Catalyst and method for producing a mixture of hydrogen and carbon monoxide

 

The invention relates to the process of obtaining mixtures of hydrogen and carbon monoxide by catalytic conversion of hydrocarbons in the presence of oxygen-containing gases and/or water vapor. Describes a catalyst which is a complex composite containing mixed oxides with the structure of peroxide or fluorite and transitional and/or noble metals, which additionally contains components with low thermal expansion coefficient. The described method of catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and/or air, or CO2or steam, or a mixture thereof, and, optionally, sulfur-containing compounds. Technical result: the resulting catalyst with improved thermal stability, resistant to superusuario and poisoning by sulfur-containing compounds. 2 S. and 4 C.p. f-crystals, 4 PL.

The invention relates to the process of obtaining mixtures of hydrogen and carbon monoxide by catalytic conversion of hydrocarbons in the presence of oxygen-containing gases and/or vapors of water and catalysts for this process.

A mixture of hydrogen and carbon monoxide (synthesis gas) are widely used in large-scale chemical processes, such as si is bhodi synthesis gas with a certain ratio of the concentrations of hydrogen and carbon monoxide (H2/CO). To obtain mixtures of hydrogen and carbon monoxide with one or another ratio of N2/WITH the use of different reaction catalytic conversion of paraffins [J. R. Rostrup-Nielsen, Production of synthesis gas. Catalysis Today, 1993, v.18, 305-324; B. C. Arutyunov, O. C. Krylov// Oxidative conversion of methane. Moscow, Nauka, 1998]. The most widely used steam conversion of natural gas (methane), which produces a synthesis gas with a ratio of N2/WITH3, which is only useful for the synthesis of ammonia. In addition, the disadvantages of this process are the high cost of superheated steam and the formation of excessive amounts of carbon dioxide. When carbon dioxide methane conversion can be obtained a mixture of hydrogen and carbon monoxide with a ratio of N2/CO~1, required for the reactions of hydroformylation, preparation of formaldehyde and other Reaction of steam and carbon dioxide reforming of methane is endothermic, accompanied by coke formation processes and require high energy costs.

Also known is a method of obtaining a synthesis gas with a ratio of2/CO~2 by 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 t is an exothermic process and proceeds effectively at low contact times, enabling it in autothermal mode and reduce the size of the reactor [D. A. Hickman and 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 reduce both energy consumption and capital investment. Conducting simultaneously exothermic reaction RMS and endothermic steam reforming of natural gas on the same catalyst allows the process of obtaining mixtures of hydrogen and carbon monoxide enriched with hydrogen, in autothermal mode [J. W. Jenkins and E. Shutt, The Hot SpotTMReactor, Platinum Metals Review, 1989, 33 (3), 118-127].

The study process RMSE of methane in the pilot installation on modular catalyst containing Pt-Pd [J. K. Hoshmuth, Catalytic partial oxidation of methane over monolith supported catalyst, Appl. Catal., B: Environmental, v.1 (1992) 89] showed that when the contact time between ~0.02 in the front layer unit runs the full oxidation of methane, and in subsequent layers of steam and carbon dioxide conversion of methane. Therefore, to obtain maximum yields of the target product is synthesis gas, the catalyst must be active simultaneously in these three reactions. In accordance with this, for the effective behavior of the slow reactions conversatory along the length of the block, the catalyst should have a high thermal stability.

For carrying out process RMS at low contact times of ~10-2with the use of Pt-Rh grid or 10% Rh/block carrier, which is very expensive and uneconomical [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].

A known method of producing hydrogen [WO 99/48805, 01 3/40, publ. 30.09.00] by performing RMS and steam reforming of hydrocarbons on the same catalyst in autothermal mode: steam reforming is carried out at the introduction of steam into the mixture of hydrocarbon and oxygen-containing gas after began the process of RMS and established autothermal mode. As catalysts for use rhodium deposited on a heat-resistant carrier containing a mixture of oxides of cerium and zirconium in the weight ratio of Ce/Zr from 0.05 to 19.

The known method RMSE of methane to obtain carbon monoxide and hydrogen [US 5149464, 01 3/26, 1992] at a temperature of 650-900oC and flow rate 40000-80000 h-1(0,05-0,09 (C) 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 smiling. the volume ratio of the element 8 to the sum of the base elements in these compounds is 1: 1 or 3:1 and the content of noble metals is 32,9-48 wt.%. The conversion of methane in the presence of mixed oxides Pr2EN2O7, Eu2Ir2O7La2MgPtO6when flow rate 40000 h-1and 777odoes not exceed 94%, and the increase in flow rate to 80000 h-1reduce the conversion of methane to 73% and the selectivity for CO and hydrogen to 82 and 90%, respectively.

In the European patent [EP 303438, 01 3/38, 15.02.89] 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 oxygen-containing gas and, optionally, water vapor, with the catalyst in the zone selective catalytic oxidation. Area SKO contains the catalyst with the ratio of the 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 claim that the speed Satara, allowing this case to use materials does not exhibit catalytic activity, but providing the necessary ratio of the geometric surface/volume. The process is carried out at temperatures in the range 760-1090oC and flow rate from 20000 to 500000 h-1.

In patents [EN 2115617, 01 3/38, 20.07.98, EN 2136581, 01 3/38, 10.09.99, EN 2137702, 01 3/38, 20.09.99, EN 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] proposed a method RMSE of 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, for example,-Al2About3exhalent barium (grain size ~1 mm) or ZrO2, 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 950-1300oC and flow rate of the gas mixture 2-10

A known process for production of synthesis gas [US 5989457, C 07 C 1/02, 23.11.99] in the interaction of methane or hydrocarbons or mixtures thereof with carbon dioxide in the presence of a catalyst containing from 0.1 to 7 wt.% Pt, Ni, Pd or on a heat-resistant carrier, which comprises at least 80 wt. % ZrO2and at least 0.5-10 mol.% one of the oxides of Y, La, Al, CA, CE, or Sc. The process is performed on the catalyst with a grain size of 0.3-0.6 mm at 700-800oWith and volumetric flow rate 12750 h-1. Under these conditions, the conversion of methane is ~60-70%, the output FROM ~30%.

There is also known a method of obtaining a mixture of hydrogen and carbon monoxide [US 5500149, C 07 C 1/02, 19.03.96] when the contact mixture containing methane, oxygen and CO2at temperatures of 600-1000oC and flow rate ~5000-20000 h-1with a solid catalyst in the form of grains of ~0.3 mm, corresponding to the following formula: MxM'yOz or MxOz or M yOz on a heat-resistant carrier, where M and M' represent a wide range of alkaline, alkaline earth, transition, and other items. The proposed effective as catalysts in carbon dioxide methane conversion and combination reactions selective catalytic oxidation and carbon dioxide methane conversion. Variation of status is the process.

In the patent [US 5741440, 01 3/38, 21.04.98] propose a method of obtaining a mixture of hydrogen and carbon monoxide by contact of the reaction mixture containing carbon dioxide, hydrogen, at least one hydrocarbon and, optionally, steam, with a catalyst based on Pt or Ni deposited on a thermostable oxide (Al2About3, MgO) at temperatures 650-1450oC. Replacement in the original mixture, at least part of the water vapor in the hydrogen can increase the number of synthesis gas and to reduce the content of carbon dioxide in the target gas, and the variation of the composition of the initial mixture to obtain a mixture of hydrogen and carbon monoxide with a ratio of N2/From 0.7 to 3. Note that for mixtures without water to produce synthesis gas with H2/WITH2 requires a high concentration of hydrogen in the feed mixture, which increases the production costs of the final product.

In the patent [US 5855815, C 07 C 1/02, 05.01.99] propose to obtain the synthesis gas by recovering carbon dioxide a mixture of natural gas, oxygen and steam in the presence of a catalyst containing Nickel and promoters - alkali or alkaline-earth elements deposited on the silicon-containing media, such as silica gel, silicate, aluminosilicate or zeolite (the lending rate 1000-500000 h-1the ratio of N2/WITH changes in the range of 1/3-3/1.

Thus, to obtain a mixture of hydrogen and carbon monoxide with different ratio of N2/CO is used as the process standard deviation, and its combination with the endothermic conversion of hydrocarbons at low contact times of the reaction mixture with the catalyst, which must meet stringent requirements: to have a low hydraulic resistance, high thermal stability, to ensure a high conversion of hydrocarbons and selectivity to hydrogen and carbon monoxide and is not deactivated due to the formation of carbon on the surface. In addition, natural gas often contains sulfur-containing impurities and catalyst must be resistant to them.

It is known that the high thermal stability and resistance to thermal shock materials is higher, the lower the coefficient of thermal expansion [D. L. Trimm, Catalytic combustion (Review), Appl.Catal. 7(1983), 249-282]. Known catalysts for processes of obtaining a mixture of hydrogen and carbon monoxide, as a rule, contain oxides, for example-Al2About3having a positive thermal expansion coefficient. A known method of reducing the volumetric coefficient of thermal RA is izuchennym or close to zero KTR General formula And2-x3+Andy4+Mz3+M3-y6+PyAbout12where And3+and M3+the metal having the oxidation state 3+ (Al, Cr, Fe, Er, Ga, In, Lu, Sc, Tm, Y, Yb, and their mixture, And4+the metal having the 4+ oxidation state (Hf, Zr), M6+metal having oxidation state 6+(W, mo, and their mixture), y varies from 0 to 2, x=y+z and varies from 0.1 to 1.9.

Closest to the claimed technical essence and the achieved effect is the way RMS to produce synthesis gas in the presence of catalysts based on mixed oxides with the structure of perovskites [U.S. Pat. RF 2144844, B 01 J 23/10, 01 31/18, 27.01.2000]. The process RMSE of methane is carried out in the presence of perovskites with the General formula ABOxor AB1-yMyOxwhere a is a rare-earth element (e.g., La), In - transition element (e.g., Ni), M is a noble metal supported on blocks cellular structure of the-Al2O3when flow rate 25000-200000 h-1. At temperatures of 700-850oTo achieve high methane conversion and selectivity to synthesis gas. However, the perovskite complex oxides containing transition metals, which is very susceptible to poisoning by sulfur-containing compounds. In addition, the carrier task of creating a thermostable catalyst to obtain a mixture of hydrogen and carbon monoxide, effective at low contact times as in the reaction of selective catalytic oxidation of hydrocarbons with oxygen and steam and carbon dioxide reforming of hydrocarbons, including in the presence of serosoderjaschei connections, and the process of obtaining a mixture of hydrogen and carbon monoxide using this catalyst.

The problem is solved by using a catalyst which is a complex composite containing mixed oxides with perovskite structure or fluorite and transitional and/or precious metals and additionally components with a low coefficient of thermal expansion and implementation of catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and/or air, or CO2or steam, or a mixture thereof, and, optionally, sulfur-containing compounds in the presence of this catalyst. This saves the high conversion of methane and selectivity, thermal stability of the catalyst, it is not nauglerozhivaniya and poisoning by sulfur-containing compounds.

This technical result is achieved by using a catalyst having a composition, wt.%: Transition or noble element is Not more than 10 Mixed oxide is Not less than 1 Material - the e more than 95 Al2O3- The rest is a Mixed oxide includes an oxide with a perovskite structure M1B1-yMyOzand/or oxides with the fluorite structure M1xM21-xOzwhere: M - 8 group (Pt, Rh, Ir), M1- rare earth or alkaline earth element,
M2element IV b group of the Periodic system (Zr, Hf),
In - transition element - 3d elements of the 4th period,
of 0.01<x<1,0y<1, z is determined by the oxidation state of the cations and their stoichiometric ratio.

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.

The introduction of the high temperature catalyst components with low or negative CTE allows you to adjust the coefficient of thermal expansion and thereby to obtain catalysts with high temperature resistance. As components having low or negative coefficient of thermal expansion, use cordierite, mullite, cleandata (MV2O7), aluminum titanate.

The obtained complex composite catalyst has a surface 2-200 m2/, the Catalyst is in the form of pellets, rings, spheres, blocks cell structure.

The process is carried out by sequential transmission of a gas mixture containing a hydrocarbon or mixture of hydrocarbons and/or air, or steam, or a mixture with a temperature of between 20 and 500oWith through a fixed bed of the catalyst, which consists of rows 1-20.

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 and/or air, or CO2or steam, or a mixture thereof, and, optionally, sulfur-containing compounds, the process is carried out at temperatures of 500-1000oC. as hydrocarbons are used, for example, natural gas, methane, propane-butane mixture, a mixture of heavier hydrocarbons, kerosene, etc. as the oxygen-containing gas, such as oxygen, air, carbon dioxide, water.

The proposed catalysts are prepared using the methods of mixing and impregnation, followed by drying and calcining. The process of obtaining a mixture of hydrogen and carbon monoxide is carried out in a flow reactor at temperature and the reaction products analyzed chromatographically. The efficiency of the catalyst is characterized by the degree of conversion of methane and selectivity for CO and hydrogen, the amount of the mixture of hydrogen and carbon monoxide and their ratio. The material balance on carbon in all cases was 1002%.

The invention is illustrated by the following examples.

Example. 1. For making blocks of Al2About3in a paddle mixer with a volume of 5 l of mixed powders of aluminum hydroxide containing 70 wt.% pseudoboehmite, and high-temperature oxide containing 35 wt.% corundum, in the amount of 1000 g with the addition of 25 g of structure-forming additives (wood flour)* and 6 g of surface active substances (glycerol)* in the presence of patinator - 6% nitric acid. The resulting paste is molded in the form of cuttings or blocks cell structure through a special nozzle. Then Al2About3dried and calcined at 800-1300oC. Specific surface 2-200 m2/, To determine KTR formed into tubes with outer diameter 6 mm, inner 2.5 mm and calcined at 1300oC. Average CTE in the temperature range 20-1000oWith is 510-6deg-1.

Example 2. For cooking smecta solutions of nitrates of calcium, strontium and oxynitride zirconium. Slowly, with continuous stirring, poured a stoichiometric amount of phosphoric acid. The resulting gel is dried and calcined at a temperature of 1300oC. the resulting powder phosphate has a composition of Ca0,5Sr0,5Zr4P6O24and structure type NZP. This powder is placed in a mixer, add the original gel and mix. The resulting mass is formed into blocks, dried and calcined at 1300oC. To determine KTR formed into tubes with outer diameter 6 mm, internal - 2.5 mm Average CTE in the temperature range 20-1000oWith is ~110-6deg-1.

Example 3. In a paddle mixer in the presence of nitric acid mixed powders of CA0,5Sr0,5Zr4P6O24obtained as in example 2, and aluminum hydroxide, taken in equal quantities. The resulting mass is molded, dried and calcined at 1300oC. To determine KTR formed into tubes with outer diameter 6 mm, inner 2.5 mm Average CTE in the temperature range 20-1000oWith is ~110-6deg-6.

Example 4. Al2O3as microbiota with the surface 100 m2/g pri cerium and zirconium oxide with an atomic ratio of Ce/Zr=0,8: 0,2. After impregnation the catalyst is dried and calcined in air at 900oWith 2 hours. The sample obtained is impregnated with a solution of H2PtCl6, dried and calcined at 900oC. the resulting catalyst containing 10 wt.% mixed oxide of cerium and zirconium and 0.3 wt.% Pt experience in a flow reactor with the reaction mixture composition: SN4- 25%, O2- 12.5%, the rest - N2and contact time ~0,09 with, the activity is given in table. 1.

Example 5. Al2O3as microbiota with the surface 100 m2/g, prepared as in 1, impregnated with regard to capacity mixed with a solution of salts of cerium and zirconium with a molar ratio of cerium and zirconium 0,8:0,2. After impregnation the catalyst is dried and calcined in air at 900oWith 2 hours. The impregnation procedure is repeated. The sample obtained is impregnated with a joint solution of H2PtCl6and RhCl3, dried and calcined at 900oC. the resulting sample contains, by weight. %: 16 mixed oxide of cerium and zirconium, 0,3 Pt, 0,3 Rh. The tests were carried out as in 4, the activity is given in table. 1.

Example 6. The catalyst is prepared as in example 4, except that the sample is impregnated with a solution of salts of cerium and zirconium with a molar ratio of cerium and zirconium 0, the example 4, activity is given in table.1.

Example 7. Al2About3as microbiota with the surface 2 m2/g, prepared as in 1, calcined at 1300oWith and impregnate with regard to capacity mixed salt solution with a molar ratio of cerium and zirconium 0,2:0,8. After impregnation the catalyst is dried and calcined in air at 900oWith 2 hours. The sample obtained is impregnated with a solution of H2PtCl6, dried, calcined and experience, as in example 4, the activity is given in table.1. The resulting sample consists of 8.5 wt.% mixed oxide of cerium and zirconium, 1 wt.% Pt.

Example 8. The catalyst is prepared as in example 7, except that impregnation using a mixed solution of salts of calcium and zirconium oxide with a molar ratio of Ca: Zr= 0,05: 0,95. The resulting sample consists of 7.5 wt.% mixed calcium oxide and zirconium oxide, 1 wt.% Pt. Experience, as in example 4, the activity is given in table. 1.

Example 9. The catalyst prepare and test as in example 7, except that used for impregnation unit, prepared as in 2. The resulting sample contains 8 wt.% mixed oxide of cerium and zirconium, 1 wt.% Pt. Experience, as in example 4, the activity is given in table. 1.

Example 10. The catalyst is prepared and the Chennai sample consists of 7.8 wt.% mixed oxide of cerium and zirconium, 1 wt.% Pt. Experience, as in example 4, the activity is given in table. 1.

Example 11. The catalyst is prepared as in example 7, except that the impregnation is used instead of H2PtCl6a solution of Nickel nitrate. The sample contains 8 wt.% mixed oxide of cerium and zirconium and 2.5 wt.% Ni and experience in the reaction of carbon dioxide methane conversion. Test conditions and activity are given in table. 2.

Example 12. The catalyst is prepared as in example 4, and experience in the reaction of selective oxidation of methane in the presence of water vapor. Test conditions and activity are given in table. 2.

Example 13. The catalyst is prepared as in example 7, and experience in the reaction of steam reforming of methane. Test conditions and activity are given in table. 2.

Example 14. The catalyst is prepared as in example 7, except that the impregnation instead of H2PtCl6use a mixed solution of H2PtCl6, nitrates of lanthanum and Nickel atomic ratio of cations La:Ni:Pt=1:0,994:0,006. The resulting catalyst contains 7 wt.% perovskite LaNi0,994Pt0,006and 10 wt. % mixed oxide of cerium and zirconium. The catalyst was tested in the reaction of selective oxidation of natural gas in the presence of SO2. Activity is given in tab the second layer the catalyst is prepared as in example 7. Spend the reaction of selective oxidation of natural gas. Activity is given in table. 4.

Example 16. In a paddle mixer in the presence of nitric acid mixed powder of cordierite and aluminum hydroxide, taken in equal quantities. The resulting mass is formed into thin microblock, dried and calcined at 1300oC. To determine KTR formed into tubes with outer diameter 6 mm, internal - 2.5 mm Average CTE in the temperature range 20-1000oWith is ~0,910-6deg-1.

Example 17. The catalyst is prepared as in example 4 except that as the carrier used unit, prepared as in example 16. The resulting sample contains 7 wt.% mixed oxide of cerium and zirconium, 0.3 wt. % Pt. The tests were carried out as in example 4, the activity is given in table. 1.

Example 18. In a paddle mixer in the presence of nitric acid mixing fine powders of Al2TiO5pre-annealed at 1500oand aluminum hydroxide, taken in equal quantities. The resulting mass is molded, dried and calcined at 1300oC. To determine KTR formed into tubes with outer diameter 6 mm, inner ->1.

Example 19. The catalyst is prepared as in example 4 except that as the carrier used unit, prepared as in example 18. The resulting sample contains 7 wt.% mixed oxide of cerium and zirconium, 0.3 wt. % Pt. The tests were carried out as in example 4, the activity is given in table. 1.

Example 20. The media is prepared as in example 16, except that the use of mullite and aluminum hydroxide. The average CTE in the temperature range 20-1000oWith is ~110-6deg-1.

Example 21. The catalyst is prepared as in example 4 except that as the carrier used unit, prepared as in example 20. The resulting sample contains 7 wt.% mixed oxide of cerium and zirconium, 0.3 wt. % Pt. The tests were carried out as in example 4, the activity is given in table. 1.

Example 22. The media is prepared as in example 16, except that the use of tungstate, zirconium and aluminum hydroxide. The average CTE in the temperature range 20-1000oWith is ~510-7deg-1.

Example 23. The catalyst is prepared as in example 4 except that as the carrier used unit, prepared as in example 22. Obtained the Yunosti are given in table. 1.

Example 24. The media is prepared as in example 16, except that the use of molybdate scandium and aluminum hydroxide. The average CTE in the temperature range 20-1000oWith is ~210-7deg-1.

Example 25. The catalyst is prepared as in example 4 except that as the carrier used unit, prepared as in example 24. The resulting sample contains 7 wt.% mixed oxide of cerium and zirconium, 0.3 wt. % Pt. The tests were carried out as in example 4, the activity is given in table. 1.

Example 26. The media is prepared as in example 16, except that the use of Vanadate zirconium and aluminum hydroxide. The average CTE in the temperature range 20-1000oWith is ~610-7deg-1.

Example 27. The catalyst is prepared as in example 4 except that as the carrier used unit, prepared as in example 26. The resulting sample contains 7 wt.% mixed oxide of cerium and zirconium, 0.3 wt. % Pt. The tests were carried out as in example 4, the activity is given in table. 1.

As seen from the above examples and tables, designed thermostable catalyst to obtain a mixture of hydrogen and carbon monoxide, effective the, and steam and carbon dioxide reforming of hydrocarbons, including in the presence of serosoderjaschei compounds.


Claims

1. The catalyst to obtain a mixture of hydrogen and carbon monoxide by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons, and/or air, or CO2or steam, or a mixture of, on the basis of aluminum oxide, mixed oxides, including rare earth and transition elements and metals of group VIII, characterized in that the catalyst is a complex composite and additionally contains components with ultra-low thermal expansion coefficient not higher than 810-6cm/deg and has the following composition, wt. %:
The transition element and/or a noble element is Not more than 10
Mixed oxide is Not less than 1
Material with a low coefficient of thermal expansion not exceeding 810-6cm/deg - 95
Al2O3- Rest
when this material with a low coefficient of thermal expansion selected from the group of cordierite, complex phosphates of zirconium with NZP structure, aluminum titanate, mullite, wolframate, molybdates, vanadates, mixed oxide on the Rita
Mx1M1-x2Aboutz,
where M is the element 8 groups, such as Pt, Rh, Ir;
M1a rare - earth element such as La, Ce, Nd or alkaline earth, such as CA, Sr;
M2- the element of IVb 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;

2. The catalyst p. 1, characterized in that the catalyst contains a transition element, such as Ni, Co, and/or noble metal - element, 8 group, such as Pt, Rh, Ir.

3. The catalyst PP. 1 and 2, characterized in that it has the form of granules, extrudates, cuttings or a honeycomb structure with surface 2-200 m2/,

4. The method of obtaining a mixture of hydrogen and carbon monoxide by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and/or air, or CO2or steam, or a mixture thereof, using a catalyst based on a mixed oxide containing rare earth and transition elements and metals of group VIII, characterized in that the process is carried out by sequential transmission of a gas mixture containing a hydrocarbon or mixture of hydrocarbons, and/or air, or steam, or a mixture, with a temperature between 20 and 500oWith through the fixed catalyst bed is in cell catalyst.

6. The method according to p. 4, characterized in that the process is carried out in the presence of serosoderjaschei compounds in the gas mixture.

 

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