RU2248932C1 - Catalyst (options), method for preparation thereof (options) and synthesis gas generation method (option) - Google Patents

Abstract

FIELD: alternate fuel manufacture catalysts.

SUBSTANCE: invention relates to generation of synthesis gas employed in large-scale chemical processes such as synthesis of ammonia, methanol, higher alcohols and aldehydes, in Fischer-Tropsch process, and the like, as reducing gas in ferrous and nonferrous metallurgy, metalworking, and on gas emission detoxification plants. Synthesis gas is obtained via catalytic conversion of mixture containing hydrocarbon or hydrocarbon mixture and oxygen-containing component. Catalyst is a complex composite containing mixed oxide, simple oxide, transition and/or precious element. Catalyst comprises metal-based carrier representing either layered ceramics-metal material containing nonporous or low-porosity oxide coating, ratio of thickness of metallic base to that of above-mentioned oxide coating ranging from 10:1 to 1:5, or ceramics-metal material containing nonporous or low-porosity oxide coating and high-porosity oxide layer, ratio of thickness of metallic base to that of nonporous or low-porosity oxide coating ranging from 10:1 to 1:5 and ratio of metallic base thickness to that of high-porosity oxide layer from 1:10 to 1:5. Catalyst is prepared by applying active components onto carrier followed by drying and calcination.

EFFECT: increased heat resistance and efficiency of catalyst at short contact thereof with reaction mixture.

13 cl, 2 tbl, 17 ex

Description

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

Synthesis gas (a mixture of hydrogen and carbon monoxide) is widely used in large-capacity chemical processes, such as the synthesis of ammonia, methanol, higher alcohols and aldehydes, in the Fischer-Tropsch process, etc. Synthesis gas is used as a reducing gas in ferrous and non-ferrous metallurgy , metalworking, used in environmental installations for the neutralization of gas emissions. Promising and extremely rapidly developing new areas for the use of synthesis gas and the hydrogen produced from it are motor vehicles and small-scale energy. In the automotive industry, synthesis gas or hydrogen can be used as an additive to the main fuel in internal combustion engines or as fuel for an engine based on fuel cells. In the energy sector, synthesis gas and hydrogen can be used in combination with fuel cells or gas turbines to produce environmentally friendly heat and energy.

The traditional method of producing synthesis gas is the endothermic process of steam conversion of natural gas on nickel catalysts [J.R. Rostrup-Nielsen, Production of synthesis gas, Catalysis Today, 1993, v. 28, 305-324; B.C. Arutyunov, O.B. Krylov. Oxidative transformations of methane. Moscow: Nauka, 1998]. This process is characterized by extremely high capital intensity, high operating costs and significant emissions of nitrogen oxides during torch heating of tubular reformers.

An alternative method for producing synthesis gas is selective catalytic oxidation of hydrocarbons by oxygen (RMS) [SCTsang, JBClaridge and MLH Green, Recent advances in the conversion of methane to synthesis gas, Catalysis Today, 1995, v.23, 3-15]. In contrast to steam conversion of natural gas, RMS has a high selectivity, is an exothermic process, and proceeds efficiently at short contact times, which makes it possible to conduct it in an autothermal mode and reduce the reactor size [DAHickman, LDSchmidt, Synthesis gas formation by direct oxidation of methane, in "Catalytic Selective Oxidation", ACS Symposium series, 1993, p. 416-426; PMTomiainen, X. Chu and LDSchmidt, 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 and capital expenditures attachments. Carrying out simultaneously the exothermal reaction of standard deviation and endothermic steam conversion of natural gas on one catalyst allows the process of obtaining mixtures of hydrogen and carbon monoxide enriched with hydrogen in autothermal mode [JWJenkins and E. Shutt, The Hot Spot ^TM Reactor, Platinum Metals Review, 1989, 33 (3), 118-127].

The selectivity of the RMS reaction in relation to the target products (carbon monoxide and hydrogen) depends on various factors, however, the chemical composition of the active component is most important. Study of the methane RMSE process in a pilot installation on a block catalyst containing Pt-Pd [J.K. Hoshmuth, Catalytic partial oxidation of methane over monolith supported catalyst, Appl. Catal., B: Environmental, v.l (1992) 89], showed that complete oxidation of methane occurs in the frontal layer of the block, and steam and carbon dioxide conversion of methane in subsequent layers, as a result of which a large temperature gradient is observed along the length of the block. Thus, in order to obtain maximum yields of the target product — synthesis gas — the catalyst must contain an active component that provides high activity in the conversion and SCO reactions.

To carry out the RMS process at short contact times of ~ 10 ^-2 s, Pt-Rh meshes or 10 wt.% Rh / block carrier are used, which is very expensive and economically disadvantageous [DAHickman, LDSchmidt, Synthesis gas formation by direct oxidation of methane, in " Catalytic Selective Oxidation ", ACS Symposium series, 1993, p. 416-426. PMTomiainen, X. Chu and LDSchmidt, 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 9948805, C 01 B 3/40, 09/30/00] by means of the standard deviation and steam conversion of hydrocarbons on one catalyst in an autothermal mode: steam conversion is carried out by introducing steam into a mixture of hydrocarbon and oxygen-containing gas after it has begun the RMS process and the autothermal mode was established. Rhodium supported on a heat-resistant carrier containing a mixture of cerium and zirconium oxides with a Ce / Zr weight ratio of 0.05 to 19 is used as a catalyst.

The known method of the RMS of methane for producing carbon monoxide and hydrogen [US 5149464, 01 B 3/26, 1992] at a temperature of 650-900 ° C and a space velocity of 40,000-80000 h ^-1 (0.05-0.09 s) the presence of a catalyst, which is either a transition metal or its oxide supported on a thermostable oxide of one of the elements (M): Mg, B, Al, Ln, Ga, Si, Ti, Zr, Hf, or a perovskite-like mixed oxide of the general formula M _x M ′ _y O _z with a pyrochlore structure, where M’ is a transition metal, including elements of group 8. The atomic ratio of the element of group 8 to the sum of the base metals in these compounds is 1: 1 or 3: 1, and the content of precious metals is 32.9-48 wt.%. The methane conversion in the presence of mixed oxides Pr ₂ Ru ₂ 0 ₇ , Eu ₂ Ir ₂ O ₇ , La ₂ MgPtO ₆ , at a space velocity of 40,000 h ^-1 and 777 ° C does not exceed 94%, and an increase in the space velocity to 80,000 h ^-1 leads to a decrease in methane conversion to 73% and selectivity for CO and hydrogen to 82 and 90%, respectively.

In the European patent [EP 303438, C 01 B 3/38, 02/15/89] to obtain a mixture of hydrogen and carbon monoxide, a method of RMS of hydrocarbons is proposed by contacting a reaction mixture containing a hydrocarbon, oxygen or an oxygen-containing gas and, optionally, water vapor, with a catalyst in the zone of selective catalytic oxidation. The SKO zone contains a catalyst with a geometric surface / volume ratio of at least 5 cm ² / cm ³ . The catalyst may contain noble metals, nickel, cobalt, chromium, cerium, lanthanum and a mixture thereof deposited on a heat-resistant oxide carrier, including cordierite, mullite, aluminum titanate, zirconium spinel, aluminum oxide. At the same time, in patent EP No. 303438 it is stated that the partial oxidation reaction rate is limited by the mass transfer rate and does not depend on the chemical nature of the catalyst, which makes it possible in this case to use materials that do not exhibit catalytic activity but provide the necessary geometric surface / volume ratio. The process is carried out at temperatures in the range of 760-1090 ° C and a space velocity from 20,000 to 500,000 h ^-1 .

In the patents [RU 2115617, C 01 B 3/38, 07/20/98; RU 2136581, C 01 B 3/38, 09/10/99; RU 2137702, C 01 B 3/38, 09/20/99; RU 2123471, C 01 B 3/38, 12.20.98; US 5486313, C 07 C 1/02 01/23/1996 and US 5639401, C 07 C 1/02, 06/17/97] offer a method of standard deviation of hydrocarbons, including sulfur-containing (0.05-100 ppm) [RU 2132299, C 01 B 3/38, 06/27/99; US 5720901, C 07 C 1/02, 04.24.98] into synthesis gas using catalysts containing noble metals (up to 10 wt.% Pt, Pd, Rh, Os) supported on a heat-resistant carrier. As carriers, for example, α-Al ₂ O ₃ , barium hexaaluminate (grain size ~ 1 mm) or ZrO ₂ thermally stabilized by oxides of elements of groups III B or II A of the Periodic Table (porous blocks in the form of ceramic foam, resistant to thermal shock) are used. The process is carried out in a reactor with a fixed catalyst bed having a large tortuosity - the ratio of the gas path length when passing through the block to its length is in the range of 1.1-10 at temperatures of 950-1300 ° C and the gas mixture flow rate is 2-10 ⁴ -10 ⁸ l / kg-h The disadvantages of this method are the high hydraulic resistance of the catalyst layer with high tortuosity and the high cost of the catalysts due to the high content of precious metals and the use of expensive zirconium-based ceramic foam, which limits their practical application.

A known process for producing synthesis gas [US 5989457, C 07 C 1/02, 11/23/99] by the interaction of methane or hydrocarbons or a mixture thereof with carbon dioxide in the presence of a catalyst containing from 0.1 to 7 wt.% Pt, Ni, Pd or Co on a heat-resistant carrier, which includes at least 80 wt.% ZrO ₂ and at least 0.5-10 mol.% Of one of the oxides Y, La, A1, Ca, Ce or Sc. The process is carried out on a catalyst with a grain size of 0.3-0.6 mm at 700-800 ° C and a volumetric flow rate of 12750 h ^-1 . Under these conditions, the methane conversion is ~ 60-70%, and the CO yield is ~ 30%.

There is also a method of producing a mixture of hydrogen and carbon monoxide [US 5500149, C 07 C 1/02, 03/19/96] by contact of a mixture containing methane, oxygen and CO ₂ at temperatures of 600-1000 ° C and a space velocity of ~ 5000-20000 h ^-1 with a solid catalyst in the form of grains ~ 0.3 mm, corresponding to the following formula: M _x M ′ _y O _z or M _x O _z or M _y O _z on a heat-resistant carrier, where M and M ′ represent a wide range of alkaline , alkaline earth, transitional and other elements. The proposed catalysts are effective both in the carbon dioxide conversion of methane and in a combination of the reactions of selective catalytic oxidation and carbon dioxide conversion of methane. Varying the composition of the reaction mixture allows you to vary the composition of the resulting synthesis gas and adjust the heat balance of the process.

In the patent [US 5741440, C 01 B 3/38, 04/21/98] a method for producing a mixture of hydrogen and carbon monoxide by contacting a 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 (Al ₂ O ₃ , MgO) at temperatures of 650-1450 ° C. Replacing at least part of the water vapor with hydrogen in the initial mixture allows to increase the amount of synthesis gas and reduce the content of carbon dioxide in the final gas, and varying the composition of the initial mixture to obtain a mixture of hydrogen and carbon monoxide with a H ₂ / CO ratio of 0.7 up to 3. Note that for mixtures without water to produce synthesis gas, with H ₂ / СО≥2), a high concentration of hydrogen in the initial mixture is required, which increases the cost of producing the final product.

In the patent [US 5855815, C 07 C 1/02, 05.01.99], it is proposed to produce synthesis gas by reducing carbon dioxide with a mixture of natural gas, oxygen and steam in the presence of a catalyst containing nickel and promoters - alkaline or alkaline earth elements deposited on a silicon-containing a carrier such as silica gel, silicate, aluminosilicate or zeolite (pentasil). The last carrier has a surface of 300 to 600 m ² / g. The process is carried out at 600-1000 ° C and a space velocity of 1000-500000 h ^-1 , the ratio of H ₂ / CO varies within 1 / 3-3 / 1.

Thus, to obtain synthesis gas, both the RMS process and its combination with endothermic hydrocarbon conversion processes are used for short contact times of the reaction mixture with the catalyst, which must meet stringent requirements: have low hydraulic resistance, high thermal conductivity, which promotes heat transfer necessary for the efficient occurrence of slow conversion reactions along the length of the catalytic layer, to ensure high hydrocarbon conversions and selectivity for synthesis gas and at Do not deactivate due to the formation of carbon on the surface.

It is known that the use of catalysts in the form of metal grids, foil, plates, foam metal, etc. can significantly improve the thermal conductivity of the catalytic layer and at the same time increase the stability of the catalysts to thermal shocks compared to catalysts based on ceramic supports.

A known method of producing synthesis gas by oxidative conversion of hydrocarbons using reduced block catalysts based on massive Ni-Cr, Ni-Co-Cr or Ni-Rh alloys [WO 0151411, C 01 B 3/38, 07/19/2001, WO 0151413 C 01 B 3/40, 07/19/2001, WO 0151414, C 01 B 3/40, 07/19/2001]. A method of preparing such catalysts involves vacuum deposition of perforated nickel foil of metal particles of Ni, Cr, Co or Rh, followed by high-temperature treatment (1200-1300 ° C) in a non-oxidizing atmosphere. As a result of the diffusion of metal atoms into the substrate lattice, bulk alloys are formed in the form of thin disks. Blocks are formed from the resulting disks. A set of disks of alloys of various compositions allows you to form blocks with the composition and concentration of metals, varying along the length of the block. The claimed catalysts based on Ni-Cr alloy at 1055 ° C and a flow rate of 7.5 l / min in a mixture of 60% CH ₄ , 30% O ₂ , 10% N ₂ provide methane conversion of 77%, selectivity of 99% (CO) and 92% (H ₂ ). However, in the applications there is no data on the stability of the catalysts during long-term tests, at the same time it is well known that nickel-based catalysts in the oxygen conversion of methane are carbonized and lose activity [BCArutyunov. O.V. Krylov. Oxidative transformations of methane. M .: Nauka, 1998. P.362].

The closest to the claimed technical essence and the achieved effect is the RMS method for producing synthesis gas in the presence of a mixed oxide catalyst with a perovskite structure M ¹ B _{1 y} M _y O _z and / or fluorite M $\genfrac{}{}{0ex}{}{\text{one}}{\text{x}}$ M $\genfrac{}{}{0ex}{}{\text{2}}{\text{1-x}}$ O _z , where: M is an element of group 8 (Pt, Rh, Ir), M ¹ is a rare-earth element (La, Ce, Nd) or alkaline earth (Ca, Sr), M ² is an element of group IV b of a group (Zr, Hf ), B is a transition element (Ni, Co), which is a complex composite containing components with an ultra-low coefficient of thermal expansion [Pat. RF 2204434, B 01 J 23/40, 05.20.2003]. At temperatures of 600-800 ° C and contact times of 0.1-0.4 s, high methane conversions and synthesis gas selectivity are achieved. However, the catalyst is a ceramic composite with low thermal conductivity, which causes the formation of local overheating in the catalyst layer and impedes the transfer of heat released in the frontal part of the layer during the course of oxidative transformations of hydrocarbons, further along the length of the block and prevents its effective use for carrying out steam and carbon dioxide conversion reactions .

The invention solves the problem of creating a thermostable catalyst with high thermal conductivity to produce synthesis gas effective at short contact times both in the reactions of selective catalytic oxidation of hydrocarbons with oxygen and in steam and carbon dioxide conversion of hydrocarbons, and the process for producing synthesis gas using this catalyst. The high thermal conductivity of the catalyst provides heat transfer along the catalytic layer and contributes to the effective occurrence of endothermic steam and carbon dioxide conversion reactions.

The problem is solved by developing a catalyst, which is a composite composite containing mixed oxides with a perovskite or fluorite structure, a simple oxide and transition and / or noble metals, and including a metal-based support, which is a layered ceramic material containing non-porous or slightly porous or non-porous or low-porous and porous oxide coating, and the implementation of the catalytic conversion of a mixture containing a hydrocarbon or a mixture of hydrocarbons and an oxygen-containing gas a mixture of oxygen-containing gas in the presence of this catalyst. The use of a layered composite, including a metal carrier, provides high thermal conductivity of the catalyst, while maintaining high hydrocarbon conversion and selectivity for synthesis gas, thermal stability of the catalyst, and its carbonization is absent.

The problem is solved by the development of a catalyst (the first option), which is a composite composite containing a mixed oxide, a simple oxide, a transition and / or a noble element, the composite composite contains a metal-based support, which is a layered ceramic material containing a non-porous or low-porous oxide coating, this ratio of the thickness of the metal base to the thickness of the non-porous or low-porous oxide coating is 10: 1-1: 5. Porosity is not more than 10%.

The catalyst contains in its composition, wt.%:

mixed oxide - not less than 1.0,

a simple oxide, for example Al ₂ O ₃ , ZrO ₂ , not more than 10.0,

transition element and / or noble element - not more than 10.0,

metal-based carrier - the rest.

The mixed oxide may be an oxide with a perovskite structure M ¹ B _1-y M _y O _z and / or an oxide with a fluorite structure M ¹ M $\genfrac{}{}{0ex}{}{\text{2}}{\text{1 x}}$ O _z , where:

M is an element of group 8, for example, Pt, Rh, Ir, Ru,

M ¹ is a rare earth element, for example La, Ce, Nd or an alkaline earth element, for example Ca, Sr,

M ² - element IV b of the group of the Periodic system, for example, Zr, Hf,

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

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, for example Ni, Co, and / or a noble element is a metal of group 8, for example Pt, Rh, Ir, Ru.

The catalyst may be a block with direct channels, including microchannel, in the form of a prism or in the form of a cylinder with a base in the form of a circle or ellipse.

The problem is also solved by the method of preparation of the catalyst described above on the basis of a mixed oxide, a simple oxide, a transition and / or a noble element, which consists in the fact that the active components are applied to a carrier, which is a layered ceramic material containing a non-porous or low-porous oxide coating, while the ratio of the thickness of the metal base to the thickness of the non-porous or low-porous oxide coating is 10: 1-1: 5.

The problem is also solved by a catalyst (the second option), which is a composite composite and contains a mixed oxide, a simple oxide, a transition and / or a noble element, the composite composite contains a metal-based support, which is a layered ceramic material containing a non-porous or low-porous oxide coating and highly porous an oxide layer, the ratio of the thickness of the metal base to the thickness of the non-porous or low-porous oxide coating is 10: 1-1: 5, and the ratio of the thickness of the metal th base to the thickness of the highly porous layer is 1: 10-1: 5.

The catalyst contains in its composition, wt.%:

mixed oxide - not less than 1.0,

a simple oxide, for example Al ₂ O ₃ , ZrO ₂ , not more than 10.0,

transition element and / or noble element - not more than 10.0,

metal-based carrier - the rest.

The mixed oxide may be an oxide with a perovskite structure M ¹ B _1-y M _at O _z and / or an oxide with a fluorite structure M $\genfrac{}{}{0ex}{}{\text{one}}{\text{x}}$ M $\genfrac{}{}{0ex}{}{\text{2}}{\text{1 x}}$ O _z , where:

M is an element of group 8, for example, Pt, Rh, Ir, Ru,

M ¹ is a rare earth element, for example La, Ce, Nd, or an alkaline earth element, for example Ca, Sr,

M ² - element IV b of the group of the Periodic system, for example Zr, Hf,

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

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, for example Ni, Co, and / or a noble element is a metal of group 8, for example, Pt, Rh, Ir, Ru.

The catalyst may be a block with direct channels, including microchannel, in the form of a prism or in the form of a cylinder with a base in the form of a circle or ellipse.

The problem is also solved by the method of preparing the catalyst described above on the basis of a mixed oxide, a simple oxide, a transition and / or a noble element, which consists in the fact that the active components are applied to a carrier, which is a layered ceramic material containing a non-porous or low-porous oxide coating and a highly porous oxide layer, while the ratio of the thickness of the metal base to the thickness of the non-porous or low-porous oxide coating is 10: 1-1: 5, and the ratio of the thickness of the metal base to the thickness of the highly porous layer is 1: 10-1: 5.

The problem is also solved by a method for producing synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or a mixture of hydrocarbons and an oxygen-containing component using the above-described catalyst based on a mixed oxide, a simple oxide, a transition and / or a noble element. The catalyst contains in its composition, wt.%:

mixed oxide - not less than 1.0,

a simple oxide, for example Al ₂ O ₃ , ZrO ₂ , not more than 10.0,

transition element and / or noble element - not more than 10.0,

metal-based carrier - the rest.

The mixed oxide is an oxide with a perovskite structure M ¹ B _{1 y} M _y O _z and / or an oxide with a fluorite structure M $\genfrac{}{}{0ex}{}{\text{one}}{\text{x}}$ M $\genfrac{}{}{0ex}{}{\text{2}}{\text{1 x}}$ O _z , where:

M is an element of group 8, for example, Pt, Rh, Ir, Ru,

M ¹ is a rare earth element, for example La, Ce, Nd or an alkaline earth element, for example Ca, Sr,

M ² - element IV b of the group of the Periodic system, for example Zr, Hf,

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

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

The catalyst also contains a transition element, for example Ni, Co and / or a noble element - a metal of group 8, for example Pt, Rh, Ir, Ru, which is not included in the structure of perovskite or fluorite.

The term "rare earth element" means elements belonging to the group of rare earth elements, including elements of group III b of the Periodic system and 4f elements, for example La, Ce, Nd.

The term alkaline earth element means elements of group II a of the Periodic system, for example, Sr, Ca.

The introduction of a metal-based support into the catalyst provides high thermal conductivity, while the layered structure of the support containing a non-porous or low-porous oxide layer with a porosity of not higher than 10%, on which a highly porous oxide layer is formed, provides high thermal stability of the catalyst.

The process is carried out by sequentially passing a gas mixture containing a hydrocarbon or a mixture of hydrocarbons and an oxygen-containing component with a temperature of 20-500 ° C through a fixed catalyst bed with high thermal conductivity, which makes it possible to efficiently use the heat of exothermic oxidation reactions for the occurrence of endothermic steam and carbon dioxide conversion reactions.

To obtain the required composition of a mixture of hydrogen and carbon monoxide, the composition of the initial mixture is varied. The initial mixture contains a hydrocarbon or a mixture of hydrocarbons and / or air, or CO ₂ , or steam, or a mixture thereof, the process is carried out at temperatures of 500-1100 ° C. As the hydrocarbon feed, for example, natural gas, methane, a propane-butane mixture, gasoline, kerosene, etc. are used. The oxygen-containing gas is oxygen, air, carbon dioxide, water.

The proposed catalysts are prepared in several stages. To obtain a non-porous or low-porous oxide layer having high thermal stability while maintaining high adhesion with a metal substrate, the method of detonation spraying is used [S. Barteniev, Yu.R. Fedko, A. I. Grigoryev Knock coatings in mechanical engineering. - L .: Engineering, 1982]. For deposition, simple oxides (for example, Al ₂ O ₃ , ZrO ₂ ) of high-temperature modifications are used. As the initial metal base, foil is used from heat-resistant or stainless steel, containing, in addition to iron, additives of nickel, chromium, etc. [Pat. RF 2106915, B 05 D 1/00, 08/01/95].

A non-porous (non-porous) ceramic oxide layer is applied to both sides of a smooth or corrugated foil, then blocks are formed from alternating layers of smooth and corrugated foil.

In the second stage of preparation, a porous oxide ceramic layer is formed, consisting of a mixture of simple oxides and / or mixed oxides, including rare earths, such as neodymium, praseodymium, lanthanum, cerium, or alkaline earths, such as calcium, strontium, and transition elements, such as hafnium, zirconium. This layer is applied by impregnating the block with a non-porous or low-porous coating with suspensions and / or solutions of the corresponding compounds, followed by drying and calcination. The non-porous or low-porous oxide layer contributes to the strong fixing of the highly porous layer. At the last stage of preparation, the active component, including a transition element and / or a noble metal, or a mixture thereof, and / or mixed oxides with a perovskite structure, is applied to the obtained layered carrier from solutions of the corresponding salts. The resulting catalysts are dried and calcined.

The synthesis gas production process is carried out in a flow reactor in an autothermal mode at a temperature of 550-1100 ° C, variation of the contact time and the composition of the reaction mixture. A reaction mixture containing natural gas or liquid hydrocarbon vapors such as octane, gasoline and, in some examples, water vapors in air is heated before entering the reactor. At the inlet and outlet of the reactor to prevent heat loss are placed screens - blocks of corundum. During the start-up and operation of the catalyst, the gas temperature at the inlet to the reactor, the temperature of the catalytic unit at the inlet, and the temperature at the outlet of the unit are controlled. The reaction products are analyzed chromatographically. The efficiency of the catalyst is characterized by the reaction start temperature, the degree of methane conversion, and the amount of synthesis gas obtained, expressed in volume percent and characterizing the synthesis gas selectivity. The composition of the initial reaction mixture and reaction products are analyzed chromatographically.

The invention is illustrated by the following examples.

Example 1. Illustrates the preparation of a carrier containing a non-porous or low-porous oxide coating with a ratio of the thickness of the metal base to the thickness of the non-porous or low-porous oxide coating of 5: 1. On both sides of a 200 μm thick smooth foil based on an FeCrAl alloy, a ceramic oxide layer of 20 μm alpha-alumina powder is applied by the known method of detonation spraying described above [Bartenev SS, Fedko Yu.R., Grigoryev AI Knock coatings in mechanical engineering. - L .: Engineering, 1982]. Similarly, the same layer is applied to the corrugated foil. Then alternating layers of smooth and corrugated foil are folded either into a spiral of Archimedes [Auth. St. USSR 1034762, B 01 J 37/00, 01/09/82], or put in parallel layers with subsequent fixing around the perimeter in a steel shell.

Example 2. Illustrates the preparation of a catalyst based on a carrier with a low porous coating. The block prepared as in example 1 is calcined at 700 ° C and impregnated with a mixed solution of cerium and zirconium salts. The block is purged with air to remove excess solution from the channels, dried and calcined at 900 ° C. If necessary, the impregnation procedure is repeated. The resulting sample is impregnated with a joint solution of H ₂ PtCl ₆ , lanthanum and nickel nitrates with an atomic ratio of cations La: Ni: Pt = 1: 0.994: 0.006, dried and calcined at 900 ° C. The resulting catalyst contains, wt.%: 4.5 mixed cerium oxide and zirconium with a fluorite structure, 2.1 perovskite composition LaNi _0,994 Pt _0,006 . The catalyst is tested in a flow reactor with the composition of the reaction mixture containing ~ 25% natural gas in air, the activity is shown in table 1.

Example 3. The catalyst is prepared as in example 2 except that a mixed solution of lanthanum nitrate and ruthenium chloride is used for impregnation. The resulting catalyst contains 4.5 wt.% Mixed cerium and zirconium oxide with a fluorite structure, 2.3 wt.% Mixed lanthanum oxide and ruthenium.

Example 4. The catalyst is prepared as in example 2 except that a mixed solution of lanthanum nitrate and nickel is used for impregnation. The resulting catalyst contains, wt.%: 4.5 mixed cerium oxide and zirconium with a fluorite structure, 2.3 perovskite composition LaNiO ₃ .

Example 5. The catalyst is prepared as in example 3 except that a mixed solution of cerium and calcium nitrate is used for impregnation. The resulting catalyst contains, wt.%: 5 mixed oxide of cerium and calcium with the structure of fluorite, 2,3 mixed oxide of lanthanum and ruthenium.

Example 6. A catalyst is prepared as in Example 2, except that a mixed solution of platinum chloride and ruthenium chloride is used for impregnation. The resulting catalyst contains, wt.%: 4.5 mixed cerium oxide and zirconium with a fluorite structure, 0.3 Pt and 1.0 Ru.

Example 7. Illustrates the preparation of a carrier containing a non-porous or low-porous oxide coating with a ratio of the thickness of the metal base to the thickness of the non-porous or low-porous oxide coating of 10: 1 and a highly porous oxide coating with the ratio of the thickness of the metal base to the thickness of the porous oxide coating 1: 1. A ceramic oxide layer of alpha-alumina powder 10 μm thick using a FeCrAl alloy is applied on both sides of a smooth foil with a thickness of 200 μm by detonation spraying, as in Example 1. In the same way, the same layer is applied to a corrugated foil. Then alternating layers of smooth and corrugated foil are rolled into a spiral of Archimedes, followed by fixing along the perimeter into a steel shell. After calcining at 700 ° C, a porous ceramic layer is applied to the resulting composite composite from both sides of the foil from a suspension containing particles of a mixed cerium and zirconium oxide in a solution of zirconyl nitrate and a surfactant (polyethylene oxide). The block is purged with air to remove the suspension from the channels, dried and calcined at 900 ° C. If necessary, the impregnation procedure is repeated.

Example 8. Illustrates the preparation of a catalyst based on a carrier containing a non-porous and highly porous coating. The block prepared as in Example 7 is impregnated with a mixed solution of H ₂ PtCl ₆ , lanthanum and nickel nitrates with an atomic cation ratio of La: Ni: Pt = 1: 0.994: 0.006. The block is purged with air to remove excess solution from the channels, dried and calcined at 900 ° C. The resulting catalyst contains, wt.%: 9 mixed cerium oxide and zirconium with a fluorite structure, 1.7 perovskite LaNi _0.994 PtO _0.006 . The tests are carried out as in example 2. The activity is shown in table 1.

Example 9. The catalyst is prepared as in example 7 except that a rhodium chloride solution is used for impregnation. The resulting catalyst contains, wt.%: 9 mixed cerium oxide and zirconium with a fluorite structure, 0.3 Rh. Tests are carried out as in pr. 2. Activity is shown in table 1.

Example 10. The catalyst is prepared as in example 7 except that a mixed solution of lanthanum nitrate and ruthenium chloride is used for impregnation. The resulting catalyst contains, wt.%: 10.9 mixed cerium and zirconium oxide with a fluorite structure, 1.2 mixed lanthanum oxide and ruthenium.

Example 11. A carrier is prepared as in Example 7 except that a suspension containing particles of mixed zirconium oxide and calcium particles is used for impregnation.

Example 12. The catalyst is prepared by impregnating the support of Example 11 with a mixed solution of H ₂ PtCl ₆ , lanthanum and nickel nitrates with an atomic ratio of La: Ni: Pt = 1: 0.994: 0.006. The resulting catalyst contains, wt.%: 9 mixed calcium oxide and zirconium with a fluorite structure, 1.7 perovskite LaNiO _0.994 PtO _0.006 .

Example 13. The catalyst prepared as in example 8 is impregnated with a mixed solution of lanthanum nitrate and ruthenium chloride, purged with air, dried and calcined. The tests are carried out as in example 2.

Example 14. The catalyst prepared as in example 13 is tested in the oxidative conversion reaction of octane. The reaction parameters and catalyst activity are shown in table 2.

Example 15. The catalyst prepared as in example 9, is tested in the reaction of steam-air conversion of octane. The reaction parameters and catalyst activity are shown in table 2.

Example 16. The catalyst prepared as in example 13 is tested in the oxidative conversion reaction of gasoline. The reaction parameters and catalyst activity are shown in table 2.

Example 17. The catalyst prepared as in example 13, is tested in the reaction of steam-air conversion of gasoline. The reaction parameters and catalyst activity are shown in table 2.

As can be seen from the above examples and tables, a thermostable catalyst has been developed for the production of synthesis gas, which ensures the effective occurrence of selective catalytic oxidation reactions and steam conversion of hydrocarbons at short contact times.

Table 1.
The activity of catalysts in the reaction of selective oxidation of methane. Concentration of methane in air ~ 24 vol.% In air
Example Block length, mm T at start ° C T at the block inlet ° C T at the block outlet ° C Contact time, sec. Methane Conversion, X% The content of CO + H ₂ , vol.% 2 fifty 630 - - 0.12 93 53 8 92 460 - - 0.175 93 55 nine fifty 510 - - 0,093 93 53 thirteen twenty 330 1030 776 0,087 80 50,4

Table 2.
The activity of catalysts in oxidative and autothermal (steam-air) reforming of hydrocarbons. Options Examples 14 fifteen 16* 17 * Isoctane (* gasoline), kg / h
Air, m ³ / h
Water, kg / h 0.757
3.00
- 0.757
3.00
0.735 0.893
3,58
- 0.757
3,58
1.14 Total flow, nm ³ / h 3.15 4.1 3.75 5.17 O ₂ / C
H ₂ O / C 0.53
- 0.53
0.8 0.53
- 0.53
1,0 Inlet gas temperature, ° С 205 265 220 280 Contact time, s 0.105 0,081 0,092 0,064 Block inlet temperature, ° С 1033-1067 985-957 1185-1085 1063-1058 Block outlet temperature, ° С 903-951 913-892 1087-1076 1001-1003 The composition of the synthesis gas: vol.%
N₂
With 26-28.1
22.2-24.8 31-31.6
19.2-17.7 22.2-22.8
26.3-27.1 27.5
17.4 The content of synthesis gas,% vol. 48.2-52.9 49.3-50.2 48.5-49.9 44.9

Claims (13)

1. The catalyst for producing synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and an oxygen-containing component, which is a composite composite containing a mixed oxide, a simple oxide, a transition and / or a noble element, characterized in that the composite composite includes a carrier on a metal base, which is a layered ceramic material containing a non-porous or low-porous oxide coating, while the ratio of the thickness of the metal base to schine nonporous or low-porosity of the oxide coating is 10: 1-1: 5. 2. The catalyst according to claim 1, characterized in that it contains in its composition, wt.%: Mixed oxide Min. 1.0 Simple oxide, for example, Al ₂ O ₃ , ZrO ₂ Not more than 10.0 Transitional element and / or noble element Not more than 10.0 Metal-based media 3. The catalyst according to claim 1, characterized in that the mixed oxide is an oxide with a perovskite structure M ¹ B _1-y M _at O _z and / or an oxide with a fluorite structure M $\genfrac{}{}{0ex}{}{\text{one}}{\text{x}}$ M $\genfrac{}{}{0ex}{}{\text{2}}{\text{1 x}}$ O _z , where M is an element of group 8, for example, Pt, Rh, Ir, Ru; M ¹ is a rare earth element, for example, La, Ce, Nd or an alkaline earth element, for example, Ca, Sr; M ² - element IV b of the group of the Periodic system, for example, Zr, Hf; B - transition element - 3d elements of the 4th period, for example, Ni, Co; 0.01 <x <1, 0≤y <1, z is determined by the oxidation state of the cations and their stoichiometric ratio. 4. The catalyst according to claim 1, characterized in that it contains a transition element, for example, Ni, Co and / or a noble element - a metal of group 8, for example, Pt, Rh, Ir, Ru. 5. The catalyst according to claim 1, characterized in that it is a block with direct channels, including microchannel, in the form of a prism or in the form of a cylinder with a base in the form of a circle or ellipse. 6. A method of preparing a catalyst for producing synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or a mixture of hydrocarbons and an oxygen-containing component based on a mixed oxide, a simple oxide, a transition and / or a noble element, characterized in that the active components are applied to a carrier, which is layered a ceramic material containing a non-porous or low-porous oxide coating, wherein the ratio of the thickness of the metal base to the thickness of the non-porous or low-porous oxide coating is 10: 1-1: 5, and then dried and calcined to give a catalyst according to any one of claims 1-5. 7. A catalyst for producing synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and an oxygen-containing component that is a composite composite and contains a mixed oxide, a simple oxide, a transition and / or a noble element, characterized in that the composite composite includes a carrier on a metal base, which is a layered ceramic material containing a non-porous or low-porous oxide coating and a highly porous oxide layer, the ratio of ins metal substrate to the thickness of nonporous or low-porosity of the oxide coating is 10: 1-1: 5 and the ratio of the thickness of the metal substrate to the thickness of a highly porous layer is 1: 10-1: 5. 8. The catalyst according to claim 7, characterized in that it contains in its composition, wt.%: Mixed oxide Min. 1.0 Simple oxide, for example, Al ₂ O ₃ , ZrO ₂ Not more than 10.0 Transitional element and / or noble element Not more than 10.0 Metal-based media 9. The catalyst according to claim 7, characterized in that the mixed oxide is an oxide with a perovskite structure M ¹ B _1-y M _at O _z and / or an oxide with a fluorite structure M ¹ M _1-x O _z , where M is an element of group 8, for example, Pt, Rh, Ir, Ru; M ¹ is a rare earth element, for example, La, Ce, Nd or an alkaline earth element, for example, Ca, Sr; M ² - element IV b of the group of the Periodic system, for example, Zr, Hf; B - transition element - 3d elements of the 4th period, for example, Ni, Co; 0.01 <x <1, 0≤y <1, z is determined by the oxidation state of the cations and their stoichiometric ratio. 10. The catalyst according to claim 7, characterized in that it contains a transition element, for example, Ni, Co and / or a noble element - a metal of group 8, for example, Pt, Rh, Ir, Ru. 11. The catalyst according to claim 7, characterized in that it is a block with direct channels, including microchannel, in the form of a prism or in the form of a cylinder with a base in the form of a circle or ellipse. 12. A method of preparing a catalyst for producing synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and an oxygen-containing component based on a mixed oxide, a simple oxide, a transition and / or a noble element, characterized in that the active components are applied to a carrier, which is layered a ceramic material containing a non-porous or low-porous oxide coating and a highly porous oxide layer, wherein the ratio of the thickness of the metal base to the thickness e non-porous or low-porous oxide coating is 10: 1-1: 5, and the ratio of the thickness of the metal base to the thickness of the highly porous layer is 1: 10-1: 5, then dried and calcined, the catalyst is obtained according to any one of claims 7-11 . 13. A method of producing synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and an oxygen-containing component using a catalyst based on a mixed oxide, a simple oxide, a transition and / or a noble element, characterized in that the process is carried out in the presence of a catalyst according to any from claims 1-12.