WO2016032357A1 - Catalyst for carbon dioxide conversion of natural gas - Google Patents

Abstract

The invention relates to the field of developing and manufacturing catalysts, and can be used in the chemical industry for the process of carbon dioxide conversion of natural gas and/or methane, with the aim of producing a synthesis gas in a wide range of temperatures and with high reagent feeding speeds. Described is a catalyst in the form of a nanocomposite Ni-containing material, composed of an oxide having a perovskite-like structure or a fluorite-like structure with high oxygen mobility, platinum metals, nickel, and an oxide additive, having a high specific surface area and/or good thermal stability. The said catalyst may be used as an active component when applying to various types of thermally-conductive carriers (FeCrAl foil or mesh, porous carriers based on nickel and aluminum or silicon carbide, microchannel plates, etc.). The technical result consists in the high activity and stability of the claimed catalysts, which allow for carrying out the process of carbon dioxide conversion of methane, including natural gas, at higher loads, up to 540,000 h^-1 (at shorter contact times, as short as 0.015 s).

Description

 CATALYST FOR CARBON CONDITION CARBON

 NATURAL GAS

The invention relates to the field of development and production of catalysts and can be used in the chemical industry for the process of carbon dioxide conversion of natural gas and / or methane in order to produce synthesis gas in a wide temperature range and high feed rates of reagents.

 There are three most promising processes for converting methane into synthesis gas.

 · Methane steam reforming (PCM),

СН ₄ -I- Н ₂ 0 -> СО + ЗИ ₂ ΔΗ ^Θ 298 = + 206 kJ * mol ^{~ 1}

 • Carbon dioxide conversion of methane (UKM)

СН ₄ + С0 ₂ -> 2СО -I- 2Н 2 ΔΗ ^Θ ₂₉₈ = + 247 kJ * mol

 • Meta Partial Oxidation (POM),

CH ₄ + Yg 0 ₂ - »CO + 2H ₂ ΔΗ ^Θ ₂₉₈ = - 38 kJ * mol ^~ '

For all three reactions, there is also a side reaction of the reverse steam reforming of CO, which affects the ratio of H ₂ / CO in the resulting synthesis gas.

С0 ₂ + Н ₂ <- »СО I- Н ₂ 0 ΔΗ ° 298 = + 1 kJ * mol

Carbon dioxide methane conversion with C0 ₂ is an alternative route for producing synthesis gas with obvious advantages, such as the ratio of H ₂ / CO in the synthesis gas is 1: 1. So, in the process of the MSN is possible to adjust the ratio of H ₂ / CO, as for Different applications require different H ₂ / CO ratios. This is achieved by combining the UKM reaction with steam reforming or with partial oxidation of methane. Finally, one can consider UKM as a “green” process, since the greenhouse gas CO2 is consumed in the process. The UKM process was first studied Fisher and Tropsch in 1928 on metal catalysts [1], and recent studies of this reaction have revealed a number of typical UKM catalysts containing Fe [2], Co [3], Ni [4]. The results of numerous studies have shown that noble metal catalysts exhibit higher activity and are less prone to carbonization.

 In addition, the CCM reaction is an endothermic process and the combination with the PCM endothermic process is more energy efficient. The stoichiometric reaction of methane and carbon dioxide with the participation of group VIII transition metals at a temperature of 780 ° C and atmospheric pressure provides synthesis gas selectivity of about 90%, with a methane and carbon dioxide conversion of more than 85% [5].

Ceramic materials that have both ionic and electronic conductivity attract attention both as hydrocarbon reforming catalysts and as anode materials for solid oxide fuel cells. These mixed ion-electron conductive materials (MIEC) include ceramic additives, such as doped cerium oxides or perovskite-like oxides such as doped LaCr0 ₃ and SrTi0 ₃ [6]. Compared to metal-based anodes, transition metal oxides with mixed ionic and electronic conductivity are less prone to coke formation or sulfur poisoning.

Various additives can be introduced to improve the properties of catalysts, such as activity in reforming, stability to carbonization, and resistance to sulfur poisoning. A study of the effect of additives of rare-earth elements on the properties of Ce0 ₂ showed that the ionic conductivity strongly depends on the ionic radius of the element. In particular, in the series from Yb to La, the conductivity increases, reaching a maximum in Sm and then decreasing towards La. A similar dependence was observed in the series with Zr, with a maximum passing through Sc. These dependences were explained in terms of distortions in the Ce0 ₂ lattice introduced by the dopant. From this point of view, the addition of Sm showed the best results, causing the least distortion and stress in the Ce0 ₂ lattice and showing the smallest change in potential energy

Cerium oxide doped with trivalent rare earths oxides (Gd ₂ 0 ₃ , Sm ₂ 0 ₃ , and Y ₂ 0 ₃ ) is a mixed ion-electron material that has an ionic conductivity of about 10 times higher than that of YSZ.

 The ability to store oxygen and migrate into the volume of cerium oxide can also increase the oxidation of hydrocarbons. In addition, these materials have good electrocatalytic activity and the ability to suppress the formation of carbon. The performance of the catalyst can be improved by the addition of metals such as Ni. For example, materials based on doped Ni-Gd and Ru-Ni-Gd cerium oxide were studied for direct electrochemical oxidation of hydrocarbon fuels. The promotion of platinum group metals increases the activity of the catalysts in the steam and carbon dioxide fuel conversions.

 The introduction of finely divided fine particles of noble metal catalysts into Sm-doped cerium oxide can significantly reduce the polarization resistance.

 Compared with Ni micron particles in cermet anodes, several percent of ultrafine nanometer nickel particles dispersed in an anode based on cerium oxide doped with Sm can significantly increase productivity [6].

Nickel deposited on cermets from perovskite-like oxides such as La-Sr-Mn-CrO ₃ , La-Pr-Mn-CrO3 and La-Sr-Ti0 ₃ were also investigated in the oxidative conversion of methane. Other interesting examples of the use of materials from this category were proposed for use in CT SOFC anodes, including Ni-M / YSZ (M = Co, Cu, Fe) La-Sr-Cr-FeC-z, La-Sr-Cr-Mn0 ₃ (LSCM), La-Sr-Fe-Cr0 ₃ and La-Sr-Ti-Mn0 ₃ (LSTM) [7].

Ni particles dispersed in cerium-zirconium-based mixed fluorite-like oxides doped with rare-earth elements (Sm, Pr, Gd, La), as well as primoscite-like oxides (AB0 ₃ ) are the main materials presented in this work. According to the literature, the addition of Zr0 ₂ , Zr-Y-0 ₂ , Ce-Gd-0 ₂ , A1 ₂ 0 ₃ increases the thermal stability and specific surface area of the oxides, especially under reducing conditions. Nickel particles and small additions of platinum group metals should activate fuel molecules, and rare-earth elements in the composition of the oxides should increase the oxygen mobility of the catalyst.

The closest to the claimed technical essence and the achieved effect is a catalyst for the process of carbon dioxide conversion of methane [RU 2453366, 20.06.2012]. The catalyst is a carrier based on a complex mixed oxide containing at least 3 metals, based on cerium-zirconium doped with rare-earth metals coated with an active component of Ni and / or La and / or platinum group metals (Pt, Ru). The general formula of the catalyst can be written as follows: MiM ₂ M3 [AxByCeo.3 ₅ Zr ₀ .35] 0 ₂ - Where: x is 0.3 at y = 0, and where x is 0.15 at y = 0.15. Where: A and / or B are selected from metals of rare earth elements Pr, La, Sm. Where: Mi - choose from metals of the platinum group - Pt or Ru, with a content of from 0 to 1.4 wt.%; M ₂ is nickel with a content of from 0 to 1, 9 to 6.6 wt.%; M ₃ is La with a content from May 0 to 4.7. %

The technical result consists in the high activity and stability of the inventive catalysts, which allow the process of carbon dioxide conversion of methane, including natural gas, at higher loads up to 540,000 h ^"1 (with shorter contact times up to 0.015 s).

 The invention solves the problem of creating a stabilized bulk catalyst for the process of producing synthesis gas by carbon dioxide conversion of methane, including as an active component for a structured catalyst of carbon dioxide natural gas, capable of working in real mixtures and with short contact times.

 The problem is solved by creating a highly efficient and stable catalyst capable of working at short contact times (at high volumetric feed rates) in the process of producing synthesis gas by carrying out the reaction of carbon dioxide conversion of methane or carbon dioxide conversion of natural gas with a wide variation of process parameters (mixture composition, temperature, loads )

The catalyst for producing synthesis gas in the process of carbon dioxide conversion of natural gas, which is a nanocomposite Ni-containing material, characterized in that it consists of oxide with A perovskite-like or fluorite-like structure with high oxygen mobility, platinum metals, nickel Ni and an oxide additive having a high specific surface area and / or good thermal stability, the composition of the catalyst has the following general formula:

 aMe + bt + cu +,

 where: a, b, c, d - mass. %, a + b + c + d = 100%,

 0 <i <5,

 10 <6 £ 95,

 2 <s <88,

 2 <d <60;

 Me is a platinum group metal;

 PO - perovskite-like or fluorite-like oxide with high oxygen mobility;

where: PO: 1) perovskite-like oxide Ln _x Ln _{) -x} M М bуОз-д, where: Ln and Ln ² - (La, Sm, Pr, Се, Gd), x = 0 - 1; M ¹ and M ² = (Mn, Fe, Ru, Co, Cr, Ni), y = 0 - 1;

2) fluorite-like oxide Ln _x Ln _x -iCeyZxy-i0 ₂ , Lni and Ln ₂ =

(La, Sm, Pr, Gd), x - 0 - 1, y = 0.1 - 0.9, x + (x - 1) + y + (y - 1) = 1;

 JO is an oxide additive having high dispersion and / or good thermal stability and / or high oxygen mobility;

 Ni is an active component. which can be introduced into the volume of a perovskite-like or fluorite-like oxide at the stage of synthesis, when a polymer oxide precursor is formed or can be represented in the nanocomposite catalyst as an individual Ni or NiO phase deposited by impregnation or other method.

 The content in the catalyst of the active component of Nickel is from 1 to 60 wt.%.

 The metal content of the platinum group of Pt and / or Ru is from 0 to 5 wt.%.

The catalyst as an oxide additive contains oxide Al ₂ 0 ₃ or Ce _x Gdi _-x 0 ₂ , or Zr _y Yi- _y 0 ₂ , where: x = 0.5 - 0.95, y = 0.70 - 0.95 in an amount of from 2 to 88 wt. % The catalyst contains perovskite-like or fluorite-like oxide with high oxygen mobility; in an amount of from 10 to 95 wt.%.

 The catalyst can be used as an active component for the manufacture of structured catalysts on heat-conducting media with a catalyst content until May 10. %

 The invention is illustrated by the following examples.

 Example 1

Nanocomposite catalyst based on perovskite-like ocheid, Ni and GDC or A1 ₂ 0 ₃ or YSZ

The basic formula is Lnl _x Ln2i. _x M _y Nii _-y 0 ₃ -5 + JO, where Ln ¹ = (La, Sm, Pr), x

= 0-1; Ln ² = (La, Sm, Pr, Ce _; Gd), x = 0 - 1; M = (Mn, Fe, Ru, Co), y = 0 - 0.9.

 12

Contents perovskite-like oxide _{Ln x Ln i, x M y} Nii -y 0 ₃ 5 in the catalyst varies from 60 to 95 May. %, and JO from 5 to 88 wt. %, respectively. Where JO is A1 ₂ 0 ₃ or Ce _x Gd ,. _x 0 ₂ (GDC) or Zr _y Yi _-y 0 ₂ (YSZ).

 Synthesis

Crystalline hydrates of nitrates La, Fe, Ni, Pr, Sm, Ce, Gd, and RuOHCl _{3 were} used as initial raw materials. Perovskite was synthesized by the Pekini method using metal nitrates (Me), RuOHCl ₃ taken in the appropriate ratios, citric acid (LA), ethylene glycol (EG) and ethylene diamine (ED) as reagents. The molar ratio of the reagents LC: EG: ED: ΣΜε is 3.75: 1 1.25: 3.75: 1. Citric acid and metal nitrates were dissolved at 80 ° C in distilled water, respectively. The prepared solutions were combined together with stirring, followed by the addition of ED. The prepared solution was stirred for 60 min and then heated at 70 ° C for 24 h, allowing the gel to form. The gel was calcined in the range of 600 - 900 ° C for 2 hours, followed by obtaining a solid.

 Catalysts were prepared using GDC powder or

 12

A1 ₂₀ 0 and oxide powder Ln _x Ln i. _x M _y Nii _-y 0 ₃ .s mixed in various mass ratios. The powders were subjected to ultrasonic dispersion using an Ika T25 ULTRA-TURRAX basic installation (IKA, Germany) with the addition of polyvinyl butyral as a surfactant, followed by drying and sintering in air in temperature range 700 - 900 ° С. In another case, the catalysts could be prepared by impregnating the moisture content of the powder of the oxide additive GDC or A1 ₂ 0 _{3 with an} aqueous solution of the salts of the corresponding oxide Ln ' _x Ln ² i. xM _y Nii _-y 03.s, followed by drying and calcination in air in the temperature range 600 - 900 ° С.

 Catalytic tests in real conditions.

The process of carbon dioxide conversion of methane (UKM) was studied under equilibrium conditions at temperatures of 750-850 ° C in a flow reactor with a reaction mixture of 45% C0 ₂ + 45% natural gas (GH) + 10% N ₂ or 52.5% C0 ₂ + 38.1% PG, N ₂ - balance at 800 ° С and contact time 0.03-0.24 s. GHG contains up to 90% CH4 and a mixture of C ₂ -C ₄ hydrocarbons. Before testing, the catalysts were activated in the reaction medium at 850 ° С for 2 h. Long-term testing was carried out at 800 ° С and contact time 0.24 s. Reagent and product concentrations were analyzed using the GC Tcvet-500.

 Table 1 presents the test results of the nanocomposite catalyst in real mixtures in the reaction of carbon dioxide conversion of natural gas.

Table 1. Catalytic activity for a sample of 90% Lao.9Pr _0. iFeo _.7 Nio.30 _3- 6 + l O% Ceo.9Gdo.1Ch, where Hash w2 - conversion of reactants _(H2 + CO) - the concentration of synthesis gas at the outlet, (Н ₂ / СО) - the ratio of the concentration of products at the outlet. Reaction conditions: 800 ° С, С0 ₂ : ПГ = 1.38 (52.5% С0 ₂ + 38.1% ПГ, N ₂ - balance), contact time (τ) = 0.253 seconds, pretreatment in the reaction medium for 2 hours at 850 ° С .

Table 2.

Equilibrium activity of 2% Ni + 10% LaMnO ₃ + 88% A1 ₂ 0 ₃ catalyst in

UKM at 700 and 800 ° C, where Hash _, Hsog - conversion of reagents, (N ₂ / СО) - ratio of product concentrations at the outlet; mixture: 31.5% СН ₄ + 46.0% С0 ₂ , Not - balance. Weighed portion = 0.1 g, contact time 0.17 s. Pure methane experiments.

Таблица 3.

Table 3.

Temperature dependence of the catalytic activity for 2% Ru + 98% (80% LaPrMnCr + 10% YSZ + 10% NiO) catalyst in UKM. Pretreatment at 0 ₂ at 700 ° С, 30 min., Composition of the mixture: 7% СН ₄ + 7% С0 ₂ + Not balance. Contact time 0.015 s.

Example 2

 Fluorite-like oxide, Ni, and YSZ nanocomposite catalyst

The basic formula is Me'Me ² + Ln ' _x Ln ² _x- iCe _y Zr _y- i0 ₂ + Ni + YSZ, where: Me' is Pt (from 0 to 5 wt.%.) And Me is Ru (from 0 up to 5 wt.%);

Ln ¹ = (La, Sm, Pr, Gd), Ln ² = (La, Sm, Pr, Gd), x = 0 - 0.5; y = 0.2 - 0.8; x + (x - 1) + y + (y - 1) = 1, YSZ = Zr _y Y [ _-y 0 ₂ , where: y = 0.70 - 0.95. The content of fluorite-like oxide Ln ' _x Ln iCeyZi iC in the catalyst varies from 10 to 95 wt.%, Ni - from 2 to 60 wt.% And YSZ from 2 to 60 may. %

 Synthesis

First, for the preparation of the starting components, aqueous nitrate solutions (Y, Sm, Ce, La, Gd, Pr), an aqueous solution of zirconium oxychloride, citric acid (LA), ethylene glycol (EG), and ethylene diamine (ED) were used. The optimal molar ratio of reagents used for the preparation of the gel is LK: EG: ED: E e this is 3.75: 1 1.25: 3.75: 1.

Citric acid was dissolved in ethylene glycol at 60 ° C. Then, aqueous salts of metal nitrates were added to the solution of LA and EG in the required ratio - Y (N0 ₃ ) ₂ .nH ₂ 0, Ce (N0 ₃ ) ₃ nH ₂ 0, Pr (N0 ₃ ) ₃ nH ₂ 0, Sm (N0 ₃ ) ₃ nH ₂ 0 dissolved in a small amount of disilitated water, followed by the addition of ZrOCl ₂ . ED was added to the solution at room temperature to give a gel after stirring.

 To prepare YSZ: the resulting gel containing yttrium and zirconium salts was heated at 100 ° C to remove traces of water. This gel was subsequently calcined in air in the temperature range 300-800 ° C for 1-5 hours to obtain a fine powder of YSZ powder.

YSZ powder and NiO powder were then added to the polymer precursor, Lnl _x Ln2 _x .iCeo gel. ₃ 5Zro. ₃ 50 ₂ . Then the mixture was heated at a temperature of 100 ° C to remove traces of water. This gel was subsequently calcined in air in the temperature range 300-800 ° C for 1-5 hours to obtain a powder.

Pt and / or Ru were applied by moisture absorption to a powder (Ln ' _x Ln ² _x- iCe _y Zr _y-1 0 ₂ + YSZ) from H ₂ PtCl ₆ and / or Ru (OH) Cl ₃ solutions with appropriate concentrations followed by drying and calcining for 1 h at 800 or 900 ° C.

 Catalytic tests

 Table 4 presents the results of catalytic experiments on CM in real conditions with natural gas. The conditions of the catalytic tests in real conditions with natural gas were the same as in example 1.

 Table 4.

The catalytic activity of nanocomposite catalysts, where Hash _, Xso ₂ - conversion of reagents, (Н ₂ + СО) is the concentration of synthesis gas at the outlet, (Н ₂ / СО) is the ratio of the concentrations of the products at the outlet. Reaction conditions: 800 ° C or 850 ° C, C0 ₂ ratio: PG = 1.38 (52.5% C0 ₂ + 38.1% PG, N ₂ balance), contact time (τ) = 0.253 seconds, pretreatment in the reaction medium for 2 hours at 850 ° C; catalyst composition: 1 - 1% Pt + 99% (10% NiO-i-10% YSZ + 80% Smo.i ₅ Pro.i ₅ Ceo.3 ₅ Zro.3 ₅ 0 ₂ ), 2 - 0.5% Pt + 0.5% Ru + 99% (10% NiO + 10% YSZ + 80% Sm _0.15 Pr ₀ i ₅ Ceo _.35 Zro _.35 0 ₂ ).

Table 5 presents the results of UKM at different temperatures, the yield of synthesis gas (H ₂ + CO), the ratio of the target products of H ₂ / CO for 1% Ru / NiO + YSZ + SmPrCeZrO.

 Table 5.

The activity of the catalyst l% Ru + 99%

(10% NiO + 10% YSZ + 80% Smo.i ₅ Pr _0. i ₅ Ceo.3 ₅ Zro. ₃₅ 0 ₂ ) in UKM at different temperatures, where Hesh _, co2 are the conversions of the reactants, (Н ₂ + СО) - the concentration of synthesis gas at the outlet, (H ₂ / CO) - the ratio of the concentrations of the products at the outlet. Reaction conditions: 20% СН ₄ + 20% С0 ₂ , contact time 0.015 s, pretreatment at 0 ₂ at 700 ° С, 30 min.

As follows from table 5, the ratio of H ₂ / CO can vary with changing reaction temperature. Table 6 presents typical time dependences of the ratio of H ₂ / CO at various temperatures, which are quite stable after an initial slight decrease due to reduction of the catalyst.

 Table 6.

The ratio of H ₂ / CO in UKM for l% Ru + 99% (10% NiO-tT O% YSZ + 80% Sm ₀ .iPr _{0. 2} Ce ₀ .3 ₅ Zro.350 ₂ ) at different temperatures, mixture of 20% CH ₄ + 20% C0 ₂ , contact time 0.015 s, pretreatment at 0 ₂ at 700 ° C, 30 min.

Nanocomposite catalysts provide a high yield of synthesis gas in the carbon dioxide conversion of real natural gas with a content of up to 6% of a mixture of C ₂ -C ₄ alkanes (table 7).

 Table 7.

Temperature dependence of the concentration of products at the outlet in UKM for 0.5% Pt -I- 0.5% Ru + 99% (10% NiO + 10% YSZ + 80% Smo.3Ce ₀ .35Zr ₀ .3 ₅ 0 ₂ ). Contact time 0.1 s, mixture: 47.8% С0 ₂ + 42% СН ₄ (47.8% ПГ) + ₂ - balance.

 The operation of the catalyst was stable under such conditions (table 8).

 Table 8.

Conversion CH ₄ in long-term experiments on GHG carbon dioxide conversion catalyst 0.5% Pt + 0.5% Ru + 99% (10% NiO + 10% YSZ + 80% Sm _{0 0} jPr. Ce _{0. 35} Zro. _3, 50 _2). Contact time 0.1 s, mixture: 47.8% С0 ₂ + 42% СН ₄ (47.8% ПГ) N ₂ - balance, 800 ° С.

 Example 3

Nanocomposite catalysts were investigated in UKM as structured catalysts on thermally conductive carriers. For the preparation of structured catalysts were used various types of heat-conducting media: fechral foil or mesh protected by a corundum layer; Ni-Al porous plates; SiC / Al-Si-0 foams; Fechral microchannel plates protected by a layer of corundum.

 The nanocomposite active component (content until May 10,%) was deposited on a structured heat-conducting carrier by applying layers of a suspension in isopropanol with polyvinyl butyral followed by drying and calcination in air in the temperature range 700 - 900 ° С for 2 hours. Platinum group metals and / or Ni was deposited on a structured catalyst by impregnation followed by drying and calcination in the temperature range of 700 - 900 ° C.

Table 9 presents the results of long-term experiments on a UKM structured catalyst with a nanocomposite active component l% Ru + 99% (80% Lao _.5 Pr _0.5 Mno _.2 Cr _0.8 0 ₃ + 10% YSZ + 10% NiO). table 9.

Dependence of the concentration of products (H ₂ , CO) and reagents (CH ₄ , C0 ₂ ) at the output of UKM on time for 8 wt.% (L% Ru + 99% (80% Lao. ₅ Pro _.5 Mno. ₂ Cro _{. 8} 0 ₃ + 10% YSZ + 10% NiO) deposited on a fechral net twisted into an Archimedes spiral (external cylinder diagonal 15 mm, height 26 mm) with the formation of triangular channels (side 1–3 mm) Mixture: 55% С0 ₂ + 35% СН ₄ + N ₂ balance, 800 ° С.

Источники информации

Information sources

[1] F. Fischer and H. Tropsch. // Brennstoff-Chem (1928) Vol. 9, P. 39.

[2] T. Sodesawa and al., Catalytic reaction of methane with carbon dioxide // React. Kinet Catal. Lett. (1979) Vol. 12, P.107 - 1 1 1.

 [3] A. Guerrero-Ruiz and al. // J. Chem. Soc, Chem. Commun. (1993) P. 487

[4] A.M. Gadalla and M.E. Sommer, Synthesis and characterization of catalysts in the system Al203 ~ MgO ~ NiO-Ni for methane reforming with C02 II J. Am. Ceram. Soc. (1989) Vol. 72, P.683 - 687.

[5] E. L. Gubanova, Etude experimentale et modelisation de I oxydation partielle du methane en gaz de synthese sur reacteur catalytique a temps court (These 2008) [6] R.J. Kee et al., Solid-oxide fuel cells with hydrocarbon fuels II Proceedings of the Combustion Institute 30 (2005) P. 2379-2404

 [7] Ovalle A, and al., Mn substituted titanates as efficient anodes for direct methane SOFCs. II Solid State Ionics 2006; 77: 1997-2003.

Claims

CLAIM 1. The catalyst for producing synthesis gas in the process of carbon dioxide conversion of natural gas, which is a nanocomposite Ni-containing material, characterized in that it consists of a perovskite-like or fluorite-like structure with high oxygen mobility, platinum metals, nickel Ni and an oxide additive having a high specific surface area and / or good thermal stability, the composition of the catalyst has the following general formula:  Me + bVO + cJO + ί / Ni,  where: a, b, c, d - mass. %, a + b + c + d = 100%,  0 <a <5,  10 <Z> <95,  2 <s <88,  2 <</ <66,  Ms - metal of the platinum group;  PO - perovskite-like or fluorite-like oxide with high oxygen mobility; where: PO: 1) perovskite-like oxide Ln ' _x Ln ² i _-x M ¹ M ² i. _y 0 _3-5 , where: Ln ¹ and Ln ² - La, Sm, Pr, Ce, Gd, x - 0 - 1; M ¹ and M ² = Mn, Fe, Ru, Co, Cr, Ni, y = 0 - 1; 2) fluorite-like oxide _{Ln'xLn ^ .iCe y Zx y .iO ^} Lni and Ln = ₂ La, Sm, Pr, Gd, x = 0 - 1, y = 0.1 - 0.9, x + (x - 1) + y + (y - 1) = 1;  JO is an oxide additive having high dispersion and / or good thermal stability and / or high oxygen mobility; Ni is an active component that can be introduced into the volume of a perovskite-like or fluorite-like oxide in the synthesis stage, when a polymer oxide precursor is formed or can be represented in a niocomposite catalyst as an individual phase of nickel Ni or nickel oxide NiO, impregnated or other method. 2. The catalyst according to claim 1, characterized in that the content of the active component of Nickel is from 1 to 60 wt.%.  3. The catalyst according to claim 1, characterized in that the metal content of the platinum group Pt and / or Ru is from 0 to 5 wt.%; 4. The catalyst according to claim 1, characterized in that the oxide additive contains oxide Al ₂ 0 ₃ or Ce _x Gdi _-x 0 ₂ , or Zr _y Yi_ _y 0 ₂ , where: x = 0.5 - 0.95, y = 0.70 - 0.95 in an amount of from 2 to 88 wt.%.  5. The catalyst according to claim 1, characterized in that it contains a perovskite-like or fluorite-like oxide with high oxygen mobility; in an amount of from 10 to 95 wt.%. "  6. The catalyst according to claim 1, characterized in that it can be used as an active component for the manufacture of structured catalysts on heat-conducting media with a catalyst content until May 10. %