperature of 80°C for 1 h

The mass remaining in the processing of the product was 2,390 g, i.e. the relative decline of the mass at this stage of processing accounted for 6.81%.

The resulting material was treated with perchloric acid for 2 h boiling at a temperature of 100°C. the Mass remaining in the processing of the product was 1,591 g, i.e. the relative decline of the mass at this stage of processing amounted to 7.99%. When exceeding the processing time more than two hours observed the destruction of the nanostructure of the material.

Obtained after processing, the material was washed with distilled water until neutral pH, dried at a temperature of 80°C.

Obtained after drying the material was annealed in order to air in a high temperature furnace at a temperature of 700°C for 4 h, the Mass remaining in the processing of the product was 1,117 g, i.e. the relative decline of the mass at this stage of processing was 4,74%.

Thus, the yield of the target product as a result of all processing stages amounted to 11.2% of the initial mass of shungite.

The share of nanocarbon forms in the final nanocarbon material amounted to arr is siteline 70 wt.%. The share of disclosed nanoparticles was approximately 40 wt.%. Typical electronic photograph of the obtained material is presented in the drawing. Clearly visible partially open multilayer nanotube 1.

Example 2 (variation alkali)

Carried out analogously to example 1, but instead of NaOH used KOH.

The mass remaining in the processing of the product at this stage amounted to 2.79 g, i.e. the relative decline of the mass at this stage of processing made up 72.1%.

The share of nanocarbon forms in the target nanocarbon material amounted to about 70 wt.%. The share of disclosed nanoparticles was approximately 30 wt.%. The yield of the target product as a result of all the processing steps of 9.9% of the initial mass of shungite.

Example 3 (variation of acid)

Carried out analogously to example 1, however, the acid was used concentrated (65 wt.%) hydrofluoric acid at a temperature of 90°C.

The relative loss of mass at this stage of processing was 9.24%. The proportion of nanoparticles in the final nanocarbon material amounted to about 60 wt.%. The share of disclosed nanoparticles was approximately 50 wt.%.

The yield of the target product in the conduct of all phases of treatment amounted to 10.01% of the initial mass of shungite.

Example 4 (variation of strong oxidizer

Carried out analogously to example 1, however, as a strong oxidant used 25 wt. %aqueous solution of peroxide of barium BaO2at a temperature of 90°C.

The relative loss of mass at this stage of processing was 4,34%. The proportion of nanoparticles in the final nanocarbon material was approximately 50 wt.%. The share of disclosed nanoparticles was approximately 40 wt.%.

The yield of the target product in the conduct of all stages of processing amounted to 13.8% of the initial mass of shungite.

Example 5 (variation of gas-phase oxidant)

Carried out analogously to example 1, however, the final gas-phase oxidation is carried out by oxygen O2when the oven temperature to 700°C for 3 hours

The relative loss of mass at this stage of processing was 13.3%. The proportion of nanoparticles in the final nanocarbon material amounted to approximately 90 wt.%. The share of disclosed nanoparticles was approximately 70 wt.%. The yield of the desired product as a result of carrying out all processing steps were 4.9% of the initial mass of shungite.

Example 6 (variation of temperature)

Carried out analogously to examples 1 however, oxidation in air was carried out at a furnace temperature of 1200°C for 3 hours

The relative loss of mass at this stage of processing was 11,82%. Share nano is ASTIC in the final nanocarbon material amounted to approximately 90 wt.%. The share of disclosed nanoparticles was approximately 70 wt.%. The yield of the desired product as a result of carrying out all processing stages amounted to 2.73 percent from the initial mass of shungite.

Example 7 (master process)

Carried out analogously to example 1, but the mass of crushed stones was 1 kg, Respectively, and increased mass of reagents used. Processing time and temperature were the same as in example 1.

The product weight remaining after treatment with molten alkali was 382,3 g, i.e. the relative conversion of methane to liquid hydrocarbons (C5H12With6H14With7H16C8H18- up to 40%, specific activity (i.e. the number of moles of CH4convertible to 1 g of catalyst) - more than 2000.

The product weight remaining after treatment with acid, was 331,0 g, i.e. the relative decline of the mass at this stage of processing amounted to 5.13%.

The product weight remaining after processing a strong oxidant, was 269,6 g, i.e. the relative decline of the mass at this stage of processing was 6,14%.

The mass remaining in the processing of the product was 221,5 g, i.e. the relative decline of the mass at this stage of processing amounted to 4.81%.

Thus, the yield of the desired product as a result of carrying out all stages of processing was 22,15% from the original is the mass of shungite.

The share of nanocarbon forms in the target product was approximately 60 wt.%. The share of disclosed nanoparticles was approximately 35 wt.%.

According to this example was also processing 100 kg of shungite in one unit volume of 70 liters per day, with the yield of the target product 20% by weight of raw materials.

The authors of the claimed invention, it was found that obtained when implementing the proposed method nanocarbon material from shungite has a great natural material specific surface area (200 to 1000 m2/g) and sorption properties with respect to pairs of hydrocarbons (primarily methane - 10-12 wt.% when N.U.), to hydrogen (up to 2-3 wt.% when N.U.), carbon oxide (II), oxygen - and nitrogen-containing compounds, and transition and heavy metals from their solutions in a wide range of temperatures and pressures.

Implementation of the claimed invention is not limited to the above examples.

The results given in examples 1-7, suggests that the implementation of the claimed invention results in comparison with the known closest to the achieved result (arc method for the synthesis of SWNT) to increase the productivity of the method for obtaining high-performance nanocarbon material to processing of at least 100 kg of shungite in one unit volume of 70 liters per day output target is on product 20% by weight of the raw material; to obtain the target product - nanocarbon material - containing nanotubes and other nano-forms from 20 to 90 wt.%, including the disclosed nano-forms - up to 70 wt.%. The content of nanotubes, specific surface area and sorption properties of the target product is similar to the best artificial nanocarbon materials - MWNT and SWNT - and, therefore, can be used for heterogeneous catalysis.

Beyond the stated interval parameters greatly reduces the efficiency of the process and its implementation on an industrial scale becomes impractical.

1. A method of obtaining a nanocarbon material from shungite, including the processing of inorganic acid and heat treatment, characterized in that shungite consistently when heated handle molten alkali, concentrated inorganic acid, which use HF or HCl, and a strong oxidant from a number of HClO4, BaO2after processing each of the reagents formed intermediate product is washed with water and dried, and heat treatment is carried out by high-temperature gas-phase oxidation with obtaining the target product.

2. The method according to claim 1, characterized in that the processing of raw materials - shungite alkali is carried out at a temperature above the temperature the s plavleni alkali, but not exceeding 500°C.

3. The method according to claim 1, characterized in that the processing of the intermediate product HF or HCl is carried out in the mode of boiling at the temperature of boiling concentrated solution of the appropriate acid.

4. The method according to claim 1, characterized in that the processing of the intermediate product is a strong oxidant is carried out in the mode of boiling at temperatures up to 150°C for no more than 2 hours

5. The method according to claim 1, characterized in that the gas-phase oxidation is carried out in an oxygen or air atmosphere.

6. The method according to claim 1, characterized in that the gas-phase oxidation is carried out at a temperature of 700-1200°C.

7. The method according to claim 1, characterized in that the gas-phase oxidation is carried out in a high temperature furnace.



 

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33 cl, 1 ex, 2 tbl

FIELD: chemical industry; other industries; devices for production of the solid-phase nanostructured materials.

SUBSTANCE: the invention is pertaining to the nanotechnologies and may be used at production of the carbonic nanotubes. The invention provides, that in the steam generator (4) they prepare multiphase mixture of the initial substance and route it under pressure to the gasodynamic resonator (9), where the mixture detonates. The products of the detonation combustion through the nozzle (2) are fed in the chamber (3), extended and cooled forming clusters. The produced clusters are routed onto the target (12) with the formation die (1) arranged in the chamber (3). The substrate (11) of the target (12) is supplied with the temperature control device providing the cyclical heating and cooling. The formation and growth of the solid-phase nanostructured materials takes place on the formation die (1). As the pressure in the gasodynamic resonator (9) drops, the feeding of the multiphase mixture in it is restarts and the process repeats. The invention allows to provide the optimal conditions of the growth of the nanostructured materials and due to it to increased efficiency of the process.

EFFECT: the invention ensures provision of the optimal conditions for the growth of the nanostructured materials and the increased efficiency of the process.

1 dwg

FIELD: chemical industry; methods of the chromatographic concentration of the fullerenes.

SUBSTANCE: the invention is pertaining to the field of the chemical industry. The mixture of the fullerenes dissolved in the organic solvent is gated through the column with the carbon-containing sorbent. At that as the sorbent they use the ground gray iron. After saturation of the ground gray iron with the mixture of the fullerenes they first eluate the fullerenes (С60 and С70) with o- xylene; then eluate the higher fullerenes (С76 and further) with 0- dichlorobenzene into the separate enriched by them fraction. The invention ensures the increased output of the higher fullerenes extracted into the enriched by them fraction and may be easily realized, since it is based on the usage of the accessible product - gray-iron and the dissolvents traditionally used in the fullerenes production process.

EFFECT: the invention ensures the increased output of the higher fullerenes, simplicity of the method realization, usage of the accessible product-gray-iron and the dissolvents traditionally used in the fullerenes production process.

2 tbl, 2 ex

FIELD: hydrogen production processes.

SUBSTANCE: invention relates to catalytic processes of hydrogen production from hydrocarbon-containing gases. Method of invention comprises elevated-pressure catalytic decomposition of methane and/or natural gas into hydrogen and carbon followed by gasification of the latter with the aid of gasification reagent in several in parallel installed interconnected reactors, each of them accommodating preliminarily reduced catalyst bed. When one of reactors is run in methane and/or natural gas decomposition mode, the other gasifies carbon, the both operation modes being regularly switched. Operation period in one of the modes ranges from 0.5 to 10 h. Carbon gasification reagent is, in particular, carbon dioxide and catalyst utilized is reduced ferromagnetic thermally stabilized product consisting of iron oxides (30-80 wt %) and aluminum, silicon, magnesium, and titanium oxides. Methane and/or natural gas is decomposed at 625-1000°C and overpressure 1 to 40 atm.

EFFECT: ensured environmental safety and increased productivity of process.

3 cl, 1 dwg, 8 ex

FIELD: electronic-vacuum engineering.

SUBSTANCE: invention is intended for implementation in manufacture of light sources, indicator lamps, and optic displays. Graphite heater is placed in working volume, into which nitrogen or nitrogen/argon blend (ratio from 1:10 to 1:1) is pumped in at pressure up to 15 MPa and removed. These operations are repeated threefold. Thereafter, above-indicated gas or gas blend is pumped in at pressure 10 to 90 MPa and working volume is heated to 2100-2200 K at velocity 1 to 100 K/min and aged for 10 min to 4 h. Temperature is the lowered to ambient value and then pressure is reduced to atmospheric value at velocity 1 MPa/sec. Resultant nitrogen-carbon nanofibers are withdrawn from working volume, dispersed in ethyl alcohol by means of ultrasonic disperser giving power 180-200 W for 5-15 min, filtered, and applied onto cathodic plate.

EFFECT: enabled manufacture of various-structure nanofibers in large amounts by easy and economic way.

3 cl, 6 dwg, 1 tbl, 7 ex

FIELD: chemical industry; steel industry; methods of production of the carbonic granulated material used for the steel alloying and the material produced by this method.

SUBSTANCE: the invention is pertaining to the carbonic materials and their production, mainly to the carbonic granulated materials and the methods of their production. The method of production of the carbonic granulated material for alloying the steel provides for heating of the layer of the granulated carbon black in reaction zone of the rotated horizontal reactor up to 800-1200°C, feeding in the moving hydrocarbon black layer of the gaseous or vaporous hydrocarbons with subsequent their thermal decomposition and the pyrocarbon settling-down on hydrocarbon black. Feeding of the hydrocarbons in the layer of the hydrocarbon black with the specific surface of 5-120 m2/g and with adsorption of dibutylphthalate of 30-160 ml/100g is conducted with the volumetric speed of 18-34 hour-1 " 1 at the ratio of the height the hydrocarbon black layer to the diameter of the reaction zone as 0.2-0.4. The carbonic material for alloying the steel produced by the offered method, possesses the value of the closed porosity of the compacted pyrocarbon granules of the hydrocarbon black equal to 33-58 %. The technical result of the invention is production of the carbonic material with the properties ensuring upgrading of the degree of absorption of the carbonic material in the process of the out-of-furnace treatment of the steel in combination with the high accuracy of the alloying the steel with the carbon (± 0.02 %).

EFFECT: the invention ensures production of the carbonic material with the properties providing upgrading of the degree of absorption of the carbonic material in the process of the out-of-furnace treatment of the steel in combination with the high accuracy of the alloying the steel with the carbon.

3 cl, 3 ex, 1 tbl

FIELD: nanotechnology, in particular, equipment for producing single nano-structures in form of metallic nano-wires, having prospective application as sensors and indicators.

SUBSTANCE: in accordance to the invention, track membranes are assembled in multi-layered sandwich, vacuum-pressed to each other and to metallic cathode-substrate and galvanic precipitation of metal is performed using through etched open-ended channels of track membranes. Because the probability of mutual engagement of statistically distributed open-ended etched channels in membranes is sufficiently low, in each following membrane, starting from cathode-substrate, number of etched channels with metallic precipitation made in galvanic fashion is reduced, and on upper membrane conditions for forming a single nanostructure are created.

EFFECT: method makes it possible to create single metallic nanostructures in galvanic fashion with high efficiency and simplicity on basis of standard track membranes, having high density of open-ended etched tracks of given dimensions.

2 cl, 3 dwg

FIELD: methods for forming nanomicrosystems, containing carbon nanotubes.

SUBSTANCE: the method for forming nano-(micro-)systems from carbon nanotubes, positioned in accordance to a given pattern, includes applying a multi-layer cover, containing a catalytic layer, onto a substrate. Carbon layer of nano-dimension thickness is applied to catalytic layer, after than given pattern is applied to catalytic layer by placing a sample into working chamber with oxidizing substance, stabilizing its composition with one of known methods - placement of a probe with nano-dimension sharp tip above the sample with creation of tunnel-transparent probe-sample system, and creating electric influence on the system of constant or impulse mode, by setting a difference of potentials on it or letting a given current through it, while the process of local oxidizing of carbon layer is controlled up to opening of catalytic layer, respectively, by current and by current derivative - for potential mode, and by voltage and voltage derivative - for current mode, after that sample is placed in a growth chamber, heated up to temperature ˜ 350...600°C in presence of gas-reagents and high frequency or ultra-high frequency radiation.

EFFECT: during forming of nanomicrosystems it possible to position single carbon nanotubes according to a given pattern.

FIELD: nanotechnology.

SUBSTANCE: method of invention comprises providing reaction mixture, which is then affected by ultraviolet emission with wavelength less than 207 nm in continuous or pulse mode such as to split molecules of the reaction mixture to form carbon and metal vapor, which is condensed to form nanoparticles. Initial components for preparing reaction mixture are volatile carbon-containing compound, in particular carbon suboxide C3O2, metal-containing compound Fe(CO)5 or Mo(CO)6, and gas diluent such as inert gas.

EFFECT: reduced power consumption and enhanced process efficiency.

4 cl, 6 dwg

FIELD: spectroscopy.

SUBSTANCE: spectroscopy method for determining atom dimensions spectrum includes determining the spectrum of atom dimensions as a set of values of its radiuses in main conditions and in conditions of its positive ions, through measured spectroscopy parameters Eiz and Efz in accordance to formula: Rz=[a(Eiz)^(0.5)(Eiz-Efz)^(-1)]n, where R - atom radius, z - spectroscopy symbol, Ei - energy, ionization potential or optical limit, Ef - energy, excitation potential of the last, sensitive resonance line of spectrum, n - integer number from the row 1,2,3,4,5,6,7, (0,5);(-1) power indicator, ^ - power operator, a=0,489, for energy values in electron-volts and radius in angstroms, or a=0,9226 for energy values in electron-volts and radius in relative Bohr units.

EFFECT: increased efficiency.

2 cl, 1 dwg, 4 ex

FIELD: nanotechnology, possible use in chemical industry, electronics, medicine, mechanical engineering for producing plastics, fuel cell components, accumulators, super-capacitors, displays, electron emitters, prosthetics materials.

SUBSTANCE: in reaction pipe having an inlet window, graphitic cover-rod is mounted with composite graphitic target located in the channel of cover-rod. The target is prepared by mixing at room temperature of powders of graphite, nickel and yttrium oxide with atomic ratio Ni:Y equal to (4-10):1. Nickel and yttrium content in composite target - 1-10% at. Then the mixture is placed in the channel of graphitic cover-rod and packed. Protective diaphragm screen is installed between the window and the target. Laser evaporation of the target is performed by continuous CO2 laser with power not less than 0,5 kWt with irradiation density not less than 1·104 Wt/cm2, with blow-off by constant flow of inert gas under atmospheric pressure. Resulting one-wall carbon nanotubes are gathered in collector, made in form of metallic substrates, positioned along the length of reaction pipe.

EFFECT: simplified manufacture of composite graphitic targets for laser ablation, ensured high quality and high nanotube output, substantially lowered labor, energy and time costs.

3 cl, 5 dwg

FIELD: synthesis of nano-diamonds or ultra-dispersion diamonds.

SUBSTANCE: nano-diamond powders are produced in UHF plasma of carbon-containing gas steams, for example, ethanol, on substrate having temperature at which polymer-like hydrocarbon film is simultaneously precipitated onto it. Synthesis of nano-diamond powders in nano-porous hydrocarbon matrix, preventing their unitizing during long storage, is realized by simplified technology, compatible with common technological processes of micro-electronic industry, capable of control over their dimensions and concentration.

EFFECT: increased efficiency.

2 cl

FIELD: carbon materials.

SUBSTANCE: invention is directed to manufacture fillers of composites or catalyst supports, sorbents, and hydrogen accumulators. Iron-containing catalyst is charged into reactor and calcined under inert gas (e.g. nitrogen or argon) at 850-1200°C for 2-3 h, after which catalyst is cooled to 400-500°C and carbon monoxide is fed into reactor to be decomposed at this temperature on iron-containing catalyst.

EFFECT: increased yield of nanofibers, narrowed their diameter variation range, and lowered synthesis temperature.

1 tbl, 3 ex

FIELD: production of nano-powder materials; processes of forming nano-composite materials.

SUBSTANCE: proposed method includes forming electrical charges of opposite polarity in nano-particles. Mixing the nano-particles is performed in gel-like or liquid non-conducting medium which is chemically neutral to materials of nano-particles. Mixing is performed in several stages: ionization of nano-particles, main mixing due to attraction of oppositely charged particles, additional mixing due to motion of charged particles and nano-particles under action of electromagnetic field and molding of nano-composite. Device proposed for mixing the nano-particles has two chambers for charging the nano-particles, main mixing chamber, additional mixing chamber in form of flat disk and molding chamber in form of cylinders provided with pistons.

EFFECT: enhanced smoothness of mixing of micro-and nano-powders.

8 cl, 9 dwg

FIELD: microelectronics, micro- and nano-technology.

SUBSTANCE: proposed method for producing submicron and nanometric structure includes formation of embossed structures on substrate surface, application of film to reduce embossed structure size to submicron and nanometric dimensions, and etching, anisotropic and selective relative to film material and source embossed layer, in chemically active plasma of structure obtained together with substrate material until embossed structure of submicron and nanometric dimensions, twice as deep as its width, is obtained.

EFFECT: provision for transferring mask pattern to bottom layer of substrate measured in terms of submicron and nanometric values.

2 cl, 3 dwg

FIELD: chemical industry; methods of manufacture of the composites, catalytic agents, the materials for the gases storing.

SUBSTANCE: the invention is pertaining to the method of the selective manufacture of the ordered carbonic nanotubes in the boiling layer and may be used at the composites, catalytic agents, the materials for the gases storing. First manufacture the catalytic agent by deposition of the transition metal particles on the grains of the carrier in the "boiling bed" in the deposition reactor at the temperature of 200-300°C. The particles of the metal have the average size of 1-10 nanometers metered after the action of the temperature of 750°C. The grains of the catalytic agent contain 1-5 % of the mass particles of the metal. Fragments of metal also have the average size of 10-1000 μ. The carrier has the specific surface above 10 m2/g and is selected from the activated charcoal, silica, silicate, magnesium oxide or titanium oxide, zirconium oxide, zeolite oxide or the mixture of the grains of several of these materials. The ordered carbonic nanotubes are manufactured by decomposition of the gaseous source of carbon, for example, hydrocarbon, at its contact with at least of one solid catalytic agent. The decomposition is conducted in the "boiling" bed of the catalytic agent in the growth reactor at the temperature of 600-800°C. The invention allows to increase the output of the pure nanotubes with in advance calculated sizes.

EFFECT: the invention allows to increase the output of the pure nanotubes with in advance calculated sizes.

31 cl, 5 dwg, 3 tbl, 15 ex

FIELD: carbon materials.

SUBSTANCE: weighed quantity of diamonds with average particle size 4 nm are placed into press mold and compacted into tablet. Tablet is then placed into vacuum chamber as target. The latter is evacuated and after introduction of cushion gas, target is cooled to -100оС and kept until its mass increases by a factor of 2-4. Direct voltage is then applied to electrodes of vacuum chamber and target is exposed to pulse laser emission with power providing heating of particles not higher than 900оС. Atomized target material form microfibers between electrodes. In order to reduce fragility of microfibers, vapors of nonionic-type polymer, e.g. polyvinyl alcohol, polyvinylbutyral or polyacrylamide, are added into chamber to pressure 10-2 to 10-4 gauge atm immediately after laser irradiation. Resulting microfibers have diamond structure and content of non-diamond phase therein does not exceed 6.22%.

EFFECT: increased proportion of diamond structure in product and increased its storage stability.

2 cl

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