Catalyst (options), method for preparation thereof (options) and synthesis gas generation method (option)

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

 

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

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

The traditional way to produce synthesis gas is an endothermic process steam reforming of natural gas Nickel catalysts [J.R.Rostrup-Nielsen, Production of synthesis gas, Catalysis Today, 1993, v.l8, 05-324; Usanational, Overruled. Oxidative conversion of methane. Moscow: Nauka, 1998]. This process is characterized by extremely high capital costs, high operating costs and significant emissions of nitrogen oxides when the flare heating a tubular reformer.

An alternative way to produce synthesis gas - selective catalytic oxidation of hydrocarbons with oxygen (RMS) [S.C.Tsang, J.B.Claridge and M.L.H.Green, Recent advances in the conversion of methane to synthesis gas, Catalysis Today, 1995, V.23 supported, 3-15]. In contrast to steam reforming of natural gas RMS has greater selectivity, is an exothermic process and proceeds effectively at low contact times, thereby enabling it in autothermal mode and reduce the size of the reactor [D.A.Hickman, L.D.Schmidt, Synthesis gas formation by direct oxidation of methane in Catalytic Selective Oxidation", ACS Symposium series, 1993, p.416-426; P.M.Tomiainen, X.Chu and L.D.Schmidt, Comparison of monolith-supported metals for the direct oxidation of methane to syngas, J.Catal., 1994, v.146, 1-10] and, thereby, reducing both energy consumption and capital investment. 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 selectivity of the reaction is TO the target products (carbon monoxide and hydrogen) depends on various factors, however, the most important is the chemical composition of the active component. The study process RMSE of methane in the pilot installation on modular catalyst containing Pt-Pd [J..Hoshmuth, Catalytic partial oxidation of methane over monolith supported catalyst, Appl. Catal., B: Environmental, v.l (1992) 89]showed that in the front layer unit runs the full oxidation of methane, and in subsequent layers of steam and carbon dioxide conversion of methane, resulting in the length of the block there is a large temperature gradient. Thus, to obtain maximum yields of the target product is synthesis gas, the catalyst should contain the active ingredient, providing high activity in reactions of conversion and SKO.

For carrying out process RMS at low contact times of ~10-2c using Pt-Rh grid or 10 wt.% 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.Tomiainen, 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 9948805, 01 3/40, 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. the quality of the rhodium catalyst is used, put on 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 650-900°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 mixed oxide of the General formula MxM′yOzwith the structure of pyrochlore, where M′-transition metal, including elements in 8 groups. The atomic ratio of the element 8 to the sum of the base elements in these compounds is 1:1 or 3:1, and the noble metal content is 32,9-48 wt.%. The conversion of methane in the presence of mixed oxides Pr2EN207, Eu2Ir2O7La2MgPtO6when flow rate 40000 h-1and 777°C is less than 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 KIS is oradatabase gas and optionally, the water vapor with the catalyst in the zone selective catalytic oxidation. Area SKO contains the catalyst with the ratio of geometric surface/volume is not less than 5 cm2/cm3. The catalyst may contain noble metals, Nickel, cobalt, chromium, cerium, lanthanum and the mixture is deposited on a heat-resistant oxide media, including cordierite, mullite, aluminum titanate, Zirconia spinel, alumina. At the same time, in the patent EP No. 303438 argue that the speed of reaction of partial oxidation is limited by the rate of mass transfer and does not depend on the chemical nature of the catalyst, which allows in this case to use materials does not exhibit catalytic activity, but providing the necessary ratio of geometric surface/volume. The process is carried out at temperatures in the range 760-1090°and volume rate of from 20000 to 500000 h-1.

In patents [EN 2115617, 01 3/38, 20.07.98; EN 2136581, C 01 B 3/38, 10.09.99; EN 2137702, C 01 B 3/38, 20.09.99; EN 2123471, C 01 B 3/38, 20.12.98; US 5486313, C 07 C 1/02 23.01.1996 and US 5639401, C 07 C 1/02, 17.06.97] offer a way SKO hydrocarbons, including serosoderjaschei (0.05 to 100 ppm) [EN 2132299, C 01 B 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 950-1300°and flow rate of the gas mixture 2 to 104-108l/kg-h the Disadvantages of this method are the large hydraulic resistance of the catalyst layer with high tortuosity and high cost of the catalysts due to the high content of noble metals and used as media of expensive foam ceramics based on zirconium, limiting their practical application.

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.% Zr2and at least 0.5 to 10 mol.% one of the oxides of Y, La, A1, CA, CE, or Sc. The process is performed on the catalyst with a grain size of 0.3-0.6 mm at 700-800°and volumetric flow rate 12750 h-1. Under these conditions, the type field, the Oia 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 600-1000°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′yOzor MxOzor M′yOzon 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. The variation of the composition of the reaction mixture can vary the composition of the produced synthesis gas and to regulate the heat balance of 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 650-1450°C. 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 of plastics technology : turning & the Yes in the end 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 N2/WITH≥2)require 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 a silicon-containing media, such as silica gel, silicate, aluminosilicate or zeolite (pentacel). Recent media has a surface of 300 to 600 m2/, the Process is carried out at 600-1000°and flow rate 1000-500000 h-1the ratio of N2/WITH changes in the range of 1/3-3/1.

Thus, to obtain the synthesis gas used as 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 conductivity, facilitating the transfer of heat necessary for the effective behavior of the slow reactions of conversion, the length kataliticheskoj the layer, to ensure a high conversion of hydrocarbons and selectivity for synthesis gas and not deactivated due to the formation of carbon on the surface.

It is known that the use of catalysts in the form of a metal mesh, foil, plates, nanostructural catalyst, etc. can significantly improve thermal conductivity of the catalyst layer and simultaneously to increase the stability of the catalysts to thermal shock compared with catalysts based on ceramic carriers.

A known method for production of synthesis gas by oxidative conversion of hydrocarbons using the reconstructed block based catalysts massive Ni-Cr, Ni-Co-Cr or Ni-Rh alloys [WO 0151411, C 01 B 3/38, 19.07.2001, WO 0151413 C 01 B 3/40, 19.07.2001, WO 0151414, C 01 B 3/40, 19.07.2001]. The method of preparation of such catalysts include vacuum deposition on a perforated Nickel foil metal particles of Ni, Cr, Co or Rh with subsequent high temperature processing (1200-1300° (C) in a non-oxidizing atmosphere. As a result of diffusion of metal atoms into the lattice of the substrate are formed of bulk alloys in the form of thin disks. The blocks are formed from the obtained disks. The set of disks from alloys of different composition allows you to create 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°and soon the STI flow 7.5 l/min in a mixture of 60% SN 4, 30% O210% of N2provide a methane conversion of 77%, a selectivity of 99% (CO) and 92% (H2). However, in applications there are no data on the stability of the catalysts with long-term tests at the same time, it is well known that catalysts based on Nickel in oxygen methane conversion nauglerozhivatelya and lose activity [Usanational. Overruled. Oxidative conversion of methane. M.: Nauka, 1998. S].

Closest to the claimed technical essence and the achieved effect is the way RMS to produce synthesis gas in the presence of a catalyst based on mixed oxides with perovskite structure M1B1-yMyOzand/or fluorite M

1
x
M
2
1-x
Ozwhere: M - 8 group (Pt, Rh, Ir), M1a rare - earth element (La, CE, Nd), or alkaline earth, (CA, Sr), M2element IV b group (Zr, Hf), In - transition elements (Ni, Co), which is a complex composite containing components with a low coefficient of thermal expansion [U.S. Pat. RF 2204434, B 01 J 23/40, 20.05.2003]. At temperatures of 600-800°and contact times of 0.1-0.4 to achieve high conversion of the meta is and selectivity to synthesis gas. However, the catalyst is a ceramic composite material with a low thermal conductivity, which causes the formation of hot spots in the catalyst bed and impedes the transfer of heat emitted in the frontal part of the layer during the oxidation reactions of hydrocarbons, then the length of the block and prevents its effective use for the implementation of the reaction of steam and carbon dioxide conversion.

The invention solves the problem of creating a stable catalyst with high thermal conductivity to produce synthesis gas, 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, and a process for production of synthesis gas using the catalyst. The high thermal conductivity of the catalyst provides the transfer of heat by catalytic layer and facilitates the efficient flow of endothermic reaction of steam and carbon dioxide conversion.

The problem is solved through the development of a catalyst which is a complex composite containing mixed oxides with perovskite structure or fluorite, a simple oxide and transitional and/or noble metals, and includes the media on a metal basis, representing layered termometricheskikh material, the content is a first non-porous or malabarista or non-porous or malabarista and porous oxide coating, and implementation of catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing gas or a mixture of oxygen-containing gases in the presence of this catalyst. The use of layered composite comprising a metal carrier, provides high thermal conductivity of the catalyst, while maintaining high hydrocarbon conversion and selectivity to synthesis gas, thermal stability of the catalyst, it is not nauglerozhivaniya.

The problem is solved by development of a catalyst (the first option), which is a complex composite containing mixed oxide, a simple oxide, transitional and/or noble element, complex composite contains media on a metal basis, representing layered termometricheskikh material containing non-porous or malabarista oxide coating, the ratio of the thickness of the metal base to the thickness of the non-porous or malabarista oxide coating is 10:1-1:5. The porosity is not more than 10%.

The catalyst contains in its composition, wt.%:

mixed oxide is not less than 1.0,

a simple oxide, for example Al2About3, ZrO2not more than 10.0,

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

media on metal base - the rest.

Mixed oxide can isone oxide with perovskite structure M 1B1-yMyOzand/or oxides with the fluorite structure M1M

2
1-x
Ozwhere:

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

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

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

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

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

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

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

The task is also solved by a method of preparation of the above catalyst based on a mixed oxide, a simple oxide, transitional and/or noble element, which is that the active components are applied to the media, representing layered termometricheskikh material containing non-porous or malabarista oxide coating, the ratio of the thickness of the metal base to the thickness of the non-porous or malabarista oxide coating is 10:1-1:5.

The task is also solved by a catalyst (the second option), which is a complex composite and contains a mixed oxide, a simple oxide, transitional and/or noble element, complex composite contains media on a metal basis, representing layered termometricheskikh material containing non-porous or malabarista oxide coating and a highly porous oxide layer, the ratio of the thickness of the metal base to the thickness of the non-porous or malabarista 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 catalyst contains in its composition, wt.%:

mixed oxide is not less than 1.0,

a simple oxide, for example Al2About3, ZrO2not more than 10.0,

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

media on metal base - the rest.

Mixed oxide can be an oxide with a perovskite structure M1B1-yMyOzand/or oxides with the fluorite structure M

1
x
M
2
1-x
Ozwhere:

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

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

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

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

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

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

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

The task is also solved by a method of preparation of the above catalyst based on a mixed oxide, a simple oxide, transitional and/or noble element, which is that the active components are applied to the media, representing layered termometricheskikh material containing non-porous or malabarista oxide coating and a highly porous oxide layer, the ratio of the thickness of the metal base to the thickness of the non-porous or malabarista 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 task is also solved by a method for production of synthesis-ha is and by catalytic conversion of the mixture, containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing component using the above described catalyst based on a mixed oxide, a simple oxide, transitional and/or a noble element. The catalyst contains in its composition, wt.%:

mixed oxide is not less than 1.0,

a simple oxide, for example Al2About3, ZrO2not more than 10.0,

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

media on metal base - the rest.

Mixed oxide is an oxide with a perovskite structure M1B1-yMyOzand/or oxides with the fluorite structure M

1
x
M
2
1-x
Ozwhere:

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

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

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

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

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

The catalyst also contains a transition element, n is the sample Ni, Co and/or noble element - metal 8 groups, such as Pt, Rh, Ir, Ru, not included in the structure of the perovskite or fluorite.

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, for example, Sr, and CA.

Introduction to the catalyst carrier on the metallic base provides high conductivity, while the layered structure of the medium containing non-porous or malority oxide layer with a porosity of not higher than 10%, which is formed by highly porous oxide layer, provides high thermal stability of the catalyst.

The process is carried out by sequential transmission of a gas mixture containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing component with a temperature of between 20 and 500°C, through a fixed bed of the catalyst with high thermal conductivity, which allows efficient use of the heat of the exothermic oxidation reactions for the occurrence of the endothermic reaction of steam and carbon dioxide conversion.

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

The proposed catalysts are prepared in several stages. To obtain a non-porous or malabarista oxide layer having a high thermal stability while maintaining high adhesion to the metal substrate, using the method of detonation spraying [Bartenev S., Fedko YU, Grigoriev A.I. Detonation coatings in mechanical engineering. - L.: Engineering, 1982]. For spray application use simple oxides (e.g., Al2About3, ZrO2) high-temperature modifications. As the original metal base use of heat-resistant foil or stainless steel containing in addition to iron supplements Nickel, chromium and other [U.S. Pat. RF 2106915, 05 D 1/00, 01.08.95].

Non-porous (mesoporosity) ceramic oxide layer is applied on both sides of the smooth or corrugated foil, then alternating layers of smooth and corrugated foil form blocks.

In the second stage of the preparation of form a layer of porous aluminum oxide ceramics, consisting of a mixture of simple oxides and/or mixed oxides, including rare earth, for example the EP neodymium, praseodymium, lanthanum, cerium or alkaline earth such as calcium, strontium, and transitory elements such as hafnium, zirconium. This layer is applied by impregnation unit with non-porous or malabaricum coating suspensions and/or solutions of appropriate compounds, followed by drying and calcination. Non-porous or malority oxide layer contributes to the strong fixation of highly porous layer. At the last stage of cooking on the obtained layered media from solutions of the corresponding salts cause an active component comprising a transition element and/or a noble metal, or a mixture thereof, and/or mixed oxides with perovskite structure. The resulting catalyst is dried and calcined.

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

The invention is illustrated by the following examples.

Example 1. Illustrates the preparation of a carrier containing non-porous or malabarista oxide coating with respect to the thickness of the metal base to the thickness of the non-porous or malabarista oxide coating 5:1. On both sides of the smooth foil having a thickness of 200 μm on the basis of the FeCrAl alloy is applied ceramic oxide layer from a powder of alpha-aluminum oxide with a thickness of 20 μm by a known method detonation spraying described above [Bartenev S., Fedko YU, Grigoriev A.I. Detonation 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 is coiled or spiral of Archimedes [Ed. St. USSR 1034762, B 01 J 37/00, 09.01.82], or put in parallel layers with subsequent consolidation perimeter in a steel shell.

Example 2. Illustrates the cooking is based catalyst carrier with malabaricum coating. Block, prepared as in example 1, calcined at 700°and impregnated with a mixed solution of salts of cerium and zirconium. The unit is blown with air to remove excess solution from the channels, dried and calcined at 900°C. If necessary, the impregnation procedure is repeated. The sample obtained is impregnated with a joint solution of H2PtCl6, nitrates of lanthanum and Nickel atomic ratio of cations La:Ni:Pt=1:0,994:0,006, dried and calcined at 900°C. the resulting catalyst contains, wt%: 4,5 mixed oxide of cerium and zirconium with the fluorite structure, 2,1 perovskite composition LaNi0,994Pt0,006. The catalyst was tested in a flow reactor with the reaction mixture containing ~25% natural gas in air, the activity is given in table 1.

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

Example 4. The catalyst is prepared as in example 2 except that impregnation using a mixed solution of lanthanum nitrate and Nickel. The resulting catalyst contains, wt%: 4,5 mixed oxide of cerium and zirconium with the fluorite structure, 2,3 perovskite composition LaNiO3 .

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

Example 6. The catalyst is prepared as in example 2 except that impregnation using a mixed solution of hexachloroplatinic acid and ruthenium chloride. The resulting catalyst contains, wt%: 4,5 mixed oxide of cerium and zirconium with the fluorite structure, 0,3 Pt and 1.0 EN.

Example 7. Illustrates the preparation of a carrier containing non-porous or malabarista oxide coating with respect to the thickness of the metal base to the thickness of the non-porous or malabarista oxide coating 10:1 and highly porous oxide coating with respect to the thickness of the metal base to the thickness of the porous oxide coating 1:1. On both sides of the smooth foil having a thickness of 200 μm on the basis of the FeCrAl alloy is applied ceramic oxide layer from a powder of alpha-aluminum oxide with a thickness of 10 μm by the method of detonation spraying, as in example 1. Similarly, the same layer is applied to the corrugated foil. Then alternating layers of smooth and corrugated foil rolled into a spiral of Archimedes with the subsequent consolidation perimeter in steel on echiko. After annealing at 700°on the received block composite on both sides of the foil is applied to a porous ceramic layer from a slurry containing particles of a mixed oxide of cerium and zirconium in the solution of nitrates of Zirconia and surfactants (polyethylene oxide). The unit is blown with air to remove the suspension of 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 media containing non-porous and highly porous coating. Block, prepared as in example 7, is impregnated with a mixed solution of H2PtCl6, nitrates of lanthanum and Nickel atomic ratio of cations La:Ni:Pt=1:0,994:0,006. The unit is blown with air to remove excess solution from the channels, dried and calcined at 900°C. the resulting catalyst contains, wt%: 9 mixed oxide of cerium and zirconium with the fluorite structure, 1.7 perovskite LaNi0,994PtO0,006. Testing is carried out as in example 2. Activity is given in table 1.

Example 9. The catalyst is prepared as in example 7 except that impregnation using a solution of rhodium chloride. The resulting catalyst contains, wt%: 9 mixed oxide of cerium and zirconium with the fluorite structure, 0,3 Rh. Testing is carried out as in the other 2. Activity is given in table 1.

PR is measures 10. The catalyst is prepared as in example 7 except that impregnation using a mixed solution of lanthanum nitrate and ruthenium chloride. The resulting catalyst contains, wt%: 10,9 mixed oxide of cerium and zirconium with the fluorite structure, 1,2 mixed oxide of lanthanum and ruthenium.

Example 11. The media is prepared as in example 7 except that impregnation using a suspension containing particles of a mixed oxide of zirconium and calcium.

Example 12. The catalyst is prepared by impregnation of the carrier according to example 11 is mixed with a solution of N2tCl6, nitrates of lanthanum and Nickel atomic ratio of La:Ni:Pt=1:0,994:0,006. The resulting catalyst contains, wt%: 9 mixed calcium oxide and zirconium oxide with a fluorite structure, 1.7 perovskite LaNiO0,994PtO0.006.

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

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

Example 15. The catalyst, prepared as in example 9, experience in the reaction air conversion octane. The parameters of the reaction and the catalyst are given in table the CE 2.

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

Example 17. The catalyst, prepared as in example 13, the experience in the reaction of the vapor reforming of gasoline. The parameters of the reaction and the catalyst are shown in table 2.

As seen from the above examples and tables, designed thermostable catalyst to produce synthesis gas, providing effective reactions selective catalytic oxidation and steam reforming of hydrocarbons at low contact times.

Table 1.

The activity of the catalysts in the reaction of selective oxidation of methane. The concentration of methane in the air ~24ob.% in the air

ExampleBlock length, mmT for trigger °T at the input of the unit °T at the output of the unit °The contact time, sec.The conversion of methane, X %The content of CO+H2,.%
250630--0,129353
892460- -0,1759355
950510--0,0939353
132033010307760,0878050,4

0,092
Table 2.

The catalytic activity in the oxidation and autothermal (vapor) the reforming of hydrocarbons.
OptionsExamples
 141516*17*
Isoctal (*petrol),kg/h

Air, m3/h

Water, kg/h
0,757

3,00

-
0,757

3,00

0,735
0,893

to 3.58

-
0,757

to 3.58

1,14
A common thread, nm3/h3,154,13,755,17
O2/C

H2O/s
0,53

-
0,53

0,8
0,53

-
0,53

1,0
The temperature of the inlet gas,°205265220280
The time of contact with0,105of 0.0810,064
The inlet temperature of the unit,°1033-1067985-9571185-10851063-1058
The outlet temperature of the unit,°903-951913-8921087-10761001-1003
The composition of the synthesis gas: vol.%

H2

CO
26-28,1

22,2-24,8
31-31,6

19,2-17,7
22,2-22,8

26,3 at 27.1
27,5

17,4
The content of the synthesis gas, % vol.48,2-52,949,3 of 50.248,5-to 49.944,9

1. Catalyst for production of synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing component, which is a complex composite containing mixed oxide, a simple oxide, transitional and/or noble element, characterized in that the complex composite includes the media on a metal basis, representing layered termometricheskikh material containing non-porous or malabarista oxide coating, the ratio of the thickness of the metallic base to the thickness of the non-porous or malabarista oxide coating is 10:1-1:5.

2. The catalyst according to claim 1, characterized in that it contains in its composition, wt.%:

Mixed the oxide is Not less than 1,0

A simple oxide, for example, Al2O3, ZrO2Not more than 10.0

The transition element and/or a noble element is Not more than 10.0

The media on a metal basis of the Rest

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

1
x
M
2
1-x
Ozwhere

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

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

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

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

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

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

5. The catalyst according to claim 1, characterized in that it is a block with direct channels, including micro is anal, in the form of a prism or cylinder shape with a base in the form of a circle or ellipse.

6. The preparation method of catalyst for production of synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing component-based mixed oxide, a simple oxide, transitional and/or noble element, characterized in that the active components are applied to the media, representing layered termometricheskikh material containing non-porous or malabarista oxide coating, the ratio of the thickness of the metallic base to the thickness of the non-porous or malabarista oxide coating is 10:1-1:5, then dried and calcined, you get a catalyst according to any one of claims 1 to 5.

7. Catalyst for production of synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing component, which is a complex composite and contains a mixed oxide, a simple oxide, transitional and/or noble element, characterized in that the complex composite includes the media on a metal basis, representing layered termometricheskikh material containing non-porous or malabarista oxide coating and a highly porous oxide layer, the ratio of the thickness of the metal core is you to the thickness of the non-porous or malabarista 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.

8. The catalyst according to claim 7, characterized in that it contains in its composition, wt.%:

Mixed oxide is Not less than 1,0

A simple oxide, for example, Al2About3, ZrO2 Not more than 10.0

The transition element and/or a noble element is Not more than 10.0

The media on a metal basis of the Rest

9. The catalyst according to claim 7, characterized in that the mixed oxide is an oxide with a perovskite structure M1B1-yMyOzand/or oxides with the fluorite structure M1M1-xOzwhere

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

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

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

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

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

10. The catalyst according to claim 7, characterized in that it contains a transition element, such as Ni, Co and/or noble element - metal 8 groups, for example, Pt, Rh, Ir, Ru.

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 cylinder shape with a base in the form of a circle or ellipse.

12. The preparation method of catalyst for production of synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing component-based mixed oxide, a simple oxide, transitional and/or noble element, characterized in that the active components are applied to the media, representing layered termometricheskikh material containing non-porous or malabarista oxide coating and a highly porous oxide layer, the ratio of the thickness of the metallic base to the thickness of the non-porous or malabarista 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, you get a catalyst according to any of claims 7-11.

13. A method for production of synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing component, by using a catalyst based on a mixed oxide, a simple oxide, transitional and/or noble element, characterized in that the process is carried out in the presence of a catalyst according to any one of claims 1 to 12.



 

Same patents:

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6 cl, 2 tbl, 16 ex

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4 cl, 1 tbl, 8 ex

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7 cl, 5 tbl, 27 ex

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6 cl, 2 tbl, 16 ex

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5 cl, 1 tbl, 4 ex

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3 cl, 4 tbl, 13 ex

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5 cl, 9 ex

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2 cl, 2 tbl, 21 ex

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40 cl, 2 tbl, 19 ex

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2 cl, 1 tbl, 3 ex

FIELD: hydrocarbon conversion catalysts.

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

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4 cl, 1 tbl, 8 ex

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3 cl, 1 tbl, 15 ex

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4 cl, 6 ex

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