Catalyst for obtaining synthesis-gas and method for obtaining synthesis-gas using same

FIELD: chemistry.

SUBSTANCE: invention relates to catalyst for obtaining synthesis-gas, which contains carbon monoxide and hydrogen as main components, from raw material, containing hydrocarbon gas, which has 1 to 5 atoms of carbon in each molecule, such as natural gas, and oxygen; as well as to method obtaining synthesis-gas using such catalyst. Catalyst for synthesis-gas production, which contains metal of group VIII applied on carrier is described. Carrier contains the first component, second component and third component. The first component represents oxide of ,at least, alkaline earth metal chosen from the group of magnesium, calcium, strontium and barium. The second component represents oxide of, at least, an element chosen from the group of scandium, iridium and lantanoids. The third component is zirconium dioxide or substance containing zirconium dioxide as main component and has property of hard electrolyte, molar ratio of the second and first components being within the range of 0.02 to 0.40, and that of the third and first components within the range of 0.04 to 1.5. Method of production of synthesis-gas in presence of the above catalyst is also described.

EFFECT: essential reduction of reaction equipment size and improvement of equipment energy efficiency.

17 cl, 2 tbl, 24 ex

 

The technical field to which the invention relates

This invention concerns a catalyst to produce synthesis gas containing carbon monoxide (CO) and hydrogen (H2) as main components, from raw materials containing hydrocarbon gas having 1 to 5 carbon atoms in each molecule, such as natural gas, and oxygen (O2), and method of producing synthesis gas using a catalyst.

The level of technology

Natural gas is attracting attention as an energy source, which in the future can replace oil. Because natural gas has combustion characteristics, which make it cleaner than other fossil fuels, it will be very beneficial to accelerate the use of natural gas as a source of primary and secondary energy from the point of view of environmental protection.

For this reason, at present, great efforts are aimed at developing technologies for the production of methanol, DME (dimethyl ether) and synthetic oils as well as other substances using chemical conversion of natural gas. The so-called indirect method transformation using synthesis gas, which creates a starting material for synthesis, represents the main focus of technological development. Technology for production of synthesis gas play VA the role in the entire process of the transformation from the point of view of economy.

Known methods for producing synthesis gas include among others (1) the steam reforming process, (2) ATC (autothermal reforming) method, and (3) PCOC (catalytic partial oxidation) method.

Since the reaction of the steam reforming process is endothermic, it is necessary to place the reaction tube in the furnace installation reformer, and the reformer needs external supply of heat. Because heat must be submitted with the set speed, the size of the installation, you must increase in proportion to the scale of production. In other words, this method provides little or no scalable advantage and, therefore, not suitable for large-scale production. Although the reforming of carbon dioxide, which can convert carbon dioxide with steam in the synthesis gas, also known, it is accompanied by a similar problem.

ATC method is a method with the reaction samorazogreva type, when oxygen is added to the feed gas to incomplete combustion and the heat generated by the combustion, is used for the subsequent reaction of the reforming process, which is an endothermic reaction. In ATK mode the hydrocarbon in the feed gas is partially burned in the burner and the resulting hot combustion gas (mainly containing steam and carbon dioxide, which predstavljaetsja combustion products, and unburned source gas into the catalyst bed. Although this method reduces the size of the installation compared to the steam reforming process, this unit is still great, if it is used for GUI (gas to liquid) production. Therefore, efforts are needed to reduce the size of the installation. In addition, the way ATC is difficult to make the installation in a cost-optimal conditions as pairs must be handed in excess of to protect the burner from premature end of its service life and other reasons.

Finally, the method of partial catalytic oxidation is a method of catalytic combustion of part of the hydrocarbon (which, basically, is a methane) on the catalyst and the reforming received hot gas burning on the same catalyst bed immediately afterwards. Although this method is still in the research and development, it includes only a simple mechanism and is promising from the point of view of thermal efficiency and performance. In addition, he demonstrates a satisfactory reaction performance, if OCSG (body clock speed gas) is increased by one digit from the steam reformer and method ATK, making it particularly suitable for krupnomasshtabnogo the production. However, the method of partial catalytic oxidation is accompanied by a problem for which heat tends to concentrate near the entrance to the catalyst bed (creating a so-called hot spot), and therefore must be of sufficient dimension to prevent the catalyst from damage due to high temperatures and reactor from damage.

The formation of a hot spot near the entrance to the catalyst bed in the way the partial catalytic oxidation is attributed to the fact that this method of generating synthesis gas contains a two-stage reaction system, which includes the reaction of incomplete combustion of methane, which is a main component of a source gas (exothermic reaction generating heat at a rate of approximately 800 kJ/mol) and the subsequent reaction of the steam reformer combustion gas (endothermic reactions absorb heat at a rate of approximately 250 kJ/mol) and the reaction of the reforming of carbon dioxide (endothermic reactions absorb heat at a rate of approximately 200 kJ/mol), and the heat release rate the first stage is very high. If such a reaction system to be implemented through direct catalytic partial oxidation or direct reaction system is expressed by the formula (1) below (endothermic reaction heat absorption with the speed of the sample is about 30 kJ/mol), it will be possible to carry out the method, which can avoid the formation of hot points.

CH4+1/2O2>CO+2H2(1)

The above prior art is described in international publications WO 97/37929 and WO 01/36323, if you give a short list.

Description of the invention

It is necessary to develop a catalyst and method that is highly selective to implement direct catalytic partial oxidation, as discussed above formula (1). However, to date not reported industrial success of such development.

In view of the above circumstances, the present invention is to provide a new catalyst to produce synthesis gas, which can realize the direct catalytic partial oxidation, expressed by the above formula (1) suppression of complete oxidation, and a new method for producing synthesis gas using a catalyst.

When synthesis gas is produced in large scale by using the method of partial oxidation and by increasing the volumetric hourly rate of gas, it is difficult to develop a device that uses a compacted layer of catalyst due to too much pressure loss that it causes. Although known carriers, which form only a small pressure loss, include cell structure and other similar structures as well as the porous body, such as foamed body such patterns and body structurally complex, and therefore, at present only a limited number of easily moldable materials, such as alumina, and stabilized zirconium oxide, can be used for this purpose. If the holders of any of these materials are made to directly cause the metal of group VIII, such as Rh, to form a catalyst, the method of catalytic partial oxidation, which uses such a catalyst is not commercially feasible because of the low speed conversion and low selectivity. In particular, the oxides of aluminum and zirconium can easily cause adverse reactions because they have weak acidic characteristic of the surface and provide only low magnitude conversion and low selectivity. In addition, they are easy to cause the deposition of carbon.

Therefore, another objective of the present invention is to provide a catalyst that can give structure, demonstrating the high value of conversion, high selectivity and an increased degree of resistance to the deposition of carbon, and at the same time adapted to the situations when you need very high speed gas flow, in order to reduce the contact time to less than 30×10-3with without the occurrence of a large pressure loss.

According to the of the invention the above objectives are achieved by the supply of catalyst to produce synthesis gas, containing carbon monoxide and hydrogen as main components, from a source gas containing a hydrocarbon having from 1 to 5 carbon atoms in each molecule, and oxygen. The specified catalyst to produce synthesis gas has a carrier and a metal of group VIII supported on a carrier; and said media contains the first component, second component and third component; the first component is an oxide of at least one alkaline earth metal selected from the group of magnesium (Mg), calcium (CA), strontium (Sr) and barium (BA); the second component is an oxide of at least one element selected from the group of scandium (Sc), yttrium (Y) and lanthanoids; the third component is an oxide of zirconium or substance containing zirconium oxide as a main component and having the properties of a solid electrolyte.

Preferably, when the molar ratio mentioned second component relative to that of the first component is from 0.02 to 0.40, and the molar ratio mentioned third component relative to that of the first component ranges from 0.04 to 1.5.

Preferably, when the said first component is a magnesium oxide (MgO) or magnesium oxide, which contains calcium oxide (Cao).

P is edocfile, when the said second component is an oxide of at least one element selected from the group of scandium (Sc), yttrium (Y), lanthanum (La), cerium (CE), praseodymium (Pr), neodymium (Nd) and samarium (Sm).

More preferably, when the said second component is an oxide of cerium (CE).

Preferably, when said third component is at least one substance selected from the group of zirconium oxide, of zirconium oxide stabilized with calcium, zirconium oxide, stabilized magnesium, zirconium oxide stabilized with yttrium, zirconium oxide stabilized with scandium, and zirconium oxide stabilized with cerium.

More preferably, when said third component is a zirconium oxide or zirconium oxide stabilized with calcium.

Preferably, when said media includes a porous body, which acts as a substrate for the recording medium, and a cover film formed on this porous body by coating, and the above-mentioned cover film contains mentioned the first component, referred to the second component and said third component.

Preferably, when the said porous body made of at least one substance selected from ceramic foam and ceramic honeycombs.

Preferred is entrusted, when mentioned porous body made of ceramic foam and has a honeycomb structure 10 to 40 cells per inch.

Preferably, when the said porous body made of a ceramic honeycomb and has a structure from 100 to 400 cells per square inch.

Preferably, when the said metal of group VIII is a metal selected from the group of rhodium (Rh), platinum (Pt), palladium (Pd), ruthenium (Ru) and iridium (Ir).

More preferably, when the said metal of group VIII is a rhodium (Rh).

Preferably, when the said metal of group VIII supported on a carrier in an amount of from 100 to 50,000 mass ppm per unit of mass media.

Preferably, when the said metal of group VIII supported on a carrier in an amount of from 2×10-7up to 5×10-3mol/m2per unit surface area of the media.

In another aspect, the present invention proposes a method of generating synthesis gas containing carbon monoxide (CO) and hydrogen (H2) as main components, by contact source gas containing a hydrocarbon having from 1 to 5 carbon atoms in each molecule, and the oxygen (O2), a catalyst for production of synthesis gas, wherein the catalyst for production of synthesis gas has a carrier and a metal of group VIII deposited on a specified device; and referred to Eitel contains the first component, the second component and the third component; the first component is an oxide of at least one alkaline earth metal selected from the group of magnesium (Mg), calcium (CA), strontium (Sr) and barium (BA); the second component is an oxide of at least one element selected from the group of scandium (Sc), yttrium (Y) and lanthanoids; said third component is a zirconium oxide or a substance containing zirconium oxide as a main component and having the properties of a solid electrolyte.

Preferably, when the molar ratio mentioned second component relative to that of the first component is from 0.02 to 0.40, and the molar ratio mentioned third component relative to that of the first component ranges from 0.04 to 1.5.

It is preferable that when the number of moles of carbon source hydrocarbon expressed as s, the value Of2/S in the feed gas lies within the range from 0.3 to 0.6, the temperature of the gas at the inlet catalyst layer filled with a catalyst to produce synthesis gas, regulate in such a way that it ranges from 100 to 500°and the gas temperature at the outlet of the catalyst layer regulate in such a way that it ranges from 600 to 1200°while the gas pressure at the inlet catalyst layer Regulus who have thus it ranges from 0.1 MPa to 10 MPa.

Preferably, when the method for production of synthesis gas according to the present invention the contact time (t) is chosen within the range from 5×10-4up to 3×10-2(C).

Thus, according to the invention proposes a new catalyst to produce synthesis gas, which allows you to implement a direct catalytic partial oxidation and, therefore, it is now possible to implement a method for production of synthesis gas using the method of catalytic partial oxidation of natural gas, has not reported any success. In addition, when implementing this method can significantly reduce the size of the unit to produce synthesis gas compared to installations using known techniques to produce synthesis gas (for example, the steam reforming process and the way ATC), and also to improve thermal efficiency. In particular, it is possible to implement a method, suitable for the production of synthesis gas, such as GUI, on a large scale.

The best way of carrying out the invention

Catalyst for production of synthesis gas and method for producing a synthesis gas according to the invention are described in detail below.

(1) a Catalyst for synthesis gas production

Catalyst to produce synthesis gas according to the invention is intended for use in synthesis-ha is a, containing carbon monoxide (CO) and hydrogen (H2) as main components, from a source gas containing a hydrocarbon having from 1 to 5 carbon atoms in each molecule, and the oxygen (O2).

Catalyst for production of synthesis gas according to the invention has a carrier and a metal of group VIII supported on a carrier.

The media contains the first component, second component and third component.

The first component contained on the media, is an oxide of at least one alkaline earth metal selected from the group of magnesium (Mg), calcium (CA), strontium (Sr) and barium (BA). Among these oxides, it is preferable that the first component consisted of a magnesium oxide (MgO) or magnesium oxide, which contains calcium oxide (Cao).

The second component contained on the media, is an oxide of at least one element selected from the group of scandium (Sc), yttrium (Y) and lanthanoids. More specifically, the second component is an oxide of at least one element selected from the group of scandium (Sc), yttrium (Y), lanthanum (La), cerium (CE), praseodymium (Pr), neodymium (Nd) and samarium (Sm). Among these oxides, it is preferable that the second component was an oxide of cerium (CE).

The third component contained on the media, represents at least one substance, the expletive from the group of zirconium oxide, zirconium oxide stabilized with calcium, zirconium oxide, stabilized magnesium, zirconium oxide stabilized with yttrium, zirconium oxide stabilized with scandium, and zirconium oxide stabilized with cerium. Among these oxides, it is preferable that the third component consisted of zirconium oxide or zirconium oxide stabilized with calcium.

The relative content of the first component, second component and third component is determined as follows. The molar ratio of the second component relative to the first component is preferably from 0.02 to 0.40, more preferably from 0.08 to 0.30, more preferably from 0.10 to 0.25. The molar ratio of the third component relative to the first component is preferably from 0.04 to 1.5, more preferably from 0.2 to 1.0, more preferably from 0.3 to 0.6.

The amount of conversion of initial hydrocarbon tends to fall when the molar ratio of the second component relative to the first component is too small and less than 0.02. The magnitude of the conversion of hydrocarbon source also tends to fall when the molar ratio is too large and exceeds 0,40.

The selectivity of the formation of hydrogen and the selectivity of the formation of carbon monoxide tend to fall when alamae the ratio of the third component relative to the first component is too small and less than 0,04. The amount of conversion of initial hydrocarbon and the selectivity of the formation of hydrogen tend to fall when the ratio is too large and exceeds 1.5.

The media containing the above three component, receive a first weighting components to obtain a predetermined composition, and then by forcing the composition sequentially pass through the stage of mixing, the step of pressing/molding, and the step of firing. If necessary, add a binder and mixed with the powder composition during extrusion/molding. The specific surface area of the obtained carrier is from 0.1 to 5 m2/g, preferably from 0.2 to 1 m2/Used here, the specific surface area represents a specific surface area by BET, as measured by adsorption of nitrogen.

The media can be in powder, granular, spherical, cylindrical or tubular. The form of media, you can choose accordingly depending on the catalyst layer.

For the purpose of the present invention, the carrier may contain a porous body, which functions as a substrate for the carrier and the cover film formed on this porous body by covering.

Porous body, which functions as a substrate for the carrier, preferably izgotovlen the Ute, at least one substance selected from a ceramic foam having a three-dimensional mesh structure, and ceramic honeycomb having a similar lattice structure, although porous ceramic plate having a two-dimensional honeycomb structure (for example, Repton, available from Kikusui Chemical Industries Co., Ltd.), can be used for alternative porous body.

A porous body having a uniform and continuous three-dimensional mesh structure, which is wonderful porous structure, get when aerated soft polyurethane foam is used as a starting material for the ceramic foam. The basic structure of the ceramic foam is produced by coating the surface of the skeleton of a cellular urethane foam ceramic material and firing or sintering the coated urethane foam for burnout urethane part foam, and only the ceramic part. Thus, the porosity of this porous body is so high that ranges from 80 to 90%. In addition, it is possible to regulate the heat resistance, impact resistance, strength, pressure losses, and other properties of the porous body by selecting the corresponding ceramic material.

The above honeycomb structure of ceramic foam has from about 10 to 40 cells per inch (obtained by averaging the number of air bubbles, close the data to straight lines in 25.4 mm), preferably from about 20 to 30 cells per inch.

The ceramic foam material is chosen from the group of materials including alumina, cordierite, alumina/cordierite, silicon carbide, mullite and alumina/Zirconia.

On the other hand, ceramic honeycombs are usually obtained by extrusion molding and have a plurality of longitudinal then directed along the axis of the body, with profile cylinder, elliptic cylinder and prism. Therefore, many physical properties of ceramic honeycombs are directional in contrast to ceramic foam. The above materials that can be used for ceramic foam can also be used for ceramic honeycomb for the purpose of the present invention. The porous structure of the ceramic honeycomb preferably is from 100 to 400 cells per square inch.

Covering film that is placed on the porous body and is external media item contains the first component, second component and third component.

The following technology is preferably used for the formation of the covering film containing the above three component on the porous body. First prepare a suspension containing the elements of the first component, second component and third component in the form of hydroxides or oxides with a predefined relative activities is essential contents, and once or repeated several times perform an operation of dipping the porous body (for example, a ceramic foam) in the suspension and its retrieval for drying to obtain a film coating. Then the desired covering film is formed by firing the porous body at a high temperature of approximately 1000°C. the Slurry can be sprayed on the porous body, when forming a film coating on a large porous body. Three components can be used separately. More specifically, it is possible to form a film coating of MgO and then to form a film coating of SEO2and film coating of ZrO2. Alternatively, they can be formed in a different sequence. Suspension three components can consistently be used to form a covering film or the process of applying suspensions of the three components can be repeated several times.

The metal of group VIII is applied to the surface of the carrier as described above with obtaining a catalyst according to the invention.

The metal of group VIII can be applied in the metal state or in a state of connection of the metal such as the oxide.

The metal of group VIII preferably represents at least one metal selected from the group of rhodium (Rh), platinum (Pt), palladium (Pd), ruthenium (Ru) and iridium (Ir). Especially preferable to use rhodium (Rh).

Met the ll group VIII is applied to the carrier is preferably in quantities of from 100 to 50,000 mass ppm, more preferably in quantities of from 500 to 5000 mass ppm, more preferably from 700 to 3000 mass ppm per unit of mass media. The reaction rate tends to fall and the value of conversion also tends to fall when the amount is less than 100 mass ppm per unit of mass media. Reactivity does not show any improvement when the amount exceeds 50,000 mass ppm per unit of mass media. Therefore, it is generally preferable, when the metal of group VIII is applied to the carrier in an amount of from 100 to 50,000 mass ppm per unit of mass media from the point of view of effective use of deposited metal of group VIII.

In other words, the metal of group VIII is applied to the carrier in an amount of from 2×10-7up to 5×10-3mol/m2per unit surface area of the media.

The metal of group VIII can be applied using any of the known conventional methods. One of the preferred ways that you can use for the purpose of the present invention, is a method of impregnation. When the catalyst according to the invention is prepared by impregnation method, a carrier is dipped in a solution containing the metal catalyst. Then the media carrying the metal oxide is separated from the mother solution, dried and calcined.

The method of adding a solution of metal salt inthe number, good for the specific surface area of the carrier, little by little, by dripping or spraying, to make the surface of the medium evenly moist, and drying and firing the media (wet component) are also effective.

When using any of these methods, as a metal salt catalyst used is a water-soluble salt. Such water-soluble salt contains inorganic salts, such as nitrates and chlorides, and organic acid salts such as acetates and oxalates. Alternative, metal acetylacetonate can be dissolved in an organic solvent, such as acetone, and the carrier can be impregnated with this solution. The carrier impregnated with the aqueous solution of metal salt catalyst is dried at a temperature of from 100 to 200°C, preferably from 100 to 150°C. When the carrier is impregnated with the organic solvent, the impregnated carrier is preferably dried at a temperature higher than the boiling point of the solvent, at from 50 to 100°C. the firing Temperature and the firing time of the dried product, you can choose accordingly depending on the obtained catalyst. Typically, the firing temperature lies between 300 and 1300°C.

(2) a Method for production of synthesis gas

Method for production of synthesis gas according to the invention consists in the use of catalysis is ora produce synthesis gas, described above. In this way the catalyst layer is formed by filling the reaction vessel, such as a column reactor, a catalyst, serves a source gas containing a hydrocarbon having from 1 to 5 carbon atoms in each molecule, and the oxygen through the inlet of the reaction vessel, causing it to contact with the catalyst bed to convert the source gas in a synthesis gas containing carbon monoxide (CO) and hydrogen (H2) as main components in the reaction vessel and remove the reaction products through the exit of the reaction vessel.

Preferred examples of the hydrocarbon having from 1 to 5 carbon atoms in each molecule, include methane, ethane, propane and butane. Natural gas containing methane as a main component, can preferably be used for the purpose of the invention. Oxygenated compounds such as alcohols, ethers and esters can also be used for purposes of the invention. Thus, for the purpose of the invention "hydrocarbons" include oxygen-containing compounds.

Oxygen, air or oxygen-enriched air is used as the oxygen source for the purpose of the present invention.

The source gas may contain an inert gas, such as argon, as a dilution gas.

When the number of moles of carbon source is of glendorado expressed as, the value Of2/C (molar ratio) in the source gas is within the range of from 0.3 to 0.6, preferably within the range from 0.4 to 0.6. The conversion rate of the source gas decreases when the molar ratio is less than 0.3, whereas complete oxidation increases and output the resulting synthesis gas is falling, when the molar ratio exceeds 0.6. When the alcohols, ethers and esters, are used for the source gas, the feed rate of the source gas and the feed rate of oxygen-containing gas is adjusted to satisfy the above requirement, after information About2the number of oxygen atoms around the gas, which is introduced into the catalyst bed.

Gas temperature respectively at the inlet and outlet of the catalyst layer, which is filled with a catalyst to produce synthesis gas according to the invention is such that the temperature of the gas from the entrance is from 100 to 500°With (preferably from 200 to 500°S, more preferably from 200 to 400° (C)while the temperature on the output side is from 600 to 1200°With (preferably from 600 to 900°S, more preferably from 600 to 800° (C)when taken into account the conversion rate of the source gas, which depends on the speed of reaction and the amount of energy required to preheat the gas. Steam which is mixed with the gas with which RAM, can be translated into a liquid state, if, in particular, the temperature is below 100°With side entrance, while methane and oxygen can give rise to spontaneous ignition when the temperature exceeds 500°C. the Degree of conversion of methane drops to economically disadvantageous, when the temperature is lower than 600°on the output side, while the rate of energy expenditure also increases to economically disadvantageous because of the need for pre-heating, when the temperature exceeds 1200°C.

The gas pressure at the inlet to the catalyst bed to determine from an economic point of view, given the fact that the equipment, including the reactor can be reduced in size, but must be used to withstand the pressure equipment when using high pressure gas. Normally, when the gas pressure is in the range from 0.1 MPa to 10 MPa, preferably from 0.5 MPa to 7 MPa, most preferably from 0.5 MPa to 5 MPa.

The contact time t (sec), which is determined by dividing the volume V(m3), occupied by the catalyst bed, the flow rate of the gas (m3/sec)is in the range from 5 x 10-4and 3 x 10-2(sec), preferably from 1×10-3up to 2×10-2(s) even more preferably, from 3×1-3up to 1×10-2sec. When time is of ntact less than 5×10-4(sec) hydrocarbons simply skips, with a reduction in the rate of conversion, while when the contact time exceeds 3×10-2(s) generated synthesis gas increases with decreasing speed conversion as a consequence of the reverse flow of the steam reforming reaction (CO+3H2CH4+H2O) and the reverse reaction of the reforming of carbon dioxide (2SD+2H2CO2+CH4).

Various types of catalytic processes gas/solid, including the type with a fixed catalyst bed, fluidized bed, with the suspended layer, and moving the layer, can be used in the production of synthesis gas using the catalyst according to the invention, although preferably adopted type fixed bed.

When the method of manufacturing a synthesis gas according to the invention uses a pre-defined catalyst for the production of synthesis gas according to the invention defined above production conditions, it is possible to implement a system of direct partial oxidation, which is a system of direct conversion (heat speeds of about 30 kJ/mol), as expressed by the formula (1) below.

CH4+1/2O2+2H2(1)

Based on the above formula it is possible directly to produce synthesis gas with a molar ratio of N2/CO = 2 or near the m to the given value in order to provide raw material for methanol, FT synthesis and DME without the need for gas separation of hydrogen from the produced gas.

EXAMPLES

Here, the present invention will be described in more detail using examples.

(Examples 1 to 6, comparative examples 1 to 16).

Magnesium hydroxide (Mg(OH)2), zirconium oxide (ZrO2·8H2O), cerium oxide (CE(OH)4·2H2O) and calcium carbonate (caso3in the state of powder was weighed and used to obtain the composition of the components for each of Examples 1 to 6 and Comparative examples 1 to 15 as listed in Table 1 below, were added to 3.5 wt.% carbon and stirred in the unit to obtain a homogeneous mixture.

The obtained powder mixture is extruded compression with getting disks with a diameter of 2 cm at a pressure of 3 t/cm2and progulivali at atmospheric pressure at a temperature of from 1100 to 1200°C for 6 hours.

Each of the products compression was crushed into pieces to obtain particles of medium size from 0.8 to 1.1 mm, the Capacity of moisture retention of the obtained carrier was determined in advance, and the media were completely soaked in the respective aqueous solutions of rhodium acetate, up to a limit defined by the capacity of moisture retention. In this case, the concentration of aqueous solutions of rhodium regulated so the m way to the concentration of rhodium in the media after the second calcination, mentioned below, was 2000 ppm, mass. (Examples 1 to 4, Comparative examples 1 to 16) 10000 ppm mass. (Example 5) and 700 ppm of the mass. (Example 6).

Media impregnated with appropriate aqueous solutions of rhodium, dried under atmospheric pressure at 50°C for 16 hours, and then again progulivali at atmospheric pressure at 950°C for 3 hours.

After the secondary annealing is 0.84 ml of each catalyst was loaded into the reaction tube having an inner diameter of 16 mm and placed in the annular electric furnace. Pocket for thermocouple was located in the center of the reaction tube to monitor the temperature distribution in the catalyst bed, at the beginning and end of the layer. The pre-catalyst was reduced by hydrogen at 950°within hours, and a raw material gas containing oxygen, methane and argon in the ratio of O2:CH4:Ar=15:30:55 (mol %) was applied under conditions comprising a pressure of 0.1 MPa and OCSG=400000 (1/hour) (contact time=9 ISS). Test synthesis gas production continued at a temperature of 650±2°at the outlet of the catalyst bed. The composition of the final gas was kept constant during the test period of about 10 hours. The degree of methane conversion, the selectivity for N2and selectivity, set forth below, determine which ranged from the flow rate of gas obtained at the outlet and the CO content, CO2and N2obtained by chromatographic analysis of the gas.

The degree of methane conversion = (speed of the incoming stream of methane - speed exhaust methane)/(speed of the incoming stream of methane).

Selectivity for hydrogen = (speed exhaust hydrogen × 0,5)/(speed of the incoming stream of methane - speed exhaust methane).

The selectivity for CO = (speed exit stream FROM)/ (speed of the incoming stream of methane - speed exhaust methane).

(The unit for the flow rate of each incoming gas and the flow rate of each gas coming is mol/hour).

In addition, after the end of the test, the carbon content of each catalyst was measured to determine the increase in mass of carbon (the rate of deposition of carbon).

The results of the experiment are summarized in table 1.

From the results, summarized in table 1, it is clear that the catalyst according to the invention and prepared when using the media containing the predefined three ingredients, showed a high conversion, high selectivity and excellent resistance to carbon deposits (a slight increase in the amount of carbon) (Examples 1 to 6).

As can be seen from the data of Comparative Examples 1 to 4, it is clear that the degree of conversion and selectivity are reduced when the Aulnay ratio of the second component and the first component and the molar ratio of the third component and the first component beyond the corresponding interval from 0.02 to 0.40 and from 0.04 to 1.5.

In addition, as can be seen from the data in Comparative Examples 5 to 9, while the addition of the third component (ZrO2to the first component (MgO) increases as the selectivity for N2and selectivity, the degree of methane conversion and resistance to deposits of carbon are not satisfactory. The addition of a third component (ZrO2) accelerates the deposition of carbon from the point of view of its connection with the first component (MgO).

In addition, as can be seen from the data in Comparative Examples 10 to 14, while adding a second component (CeO) to the first component (MgO) leads to an improvement in methane conversion, the selectivity for N2and selectivity along WITH a little reduced and resistance to deposits of carbon is not satisfactory.

In addition, it is seen that the conversion rate falls sharply in the case of media, obtained using the second component (SEO2and the third component (ZrO2) (Comparative example 15).

Finally, when using the carrier of Al2O3that is a common used by the carrier for catalyst for partial oxidation (Comparative example 16), the degree of methane conversion and selectivity for H2and the selectivity to CO is not satisfactory, and resistance to carbon deposition is small, so the carbon is deposited in b is Lishou degree.

Thus, from the above experiment results, it is clear that all the catalysts of the above examples work very well. In addition, a high degree of conversion was achieved at gas temperature of approximately 650°With all the examples. This shows that the equilibrium value of the reformer 66% at 650°exceeded, and therefore, the method of manufacturing a synthesis gas according to the invention provides high thermal efficiency in comparison with conventional methods of oxygen reforming, including the popular ATC method.

(Example 7)

Ring-shaped porous body frothy aluminum oxide (20 cells per inch, available at Kurosaki Harima), having an external diameter of 16 mm and an inner diameter of 7 mm and a height of 5 mm, was prepared for the substrate carrier.

The porous body was dipped in a suspension containing magnesium hydroxide (MgO content after strong ignition: 97.8 per cent), cerium oxide (98%) and the hydroxide of zirconium (ZrO2··nH2O: ZrO2content: 73%) as an oxide with a ratio MgO/CeO2/ZrO2=33,3/33,3/33,3 (wt.%) and was taken out for drying. The specified cyclic operation is repeated several times.

Then soaked in a suspension of the porous body was progulivali in air at 1200°for formation of the coating film containing the three components MgO/CeO2/ZrO2on the surface (preparation of media).

<> After this pre-determined capacity for holding water carrier, and the carrier impregnated with the aqueous solution of rhodium acetate equal to a specific amount of water held by the carrier. The concentration of rhodium acetate in aqueous solution was adjusted so that the concentration of rhodium in the media has become equal to 2000 mudmats. (the equivalent at Rh=3,8×10-5mol/m2after the secondary stage calcination.

Further, the carrier impregnated with an aqueous solution of Rh, subjected to the secondary calcination at 400°C for 6 hours to obtain the catalyst of this example.

The prepared catalyst was loaded in the reaction tube having an inner diameter equal to 16 mm, and located in the annular electric furnace. Then there was a test for the production of synthesis gas, as in the examples 1 to 6 and Comparative examples 1 to 16 (except that the time of the test was 3 hours, and the temperature of the gas at the outlet of the catalyst layer was 900° (C)to determine the degree of methane conversion, the selectivity for N2, selectivity and increase the amount of carbon, as in the previous experiments.

The results obtained are summarized in table 2.

(Comparative example 17)

The sample of example 17 was prepared as in example 7, except that used for media tol is to frothy alumina (20 cells per inch, available at Kurosaki Harima), and used the covering film of MgO/CeO2/ZrO2. The obtained sample was subjected to similar testing to obtain synthesis gas (except that the temperature of the gas at the outlet of the catalyst layer was 925°).

The results obtained are summarized in table 2.

From the results listed in table 2, it is clear that the catalyst obtained using the media from the foaming of aluminium oxide and having a covering film of MgO/CeO2/ZrO2and bearing Rh, shows a high degree of conversion, high selectivity as H2and WITH high resistance to deposition of carbon (a slight increase in the amount of carbon).

(Example 8)

The experiment was carried out to verify the advantage of the catalyst according to the invention in terms of pressure loss in the catalyst.

In the experiment measured the loss of pressure on the foam catalyst. More specifically, the catalyst was prepared from the molded product of foamed aluminum oxide having a diameter of 80 mm and a width of 40 mm, as in Example 7, and was loaded into a tube with an internal diameter of 80 mm, then the output tube was left in the atmosphere and was passed through the catalyst in the air to observe the pressure loss. It was found that the pressure loss in line soon is Ty = 4.8 m/sec was 0.04 MPa.

(Comparative example 18)

In order to compare the pressure loss in the catalyst bed was determined by calculation for the situation when the object were used for comparison annular catalyst (16 mm x 16 mm) and loaded into the reaction tube in the assumed conditions, when the pressure at the outlet of the catalyst layer is equal to the atmospheric pressure, the contact time is 10 ľs (linear velocity = 4.8 m/sec) and the height of the catalyst layer is 50 mm, the Evaluation formula described in the catalytic tutorial, which released Sud-Chemie Japan, was used for calculations.

As a result, it was found that the pressure loss with the use of an object for comparison was 0.3 MPa.

It is clear from the results, the catalyst for catalytic partial oxidation according to the present invention showed a high conversion, high selectivity as H2and WITH high resistance to the deposition of carbon (a slight increase in the number of carbon) compared with any of the known catalysts for the catalytic partial oxidation, and makes it possible to implement a method for catalytic partial oxidation, which requires a very high velocity of the gas stream, which can reduce the contact time to less than 30 MS due to low pressure loss.

Table 1
Sample # Media components wt.%

(unit values in (): 100 mol/g)
Activemeter Rh (ppm)The second/ first component (mol/mol)Third/ first component (mol/mol)The degree of methane conversion (%)H2selek-efficiency

(%)
CO, selecti-you want to make

(%)
The increasing amounts of carbon in the used catalyst (%)
MgOZrO2CeO2CaOAl2O3
Example 133 (0,819)33 (0,268)33 (0,192)--20000,2340,32779,9to 91.191,20,005
Example 240 (0,993)40 (0,325)20 (0,116)--20000,1170,32779,590,290,70,003
Example 335 (0,863)50 (0,406)15 (0,087) --20000,1000,46779,091,291,40,003
Example 4-33 (0,268)33 (0,192)33 (0,588)-20000,3260,45578,890,591,50,004
Example 533 (0,819)33 (0,268)33 (0,192)--100000,2340,32780,091,291,50,006
Example 633 (0,819)33 (0,268)33 (0,192)--7000,2340,32780,091,291,50,002
Comparative example 162 (1,538)33 (0,268)5

(0,029)
--20000,0190,17469,5to 89.9to 91.10,005
Comparative example 233 (0,819)10 (of 0.081)57 (0,331)--20000,4040,09976,3to 89.99,6 0,003
Comparative example 350 (1,241)5

(0,041)
45 (0,261)--20000,2110,03379,088,589,00,006
Comparative example 415 (0,372)70 (0,568)15 (0,087)--20000,2341,52774,486,291,20,053
Comparative example 5-100 (0,812)---2000--60,685,093,80,215
Comparative example 610 (0,248)90 (0,731)---2000-2,94472,687,190,20,139
Comparative example 750 (1,241)50 (0,406)---2000-0,32768,893,892,00,019
Comparative example 890 (2,233)10 (of 0.081) ---2000-being 0.03669,2to 91.190,60,011
Comparative example 9100 (2,481)----2000--71,991.1to 89.50,008
Comparative example 10--100 (0,581)--2000--64,479,684,10,006
Comparative example 1110 (0,248)-90 (0,523)--20002,107-77,990,689,20,007
Comparative example 1250 (1,241)-50 (0,291)--20000,234-79,290,289,40,007
Comparative example 1370 (1,737)-30 (0,174)--20000,100-77,08,0 of 89.10,007
Comparative example 1490 (2,233)-10 (0,058)--20000,026-76,589,887,60,008
Comparative example 15-50 (0,406)50 (0,291)--2000--65,284,590,00,005
Comparative example 16----100 (0,98)2000--75,084,190,70,099

Table 2
Sample # MediaActive metalThe outlet gas temperature catalyst layer (°)The degree of methane conversion (%)H2selek-efficiency

(%)
CO selek ciency (%)The increasing amounts of carbon in the used catalyst (%)
Example 7MgO/CeO2/ZrO2Foamy aluminum oxideRh:3,8×10-5< / br>
mo the e/m 2
90061,187,5to 92.10,02
Comparative example 17Foamy aluminum oxideRh:3,8×10-5< / br>
mol/m2
92545,061,090,90,09

1. The catalyst for the production of synthesis gas containing carbon monoxide and hydrogen as main components, from raw material gas containing hydrocarbon having from 1 to 5 carbon atoms in each molecule and oxygen, characterized in that

the catalyst for the production of synthesis gas is a carrier and the metal of group VIII supported on a carrier;

said media contains the first component, second component and third component;

mentioned first component is an oxide of at least alkaline earth metal selected from the group of magnesium, calcium, strontium and barium;

mentioned second component is an oxide of at least element selected from the group of scandium, yttrium and lanthanides; said third component is a zirconium dioxide or a substance containing Zirconia as a main component, and has properties of a solid electrolyte,

when this molar of sootnoshenie the mentioned second component and said first component is in the range from 0.02 to 0.40 and the molar ratio mentioned third component and said first component is in the range from 0.04 to 1,5.

2. The catalyst according to claim 1, in which the first mentioned component is a magnesium oxide or magnesium oxide containing calcium oxide.

3. The catalyst according to claim 1, in which the aforementioned second component is an oxide of at least member selected from the group of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium and samarium.

4. The catalyst according to claim 3, in which the aforementioned second component is an oxide of cerium.

5. The catalyst according to claim 1, in which said third component represents at least a substance selected from the group of zirconium dioxide stabilized with calcium zirconium dioxide stabilized with magnesium zirconium dioxide, yttrium-stabilized zirconium dioxide, scandium stabilized Zirconia, stabilized cerium zirconium dioxide.

6. The catalyst according to claim 5, in which said third component is a Zirconia or stabilized calcium zirconium dioxide.

7. The catalyst according to claim 1, wherein said media includes a porous body, which is a substrate for the carrier and the cover film formed on the porous body by coating, and the above-mentioned cover film contains mentioned the first component, referred to the second component and said third component.

8. It is talization according to claim 7, in which mentioned porous body made at least from a material selected from a ceramic foam of ceramic cell coverage.

9. The catalyst according to claim 8, in which the aforementioned porous body made of ceramic foam and has a honeycomb structure 10 to 40 cells per inch.

10. The catalyst according to claim 8, in which the aforementioned porous body made of a ceramic honeycomb coating and has a structure from 100 to 400 cells per square inch.

11. The catalyst according to claim 1 in which the said metal of group VIII represents at least a metal selected from the group of rhodium, platinum, palladium, ruthenium and iridium.

12. The catalyst according to claim 11, in which the said metal of group VIII is rhodium.

13. The catalyst according to claim 1 in which the said metal of group VIII supported on a carrier level from 100 to 50000 ppm wt. per unit of mass media.

14. The catalyst according to claim 1 in which the said metal of group VIII supported on a carrier on level 2×10-7up to 5×10-3mol/m2per unit surface area of the media.

15. Method for the production of synthesis gas containing carbon monoxide and hydrogen as the main ingredients, in which raw material gas containing hydrocarbon having from 1 to 5 carbon atoms in each molecule and oxygen, in contact with the catalyst to produce synthetic the gas, characterized in that

the above-mentioned catalyst for the production of synthesis gas is a carrier and the metal of group VIII supported on a carrier;

said media contains the first component, second component and third component;

mentioned first component is an oxide of at least alkaline earth metal selected from the group of magnesium, calcium, strontium and barium;

mentioned second component is an oxide of at least member selected from the group of scandium, yttrium and lanthanides;

said third component is a zirconium dioxide or a substance containing Zirconia as a main ingredient, and has a property of a solid electrolyte,

when this molar ratio mentioned second component and said first component is in the range from 0.02 to 0.40 and the molar ratio mentioned third component and said first component is in the range from 0.04 to 1.5.

16. The method according to item 15, characterized in that

if the number of moles of carbon, calculated from the hydrocarbon, expressed as the ratio of O2/S in the raw material gas is in the range from 0.3 to 0.6, the temperature of the gas at the inlet catalyst layer filled with a catalyst for the production is odstv synthesis gas, is regulated so that is in the range from 100 to 500°and the gas temperature at the outlet of the catalyst layer is regulated so that is in the range from 600 to 1200°C, while the pressure at the inlet catalyst layer is regulated so that is in the range from 0.1 to 10 MPa.

17. The method according to item 15, wherein the contact time (t) is in the range from 5×10-4up to 3×10-2C.



 

Same patents:

FIELD: technological processes.

SUBSTANCE: inventions may be used for preparation of shielded arc atmospheres, which contain nitrogen with hydrogen or nitrogen with hydrogen and carbon oxide that are used in glass, metallurgical, machine building industries. The first variant of shielded arc atmosphere preparation includes conversion of hydrocarbon gas, steam conversion of carbon oxide, cooling of conversion products with separation of condensed moisture and final purification of gas mixture from carbon dioxide and moisture at adsorption plants. Conversion of hydrocarbon gas is carried out in three stages: the first stage is carried out in free volume of device for oxidation of hydrocarbon gas with air; the second stage is carried out in volume of device that is filled with granular fire-resistant material for performance of steam and carbon-dioxide conversion of remaining hydrocarbon gas; the third stage is carried out in volume of device, which is filled with heat-resistant metal rings for saturation of gas flow with moisture and performance of steam conversion of carbon oxide. The second variant of shielded arc atmosphere includes conversion of hydrocarbon gas, steam conversion of carbon oxide, cooling of conversion products with separation of condensed moisture and final purification of gas mixture from carbon dioxide and moisture at adsorption plants. At that catalytic conversion of carbon oxide is regulated by amount of water vapors condensate, which is supplied into volume of device that is filled with heat-resistant metal rings for saturation of gas flow with moisture. The third variant of shielded arc atmosphere includes conversion of hydrocarbon gas, steam conversion of carbon oxide, cooling of conversion products with separation of condensed moisture and final purification of gas mixture from carbon dioxide and moisture at adsorption plants. At that part of hydrocarbon gas conversion products is sent to cooling device, bypassing device of steam conversion of carbon oxide, and further to adsorption purification unit in order to maintain preset content of carbon oxide in shielded arc atmosphere.

EFFECT: inventions allow to intensify the process and to prepare shielded arc atmosphere of triple composition.

4 cl

FIELD: chemistry.

SUBSTANCE: way of syngas cleaning includes: introduction of the flow of initial syngas, into the feed zone of the distillation column, flow expansion of the liquid remainder from the distillation column by means of a dilator of liquids with the extraction of work for forming the flow of the cooled waste liquid, the rectification of vapour from the feed zone for forming the upper flow of vapour with the decreased content of nitrogen and inert gases, cooling of the upper vapour flow in the indirect heat exchange with the flow of the cooled waste liquid for forming the of partially condensed upper flow and flow of the partially heated waste liquid, separation of the partially condensed upper flow into the flow of condensate and the flow of the purified vapour of syngas with the decreased content of nitrogen and inert gases and the irrigation of distillation column by the flow of condensate. By the first variant the method of production of ammonia includes reforming of hydrocarbon for forming syngas, cooling the flow of initial syngas, expansion of the cooled flow of initial syngas, introduction of the extended flow of initial syngas in the feed zone in the distillation column, flow expansion of liquid remainders from the distillation column with the aid of the dilator of liquid forming the flow of cooled waste liquid, according to the first variant the method of the production of ammonia includes reforming of hydrocarbon for forming syngas, cooling of a stream initial syngas, expansion of the cooled stream initial syngas, introduction of the extended flow of initial syngas in the feed zone in the distillation column, flow expansion of liquid remainders from the distillation column with the aid of the dilator of liquid for forming the flow of the cooled waste liquid, the rectification of vapour from the feed zone in the distillation column for forming the upper flow of vapour with the decreased content of nitrogen and inert gases, cooling the upper flow of vapour in the indirect heat exchange with the flow of the cooled waste liquid for forming of partially condensed upper flow and flow of the partially heated waste liquid, the separation of the partially condensed upper flow into the flow of condensate and the flow of purified vapour of syngas with the decreased content of nitrogen and inert gases, the irrigation the distillation column by the flow of condensate, heating the flow of the purified vapour of syngas in the heat exchanger with the cross-section flow, heating the flow of partially heated waste liquid in the heat exchanger with a cross-section flow, the supply of the flow of the purified vapour of syngas from the heat exchanger with the cross-section flow into the outline of synthesis of ammonia. According to the second variant the method of the production of ammonia includes the reforming hydrocarbon with excess air for forming the flow of initial syngas, removal of nitrogen and inert gases from the flow of the syngas by distillation, thus provide cooling with the aid of the expansion of the liquid by means of the dilator-generator, and the upper flow partially condense the waste flow, cooled by means of expansion of the liquid remainder from the distillation column, and the supply of syngas with the decreased content of nitrogen and inert gases from distillation into the contour of the synthesis of ammonia at which the liquid remainders expand by means of the dilator of liquid with the extraction of work.

EFFECT: invention makes it possible to improve industrial and economic characteristics.

18 cl, 5 dwg, 3 tbl

FIELD: chemistry.

SUBSTANCE: way of syngas cleaning includes: introduction of the flow of initial syngas, into the feed zone of the distillation column, flow expansion of the liquid remainder from the distillation column by means of a dilator of liquids with the extraction of work for forming the flow of the cooled waste liquid, the rectification of vapour from the feed zone for forming the upper flow of vapour with the decreased content of nitrogen and inert gases, cooling of the upper vapour flow in the indirect heat exchange with the flow of the cooled waste liquid for forming the of partially condensed upper flow and flow of the partially heated waste liquid, separation of the partially condensed upper flow into the flow of condensate and the flow of the purified vapour of syngas with the decreased content of nitrogen and inert gases and the irrigation of distillation column by the flow of condensate. By the first variant the method of production of ammonia includes reforming of hydrocarbon for forming syngas, cooling the flow of initial syngas, expansion of the cooled flow of initial syngas, introduction of the extended flow of initial syngas in the feed zone in the distillation column, flow expansion of liquid remainders from the distillation column with the aid of the dilator of liquid forming the flow of cooled waste liquid, according to the first variant the method of the production of ammonia includes reforming of hydrocarbon for forming syngas, cooling of a stream initial syngas, expansion of the cooled stream initial syngas, introduction of the extended flow of initial syngas in the feed zone in the distillation column, flow expansion of liquid remainders from the distillation column with the aid of the dilator of liquid for forming the flow of the cooled waste liquid, the rectification of vapour from the feed zone in the distillation column for forming the upper flow of vapour with the decreased content of nitrogen and inert gases, cooling the upper flow of vapour in the indirect heat exchange with the flow of the cooled waste liquid for forming of partially condensed upper flow and flow of the partially heated waste liquid, the separation of the partially condensed upper flow into the flow of condensate and the flow of purified vapour of syngas with the decreased content of nitrogen and inert gases, the irrigation the distillation column by the flow of condensate, heating the flow of the purified vapour of syngas in the heat exchanger with the cross-section flow, heating the flow of partially heated waste liquid in the heat exchanger with a cross-section flow, the supply of the flow of the purified vapour of syngas from the heat exchanger with the cross-section flow into the outline of synthesis of ammonia. According to the second variant the method of the production of ammonia includes the reforming hydrocarbon with excess air for forming the flow of initial syngas, removal of nitrogen and inert gases from the flow of the syngas by distillation, thus provide cooling with the aid of the expansion of the liquid by means of the dilator-generator, and the upper flow partially condense the waste flow, cooled by means of expansion of the liquid remainder from the distillation column, and the supply of syngas with the decreased content of nitrogen and inert gases from distillation into the contour of the synthesis of ammonia at which the liquid remainders expand by means of the dilator of liquid with the extraction of work.

EFFECT: invention makes it possible to improve industrial and economic characteristics.

18 cl, 5 dwg, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to dehydrogenation or reforming of alcohols, in particular to a method of dehydrogenation of the primary alcohol, such as methanol or ethanol, for obtaining hydrogen, in particular for use in a fuel element with the purpose of obtaining electrical energy. In the method of dehydrogenation a catalyst containing copper is used, which includes a metallic carrier. To solve the given challenge the method includes bringing to contact of the initial raw mixture of the gases containing alcohol, with the catalyst of reforming in order to obtain a mixture of products of reforming, containing hydrogen, and the catalyst for reforming the contains a metallic spongy carrier and a coating on copper, at least, partially covering surface of the given metal spongy carrier where the given metal spongy carrier is obtained by means of the method including the leaching of aluminium from an alloy, containing aluminium and the main metal.

EFFECT: increased activity in the gas-phase reforming of primary spirits and increased stability.

129 cl, 13 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention relates to dehydrogenation or reforming of alcohols, in particular to a method of dehydrogenation of the primary alcohol, such as methanol or ethanol, for obtaining hydrogen, in particular for use in a fuel element with the purpose of obtaining electrical energy. In the method of dehydrogenation a catalyst containing copper is used, which includes a metallic carrier. To solve the given challenge the method includes bringing to contact of the initial raw mixture of the gases containing alcohol, with the catalyst of reforming in order to obtain a mixture of products of reforming, containing hydrogen, and the catalyst for reforming the contains a metallic spongy carrier and a coating on copper, at least, partially covering surface of the given metal spongy carrier where the given metal spongy carrier is obtained by means of the method including the leaching of aluminium from an alloy, containing aluminium and the main metal.

EFFECT: increased activity in the gas-phase reforming of primary spirits and increased stability.

129 cl, 13 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to the method of obtaining porous substances on a substrate for catalytic applications, to the method of obtaining porous catalysts for decomposition of N2O and their use in decomposing N2O, oxidising ammonia and reforming methane with water vapour. Description is given of the method of obtaining porous substances on a substrate for catalytic applications, in which one or more soluble precursor(s) metal of the active phase is added to a suspension, consisting of an insoluble phase of a substrate in water or an organic solvent. The suspension undergoes wet grinding so as to reduce the size of the particles of the substrate phase to less than 50 mcm. The additive is added, which promotes treatment before or after grinding. A pore-forming substance is added and the suspension, viscosity of which is maintained at 100-5000 cP, undergoes spray drying, is pressed and undergoes thermal treatment so as to remove the pore-forming substance, and is then baked. Description is also given of the method of obtaining porous catalysts on a substrate for decomposing N2O, in which a soluble cobalt precursor is added to a suspension of cerium oxide and an additive, promoting treatment, in water. The suspension is ground to particle size of less than 10 mcm. A pore-forming substance, viscosity of which is regulated to approximately 1000 cP, is added before the suspension undergoes spray drying with subsequent pressing. The pore-forming substance is removed and the product is baked. Description is given of the use of the substances obtained above as catalysts for decomposition of N2O, oxidation of ammonia and reforming of methane with water vapour.

EFFECT: obtaining catalysts with homogenous distribution of active phases and uniform and regulated porosity for optimisation of characteristics in catalytic applications.

FIELD: chemistry.

SUBSTANCE: converter includes housing and devices for input oxygen enriched air, fed of vapour-hydrocarbon mix and bleeding of converted gas. The housing is provided with inner fikking designed as two cylindrical tubes installed one inside the other and forming with the converter housing two radial clearances: the outer clearance for input vapour-hydrocarbon mix and inner one for output of converted gas. At that the packing made of channeled plates is provided for inner fikking, this packing forms the channels of square section; the upper part (1/20-1/25) of channels is provided with perforation track, the middle part (1/5-1/6) of channels height located lower than perforation track is filled with catalyst used for primary and secondary hydrocarbon conversions; and the lowest part (1/6-1/8) of channels height is filled with catalyst used for preliminary hydrocarbon conversion. The device for input oxygen enriched air is positioned in the upper part of channels. The method is implemented in converter. Hydrocarbon material heating and converted gas cooling are carried out by the way of its passing through heat exchanger and mixing of hydrocarbon material with water vapour, then vapour-hydrocarbon mix is fed downstream through outer radial clearance and further it is delivered up the channels through catalyst bed for implementing of preliminary and primary conversions. Then through perforation track it is fed down the channels for converted gas oxidizing and secondary vapour conversion with subsequent converted gas upflow takeoff through inner radial clearance.

EFFECT: increasing of hydrocarbon material conversion and reduction of probability of free carbon formation.

2 cl, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to two methods (two variants) of reforming process using oxidizing gas at temperature 980-1000°C. The recirculation of the flow part outgoing from the autothermic reformer to the flowrate vapour-hydrocarbon is described at that the said recirculation is implemented throught the instrumentality of thermocompressor ejector using heated beforehand supplied mix as operative fluid. For the optimization of general configuration the mole ratio of recirculating synthesis gas and operative fluid was chosen in the range 0.2-1.0. In order to prevent the carbon black formation in the reforming process recirculated hydrogen and vapour are fed to the input flow and the temperature of feeding is increased. Since there is a certain pressure drop between initial mixture of vapour and natural gas and the mix fed to reformer it is necessary to increase the pressure of initial mixture but it is compensated with the lower pressure drop in the heater and other equipment laid out upstream and downstream because of decreasing of vapour capacity.

EFFECT: reforming process is carried out without carbon black formation.

27 cl, 2 dwg, 1 tbl

FIELD: chemistry; processing of hydrocarbon material to synthesis gas.

SUBSTANCE: porous ceramic catalytical module represents the product of exothermic finely dispersed nickel-aluminium mixture exposed to vibration compaction and to sintering. The said product contains: nickel 55.93-96.31 Wt%; aluminium 3.69-44.07 Wt%. Porous ceramic catalytical module may contain up to 20 Wt% (based on the module weight) of titanium carbide as well as catalytic coating including following groups: La and MgO, or Ce and MgO, or La, Ce and MgO, or ZrO2, Y2O3 and MgO, or Pt and MgO, or W2O5 and MgO in quantity 0,002-6 Wt% based on the module weight synthesis gas is produced by conversion of methane and carbon dioxide mixture on porous ceramic catalytical module in filtration mode The process conditions are as follows: temperature 450-700°C, pressure 1-10 atm, rate of CH4-CO2 mixture delivery to catalytical module 500-5000 l/dm3*hr.

EFFECT: inventions permit to carry out the process at lower temperatures.

5 cl, 37 dwg

FIELD: hydrogen production processes.

SUBSTANCE: invention relates to catalysts for hydrolysis of hydride compounds to produce pure hydrogen for being supplied to power installations, including fuel cells. Invention provides catalyst for production of hydrogen from aqueous or water-alkali solutions of hydride compounds containing platinum group metal deposited on complex lithium-cobalt oxide and, additionally, modifying agent selected from series: titanium dioxide, carbon material, oxide of metal belonging to aluminum, magnesium, titanium, silicon, and vanadium subgroups. According to second variant, catalyst contains no platinum group metal. Described are also catalyst preparation method (variants) and hydrogen generation process, which is conducted at temperature no higher than 60°C both in continuous and in periodic mode. As hydrogen source, sodium borohydride, potassium borohydride, and ammine-borane can be used.

EFFECT: increased catalyst activity at environmental temperatures (from -20 to 60°C), prolonged time of stable operation of catalytic system, and reduced or suppressed platinum metals in composition of catalyst.

14 cl, 1 tbl, 20 ex

FIELD: chemistry.

SUBSTANCE: invention relates to processes of catalytic hydration. Claimed is catalyst for liquid-phase hydration of organic substances of various classes i.e. nitro-compounds, aldehides, unsaturated and aromatic compounds, with molecular hydrogen, which includes unit-type carrier of low density and high porosity and metallic palladium. Carrier is made from aluminium oxide by method of doubling foam-polyurethane matrix by impregnating it with slip Al2O3 with further calcination. Layers of γ-Al2O3 are applied on carrier successively in such a way that weight of active layer from γ-Al2O3 is not less than 6% of total weight of catalyst, and of metallic palladium in amount of 0.16-3.7%. Alternatively, instead of γ-Al2O3 layer, layer of sulphated oxide of titanium or zirconium in amount of 8-9% is applied on carrier. Due to developed surface, the claimed catalyst is efficient when hydrating compounds of various classes, and has high mechanical strength, which eliminates its abrasion in the process of exploitation.

EFFECT: obtaining catalyst efficient when hydrating compounds of various classes, and having high mechanical strength, which eliminates its abrasion in the process of exploitation.

2 cl, 1 tbl, 14 ex

FIELD: physics.

SUBSTANCE: invention pertains to a foil, meant to be used mainly for carrying catalytic active materials for neutralisation or reduction of toxicity of waste gases. Description is given of the foil (1), which has at least, one groove (2), which is tone in the inner part (3) of the foil sheet (1) and at least, partially borders the microprofile structure of the foil (1), which protrudes from the profile structure (5) of its surface. At least one groove (2) has at least one cut (7) on at least one of its end parts (6). Description is also given of a carrier (21) meant for neutralisation or reduction of toxicity of waste gases of a component, made from a number of at least partially profiled sheets of foil (1), which are gathered in a packet and/or rolled in such a way that they provide for passage of a flowing medium through the carrier, and at least one of which is mate in the form of sheet of the foil (1) described here above (fig.1). Description is also given of the use of carrier (21) in a system of releasing waste gases (35).

EFFECT: prevention of crack propagation from bordering microprofile structures of agroove in a foil and longer life service of the carrier.

16 cl, 9 dwg

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to catalysts exhibiting activity in hydrogenation of vegetable oils and fats and suitable for use in food processing industry, perfumery, petrochemical and petroleum processing industries. Invention describes a method for preparing granulated catalysts intended for liquid-phase hydrogenation of vegetable oils and distilled fatty acids and representing metallic palladium deposited in amount 0.5-2.0 wt % on carbon carrier, fraction 0.5-6.0 mm, having specific surface area 100-450 m2/g and pore volume 0.2-0.6 cm3/g. Hydrogenation process is conducted on fixed catalyst bed at 140-210°C, hydrogen pressure 2 to 12 atm and consumption or raw material 100 to 1500 g/h per 1 kg catalyst.

EFFECT: increased hydrogenation rate in production of technical sorts of solidified fat and increased stability of catalysts.

4 cl, 1 dwg, 3 tbl, 20 ex

FIELD: alternative fuels.

SUBSTANCE: invention relates to autothermal conversion of hydrocarbon fuel to produce synthesis gas, which can be used in chemical production, for burning at catalytic heat plants, and in hydrogen power engineering. Proposed catalyst contains, as active components, cobalt oxide, manganese oxide, and barium oxide, and, as carrier, refractory reinforced metalporous carrier. Catalyst is prepared by impregnation of carrier with barium and manganese salt solution at Ba/Mn =5:4 followed by drying, calcination, impregnation with cobalt salt solution, drying, and calcination. Invention further describes generation of synthesis gas via autothermal conversion of hydrocarbon fuel performed utilizing above-described catalyst.

EFFECT: enabled catalyst exhibiting high heat conductivity, high activity in production of synthesis gas, and resistance to coking and deactivation with sulfur compounds present in diesel fuel and gasoline.

6 cl, 1 tbl, 3 ex

FIELD: oil and fat industry and technology.

SUBSTANCE: invention relates to an improved method for hydrogenation of vegetable oils and distilled fatty acids. Method involves the hydrogenation reaction that is carried out on a catalyst stationary layer representing crystallites of active palladium applied on surface of carbonic material wherein mesoporous graphite-like material is used as carbonic material with granules size 0.5-6.0 mm but preferably 3.0-6.0 mm, specific surface 100-450 m2/g, average size of mesopores in the range from 40 to 400 Å, total volume of pores 0.2-0.6 cm3/g and part of mesopores in the total volume of pores 0.6, not less. Palladium crystallites in volume of carbonic material are distributed by so manner that the distribution maximum values of active component are in distance from external granule surface corresponding to 1-30% of its radius and in the content of applied palladium in the range from 0.5 to 2.0 wt.-%. Invention provides the high hydrogenation rate of raw in production of technical sorts of hydrogenated fats and high stability of product.

EFFECT: improved method of hydrogenation.

2 cl, 1 dwg, 3 tbl, 16 ex

FIELD: inorganic synthesis catalysts.

SUBSTANCE: invention relates to catalytic elements including ceramic contact of regular honeycomb structure for heterogeneous high-temperature reactions, e.g. ammonia conversion, and can be used in production of nitric acid, hydrocyanic acid, and hydroxylamine sulfate. Described is catalytic element for heterogeneous high-temperature reactions comprising two-step catalytic system consisting of ceramic contact of regular honeycomb structure made in the form of at least one bed constituted by (i) separate prisms with honeycomb canals connected by side faces with gap and (ii) platinoid grids, ratio of diameter of unit honeycomb canal to diameter of wire, from which platinoid grids are made, being below 20.

EFFECT: increased degree of conversion and degree of trapping of platinum, and prolonged lifetime of grids.

5 cl, 6 ex

FIELD: disproportionation reaction catalysts.

SUBSTANCE: invention relates to Fischer-Tropsch catalyst containing cobalt and zinc, to a method for preparation thereof, and to Fischer-Tropsch process. Catalyst according to invention containing co-precipitated cobalt and zinc particles, which are characterized by volume-average size below 150 μm and particle size distribution wherein at least 90% of the catalyst particle volume is occupied by particles having size between 0.4 and 2.5 times that of the average particle size and wherein zinc/cobalt atomic ratio within a range of 40 to 0.1. Catalyst is prepared by introducing acid solution containing zinc and cobalt ions at summary concentration 0.1 to 5 mole/L and alkali solution to reactor containing aqueous medium wherein acid solution and alkali solution come into contact with each other in aqueous medium at pH 4-9 (deviating by at most 0.2 pH units) at stirring with a speed determined by supplied power between 1 and 300 kW/L aqueous medium and temperature from 15 to 75°C. Resulting cobalt and zinc-including precipitate separated from aqueous medium, dried, and further treated to produce desired catalyst. Employment of catalyst in Fischer-Tropsch process is likewise described.

EFFECT: enhanced strength and separation properties suitable for Fischer-Tropsch process.

13 cl, 2 dwg, 1 tbl, 5 ex

FIELD: exhaust gas afterburning means.

SUBSTANCE: invention relates to catalytic neutralizer for treating internal combustion engine exhausted gases. Proposed catalyst is composed of catalytically active coating on inert ceramic or metallic honeycomb structure, wherein coating contains at least one platinum group metal selected from series including platinum, palladium, rhodium, and iridium on fine-grain supporting oxide material, said supporting oxide material representing essentially nonporous silica-based material including aggregates of essentially spherical primary particles 7 to 60 nm in diameter, while pH of 4% water dispersion of indicated material is below 6.

EFFECT: increased catalyst activity and imparted sufficient resistance to aggressive sulfur-containing components.

27 cl, 2 dwg, 7 tbl, 6 ex

FIELD: chemical industry; methods of manufacture of the building structures.

SUBSTANCE: the invention is pertaining to the field of the chemical industry, in particular, to production of the nitric acid, nitric fertilizers, the cyanhydric acid, the nitrites and nitrates and to other productions of chemical products, where the flow sheet of production provides for the catalytic conversion of ammonia up to the nitrogen oxides with usage of the platinoid mesh catalytic agents. The platinoid mesh catalytic agent formed in the form of the catalytic package produced out of the layer-by-layer stacked wire catalytic meshes and weaved out of the wires with the diameter of 0.06-0.1 mm consisting of the alloys of platinum with rhodium, palladium, ruthenium and other metals of the platinum group differs that the catalytic package consists of two different in the geometry of the braiding types of the meshes sequentially alternating in the height of the package. At that the geometry of the braiding of the first type of the catalytic meshes is characterized by the number of the wires interlacing per 1 cm2 in the interval of 1024-450, and the geometry of the braiding of the second type of the catalytic meshes is characterized by the number of the wires interlacing per 1 cm2 in the interval of 400-200. The technical result of the invention is the increased conversion of ammonia and the decreased share of the platinoids included in the mesh catalytic agent production processes providing for the catalytic conversion of ammonia in the flow sheet of the chemical goods production.

EFFECT: the invention ensures the increased conversion of ammonia and the decreased share of the platinoids included in the mesh catalytic agent production processes providing for the catalytic conversion of ammonia in the flow sheet of the chemical goods production.

3 ex

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: chemistry.

SUBSTANCE: invention pertains to a catalyst and a method for selective increase in quality of paraffin raw material, with the aim of obtaining concentrated isoparaffin product as a benzine component. Description is given of the catalyst, which consists of a carrier from a sulphated oxide or hydroxide of group IVB (IUPAC 4) metals. The first component is, at least, from one lanthanide element or an yttric component, which is mainly ytterbium, and at least, one metal of the platinum group, which is mainly platinum, and a fireproof oxide binding substance, on which is dispersed at least, one metal of the platinum group. Description is given of the method of making the above mentioned catalyst, including a sulphated oxide or hydroxide of a group 1VB metal, depositing of the first component, mixing the sulphated carrier with the fireproof inorganic oxide of the oxide carrier, burning, depositing of the second component and subsequent burning. Description is given of the method of converting hydrocarbons through contacting with raw materials with the catalyst described above.

EFFECT: selective increase in quality of paraffin raw materials.

12 cl, 2 tbl, 2 dwg, 7 ex

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