Catalyst (variants), method of preparation thereof, and a method for production of hydrogen from hydride solutions

FIELD: hydrogen production processes.

SUBSTANCE: invention relates to catalysts for hydrolysis of hydride compounds to produce pure hydrogen for being supplied to power installations, including fuel cells. Invention provides catalyst for production of hydrogen from aqueous or water-alkali solutions of hydride compounds containing platinum group metal deposited on complex lithium-cobalt oxide and, additionally, modifying agent selected from series: titanium dioxide, carbon material, oxide of metal belonging to aluminum, magnesium, titanium, silicon, and vanadium subgroups. According to second variant, catalyst contains no platinum group metal. Described are also catalyst preparation method (variants) and hydrogen generation process, which is conducted at temperature no higher than 60°C both in continuous and in periodic mode. As hydrogen source, sodium borohydride, potassium borohydride, and ammine-borane can be used.

EFFECT: increased catalyst activity at environmental temperatures (from -20 to 60°C), prolonged time of stable operation of catalytic system, and reduced or suppressed platinum metals in composition of catalyst.

14 cl, 1 tbl, 20 ex

 

The invention relates to catalysts for hydrolysis of a hydride compounds with the aim of obtaining pure hydrogen, to methods for their preparation and to a method of producing hydrogen for submission to the power plant, including fuel cells.

One of the main issues of hydrogen energy is the storage of hydrogen and the development of compact fuel processors (generators), which could provide the generation of hydrogen by "request".

Typically the hydrogen is stored and transported in standard containers under pressure up to 20 MPa. This technology is well established, but becomes uneconomical when storing large quantities of hydrogen. The increase in pressure in cylinders up to 70 MPa [N. Takeichi, H. Senoh, T. Yokota et al., International Journal of Hydrogen Energy, 2003, 28, 1121-1129] requires special security measures during their operation, as well as large energy consumption for multi-stage compression at refueling.

LPG has a higher density of hydrogen and therefore has more of its stock, but when stored in cryogenic conditions, there is considerable loss of gas due to evaporation [Kaplan R.L., Cornell Eng., 1961, v.27, No. 3, 21-23].

Intensive development of adsorption technology has led to the creation of a wide range Bogorodskaya materials (metals, alloys, and carbon nanotubes), which are characterized by a higher the Oh volume density of hydrogen compared to compressed and liquefied gas [V.A. Yartys, Lototsky, M.V., Hydrogen Materials Science and Chemistry of Carbon Nanomaterials, Ed. by T.N.Veziroglu et al., Kluwer Academic Publishers, 2004, 75-104]. The main disadvantage of these systems is the high process temperature sorption-desorption, resulting in sintering of the particles of sorbent and degradation kinetics of the process of hydrogen generation. In addition, for wide application of these compositions requires the creation of a sealed, explosion - and fire-proof structures.

Recently, special attention is paid to chemical compounds (hydrocarbons, water and hydrides) as a compact forms of hydrogen storage. The reasons for their use as sources of H2are high gravimetric and volumetric density of hydrogen in these compounds.

Today the main source of hydrogen is natural gas and oil, and the traditional way of obtaining N2in industry and catalytic conversion of hydrocarbons, mainly methane and its homologues [Eyubov AGRICULTURAL Catalysis in industry, 2001, No. 2; U.S. Pat. RF 2241657, SW 3/38, 2004.12.10; U.S. Pat. RF 2266252, SW 3/38, B01J 21/04, 2005.12.20]. The disadvantages of this method is a multistage process [U.S. Pat. RF 2274600, SW 3/38, 2006.04.20], high energy production (up to 20 MJ/m3H2) [Shpilrain EE, S. p. Malyshenko, Kuleshov, an Introduction to hydrogen energy. Ed. by V.A. Legasov M.: Energoatomizdat, 1984], is that technology does not meet modern environmental requirements, requirements for the process. In addition, the resulting hydrogen can be used to power fuel cells only after additional purification from carbon oxides [U.S. Pat. RF 2271333, SW 3/38, SC 3/04, 2006.03.10].

In some works suggest the use of biomass as a renewable source of hydrogen [Armstrong TR, hare M. J. Alternative energy and ecology. 2004, No. 2. 15-20; U.S. Pat. RF 2282582, SW 3/02, SR 1/00, 2006.03.27]. Unfortunately, today this area is not observed qualitative breakthroughs, despite many years of research, hundreds of research teams. The main disadvantage is low efficiency generation of hydrogen.

An inexhaustible source of hydrogen is water, and the most common way of its decomposition - the process of electrolysis. In industry, this process is used to produce hydrogen and oxygen with a purity of 99.99%. However, it should be noted that this technology requires high energy costs. Thus, to obtain 1 m3hydrogen must 20-22 MJ. [A. Koroteev, Smolyarov B.C., Military parade, 2005, may-April, 26-28].

The most attractive sources of hydrogen for portable fuel cells as well as simple and complex hydrides. The reasons for their potential use are high volumetric and gravimetric density N2and soft is their terms of getting H 2. For example, the density of hydrogen potassium borohydride is 0.083 g/cm3in the sodium borohydride - 0,112 g/cm3and aminoborane - 0,145 g/cm3that exceeds the density of liquid hydrogen (0.07 g/cm3). In the case of interaction hydride compounds with water produces 2 times more hydrogen than is contained in the original hydride as an extra source is water.

Currently actively developing hydrogen generators based on hydride compounds [Kong V.C.Y., F.R. Foulkes, D.W. Kirk, Hinatsu J.T., International Journal of Hydrogen Energy, 1999, 24, 665-675; .DE 10065269, 2002]. Analysis of patent and scientific literature showed that the most common source N2for portable generators use solutions of sodium borohydride [Kojima Y., Suzuki K., Fukomoto K., Kawai Y., Kimbara M., Nakanishi, H., Matsumoto, S., J. Power Sources, 2004, 125, 22-26; U.S. Pat. US 6932847, 2005], which are stable at room temperature [Application WO 03042096, 2003], but in the presence of a catalyst there is a rapid release of hydrogen without the formation of toxic by-products. The main direction of development of the process of hydrogen generation is based on the hydrolysis of sodium borohydride is associated with the creation of the catalysts. The main requirements that must be met for the catalytic systems are their high activity and stability.

It is known that catalysts of hydrolysis Borg is drid sodium are metals of group VIII [C.M. Kaufman, Sen .J. Chem. Soc., Dalton Trans, 1985, S-313], in the presence of which there is a complex multistage process, involving the restoration of the protons of water with the formation of gaseous hydrogen.

The process of catalytic hydrolysis of sodium borohydride proceeds at ambient temperatures (-20°C to 60°), it should be noted the high purity N2saturated only water vapor, allowing it to be served in the anode space of the fuel element without additional cleaning and moisturizing.

Known, for example, Nickel and cobalt massive system [Jin-Ho Kim et al. International Journal of Hydrogen Energy. 2004. 29. p.263-267]used as catalysts for the hydrolysis of sodium borohydride. The disadvantages of these catalysts is low activity. While there is a noticeable decrease in the rate of generation of hydrogen during the reaction, which is not typical for catalysts containing metals of platinum group.

In the publication [S. Ozkar, Zahmakiran M., J. Alloys and Compounds, 404-406, 2005, p.728-731] described the application as catalysts ruthenium nanoclusters stabilized in water with sodium acetate. It was shown that these catalytic systems are characterized by high activity in the hydrolysis of sodium borohydride. However, the main drawback of the application of Mas is active catalysts is the loss of precious metals in the process of hydrogen generation, since the size of the metal particles is not possible to completely separate them from the liquid reaction products.

Known applied catalysts [U.S. Pat. US 6683025, 2004], prepared on the basis of ceramic, polymer, plastic, ion exchange, glass, woven, non-woven, fibrous, carbon, metal (mesh and wire) media and their combinations. As the active component may use the transition metals of subgroups of copper, zinc, scandium, titanium, vanadium, chromium, manganese, iron, and platinum. The active component of the catalyst is applied from aqueous solutions of the corresponding salts by ion exchange, adsorption and electrochemical deposition. To restore the use of water-alkaline solution of sodium borohydride, with a mass fraction NaBH420%. Mass fraction of active component in the catalyst is 5%. The catalyst was prepared in the form of powder, fibers and wire with a diameter of 20-100 μm.

Despite the large variety of catalytic systems, their main disadvantage is the high content of metals, including platinum group, as well as multiple and high energy methods preparation of catalysts. In addition, demonstrated low activity of ruthenium-based catalyst ion-exchange resin IRA-400, selected as an example. So, when is the temperature of 25° With the rate of hydrogen generation from aqueous-alkaline solution of sodium borohydride, with a mass fraction NaBH420% and 10% NaOH was about 3.5 ml of N2/s·gcat-RA.

The closest analogue to the invention, the technical essence and the achieved result can be applied platinum catalyst based on non-traditional media LiCoO2(complex lithium cobalt oxide or cobaltic lithium) [Yoshitsugu Kojima et al. International Journal of Hydrogen Energy. 2002. 27. p.1029-1034]. Mass fraction of platinum in the catalyst is 1.5%, the rest is media LiCoO2. In the presence of this catalyst the rate of hydrogen generation is increased 10 times compared with the ruthenium catalyst on the basis of ion-exchange resin IRA-400 [Amendola, S.C., Sharp-Goldman, S.L., Janjua M.S., N.C. Spencer, Kelly M.T., Petillo P.J. Binder M. International Journal of Hydrogen Energy 2000, 25, p.969-975].

The disadvantage of the prototype is to reduce the activity of catalysts based on complex lithium cobalt oxide during the reaction, even though the increase in the mass fraction of precious metals up to 10% and reducing the molar ratio of metal to sodium borohydride to 300 [Palanichamy Krishnan et al. Journal of Power Sources, 2005, 143, p.17-23].

The objective of the invention is the development of highly active nano-catalysts with high stability for generation of hydrogen from aqueous or aqueous-alkaline solutions guide is innych compounds at ambient temperatures (-20° With up to 60° (C), as well as reducing the number of platinum metals in the catalyst composition.

The problem is solved in two versions of the catalyst for producing hydrogen from water or aqueous-alkaline solutions hydride compounds.

The first option. The catalyst contains a complex lithium cobalt oxide LiCoO2(cobaltic lithium), a platinum group metal and modifying additive selected from a range of titanium dioxide, carbon material, an oxide of a metal of subgroups of aluminum, magnesium, titanium, silicon and vanadium.

The content of the modifying additive is not more than 40 wt.% The content of the platinum group metal is not more than 1 wt.%.

The second option. The catalyst contains a complex lithium cobalt oxide LiCoO2(cobaltic lithium) and modifying additive selected from a range of titanium dioxide, carbon material, an oxide of a metal of subgroups of aluminum, magnesium, titanium, silicon and vanadium.

The content of the modifying additive is not more than 40 wt.%. The proposed catalysts provide high activity catalysts at ambient temperatures (-20°C to 60° (C), as well as increased time stable operation of the catalytic system.

The task is also solved by a method of preparation of the proposed catalysts.

In the first embodiment the catalyst is prepared by deposition of platinum metal is th group in the media on the basis of complex lithium cobalt oxide, before applying the platinum group metal on a carrier in the composition of the lithium-cobalt oxide is administered titanium dioxide and/or at least a carbon material, or one oxide of a metal of subgroups of aluminum, magnesium, titanium, silicon and vanadium by mechanical mixing, followed by drying, calcination and recovery.

As starting compounds of the platinum group metals used inorganic compounds of metals selected from a number of chlorinated compounds.

The recovery process is applied to the carrier compounds of platinum group metals is carried out in the reaction medium hydride compounds.

According to the second variant, the catalyst is prepared by introduction by mechanical mixing in the composition of the lithium-cobalt oxide, titanium dioxide and/or at least a carbon material or a metal oxide of subgroups of aluminum, magnesium, titanium, silicon and vanadium, followed by drying, calcination and recovery. The process of recovery of the catalyst is carried out in the reaction medium hydride compounds.

The task is also solved by a method of producing hydrogen from water or aqueous-alkaline solutions hydride compounds in the presence of a catalyst based on a complex lithium cobalt oxide modified with titanium dioxide and/or at least one modifying EXT the Cai of a carbon material or oxides of metals of subgroups of aluminum, magnesium, silicon, titanium and vanadium, as well as not containing or containing at least one active component selected from the group of platinum metals.

As a source of hydrogen using water or an aqueous-alkaline solution of sodium borohydride (NaBH4), but does not exclude the use of aqueous or aqueous-alkaline solutions of potassium borohydride (KBH4and aminoborane (NBH6).

The process is conducted as in the continuous (1 cycle), and periodic (more than 2 cycles) modes.

The hydrolysis of sodium borohydride is carried out at a temperature of not more than 60°C.

Salient features of the invention are:

1) introduction to the composition of the source media LiCoO2titanium dioxide and/or at least one of the modifying additive of carbon material or oxides of metals of subgroups of aluminum, magnesium, silicon, titanium and vanadium to increase the stability of the catalytic system;

2) the absence or presence of metals of the platinum group in the amount of not more than 1 wt.% without a significant reduction in the activity of the catalytic system. The process of preparation of the catalyst comprises the following stages:

- introduction to complex lithium cobalt oxide LiCoO2titanium dioxide and/or at least one of the modifying additive of carbon material or metal oxides is of thrupp aluminum, magnesium, silicon, titanium and vanadium;

add water or hydrochloric acid solution of the precursor of the active component;

- mixing of the mass when heated;

- drying, calcination;

the recovery in the reaction medium sodium borohydride.

Such method of preparation of catalysts provides a uniform distribution of metal particles on the carrier surface, their size does not exceed 5 nm, which leads to high activity of the obtained catalyst systems.

The invention is illustrated by the following examples.

Example 1 (test prototype patentable in terms of the method of producing hydrogen)

For the preparation of the catalyst for producing hydrogen from a water solution of sodium borohydride as a heterogeneous media use LiCoO2(production of the Novosibirsk chemical concentrates plant, Novosibirsk), in which the impregnation put platinum in the amount of 1.5 wt.%. The recovery process is carried out directly in the reaction medium sodium borohydride. Using the obtained catalyst to carry out the hydrolysis of sodium borohydride with the formation of pure hydrogen at a temperature of 40°C.

As a starting compound for the synthesis media take LiCoO2with a specific surface area of 1.2 m2/year

In a glass container is placed here 4,925 g media and add 19 ml 0,0196 M solution of N 2PtCl6. The excess liquid is evaporated at a temperature of 80°and With constant stirring. After you carry out the drying at 110-150°C for 4 h, the Catalyst restore directly in the reaction medium NaBH4.

The resulting catalyst has the following characteristics:

the Pt content of 1.5 wt.%;

the generation rate H21 cycle - 119 ml of N2/s·gcat-RA;

the relative activity, 5 cycle - to 24.3%.

The method of producing hydrogen. The process is carried out at a temperature of 40°in temperature-controlled glass reactor internal mixing, equipped with a magnetic stirrer, the stirring speed of 800 rpm. Initially in the reactor pour 10 ml of water, in which dissolve 0,039 g of sodium borohydride. A portion of NaBH4expect considering the fact that the total amount of hydrogen does not exceed 110 ml at 20°because of its quantitative analysis is performed using a burette in 110 ml. Then placed in the reactor 0,0067 g of the catalyst on the basis of LiCoO2containing 1.5 wt.% platinum. A portion of the catalyst is calculated from the molar relationship Pt:NaBH4=1:2000. The reactor was tightly closed with the cap with vent tube attached to the burette.

In subsequent cycles the spent solution from the reaction products removed from the reactor by decantation until ablaut a new batch of solution of NaBH 4.

The rate of hydrogen generation (and) was calculated by the equation

where ν - the reaction rate, ml H2/s·gcat-RA,

- the volume of hydrogen (N.U.), ml released during the half-transformation t1/2in s, m is the mass of the catalyst,

The relative activity of the catalyst during the fifth cycle was calculated by the equation

where a is the relative activity of the catalyst in cycle 5,

ν1 cycleand ν5 cycle- the reaction rate calculated by the formula (2), for 1 and 5 cycles, respectively.

Example 2 (test prototype patentable in terms of the method of producing hydrogen)

The composition and the stage of preparation of the catalyst for producing hydrogen from aqueous-alkaline solution of sodium borohydride as described in example 1.

The resulting catalyst has the following characteristics:

the Pt content of 1.5 wt.%;

the generation rate H21 cycle - 153 ml of N2/s·gcat-RA;

the relative activity, 5 cycle - to 13.7%.

The method of producing hydrogen. Described in comparative example 1, with the difference that in the reaction medium was added 0,021 g of sodium hydroxide (NaOH). A portion of NaOH is calculated from the molar relationship NaBH4:NaOH=2:1.

Example 3.

For the preparation of the catalyst p is produce hydrogen from water or aqueous-alkaline solutions of sodium borohydride as a heterogeneous media use LiCoO 2(production of the Novosibirsk chemical concentrates plant, Novosibirsk), modified TiO2in the amount of 24 wt.%, on which the impregnation put platinum in the amount of 1 wt.%. The recovery process is carried out directly in the reaction medium sodium borohydride. Using the obtained catalyst to carry out the hydrolysis of sodium borohydride with the formation of pure hydrogen at a temperature not above 60°C.

As a starting compound for the synthesis media take 3,762 g LiCoO2with a specific surface area of 1.2 m2/, as modifying additives take 1,188 g TiO2with a specific surface area of 79 m2/, Modifying additive is introduced by mechanical mixing of LiCoO2with TiO2in a mortar.

In a glass bowl placed of 4.95 g of carrier and type of 13.1 ml 0,0196 M solution of H2PtCl6. The excess liquid is evaporated at a temperature of 80°and With constant stirring. After you carry out the drying at 110-150 C for 4 h, the Catalyst restore directly in the reaction medium NaBH4.

The resulting catalyst has the following characteristics:

- contents Pt - 1 wt.%,

the generation rate H21 cycle - 131 ml of N2/s·gcat-RA,

the relative activity, 5 cycle - 40,5%.

The method of producing hydrogen. The process is carried out at temperature is re 40° With glass thermostated reactor internal mixing, equipped with a magnetic stirrer, the stirring speed 800 rpm Initially in the reactor pour 10 ml of water, in which dissolve 0,039 g of sodium borohydride. A portion of NaBH4expect considering the fact that the total amount of hydrogen does not exceed 110 ml at 20°because of its quantitative analysis is performed using a burette in 110 ml. Then placed in the reactor 0,0101 g of the catalyst on the basis of LiCoO2modified TiO2and containing 1 wt.% platinum. A portion of the catalyst is calculated from the molar relationship Pt:NaBH4=1:2000. The reactor was tightly closed with the cap with vent tube attached to the burette.

In subsequent cycles the spent solution from the reaction products removed from the reactor by decantation and add a new batch of solution of NaBH4.

Example 4.

Similar to example 3, different composition of the reaction medium. In the reaction medium was added 0,021 g of sodium hydroxide (NaOH). A portion of NaOH is calculated from the molar relationship NaBH4:NaOH=2:L catalyst Composition, its characteristics and test conditions are given in the table.

Example 5.

For the preparation of the catalyst for producing hydrogen from water or aqueous-alkaline solutions of sodium borohydride as a heterogeneous wear what I use LiCoO 2(production of the Novosibirsk chemical concentrates plant, Novosibirsk), modified TiO2in the amount of 35 wt.%, on which the impregnation is applied rhodium in the amount of 1 wt.%. The recovery process is carried out directly in the reaction medium sodium borohydride. Using the obtained catalyst to carry out the hydrolysis of sodium borohydride with the formation of pure hydrogen at a temperature not above 60°C.

As a starting compound for the synthesis media take 1,9305 g LiCoO2with a specific surface area of 1.2 m2/, as modifying additives take 1,0395 g TiO2with a specific surface area of 75 m2/, Modifying additive is introduced by mechanical mixing of LiCoO2with TiO2in a mortar.

In a glass bowl placed 2,97 g media and add 5.8 ml of 0.05 M solution of RhCl3. The excess liquid is evaporated at a temperature of 80°and With constant stirring. After you carry out the drying at 110-150°C for 4 h, the Catalyst restore directly in the reaction medium NaBH4.

The resulting catalyst has the following characteristics:

- contents Rh - 1 wt.%,

the generation rate H21 cycle - 128 ml of N2/s·gcat-RA,

the relative activity, 5 cycle - to 48.4%.

The method of producing hydrogen. Described in example 3, characterized in that Thu is in the reactor is placed 0,0053 g of the catalyst on the basis of LiCoO 2modified TiO2and containing 1 wt.% rhodium. A portion of the catalyst is calculated from the molar relationship Rh:NaBH4=1:2000.

Example 6.

For the preparation of the catalyst for producing hydrogen from water or aqueous-alkaline solutions of sodium borohydride as a heterogeneous media use LiCoO2(production of the Novosibirsk chemical concentrates plant, Novosibirsk), modified TiO2in the amount of 40 wt.%, on which the impregnation is applied ruthenium in the amount of 1 wt.%. The recovery process is carried out directly in the reaction medium sodium borohydride. Using the obtained catalyst to carry out the hydrolysis of sodium borohydride with the formation of pure hydrogen at a temperature not above 60°C.

As a starting compound for the synthesis media take 1,188 g LiCoO2with a specific surface area of 1.2 m2/, as modifying additives take 0,792 g TiO2with a specific surface area of 75 m2/, Modifying additive is introduced by mechanical mixing of LiCoO2with TiO2in a mortar.

In a glass bowl placed 1.98 g of carrier and type of 7.9 ml of a 0.025 M solution of Rh(OH)Cl3. The excess liquid is evaporated at a temperature of 80°and With constant stirring. After you carry out the drying at 110-150°C for 4 h, the Catalyst vosstanavlivat the t directly in the reaction medium NaBH 4.

The resulting catalyst has the following characteristics:

- contents EN - 1 wt.%,

the generation rate H21 cycle - 124 ml of N2/s·gcat-RA.,

the relative activity, 5 cycle - to 39.3%.

The method of producing hydrogen. Described in example 3, characterized in that the reactor is placed 0.0052 g of the catalyst on the basis of LiCoO2modified TiO2and containing 1 wt.% ruthenium. A portion of the catalyst is calculated from the molar relationship EN:NaBH4=1:2000.

Example 7.

Similar to example 3, the different nature of the modifying additive. As builders use aluminum oxide with a specific surface area of 175 m2/, catalyst Composition, its characteristics and test conditions are given in the table.

Example 8.

Similar to example 4, the different nature of the modifying additive. As modifying additives used carbon material with a specific surface area of 510 m2/, catalyst Composition, its characteristics and test conditions are given in the table.

Example 9.

Similar to example 5 differs by the nature of the modifying additive. As modifying additives used silicon dioxide with a specific surface area of 256 m2/, catalyst Composition, its characteristics and test conditions are given in the table.

Example 10.

For p the production of the catalyst for producing hydrogen from water or aqueous-alkaline solutions of sodium borohydride as a heterogeneous media use LiCoO 2(production of the Novosibirsk chemical concentrates plant, Novosibirsk), modified TiO2in the amount of 24 wt.% and Nb2O5in the amount of 8 wt.%, on which the impregnation put platinum in the amount of 0.5 wt.%. The recovery process is carried out directly in the reaction medium sodium borohydride. Using the obtained catalyst to carry out the hydrolysis of sodium borohydride with the formation of pure hydrogen at a temperature not above 60°C.

As a starting compound for the synthesis media take 2,7064 g LiCoO2with a specific surface area of 1.2 m2/, as modifying additives take 0,9552 g TiO2with a specific surface area of 79 m2/g and 0,3184 g Nb2O5with a specific surface area of 0.7 m2/, Modifying additive is injected by mechanical mixing of LiCoO2with TiO2and NO2O5.

In a glass bowl placed 3,98 g of carrier and type of 5.2 ml 0,0196 M solution of N2PtCl6. The excess liquid is evaporated at a temperature of 80°and With constant stirring. After you carry out the drying at 110-150°C for 4 h, the Catalyst restore directly in the reaction medium NaBH4.

The resulting catalyst has the following characteristics:

the Pt content of 0.5 wt.%,

the generation rate H21 cycle - 116 ml of N2/s·g cat-RA,

the relative activity, 5 cycle - to 36.2%.

The method of producing hydrogen. Described in example 3, characterized in that the reactor is placed 0,021 g of the catalyst on the basis of LiCoO2modified TiO2and NO2O5containing 0.5 wt.% platinum. A portion of the catalyst is calculated from the molar relationship Pt:NaBH4=1:2000.

Example 11.

For the preparation of the catalyst for producing hydrogen from water or aqueous-alkaline solutions of sodium borohydride as a heterogeneous media use LiCoO2(production of the Novosibirsk chemical concentrates plant, Novosibirsk), modified TiO2in the amount of 15 wt.% and carbon material (C) in an amount of 18 wt.%, on which the impregnation is applied rhodium in the amount of 0.5 wt.%. The recovery process is carried out directly in the reaction medium sodium borohydride. Using the obtained catalyst to carry out the hydrolysis of sodium borohydride with the formation of pure hydrogen at a temperature not above 60°C.

As a starting compound for the synthesis media take 1,9999 g LiCoO2with a specific surface area of 1.2 m2/, as modifying additives take 0,4478 g TiO2with a specific surface area of 79 m2/g and 0,5373 g carbon material with a specific surface area of 1120 m2/, Modifying additives enter the way of the mechanical mixing LiCoO 2with TiO2and carbon material.

In a glass bowl placed 2,985 g media and added to 2.9 ml of 0.05 M solution of RhCl3. The excess liquid is evaporated at a temperature of 80°and With constant stirring. After you carry out the drying at 110-150°C for 4 h, the Catalyst restore directly in the reaction medium NaBH4.

The resulting catalyst has the following characteristics:

- a Rh content of 0.5 wt.%,

the generation rate H21 cycle - 123 ml of N2/s·gcat-RA,

the relative activity, 5 cycle - 41,5%.

The method of producing hydrogen. Described in example 3, characterized in that the reactor is placed 0,0106 g of the catalyst on the basis of LiCoO2modified TiO2and a carbon material containing 0.5 wt.% rhodium. A portion of the catalyst is calculated from the molar relationship Rh:NaBH4=1:2000.

Example 12.

For the preparation of the catalyst for producing hydrogen from water or aqueous-alkaline solutions of sodium borohydride as a heterogeneous media use LiCoO2(production of the Novosibirsk chemical concentrates plant, Novosibirsk), modified TiO2in the amount of 28 wt.% and V2O5in the amount of 12 wt.%, on which the impregnation is applied ruthenium in the amount of 0.5 wt.%. The recovery process is carried out directly in Rea the operating environment of sodium borohydride. Using the obtained catalyst to carry out the hydrolysis of sodium borohydride with the formation of pure hydrogen at a temperature not above 60°C.

As a starting compound for the synthesis media take 1,194 g LiCoO2with a specific surface area of 1.2 m2/, as modifying additives take 0,5572 g TiO2with a specific surface area of 79 m2/g and 0,2388 g V2O5with a specific surface area of 1,2m2/, Modifying additive is injected by mechanical mixing of LiCoO2with TiO2and V2O5in a mortar.

In a glass bowl placed 1,99 g medium and add 4 ml of 0.025 M solution of RH(OH)Cl3. The excess liquid is evaporated at a temperature of 80°and With constant stirring. After you carry out the drying at 110-150°C for 4 h, the Catalyst restore directly in the reaction medium NaBH4.

The resulting catalyst has the following characteristics:

- contents EN - 0.5 wt.%,

the generation rate H21 cycle - 104 ml of N2/s·gcat-RA,

the relative activity, 5 cycle - to 32.8%.

The method of producing hydrogen. Described in example 3, characterized in that the reactor is placed 0,0104 g of the catalyst on the basis of LiCoO2modified TiO2and V2O5containing 0.5 wt.% ruthenium. A portion of the catalyst is calculated from the molar Rel shall provide EN:NaBH 4=1:2000.

Example 13.

Similar to example 3, with the difference that the catalyst does not contain an active component selected from the group of platinum metals. To obtain hydrogen from water solution of sodium borohydride took 0,0101 g of catalyst. The catalyst composition, its characteristics and test conditions are given in the table.

Example 14.

Similar to example 4, with the difference that the catalyst does not contain an active component selected from the group of platinum metals. For hydrogen production from aqueous-alkaline solution of sodium borohydride take 0,0101 g of catalyst. The catalyst composition, its characteristics and test conditions are given in the table.

Example 15.

For the preparation of the catalyst for producing hydrogen from water or aqueous-alkaline solutions of sodium borohydride as the source material used LiCoO2(production of the Novosibirsk chemical concentrates plant, Novosibirsk), modified TiO2in the amount of 24 wt.% and MgO in an amount of 12 wt.%. Using the obtained catalyst to carry out the hydrolysis of sodium borohydride with the formation of pure hydrogen at a temperature not above 60°C.

As the initial connection charge of 2.56 g LiCoO2with a specific surface area of 1.2 m2/, as modifying additives take 0.96 g TiO2with a specific surface area of 75 m2g and of 0.48 g of MgO with a specific surface area of 8 m 2/year

The modifying additive is injected by mechanical mixing of LiCoO2with TiO2and MgO.

The resulting catalyst has the following characteristics:

the content of platinum group metals - 0 wt.%

the generation rate H21 cycle - 47 ml of N2/s·gcat-RA;

the relative activity, 5 cycle - to 74.5%.

The method of producing hydrogen. Described in example 3, characterized in that the reactor is placed 0,0101 g of the catalyst on the basis of LiCoO2modified TiO2and MgO.

Example 16.

For the preparation of the catalyst for producing hydrogen from water or aqueous-alkaline solutions of sodium borohydride as the source material used LiCoO2modified Al2About3in the amount of 25 wt.% and the carbon material in the amount of 18 wt.%. Using the obtained catalyst to carry out the hydrolysis of sodium borohydride with the formation of pure hydrogen at a temperature not above 60°C.

As the initial connection charge 1.24 g LiCoO2with a specific surface area of 1.2 m2/, as modifying additives take 0.5 g of Al2About3with a specific surface area of 175 m2/g and 0.26 g of the carbon material with a specific surface area of 510 m2/, Modifying additive is injected by mechanical mixing of LiCoO2with Al2O3and carbon material.

who received the catalyst has the following characteristics:

the content of platinum group metals - 0 wt.%

the generation rate H21 cycle - 42 ml of N2/s·gcat-RA,

the relative activity, 5 cycle - 78,6%.

The method of producing hydrogen. Described in example 3, characterized in that the reactor is placed 0,0101 g of the catalyst on the basis of LiCoO2modified Al2O3and carbon material.

Example 17.

Analogous to example 5, characterized in that as the source of hydrogen using an aqueous-alkaline solution of potassium borohydride (KBH4). The composition of the catalyst and its characteristics are given in the table.

The method of producing hydrogen. The process is carried out at a temperature of 40°in temperature-controlled glass reactor internal mixing, equipped with a magnetic stirrer, the stirring speed 800 rpm Initially in the reactor pour 10 ml of water, in which dissolve 0,021 g of sodium hydroxide NaOH and 0,056 g of potassium borohydride. A portion of KVN4expect considering the fact that the total amount of hydrogen does not exceed 110 ml at 20°because of its quantitative analysis is performed using a burette 110 ml Sample of NaOH is calculated from the molar relationship KBH4:NaOH=2:1. Then the reactor was placed 0,0053 g of the catalyst on the basis of LiCoO2modified TiO2and containing 1 wt.% rhodium. A portion of the catalyst Russ is icyhot based on molar relationships Rh:NaBH 4=1:2000. The reactor was tightly closed with the cap with vent tube attached to the burette.

Example 18.

Similar to example 13, characterized in that as the source of hydrogen used 0,056 g of potassium borohydride (KVN4). The catalyst composition, its characteristics and test conditions are given in the table.

Example 19.

Similar to example 3, characterized in that as the source of hydrogen using an aqueous-alkaline solution of aminoborane (NBH6). The composition of the catalyst and its characteristics are given in the table.

The method of producing hydrogen. The process is carried out at a temperature of 40°in temperature-controlled glass reactor internal mixing, equipped with a magnetic stirrer, the stirring speed 800 rpm Initially in the reactor pour 10 ml of water, in which dissolve 0,021 g of sodium hydroxide NaOH and to 0.032 g of aminoborane. Sample NBH6expect considering the fact that the total amount of hydrogen does not exceed 110 ml at 20°because of its quantitative analysis is performed using a burette 110 ml Sample of NaOH is calculated from the molar relationship NBH6:NaOH=2:1. Then the reactor was placed 0,0101 g of the catalyst on the basis of LiCoO2(production of the Novosibirsk chemical concentrates plant, Novosibirsk), modified TiO2and containing 1 wt.% platinum. A portion of the AC is of Aligator calculated from the molar relationship Pt:NaBH 4=1:2000. The reactor was tightly closed with the cap with vent tube attached to the burette.

Example 20.

For the preparation of the catalyst for producing hydrogen from water and aqueous-alkaline solutions of aminoborane as the source material used LiCoO2modified carbon material in an amount of 23 wt.%. Using the obtained catalyst to carry out the hydrolysis of sodium borohydride with the formation of pure hydrogen at a temperature not above 60°C.

As the initial connection charge 2,31 g LiCoO2with a specific surface area of 1.2 m2/, as modifying additives take 0,69 g of the carbon material with a specific surface area of 510 m2/, Modifying additive is injected by mechanical mixing of LiCoO2with the carbon material.

The resulting catalyst has the following characteristics:

the content of platinum group metals - 0 wt.%

the generation rate H21 cycle - 53 ml of N2/s·gcat-RA,

the relative activity, 5 cycle - to 77.4%.

The method of producing hydrogen. Described in example 19, characterized in that the reaction mixture does not add NaOH, and the reactor is placed 0,0101 g of the catalyst on the basis of LiCoO2modified carbon material.

Developed catalysts have a number of significant differences from those described in the liter is round:

- part of the source media, embodying the industrial design of complex lithium cobalt oxide LiCoO2administered titanium dioxide and/or at least one of the modifying additive of carbon material or oxides of metals of subgroups of aluminum, magnesium, silicon, titanium and vanadium, which provides an increase in the activity of the catalysts at ambient temperatures (-20°C to 60° (C), as well as increased time stable operation of the catalytic system;

- the absence or presence of metals of the platinum group in the amount of not more than 1 wt.%, without a significant reduction in the activity of the catalytic system. In addition, replacement parts are expensive LiCoO2on titanium dioxide or carbon material, oxides of metals of subgroups of aluminum, magnesium, silicon, titanium and vanadium reduces the cost of the catalytic system as a whole.

The use of chlorides and derivatives thereof as a cheaper compounds of platinum group metals as precursors of the active component of catalysts can also reduce the cost of the catalytic system as a whole.

Thus, the present invention may find application as a catalyst for generating hydrogen from water, aqueous alkaline solutions hydride compounds.

1. The catalyst for producing hydrogen from water or aqueous-alkaline solutions hydride compounds containing the platinum group metal deposited on a complex lithium cobalt oxide, characterized in that it further comprises modifying additive selected from a range of titanium dioxide, carbon material, an oxide of a metal of subgroups of aluminum, magnesium, titanium, silicon, and vanadium or mixtures thereof.

2. The catalyst according to claim 1, characterized in that the content of the modifying additive is not more than 40 wt.%.

3. The catalyst according to claim 1, characterized in that the content of the platinum group metal is not more than 1 wt.%.

4. The method of preparation of the catalyst for producing hydrogen from water or aqueous-alkaline solutions hydride compounds, including the stage of deposition of the platinum group metal in the carrier on the basis of complex lithium cobalt oxide, drying, calcining and recovery, characterized in that before applying the platinum group metal on a carrier in the composition of the lithium-cobalt oxide is administered titanium dioxide, and/or at least a carbon material, or one oxide of a metal of subgroups of aluminum, magnesium, titanium, silicon and vanadium by mechanical mixing.

5. The method according to claim 4, characterized in that as starting compounds of platinum group metals use neorganic the ski metal compounds, selected from a number of chlorinated compounds.

6. The method according to claim 4, characterized in that the process of recovery of the catalyst is carried out in the reaction medium hydride compounds.

7. The catalyst for producing hydrogen from water or aqueous-alkaline solutions hydride compounds representing complex lithium cobalt oxide, characterized in that it further comprises modifying additive selected from a range of titanium dioxide, carbon material, an oxide of a metal of subgroups of aluminum, magnesium, titanium, silicon, and vanadium or mixtures thereof.

8. The catalyst according to claim 7, characterized in that the content of the modifying additive is not more than 40 wt.%.

9. The method of preparation of the catalyst based on a complex lithium cobalt oxide for hydrogen production from aqueous or aqueous-alkaline solutions hydride compounds, characterized in that the composition of the lithium-cobalt oxide is administered titanium dioxide, and/or at least a carbon material, or one oxide of a metal of subgroups of aluminum, magnesium, titanium, silicon and vanadium by mechanical mixing.

10. The method according to claim 9, characterized in that the process of recovery of the catalyst is carried out in the reaction medium hydride compounds.

11. The method of producing hydrogen from water or aqueous-alkaline solutions hydride compounds in the presence of the catalyst is as complex lithium cobalt oxide, characterized in that the catalyst used, the catalyst according to claims 1 to 3 or claims 7 and 8.

12. The method according to claim 11, wherein the process is conducted both in continuous and periodic mode.

13. The method according to claim 11, wherein the process is carried out at a temperature of not more than 60°C.

14. The method according to claim 11, wherein the source of hydrogen can be used sodium borohydride, potassium borohydride, aminoborane.



 

Same patents:

FIELD: method and torch for producing synthesis gas at decomposition of liquid hydrocarbons such as oil and natural gas at elevated temperatures without usage of catalyst by CO and hydrogen.

SUBSTANCE: method is realized by partial oxidation of liquid and solid combustible materials at presence of oxygen and oxygen containing gases. Fuel, oxygen-containing gas and atomizing fluid are fed to torch separately. Atomizing fluid is expanded just in front of inlet opening for fuel by means of one or several nozzles providing speed of atomizing fluid in range 20 - 300 m/s. Relation of diameter of outlet opening of nozzle for liquid fuel to diameter of opening of nozzle for atomizing fluid is in range 1/1.1 - 1/5.

EFFECT: possibility for simplifying process.

2 dwg, 2 ex

FIELD: method for producing synthetic gas, which may be used in oil chemistry for producing motor fuels.

SUBSTANCE: method includes processing of biogas under temperature of 1420-1800°C and following cooling of resulting synthetic gas. Thermal processing of biogas is performed in liquid heat carrier with ratio of volume of liquid heat carrier to volume of barbotaged gas, equal to 10-100 during 0,3-2 seconds, or in boiling layer of solid particles, where the speed of biogas is selected to be greater than minimal speed of fluidization.

EFFECT: increased purity of produced synthetic gas.

8 cl, 6 ex

FIELD: alternative fuels.

SUBSTANCE: invention relates to catalysts and process of steam conversion of hydrocarbons to produce synthesis gas. Proposed catalyst for steam conversion of hydrocarbons contains nickel oxide (4.0-9.2%) and magnesium oxide (4.0-6.5%) supported by porous metallic nickel (balancing amount). Carrier has specific surface area 0.10-0.20 m2/g, total pore volume 0.07-0.12 cm3/g, predominant pore radius 1-30 μm, and porosity at least 40%. Described are also catalyst preparation method and generation of synthesis gas via steam conversion of hydrocarbons.

EFFECT: increased heat conductivity of catalyst resulting in stable activity in synthesis gas generation process.

8 cl, 1 tbl, 5 ex

FIELD: production of synthesis-gas.

SUBSTANCE: proposed method is carried out at temperature of 750-900 C due to external heating of tubular furnace reaction tubes filled with catalyst; mixture of natural gas and superheated steam is fed to reaction tubes. External heating of reaction tubes filled with catalyst is first performed by burning the natural gas in air; after attaining the required mode of operation, external heating is carried out by burning the synthesis-gas fed from tubular furnace outlet to reaction tube external heating chamber. Device proposed for realization of this method includes tubular furnace with reaction tubes filled with catalyst, chamber for mixing the natural gas with superheated steam and external heating chamber for heating the reaction tubes filled with catalyst for maintenance of conversion process; heating chamber is provided with air inlet. Device is also provided with gas change-over point whose one inlet is used for delivery of natural gas fed to chamber of external heating tubular furnace reaction tubes during starting the mode of steam conversion process; other inlet of gas change-over point is used for delivery of synthesis-gas from tubular furnace outlet through distributing synthesis-gas delivery point. Device is also provided with regulator for control of delivery of synthesis-gas to reaction tube external heating chamber required for combustion.

EFFECT: enhanced economical efficiency of process.

3 cl, 1 dwg

FIELD: steam catalytic conversion of natural gas into synthesis-gas with the use of thermal and kinetic energy of synthesis-gas.

SUBSTANCE: proposed method includes external heating of reaction tubes of tubular furnace filled with nickel catalyst on aluminum oxide substrate by passing mixture of natural gas and superheated steam through them. External heating of reaction tubes filled with catalyst is performed by burning the natural gas in air at exhaust of flue gases from heating zone. After tubular furnace, the synthesis-gas is directed to gas turbine for utilization of thermal and kinetic energy; gas turbine rotates electric generator; then, synthesis-gas is directed to synthesis-gas burner of electric power and heat supply system; flue gases from external heating zone are directed to heat exchangers for preheating the natural gas and steam before supplying them to reaction tubes of tubular furnace. Device proposed for realization of this method includes sulfur cleaning unit, tubular furnace with reaction tubes filled with nickel catalyst on aluminum oxide substrate with inlet for gas mixture of natural gas and superheated steam; device also includes external heating zone for reaction tubes with flue gas outlet and gas burner for external heating of reaction tubes of tubular furnace with inlet for natural gas and air. For utilization of thermal and kinetic energy of synthesis-gas, device is provided with gas turbine and electric generator at tubular furnace outlet and synthesis-gas burner of electric power and heat supply system; device is also provided with heat exchangers for preheating the natural gas and steam before supplying them to tubular furnace.

EFFECT: improved ecological parameters; enhanced power efficiency of process.

3 cl, 1 dwg

FIELD: processing of hydrocarbon raw materials; oxidizing conversion of hydrocarbon gases into synthesis-gas.

SUBSTANCE: proposed method is carried out in flow-through two-chamber reactor in turbulent mode at combustion of mixture of hydrocarbon raw material and oxidizer. Superheated water steam is additionally introduced into said mixture in the amount of 5-20 mass-% relative to mass of carbon fed in form of hydrocarbon raw material. Three-component mixture is ignited in combustion chamber by jet of hot gas fed from external source where pressure exceeds pressure in first chamber during ignition. Combustion products from first chamber of reactor are directed to second chamber via nozzle at critical difference in pressure and combustion process is continued till content of oxygen in combustion products does not exceed 0.3 vol-%. Process is carried out in combustion reactor which is made in form of two coaxial cylindrical chambers with cooled nozzle located in between them; section of this nozzle ensures required pressure differential between chambers. Injector unit mounted at inlet of first chamber is used for delivery of working mixture components. Turbulator is mounted in first chamber. Lateral surface of first chamber has one or several holes for introducing the jet of hot gas from external source whose pressure exceeds pressure of first chamber and volume of second chamber exceeds that of first chamber. Proposed method makes it possible to produce synthesis-gas at H2/CO ratio approximately equal to 2.0; residual content of oxygen does not exceed 0.3 vol-% and content of carbon black does not exceed trace amount.

EFFECT: enhanced efficiency.

9 cl, 2 dwg, 11 ex

FIELD: carbon monoxide conversion catalysts.

SUBSTANCE: invention relates to a method of preparing catalysts for middle-temperature conversion of carbon monoxide, which can be used in industry when producing nitrogen-hydrogen mix for ammonia synthesis. Preparation of catalyst for middle-temperature conversion of carbon monoxide with water steam, comprising precipitation of iron hydroxide from iron nitrate solution with ammonia-containing solvent, washing of iron hydroxide with water to remove nitrate ions, mixing with calcium and copper ions, mechanical activation of components, molding, drying, and calcination of granules, is characterized by that, in the component mixing step, lanthanum oxide is supplementary added, in which case molar ratio of components is as follows: Fe2O3/CaO/CuO/La2O3 = 1:(0.8-0.9):(0.045-0.08):(0.005-0.01).

EFFECT: increased catalytic activity and more than thrice reduced content of by-products in condensate.

1 tbl, 3 ex

FIELD: alternative fuels.

SUBSTANCE: invention relates to autothermal conversion of hydrocarbon fuel to produce synthesis gas, which can be used in chemical production, for burning at catalytic heat plants, and in hydrogen power engineering. Proposed catalyst contains, as active components, cobalt oxide, manganese oxide, and barium oxide, and, as carrier, refractory reinforced metalporous carrier. Catalyst is prepared by impregnation of carrier with barium and manganese salt solution at Ba/Mn =5:4 followed by drying, calcination, impregnation with cobalt salt solution, drying, and calcination. Invention further describes generation of synthesis gas via autothermal conversion of hydrocarbon fuel performed utilizing above-described catalyst.

EFFECT: enabled catalyst exhibiting high heat conductivity, high activity in production of synthesis gas, and resistance to coking and deactivation with sulfur compounds present in diesel fuel and gasoline.

6 cl, 1 tbl, 3 ex

FIELD: gas treatment.

SUBSTANCE: invention relates to processes of removing carbon monoxide from gas mixtures containing, except hydrogen, carbon dioxide. This process is an important step for production of pure hydrogen or hydrogen-containing gas, e.g. in ammonia synthesis. Catalyst for removing carbon monoxide from hydrogen-containing gas represents permeable composite material containing combination of phases of catalytically active group VIII metal or their alloy, oxide-type carrier, and metallic copper or copper metal containing alloy, composite-forming grain size being less than 0.5 mm and permeability of composite exceeding 10-14 m2. Catalyst preparation procedure as well as processes of removing carbon monoxide from hydrogen-containing gas using it are also described.

EFFECT: increased activity and selectivity of catalyst.

20 cl, 3 dwg, 8 ex

FIELD: electronic industry; petrochemical industry; other industries; plasma converters of the gaseous and liquid hydrocarbon raw and the fuels into the synthesis gas on the basis of microwave discharge.

SUBSTANCE: the invention is pertaining to the microwave plasma converters of the hydrocarbon raw and the fuels into the synthesis gas of the low-power, for usage, for example, in the capacity of the source of the hydrogen and the synthesis gas in the developments of the mobile and self-contained power plants on the basis of fuel cells. The invention allows to simplify and to make cheaper production of the plasma converter. The plasma converter for transformation of the gaseous and liquid hydrocarbon raw and the fuels into the synthesis gas on the basis of the microwave discharge includes the plasmatron of the microwave spark plug consisting of the magnetron and the cylindrical coaxial bundle of the transportation line of the microwave emission of the magnetron to the discharge zone, formed beyond the butt the of the inner conductor of the coaxial transportation line, and the reactor of mixing connected to the discharge zone of the plasmatron by means of the hole of communication made in butt of the outer conductor, in which wall there are the holes for feeding of the plasma-forming gas. The magnetron has the antenna output terminal of the microwave emission made in the form of the cylindrical ceramic component having the metallic end cap. The inner conductor of the coaxial transportation line is fixed on the indicated metallic end cap. The outer conductor is fixed on the magnetron. In the outer conductor opposite to the ceramic component of the antenna output terminal of the microwave emission there are at least two tangentially directed holes for feeding of the plasma-forming gas. The inner diameter of the outer conductor D is equal to (2.3÷2.6)d, where d - is the diameter of the inner conductor. At that the length of the inner conductor makes no less than λ/4where λ is the wavelength of the microwave emission of the magnetron.

EFFECT: the invention allows to simplify and to make cheaper production of the plasma converter.

6 cl, 2 dwg

FIELD: catalytic gas treatment.

SUBSTANCE: invention proposes catalyst for treating hydrogen-rich gas mixtures to remove carbon monoxide via methanation of carbon monoxide, said catalyst containing nickel-cerium oxide system. Catalyst is prepared by reaction of nickel compounds with cerium compound. Methanation of carbon monoxide is conducted at temperature not below 20°C and pressure not below 0.1 atm in presence of above-indicated catalyst.

EFFECT: enhanced removal of carbon monoxide to level below 10 ppm.

8 cl, 5 tbl, 9 ex

FIELD: gas treatment catalysts.

SUBSTANCE: invention relates to a method for preparing catalyst and to catalyst supported by block ceramic and metallic carrier having honeycomb structure for treating internal combustion engine exhaust gases. Preparation of catalyst comprises preliminary calcination of inert honeycomb block carrier followed by simultaneously depositing at 550-800°C, on its surface, intermediate coating of modified alumina and active phase consisting of one or several platinum group metals from water-alcohol suspension including aluminum hydroxide (boehmite, AlOOH), cerium nitrate, and one or several inorganic salts of platinum group metals. Coated material is then dried and subjected to heat treatment and reduction. According to invention, aforesaid suspension contains boehmite and cerium nitrate at 1:2 ratio and further contains reducing disaccharide so that suspension has following composition, wt %: AlOOH 18-20, Ce(NO3)3·6H2O 36-40, one or several platinum group metal salts (e.g., H2PtCl6, PdCl3, or RhCl3 calculated as metals) 1.5-1.8, reducing disaccharide 5-6, and water/alcohol (between 5:1 and 10:1) the rest. Thus obtained catalyst for treating internal combustion engine exhaust gases is characterized by: specific surface area of coating 80-100 m2/g, Al2O3 content 2.5-6.5%, CeO2 content 2.5-6.5%, active phase (calculated for platinum group metals) 0.2-0.4%, and block carrier to 100%.

EFFECT: simplified technology due to reduced number of technological stages and shortened process time, and enabled preparation of high-activity catalyst.

6 cl, 1 tbl, 8 ex

Ruthenium catalysts // 2322293

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to novel ruthenium catalysts, method for preparation thereof, and to employment thereof for catalytic hydrogenation of mono- and oligosaccharides in production of corresponding sugar alcohols. Ruthenium hydrogenation catalyst contains ruthenium supported by amorphous silica-based carrier, content of ruthenium being 0.2 to 7% of the weight of carrier, while carrier contains at least 90% silica and less than 10% of crystalline silicon dioxide phases. Catalyst is prepared by single or multiple treatment of carrier material with halogen-free solution of low-molecular weight ruthenium compound and subsequent drying of treated material at temperature not lower than 200°C immediately followed by reduction of dried material with hydrogen at 100 to 350°C. Herein disclosed is also a process for liquid-phase production of sugar alcohols (excepting sorbitol) via catalytic hydrogenation of corresponding mono- and oligosaccharides in presence of proposed catalysts.

EFFECT: increased activity and selectivity of catalysts.

16 cl, 4 tbl, 7 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention relates to the area of production of olefin hydrocarbons via catalytic dehydrogenation of corresponding C3-C5-paraffin hydrocarbons and can be applied in chemical and petrochemical industries. C3-C5-Paraffin hydrocarbon dehydrogenation catalyst is described containing chromium oxide, alkaline metal oxide, transition metals, and carrier, said carrier being nanostructured oxygen-containing aluminum compound of general formula: Al2O3-x(OH)x*nH2O, wherein x=0-0.28 and n=0.03-1.8, consisting of nanostructured primary particles 2-5 nm in size and characterized by disordered/imperfect layered structure similar to byerlyte structure. Method of preparing this catalyst as well as process of dehydrogenating C3-C5-paraffin hydrocarbons into olefins are also described, the latter being conducted in fluidized bed of described catalyst, which is recycled within the circuit: dehydrogenation reactor - regeneration reactor.

EFFECT: increased mechanical strength at high catalytic activity and stability.

20 cl, 1 dwg, 2 tbl, 10 ex

FIELD: alternative fuels.

SUBSTANCE: invention relates to catalysts and process of steam conversion of hydrocarbons to produce synthesis gas. Proposed catalyst for steam conversion of hydrocarbons contains nickel oxide (4.0-9.2%) and magnesium oxide (4.0-6.5%) supported by porous metallic nickel (balancing amount). Carrier has specific surface area 0.10-0.20 m2/g, total pore volume 0.07-0.12 cm3/g, predominant pore radius 1-30 μm, and porosity at least 40%. Described are also catalyst preparation method and generation of synthesis gas via steam conversion of hydrocarbons.

EFFECT: increased heat conductivity of catalyst resulting in stable activity in synthesis gas generation process.

8 cl, 1 tbl, 5 ex

FIELD: alternative fuels.

SUBSTANCE: invention relates to autothermal conversion of hydrocarbon fuel to produce synthesis gas, which can be used in chemical production, for burning at catalytic heat plants, and in hydrogen power engineering. Proposed catalyst contains, as active components, cobalt oxide, manganese oxide, and barium oxide, and, as carrier, refractory reinforced metalporous carrier. Catalyst is prepared by impregnation of carrier with barium and manganese salt solution at Ba/Mn =5:4 followed by drying, calcination, impregnation with cobalt salt solution, drying, and calcination. Invention further describes generation of synthesis gas via autothermal conversion of hydrocarbon fuel performed utilizing above-described catalyst.

EFFECT: enabled catalyst exhibiting high heat conductivity, high activity in production of synthesis gas, and resistance to coking and deactivation with sulfur compounds present in diesel fuel and gasoline.

6 cl, 1 tbl, 3 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides isodewaxing catalyst for petroleum fractions containing supported platinum and modifiers wherein supporting carrier is fine powdered high-purity alumina mixed with zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40 at following proportions of components, wt %: platinum 0.15-0.60, alumina 58.61-89.43, zeolite 5-40, tungsten oxide (modifier) 1-4, and indium oxide (modifier) 0.24-0.97. Preparation of catalyst comprises preparing carrier using method of competitive impregnation from common solution of platinum-hydrochloric, acetic, and hydrochloric acids followed by drying and calcinations, wherein carrier is prepared by gelation of fine powdered high-purity alumina with the aid of 3-15% nitric acid solution followed by consecutive addition of silicotungstenic acid solution and indium chloride solution, and then zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40.

EFFECT: increased yield of isoparaffin hydrocarbons.

7 cl, 2 tbl, 7 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to a method for preparing spherical supported metal catalysts with metal content from 10 to 70%, to spherical metal catalyst, to a process of hydrogenation of aromatic compounds wherein the latter are hydrogenised using spherical metal catalyst, and to a process of hydrogenation of aromatic compounds wherein the latter are hydrogenised using spherical supported metal catalyst.

EFFECT: increased activity and selectivity of catalyst having high porosity and uniform pore size distribution.

13 cl, 5 tbl, 12 ex

FIELD: reduction-oxidation catalysts.

SUBSTANCE: invention relates to mono- and bimetallic palladium and platinum catalysts if carbon carriers that can be used in processes involving oxygen and/or hydrogen. A method for preparing catalyst is described comprising pretreatment of carbon carrier in 3-15 M nitric acid at temperature not exceeding 80°C, impregnation of resulting carrier by nitric acid solutions of chloride-free compounds of palladium and/or platinum or palladium and at least one group I metal, drying at temperature up to 105°C, decomposition at 150-350°C, and reduction in hydrogen flow at 110-350°C. Specified preparation conditions allow one to obtain fine particles of platinum group metals 1-10 nm in size localized in pores 2-20 nm in size, concentrations of deposited palladium and/or platinum being 3 to 50 wt % or palladium and/or platinum and silver 0.1 to 1.4 wt %. Catalyst is suitable for use in processes of oxidation of alcohols into aldehydes and carboxylic acids; hydrogenation of olefin, acetylene, and diene bonds in aliphatic and carbocyclic compounds; hydrogenation of nitro compounds into amines or intermediate compounds; disproportionation of abietic and other resin acids contained in colophony and similar natural- or artificial-origin mixtures.

EFFECT: augmented assortment of redox catalysts and optimized methods of preparation thereof.

8 cl, 1 tbl, 34 ex

FIELD: chemical industry; non-ferrous metallurgy industry; other industries; methods of production of the catalyst for oxidization of the vanadium oxide particles in the gaseous phase with the definite size distribution.

SUBSTANCE: the invention is pertaining to the method of production of the catalyst for oxidization in the gaseous phase of the vanadium oxide particles with the definite size distribution. The invention describes the method of production of the catalyst for oxidization in the gaseous phase, at which on the fluidized inert carrier they deposit the suspension of TiO2 and V2O5 particles, in which, at least, 90 volumetric % of the particles of V2O5 have the diameter of 20 microns or less and, at least, 95 volumetric % of the particles of V2O5 have the diameter of 30 microns or less. The technical result of the invention is that the certain particle-size distribution allows to achieve the high efficiency of the coating.

EFFECT: the invention allows to achieve the high efficiency of the coating.

6 cl, 2 ex

FIELD: chemical engineering.

SUBSTANCE: invention relates to chemical process and catalytic reactors suitable for carrying out the process. In particular, Fischer-Tropsch synthesis is described involving compact block of catalytic reactor (10) forming passages wherein gas-permeable catalyst structure (16) is present, said passages extending between manifolds (18). Synthesis is performed in at least two steps since reactor block provides at least two consecutive passages (14, 14a) for Fischer-Tropsch synthesis process interconnected through manifold wherein gas flow velocity in the first passages is high enough to limit conversion of carbon monoxide to 65%. Gases are cooled in manifold between two steps so as to condense water steam and then passes through the second passage at flow velocity high enough to limit conversion of the rest of carbon monoxide to 65%.

EFFECT: reduced partial pressure of water steam and suppressed oxidation of catalyst.

17 cl, 3 dwg

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