The synthesis-gas steam reforming using catalyzed equipment
This invention is directed to the production of synthesis gas by steam reforming of hydrocarbons by contact with catalyzed equipment. A method of obtaining a gas enriched in hydrogen and carbon monoxide by catalytic reforming of hydrocarbon raw materials, includes the operation and transmission process gas containing hydrocarbon raw material, through a tubular reactor with a steam reforming catalyst heated by burning fuel. Moreover, the steam reforming catalyst deposited on a metal sheet having the same shape as the wall of the reactor, and is in close thermal communication with the inner pipe wall of the tubular reactor. The method further includes an operation bandwidth before surgery (a) of hydrocarbons through the first reactor catalyst for steam reforming. The reforming catalyst in the reactor in operation (a) used in combination with granules of catalyst reforming process. The reforming catalyst comprises Nickel and/or noble metals. This invention allows to increase service life of reactors and leads to better use of raw materials. 3 C.p. f-crystals, 1 Il., table 1. the contact with the catalyzed equipment.The term "catalyzed the equipment used for the catalytic system, where the catalyst layer is fixed on the surface of another material, such as metallic surfaces. This other material is used as a catalyst carrier, giving the system strength. This allows you to create catalysts such configurations, the mechanical strength of which by itself would be insufficient.Synthesis gas is produced from hydrocarbons by steam reforming in accordance with the following reactions (1)-(3): CnHm+nH2O _nCO+(n+m/2)H2(H°298<0) (1) CO+H2OCO2+H2(H°298= 41 kJ/mol) (2) CH4+H2OCO+3H2(H°298= -206 kJ/mol) (3) At the present level of technology in the technology of the steam reforming process using the catalyst of the reforming process in the form of granules of various sizes and shapes. Granules of the catalyst placed in the reactor with fixed bed (pipe reforming process-setup). The reaction of reforming endothermic. In the reforming-installations of conventional type, the necessary heat is supplied from the ing-installation. Heat is transferred through the pipe wall on the inner surface of the pipe by conduction and is transferred to the gas phase by convection. Finally, heat is transferred from the gas phase to the catalyst granules by means of convection. The temperature of the catalyst can be more than 100oC lower than the temperature of the inner wall of the tube at the same axial position of the pipe reforming installation.It was found that the heat transfer is more effective when used in a process catalyzed steam reforming equipment. The transfer of heat to the catalyst occurs from the inner wall of the pipe by conduction. This transfer mechanism is much more efficient than transfer by convection through the gas phase. The result is that the temperature of the inner wall of the pipe and catalyst are almost identical (the difference is less than 5oC). Moreover, it is possible to reduce the thickness of the pipe, which reduces the temperature difference between the inner and outer sides of the tubes of the reformer installation. Consequently, it is possible to have both a higher temperature of the catalyst and lower the temperature of the pipe, when the pipe replacement reforming-install conventional type of pipe katalizirovannogo low, as this prolongs the service life of the pipe. The high temperature of the catalyst has advantages, since the reaction rate increases with temperature, and since the equilibrium of reaction (3) is moved to the right, which leads to better use of raw materials.The pressure drop in the catalyzed pipe reformer installation is much lower than in the normal case, for the same pipe diameter. This allows the use of a pipe reactor with a smaller diameter and nevertheless support an acceptable pressure drop. When using a smaller diameter pipe, the service life of the pipe increases, the pipe is resistant to higher temperatures, reduced material consumption.Finally, the amount of the catalyst when using catalyzed equipment pipe reformer installation is reduced compared to the reforming-installations of conventional type with a fixed catalyst bed reformer.The drawing shows the front part of the installation for the production of synthesis gas.Raw material 2 is heated, disulfiram in unit 4, is mixed with process steam 6 and further heated before serving in the adiabatic pre-reforming-installation 8. Flow arising from pre-reforming is in a tubular steam reforming process-setting 14, where the conversion of methane to hydrogen, carbon monoxide and carbon dioxide. Processing resulting from the reforming process is the installation of the gas flow depends on the use of the product.Catalyzed equipment can be used in both blocks shown in the drawing: in the heating coil 10 to heat resulting from the pre-reforming process is the installation of the gas stream prior to its entrance into the tubular reformer installation 14; in the tubular reformer installation 14.The catalytic coating of metal surfaces (thin layer) is a well - known process (its description can be found, for example, Cybulski, A. , Moulijn, J. A. , Structured catalysts and reactors, Marcel Dekker, Inc. , New York, 1998, Chapter 3 and references therein). A thin layer of a slurry containing a ceramic precursor, is applied to the surface, for example by spraying, painting or dipping. After coating the slurry is dried and calcined usually at a temperature in the range from 350 to 1000oC. Finally, the ceramic layer is impregnated with a catalytically active material. Alternatively, you can apply a catalytically active material simultaneously with the ceramic precursor.Unfortunately, the reactor catalyzed equipment is ü, if he's going to lose their activity with time or as a result of poisoning of the catalyst layer can be applied only on certain materials. And pipes of the reactor must be made of this type of material, and it may be more expensive than the usual material for pipes. The reaction of the steam reforming process flow at high pressure, and the pipe has a large thickness, therefore, the cost of the material significantly affects the price; moreover, the production of long tubes catalyzed reactor equipment can be difficult. The length of the pipe reactor can reach 10 m or more. It would be difficult to obtain a layer of the catalyst for reforming a uniform thickness along the entire length of such pipe, and means for obtaining a uniform layer, which can be used on a small scale, such as centrifugation tubes, it is more difficult to apply for a pipe of this size. Moreover, the corresponding heat treatment of pipes of this size is difficult.These disadvantages can be overcome if the manufacturing catalyzed equipment separately from the reactor, as described below.The metal substrate is cut into pieces of suitable size. On sheet a thin layer as described above. After n is th form before applying a thin layer. Metal substrate give essentially the same form that has a reactor wall, and positioned so that she was directly in thermally conductive communication with the reactor wall.You can replace the catalyst bed, if he will not have sufficient catalytic activity. Expensive steel, used for connection of the catalyst metal surface will constitute only a small share in the total consumption of the metal. Catalyzed equipment can be made in smaller sections that are easier to manufacture and handle.Accordingly, this invention provides a method of obtaining a gas enriched in hydrogen and carbon monoxide by catalytic steam reforming of hydrocarbons, including operation:
(a) passing the process gas containing hydrocarbon raw material, through a tubular reactor with a steam reforming catalyst heated by burning fuel, and the steam reforming catalyst deposited on a metal substrate, having essentially the same shape as the wall of the reactor, and is in close heat-conducting relation with the inner wall of the pipe t (a) of hydrocarbons through the first reactor catalyst for steam reforming, heated hot gas stream, and a steam reforming catalyst deposited on a metal substrate, having essentially the same shape as the wall of the reactor, and is in close heat-conducting relation with the inner wall of the pipe reactor.In a specific embodiment of this invention, the reforming catalyst in the reactor in operation (a) deposited on a metal substrate, used in combination with the catalyst granules reformer.The steam reforming catalyst used in the proposed method may include Nickel and/or noble metals.Example
System reactor with heating coil for conversion of hydrocarbons consists of 16 pipe length 20 m Pipes have an internal diameter of 100 mm and an outer diameter of 120 mm, an Inner wall of each tube is designed to cover a thin layer of catalyst reforming process.The mechanical strength of each pipe is satisfactory when using steel 18Cr/8Ni containing Cr, Ni and Fe in the ratio of 18:8:74. However, the material of the catalyst has no adhesion to this type of steel. He has adhesion to high-alloy Nickel steel, such as Inconel 600, which contains CR, Ni and Fe in sootnosheniem steel that would be extremely expensive, as can be seen from the above table. In addition, it would be difficult for the entire length of each pipe (20 m) to obtain a uniform coating thickness of the catalyst.According to the proposed method, using a reactor in which each pipe is made of cheaper steel 18Cr/8Ni, and the pipe is a sheet of foil alloyed Nickel steel, coated with catalyst. This plate is made by cutting the foil into sheets with dimensions corresponding to the internal dimensions of the tube, with the subsequent implementation of the covering foil from the liquid phase reforming catalyst and forming it into a tubular form corresponding to each pipe. Then it is introduced into the pipe and is placed in close thermal communication with the inner pipe wall.Characteristics of the reactor containing tubes of high-alloy Nickel steel reactor containing steel pipe 18Cr/8Ni and foil alloyed Nickel steel, are identical. However, the price of the reactor tubes containing foil, approximately 50% lower, as can be seen from the table.
1. A method of obtaining a gas enriched in hydrogen and carbon monoxide by catalytic R is the hydrocarbon feedstock, through a tubular reactor with a steam reforming catalyst heated by burning fuel, and the steam reforming catalyst deposited on a metal sheet having the same shape as the wall of the reactor, and is in close thermal communication with the inner pipe wall of the tubular reactor.2. The method according to p. 1, further comprising an operation bandwidth before surgery (a) of hydrocarbons through the first reactor with the steam reforming catalyst heated by a hot gas stream, and a steam reforming catalyst deposited on a metal sheet having the same shape as the wall of the reactor, and is in close heat-conducting relation with the inner wall of the pipe reactor.3. The method according to p. 1 or 2, in which the reforming catalyst in the reactor in operation (a) used in combination with the catalyst granules reformer.4. The method according to any of paragraphs.1-3, in which the steam reforming catalyst comprises Nickel and/or noble metals.
FIELD: hydrocarbon conversion catalysts.
SUBSTANCE: catalyst for generation of synthesis gas via catalytic conversion of hydrocarbons is a complex composite composed of ceramic matrix and, dispersed throughout the matrix, coarse particles of a material and their aggregates in amounts from 0.5 to 70% by weight. Catalyst comprises system of parallel and/or crossing channels. Dispersed material is selected from rare-earth and transition metal oxides, and mixtures thereof, metals and alloys thereof, period 4 metal carbides, and mixtures thereof, which differ from the matrix in what concerns both composition and structure. Preparation procedure comprises providing homogenous mass containing caking-able ceramic matrix material and material to be dispersed, appropriately shaping the mass, and heat treatment. Material to be dispersed are powders containing metallic aluminum. Homogenous mass is used for impregnation of fibrous and/or woven materials forming on caking system of parallel and/or perpendicularly crossing channels. Before heat treatment, shaped mass is preliminarily treated under hydrothermal conditions.
EFFECT: increased resistance of catalyst to thermal impacts with sufficiently high specific surface and activity retained.
4 cl, 1 tbl, 8 ex
FIELD: power engineering.
SUBSTANCE: method includes searching for continental or oceanic rift generation zones, supported by abnormal mantle with output of substance branches to earth crust. Drilling of wells by turbodrills into mantle substance. After well enters mantle substance a reaction hollow is formed in it by putting together force and product wells or by expanding force and/or product wells. Water is pumped into force well and gas-like hydrogen is outputted to surface through product well forming during reaction of inter-metallic substances fro mantle substance to water. Water is fed in amount, adjusting output of hydrogen, while reaction surface of reaction hollow is periodically regenerated, for example, by high pressure water flow, supplied through jets in reaction hollow, on remotely controlled manipulators. Expansion of well may be performed via explosions of explosive substances charges, and it is possible to separate forming gaseous hydrogen and water steam by separator mounted therein.
EFFECT: higher effectiveness of hydrogen production.
FIELD: alternative fuel production and catalysts.
SUBSTANCE: invention relates to (i) generation of synthesis gas useful in large-scale chemical processes via catalytic conversion of hydrocarbons in presence of oxygen-containing components and to (ii) catalysts used in this process. Catalyst represents composite including mixed oxide, simple oxide, transition element and/or precious element, carrier composed of alumina-based ceramic matrix, and a material consisting of coarse particles or aggregates of particles dispersed throughout the matrix. Catalyst has system of parallel and/or crossing channels. Catalyst preparation method and synthesis gas generation method utilizing indicated catalyst are as well described.
EFFECT: enabled preparation of cellular-structure catalyst with high specific surface area, which is effective at small contact times in reaction of selective catalytic oxidation of hydrocarbons.
6 cl, 2 tbl, 16 ex
FIELD: autothermal catalytic reforming of hydrocarbon feed stream.
SUBSTANCE: method relates to method for reforming of hydrocarbon feed stream with water steam at elevated temperature to produce gas enriched with hydrogen and/or carbon oxide. Hydrocarbon stream is passed through water steam reforming catalyst bed wherein oxygen is fed through oxygen-permeable membrane followed by removing of finished product from this bed. Said catalyst bed contains in input region catalyst with reduced or without water steam reforming activity, but having hydrocarbon feed oxidation activity.
EFFECT: process with improved characteristics due to temperature controlling in reactor.
3 cl, 1 dwg
FIELD: alternate fuel manufacture catalysts.
SUBSTANCE: invention relates to generation of synthesis gas employed in large-scale chemical processes such as synthesis of ammonia, methanol, higher alcohols and aldehydes, in Fischer-Tropsch process, and the like, as reducing gas in ferrous and nonferrous metallurgy, metalworking, and on gas emission detoxification plants. Synthesis gas is obtained via catalytic conversion of mixture containing hydrocarbon or hydrocarbon mixture and oxygen-containing component. Catalyst is a complex composite containing mixed oxide, simple oxide, transition and/or precious element. Catalyst comprises metal-based carrier representing either layered ceramics-metal material containing nonporous or low-porosity oxide coating, ratio of thickness of metallic base to that of above-mentioned oxide coating ranging from 10:1 to 1:5, or ceramics-metal material containing nonporous or low-porosity oxide coating and high-porosity oxide layer, ratio of thickness of metallic base to that of nonporous or low-porosity oxide coating ranging from 10:1 to 1:5 and ratio of metallic base thickness to that of high-porosity oxide layer from 1:10 to 1:5. Catalyst is prepared by applying active components onto carrier followed by drying and calcination.
EFFECT: increased heat resistance and efficiency of catalyst at short contact thereof with reaction mixture.
13 cl, 2 tbl, 17 ex
FIELD: electric power and chemical industries; methods of production of the electric power and liquid synthetic fuel.
SUBSTANCE: the invention presents a combined method of production of the electric power and liquid synthetic fuel with use of the gas turbine and steam-gaseous installations and is dealt with the field of electric power and chemical industries. The method provides for the partial oxidation of hydrocarbon fuel in a stream of the compressed air taken from the high-pressure compressor of the gas turbine installation with its consequent additional compression, production of a synthesis gas, its cooling and ecological purification, feeding of the produced synthesis gas in a single-pass reactor of a synthesis of a liquid synthetic fuel with the partial transformation of the synthesis gas into a liquid fuel. The power gas left in the reactor of synthesis of liquid synthetic fuel is removed into the combustion chamber of the gas-turbine installation. At that the degree of conversion of the synthesis gas is chosen from the condition of maintenance of the working medium temperature at the inlet of the gas turbine depending on the type of the gas-turbine installation used for production of the electric power, and the consequent additional compression of the air taken from the high-pressure compressor of the gas-turbine installation is realized with the help of the gas-expansion machine powered by a power gas heated at the expense of the synthesis gas cooling before the reactor of synthesis. The invention allows simultaneously produce electric power and synthetic liquid fuels.
EFFECT: the invention ensures simultaneous production of electric power and synthetic liquid fuels.
2 cl, 2 dwg
FIELD: petrochemical industry.
SUBSTANCE: the invention is dealt with petrochemical industry, in particular with a method of catalytic preliminary reforming of the hydrocarbon raw materials containing higher hydrocarbons. The method provides for the indicated hydrocarbon raw materials gating through a zone of a catalyst representing a fixed layer containing a noble metal on magnesia oxide (MgO) and-or spinel oxide (MgAl2O4) at presence of oxygen and water steam. The technical result is a decrease of a carbon share on the catalyst.
EFFECT: the invention allows to decrease a carbon share on the catalyst.
3 cl, 2 tbl, 2 ex
FIELD: technology for production of methanol from syngas.
SUBSTANCE: claimed method includes mixing of hydrocarbon raw material with water steam to provide syngas by steam conversion of hydrocarbon raw material and subsequent methanol synthesis therefrom. Conversion of hydrocarbon raw material and methanol synthesis are carried out under the same pressure from 4.0 to 12.0 MPa. In one embodiment hydrocarbon raw material is mixed with water steam and carbon dioxide to provide syngas by steam/carbonic acid conversion of hydrocarbon raw material in radial-helical reactor followed by methanol synthesis therefrom under the same pressure (from 4.0 to 12.0 MPa). In each embodiment methanol synthesis is carried out in isothermal catalytic radial-helical reactor using fine-grained catalyst with grain size of 1-5 mm. Methanol synthesis is preferably carried out in two steps with or without syngas circulation followed by feeding gas from the first or second step into gasmain or power plant.
EFFECT: simplified method due to process optimization.
12 cl, 3 tbl, 3 dwg
FIELD: methods of production a synthesis gas.
SUBSTANCE: the invention is pertaining to the process of production of hydrogen and carbon oxide, which mixture is used to be called a synthesis gas, by a selective catalytic oxidation of the hydrocarbonaceous (organic) raw material in presence of the oxygen-containing gases. The method of production of the synthesis gas includes a contacting with a catalyst at a gas hourly volumetric speed equal to 10000-10000000 h-1, a mixture containing organic raw material and oxygen or an oxygen-containing gas in amounts ensuring the ratio of oxygen and carbon of no less than 0.3. At that the process is conducted at a linear speed of the gas mixture of no less than 2.2 · 10-11 · (T1 + 273)4 / (500-T2) nanometer / s, where: T1 - a maximum temperature of the catalyst, T2 - a temperature of the gas mixture fed to the contacting. The linear speed of the gas mixture is, preferably, in the interval of 0.2-7 m\s. The temperature of the gas mixture fed to the contacting is within the interval of 100-450°C. The maximum temperature of the catalyst is within the interval of 650-1500°C. The technical effect is a safe realization of the process.
EFFECT: the invention ensures a safe realization of the process.
10 cl, 5 ex
FIELD: chemical industry; petrochemical industry; oil refining industry and other industries; methods of production a synthesis gas.
SUBSTANCE: the invention is pertaining to the field of the methods of production of a synthesis of gas and may be used in chemical, petrochemical, oil refining and other industries. The method of production of synthesis gas using a vapor or a vapor-carbon dioxide conversion of a hydrocarbonaceous raw material provides for purification of the hydrocarbonaceous raw material from sulfuric compounds, its commixing with steam or with steam and carbon dioxide with formation of a steam-gas mixture. The catalytic conversion of the steam-gas mixture is conducted in a reactor of a radially-spiral type, in which in the ring-shaped space filled with a nickel catalyst with a size of granules of 0.2-7 mm there are the hollow spiral-shaped walls forming the spiral-shaped channels having a constant cross section for conveyance of a stream of the steam-gaseous blend in an axial or in a radially-spiral direction. At that into the cavities of the walls feed a heat-transfer agent to supply a heat into the zone of reaction. The invention ensures intensification the process.
EFFECT: invention ensures intensification the process.
4 cl, 4 dwg, 2 tbl, 3 ex