Catalyst, method of preparation thereof, and synthesis gas generation method

FIELD: alternative fuel production and catalysts.

SUBSTANCE: invention relates to (i) generation of synthesis gas useful in large-scale chemical processes via catalytic conversion of hydrocarbons in presence of oxygen-containing components and to (ii) catalysts used in this process. Catalyst represents composite including mixed oxide, simple oxide, transition element and/or precious element, carrier composed of alumina-based ceramic matrix, and a material consisting of coarse particles or aggregates of particles dispersed throughout the matrix. Catalyst has system of parallel and/or crossing channels. Catalyst preparation method and synthesis gas generation method utilizing indicated catalyst are as well described.

EFFECT: enabled preparation of cellular-structure catalyst with high specific surface area, which is effective at small contact times in reaction of selective catalytic oxidation of hydrocarbons.

6 cl, 2 tbl, 16 ex

 

The invention relates to a process for production of synthesis gas by catalytic conversion of hydrocarbons in the presence of oxygen-containing gases and/or vapors of water and catalysts for this process.

Synthesis gas (mixture of hydrogen and carbon monoxide) are widely used in large-scale chemical processes such as the synthesis of ammonia, methanol, higher alcohols and aldehydes, in the Fischer-Tropsch process and other Synthesis gas used as a reducing gas in ferrous and nonferrous metallurgy, metal working, use environmental settings for neutralization of gas emissions. Promising and rapidly developing new areas of utilization of synthesis gas and derived from it are hydrogen vehicles and small energy. Automotive synthesis gas or hydrogen can be used as a Supplement to the main fuel in internal combustion engines or as fuel for an engine based on fuel cells. Energy synthesis gas and hydrogen can be used in combination with fuel cells or gas turbines for the production of environmentally friendly heat and power.

The traditional way to produce synthesis gas is an endothermic process steam reforming of natural gas Nickel catalysts [J.R.Rostrup-Nielsen, Production of synthesis gas, Catalysis Today, 1993, v.l8, 305-24; Usanational, Ovilo// Oxidative conversion of methane. Moscow, Nauka, 1998]. This process is characterized by extremely high capital costs, high operating costs and significant emissions of nitrogen oxides when the flare heating a tubular reformer.

An alternative way to produce synthesis gas - selective catalytic oxidation of hydrocarbons with oxygen (RMS) [S.C.Tsang, J.B.Claridge and M.L.H.Green, Recent advances in the conversion of methane to synthesis gas, Catalysis Today, 1995, V.23 supported, 3-15]. In contrast to steam reforming of natural gas RMS has greater selectivity, is an exothermic process and proceeds effectively at low contact times, thereby enabling it in autothermal mode and reduce the size of the reactor [D.A.Hickman, L.D.Schmidt, Synthesis gas formation by direct oxidation of methane in Catalytic Selective Oxidation", ACS Symposium series, 1993, p.416-426; P.M.Torniainen, X.Chu and L.D.Schmidt, Comparison of monolith-supported metals for the direct oxidation of methane to syngas, J.Catal., 1994, v.146, 1-10] and, thereby, reducing both energy consumption and capital investment.

The selectivity of the reaction RMSE for target products (carbon monoxide and hydrogen) depends on various factors, but the most important is the chemical composition of the active component. To obtain maximum yields of the target product is synthesis gas, the catalyst should contain the active ingredient, providing high activity and villages shall aktivnosti at low contact times in the reaction conversion and the standard deviation of hydrocarbons. In addition, for the implementation of this process requires catalysts with low hydraulic resistance, resistant to thermal shocks and superusuario.

The known method RMSE of methane to produce synthesis gas [US 5149464, 01 3/26, 1992] at a temperature of 650-900°C and flow rate 40000-80000 hour-1(0,05-0,09 sec) in the presence of a catalyst comprising a transition metal or its oxide, deposited on a thermally stable oxide of one of the elements (M): Mg, B, Al, Ln, Ga, Si, Ti, Zr, Hf, or perovskite-like mixed oxides of General formula MxM'yOz with pyrochlore structure, where M’ is a transition metal, including elements in 8 groups. The atomic ratio of the element 8 to the sum of the base elements in these compounds is 1:1 or 3:1, and the noble metal content is 32,9-48 wt.%. The conversion of methane in the presence of mixed oxides Pr2EN2O7, Eu2Ir2O7La2MgPtO6when flow rate 40000 h-1and 777°C is less than 94%, and the increase in flow rate up to 80000 hours-1reduce the conversion of methane to 73% and the selectivity for CO and hydrogen to 82 and 90%, respectively.

In the patent [EP 303438, 01 3/38, 15.02.1989] to obtain a mixture of hydrogen and carbon monoxide offer a way SKO hydrocarbons upon contact of the reaction mixture containing the hydrocarbon, oxygen or coloroda is containing a series of gas and, optionally, the water vapor with the catalyst in the zone selective catalytic oxidation. Area SKO block contains the catalyst with the ratio of geometric surface/volume is not less than 5 cm2/cm3. The catalyst may contain noble metals, Nickel, cobalt, chromium, cerium, lanthanum and the mixture is deposited on a heat-resistant oxide media, including cordierite, mullite, aluminum titanate, Zirconia spinel, alumina. At the same time, in the patent EP 303438 argue that the speed of reaction of partial oxidation is limited by the rate of mass transfer and does not depend on the chemical nature of the catalyst, which allows in this case to use materials does not exhibit catalytic activity, but providing the necessary ratio of geometric surface/volume. The process is carried out at temperatures in the range 760-1090°and volume rate of from 20000 to 500000 h-1.

In patents [EN 2115617, 01 3/38, 20.07.98; 2136581, 01 3/38, 10.09.99; 2137702, 01 3/38, 20.09.99; 2123471, 01 3/38, 20.12.98; US 5486313, C 07 C 1/02, 23.01.1996 and US 5639401, C 07 C 1/02, 17.06.97] offer a way SKO hydrocarbons, including serosoderjaschei (0.05-100 ppm) [EN 2132299, 01 3/38, 27.06.99; US 5720901, C 07 C 1/02, 24.04.98], in the synthesis gas using catalysts containing precious metals (up to 10 wt.% Pt, Pd, Rh, Os), deposited on a heat-resistant carrier. As carriers are used, e.g. the measures α-Al2About3exhalent barium (grain size ~1 mm) or Zr2, thermally stabilized oxides of elements of groups III-V or II a of the Periodic table (porous blocks in the form of foam ceramics, resistant to thermal shocks). The process is carried out in a reactor with a fixed bed of catalyst having greater tortuosity is the ratio of the path length of the gas passing through the unit to its length is in the range 1.1-10 at temperatures 950-1300°and flow rate of the gas mixture 2 to 104-108l/kg-HR. The disadvantages of this method are the large hydraulic resistance of the catalyst layer with high tortuosity and high cost of the catalysts due to the high content of noble metals and used as media of expensive foam ceramics based on zirconium, limiting their practical application.

Thus, the literature describes catalysts based on a block of ceramic substrates with different composition of the active component for the process of selective oxidation of hydrocarbons into synthesis gas at low contact times. Basically, it's the media, representing Panoramico, however, such blocks at low contact times of the reaction mixture have a large hydraulic resistance due to high sinuosity channels. By increasing the size of the macropores with the purpose of reducing the hydraulic resistance decreases the mechanical strength and the efficiency of such catalysts by reducing the geometric surface.

It is known that the use of blocks with direct channels (cell blocks) allows to reduce the hydraulic resistance. In the patent [US 5648582, C 07 C 004/02, 30.11.1995] for the process SKO hydrocarbons at space velocities of 800000-12000000 h-1use Pt, Rh or Ni deposited on non-porous ceramic blocks (cordierite) with straight channels. However, these catalysts contain up to 10 wt.% noble metals are very expensive, in addition observed ablation of metals because of the high temperatures developing in the block layer of the catalyst. Note that the use of native honeycomb structure of cordierite for high temperature processes is limited by their thermal stability (up to 1000°).

The usual lack of catalysts based on non-porous cellular carriers is their low specific surface area [GB 1375830, B 01 J 11/06, 1973; EP 0197681, B 01 J 37/00,18.03.1986], which does not provide them with sufficient activity.

To increase the geometric surface of the catalyst to reduce the thickness of the walls of the cell blocks and increase the number of channels per unit of cross-section of the block. To increase the total surface of the cell carriers in addition put a porous substrate with a high surface area of the oxides of aluminum, silicon, rare earth elements. The latter technique requires special preparation of the materials from which zagotavlivaetsya substrate, the introduction of additional stages in the process of manufacture of catalysts [US 3824196, B 01 J 11/06, 16.07.1974]. In addition, due to differences in coefficients of thermal expansion may exfoliation of the porous layer during thermal shock, which is typical for any exothermic catalytic processes. Catalysts prepared on the basis of these media have a scarce resource, less resistant to catalytic poisons.

A fundamentally different approach is focused on the manufacture of the monolithic honeycomb catalyst having a high specific surface area. In applications [WO 0134517, 01 3/40, 17.05.2001; WO 0160740, 23.08.2001; WO 0160515, B 01 J 37/00, 23.08.2001; WO 0160742, 01 3/40, 23.08.2001] the synthesis gas is produced upon contact of the reaction mixture containing the hydrocarbon, C1-C5and oxygen-containing gas with a catalyst, mainly in the form of blocks of foam ceramics based on oxides of transition metals (CR, Co, Ni, Mn), alkaline earth and rare earth elements with a specific surface area 5-250 m2. The proposed catalysts are not destroyed at a temperature of ~1120-1160°With, however, have a high ignition temperature of the reaction. In addition, the blocks in the form of foam ceramics, as mentioned above, have a large hydraulic resistance.

Thus, the catalysts of honeycomb structure for a process of selective oxidation of uglevodorodov synthesis gas at low contact times must meet stringent requirements, applicable to such catalysts, namely to have a high thermal stability and high specific surface area to ensure high conversion of hydrocarbons and selectivity to synthesis gas and not deactivated due to the formation of carbon on the surface. A particularly important property is the stability of the catalysts to thermal shocks.

Closest to the claimed technical essence and the achieved effect is a block cell catalyst to produce synthesis gas by selective catalytic oxidation of hydrocarbons on the basis of mixed oxides with perovskite structure M1B1-yMyOzand/or fluorite M

1
x
M
2
1-x
Ozwhere M - 8 group (Pt, Rh, Ir), M1a rare - earth element (La, Ce, Nd) or alkaline earth (CA, Sr), M2element IV b group (Zr, Hf), In - transition elements (Ni, Co), which is a complex composite containing components with a low coefficient of thermal expansion [U.S. Pat. RF 2204434, 01 31/18, 20.05.2003]. At temperatures of 600-800°and With contact times of 0.1-0.4 seconds to achieve high conversion of ETANA and selectivity to synthesis gas. However, the catalyst is a ceramic composite honeycomb structure, which is prepared by extrusion, resulting in mechanical stresses and to reduce thermal and mechanical stability of the catalyst.

The invention solves the problem of creating a thermostable catalyst honeycomb structure with high surface area to produce synthesis gas, effective at low contact times in the reaction of selective catalytic oxidation of hydrocarbons, oxygen-containing component, and process for production of synthesis gas using the catalyst. The high thermal stability of the catalyst ensures its effective operation in the reaction of selective oxidation of hydrocarbons at high temperatures.

The problem is solved by use of a block of the catalyst honeycomb structure, which is a complex composite containing mixed oxide, a simple oxide, a transition element and/or a noble element, as well as media, including ceramic matrix material consisting of coarse particles or aggregates of particles dispersed throughout the matrix, and the catalyst has a system of parallel and/or intersecting channels

The catalyst contains in its composition, wt.%:

mixed oxide is not less than 1.0,

a simple oxide, for example Al2About , ZrO2- not more than 10.0,

the transition element and/or a noble element is not more than 10.0,

media - the rest.

Mixed oxide is an oxide with a perovskite structure M1B1-yMy

Ozand/or oxides with the fluorite structure M

1
x
M
2
1-x
Ozwhere

M - 8 group, such as Pt, Rh, Ir, Ru

M1a rare - earth element such as La, Ce, Nd, or alkaline earth element such as CA, Sr,

M2element IV b group of the Periodic system, such as Zr, Hf,

In - transition element - 3d elements of the 4th period, such as Ni, Co,

of 0.01<x<1, 0≤y<1, z is determined by the oxidation state of the cations and their stoichiometric ratio.

The catalyst may contain a transition element, such as Ni, Co, and/or noble element - metal 8 groups, such as Pt, Rh, Ir, Ru.

The carrier is a ceramic matrix based on aluminum oxide and dispersed throughout the matrix material, wherein the composition and structure of the matrix material and selected from the oxides of transition and/or rare earth metals, or mixtures thereof, and/or metals and/Ilia alloys, and/or carbides of metals of the 4th period of the Periodic table, or mixtures thereof, in the form of particles or aggregates of particles with size from 1 to 250 μm, when the content of the dispersed material in the matrix of 0.5-7 wt.%.

The catalyst has a system of parallel and/or intersecting channels and may have a hole in the middle that is different from the channel size and shape.

The term "rare earth element" refers to elements belonging to the group of rare earth elements, including elements of group III b of the Periodic system and 4f elements such as La, CE, Nd. The term alkaline earth element implies the elements of group II a of the Periodic system, such as Sr, CA.

Introduction to the catalyst composite block media system of parallel and/or intersecting channels, comprising a ceramic matrix and dispersed throughout the matrix material, representing oxides, or metals, or alloys of metals and consisting of coarse particles or aggregates of particles, allows to obtain thermostable catalyst, resistant to thermal shocks. And the introduction of metals or their alloys contributes to heat the catalyst, and thereby increases the efficiency of the flow in the catalyst bed of the reaction of steam and carbon dioxide reforming of hydrocarbons and increases the selectivity for the target PR is the product of - synthesis gas.

The task is also solved by a method of preparation of the catalyst for production of synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing component on the basis of mixed oxides, a simple oxide of the transition element and/or a noble element, which is prepared by impregnation of the active components of media, including ceramic matrix material consisting of coarse particles or aggregates of particles dispersed throughout the matrix, and the catalyst has a system of parallel and/or intersecting channels.

The method of preparation of the catalyst honeycomb structure according to the invention includes:

1) use as a material for ceramic matrix of aluminum powder or powders on the basis of the oxides or hydroxides of aluminum with the addition of aluminum powder;

2) use as an additional material powder particles of large size 1-250 μm, which perform a reinforcing function, and application of metals and carbides improve thermal properties of the media;

3) obtaining a homogeneous mass by mixing and impregnation of this homogeneous mass of fibrous or textile materials, fade with the heat treatment in the air;

4) loading g is megenney mass vigorelli materials in the mold, permeable to gaseous substances;

5) processing a homogeneous mass under hydrothermal conditions;

6) calcining the obtained carrier in air at 1000-1200°

7) impregnation of the received carrier corresponding solutions of salts, drying and calcination of the catalyst at 900°C.

The task is also solved by a method for production of synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing component in the presence of the inventive catalyst. The use of a composite comprising a carrier of this type, provides a high specific surface of the catalyst while maintaining high thermal stability and high hydrocarbon conversion and selectivity to synthesis gas.

The process is carried out by sequential transmission of a gas mixture containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing component with a temperature of between 20 and 500°through the fixed bed of the catalyst system of parallel and/or intersecting channels that contribute to the increased thermal stability of the catalyst and its high efficiency in the process for production of synthesis gas.

To obtain the required composition of the mixture of hydrogen and carbon monoxide vary the composition of the initial mixture. The initial mixture contains a hydrocarbon or mixture of hydrocarbons is in and/or air, or CO2or steam, or a mixture thereof, the process is carried out at a temperature of 500-1100°C. as hydrocarbons are used, for example, natural gas, methane, propane-butane mixture, gasoline, kerosene, etc. as the oxygen-containing gas, such as oxygen, air, carbon dioxide, water.

Process for production of synthesis gas is carried out in a flow reactor in autothermal mode at a temperature of 550-1100°With the variations of time of contact and the composition of the reaction mixture. The reaction mixture containing natural gas or vapors of liquid hydrocarbons, such as octane gasoline and, in some examples, the water vapor in the air, before entering the reactor is heated. At the inlet and outlet of the reactor to prevent heat loss put the blocks of corundum. During start-up and operation of the catalyst to control the gas temperature at the inlet of the reactor, the temperature of the catalytic unit at the inlet, the outlet temperature of the unit. The reaction products analyzed chromatographically. The efficiency of the catalyst is characterized by the starting temperature of the reaction, the degree of conversion of methane and the amount of produced synthesis gas (mixture of hydrogen and carbon monoxide), expressed in volume% and characterizing the selectivity to synthesis gas. The composition of the initial reaction mixture and the reaction products analyzed chromatographies is.

The invention is illustrated by the following examples.

Example 1. The aluminum powder is mixed with dispergirovannom material is a mixed oxide LaNiO2.5with perovskite structure with an average size of aggregates of particles of about 15 μm, but with a wide range of size distribution from 1 to 25 μm. The resulting powder was mixed with a solution of glycerine in water. The obtained suspension moisten a cotton cloth in the form of a tape, on top of which is placed cotton yarn thickness 1 mm parallel to each other and perpendicular to the length of the tape. Then the tape rolled into a cylindrical body, which lay in the molding device and placed in the autoclave. Autoclave molding device steamed, resulting in part of aluminum powder is oxidized, and the powder is grasped in the monolith. After autoclaving the moulder is dried and calcined to a temperature of at least 1000°C, resulting in the remaining part of the aluminum cookislands, and organic materials burn with the formation of channels. The resulting unit cell structure has a specific surface of 5 m2/, the Number of parallel channels per unit geometric surface of the end plane is 56 cm-2. The content of the dispersed material is 22 wt.%. The resulting carrier p is oputyvayut mixed solution of salts of cerium and zirconium. The unit is blown with air to remove excess solution from the channels, dried and calcined at 900°C. the Obtained sample is impregnated with a solution of H2PtCl6, dried and calcined at 900°C. the catalyst containing 4.8 wt.% mixed oxide of cerium and zirconium with the fluorite structure, 1 wt.% Pt. The catalyst was tested in a flow reactor with the reaction mixture containing ~25% natural gas in air in the reaction of selective oxidation of natural gas into synthesis gas. Activity is given in table 1.

Example 2. The media is prepared as in example 1 except that as the dispersed material used powder CEO2with the average size of aggregates of particles of 7 μm. The resulting carrier of honeycomb structure has a specific surface area of 10 m2/, the Number of channels per unit geometric surface of the end plane is 40 cm-2. The content of the dispersed material is 26 wt.%. The resulting carrier is impregnated with a joint solution of H2PtCl6, nitrates of lanthanum and Nickel atomic ratio of cations La:Ni:Pt=1:0,994:0,006, dried and calcined at 900°C. the sample was Then impregnated with a mixed solution of lanthanum nitrate and ruthenium chloride. The resulting catalyst contains 8.4 wt.% perovskite LaNi0,994Pt0,006and 0.7 wt.% mixed oxide Lanta is a and ruthenium. The catalyst was tested in a flow reactor with the reaction mixture containing ~25% natural gas in air in the reaction of selective oxidation of natural gas into synthesis gas. Activity is given in table 1.

Example 3. The media is prepared as in example 1 except that as the dispersed material used powdered Nickel (fraction of 100-250 μm)and aluminum powder added powdered aluminum hydroxide. The resulting carrier of honeycomb structure has a specific surface area of 3 m2/, the Number of channels per unit geometric surface of the end plane is 40 cm-2. The content of the dispersed material is 0.5 wt.%. The catalyst is prepared by impregnation of a received carrier as in example 1. The catalyst containing 7.4 wt.% mixed oxide of cerium and zirconium with the fluorite structure, 0.5 wt.% Pt.

Example 4. The media is prepared as in example 3 except that as the dispersed material used powdered alloy Fe-Cr-Al, having the average particle size of 5 μm. The number of concurrent channels per unit geometric surface of the end plane is 35 cm-2. The content of the dispersed material is 70 wt.%. The catalyst is prepared by impregnation of a received carrier as in example 1, except that what about that instead of a solution platinumcollection acids share a solution of H2PtCl6, nitrates of lanthanum and Nickel atomic ratio of cations La:Ni:Pt=1:0,994:0,006. The catalyst containing 7.5 wt.% mixed oxide of cerium and zirconium with the fluorite structure, 5.4 wt.% perovskite LNi0,994PT0,006.

Example 5. The media is prepared as in example 1 except that as the dispersed material used powder of solid solution on the basis of oxides of La, CE, Zr having an average size of aggregates of particles of 8 μm, and a powder alloy Ni-Cr, having an average particle size of 60 μm. The resulting carrier of honeycomb structure has a specific surface area of 12 m2/, the Number of channels per unit geometric surface of the end plane is 230 cm-2. The content of the dispersed material is 26 wt.%. solid solution on the basis of oxides of La, CE, Zr and 9 wt.% alloy Ni-Cr. The catalyst is prepared by impregnation of a received carrier, as in example 2, and optionally impregnated with a solution of rhodium chloride. The catalyst containing 8.2 wt.% perovskite LaNi0,994Pt0,006and 0.84 wt.% mixed oxide of lanthanum and ruthenium, 0.2 wt.% Rh. The catalyst was tested in a flow reactor with the reaction mixture containing ~25% natural gas in air in the reaction of selective OK the comprehension of natural gas into synthesis gas. Activity is given in table 1.

Example 6. The media is prepared as in example 3 except that as the dispersed material used TiC powder having an average particle size of 3 μm. The resulting carrier of honeycomb structure has a specific surface area of 2 m2/, the Number of channels per unit geometric surface of the end plane is 40 cm-2. The content of the dispersed material is 20 wt.%. The catalyst is prepared by impregnation of a received carrier, as in example 2, except that impregnation using a mixed solution of the nitrates of lanthanum and Nickel sootnosheniem La:Ni=1:1. The resulting catalyst contains 6 wt.% perovskite LaNiO3.

Example 7. The media is prepared as in example 5 except that as the dispersed material used TiC powder analogously to Example 6 and the powder CEO2analogously to example 2. The resulting carrier of honeycomb structure has a specific surface area of 9 m2/, the Number of channels per unit geometric surface of the end plane is 40 cm-2. The content of the dispersed material is 12 wt.% TiC and 8 wt.% SEO2. The catalyst is prepared by impregnation of a received carrier, as in example 2, except that impregnation using a solution of rhodium chloride. The catalyst sod is RIT 0.4 wt.% Rh.

Example 8. The media is prepared as in example 7, except that the dispersed material is also used powdered alloy NiCr having an average particle size of 60 μm. The resulting carrier of honeycomb structure has a specific surface area of 4 m2/, the Number of channels per unit geometric surface of the end plane is 230 cm-2. The content of the dispersed material is 12 wt.% TiC; 8 wt.% SEO2; 6 wt.% NiCr. The catalyst is prepared by impregnation of a received carrier, as in example 2, except that impregnation using a solution of Nickel nitrate. The catalyst containing 2.7 wt.% Ni.

Example 9. The media is prepared as in example 7 except that as the dispersed material instead of TiC use powdered alloy NiCr having an average particle size of 60 μm. The resulting carrier of honeycomb structure has a specific surface area of 4 m2/, the Number of channels per unit geometric surface of the end plane is 230 cm-2. The content of the dispersed material is 15 wt.% CeO2; 25 wt.% NiCr. The catalyst is prepared by impregnation of a received carrier, as in example 2. The resulting catalyst contains about 7.8 wt.% perovskite LaNi0,994Pt0,006and 0.9 wt.% mixed oxide of lanthanum and ruthenium. The catalyst tested who live in a flow reactor with the reaction mixture, containing ~25% natural gas in air in the reaction of selective oxidation of natural gas into synthesis gas. Activity is given in table 1.

Example 10. The catalyst, prepared as in 9 experience in the reaction of oxidative conversion of octane. The parameters of the reaction and the catalyst are shown in table 2.

Example 11. The catalyst, prepared as in 9 experience in the reaction air conversion octane. The parameters of the reaction and the catalyst are shown in table 2.

Example 12. The media is prepared analogously to example 1. Characterized in that, as the dispersed material used powder CEO2and the oxide powder LaNiO2.5. Received the product cell structure has a specific surface area of 7 m2/, the Number of parallel channels per unit geometric surface of the end plane is 40 cm-2. The content of the dispersed material is 12 wt.% LaNiO3+xand 10 wt.% SEO2. Further, the catalyst prepared according to example 2.

Example 13. The media is prepared analogously to example 3. Characterized in that, as the dispersed material used powder CEO2and powdered Nickel. Received the product cell structure has a specific surface area of 4 m2/, the Number of channels per unit geometric surface of the end plane is 40 cm -2. The distance between the intersecting channels is 5 mm, the content of the dispersed material is 1.0 wt.% Ni and 12 wt.% SEO2. Further, the catalyst prepared according to example 1.

Example 14. The media is prepared analogously to example 1. Characterized in that, as the dispersed material is used, the Ni powder and the powder of TiC. Received the product cell structure has a specific surface area of 6 m2/, the Number of channels per unit geometric surface of the end plane is 56 cm-2. The distance between the intersecting channels is 0.5 mm, the content of the dispersed material is 5 wt.% TiC and 1 wt.% Ni. Further, the catalyst prepared according to example 1.

Example 15. The media is prepared analogously to example 1. Characterized in that, as the dispersed material used powders SEO2, FeCrAl, the Ni powder and the powder of TiC. Received the product cell structure has a specific surface area of 13 m2/, the Number of channels per unit geometric surface of the end plane is 56 cm-2. The distance between the intersecting channels is 0.5 mm, the content of the dispersed material is 5 wt.% TiC, 1 wt.% Ni, 5 wt.% SEO2, 2 wt.% FeCrAl. Further, the catalyst prepared according to example 2.

Example 16. The catalyst is prepared analogously to example 1 except that novtel is impregnated with a solution of salt of zirconium. The catalyst containing 7.4 wt.% zirconium oxide and 0.5 wt.% Pt.

1. Catalyst for production of synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing component, which is a complex composite containing mixed oxide in an amount of not less than 1.0, a simple oxide is not more than 10.0, the transition element and/or a noble element is not more than 10.0, characterized in that the complex composite contains media, including ceramic matrix based on aluminum oxide and dispersed throughout the matrix material is selected from oxides of transition and/or rare earth metals, or mixtures thereof, and/or metals and/or alloys thereof, and/or carbides of metals of the 4th period of the Periodic table, or mixtures thereof, in the form of particles or aggregates of particles with size from 1 to 250 μm at a content of dispersed material in the matrix of 0.5-70,0 wt.%, the catalyst has a system of parallel and/or intersecting channels.

2. The catalyst according to claim 1, characterized in that the mixed oxide is an oxide with a perovskite structure M1B1-yMyOzand/or oxides with the fluorite structure

M

1
x
M
2
1-x
Ozwhere

M - 8 group, for example, Pt, Rh, Ir, Ru;

M1a rare - earth element such as La, Ce, Nd or alkaline earth element, such as CA, Sr;

M2element IV b group of the Periodic system, for example, Zr, Hf;

In - transition element - 3d elements of the 4th period, for example, Ni, Co;

of 0.01<x<1, 0≤y<1, z is determined by the oxidation state of the cations and their stoichiometric ratio.

3. The catalyst according to claim 1, characterized in that it contains a transition element, such as Ni, Co and/or noble element - metal 8 groups, for example, Pt, Rh, Ir, Ru.

4. The catalyst according to claim 1, characterized in that it can have a hole in the middle that is different from the channel size and shape.

5. The preparation method of catalyst for production of synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing component, which is a complex composite containing mixed oxide in an amount of not less than 1.0, a simple oxide is not more than 10.0, the transition element and/or a noble element is not more than 10.0, characterized in that it is prepared by impregnation of a corresponding salt solutions of media, including slabs, the second matrix based on aluminum oxide and dispersed throughout the matrix material, selected from the oxides of transition and/or rare earth metals, or mixtures thereof, and/or metals and/or alloys thereof, and/or carbides of metals of the 4th period of the Periodic table, or mixtures thereof, in the form of particles or aggregates of particles with size from 1 to 250 μm at a content of dispersed material in the matrix of 0.5-70,0 wt.%, the media has a system of parallel and/or intersecting channels, you get a catalyst according to any one of claims 1 to 4.

6. A method for production of synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing component, by using a catalyst which is a complex composite containing mixed oxide in an amount of not less than 1.0, a simple oxide is not more than 10.0, the transition element and/or a noble element is not more than 10.0, wherein the process is carried out in the presence of a catalyst according to any one of claims 1 to 5.



 

Same patents:

FIELD: power engineering.

SUBSTANCE: method includes searching for continental or oceanic rift generation zones, supported by abnormal mantle with output of substance branches to earth crust. Drilling of wells by turbodrills into mantle substance. After well enters mantle substance a reaction hollow is formed in it by putting together force and product wells or by expanding force and/or product wells. Water is pumped into force well and gas-like hydrogen is outputted to surface through product well forming during reaction of inter-metallic substances fro mantle substance to water. Water is fed in amount, adjusting output of hydrogen, while reaction surface of reaction hollow is periodically regenerated, for example, by high pressure water flow, supplied through jets in reaction hollow, on remotely controlled manipulators. Expansion of well may be performed via explosions of explosive substances charges, and it is possible to separate forming gaseous hydrogen and water steam by separator mounted therein.

EFFECT: higher effectiveness of hydrogen production.

9 cl

FIELD: hydrocarbon conversion catalysts.

SUBSTANCE: catalyst for generation of synthesis gas via catalytic conversion of hydrocarbons is a complex composite composed of ceramic matrix and, dispersed throughout the matrix, coarse particles of a material and their aggregates in amounts from 0.5 to 70% by weight. Catalyst comprises system of parallel and/or crossing channels. Dispersed material is selected from rare-earth and transition metal oxides, and mixtures thereof, metals and alloys thereof, period 4 metal carbides, and mixtures thereof, which differ from the matrix in what concerns both composition and structure. Preparation procedure comprises providing homogenous mass containing caking-able ceramic matrix material and material to be dispersed, appropriately shaping the mass, and heat treatment. Material to be dispersed are powders containing metallic aluminum. Homogenous mass is used for impregnation of fibrous and/or woven materials forming on caking system of parallel and/or perpendicularly crossing channels. Before heat treatment, shaped mass is preliminarily treated under hydrothermal conditions.

EFFECT: increased resistance of catalyst to thermal impacts with sufficiently high specific surface and activity retained.

4 cl, 1 tbl, 8 ex

The invention relates to power equipment and can be used to produce hydrogen as in fixed installations and transport

The invention relates to a method of catalytic conversion of methane and its homologues to produce hydrogen, which is widely used in the production of ammonia from natural gas

The invention relates to a method of storing and producing hydrogen in Autonomous power systems with electrochemical generators with a cycle of operation from several hours to several thousand hours
The invention relates to the field of gas and oil, and in particular to methods of decomposition and recycling of hydrogen sulfide, and can be used for the production of hydrogen and sulfur from hydrogen sulfide, and also for purification from hydrogen sulfide gas mixtures
The invention relates to the field of gas and oil, and in particular to methods of decomposition and recycling of hydrogen sulfide and/or mercaptans, and can be used for the production of hydrogen and sulfur from hydrogen sulfide, and also for purification from hydrogen sulfide and mercaptans gas mixtures
The invention relates to the field of gas and oil, and in particular to methods of decomposition and recycling of hydrogen sulfide and/or mercaptans, and can be used for the production of hydrogen and sulfur from hydrogen sulfide, and also for purification from hydrogen sulfide and mercaptans gas mixtures

FIELD: petrochemical process catalysts.

SUBSTANCE: catalyst constitutes cements formed during heat treatment and depicted by general formula MeO·nAl2O3, where Me is at least one group IIA element and n is number from 1.0 to 6.0, containing modifying component selected from at least one oxide of magnesium, strontium, copper, zinc, indium, chromium, manganese, and strengthening additive: boron and/or phosphorus oxide. The following proportions of components are used, wt %: MeO 10.0-40.0, modifying component 1.0-5.0, boron and/or phosphorus oxide 0.5-5.0, and alumina - the balance. Catalyst is prepared by dry mixing of one group IIA element compounds, aluminum compounds, and strengthening additive followed by mechanochemical treatment on vibromill, molding of catalyst paste, drying, and calcination at 600-1200°C. Modifying additive is incorporated into catalyst by impregnation and succeeding calcination. Method of pyrolysis of hydrocarbon feedstock producing C2-C4-olefins is also described.

EFFECT: increased yield of lower olefins.

3 cl, 2 tbl, 18 ex

FIELD: supported catalysts.

SUBSTANCE: invention claims a method for preparation of catalyst using precious or group VIII metal, which comprises treatment of carrier and impregnation thereof with salt of indicated metal performed at working pressure and temperature over a period of time equal to or longer than time corresponding most loss of catalyst metal. According to invention, treated carrier is first washed with steam condensate to entirely remove ions or particles of substances constituted reaction mixture, whereupon carrier is dried at 110-130oC to residual moisture no higher than 1%.

EFFECT: achieved additional chemical activation of catalyst, reduced loss of precious metal from surface of carrier, and considerably increased lifetime.

5 cl, 9 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides reforming catalyst containing Pt and Re on oxide carrier, in particular Al2O3, wherein content of Na, Fe, and Ti oxides are limited to 5 (Na2O), 20 (Fe2O3), and 2000 ppm (TiO2) and Pt is present in catalyst in reduced metallic state and in the form of platinum chloride at Pt/PtCl2 molar ratio between 9:1 and 1:1. Contents of components, wt %: Pt 0.13-0.29, PtCl2 0.18-0.04, Re 0.26-0.56, and Al2O3 99.43-99.11. Preparation of catalyst comprises impregnation of alumina with common solution containing H2PtCl6, NH4ReO4, AcOH, and HCl followed by drying and calcination involving simultaneous reduction of 50-90% platinum within the temperature range 150-550оС, while temperature was raised from 160 to 280оС during 30-60 min, these calcination conditions resulting in creation of reductive atmosphere owing to fast decomposition of ammonium acetate formed during preparation of indicated common solution.

EFFECT: increased catalytic activity.

2 cl, 1 tbl, 3 ex

FIELD: hydrocarbon conversion catalysts.

SUBSTANCE: catalyst for generation of synthesis gas via catalytic conversion of hydrocarbons is a complex composite composed of ceramic matrix and, dispersed throughout the matrix, coarse particles of a material and their aggregates in amounts from 0.5 to 70% by weight. Catalyst comprises system of parallel and/or crossing channels. Dispersed material is selected from rare-earth and transition metal oxides, and mixtures thereof, metals and alloys thereof, period 4 metal carbides, and mixtures thereof, which differ from the matrix in what concerns both composition and structure. Preparation procedure comprises providing homogenous mass containing caking-able ceramic matrix material and material to be dispersed, appropriately shaping the mass, and heat treatment. Material to be dispersed are powders containing metallic aluminum. Homogenous mass is used for impregnation of fibrous and/or woven materials forming on caking system of parallel and/or perpendicularly crossing channels. Before heat treatment, shaped mass is preliminarily treated under hydrothermal conditions.

EFFECT: increased resistance of catalyst to thermal impacts with sufficiently high specific surface and activity retained.

4 cl, 1 tbl, 8 ex

The invention relates to the field of technical chemistry, namely, carriers for catalysts that can be used in various heterogeneous catalytic processes in the chemical industry

The invention relates to a method for preparing a multi-component catalyst for the oxidation of propylene to acrolein

The invention relates to the field of preparation of supported catalysts and can find application in various sectors of the chemical industry

FIELD: polymerization catalysts.

SUBSTANCE: catalyst is prepared by mixing hydrocarbon solutions of titanium tetrachloride, triisobutylaluminum-diphenyl oxide complex, and 1,3-pentadiene at Al/Ti molar ratio from 0.9:1 to 1.2:1 and at temperature form -70 to +20°C, after which mixture of paraffin, aromatic, and naphthene hydrocarbons is added, in particular industrial or transformer oil in amount 0.05 to 2% on the weight of catalyst suspension.

EFFECT: increased catalytic activity and reduced dosage of catalyst in polymerization process, which allows production of rubber with reduced titanium compound level without increasing intensity of washing away titanium compounds.

2 cl, 1 tbl, 11 ex

Up!