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  • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
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  • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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  • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
  • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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  • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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Definitions

• the invention relates to a common exothermic catalyst stage with at least one shift stage for the catalytic conversion of a mixture of hydrogen, carbon monoxide and excess water vapor and a fine cleaning stage downstream of the shift stage for the catalytic reduction of the remaining carbon monoxide content by selective methanation, a process for producing the common exothermic catalyst gate stage, and a device for generating hydrogen, with a steam reforming stage, at least one conversion stage (shift stage) and a fine cleaning stage.
• Fuel cells offer the possibility of pollutant-free electricity generation. If pure hydrogen gas is used as the fuel gas, which is reacted with atmospheric oxygen in the fuel cell, only water vapor is produced as exhaust gas during energy generation. The use of fuel cells should be possible both in the stationary area and mobile (in motor vehicles). The difficulty, however, is to provide sufficient gaseous hydrogen at the location of the fuel cell. Hydrogen cannot be stored safely without further ado. Storage must take place either at a very low temperature at which the hydrogen is in liquid form or under very high pressure in order to provide a sufficient storage density.
• a possible way of generating fuel gas for fuel cells is to obtain hydrogen gas from hydrocarbons.
• hydrogen and carbon monoxide are generated from a hydrocarbon and water in a steam reforming stage.
• the temperature in the steam reforming stage is generally about 500 to 800 ° C, preferably about 600 ° C.
• the term "further reformer products" means carbon dioxide and unreacted hydrocarbons.
• the fuel gas can be fed to a fuel cell, for example a polymer membrane (PEM) fuel location for generating electricity and heat, in which the hydrogen generated is then converted in a manner known per se for generating electricity, the carbon monoxide must still be removed from the fuel gas stream, because this is harmful to the polymer membrane.
• PEM polymer membrane
• the reforming stage is therefore generally followed by several catalyst stages which, at different temperature levels, reduce the concentration of carbon monoxide which is harmful to the fuel cell.
• a so-called high-temperature conversion stage can be arranged downstream of the reforming stage, which is also referred to as a high-temperature shift stage or HTS stage, which ensures a considerable reduction in the carbon monoxide concentration at a temperature level of approximately 350 to 400 ° C.
• the shift reaction is an exothermic equilibrium reaction.
• a certain residual concentration of carbon monoxide is therefore still present in the gas mixture emerging from the high-temperature shift stage.
• a further reduction in the carbon monoxide concentration can subsequently take place in a low-temperature conversion stage at a temperature of around 200 ° C. This level is also called the low temperature shift level or LTS level.
• a fine cleaning stage is usually added, in which the remaining carbon monoxide content is reduced to a value of ⁇ 100 ppm by selective oxidation (SelOx stage) or selective methanation.
• the CO is selectively methanized according to the reaction equation
• WO 03/080505 AI describes a device for generating hydrogen. This device contains:
• the conversion stage (s) and the fine cleaning stage are each designed as a hollow body with an annular space for receiving the corresponding catalysts.
• the individual conversion stages are produced individually, in each case by applying the appropriate catalyst to the walls of the hollow bodies and, if appropriate, calcining them in order to set an optimal activity of the catalyst.
• the individual hollow bodies are then connected to one another in order, for example, to obtain a common exothermic catalyst stage in which both conversion and fine cleaning can take place.
• the connection is made, for example, by welding the individual hollow bodies together.
• DE 195 44 895 C1 describes a process for the selective catalytic oxidation of gas mixtures containing hydrogen described contain carbon monoxide.
• the mixed gas stream is passed through a CO oxidation reactor containing the catalyst material.
• the CO oxidation reactor can additionally be supplied with oxidizing gas at several points.
• the CO oxidation reactor also has a cooling device through which a coolant is passed. The coolant flow is adjusted accordingly to regulate the reactor temperature.
• the temperature of the gas mixture stream as it enters the CO oxidation reactor is reduced with the aid of static mixer structures and the oxidizing gas is introduced into the gas mixture stream at a flow rate which is predetermined as a function of the operating parameters.
• DE 101 44 681 A1 describes a flow reactor which has at least one catalyst unit which can be passed through by a feed stream and coated with a catalyst. Furthermore, the reactor has a feed unit which can be penetrated by a reactant stream, with an adjusting element which can be moved relative to the catalyst unit and by means of which a passage area of the reactant stream into the catalyst unit can be influenced.
• EP 1 304 311 A2 describes an apparatus for generating hydrogen for operating fuel cells.
• the apparatus includes a reformer for converting hydrocarbon gas and water to hydrogen and other reformer products.
• the reformer is provided with a heat source designed as a burner, with which a defined amount of process heat can be provided. Chemical preparation of the reformer products are the reformer reaction-specific customized, would ⁇ meabbinede catalyst stages downstream.
• the heat source is oversized in relation to the amount of process heat actually required for reforming.
• Apparatus means are provided for decoupling a quantity of heat additionally generated if necessary, the decoupling not impairing the reforming.
• the heat source provided with a first flue gas duct is connected to a second flue gas flue, which is designed to be closable as required and is provided with at least one heat exchanger for the defined coupling of the additionally released amount of heat if necessary.
• EP 1 019 317 B1 describes a device for cleaning a hydrogen-rich gas stream which contains carbon monoxide.
• the device comprises a reaction zone in which carbon monoxide is selectively removed from the gas stream in a catalyzed reaction. Furthermore, a device is provided in front of the reaction zone with which a controlled amount of liquid water can be introduced into the gas stream. Furthermore, a device for mixing the liquid water with the gas stream and for evaporating the liquid water is provided in front of the reaction zone. By evaporating the water, the temperature of the gas stream can be reduced to such an extent that a preferred removal of carbon monoxide from the gas stream takes place in the reaction zone.
• DE 101 42 794 A1 describes a catalytic coating for a gas generation unit, which comprises a reforming reactor for gas generation, a reformate cooler and a shift stage connected downstream for cleaning the reformate gas.
• the surfaces of the reformate cooler flowed by the reformate gas have a coating that comprises at least one catalytic component.
• the coating protects against corrosion or against sooting in oxidizing, reducing and kohlenstoffhal ⁇ term gases.
• the invention was therefore based on the object of providing a common exothermic catalyst stage with at least one shift stage for the catalytic conversion of a mixture of hydrogen, carbon monoxide and excess water vapor and a fine cleaning stage downstream of the shift stage for the catalytic reduction of the remaining carbon monoxide content by selective methanation, which are simple and can thus be manufactured inexpensively.
• the shift stage and the fine cleaning stage is designed as a uniform hollow body.
• a uniform hollow body is understood to mean a continuous hollow body which was not obtained by joining at least two shorter hollow bodies, but which was originally produced in its final length.
• two different catalysts can also be arranged in a common hollow body, which were applied in the hollow body in such a way that both catalysts, both the shift catalyst and the methanation catalyst, achieve their optimal activity. It has previously been assumed that each of the catalysts must be applied to an individual hollow body in order to be able to control the production of the hollow bodies in such a way that the catalyst can develop its optimal properties.
• the application of the shift catalyst generally requires conditions that are incompatible with the conditions used in the application of the methanation catalyst, and vice versa.
• the fixation of one catalyst on the hollow body may require calcination at a temperature at which the other catalyst is already deactivated again.
• the application of one catalyst can influence the properties of the other catalyst if the application comprises, for example, impregnation steps and the impregnation also takes place at least partially on the other catalyst, since the impregnation solution also passes into the coating of the other catalyst by capillary forces.
• Pt on Ti0 2 and / or Zr0 2 and / or Ce0 2 can be used as shift catalysts.
• Ti0 2 and / or Zr0 2 and / or Ce0 2 generally tetravalent metals
• CuO / ZnO can be used as shift catalysts.
• At least one shift catalyst is provided in the shift stage, which comprises at least one transition metal on a first support containing a metal oxide, which is selected from the group formed from the metals of groups IB and VIIIB of the periodic system of the elements, as well as rhenium and Cadmium.
• a metal oxide which is selected from the group formed from the metals of groups IB and VIIIB of the periodic system of the elements, as well as rhenium and Cadmium.
• the transition metal can preferably be selected from iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold, rhenium, cadmium or a combination of these metals and in concentrations of up to about 20% by weight. % are present, based on the weight of the shift catalyst.
• the carrier being in the first metal oxide contained ⁇ is selected from ceria and zirconia, wherein the metal oxides alone or may be contained in the mixture in the carrier.
• the shift catalyst can contain at least one transition metal promoter.
• the promoter can be lithium, potassium, rubidium, cesium, titanium, vanadium, niobium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver osmium, iridium, platinum, gold or one A combination of these metals can be selected and is present in concentrations of up to about 20% by weight, based on the weight of the shift catalyst.
• the transition metal can be applied to the first carrier by impregnating the carrier with a solution of the transition metal to form a carrier impregnated with the transition metal.
• This impregnated support can then or subsequently be impregnated with the promoter to form the catalyst.
• the shift catalyst can also contain additives from the group consisting of gadolinium, samarium, zirconium, lithium, cesium, lanthanum, manganese, titanium or combinations of these additives, which can be present in concentrations of up to about 90% by weight, based on the weight of the shift catalyst.
• the first carrier can contain zirconium oxide in amounts of up to approximately 80% by weight, based on the weight of the first carrier.
• the first carrier is then formed by a cerium-zirconium oxide with about 3 cerium atoms per zirconium atom.
• the first carrier can have a surface area of approximately 50 to 150 m 2 / g.
• the shift catalyst can be produced, for example, by applying the first support to the corresponding part of the hollow body and, after fixing, if appropriate, impregnated with a solution of a compound of the transition metal. After the solvent is removed, the impregnated material is calcined.
• the known methanation catalysts can be used as catalysts in the fine cleaning stage, for example ruthenium on different metal oxide supports (for example A1 2 0 3 , Ti0 2 , Ce0 2 and / or zeolites).
• At least one methanation catalyst is provided in the fine cleaning stage, which contains at least one metal on a second carrier that is capable of forming a metal carbonyl species.
• the metal is preferably selected from the group consisting of ruthenium, rhodium, platinum, palladium, rhenium, nickel, iron, cobalt, lead, tin, silver, iridium, gold, copper, manganese, zinc, zirconium, molybdenum.
• the carrier is preferably selected from a crystalline aluminosilicate (e.g. a molecular sieve, ⁇ -zeolite, mordenite, faujasite), aluminum oxide, cerium oxide, titanium oxide and combinations thereof.
• a crystalline aluminosilicate e.g. a molecular sieve, ⁇ -zeolite, mordenite, faujasite
• the methanation catalysts can also contain inert binders, such as ⁇ -Al 2 0 3 , Si0 2 and / or pseudo-boehmite.
• the hollow body preferably has a jacket space for accommodating the shift catalyst or the methanation catalyst.
• the hollow body is preferably designed as a hollow cylinder.
• the jacket space is then designed as an annular space running around the circumference.
• hollow bodies with, for example, triangular or rectangular hollow cross sections can also be used. Because the common exothermic catalyst stage is preferably designed as a hollow cylinder with a jacket space, an essentially isothermal, radial temperature profile is formed over the flow cross-section of the common exothermic catalyst stage, since with the same flow cross-sectional area, compared to that of a fully cylindrical catalyst body, the distance between the Marginal areas are significantly lower.
• the temperature distribution in the design of the common exothermic catalyst stage as a hollow cylinder is more favorable in the radial direction, i.e. the temperature gradient is much smaller than that of conventional solid cylinders.
• the carbon monoxide concentration in the fuel gas must be very low for the operation of a fuel cell. Therefore, only small temperature windows can be allowed in the common exothermic catalyst stage, since otherwise the carbon monoxide content would increase too much.
• the configuration as a hollow cylinder is therefore particularly well suited for the common exothermic catalyst stage according to the invention.
• the jacket space preferably has a cross-sectional thickness that is approximately 2 to 20% of the outer diameter of the hollow body.
• flow channels are provided in the jacket space.
• the flow channels are preferably arranged in a honeycomb structure.
• honeycombs can be used the.
• the catalysts are preferably arranged on a (corrugated) metal foil delimiting the flow channels.
• perforations are preferably provided between the individual flow channels.
• the perforations increase the turbulence, so that the gas mixtures in the interior of the jacket space, i.e. the section of the jacket space which is arranged closer to the longitudinal axis of the common exothermic catalyst stage, with the gas mixtures in the exterior area of the jacket space, which have a slightly different composition, are good be mixed.
• the main flow direction of the hydrogen and the reformer products within the hollow body or jacket space is preferably oriented essentially parallel to the longitudinal axis of the common exothermic catalyst stage.
• the flow channels are therefore preferably arranged essentially parallel to the longitudinal axis of the common exothermic catalyst stage or of the hollow body.
• a particularly preferred embodiment of the common exothermic catalyst stage is characterized in that the hollow body has at least one central flow channel.
• the central flow passage is preferably formed inside the jacket space, so that a heat exchange between center ⁇ ralem flow duct and shell space is possible.
• the hydrocarbons for example, fe are passed to the steam reforming stage, while the gaseous products emerging from the steam reforming stage flow in the jacket space, the carbon monoxide being removed by the shift stage and the fine cleaning stage.
• heat is exchanged with the hydrocarbon flowing into the steam reforming stage, as a result of which the heat generated in the shift stage and the fine cleaning stage is dissipated evenly, so that the temperature gradient in the jacket space also becomes smaller in the axial direction.
• the common exothermic catalyst stage comprises a flow supply housing for a cooling medium surrounding it from the outside for cooling the catalyst stage.
• Water for example, can be used as the cooling medium, which is preheated in this way, in order to be subsequently fed to the steam reforming stage in vapor form, if necessary after further heating.
• hydrocarbons for example, hydrocarbons as the cooling medium, which are fed to the steam reforming stage after passing through the flow supply housing.
• the heat generated on the common exothermic catalytic converter stage is dissipated by the cooling medium, which has the additional advantage that the heat accumulating in the catalytic converter stage can be dissipated in a targeted manner and is not uselessly released to the environment. Due to the outer jacket cooling, there is a further advantage of a considerable homogenization of the axial temperature profile.
• the flow supply housing preferably has supply and discharge connections for the cooling medium, with which the cooling medium can be supplied, for example, to the steam reforming stage.
• the flow supply housing is optionally in the same or countercurrent to the flow direction of the reformer products within the catalyst stage.
• control devices for setting the mass flow of the cooling medium can be provided on the inlet and / or outlet connections of the flow feed housing.
• Another object of the invention relates to a method for producing a common exothermic catalyst stage as described above.
• the process is characterized by the steps:
• metal selected from the group consisting of the metals from Groups IB and VIIIB of the Periodic Table of the Elements, rhenium and cadmium;
• a tubular hollow body which has a central flow channel running along the longitudinal axis in its interior.
• the central flow channel is surrounded by a jacket space which is crossed by flow channels which run essentially parallel to the longitudinal axis of the hollow body.
• the hollow body preferably consists of a suitable metal, that is to say it is designed as a metal honeycomb.
• the catalyst components of the shift stage and the fine cleaning stage are generally applied as follows to the hollow body or to the walls of the flow channels running in the jacket space:
• the hollow body is immersed from its one end in a suspension of a first carrier containing a metal oxide over a first part of its length.
• the length over which the hollow body is immersed in the suspension of the first carrier depends on the activity of the catalyst and the reaction conditions of the shift reaction and can be estimated by the person skilled in the art on the basis of the corresponding data.
• excess suspension of the first carrier can be removed, for example by blowing it out. Care is taken to ensure that no suspension passes into the part of the hollow body which is still uncovered and in which the other catalyst is to be applied in a later step.
• the first suspension can then optionally be dried in order to fix the first carrier on the surface of the hollow body or the flow channels. Should be a larger amount of the first Applied, the diving process can be repeated many times.
• a calcination is preferably carried out.
• the calcining temperature depends on the carrier material used.
• the calcining temperature is selected, for example, in the range from 200 to 800 ° C., preferably 400 to 700 ° C., particularly preferably 500 to 600 ° C.
• a first coating which covers the hollow body for a first length.
• a catalytically active metal is now applied to the first coating, the metal being selected from the group which is formed from the metals of groups IB and VIIIB of the periodic system of the elements, as well as rhenium and cadmium.
• a solution of a suitable metal salt is produced, for example an aqueous solution of the corresponding nitrate, and the first coating is impregnated with the solution.
• the solvent is then evaporated.
• calcination can then optionally be carried out in order to convert the metal salts into the form of their oxides or already into the metal. Possibly. the impregnation with the metal salt and its fixation can be repeated in order to apply a larger amount of the metal salt.
• the shift catalyst has now been applied and fixed on the first part of the hollow body.
• the hollow body is now turned over and immersed in a suspension of a second carrier, which contains at least one metal that is capable of forming a metal carbonyl species.
• the hollow body is immersed so far in the suspension of the second carrier that at least a second coating part of the length of the hollow body is applied, which is not covered with the first coating.
• the solvent for example water
• Calcination is preferably carried out again for fixation and activation.
• the calcination is preferably carried out at a temperature at which the other catalyst, for example the shift catalyst, is not deactivated. Suitable temperatures can be chosen, for example, in the range from 200 to 800 ° C., preferably 400 to 700 ° C., particularly preferably 400 to 550 ° C.
• the calcining temperature for calcining the second coating is chosen to be lower than the calcining temperature for the first coating.
• the second coating can be produced in such a way that the second carrier is first applied to the hollow body and fixed, if necessary by a calcining step.
• the metal can then be applied by an impregnation step.
• the procedure is preferably such that first the metal or a suitable precursor, such as, for example, a nitrate salt or the metal oxide, is applied to the second support and fixed thereon, for example by a calcining step.
• the second carrier is then applied to the hollow body and, if necessary, fixed by a calcination. In this way it is avoided that the impregnation solution is drawn into the first coating by capillary forces and deactivates the (shift) catalyst there.
• the procedure is such that the hollow body with the uncovered side in the suspension of the second Tragers turned ⁇ is immersed, and excess after removal suspension is blown out from the side of the first coating so that the first coating is not contaminated or covered with the second suspension. After drying, a final calcination is then carried out.
• the common exothermic catalyst stage according to the invention is very suitable in combination with a steam reforming stage for the generation of a fuel gas for use in a fuel cell.
• Another object of the invention therefore relates to a device for generating hydrogen, comprising:
• shift stage and the fine cleaning stage are designed as a common exothermic catalyst stage, as described above.
• the common exothermic catalyst stage is designed as a single hollow body, preferably as an annular honeycomb, preferably with a flow supply housing enclosing the outside for a cooling medium for cooling the catalyst stages. Internal cooling can also be used.
• the heated steam reforming stage is therefore preferably designed as a hollow body and comprises a burner which is arranged centrally in the hollow cylinder of the steam reforming stage.
• the gas passes from the steam reforming stage into the shift stage.
• the shift stage can be divided into a high-temperature shift stage (temperature range 230 to 300 ° C) and a separate low-temperature pen stage (180 to 220 ° C).
• the common exothermic catalyst stage can be constructed from the low-temperature pin stage and the fine cleaning stage.
• a heat exchanger can be provided between the high-temperature shift stage and the low-temperature shift stage, in which the reaction products coming from the high-temperature shift stage are cooled to a suitable temperature before they enter the low-temperature shift stage.
• a single shift stage is used, which is preferably operated in the range from 190 to 300 ° C.
• the C0 content after the shift stage is about 0.4 to 1.0% by volume.
• An indirect heat exchanger is preferably provided between the exothermic catalyst stage and the steam reforming stage, through which the water required for steam reforming is conducted in countercurrent to the gaseous products coming from the exothermic catalyst stage.
• the gas passes into the fine cleaning stage, in which the carbon monoxide concentration is below 100 ppm is reduced.
• the temperature in the fine cleaning stage (c) is approximately 200 to 250 ° C.
• the methane formed in the selective methanation does not interfere when used in a fuel cell.
• the CH 4 content, including the methane not converted in the reforming stage, is about 1 to 4% by volume.
• FIG. 2 shows a longitudinal section through a device which comprises a common exothermic catalyst stage
• steam reforming stage 1 schematically shows in the form of a longitudinal section a device for generating hydrogen, as described for example in WO 03/080505.
• steam reforming stage 1 gaseous or vaporizable hydrocarbons, in particular methane, are reacted with water vapor to form hydrogen, carbon monoxide and other reformer products.
• the steam reforming stage 1 is designed in the form of a hollow cylinder, in the center of which a burner 4 is arranged.
• the steam-reforming stage are connected downstream 1 three catalytic stages, the Katalysatorstu ⁇ fe 2a is a high temperature shift step (HTS step), the step 2b, a low-temperature shift stage (LTS stage) and stage 3 represents a gas purification stage (methanation stage).
• HTS step high temperature shift step
• LTS stage low-temperature shift stage
• stage 3 represents a gas purification stage (methanation stage).
• a flow channel 5 is provided for the hollow cylindrical catalyst stages 2a, 2b, 3, through which the gaseous or vaporizable hydrocarbons are guided in the direction of the arrow for preheating against the flow direction of the reformer products.
• the heat generated at the catalyst stages 2a, 2b and 3 in the exothermic reaction is used directly to heat the starting materials for steam reforming.
• the flow channel 5 can also be configured as an annular channel in order to heat the hydrocarbons which are passed through more uniformly.
• a partition 7 is provided to separate the hollow cylindrical reformer space of the steam reforming stage 1 from the flow channel 5, i.e. the hydrocarbon gas enters the steam reforming stage 1 via the connection 8 shown schematically.
• heat exchangers 6 for example spiral tube heat exchangers
• stages 2a and 2b are provided between stages 2a and 2b and at the end of stage 3, through which the process water flows and which are thermally connected to the flow channel 5.
• Another heat exchanger can be provided between stages 2b and 3.
• the low-temperature shift stage 2b and the fine cleaning stage 3 have each been produced as separate units and have subsequently been combined by means of a weld seam 9 to form a common cylindrical exothermic catalyst stage.
• two shorter cylindrical hollow bodies have to be produced, the length of which corresponds to LTS level 2b or fine cleaning level 3.
• the hollow bodies are then initially each coated with a catalyst for the low temperature shift reaction or a methanation be ⁇ .
• the two finished hollow bodies are then in a further step connected by welding.
• FIG. 2 shows a device according to the invention which comprises a common exothermic catalyst stage (2, 3) with a uniform hollow body.
• the device according to the invention comprises a steam reforming stage 1. As in the device shown in FIG. 1, this is designed as a cylindrical hollow body, in the center of which a burner 4 is arranged in order to provide the energy required for endothermic steam reforming.
• a suitable reforming catalyst is arranged in the jacket space of steam reforming stage 1, through which the starting materials of the reaction, water vapor and hydrocarbons, are passed.
• steam reforming stage 1 is followed by a common exothermic catalyst stage, section 2 forming a shift stage and section 3 forming a gas cleaning stage by selective methanation.
• the common exothermic catalyst stage 2, 3 has a jacket space which is arranged along its circumference and through which flow channels (not shown) pass.
• the flow channels are connected by perforations (not shown) so that gas exchange can take place between the individual flow channels.
• the reformer products from steam reforming stage 1 enter the jacket space of the common exothermic catalyst stage (2, 3) and pass through it, the carbon monoxide being converted into carbon dioxide in shift stage 2 and methane in fine cleaning stage 3.
• the gas emerging from the fine cleaning stage has a remaining carbon lenmonoxide content of ⁇ 100 ppm and a methane content of about 1 to 4 vol .-%.
• a flow channel 5 is provided in the center of the hollow cylindrical common exothermic catalyst stage 2, 3.
• the gaseous or vaporized hydrocarbons are passed through the flow channel 5 in the direction of the arrow for preheating against the flow direction of the reformer products flowing in the outer jacket space, i.e. the heat accumulating at the common catalyst stage 2, 3 in the exothermic reactions is used directly to heat the reformed products.
• the flow channel 5 can also be designed as an annular channel (not shown).
• a partition 7 is provided to separate the hollow cylindrical reformer space of the steam reforming stage 1 from the flow channel 5, i.e. the hydrocarbon gas guided in the central flow channel 5 enters the steam reforming stage 1 via the connection 8 shown schematically.
• heat exchangers 6 for example spiral tube heat exchangers
• the process water flows can be provided between the steam reforming stage 1 and the common exothermic catalyst stage 2, 3 (not shown) and at the end of the fine cleaning stage 3 and which are thermally connected to the flow channel 5.
• a heat exchanger (not shown) is provided between the steam reforming stage 1 and the shift stage 2, the reformer gases emerging from the steam reforming stage 1 can be cooled to a temperature suitable for the shift reaction.
• the common exothermic catalyst stage 2, 3 is outside of a flow supply housing 10 for a cooling medium for cow enclosed the common exothermic catalyst stage.
• a cooling medium for cow enclosed the common exothermic catalyst stage.
• water or a hydrocarbon can be passed through the flow supply housing 10 as the cooling medium.
• the heat generated on the common exothermic catalyst stage (2, 3) is dissipated through the cooling medium, which has the additional advantage that the heat accumulating in the catalyst stage can be dissipated in a targeted manner and is not uselessly released to the environment. Due to the outer jacket cooling, the axial temperature profile is considerably evened out.
• the cooling medium is supplied to the flow supply housing 10 for the cooling medium via supply and discharge connections (not shown).
• the cooling medium can be guided in the flow supply housing 10 either in cocurrent or countercurrent to the flow direction in the jacket space of the common exothermic catalyst stage. If water or a hydrocarbon is used as the cooling medium, this can then be fed to the steam reforming stage 1.
• Control devices for mass flow adjustment of the cooling medium are provided on the supply and / or discharge connections of the power supply housing 10.
• the common exothermic catalyst stage 2, 3 comprises a uniform hollow body.
• This is designed as a ring honeycomb, which in the exemplary embodiment shown in FIG. 2 consists of metal.
• the ring honeycomb is coated from its two ends to the middle with suspensions of two different catalysts (wash-coat).
• the hollow body itself is thus constructed from a uniform piece and not, as in the device from FIG. 1 known from the prior art, assembled from two individually made shorter hollow bodies.
• FIG. 3 shows a cross section through the common exothermic catalyst stage 2, 3 according to the invention.
• a flow channel 5 runs in the center of the hollow body, through which, as explained above, hydrocarbons, for example, are passed in order to be preheated for steam reforming.
• a jacket space is arranged around the central flow channel 5 and is traversed by flow channels (not shown). Either the shift catalyst (2) or the methanation catalyst (3) of the fine cleaning stage is arranged in the jacket space.
• the jacket space is in turn enclosed by a flow supply housing 10 in which, for example, water is conducted as the cooling medium in order to be preheated for steam reforming.
• the shift reaction taking place in the jacket space (shift stage 2) or methanization (fine cleaning stage 3) is] exothermic.
• the energy released at least partially passes from the jacket space into the central flow channel 5 and the power supply housing 10, where it can be used to preheat the starting materials for steam reforming.
• the first method is based on first coating the carrier and passing the active component (eg precious metal) through Apply impregnation.
• the advantage of this method is that all precious metal is also accessible.
• the disadvantage is that when the precious metal solution dries after impregnation, the active component can still migrate.
• the second method is based on first producing a finished catalyst including the active component (for example noble metal) in powder form and then producing a suspension as a wash coat and using this to coat the honeycomb carrier.
• the active component for example noble metal
• catalysts and reaction conditions are selected for the first coating (shift stage) and the second coating (fine cleaning; selective methanization), in which the exit temperature from the shift reaction which takes place essentially corresponds to the inlet temperature of the selective methanization.
• ruthenium catalysts are mainly suitable for methanation.
• the methanization of C0 2 becomes too strong above 250 ° C, making selective methanization difficult.
• the shift catalyst should therefore still work at 250 ° C and withstand the higher calcining temperature of the ruthenium catalyst.
• a plurality of platinum catalysts for the shift reaction on various carriers, such as Ti0 2, Zr0 2, Ce0 2 and mixed oxides be ⁇ known (Appl. Catal.
• a suitable selection of the catalysts and the coating method can therefore be used to produce a shift stage and a selective methanization stage on a single metal honeycomb.
• a suspension of the carrier material (T ⁇ 0 2 or Zr / Ce0 2 -M ⁇ schox ⁇ d) is first prepared in water.
• the metal honeycomb is partially immersed in this suspension and then blown out from the end that was not immersed. This ensures that the coating covers only a part of the channels. It is then calcined. Then the honeycomb is immersed again in a platinum-rhenium solution to the same height and the coating is impregnated with it. After drying, it is calcined again.
• the honeycomb is now coated with a shift catalyst up to a certain height. The ratio of the space velocities of the two catalytic stages determines the height ratio when immersed. At the same space velocities for the shift reaction and the selective methanation, the shift catalyst is coated right up to the middle.
• a powder catalyst for selective methanization is now being produced. Suitable for this purpose s ch ruthenium on oxide supports such as T ⁇ 0 2, A1 2 0 3, Zr0 2, zeolites or mixtures of these Oxi ⁇ .
• a watery suspension is now produced again and the honeycomb is immersed in the suspension so that the previously uncoated part of the honeycomb is wetted.
• the honeycomb is blown out again so that no ruthenium catalyst is blown into the part of the honeycomb that is already occupied by the shift catalyst. Then the honeycomb is blown out from the side that is already covered with a shift catalyst. It is then calcined.
• the uniform exothermic catalyst stage which consists of a shift stage and a stage of selective methanization, is designed as a ring honeycomb.
• the metal honeycomb which has a length of approximately 180 mm, an outer diameter of approximately 180 mm and an inner diameter of approximately 135 mm, is used to produce the uniform exothermic catalyst stage.
• the honeycomb is dipped halfway into the suspension from a mixed oxide from ⁇ Ce0 2 and Zr0 2 (weight ratio 75/25) having a solids content of 50 wt .-%, which had been previously ground in a pearl mill.
• the excess suspension is removed by blowing out the honeycomb from the non-immersed end. This means that the coating only covers half of the honeycomb channels.
• honeycomb It is then dried and calcined at 550 ° C. The process is repeated until a coating tightness of 200 g per liter of honeycomb volume is reached.
• a solution of platinum tetrammine hydroxide and ammonium perrhenate is then prepared which contains 8% by weight of platinum and has a Pt / Re molar ratio of 3.
• the honeycomb is immersed again in the platinum-rhenium solution up to the same height and the coating is impregnated with it. After drying, it is calcined again at 550 ° C.
• the honeycomb is now coated with a shift catalyst up to the middle.
• a powder catalyst for selective methanization is then produced.
• a suspension of ammonium mordenite-20 is prepared in a solution of ruthenium nitrosyl nitrate.
• the ruthenium concentration in the suspension is calculated in such a way that 2% by weight of ruthenium account for the dry weight of ammonium mordenite-20.
• This suspension is dried and then calcined at 475 ° C.
• An aqueous suspension is then produced from this ruthenium-containing oxide powder and ground in a pearl mill. Then the honeycomb is inverted and immersed in the suspension so that the previously uncoated half is wetted.
• the Ringwabe thus obtained may be provided with an outer or inner sheath, wherein a cooling medium is guided in the intermediate space between the outer and inner jacket and the ⁇ Ringwabe.

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