Catalyst, method for preparation thereof, and synthetic gas production process

FIELD: alternate fuels.

SUBSTANCE: invention relates to production of synthetic gas via catalytic hydrocarbon conversion in presence of oxygen-containing gases and/or water steam as well as to catalysts suitable for this process. Invention provides catalyst, which is complex composite constituted by supported precious element, or supported mixed oxide, simple oxide, transition element, wherein support is a metallic carrier made from metallic chromium and/or chromium/aluminum alloy coated with chromium and aluminum oxides or coated with oxides of chromium, aluminum, or mixtures thereof. Catalyst preparation procedure and synthetic gas production process are also described.

EFFECT: increased conversion of hydrocarbons, selectivity regarding synthetic gas, and heat resistance of catalyst at lack of carbonization thereof.

4 cl, 3 tbl, 9 ex

 

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

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

The traditional way to produce synthesis gas is an endothermic process steam reforming of natural gas Nickel catalysts [J.R.Rostrup-Nielsen, Production of synthesis gas. Catalysis Today, 1993, v.18, 305-24; Usanational, Ovilo // Oxidative conversion of methane. Moscow, Nauka, 1998]. This process is characterized by extremely high capital costs, high operating costs and significant emissions of nitrogen oxides when the flare heating a tubular reformer.

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

For carrying out process RMS at low contact times ˜10-2with the use of 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 uglev the liquids 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 how began the process of RMS and established autothermal mode. As the catalyst used rhodium deposited on a heat-resistant carrier containing a mixture of oxides of cerium and zirconium in the weight ratio of Ce/Zr from 0.05 to 19.

The known method RMSE of methane to obtain carbon monoxide and hydrogen [US 5149464, 01 3/26, 1992] at a temperature of 650-900°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 oxides of General formula MxM'yOz with pyrochlore structure, where M' is a transition metal, including elements in 8 groups. The atomic ratio of the element 8 to the sum of the base elements in these compounds is 1:1 or 3:1, and the noble metal content is 32,9-48 wt.%. The conversion of methane in the presence of mixed oxides Pr2EN2O7, Eu2Ir2O7La2MgPtO6when flow rate 40000 h-1and 777° not greater 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 uglevodorodami contact of the reaction mixture, containing hydrocarbons, oxygen or oxygen-containing gas and, optionally, water vapor, with the catalyst in the zone selective catalytic oxidation. Area SKO contains the catalyst with the ratio of 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, 01 3/38, 10.09.99; EN 2137702, 01 3/38, 20.09.99; EN 2123471, 01 3/38, 20.12.98; US 5486313, C 07 C 1/02 23.01.1996 and US 5639401, C 07 C 1/02, 17.06.97] offer a way SKO hydrocarbons, including serosoderjaschei (0.05 to 100 ppm) [EN 2132299, 01 3/38, 27.06.99; US 5720901, C 07 C 1/02, 24.04.98] in the synthesis-gas using catalysts containing precious metals (up to 10 wt.% Pt, Pd, Rh, Os), applied to those who Mosconi media. As carriers are used, for example, α-Al2About3exhalent barium (grain size ˜1 mm) or ZrO2, thermally stabilized oxides of elements of groups IIIB or IIA 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 from 1.1 to 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.% ZrO2and at least 0.5 to 10 mol.% one of the oxides of Y, La, Al, CA, CE, or Sc. The process is performed on the catalyst with a grain size of 0.3-0.6 mm at 700-800°and volumetric soon the Ty stream 12750 h -1. Under these conditions, the conversion of methane is ˜60-70%, exit - ˜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 ˜0.3 mm, corresponding to the following formula: MxM'yOz or MxOz or M yOz on a heat-resistant carrier, where M and M' represent a wide range of alkaline, alkaline earth, transition, and other items. The proposed effective as catalysts in carbon dioxide methane conversion and combination reactions selective catalytic oxidation and carbon dioxide methane conversion. 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 (Al2O3, 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 dio the sid of the carbon in the target gas, and the variation of the composition of the initial mixture to obtain a mixture of hydrogen and carbon monoxide with a ratio of N2/From 0.7 to 3. Note that for mixtures without water to produce synthesis gas (H2/CO≥2) requires a high concentration of hydrogen in the feed mixture, which increases the production costs of the final product.

In the patent [US 5855815, C 07 C 1/02, 05.01.99] propose to obtain the synthesis gas by the reduction of 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 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 within 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 of kataliticheski 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].

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

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

Thus, the catalysts of honeycomb structure for a process of selective oxidation of hydrocarbons into synthesis gas at low contact times must meet stringent requirements for such catalysts, namely: to have a high thermal stability and conductivity, a sufficiently high specific surface area to ensure high conversion of hydrocarbons and selectivity to synthesis gas and not deactivated due to the formation of carbon on the surface.

Closest to the claimed technical essence and the achieved effect is the way RMS to produce synthesis gas in the presence of block cell catalyst which is a complex composite material containing a noble metal is not more than 10.0 wt.% and the media, or a mixed oxide of at least 1.0 wt.%, a simple oxide is not more than 10.0 wt.%, the transition element and/or a noble element is not more than 10.0 wt.% and the media, the media contains ceramic matrix based on aluminum oxide and dispersed throughout the matrix material is selected from oxides of transition and/or rare earth metals, or mixtures thereof, and/or metals, and/or the alloys, and/or carbides of metals of the 4th period of the Periodic table, or mixtures thereof, in the form of particles or aggregates of particles with size from 1 to 250 μm at a content of dispersed material in the matrix of 0.5-70,0 wt.%.

Mixed oxide is an oxide with a perovskite structure

M1In1-yMyAboutzand/or oxides with the fluorite structure M1xM21-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.

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

The catalyst has a system of parallel and/or intersecting channels (RU 2248240, B 01 J 21/04, 20.03.05).

At temperatures of 600-800°and With contact times of 0.1-0.4 achieved with high methane conversion and selectivity to synthesis gas. However, the content of metal component in the catalyst carrier is not more than 10 wt.%, that does not provide the necessary conductivity and heat transfer, released in Lobov the second part layer by the oxidation reactions of hydrocarbons, next along the length of the block and its effective use for the reactions 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, and 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 by using a catalyst which is a complex composite material containing a noble metal is not more than 10.0 wt.% and the media or mixed oxide of at least 1.0 wt.%, a simple oxide is not more than 10.0 wt.%, the transition element and/or a noble element is not more than 10.0 wt.%, the medium includes a metal base made of metal chromium and/or alloys of chromium and aluminum with a coating formed by the oxides of chromium, aluminum, or chromium oxides, aluminum, rare earths or mixtures thereof. The content of the metallic base in the medium is not less than 12.0 wt.%.

The catalyst contains in its composition, wt.%:

mixed oxide is not less than 1.0,

a simple oxide, selected from the group of Al2About3, ZrO2- not more than 10.0,

the transition of the first element and/or a noble element - not more than 10.0,

media - the rest.

Mixed oxide is an oxide with a perovskite structure M1B1yMyOzand/or oxides with the fluorite structure M1xM21-xOzwhere

M - 8 group selected from the group of Pt, Rh, Ir, Ru

M1a rare - earth element selected from the group: La, Ce, Nd or alkaline earth element selected from the group of CA, Sr,

M2element IV b group of the Periodic system, selected from the group of Zr, Hf,

In - transition element - 3d elements of the 4th period, selected from the group of 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 selected from the group of Ni, Co and/or noble element - metal 8 groups selected from the group of Pt, Rh, Ir, Ru.

As the metallic base media use of metallic chromium, and alloys of chromium and aluminum as on the basis of solid solutions of aluminum in chrome, and on the basis of intermetallic compounds chromium and aluminium certain structure and stoichiometry (CrAl7, Cr2Al11, CrAl4, Cr4Al9, Cr5Al8, Cr2Al) and other [Pasang "the structure of double alloys", 1973, M.: metallurgy, p.55-57]. The total content of the metal phase (basics) in the carrier extending t is not lower than 12.0 wt.%, preferably, 12,3 reached 98.9 wt.%. As coverage in the media use the oxides of chromium and aluminum, the same structure of corundum with high thermostability or use the oxides of chromium, aluminum, rare earths or mixtures thereof. The chromium oxides have moderate activity in oxidation reactions involving hydrocarbons, which increases the activity of the platinum metals when they are applied to the media. A relatively high content of aluminum oxide provides a relatively large porosity of the obtained catalyst.

The essential feature of the catalyst is the use of new media.

The task is also solved by a method of preparation of the above catalyst containing a noble metal is not more than 10.0 wt.% and the media or mixed oxide of at least 1.0 wt.%, a simple oxide is not more than 10.0 wt.%, the transition element and/or a noble element is not more than 10.0 wt.% and the media, which is that the active components are applied to the carrier, comprising a metal base made of metal chromium and/or alloys of chromium and aluminum with a coating formed by the oxides of chromium and aluminum, or a carrier comprising a metal base made of metal chromium and/or alloys of chromium and aluminum with a coating formed by the oxides of chromium, aluminum, redcot the land of elements or mixtures thereof. The content of the metallic base in the medium is not less than 12.0 wt.%.

The problem is solved through the use of the above catalyst for catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and/or air, or CO2or steam, or a mixture.

The technical result - the 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 process is performed at a pressure of 1-8 ATM through serial transmission of a gas mixture containing a hydrocarbon or mixture of hydrocarbons and/or air, or steam, or a mixture with a temperature of between 20 and 500°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 a hydrocarbon or mixture of hydrocarbons and/or air, or CO2or steam, or a mixture thereof, the process is performed at a pressure of 1-8 ATM and temperatures 500-1100°C. as hydrocarbons are used, for example, natural gas, methane, propane bout the new mixture, gasoline, kerosene, etc. as the oxygen-containing gas, such as oxygen, air, carbon dioxide, water.

The proposed catalysts prepared as follows.

The first stage is the preparation of a carrier (the first option) includes mechanical activation powder components in the form of a mechanical mixture of powders of aluminum and chromium in energonaprjazhenie planetary mill during acceleration of the grinding bodies 600-1000 m/s2[EN 2118669, WITH 22 33/02, D 22 F 3/16, 20.08.1996]. The ratio of SG:Al powder can be changed in range (wt. share): from 75:25 to 99:1. At higher content of aluminum powder in the process of mechanisatie is the spontaneous oxidation of aluminum. Mechanically activated powder is placed in the mold, providing access of water vapor and treated under hydrothermal conditions. The result is the formation of the monolith with high mechanical strength, which is extracted from the mold, dried and calcined in air. In the resulting monolithic carrier is formed of a metallic phase based alloys of chromium and/or chromium metal resistant to oxidation in air up to 1100°C. On the surface of the metal particles is formed by a coating consisting of oxides of chromium and aluminum with the structure of corundum and providing a sufficiently high specific surface area. Preliminary fur the technical activation facilitates the formation of alloys of chromium and aluminum, after annealing. The hydrothermal treatment leads to the formation of the monolith with high mechanical strength without calcinations at high temperatures in a reducing or inert atmosphere and contributes to the formation of high specific surface coverage of the carrier.

Preparation of the second version of the media includes an additional stage in which is formed a layer of oxide ceramics, consisting of a mixture of simple oxides and/or mixed oxides containing rare earth (e.g., neodymium, praseodymium, lanthanum, cerium) or alkaline earth (for example, calcium, strontium) and transition elements (e.g., hafnium, zirconium). This layer is applied by impregnation unit suspensions and/or solutions of appropriate compounds, followed by drying and calcination.

At the last stage of cooking on the received 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 vapours of a liquid hydrocarbon (e.g., is kitana, 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 and outlet of the reactor, the temperature of the catalytic unit to the input and output. The efficiency of the catalyst is characterized by the starting temperature of the reaction, the degree of conversion of methane and the amount of produced synthesis gas (mixture of hydrogen and carbon monoxide), expressed in volume% and characterizing the selectivity to synthesis gas. The composition of the initial reaction mixture and the reaction products analyzed chromatographically.

The invention is illustrated by the following examples.

Example 1. Chromium powder is mixed with aluminum powder in the ratio (wt. shares) 75:25, is subjected to mechanisatie for 1 min. the resulting powder was placed in a mold made of stainless steel and is subjected to hydrothermal treatment. Mechanically strong monolith is removed from the mold, dried and calcined at 1100°C for 4 h in air. Monolith contains phase of chromium oxide, aluminum oxide and metallic chromium. The content of the metal phase of 12.8 wt.%. The sample obtained is impregnated with a solution of H2PtCl6, dried and calcined pri° C. the catalyst containing 1 wt.% Pt media - the rest up to 100 wt.%.

The catalyst was tested in a flow reactor at atmospheric pressure and composition of the reaction mixture, containing ˜25% natural gas in air in the reaction of selective oxidation of natural gas into synthesis gas. Activity is given in table 1.

Example 1. Chromium powder is mixed with aluminum powder in the ratio (wt. shares) 75:25, is subjected to mechanisatie for 1 min. the resulting powder was placed in a mold made of stainless steel and is subjected to hydrothermal treatment. Mechanically strong monolith is removed from the mold, dried and calcined at 1100°C for 4 h in air. Monolith contains phase of chromium oxide, aluminum oxide and metallic chromium. The content of the metal phase of 12.8 wt.%. Monolithic carrier is 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. the Obtained sample is impregnated with a solution of H2PtCl6, dried and calcined at 900°C. the catalyst containing 4.8 wt.% mixed oxide of cerium and zirconium with the fluorite structure, 1 wt.% Pt media - the rest up to 100 wt.%.

Example 3. Chromium powder is mixed with aluminum powder in the ratio (wt. shares) 80:20, is subjected to Makhachev the tion for 3 minutes The resulting powder was placed in a mold of largescale and subjected to hydrothermal treatment. Mechanically strong monolith is removed from the mold, dried and calcined at 1100°C for 4 h in air. Monolith contains phase of chromium oxide, aluminum oxide, metallic chromium and chromium alloys and aluminum. The content of the metal phase to 12.3 wt.%. Monolithic carrier with a diameter of 22 mm is impregnated with a mixed solution of salts of cerium and zirconium, dried and calcined at 900°C. the sample was Then impregnated with a solution of RhCl3dried and calcined at 900°C. the catalyst containing 8.2 wt.% mixed oxide of cerium and zirconium with the fluorite structure, 0.4 wt.% Rh, media - the rest up to 100 wt.%.

The catalyst was tested in a flow reactor as in example 1. Activity is given in table 1.

Example 4. Chromium powder is mixed with aluminum powder in the ratio (wt. shares) 80:20, is subjected to mechanisatie within 5 minutes the resulting powder was placed in a mold made of stainless steel and is subjected to hydrothermal treatment. Mechanically strong monolith is removed from the mold, dried and calcined at 1100°C for 4 h in air. Monolith contains phase of chromium oxide, aluminum oxide, metallic chromium and chromium alloys and aluminum. The content of the metal phase to 35.0 wt.%. Media PROPET shall provide a joint solution of H 2PtCl6, nitrates of lanthanum and Nickel atomic ratio of cations La:Ni:Pt=1:0,994:0,006, dried and calcined at 900°C. the catalyst containing 5.4 wt.% perovskite LaNi0,994Pt0,006media - the rest up to 100 wt.%.

The catalyst was tested in a flow reactor, as in example 1. Activity is given in table 1.

Example 5. Chromium powder is mixed with aluminum powder in the ratio (wt. shares) 80:20, is subjected to mechanisatie within 5 minutes the resulting powder was placed in a mold made of stainless steel and is subjected to hydrothermal treatment. Mechanically strong monolith is removed from the mold, dried and calcined at 1100°C for 4 h in air. Monolith contains phase of chromium oxide, aluminum oxide, metallic chromium and chromium alloys and aluminum. The content of the metal phase to 35.0 wt.%. Monolithic carrier with a diameter of 20 mm is impregnated with a mixed solution of salts of cerium and zirconium, dried and calcined at 900°C. the sample was Then impregnated with sovmestnim 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 about 7.2 wt.% mixed oxide of cerium and zirconium with the fluorite structure, 5.4 wt.% perovskite LaNi0,994Pt0,006media - the rest up to 100 wt.%.

The catalyst test is to see in a flow reactor, as in example 1. Activity is given in table 1.

Example 6. The media is prepared as in example 5, except that the diameter of the resulting monolithic carrier is 48 mm, the Catalyst is prepared as in example 3, and in addition put Rh impregnation from a solution of rhodium chloride, followed by drying and calcination at 900°C. the resulting catalyst contains 6.25 wt.% mixed oxide of cerium and zirconium with the fluorite structure, 3.6 wt.% perovskite LaNi0,994Pt0,006and 0.3 wt.% Rh, media - the rest up to 100 wt.%.

The catalyst was tested in a flow reactor at atmospheric pressure and composition of the reaction mixture, containing ˜25% natural gas in air in the reaction of selective oxidation of natural gas into synthesis gas. Activity is given in table 1.

Example 7. Chromium powder is mixed with aluminum powder in the ratio (wt. shares) 80:20, is subjected to mechanisatie within 10 minutes the resulting powder was placed in a mold made of stainless steel and is subjected to hydrothermal treatment. Mechanically strong monolith is removed from the mold, dried and calcined at 1100°C for 4 h in air. Monolith contains phase of chromium oxide, aluminum oxide, metallic chromium and chromium alloys and aluminum. The content of the metal phase of 74.0 wt.%. Monolithic carrier with a diameter of 20 mm is impregnated with smiling is s ' solution of salts of cerium and zirconium, dried and calcined at 900°C. the sample was Then impregnated with a solution of RhCl3dried and calcined at 900°C. the catalyst containing 5.9 wt.% mixed oxide of cerium and zirconium with the fluorite structure, 0.4 wt.% Rh, media - the rest up to 100 wt.%.

The catalyst was tested in a flow reactor at a pressure of 1.5 to 8 bar and the reaction mixture containing ˜25% natural gas in air in the reaction of selective oxidation of natural gas into synthesis gas. Activity is given in table 2.

Example 8. The media is prepared as in 3, except that mechanisatie mixture of powders of chromium and aluminum is 15 minutes monolithic carrier with a diameter of 48 mm is impregnated with a mixed solution of salts of cerium and zirconium, dried and calcined at 900°C. the sample was Then impregnated with a solution of RhCl3, dried and calcined at 900°C. the catalyst containing 5.7 wt.% mixed oxide of cerium and zirconium with the fluorite structure, 0.4 wt.% Rh, media - the rest up to 100 wt.%.

The catalyst was tested in a flow reactor at atmospheric pressure and composition of the reaction mixture, containing ˜25% natural gas in air in the reaction of selective oxidation of natural gas into synthesis gas. Activity is given in table 1.

Example 9. The catalyst is prepared as in example 6, and experience in the reaction ocil the positive reforming of gasoline. Activity is given in table 3.

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Table 1

The activity of the catalysts in the reaction of selective oxidation of methane at atmospheric pressure.
ExampleCH4/O2The time of contact withXCH4%Sco%SH2%Temperature, °
TZapTgashTbluhTblah
11,60,100807675560440
31,60,1078888865504381080
41,60,97676745104351080
51,60,0878186835054381080
6 1,10,1008373724404351216746
1,50,0958190854251145680
1,30,0689090884221143756
1,40,0568288854401163759
1,60,084969594440423933773
1,8amount of 0.118839292218792655
Table 2

Example 7. The activity of the catalyst when the variation of the pressure and flow of the reaction mixture.
Pressure, ATMConsumption,

l/h
The time of contact withXCH4,

%
SH2,

%
Sco,

%
CO+H2About. %The temperature of the block, °
Inputoutput
830000,075838987 451152981
88200,276869190501097825
430000,0387884864110431013
4820was 0.138849190501063832
1,58200,05288909150969833

Table 3.

Example 9. The activity of the catalyst in the oxidative reforming of gasoline.
Options Example 9
Gas, kg/h0.673
Air, m3/h2.86
A common thread, nm3/h3
O2/S0,6
The temperature of the inlet gas, °290
The time of contact with0.065
The inlet temperature of the unit, °1170
The outlet temperature of the unit, °817
The composition of the synthesis gas % vol.

H2


20.6
CO24.2
The content of the synthesis gas, % vol.44.8

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 a noble metal is not more than 10.0 wt.% and the media, or a mixed oxide of at least 1.0 wt.%, a simple oxide is not more than 10.0 wt.%, the transition element and/or a noble element is not more than 10.0 wt.% and the carrier, wherein the carrier is a metal base made of metal chromium and/or alloys of chromium and aluminum with a coating formed by the oxides of chromium, aluminum, is whether the carrier is a metal base made of metal chromium and/or alloys of chromium and aluminum coated, formed by the oxides of chromium, aluminum, rare earths or mixtures thereof.

2. The catalyst according to claim 1, characterized in that the mixed oxide is an oxide with a perovskite structure M1B1-yMyOzand/or oxides with the fluorite structure M1xM21-xOzwhere

M - element 8-th group, selected from the group of Pt, Rh, Ir, Ru;

M1a rare - earth element selected from the group: La, Ce, Nd, or alkaline earth element selected from the group of CA, Sr;

M2element IV b group of the Periodic system, selected from the group of Zr, Hf;

In - transition element - 3d elements of the 4th period, selected from the group of Ni, Co;

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

3. The catalyst according to claim 1, characterized in that it contains a transition element selected from the group of Ni, Co, and/or noble element is a metal of the 8th group selected from the group of Pt, Rh, Ir, Ru.

4. The preparation method of catalyst for production of synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing component, which is a complex composite containing a noble metal is not more than 10.0 wt.% and the media, or a mixed oxide in an amount of not less than 1.0 wt.%, a simple oxide is e more than 10.0 wt.%, the transition element and/or a noble element is not more than 10.0 wt.%, and the media, characterized in that it is prepared by impregnation of a corresponding salt solutions of media, including metal base of metallic chromium and/or alloys of chromium and aluminum with a coating formed by the oxides of chromium and aluminum, or media, comprising a metal base made of metal chromium and/or alloys of chromium and aluminum with a coating formed by the oxides of chromium, aluminum, rare earths or mixtures thereof.

5. A method for production of synthesis gas by catalytic conversion of a mixture containing a hydrocarbon or mixture of hydrocarbons and oxygen-containing component, with catalyst, wherein the process is carried out in the presence of a catalyst according to any one of claims 1 to 3.



 

Same patents:

FIELD: hydrogen production processes.

SUBSTANCE: invention relates to catalytic processes of hydrogen production from hydrocarbon-containing gases. Method of invention comprises elevated-pressure catalytic decomposition of methane and/or natural gas into hydrogen and carbon followed by gasification of the latter with the aid of gasification reagent in several in parallel installed interconnected reactors, each of them accommodating preliminarily reduced catalyst bed. When one of reactors is run in methane and/or natural gas decomposition mode, the other gasifies carbon, the both operation modes being regularly switched. Operation period in one of the modes ranges from 0.5 to 10 h. Carbon gasification reagent is, in particular, carbon dioxide and catalyst utilized is reduced ferromagnetic thermally stabilized product consisting of iron oxides (30-80 wt %) and aluminum, silicon, magnesium, and titanium oxides. Methane and/or natural gas is decomposed at 625-1000°C and overpressure 1 to 40 atm.

EFFECT: ensured environmental safety and increased productivity of process.

3 cl, 1 dwg, 8 ex

FIELD: petrochemical industry; integral reactors and the methods of realization of exothermal and endothermic reactions.

SUBSTANCE: the invention is pertaining to the integral reactors of combustion (IRC), intended for realization of the exothermal and endothermic reactions. The IRC contains the exothermal reaction chamber (12) with the catalytic agents of the exothermic reaction (14,16), the endothermic reaction chamber (15) with the catalytic agent of the endothermic reaction (17), the open channels (18,19) for free flow of the of the medium stream through the chamber and the heat-conducting partition separating the chambers. It is preferable, that the exothermal or endothermic chambers would have the width (the minimum size in a direction perpendicular to the stream) - 2 mm or less. The invention also describes the separate models of the reactors and the methods of realization of the reactions in them. The invention ensures the safe work with the fuel, realization of the vapor reforming during the short time of the contact, the increased productivity per the unit of the volume of the reactor, extinguishing/inhibition of the gaseous-phase reactions.

EFFECT: The invention ensures the safe work with the fuel, realization of the vapor reforming during the short time of the contact, the increased productivity per the unit of the volume of the reactor, extinguishing/inhibition of the gaseous-phase reactions.

12 cl, 9 tbl, 27 dwg

FIELD: composition and structure of composite metal semiconductor meso-porous materials; titanium-dioxide-based catalyst for photo-chemical reactions.

SUBSTANCE: proposed catalyst is meso-porous titanium-dioxide-based material containing crystalline phase of anatase in the amount no less than 30 mass-% and nickel in the amount no less than 2 mass-%; material has porous structure at average diameter of pores from 2 to 16 nm and specific surface no less than 70 m2/g; as catalyst of photo-chemical reaction of liberation of hydrogen from aqua-alcohol mixtures, it ensures quantum reaction yield from 0.09 to 0.13. Method of production of such catalyst includes introduction of precursor - titanium tetraalkoxyde and template of organic nature, holding reagent mixture till final molding of three-dimensional structure from it at successive stages of forming sol, then gel, separation of reaction product and treatment of this product till removal of template; process is carried out in aqua-alcohol solvent containing no more than 7 mass-% of water; at least one of ligands is introduced into solvent as template; ligand is selected from group of macro-cyclic compounds containing no less than four atoms of oxygen and/or from complexes of said macro-cyclic compounds with ions of metals selected from alkaline or alkaline-earth metals or F-metals containing lithium, potassium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum and cerium; mixture is stirred before forming of sol maintaining its temperature not above 35°C till final molding of three-dimensional structure from reagent mixture; mixture is held in open reservoir at the same temperature at free access of water vapor; after removal of template from three-dimensional structure, mixture is first treated with nickel salt solution during period of time sufficient for withdrawal of nickel ions from solution by pores of structure, after which is it kept in hydrogen-containing medium during period of time sufficient for reduction of nickel ions in pores of structure to metallic nickel.

EFFECT: enhanced sorption and photo-catalytic parameters; reproducibility of catalyst properties.

7 cl, 68 ex

FIELD: chemical industry; installations and the methods of production of the synthesis-gas from the natural gas.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the installation and the method for simultaneous production from the natural gas of the methanol synthesis-gas, the ammoniac synthesis-gas, carbon monoxide and carbon dioxide. The installation consists of the in-series connected to each other assembly units and includes: the first reactor (A), in which at feeding of oxygen realize the transformation of the natural gas into the synthesis gas consisting of carbon monoxide, carbon dioxide, hydrogen and the steam; the second reactor (B), in which exercise the regular transformation of carbon monoxide into carbon dioxide; if necessary the compressor (C) using which the formed gases may be contracted; absorbing apparatus D, which serves for absorption of carbon dioxide and production of he mixture of monoxide with hydrogen used for synthesizing methanol; the refrigerating separator E, in which at feeding of the liquid nitrogen receive the ammoniac synthesis gas and simultaneously produces carbon monoxide, argon and methane. The invention allows to increase profitability of the installation due to production at one installation of several products.

EFFECT: the invention ensures the increased profitability of the installation due to production at one installation of several products.

15 cl, 1 dwg, 1 tbl

FIELD: power engineering, in particular, hydrogen and oxygen production system.

SUBSTANCE: hydrogen and oxygen production system has electric plasmochemical reactor made in the form of high-pressure cylinder with spherical bottoms provided at its ends, said bottoms being equipped with screens, through which superhigh-frequency radiation waveguides are inserted. Waveguides are separated from internal volume of reactor by metal diaphragms with supporting grids and are provided with nozzles for supplying of carbonic acid and water steam, and hollow perforated electrodes of different poles for producing and separating of hydrogen and oxygen, with internal volumes of said electrodes being connected with driers, molecular sieves for separation of hydrogen, oxygen and carbonic acid, output refrigerators, gas holder and receiver.

EFFECT: increased energy efficiency owing to reduced consumption of power, consumption of hydrogen from storages in gas-and-steam units of auxiliary electric stations at night time.

2 dwg

FIELD: chemical industry; devices for production of the synthesis gas.

SUBSTANCE: the invention is pertaining to the radial type device for realization of oxidation of the gaseous hydrocarbon fuels with the help of the catalytic agent and may be used for production of the synthesis gas. The radial type device for production synthesis gas contains the gas-distribution perforated tube 3 and the catalytic agent 4. The catalytic agent is made in the form of the annular heat-conducting dispensing catalytic plates and the heat-conducting separators with the grooves alternating among themselves with formation of channels for the gaseous streams running and connected among themselves. On the both sides of the separator 6 there are grooves 7 made in the form of the evolvent from the center to the periphery. The annular plates of the catalytic agent are mounted perpendicularly to the axis of the shafts of the gas-distribution perforated tube 3. Inside of the gas-distribution perforated tube 3 there is the starting system, which consists of the mixer 1 with the ignition plug 2 or the electric heating component. The invention presents the compact and effective device.

EFFECT: the invention presents the compact and effective radial type device used for realization of oxidation of the gaseous hydrocarbon fuels with the help of the catalytic agent and for production of the synthesis gas.

6 cl, 3 dwg

FIELD: hydrogen power engineering; the catalytic method of realization of the dimethyl ether steam conversion reaction.

SUBSTANCE: the invention is pertaining to the catalytic method of realization of the dimethyl ether (DME) steam conversion reaction for the purpose to produce the hydrogen-enriched gas mixture, which may be used in the hydrogen power engineering, in particular, as the fuel for feeding the fuel cells of the different designation. The invention presents the bifunctional catalyst of the dimethyl ether (DME) steam conversion containing the acidic centers for hydration of DME into the methanol, and the copper-containing centers for the steam conversion of methanol, and representing by itself the copper-ceric oxide deposited on the aluminum oxide. The invention also presents the method of production of the hydrogen-enriched gas mixture by interaction of DME and steam at the temperature of 200-400°C, pressure of 1-100 atm, molar ratio of H2О/DME equal to 2-10 at presence of the described above catalyst. The technical result of the invention is the high hydrogen efficiency, production of the hydrogen-containing gas with the low contents of carbon oxide at the ratio steam/DME equal to the stoichiometric (H2O/DME=3), that has the relevant technological value.

EFFECT: the invention ensures the high hydrogen efficiency, production of the hydrogen-containing gas with the low contents of carbon oxide at the suitable ratio steam to DME, that has the relevant technological value.

5 cl, 15 ex, 6 tbl

FIELD: chemical industry; methods of production of hydrogen and a methanol.

SUBSTANCE: the invention is pertaining to the method of production of the industrial hydrogen and methanol from the converted gas consisting mainly of CO2, H2. The method of production of hydrogen and methanol from the converted gas containing carbon oxides and hydrogen includes the synthesis of methanol. For execution of the methanol synthesis feed the converted gas with the volumetric ratio of H2-CO2/CO+CO2, equal to 2.03-5.4, which is conducted in the reactor system including the flow reactor or the cascade of the floe reactors and / or the reactor with the recycle of the gas mixture with production of methanol, the unreacted gas and the blow-down gas. At that the mixture of the unreacted and converted gases is fed for purification from carbon carbon dioxide with its extraction and batch feeding of the carbon dioxide into the converted gas delivered for the synthesis of methanol. The blow-down gases are subjected to the fine purification from the impurities with production of hydrogen. The invention allows to upgrade the method due to maximum usage of the carbon dioxide.

EFFECT: the invention ensures improvement of the method of production of hydrogen and a methanol due to maximum usage of the carbon dioxide.

2 cl, 1 dwg, 1 tbl, 5 ex

FIELD: hydrocarbon conversion processes.

SUBSTANCE: process consists in catalytic decomposition of hydrocarbon-containing gas at elevated temperature and pressure 1 to 40 atm, catalyst being reduced ferromagnetic cured product isolated by magnetic separation from ashes produced in coal combustion process at power stations. The catalytic product represents spinel-type product containing 18 to 90% iron oxides with balancing amounts of aluminum, magnesium, titanium, and silicon oxides. Prior to be used, catalyst is subjected to hydrodynamic and granulometric classification.

EFFECT: reduced total expenses due to use of substantially inexpensive catalyst capable of being repetitively used after regeneration, which does not deteriorate properties of original product.

2 cl, 6 ex

FIELD: petrochemical industry; methods of the synthesis of ammonia from the nitrogen and hydrogen mixture produced from the natural gases.

SUBSTANCE: the invention is pertaining to the field of petrochemical industry, in particular, to the method of the synthesis of ammonia from the nitrogen and hydrogen mixture produced from the natural gases. The method of the catalytic synthesis of ammonia from the mixture of nitrogen and hydrogen provides, that the natural gas together with the oxygen-enriched gas containing at least 70 % of oxygen is subjected to the autothermal reforming at temperature from 900 up to 1200°C and the pressure from 40 up to 100 bar at the presence of the catalyzer of cracking, producing the unstripped synthesis gas containing in terms of the dry state 55-75 vol.% of H2, 15-30 vol.% of C and 5-30 vol.% CO2. At that the volumetric ratio of H2: CO makes from 1.6 : 1 up to 4 : 1. The unstripped synthesis gas is removed from the furnace of the autothermal reforming, cooled and subjected to the catalytic conversion producing the converted synthesis gas containing in terms of the dry state at least 55 vol.% of H2 and no more than 8 vol.% of CO. The converted synthesis gas is subjected to the multistage treatment for extraction ofCO2, CO and CH4. At that they realize the contact of the synthesis gas with the liquid nitrogen and using at least one stage of the absorption treatment produce the mixture of nitrogen and hydrogen, which is routed to the catalytic synthesizing of ammonia. At that at least a part of the synthesized ammonia may be transformed into carbamide by interaction with carbon dioxide. The realization of the method allows to solve the problem of the ammonia synthesis efficiency.

EFFECT: the invention ensures solution of the problem of the ammonia synthesis efficiency.

8 cl, 1 ex, 2 tbl, 2 dwg

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides gasoline fraction reforming catalyst containing 0.1-0.5% platinum, 0.1-0.4% rhenium, halogen (chorine, 0.7-1.5%, or chorine and fluorine, 0.05-0.1%), and carrier: surface compound of dehydrated aluminum monosulfatozirconate of general formula Al2O3·[ZrO(SO4)]x with weight stoichiometric coefficient x = 0.45·10-2 - 9.7·10-2 and real density 3.3±0.01 g/cm3. Catalyst preparation process comprises preparation of carrier by mixing (i) aluminum hydroxide, from which iron and sodium impurities were washed out (to 0.02%) and which has pseudoboehemite structure, with (ii) aqueous solution of monosulfatozirconic acid HZrO(SO4)OH containing organic components (formic, acetic, oxalic, and citric acids) followed by drying, molding, and calcination. Carrier is treated in two steps: first at temperature no higher than and then at temperature not below 70°C.

EFFECT: enabled production of reforming gasolines with octane number not below 97 points (research method) with yield not less than 86% and increased activity and selectivity of catalyst.

4 cl, 2 tbl, 13 ex

FIELD: inorganic synthesis catalysts.

SUBSTANCE: ammonia synthesis catalyst is based on ruthenium on carrier of inoxidizable pure polycrystalline graphite having specific BET surface above 10 m2/g, said graphite being characterized by diffraction pattern comprising only diffraction lines typical of crystalline graphite in absence of corresponding bands of amorphous carbon and which graphite being activated with at least one element selected from barium, cesium, and potassium and formed as pellets with minimal dimensions 2x2 mm (diameter x height). Catalyst is prepared by impregnating above-defined catalyst with aqueous potassium ruthenate solution, removing water, drying, reduction to ruthenium metal in hydrogen flow, cooling in nitrogen flow, water flushing-mediated removal of potassium, impregnation with aqueous solution of BaNO3 and/or CsOH, and/or KOH followed by removal of water and pelletizing of catalyst.

EFFECT: increased activity of catalyst even when charging ruthenium in amount considerably below known amounts and increased resistance of catalyst to methane formation.

12 cl, 1 tbl

FIELD: methods of preparation of catalysts for reforming of gasoline fractions in oil producing and petrochemical industries for production of high-octane motor fuels, aromatic hydrocarbons and commercial hydrogen.

SUBSTANCE: proposed method includes vacuum treatment of carrier, recirculation through aqueous solution of hydrochloric and acetic acids under vacuum, recirculation of impregnating solution; solutions of chloro-platinous and rhenium acids are introduced into impregnating solution at constant rate, after which solution is subjected to drying and calcination; treatment of carrier with impregnating solution is carried out at three stages: at first and second stages, temperature of circulating impregnating solution does not exceed 30°C and at third stage its temperature is not below 70°C.

EFFECT: enhanced activity, selectivity and stability of catalyst; reduced usage of metals; reduction of wastes and losses of platinum and rhenium.

10 cl, 2 dwg, 1 tbl, 8 ex

FIELD: oil refining; preparation of catalysts for refining of oil fractions; preparation of catalysts for benzene hydroisomerization process.

SUBSTANCE: proposed method includes mixing of components: zeolite component-mordenite with binder-aluminum hydroxide, plastification by means of peptizing by acid solution, granulation, application of platinum and reduction of catalyst; components are mixed at mass ratio of from 1:9 to 2:3 in terms of calcined mordenite and aluminum hydroxide; after application of platinum, heat treatment is carried out at two stages at temperature of 100-110°C at first stage and not above 250-300°C at second stage; reduction of catalyst is performed at temperature not below 500°C. Used as aluminum hydroxide is pseudo-boehmite of Catapal A grade. Used as zeolite component is high-modulus mordenite at silicate modulus M=20-30 at its content in catalyst of 20-30%. Used as zeolite component is low-modulus mordenite at silicate modulus M=10 at its content in catalyst not exceeding 10%.

EFFECT: enhanced selectivity of catalyst; considerable reduction of power requirements.

1 tbl, 3 ex

FIELD: catalytic chemistry; method of afterburning of organic admixtures and waste gases; chemical and petrochemical industries.

SUBSTANCE: proposed method is used for cleaning waste gases from styrene, toluene, isopropyl benzene, formaldehyde and oxidation products of higher fatty acids. Proposed method includes evacuation and impregnation of globular aluminosilicate zeolite-containing carrier; used as carrier is highly thermostable cracking catalyst to 100-% absorption by aqua solution of H2PtCl6 or PdCl2 at concentration of platinum or palladium of 0.4-0.8 g/l and volume ratio of impregnating solution to carrier of (0.6-0.08):1.0 of followed by sulfidizing with hydrogen sulfide and drying of catalyst. Proposed method makes it possible to clean waste gases from organic admixtures by 99.5-100%.

EFFECT: enhanced efficiency.

1 tbl, 5 ex

FIELD: organic chemistry, chemical technology, catalysts.

SUBSTANCE: invention describes a catalyst for dehydrogenation of (C2-C5)-hydrocarbons that comprises aluminum, chrome oxides, compound of modifying metal, alkaline and/or alkaline-earth metal. Catalyst comprises additionally silicon and/or boron compounds and as a modifying agent the proposed catalyst comprises at least one compound chosen from the following group: zirconium, titanium, iron, gallium, cobalt, molybdenum, manganese, tin. The catalyst is formed in the process of thermal treatment of aluminum compound of the formula Al2O3. n H2O wherein n = 0.3-1.5 and in common with compounds of abovementioned elements and shows the following composition, wt.-% (as measure for oxide): chrome oxide as measured for Cr2O3, 12-23; compound of a modifying metal from the group: Zr, Ti, Ga, Co, Sn, Mo and Mn, 0.1-1.5; silicon and/or boron compound, 0.1-10.0; alkaline and/or alkaline-earth metal compound, 0.5-3.5, and aluminum oxide, the balance. Catalyst shows the specific surface value 50-150 m2/g, the pore volume value 0.15-0.4 cm3/g and particles size 40-200 mcm. Also, invention describes a method for preparing this catalyst. Invention provides preparing the catalyst showing the enhanced strength and catalytic activity.

EFFECT: improved and valuable properties of catalyst.

12 cl, 2 tbl

FIELD: petroleum processing catalysts.

SUBSTANCE: catalyst designed for using in petroleum fraction hydrofining, which contains oxides of cobalt, molybdenum, phosphorus, lanthanum, boron, and aluminum, is prepared by mixing aluminum hydroxide with boric acid solution and nitric acid solution of lanthanum carbonate followed by drying, calcination, impregnation of resulting carrier with cobalt nitrate and ammonium paramolybdate solution in nitric acid at pH 2.0-3.5 and 40-80°C in presence of phosphoric acid followed by drying and calcination at elevated temperature.

EFFECT: enabled production of hydrogenate with reduced content of sulfur compounds.

2 ex

FIELD: engineering of Fischer-Tropsch catalysts, technology for producing these and method for producing hydrocarbons using said catalyst.

SUBSTANCE: catalyst includes cobalt in amount ranging from 5 to 20 percents of mass of whole catalyst on argil substrate. Aforementioned substrate has specific surface area ranging from 5 to 50 m2/g. Catalyst is produced by thermal processing of argil particles at temperature ranging from 700 to 1300°C during period of time from 1 to 15 hours and by saturating thermally processed particles with cobalt. Method for producing hydrocarbon is realized accordingly to Fischer-Tropsch method in presence of proposed catalyst.

EFFECT: possible achievement of high selectivity relatively to C5+ at low values of diffusion resistance inside particles.

3 cl, 9 ex, 9 dwg

FIELD: structural chemistry and novel catalysts.

SUBSTANCE: invention provides composition including solid phase of aluminum trihydroxide, which has measurable bands in x-ray pattern between 2Θ=18.15° and 2Θ=18.50°, between 2Θ=36.1° and 2Θ=36.85°, between 2Θ=39.45° and 2Θ=40.30°, and between 2Θ=51.48° and 2Θ=52.59°, and has no measurable bands between 2Θ=20.15° and 2Θ=20.65°. Process of preparing catalyst precursor composition comprises moistening starting material containing silicon dioxide-aluminum oxide and amorphous aluminum oxide by bringing it into contact with chelating agent in liquid carrier and a metal compound; ageing moistened starting material; drying aged starting material; and calcining dried material. Catalyst includes carrier prepared from catalyst composition or catalyst precursor and catalytically active amount of one or several metals, metal compounds, or combinations thereof. Catalyst preparation process comprises preparing catalyst carrier from starting material containing silicon dioxide-aluminum oxide and amorphous aluminum oxide by bringing it into contact with chelating agent and catalytically active amount of one or several metals, metal compounds, or combinations thereof in liquid carrier, ageing starting material; drying and calcinations. Method of regenerating used material involves additional stage of removing material deposited on catalyst during preceding use, while other stages are carried out the same way as in catalyst preparation process. Catalyst is suitable for treating hydrocarbon feedstock.

EFFECT: improved activity and regeneration of catalyst.

41 cl, 3 dwg, 8 tbl, 10 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to methods for preparing catalyst precursors and group VIII metal-based catalysts on carrier, and to a process of producing hydrocarbons from synthesis gas using catalyst of invention. Preparation of precursor of group VIII metal-based catalyst comprises: (i) imposing mechanical energy to mixture containing refractory oxide, combining catalyst precursor with water to form paste comprising at least 60 wt % of solids, wherein ratio of size of particles present in system in the end of stage (i) to that in the beginning of stage (i) ranges from 0.02 to 0.5; (ii) mixing above prepared paste with water to form suspension containing no more than 55% solids; (iii) formation and drying of suspension from stage (ii); and (iv) calcination. Described are also method of preparing group VIII metal-based catalyst using catalyst precursor involving reduction reaction and process for production of hydrocarbons by bringing carbon monoxide into contact with hydrogen are elevated temperature and pressure in presence of above-prepared catalyst.

EFFECT: increased catalytic activity and selectivity.

12 cl, 1 tbl, 3 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to creating carriers for catalysts used in epoxidation of olefins and provides catalyst containing at least 95% α-alumina with surface area 1.0 to 2.6 m2/g and water absorption 35 to 55%, and which has pores distributed such that at least 70% pore volume is constituted by pores 0.2 to 10 μm in diameter, wherein pores with diameters 0.2 to 10 μm form volume constituting at least 0.27 ml/g of carrier. Also described is a method for preparing catalyst carrier, which envisages formation of mixture containing 50-90% of first α-alumina powder with average particle size (d50) between 10 and 90 μm; 10-50% (of the total weight of α-alumina) of second α-alumina powder with average particle size (d50) between 2 and 6 μm; 2-5% aluminum hydroxide; 0.2-0.8% amorphous silica compound; and 0.05-0.3% alkali metal compound measured as alkali metal oxide, all percentages being based on total content of α-alumina in the mixture. Mixture of particles is then calcined at 1250 to 1470°C to give target carrier.

EFFECT: increased activity of catalyst/carrier combination and prolonged high level of selectivity at moderated temperatures.

21 cl, 3 tbl

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