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INVENTION
Russian Federation Patent RU2284962

METHOD FOR PRODUCING HYDROGEN AND CARBON FIBER

Name of the inventor: Oruzheynikov Alexander (RU); Semenova Olga (RU); Likholobov Vladimir (RU); Anshits Alexander G. (RU); Borbat Vladimir Fedorovich (RU)
The name of the patentee: Institute of the Siberian Branch of Hydrocarbon Processing, Russian Academy of Sciences (SB RAS IPPU) (RU)
Address for correspondence: 644018, Omsk, ul. 5th Cord, 29, IPPU SB RAS, the patent office
Starting date of the patent: 2004.12.20

The invention relates to catalytic processes for producing hydrogen and carbon from hydrocarbon gases. A method of producing hydrogen and carbon fiber comprises decomposing hydrocarbon-containing gas at elevated temperature and pressure of 1-40 atm on the catalyst which is used as heat stabilized ferromagnetic reconstituted product isolated by magnetic separation of ash from coal burning in thermal power plants. This product is a spinel type structure, consisting at 18-90% iron oxide, and the rest - aluminum oxides, magnesium, titanium and silicon. Before using it previously subjected to hydrodynamic and particle size classification. Effect of the Invention: receiving cost reduction target products by substantially reduce the cost and the possibility of catalyst reusable after regeneration, which does not degrade the properties of the original product.

DESCRIPTION OF THE INVENTION

The invention relates to catalytic processes for producing hydrogen and carbon from hydrocarbon gases. Hydrogen after its isolation from a mixture of gases may be used as a reducing agent in various chemical industries, steel and other industries, but also as a reagent for fuel cell vehicles, and independent sources of electrical energy. The resulting carbon material due to its ferromagnetic properties can be used as a reinforcing filler for obtaining graphite pigments, fillers, rubber materials, plastics and ferromagnetic materials. Furthermore, resulting from the pyrolysis of carbon can be widely used in the building industry as an additive to asphalt compositions, concrete, ceramics, and also as additives in reclaiming inorganic soils.

A large number of methods for producing hydrogen and carbon by pyrolysis of hydrocarbon gas using various types of catalysts:

1. The decomposition of methane in the presence of SiO 2 deposited on nickel compounds at a temperature of 630 ° C.

2. The decomposition of methane in the presence of catalysts with a different content of iron supported on aluminum or silicon oxides (Fe / Al 2 O 3 or Fe / SiO 2), Co and additives at temperatures of 600-675 ° C. (LBAvdeeva et al Iron-containing catalyst of methane decomposition:. Accumulation of filamentous carbon Appl Catal A:.... General 2002. 228 r.53-63.)

3. The decomposition of methane on the surface of Fe / SiO 2 catalyst with different contents of SiO 2 at temperatures of 650-800 ° C. (MAErmakova et. Al. Decomposition of methane over iron catalysts at the range of moderate temperatures. J. Catal. 2001. 201. №2, 183-197.)

The disadvantages of these methods for producing carbon and hydrogen are the high cost of the catalysts and their inability to re-use due to destruction of the catalyst when attempting to regenerate.

The closest to the claimed invention is a method for producing carbon and hydrogen, including methane decomposition at a temperature of 651-800 ° C over a catalyst which is a mixture of oxides of nickel, copper, iron, and aluminum hydroxide, hydrogen recovered by heating to 651-800 ° C, the following component ratio in the catalyst, wt.%:

(RF Patent №2116829 on cells. In 01 J 23/755, 23/72, 23/745, publ. In the Bulletin. №22, 1998).

The obvious disadvantage of this method of producing carbon and hydrogen, the catalyst used is the high cost due to a high content of expensive nickel. Furthermore, the use of the catalytic decomposition of hydrocarbons to produce hydrogen processes necessitates regeneration of the catalyst with a view to its reuse. All previously used in the preparation of hydrogen and carbon catalysts showed low chemical and mechanical stability during regeneration by carbon gasification. Almost all of the known catalysts for this process is irreversibly inactivated or kept no more than 3-4 cycles of regeneration. The reason for this fact are the properties and characteristics of the metal catalyst particles and a method for its preparation. In the pyrolysis of hydrocarbons mass transfer of carbon atoms is due to their diffusion through the mass of metal particles from the site of crystallization centers. This process leads to disruption of the integrity of the catalysts prepared by impregnation or coprecipitation methods.

The present invention is to reduce the cost of producing the desired products due to substantial price reduction of the catalyst and the possibility of reuse after regeneration, which does not degrade the properties of the original product.

The proposed method of producing hydrogen and carbon fiber comprises decomposing hydrocarbon-containing gas at elevated temperature and pressure of 1-40 atm on the catalyst. The reduced use ferromagnetic heat stabilized product is isolated by magnetic separation of the ash from coal in thermal power plants, which is a spinel-type structure consisting at 18-90% iron oxide, and the rest as a catalyst - alumina, magnesium, titanium and silicon. This product can be previously subjected to a hydrodynamic and granulometric classification.

Hallmarks of the present invention is conducting the process of decomposition of hydrocarbons at a pressure of 1-40 atm and reduced use as catalyst ferromagnetic thermostabilized product isolated by magnetic separation of coal ash from thermal power plants. This product is a spinel type structure, consisting for 18-90% of iron oxides and aluminum oxides, magnesium, titanium and silicon, and conducting a process at elevated temperature and pressure of 1-40 atm.

Another feature is a preliminary hydrodynamic and grading classification ferromagnetic thermally stabilized product.

Thus, the proposed set of essential features will reduce the cost of desired products at the expense of catalyst cheaper and have its reuse after regeneration, which does not degrade the properties of the original product.

It should be noted that all used in the process of decomposition of hydrocarbons to hydrogen and carbon are synthetic catalysts. They are prepared either by coprecipitation of the various components, either by impregnating the active components of salts (Fe, Cu, Ni, etc.) of the catalyst carrier - silica alumina. The proposed application material is formed by high-temperature thermochemical transformation of the mineral solid fossil fuel during combustion in thermal power plants. The resulting particles can be isolated and used in various industrial fields. A variety of these particles exhibit ferromagnetic properties, the microspheres are glass ceramic based on Fe - spinels based on SiO 2 and / or Al 2 O 3. Heat Treatment of such systems by burning coal (1200-1600 ° C) promotes lasting fixation of active ingredients in a carrier matrix and especially the stability of the catalyst in the "hydrogen synthesis - regeneration". Technology selection of magnetic microspheres based on a combination of magnetic separation processes, hydrodynamic and particle size classification of the dispersed energy evils. The result is a thermally stabilized ferromagnetic structure of the spinel type, comprising at 18-90% of iron oxide and aluminum oxide, magnesium, titanium and silicon.

SUMMARY OF THE INVENTION The following examples illustrate

Example 1 (the prototype)
A catalyst consisting of 72 wt.% NiO, 11 wt.% CuO, 11 wt.% Al (OH) 3 and 6 wt.% Fe 2 O 3 obtained 30 minutes of mechanochemical activation in a planetary centrifugal mill, in an amount of 0, 0033 g was charged in a flow reactor with weights Mc Ben heated for 30-35 minutes in a hydrogen flow of 20 l / h to a temperature of 651 ° C. Then hydrogen is replaced by methane and reacted at 651 ° decomposition C. for 4 hours and the methane flow rate of 3 l / h. Weight gain due to carbon catalyst was 5433 wt.% Relative to the weight of reduced catalyst. Regeneration of the catalyst by carbon gasification at 800 ° C leads to its destruction and further use impossible.

Example 2 (prototype)
A catalyst consisting of 72 wt.% NiO, 11,5 wt.% CuO, 11,5 wt.% Al (OH) 3 and 4 wt.% Fe 2 O 3 obtained 30 minutes of mechanochemical activation in a planetary centrifugal mill in an amount of 0.0034 g was charged in a flow reactor with weights Mc Ben heated for 30-35 minutes in a hydrogen flow of 20 l / h to 800 ° C temperature. then replaced by hydrogen and methane decomposition reaction is carried out at 800 ° C for 3 hours, and the methane flow rate of 3 l / h. Weight gain due to carbon catalyst was 423 wt.% Based on the weight of reduced catalyst. The regenerated catalyst was not possible.

Example 3 (according to the invention)
The ash from the combustion of coal is subjected to separation in a magnetic field. The resulting ferromagnetic thermally stabilized product, which contains 18.3 wt.% Fe 2 O 3, 26.0 wt.% Al 2 O 3, 53.0 wt.% SiO 2, 1.6 wt.% 1,6 MgO and 1 1 wt.% TiO 2 is subjected to mechanochemical activation in a planetary centrifugal mill. The resulting material was subjected to vertical water flow of water at high speeds. Due to this separation occurs by the specific gravity material particles. The heavy fraction is dried and recovered on the sieve particle size of 50 microns. Next, this product fraction in an amount of 0.1 g was charged in a fluidized bed flow reactor and heated to 650 ° C. At a temperature of 650 ° C and a pressure of 1.0 atm is carried out its restoration in a stream of hydrogen. Then hydrogen is replaced by a hydrocarbon gas (natural gas) and the reaction of decomposition at 650 ° C, 1.0 atm pressure for 15 hours. Gas is supplied at the rate of 45 liters per 1.0 gram of catalyst. The reaction catalyst weight gain due to carbon formation is 350 wt.% Relative to its weight, the resulting concentration of hydrogen 2 vol.%. The used catalyst with carbon fiber postpone it removed from the process and used for its intended purpose. Furthermore, it may be subjected to heat treatment at 800 ° C for 5 hours to carbon gasification and catalyst regeneration. The regenerated catalyst is re-loaded into a flow reactor and process are described in the procedure above.

example 4
As in example 3, it differs only in the pressure of decomposition of natural gas 40 at. Catalyst weight gain due to carbon formation was 680 wt.%, the average concentration of the hydrogen 4 vol.%.

example 5
As in example 3, differs only in the catalyst composition of 69.8 wt.% Fe 2 O 3, 8.2 wt.% Al 2 O 3, 20.8 wt.% SiO 2, 0.6 wt.% MgO and 0.6 wt.% TiO 2. Catalyst weight gain due to carbon formation amounted to 650 wt.%, the average hydrogen concentration of 3.8 vol.%.

example 6
As in example 3, characterized by the temperature of decomposition of natural gas of 800 ° C. Catalyst weight gain due to carbon formation amounted to 340 wt.%, the average concentration of the hydrogen 2 vol.%.

Thus, analysis of the above examples show that by using the proposed invention reduces the cost of producing the desired products by significantly reduce the cost of the catalyst in connection with the use as a raw material for its manufacture technological wastes. The possibility of its reuse after regeneration, which does not impair the original properties of the product and improves process economics. The yield of the desired products per cycle to regenerate the catalyst remains at a slightly increased or prototype.

CLAIM

1. A method of obtaining fibrous carbon and hydrogen by decomposition at elevated temperature of the hydrocarbon-containing gas to a catalyst comprising hydrogen recovered oxides of iron and aluminum compounds, characterized in that the decomposition is carried out at a pressure of 1-40 atm, and the catalyst is thermally stabilized ferromagnetic reconstituted product isolated by magnetic separation of the ash from the combustion of coal in thermal power plants and represents a spinel-type structure consisting at 18-90% of iron oxide and aluminum oxide, magnesium and silicon - the rest.

2. A method of producing hydrogen and carbon fiber according to claim 1, characterized in that the ferromagnetic heat stabilized product is previously subjected to a hydrodynamic and granulometric classification.

print version
Publication date 04.01.2007gg