• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a system (100, 200) for the catalytic methanation of carbon dioxide and / or carbon monoxide with hydrogen, wherein the electrical energy required for the electrolytic production of hydrogen from water is obtained from a renewable energy source, for example wind energy, and that used for methanation Catalyst has a support structure with a high heat storage capacity.
    公开号:AT518013A1
    申请号:T51029/2015
    申请日:2015-12-01
    公开日:2017-06-15
    发明作者:
    申请人:Christof Int Man Gmbh；
    IPC主号:
    专利说明:

    The invention relates to a system for the catalytic methanation of educt gases, namely carbon dioxide and / or carbon monoxide with hydrogen, wherein the electrical energy required for the electrolytic production of hydrogen from a renewable energy source, such as wind energy is obtained, and a method thereof.
    Renewable electricity, in particular from wind and photovoltaic systems, fluctuates greatly, both in terms of time and space. Thus, there is a need to balance supply and demand with the expansion of renewable energy production. If necessary, large quantities of energy must also be stored over several days or weeks. A suitable form of energy storage for this purpose is the so-called "power-to-gas" technology, in which hydrogen is produced by means of water electrolysis, wherein the necessary electrical energy comes from a renewable energy source. The hydrogen thus produced is reacted in a heterogeneous gas-catalytic reaction with, in particular carbon dioxide to methane, the methane, optionally after appropriate treatment, then fed into the existing natural gas infrastructure. In this way, the primary electrical energy is stored outside the grid in the form of natural gas. This natural gas can then be converted back into electrical energy as needed or used in the form of heat by combustion or as fuel, for example for driving vehicles.
    Such a "power-to-gas" method can be found in DE 10 2013 102 669 A1. It describes the preparation of predominantly liquid hydrocarbons from carbon dioxide, water and regenerative electric energy.
    The methanation of carbon dioxide with hydrogen has usually been used commercially for years in the gasification of coal or biomass. Another area of application is the purification of gas mixtures in production plants of the chemical industry, for example in the removal of small amounts of carbon monoxide and / or carbon dioxide from the synthesis gas of ammonia plants. These processes are usually carried out in fixed bed or fluidized bed reactors, whereby these are usually operated continuously, so that no or only very small load changes are present. Since the methanation is a highly exothermic reaction, the catalysts used, usually pellet-shaped bulk catalysts in the case of fixed bed reactors, must be protected from excessive temperature increase in the bed. This is usually realized by product gas recirculation and intermediate cooling.
    In the case of power-to-gas processes, the amount of the reaction gas produced by electrolysis, namely hydrogen gas, decreases as a function of the available electric current, namely a time-limited current surplus. Since this naturally can vary greatly, the conventional methods for methanation are not or only poorly suited, because such load fluctuations can only be compensated for by means of very large hydrogen buffer stores.
    It is therefore an object of the invention to provide a plant or a method available, which eliminate the disadvantages of the prior art and in particular a continuous methanation of carbon dioxide and / or carbon monoxide with hydrogen largely independent of load fluctuations of the electrical energy used for the electrolysis of water enable.
    This object is achieved in that the catalyst used for the methanation has a support structure with a high heat storage capacity. Since the methanation represents an exothermic reaction, the resulting heat is stored in the support structure of the catalyst. As a result, the reactor space is kept at reaction temperature through the catalyst arranged in the reactor for longer periods, even if the methanation is interrupted in the reactor due to load fluctuations and the resulting lack of hydrogen.
    In a particularly preferred embodiment of the invention, the support structure of the catalyst has a honeycomb structure with honeycomb-shaped basic bodies, wherein advantageously the honeycomb-shaped basic bodies have a rectangular, square, uniform triangular or uniform hexagonal cross-section. These cross sections allow the construction of catalyst layers within a reactor space, wherein preferably the honeycombs are arranged along their side edges to each other. Honeycombs with a side length of 0.05 m to 0.3 m and a honeycomb height of 0.1 m to 0.6 m have proved to be particularly suitable for the construction of catalyst layers.
    The support structure of the catalyst is advantageously made of a material selected from a group including ceramic oxides such as silica, titania, alumina, ceria, zirconia, or mixtures thereof. Due to the liberated during the methanation reaction heat and the resulting high temperatures in particular support structures have proven that are made of fired at 1300 ° C to 1600 ° C cordierite, mullite or alumina. In particular, these materials withstand the high temperature stresses associated with methanation.
    In this case, the invention provides that at least partially on the surface of the support structure, a catalytically active material, preferably as a washcoat is applied, wherein the catalyst contains at least one element of the Group VIII elements, in particular from the nickel group, the cobalt group and / or the iron group is selected. For the production of the washcoat, an acid metal oxide suspension, for example aluminum oxide or zirconium oxide, is usually applied to the support structure, and the support structure coated in this way is subsequently dried and fired. Finally, this layer is impregnated with a salt solution of the selected catalyst, and the catalyst is fixed on the support structure by further drying and optionally firing.
    In a particularly preferred embodiment of the invention, a reactor system with at least two reactor chambers is provided in which the catalyst, in particular ceramic honeycomb catalysts, are arranged, wherein advantageously each reactor chamber has at least one gas line and preferably at least one heat exchanger device. As a result, the partial load behavior of the reactor system, which is particularly preferably designed as a tray reactor system, is considerably improved.
    In a further preferred embodiment, each chamber is additionally subdivided into at least two compartments or compartments, each compartment being able to be flowed on independently with educt gas. This results in an additional higher load flexibility.
    In the case of low Eduktgasströme, in particular with respect to the hydrogen produced by electrolysis, for example, only a first compartment of a first chamber can be flown, while the other compartments remain at rest. Due to the large ceramic mass of the support structure, in particular in honeycomb catalysts, the heat generated during the reaction is stored, wherein the compartment (s) remain at rest by the heat emitted by the support structure to the reaction temperature. The supply of reactant gas can be alternately controlled between the individual compartments or compartments of the tray reactor such that in all compartments alternately exothermic heat of reaction is released and stored, and so the compartments are each kept at reaction temperature. In continuous operation, the heat exchanger devices in the respective reaction chambers allow removal of excess heat to avoid overheating of the catalyst and / or the reactor space.
    For purposes of this disclosure, the terms "reactor chamber," "chamber," and "reactor space" are used interchangeably. The same applies to the terms "compartment" and "compartment".
    The system according to the invention can be adapted in size to the respective throughputs, in particular in tray reactors is an extension of the system when using honeycomb catalysts in a simple manner possible.
    In this case, only the number of honeycombs used has to be adapted to the maximum expected educt gas flow.
    In an alternative embodiment of the invention, a reactor system with at least two fixed bed reactors is provided, in which the catalyst is arranged, wherein advantageously each reactor has at least one gas supply line and preferably at least one heat exchanger device.
    Particularly preferably, it is provided that the support structure of the catalyst is arranged within the respective Rectors or reaction chambers in layers, wherein the layer structure preferably has 4 to 30 channels per square centimeter, so a cell density of 25 cpsi to 200 cpsi. These
    Channels allow the respective layers to pass through reaction gases with no significant pressure drop while providing a sufficiently high contact area of the gases with the active sites of the catalyst.
    The storage capacity in the respective reaction chamber can be improved by the layer structure having at least one catalytically active layer or area and additionally at least one catalytically inactive layer or area, wherein the inactive layer is preferably formed from the support structure for the catalyst. In this case, the respective layers particularly preferably have the already described honeycomb structure, the honeycomb basic bodies of the catalytically inactive layer having no catalytically active constituents and / or coating and serving exclusively for heat storage. It can likewise be provided that catalytically active and catalytically inactive honeycomb bodies are mixed in any ratio within a layer.
    The object is further achieved by a process for the catalytic methanation of reactant gases, namely carbon dioxide and / or carbon monoxide with hydrogen in a reactor, wherein in a first step hydrogen gas is electrolytically produced from water, and the electricity required for the electrolysis of a renewable Energy source, for example, wind energy is obtained. The catalytic methanation itself takes place in a subsequent second step, wherein it is provided according to the invention that the catalyst used for the methanation is arranged on a carrier structure, preferably designed as a honeycomb structure, with a high heat storage capacity, which is used as the storage mass for the heat of reaction produced during the methanation.
    It is particularly preferred in this case for the reactor to have at least two chambers which are fed in series, in parallel or alternately with educt gas. The chambers preferably contain at least two switchable compartments in which the catalysts are arranged. As already described above, this has the advantage that at partial load operation only at least one chamber and / or compartment is charged with reaction gas, namely hydrogen and carbon dioxide and / or carbon monoxide for carrying out the methanation reaction, while at least a second
    Chamber is kept in standby mode, wherein the heat of reaction stored in the support structure keeps this second chamber and / or compartment at reaction temperature. During the methanation, at least one heat exchange device ensures the removal of excess heat of reaction, which can optionally be used to control the temperature of further reaction chambers.
    The invention is explained in more detail below with reference to non-limiting exemplary embodiments with associated figures. Show in it
    FIG. 1 shows a schematic view of a first embodiment of the device according to the invention,
    FIG. 2 shows a schematic cross section of a reaction chamber of the device from FIG. 1,
    Figure 3 is a schematic view of a second embodiment of the device according to the invention, and
    Figure 4 is a schematic view of a third embodiment of the device according to the invention.
    FIG. 1 shows a schematic representation of a reactor 100 according to the invention, which is designed as a tray reactor in this embodiment of the invention. This tray reactor 100 has three reactor chambers 110a, 110b, 110c, each having a gas distribution layer 120a, 120b, 120c, usually of porous material, which serves to uniformly distribute the gas within the reactor chambers 110a, 110b, 110c.
    In each reactor chamber 110a, 110b, 110c, in this embodiment of the invention, catalyst material 140 in the form of honeycomb catalysts is arranged in two compartments 131, 132 (FIG. 2).
    The feed of educt gases (arrow A) via a gas distribution system 150a, 150b, 150c, which is cyclically switchable, so that the respective compartments 131, 132 can be flowed independently of each other. This cyclical
    Circuit allows a staggered sequence of methanation reactions in the individual compartments 131, 132 or in the catalyst layers therein. Here, the time sequence is chosen such that in the individual compartments 131, 132 recurrently exothermic heat of reaction is released so as to keep the compartments 131, 132 and subsequently the reactor chambers 110a, 110b, 110c to operating temperature. The heat of reaction is hereby stored in the honeycomb basic bodies of the support structure of the catalyst 140.
    A bypass system 160 permits a cyclical switching of the educt gas in the individual reactor chambers 110a, 110b, 110c, shut-off valves 161 provided for this purpose in the gas distribution system 150a, 150b, 150c possibly preventing the gas supply in the gas distribution layers 120a, 120b, 120c. If the educt gas streams are available in an insufficient amount for operation of all reactor chambers 110a, 110b, 110c or compartments 131, 132, this cyclic circuit allows a time-staggered sequence of methanation reactions in the individual reactor chambers 110a, 110b, 110c and compartments 131, 132, respectively ,
    Furthermore, each reactor chamber 110a, 110b, 110c is equipped with heat exchanger devices 170 which allow a dissipation of excess heat and / or temperature of the respective reactor chamber 110a, 110b, 110c.
    The removal of the product gas, namely the raw methane is preferably carried out at the top of the tray reactor 100 (arrow B).
    FIG. 2 shows, by way of example, the reactor chamber 110a in a plan view, with catalyst material 140 being arranged in each of the two compartments 131, 132. The catalyst layer 140 consists of a plurality of honeycomb-shaped basic bodies, which have a catalytically active salt, for example in the form of a washcoat, wherein the base bodies are arranged along their side edges to each other.
    The honeycomb main body of this catalyst material 140 have parallel to the longitudinal axis of the tray reactor 100 extending channels (not shown), which allow a flow of the catalyst material 140 in the compartments 131, 132.
    A further embodiment of the invention is shown in FIG. 3, wherein the tray reactor 100 shown therein has substantially the same structure as shown in FIG. In this variant, the compartments 131, 132 are filled with catalyst material 140, wherein the catalyst material 140 is penetrated by heat storage layers 141. These heat storage layers 141 are catalytically inactive, and are particularly preferably formed from the honeycomb basic bodies of the support structure of the catalytically active layer 140, but in contrast to this have no catalytically active equipment. The arrangement of these heat storage layers 141 may surround or pass through the catalyst layer 140.
    A third embodiment of the device 200 according to the invention can be seen from FIG. Herein are three fixed bed reactors 210 are provided, which in turn are filled with catalyst material 140, which consists according to the invention of honeycomb-shaped basic bodies. In turn, a gas distribution layer 220 is provided which effects a uniform distribution of the gas flowing in via a gas distribution system 250 (arrow A) within the reactor chamber. If necessary, the incoming gas can be tempered by means of a heat exchanger device 270.
    Furthermore, 250 shut-off valves 261 are provided in the gas distribution system, which allow a cyclic and / or alternating supply of educt gases to the respective fixed bed reactors 210.
    It is understood that the present invention is not limited to the embodiments shown above. In particular, different types of fixed bed reactors may be used, which are suitable for receiving the catalyst layers described above. It is essential to the invention that these catalyst layers have a high heat storage capacity and / or further catalytically inactive layers with a high heat storage capacity are provided. This heat storage capacity allows a partial load operation of the reactor or of a system consisting of several reactors according to the invention, which has at least two independently operable reactor chambers and / or reactors, which can be operated either simultaneously or at different times depending on the load. A significant advantage of the system according to the invention is that it can be extended as required by further reactor chambers and / or reactors with associated catalyst layer in a simple manner. Furthermore, this structure allows a very flexible operation that tolerates highly fluctuating load changes due to the coupling of the methanation process with the electrolysis used to produce the hydrogen gas with electrical energy from renewable energy sources.
    权利要求:
    Claims (14)
    [1]
    1. Plant (100, 200) for the catalytic methanation of educt gases, namely carbon dioxide and / or carbon monoxide with hydrogen, wherein the required for the electrolytic production of hydrogen from water electrical energy from a renewable energy source, such as wind energy is related, characterized in that the catalyst (140) used for the methanation has a carrier structure with a high heat storage capacity.
    [2]
    2. Plant (100, 200) according to claim 1, characterized in that the support structure of the catalyst (140) has a honeycomb structure with honeycomb-shaped basic bodies.
    [3]
    3. Plant (100, 200) according to claim 2, characterized in that the honeycomb-shaped base body has a rectangular, square, uniform triangular or uniform hexagonal cross-section, wherein the honeycomb preferably has a side length of 0.05 m to 0.3 m and a Honeycomb height from 0.1 m to 0.6 m.
    [4]
    A plant (100, 200) according to any one of claims 1 to 3, characterized in that the support structure of the catalyst (140) is made of a material selected from a group consisting of ceramic oxides such as silica, titania, alumina , Cerium oxide, zirconium oxide, or mixtures thereof, wherein the support structure is more preferably prepared from 1300 ° C to 1600 ° C fired cordierite, mullite or alumina.
    [5]
    5. Plant (100, 200) according to one of claims 1 to 4, characterized in that at least partially on the surface of the support structure, a catalytically active material, preferably as a washcoat, is applied, wherein the catalyst is at least one element of the group VIII elements, in particular from the nickel group, the cobalt group or the iron group.
    [6]
    6. Plant (100) according to one of claims 1 to 5, characterized in that a reactor system with at least two reactor chambers (110a, 110b, 110c) is provided, in which the catalyst (140) is arranged, wherein advantageously each reactor chamber (110a , 110b, 110c) has at least one gas supply line (150a, 150b, 150c) and preferably at least one heat exchanger device (170).
    [7]
    7. Plant (100) according to claim 6, characterized in that the reactor chambers (110a, 110b, 110c) in at least two compartments (131, 132) are divided, each compartment (131, 132) is independently flowed with educt gas.
    [8]
    8. Plant (200) according to one of claims 1 to 5, characterized in that a reactor system with at least two fixed bed reactors (210) is provided, in which the catalyst (140) is arranged, wherein advantageously each reactor (210) via at least one Gas supply line (250) and preferably at least one heat exchanger means (270) has.
    [9]
    9. plant (100, 200) according to one of claims 1 to 8, characterized in that the support structure of the catalyst (140) within the respective reactor chamber (110a, 110b, 110c) is arranged in layers, wherein the layer structure preferably 4 to 30 Channels per cm2, so has a cell density of 25 cpsi to 200 cpsi.
    [10]
    10. plant (100, 200) according to claim 9, characterized in that the layer structure comprises at least one catalytically active layer (140) and at least one catalytically inactive layer (141), which is preferably formed from the support structure for the catalyst (140) ,
    [11]
    11. A process for the catalytic methanation of educt gases, namely carbon dioxide and / or carbon monoxide with hydrogen in a reactor (100, 200), with a first step, in which hydrogen gas is produced electrolytically from water, wherein the required for the electrolysis of electrical energy from a in a second step, the catalytic methanation of carbon dioxide and / or carbon monoxide with the recovered hydrogen, characterized in that the catalyst used for the methanation (140) on a preferably designed as a honeycomb support structure with high heat storage capacity is arranged, which is used as a storage mass for the resulting during the methanation reaction heat.
    [12]
    12. The method according to claim 11, characterized in that the reactor (100) has at least two reactor chambers (110a, 110b, 110c) which are fed in series, in parallel or alternately with educt gas.
    [13]
    13. The method according to claim 12, characterized in that the at least two reactor chambers (110a, 110b, 110c) in at least two compartments (131, 132) are divided, which are fed in series, in parallel or alternately with reactant gas.
    [14]
    14. The method according to claim 11, characterized in that the heat of reaction stored in the carrier structure is dissipated via at least one heat exchanger device (170, 270).
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20120063963A1|2009-04-24|2012-03-15|University Of Yamanashi|Selective co methanation catalyst, method of producing the same, and apparatus using the same|
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    法律状态:
    2021-11-15| PC| Change of the owner|Owner name: CHRISTOF GLOBAL IMPACT LTD., GB Effective date: 20211005 |
    优先权:
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    CA3007100A| CA3007100C|2015-12-01|2016-11-30|Method and system for the catalytic methanization of reactant gases|
    EP16822366.7A| EP3383980B1|2015-12-01|2016-11-30|Process and apparatus for catalytic methanisation of gases|
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