WO2019149435A1 - Plug flow reactor and method for operating a plug flow reactor - Google Patents
Plug flow reactor and method for operating a plug flow reactor Download PDFInfo
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- WO2019149435A1 WO2019149435A1 PCT/EP2018/097025 EP2018097025W WO2019149435A1 WO 2019149435 A1 WO2019149435 A1 WO 2019149435A1 EP 2018097025 W EP2018097025 W EP 2018097025W WO 2019149435 A1 WO2019149435 A1 WO 2019149435A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
- B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
- B01J8/0453—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/001—Controlling catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0403—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
- B01J8/0407—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more cylindrical annular shaped beds
- B01J8/0415—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more cylindrical annular shaped beds the beds being superimposed one above the other
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0403—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
- B01J8/0423—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds
- B01J8/0426—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds the beds being superimposed one above the other
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0496—Heating or cooling the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
- B01J8/067—Heating or cooling the reactor
Definitions
- the invention relates to a tubular reactor for converting hydrogen to methane and a method for operating the tubular reactor.
- Electricity generation fluctuates with increasing share of electricity from renewable energies during the course of the day.
- controllable power plants or storage facilities are needed to store this energy.
- One of the currently contemplated solutions is the conversion of electrical energy into value products, in particular organic platform chemicals or synthesis gas comprising carbon monoxide and hydrogen.
- One possible technique for converting electrical energy into value products is electrolysis.
- the electrolysis of water to hydrogen and oxygen is a method known in the art.
- the hydrogen produced in the electrolysis process can react with a component comprising carbon dioxide to form methane and water.
- the methane can then advantageously be fed directly into the existing natural gas infrastructure.
- the object is achieved with a tubular reactor according to claim 1 and a method for operating a tubular reactor according to claim 14.
- the tubular reactor according to the invention for converting hydrogen to methane comprises a first reaction zone with a first catalyst bed having a first density and a temperature in a first temperature range. Furthermore, the tubular reactor comprises a second reaction zone with a second Kata lysatorbett having a second density and a temperature in a second temperature range. Furthermore, the tubular reactor comprises a third reaction zone with a third cata- torbate having a third density and a temperature in a third temperature range, the first density being lower than the first density. half of the second density, and the second density is below the third density. In other words, the density of the catalyst bed increases in the direction of flow of the educt gas, in particular of the hydrogen.
- the reaction zones are arranged in the tubular reactor in the flow direction one behind the other.
- the inventive method for operating the tubular reactor for converting hydrogen to methane comprises several
- a tubular reactor having at least three reaction zones wherein each of the three reaction zones comprises a catalyst bed.
- each reaction zone comprises a catalyst bed having a defined density, where the respective densities of the catalyst bed increase in the flow direction of the educt gas.
- a reactant gas comprising hydrogen and carbon dioxide is added to a first reaction zone.
- this first reaction zone is a temperature in a first temperature range, in which a first portion of hydrogen and carbon dioxide is converted to a first portion of methane.
- both the unreacted educt gas, in particular the hydrogen and the carbon dioxide, and the methane are fed into a second reaction zone.
- a second portion of methane is produced at a temperature in a second temperature range from a second hydrogen fraction and the carbon dioxide.
- This second methane content is greater than the first methane content.
- a larger amount of methane is produced in the second reaction zone than in the first reaction zone.
- the educt gas, which comprises unreacted hydrogen, and the methane, which was prepared in the first and second reaction zone are fed into a third reaction zone.
- a third portion of the hydrogen is reacted with carbon dioxide to form a third portion of methane at a temperature in a third temperature range.
- the guiding of the educt gas comprehensively allows hydrogen through the different reaction zones increasing catalyst bed density, a flexible reaction of hydrogen and carbon dioxide without the use of a large cost-intensive hydrogen storage and without the use of a temperature control during a reaction interruption, so that the flexible reaction of hydrogen is possible with low energy consumption.
- the first reaction zone represents a start-up zone.
- the first temperature range of this zone should expediently be above a minimum temperature which is above the reaction ignition temperature and above the condensation temperature of water, in particular 100 ° C.
- the first reaction zone comprises the catalyst bed with the lowest density.
- the second reaction zone has a temperature in a second temperature range. In particular, this should be below the temperature that limits the stability of the cata- sector. In this zone, the largest conversion of hydrogen takes place.
- the second catalyst bed has a higher density compared to the first reaction zone.
- the hydrogen is reacted, which was not yet reacted in the first two reaction zone. It is advantageous if the temperature in the third temperature range is lower than in the second temperature range Tempe. As in the first reaction zone, the temperature in this third reaction zone should, however, advantageously be above the condensation temperature of water and above the reaction start temperature. This is achieved by a particularly dense catalyst bed.
- the third reaction zone has a catalyst bed with a third density, this third density being higher than the first and second densities, ie having the highest density of the tubular reactor. Since the educt gas volume flow can fluctuate at the beginning of the respective zone and a conversion in the respective reaction zone is still guaranteed, this reactor structure can be operated with fluctuating educt gas stream.
- the entire volume flow fluctuates of the educt gas.
- the ratio of hydrogen and carbon dioxide remains constant in the educt gas, in particular a stoichiometric ratio of the educt gases is set.
- the third reaction zone ensures that a residual amount of hydrogen is reacted, which may be low or high depending on the input volume flow of educt gas.
- reaction zones dersel ben type ie in particular te with the same Katalysatorbettdich. These are then separated from each other by a feeding device for the cooling medium.
- a supply device for a cooling fluid is arranged between the second and third reaction zone.
- a cooling fluid is added directly into the third reaction zone.
- the third reaction zone is cooled by means of an indirect cooling, in particular via an introduced heat exchanger.
- direct cooling by means of a cooling fluid in particular water
- a cooling fluid in particular water
- the conversion of hydrogen to methane is exothermic, thereby releasing at a high conversion a high amount of energy that must be brought out of the system before the mixture of hydrogen and methane flows through the third reaction zone.
- the temperature in the third Temperaturbe is rich below the temperature in the second Temperaturbe rich. Since the density of the catalyst bed in the third reaction zone but above the second density of the cata- torbett in the second reaction zone, it is ensured tet the fact that the proportion of hydrogen, which was not reacted in the first two reaction zone, is reacted here.
- Advantageously contributes to both the high catalyst bed density, as well as the low temperature in the third reac tion zone, since it is an exothermic reaction.
- the temperature in the first reaction onszone in a first temperature range ranging from 100 ° C to 400 ° C. Particularly advantageous is the temperature in the first temperature range between 150 ° C and 250 ° C.
- the heat generated in the first reaction zone is transported into the second reaction zone by means of the educts and products and thus used to heat the second reaction zone.
- the inlet temperature in the first reaction zone, in the second reaction zone and / or in the third reaction zone is adjusted depending on the volume flow of the educt gas.
- the heating power in the first zone is turned down, since the residence time of the educt gas in the first reac tion zone is higher and thus proportionately more reactant gas can be set.
- the inlet temperature, in particular in the first reaction zone is set higher because the residence time of the educt gas in the first reaction zone is shorter.
- the proportionate, in other words relative to the Eduktgasmenge, sales is lower than at low Eduktgasströmen.
- the maximum temperature of the second temperature range is 500 ° C.
- this maximum temperature is chosen such that both the strength of the reactor material and the Sta can be ensured stability of the catalyst.
- a high conversion of hydrogen is achieved with carbon dioxide to methane, resulting in high amounts of heat. This heat must be dissipated so as not to exceed the maximum temperature.
- This can be done by means of indirect cooling, in particular by the introduction of cooling media through flow components, in particular in the form of heat exchangers.
- a direct cooling by means of a cooling fluid, in particular water can be carried out, the water being injected into the second reaction zone.
- the temperature in the third temperature range is between 200 ° C and 400 ° C. Particularly advantageous is the temperature in the third temperature range between 250 ° C and 350 ° C.
- the temperature in the third temperature range is below the temperature of the second temperature range at high catalyst bed density, thereby ensuring that the unreacted hydrogen material and the carbon dioxide in the third reaction zone is converted to methane.
- the first reaction zone comprises a Hei tion.
- This heater advantageously ensures that the mini maltemperatur is reached for the reaction start. Furthermore, the heater ensures that the temperature is above the condensation temperature of the water. Water is produced as a product during the conversion of the hydrogen with carbon dioxide to methane. Additional water can be fed into the tubular reactor as cooling fluid as needed. The water should be in vapor form to maintain the stability of the catalyst bed.
- the first, the second and / or the third catalyst bed comprise a porous metal structure for accommodating the catalyst.
- the metal structure is advantageously electrically conductive.
- such metallic Grundstruktu ren a high thermal conductivity and high electrical conductivity.
- these structures allow a high surface area to volume ratio, allowing for efficient heat input into the reactor.
- the heat input can via a heating of the reactor wall, which is in direct contact with the metal structure, take place. This allows a better heat input compared to conventional catalyst pellets. This is particularly advantageous in the first reaction zone.
- the metal structure may be connected to electrodes. By applying a voltage to the electrodes and the electrical resistance in the metal structure, a temperature increase of the metal structure, it can be sufficient.
- the contacting of the metal structure with Elekt roden allows even faster heat input in the United equal to the contacting of the metal structure with a Hei tion.
- the rapid heating of the first reaction zone is particularly advantageous if the reactor is cooled at an interruption of the Eduktzussel below a minimum temperature and therefore must be heated quickly when re-use of the reactor to reach the starting temperature to it.
- the catalyst is introduced as a porous bulk material in the tubular reactor.
- An alternative embodiment and development of the inven tion is to coat a metal structure with catalyst.
- Particularly advantageous is the combination of a metal-coated catalyst structure, which is coated with electrodes. is bound to achieve a direct and therefore advantageous fast heating of the metal structure and thus of the cata- gate.
- the hydrogen comes from the electrolysis of water.
- the tubular reactor with the three reaction zones with the fluctuating hydrogen flow from the electrolysis in dependence on the available electrical energy can be operated dynamically.
- FIG. 2 shows a tube reactor with three reaction zones, reaction onsumsatz and three temperature ranges.
- FIG. 3 shows a metal structure of a catalyst bed of the
- FIG. 4 shows a process diagram of the methanation of the hydrogen by means of the tubular reactor.
- FIG. 1 shows a tube reactor 1 having a first reaction zone 11, a second reaction zone 12 and a third reaction zone 13.
- the first reaction zone 11 comprises a first catalyst bed 14 having a first density.
- the second reaction zone 12 comprises a second catalyst bed 15 having a second density.
- the third reaction zone 13 comprises a third catalyst bed 16 having a third density.
- the reaction zones are in the tubular reactor 1 in a row Lich respect of the flow direction of the educt gas including hydrogen material 2 and carbon dioxide 3 is arranged. Between the second reaction zone 12 and the third reaction zone 13 there is a supply device 9 for a cooling fluid. At the end of the tubular reactor 1, methane 4 and water 5 leave the tubular reactor 1 as product stream.
- the density of the catalyst bed in the respective reaction zone increases in the direction of the flow of educt gas. That is, the first reaction zone has the catalyst bed with the lowest density, the third reaction zone, the catalyst bed with the highest density.
- the catalyst is particularly advantageously arranged in a metal structure 30. This metal structure is explained in more detail in FIG.
- FIG. 2 also shows the tubular reactor 1 with the first reaction zone 11, the second reaction zone 12 and the third reaction zone 13. Furthermore, FIG. 2 shows a y-axis 8 in the longitudinal direction of the tubular reactor 1, ie in the flow direction of the educt gas Length of the tubular reactor 1 describes. FIG. 2 shows, transversely to the flow direction of the educt gases, an x-axis 7 which describes both the reaction conversion and the temperature ranges.
- the methanation reaction can be described by Equation 1.
- first reaction zone 11 with the first catalyst bed 14 with a first density ei ne start-up zone for the methanation reaction of Equation 1 represents.
- a first temperature prevails in a first temperature range between 100 ° C and 400 ° C, more preferably between 150 ° C and 250 ° C.
- This temperature range is set in Figure 2 as a tape is.
- the temperature must suitably exceed the reaction onset temperature.
- the temperature should be above 100 ° C, so that during the reaction tion resulting vapor water.
- FIG. 2 shows on the basis of the conversion that the reaction starts in this first reaction zone.
- the density of the catalyst bed 14 in this first reaction zone 11 is low in order to avoid pronounced temperature peaks due to the exothermic reaction. On the other hand, the density of the catalyst bed 14 must be sufficiently high to produce so much heat that the heating of the following second reaction zone 12 can be ensured. The amount of heat generated in the first reaction zone 11 is used to heat the second reaction zone 12 by convection.
- FIG. 2 further shows that the second reaction zone 12 has a higher temperature level than the first reaction zone 11.
- the temperature in the second reaction zone 12 is typically at most 600 ° C, especially at most 500 ° C. This maximum temperature must not be exceeded in order to maintain the strength of the reactor material and the stability of the catalyst.
- FIG. 2 also shows that the greatest reaction conversion takes place in this second reaction zone 12. Due to the higher catalyst torêt this high turnover is possible. However, the conversion in this second reaction zone 12 is limited by the temperature, since the maximum temperature must not be exceeded despite the exothermic reaction.
- FIG. 2 further shows that the temperature in the third reaction zone 13 is below the temperature in the second reaction zone 12.
- the temperature in the third reaction zone 13 is typically in a range of 200 ° C to 400 ° C, more preferably in a range of 250 ° C to 350 ° C. In order to achieve these temperature differences from the second reaction zone 12 into the third reaction zone 13, it may be necessary for cooling to take place either between the two reaction zones or within the third reaction zone 13.
- 9 is added by means of Zuzhouvorrich device as coolant water 5. It is about in this example, therefore, a direct cooling.
- the third reaction zone 13 is ge indirectly cooled by means of heat exchanger structures. Water as a coolant is particularly advantageous in the direct cooling, since it on the one hand, in particular due to the enthalpy of vaporization, can achieve a sufficiently large cooling effect and on the other hand already as Pro product in the tubular reactor 1 is present, so that no addi tional components must be performed in the system.
- the third catalyst density 16 should be higher than the first two catalyst bed densities in order to achieve a sufficient reaction rate at low temperatures and low educt concentrations. As in the first reaction zone 11, the temperature range is limited downwards by the reaction start temperature and the condensation temperature of the water 5.
- Figure 2 illustrates that after the third reaction zone 13 almost full conversion is achieved.
- the three reaction zones 11, 12, 13 allow by the un ferent densities of the three catalyst beds 14, 15 and
- the cooling fluid water 5 can be guided flexibly in different amounts through the supply device 9 and so the third reaction zone accordingly the conversion and the temperature of the first two reac tion zones temperature such that the educt gas hydrogen 2 with carbon dioxide 3 almost completely to methane vice versa.
- a large hydrogen storage for storing the hydrogen in times of high hydrogen production is advantageously not necessary.
- FIG. 1 and FIG. 2 show by way of example that the second reaction zone has the greatest length. In this second reaction zone, the highest conversion is achieved. Both in Figure 1 and in Figure 2, three reaction zones are provided. But it is especially possible that several second reaction zones 12 are arranged one behind the other. Then, the length of the second reaction zone 12 may be smaller. In this case, it is expedient that water supply means for the coolant are present between these second reaction zones 12 in order to achieve a temperature below the maximum temperature for each of the second reaction zones 12.
- FIG. 3 shows a metal structure 30 on which the cata- capacitor can be applied.
- This metal structure 30 has in particular a diamond unit cell, which has spaces between.
- the Me tall Vietnamese was coated with catalyst, so that a cata- sator für 32 is formed on the metal substrate 33.
- this metallic basic structure has a high heat conductivity and a high electrical conductivity.
- this structure has a high surface to Volumenver ratio, which allows effective heat input into the reactor 1.
- the heat input into the tubular reactor 1 can take place via the heating of a reactor wall of the tubular reactor 1. Then it is useful if the reactor wall of the tube reactor 1, the tall tall structure 30 Me directly contacted.
- the metal structure 30 is contacted by electrodes and heated when a voltage is applied due to the electrical resistance. This allows a very efficient and rapid heating of the metal structure 30, which makes the heat input into the Rohrreak gate 1 energy-efficient.
- the cooled Rohrre actuator 1 can be heated electrically quickly and thus quickly return the operating temperature of the first reaction zone 11 he testifies.
- This coated metal structure 30 is particularly advantageous in the first reaction zone 11 before. But it is also possible that the metal structure 30 in the second reaction zone 12 and in the third reaction zone 13 is arranged.
- FIG. 4 schematically shows the interconnection of the tubular reactor 1, ie the methanation 10, with the electrolysis 40, a treatment plant 50 and the natural gas network 60.
- Water 5 is split into hydrogen 2 and oxygen 17 by means of electrical energy, in particular if excess energy is present in a large amount of wind and sun.
- the hydrogen 2 is fed into the tubular reactor 1 to methanation 10.
- carbon dioxide 3 is supplied.
- metha nization 10 is made of the carbon dioxide 3 and the water methane 4 and water 5 produced.
- the methane 4 is then fed into a methane treatment plant 50, where it is worked up so that it can be Gelei tet in the natural gas network 60.
- the methane 4 is used for subsequent reactions.
- Another alternative is the onset of methane as a fuel, especially for locomotion means, especially vehicles.
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Abstract
The invention relates to a plug flow reactor and a method for operating the plug flow reactor in order to convert hydrogen into methane. The plug flow reactor comprises three reaction zones. The first reaction zone comprises a first catalyst bed with a first density and a temperature in a first temperature range, the second reaction zone comprises a second catalyst bed with a second density and a temperature in a second temperature range, and the third reaction zone comprises a third catalyst bed with a third density and a temperature in a third temperature range, wherein the first density lies below the second density, and the second density lies below the third density, i.e. the density of the catalyst beds increases in the direction of the reactant gas flow, thus advantageously allowing a dynamic operation of the plug flow reactor for a methanation process.
Description
Beschreibung description
Rohrreaktor und Verfahren zum Betreiben eines Rohrreaktors Tubular reactor and method for operating a tubular reactor
Die Erfindung betrifft einen Rohrreaktor zum Umsetzen von Wasserstoff zu Methan und ein Verfahren zum Betreiben des Rohrreaktors . The invention relates to a tubular reactor for converting hydrogen to methane and a method for operating the tubular reactor.
Die Stromerzeugung schwankt mit zunehmendem Anteil an Strom aus erneuerbaren Energien während des Tagesverlaufs. Um ein Überangebot an Strom in Zeiten mit viel Sonne und starkem Wind bei niedriger Nachfrage nach Strom ausgleichen zu kön nen, benötigt man regelbare Kraftwerke oder Speicher, um die se Energie zu speichern. Electricity generation fluctuates with increasing share of electricity from renewable energies during the course of the day. In order to be able to compensate for an oversupply of electricity in times of high sunshine and strong wind with low demand for electricity, controllable power plants or storage facilities are needed to store this energy.
Eine der derzeitig angedachten Lösungen ist das Umwandeln von elektrischer Energie in Wertprodukte, die insbesondere orga nische Plattformchemikalien oder Synthesegas, welches Kohlen stoffmonoxid und Wasserstoff umfasst, darstellen. Eine mögli che Technik zur Umwandlung der elektrischen Energie in Wert produkte stellt die Elektrolyse dar. One of the currently contemplated solutions is the conversion of electrical energy into value products, in particular organic platform chemicals or synthesis gas comprising carbon monoxide and hydrogen. One possible technique for converting electrical energy into value products is electrolysis.
Die Elektrolyse von Wasser zu Wasserstoff und Sauerstoff stellt eine im Stand der Technik bekannte Methode dar. Der in dem Elektrolyseprozess hergestellte Wasserstoff kann mit ei ner Kohlenstoffdioxid umfassenden Komponente zu Methan und Wasser reagieren. Das Methan kann dann vorteilhaft direkt in die bestehende Erdgasinfrastruktur eingespeist werden. The electrolysis of water to hydrogen and oxygen is a method known in the art. The hydrogen produced in the electrolysis process can react with a component comprising carbon dioxide to form methane and water. The methane can then advantageously be fed directly into the existing natural gas infrastructure.
Da die regenerativen Energiequellen wie Windenergie und So larenergie nicht regelmäßig bereitstehen, kommt es bei der Produktion von Wasserstoff aus der Elektrolyse zu Schwankun gen hinsichtlich der produzierten Wasserstoffmenge. Diese Schwankungen führen zu Fluktuationen des Wasserstoffvolumen- stroms in einen Methanisierungsreaktor und können daher bei der Methanisierungs-Reaktion nachteilig zu einer Fluktuation der Produktgasqualität führen. Dadurch ist es nachteilig nö tig, das produzierte Erdgas vor einer Einspeisung in das Erd-
gasnetz aufzubereiten. Ein zusätzlicher Aufbereitungsprozess führt nachteilig zu einem komplexeren Gesamtaufbau der Anlage und zu höheren Prozesskosten. Since the regenerative energy sources such as wind energy and So larenergie not available regularly, it comes in the production of hydrogen from the electrolysis Schwankun conditions in terms of the amount of hydrogen produced. These fluctuations lead to fluctuations of the hydrogen volume flow in a methanization reactor and can therefore disadvantageously lead to a fluctuation of the product gas quality in the methanation reaction. As a result, it is disadvantageously necessary to reduce the natural gas produced before it is fed into the earth. to reprocess the gas network. An additional treatment process leads disadvantageously to a more complex overall structure of the plant and to higher process costs.
Eine Möglichkeit diesen schwankenden Wasserstoffström auszu gleichen besteht darin, einen WasserstoffSpeicher zwischen dem Wasserelektrolyseur und dem Reaktor zur Methanisierung anzuordnen. Die Wasserstoff-Fluktuationen werden auf diese Weise gepuffert. Nachteilig sind diese WasserstoffSpeicher aber sehr groß, wartungs- und kostenintensiv. One way to compensate for this fluctuating hydrogen flow is to arrange a hydrogen storage between the water electrolyzer and the reactor for methanation. The hydrogen fluctuations are buffered in this way. The disadvantage of these hydrogen storage but very large, maintenance and cost-intensive.
Trotz Einsatz eines WasserstoffSpeichers kann es dennoch zu langfristigen Unterbrechungen der Wasserstoffzufuhr kommen, sodass der Reaktor nicht betrieben werden kann. Um das anfäh ren des Reaktors nach einer Unterbrechung möglichst kurzfris tig gewährleisten zu können, werden die Reaktoren während der Stillstandzeit beheizt. Dieses Beheizen ist nachteilig kos ten- und energieintensiv. Despite the use of a hydrogen storage, it may nevertheless lead to long-term interruptions of the hydrogen supply, so that the reactor can not be operated. In order to ensure that the reactor can be cooled as quickly as possible after an interruption, the reactors are heated during the downtime. This heating is adversely kos ten- and energy-intensive.
Es ist daher Aufgabe der Erfindung einen Reaktor und ein Ver fahren zum Betreiben eines Reaktors anzugeben, welcher eine flexible und energieoptimierte Herstellung von Methan bei fluktuierender Wasserstoffzufuhr ermöglicht. It is therefore an object of the invention to provide a reactor and a Ver drive to operate a reactor, which allows a flexible and energy-optimized production of methane with fluctuating hydrogen supply.
Die Aufgabe wird mit einem Rohrreaktor gemäß Anspruch 1 und einem Verfahren zum Betreiben eines Rohrreaktors gemäß An spruch 14 gelöst. The object is achieved with a tubular reactor according to claim 1 and a method for operating a tubular reactor according to claim 14.
Der erfindungsgemäße Rohrreaktor zum Umsetzen von Wasserstoff zu Methan umfasst eine erste Reaktionszone mit einem ersten Katalysatorbett mit einer ersten Dichte und einer Temperatur in einem ersten Temperaturbereich. Weiterhin umfasst der Rohrreaktor eine zweite Reaktionszone mit einem zweiten Kata lysatorbett mit einer zweiten Dichte und einer Temperatur in einem zweiten Temperaturbereich. Weiterhin umfasst der Rohr reaktor eine dritte Reaktionszone mit einem dritten Katalysa torbett mit einer dritten Dichte und einer Temperatur in ei nem dritten Temperaturbereich, wobei die erste Dichte unter-
halb der zweiten Dichte, und die zweite Dichte unterhalb der dritten Dichte liegen. In anderen Worten nimmt die Dichte des Katalysatorbetts in Flussrichtung des Eduktgases, insbesonde re des Wasserstoffs, zu. Die Reaktionszonen sind im Rohrreak tor in Flussrichtung hintereinander angeordnet. The tubular reactor according to the invention for converting hydrogen to methane comprises a first reaction zone with a first catalyst bed having a first density and a temperature in a first temperature range. Furthermore, the tubular reactor comprises a second reaction zone with a second Kata lysatorbett having a second density and a temperature in a second temperature range. Furthermore, the tubular reactor comprises a third reaction zone with a third cata- torbate having a third density and a temperature in a third temperature range, the first density being lower than the first density. half of the second density, and the second density is below the third density. In other words, the density of the catalyst bed increases in the direction of flow of the educt gas, in particular of the hydrogen. The reaction zones are arranged in the tubular reactor in the flow direction one behind the other.
Das erfindungsgemäße Verfahren zum Betreiben des Rohrreaktors zum Umsetzen von Wasserstoff zu Methan umfasst mehrere The inventive method for operating the tubular reactor for converting hydrogen to methane comprises several
Schritte. Zunächst wird ein Rohrreaktor mit wenigstens drei Reaktionszonen bereitgestellt, wobei jede der drei Reaktions zonen ein Katalysatorbett umfasst. Dabei umfasst jede Reakti onszone ein Katalysatorbett mit einer definierten Dichte, wo bei die jeweiligen Dichten des Katalysatorbetts in Flussrich tung des Eduktgases zunehmen. In diesen Rohrreaktor wird ein Eduktgas umfassend Wasserstoff und Kohlenstoffdioxid in eine erste Reaktionszone hinzugeführt. In dieser ersten Reaktions zone liegt eine Temperatur in einem ersten Temperaturbereich vor, bei der ein erster Anteil von Wasserstoff und Kohlen stoffdioxid zu einem ersten Anteil von Methan umgesetzt wird. Anschließend werden sowohl das nicht reagierte Eduktgas, ins besondere der Wasserstoff und das Kohlenstoffdioxid, und das Methan in eine zweite Reaktionszone geführt. In dieser zwei ten Reaktionszone wird bei einer Temperatur in einem zweiten Temperaturbereich aus einem zweiten Wasserstoffanteil und dem Kohlenstoffdioxid ein zweiter Methananteil produziert. Dieser zweite Methananteil ist größer als der erste Methananteil. In anderen Worten wird in der zweiten Reaktionszone eine größere Menge Methan als in der ersten Reaktionszone hergestellt. An schließend werden das Eduktgas, welches nicht umgesetzten Wasserstoff umfasst, und das Methan, welches in der ersten und zweiten Reaktionszone hergestellt wurde, in eine dritte Reaktionszone geführt. In der dritten Reaktionszone wird ein dritter Anteil des Wasserstoffs mit Kohlenstoffdioxid zu ei nem dritten Anteil Methan bei einer Temperatur in einem drit ten Temperaturbereich umgesetzt. Steps. First, a tubular reactor having at least three reaction zones is provided, wherein each of the three reaction zones comprises a catalyst bed. In this case, each reaction zone comprises a catalyst bed having a defined density, where the respective densities of the catalyst bed increase in the flow direction of the educt gas. In this tube reactor, a reactant gas comprising hydrogen and carbon dioxide is added to a first reaction zone. In this first reaction zone is a temperature in a first temperature range, in which a first portion of hydrogen and carbon dioxide is converted to a first portion of methane. Subsequently, both the unreacted educt gas, in particular the hydrogen and the carbon dioxide, and the methane are fed into a second reaction zone. In this second reaction zone, a second portion of methane is produced at a temperature in a second temperature range from a second hydrogen fraction and the carbon dioxide. This second methane content is greater than the first methane content. In other words, a larger amount of methane is produced in the second reaction zone than in the first reaction zone. At closing, the educt gas, which comprises unreacted hydrogen, and the methane, which was prepared in the first and second reaction zone, are fed into a third reaction zone. In the third reaction zone, a third portion of the hydrogen is reacted with carbon dioxide to form a third portion of methane at a temperature in a third temperature range.
Vorteilhaft ermöglicht das Führen des Eduktgases umfassend Wasserstoff durch die unterschiedlichen Reaktionszonen mit
zunehmender Katalysatorbett-Dichte ein flexibles Umsetzen von Wasserstoff und Kohlenstoffdioxid ohne den Einsatz eines gro ßen kostenintensiven WasserstoffSpeichers und ohne den Ein satz einer Temperierung während einer Reaktionsunterbrechung, sodass das flexible Umsetzen des Wasserstoffs bei geringem Energieverbrauch möglich ist. Advantageously, the guiding of the educt gas comprehensively allows hydrogen through the different reaction zones increasing catalyst bed density, a flexible reaction of hydrogen and carbon dioxide without the use of a large cost-intensive hydrogen storage and without the use of a temperature control during a reaction interruption, so that the flexible reaction of hydrogen is possible with low energy consumption.
Die erste Reaktionszone stellt eine Anfahrzone dar. Der erste Temperaturbereich dieser Zone sollte zweckmäßigerweise über einer Mindesttemperatur liegen, die oberhalb der Reaktions zündtemperatur und oberhalb der Kondensationstemperatur von Wasser, insbesondere 100 °C, liegt. Die erste Reaktionszone umfasst das Katalysatorbett mit der geringsten Dichte. The first reaction zone represents a start-up zone. The first temperature range of this zone should expediently be above a minimum temperature which is above the reaction ignition temperature and above the condensation temperature of water, in particular 100 ° C. The first reaction zone comprises the catalyst bed with the lowest density.
Die zweite Reaktionszone weist eine Temperatur in einem zwei ten Temperaturbereich auf. Diese sollte insbesondere unter halb der Temperatur liegen, die die Stabilität des Katalysa tors begrenzt. In dieser Zone erfolgt der größte Umsatz des Wasserstoffs. Das zweite Katalysatorbett weist eine höhere Dichte verglichen mit der ersten Reaktionszone auf. The second reaction zone has a temperature in a second temperature range. In particular, this should be below the temperature that limits the stability of the cata- sector. In this zone, the largest conversion of hydrogen takes place. The second catalyst bed has a higher density compared to the first reaction zone.
In der dritten Reaktionszone wird der Wasserstoff umgesetzt, welcher in den ersten beiden Reaktionszone noch nicht umge setzt wurde. Vorteilhaft ist, wenn die Temperatur in dem dritten Temperaturbereich geringer als in dem zweiten Tempe raturbereich ist. Wie bereits in der ersten Reaktionszone sollte die Temperatur in dieser dritten Reaktionszone zweck mäßigerweise aber oberhalb der Kondensationstemperatur von Wasser und oberhalb der Reaktionsstarttemperatur liegen. Dies wird durch ein besonders dichtes Katalysatorbett erreicht Die dritte Reaktionszone weist ein Katalysatorbett mit einer dritten Dichte auf, wobei diese dritte Dichte höher als die erste und zweite Dichte ist, also die höchste Dichte des Rohrreaktors aufweist. Da der Eduktgasvolumenstrom zu Beginn der jeweiligen Zone schwanken kann und ein Umsatz in der je weiligen Reaktionszone dennoch noch gewährleistet ist, kann dieser Reaktoraufbau mit fluktuierendem Eduktgasstrom betrie ben werden. Typischerweise schwankt der gesamte Volumenstrom
des Eduktgases. Das Verhältnis von Wassersstoff und Kohlen stoffdioxid bleibt dabei aber im Eduktgas konstant, insbeson dere wird ein stöchiometrisches Verhältnis der Eduktgase ein gestellt. Insbesondere die dritte Reaktionszone sorgt dafür, dass ein Restanteil an Wasserstoff umgesetzt wird, der je nach Eingangsvolumenstrom des Eduktgases niedrig oder hoch sein kann. In the third reaction zone, the hydrogen is reacted, which was not yet reacted in the first two reaction zone. It is advantageous if the temperature in the third temperature range is lower than in the second temperature range Tempe. As in the first reaction zone, the temperature in this third reaction zone should, however, advantageously be above the condensation temperature of water and above the reaction start temperature. This is achieved by a particularly dense catalyst bed. The third reaction zone has a catalyst bed with a third density, this third density being higher than the first and second densities, ie having the highest density of the tubular reactor. Since the educt gas volume flow can fluctuate at the beginning of the respective zone and a conversion in the respective reaction zone is still guaranteed, this reactor structure can be operated with fluctuating educt gas stream. Typically, the entire volume flow fluctuates of the educt gas. However, the ratio of hydrogen and carbon dioxide remains constant in the educt gas, in particular a stoichiometric ratio of the educt gases is set. In particular, the third reaction zone ensures that a residual amount of hydrogen is reacted, which may be low or high depending on the input volume flow of educt gas.
Es ist weiterhin möglich, dass mehrere Reaktionszonen dersel ben Art, also insbesondere mit derselben Katalysatorbettdich te, hintereinander angeordnet sind. Diese werden dann von ei ner Zuführvorrichtung für das Kühlmedium voneinander ge trennt . It is also possible that a plurality of reaction zones dersel ben type, ie in particular te with the same Katalysatorbettdich, are arranged one behind the other. These are then separated from each other by a feeding device for the cooling medium.
In einer vorteilhaften Ausgestaltung und Weiterbildung der Erfindung ist zwischen der zweiten und dritten Reaktionszone eine Zuführvorrichtung für ein Kühlfluid angeordnet. In die ser vorteilhaften Ausgestaltung wird direkt in die dritte Reaktionszone ein Kühlfluid gegeben. Alternativ ist denkbar, dass die dritte Reaktionszone mittels einer indirekten Küh lung, insbesondere über einen eingebrachten Wärmetauscher, gekühlt wird. In an advantageous embodiment and development of the invention, a supply device for a cooling fluid is arranged between the second and third reaction zone. In the water advantageous embodiment, a cooling fluid is added directly into the third reaction zone. Alternatively, it is conceivable that the third reaction zone is cooled by means of an indirect cooling, in particular via an introduced heat exchanger.
Vorteilhaft lässt sich eine direkte Kühlung mittels eines Kühlfluids, insbesondere Wasser, dynamisch, also nach Bedarf, zudosieren. Das Umsetzen von Wasserstoff zu Methan ist exo therm, wodurch bei einem hohen Umsatz eine hohe Energiemenge freigesetzt wird, welche aus dem System herausgebracht werden muss, bevor das Gemisch aus Wasserstoff und Methan die dritte Reaktionszone durchströmt. So ist es möglich, bei Zuführen einer geringen Eduktgasmenge in den Rohrreaktor, also bei ei nem hohen relativen Umsatz, insbesondere in der zweiten Reak tionszone, eine große Kühlleistung durch einen hohen Kühl fluidstrom vor der dritten Reaktionszone zu erreichen. Für den Fall dass eine große Eduktgasmenge zu Beginn in den Rohr reaktor geführt wird, da gerade viel Energie im Stromnetz zur Herstellung von Wasserstoff vorhanden ist, kann ein geringe rer Kühlfluidstrom zugeführt werden.
In einer vorteilhaften Ausgestaltung und Weiterbildung der Erfindung liegt die Temperatur in dem dritten Temperaturbe reich unterhalb der Temperatur in dem zweiten Temperaturbe reich. Da die Dichte des Katalysatorbetts in der dritten Reaktionszone aber oberhalb der zweiten Dichte des Katalysa torbetts in der zweiten Reaktionszone liegt, ist gewährleis tet, dass der Anteil an Wasserstoff, der in den ersten beiden Reaktionszone nicht umgesetzt wurde, hier umgesetzt wird. Vorteilhaft trägt dazu sowohl die hohe Katalysatorbett- Dichte, als auch die niedrige Temperatur in der dritten Reak tionszone bei, da es sich um eine exotherme Reaktion handelt. Advantageously, direct cooling by means of a cooling fluid, in particular water, can be added dynamically, ie as required. The conversion of hydrogen to methane is exothermic, thereby releasing at a high conversion a high amount of energy that must be brought out of the system before the mixture of hydrogen and methane flows through the third reaction zone. Thus, it is possible, when supplying a small educt gas in the tube reactor, ie at egg nem high relative conversion, especially in the second reac tion zone, a large cooling capacity by a high cooling fluid flow in front of the third reaction zone to achieve. In the event that a large educt gas is initially fed into the reactor tube, just because much energy in the power grid for the production of hydrogen is present, a small rer cooling fluid flow can be supplied. In an advantageous embodiment and development of the invention, the temperature in the third Temperaturbe is rich below the temperature in the second Temperaturbe rich. Since the density of the catalyst bed in the third reaction zone but above the second density of the cata- torbett in the second reaction zone, it is ensured tet the fact that the proportion of hydrogen, which was not reacted in the first two reaction zone, is reacted here. Advantageously contributes to both the high catalyst bed density, as well as the low temperature in the third reac tion zone, since it is an exothermic reaction.
In einer weiteren vorteilhaften Ausgestaltung und Weiterbil dung der Erfindung liegt die Temperatur in der ersten Reakti onszone in einem ersten Temperaturbereich, der von 100 °C bis 400 °C reicht. Besonders vorteilhaft liegt die Temperatur in dem ersten Temperaturbereich zwischen 150 °C und 250 °C. Vor teilhaft wird die in der ersten Reaktionszone entstehende Wärme in die zweite Reaktionszone mittels der Edukte und Pro dukte transportiert und somit zum Heizen der zweiten Reakti onszone verwendet. Vorteilhaft wird in Abhängigkeit des Volu menstroms des Eduktgases die Eintrittstemperatur in die erste Reaktionszone, in die zweite Reaktionszone und/oder in die dritte Reaktionszone angepasst. Bei geringen Volumenströmen wird die Heizleistung in der ersten Zone niedriger einge stellt, da die Verweilzeit des Eduktgases in der ersten Reak tionszone höher ist und damit anteilig am Eduktgas mehr umge setzt werden kann. Bei hohen Volumenströmen des Eduktgases durch die erste Reaktionszone wird die Eintrittstemperatur, insbesondere in die erste Reaktionszone höher eingestellt, da die Verweilzeit des Eduktgases in der ersten Reaktionszone kürzer ist. Weiterhin ist der anteilige, in anderen Worten relativ zur Eduktgasmenge, Umsatz geringer als bei niedrigen Eduktgasströmen . In a further advantageous embodiment and further development of the invention, the temperature in the first reaction onszone in a first temperature range, ranging from 100 ° C to 400 ° C. Particularly advantageous is the temperature in the first temperature range between 150 ° C and 250 ° C. Advantageously, the heat generated in the first reaction zone is transported into the second reaction zone by means of the educts and products and thus used to heat the second reaction zone. Advantageously, the inlet temperature in the first reaction zone, in the second reaction zone and / or in the third reaction zone is adjusted depending on the volume flow of the educt gas. At low flow rates, the heating power in the first zone is turned down, since the residence time of the educt gas in the first reac tion zone is higher and thus proportionately more reactant gas can be set. At high volumetric flows of the educt gas through the first reaction zone, the inlet temperature, in particular in the first reaction zone is set higher because the residence time of the educt gas in the first reaction zone is shorter. Furthermore, the proportionate, in other words relative to the Eduktgasmenge, sales is lower than at low Eduktgasströmen.
In einer weiteren vorteilhaften Ausgestaltung und Weiterbil dung der Erfindung beträgt die maximale Temperatur des zwei-
ten Temperaturbereichs 600 °C. Besonders vorteilhaft beträgt die Maximaltemperatur des zweiten Temperaturbereichs 500 °C. Vorteilhaft wird diese Maximaltemperatur derart gewählt, dass sowohl die Festigkeit des Reaktormaterials als auch die Sta bilität des Katalysators gewährleistet werden können. In die ser zweiten Reaktionszone wird ein hoher Umsatz von Wasser stoff mit Kohlenstoffdioxid zu Methan erzielt, was zu hohen Wärmemengen führt. Diese Wärme muss abgeführt werden, um die maximale Temperatur nicht zu überschreiten. Das kann mittels einer indirekten Kühlung, insbesondere durch das Einbringen von Kühlmedien durchströmten Bauteilen, insbesondere in Form von Wärmetauschern, erfolgen. Alternativ kann auch ein direk tes Kühlen mittels eines Kühlfluids, insbesondere Wasser, durchgeführt werden, wobei das Wasser in die zweite Reakti onszone eingedüst wird. In a further advantageous embodiment and further development of the invention, the maximum temperature of the two temperature range 600 ° C. Particularly advantageously, the maximum temperature of the second temperature range is 500 ° C. Advantageously, this maximum temperature is chosen such that both the strength of the reactor material and the Sta can be ensured stability of the catalyst. In the water second reaction zone, a high conversion of hydrogen is achieved with carbon dioxide to methane, resulting in high amounts of heat. This heat must be dissipated so as not to exceed the maximum temperature. This can be done by means of indirect cooling, in particular by the introduction of cooling media through flow components, in particular in the form of heat exchangers. Alternatively, a direct cooling by means of a cooling fluid, in particular water, can be carried out, the water being injected into the second reaction zone.
In einer weiteren vorteilhaften Ausgestaltung und Weiterbil dung der Erfindung liegt die Temperatur im dritten Tempera turbereich zwischen 200 °C und 400 °C. Besonders vorteilhaft liegt die Temperatur im dritten Temperaturbereich zwischen 250 °C und 350 °C. Vorteilhaft liegt die Temperatur im drit ten Temperaturbereich unterhalb der Temperatur des zweiten Temperaturbereichs bei hoher Katalysatorbettdichte, wodurch sichergestellt wird, dass der noch nicht umgesetzte Wasser stoff und das Kohlenstoffdioxid in der dritten Reaktionszone zu Methan umgesetzt wird. In a further advantageous embodiment and further development of the invention, the temperature in the third temperature range is between 200 ° C and 400 ° C. Particularly advantageous is the temperature in the third temperature range between 250 ° C and 350 ° C. Advantageously, the temperature in the third temperature range is below the temperature of the second temperature range at high catalyst bed density, thereby ensuring that the unreacted hydrogen material and the carbon dioxide in the third reaction zone is converted to methane.
In einer weiteren vorteilhaften Ausgestaltung und Weiterbil dung der Erfindung umfasst die erste Reaktionszone eine Hei zung. Diese Heizung gewährleistet vorteilhaft, dass die Mini maltemperatur für den Reaktionsstart erreicht wird. Weiterhin gewährleistet die Heizung, dass die Temperatur oberhalb der Kondensationstemperatur des Wassers liegt. Wasser wird als Produkt während des Umsetzens des Wasserstoffs mit Kohlen stoffdioxid zu Methan produziert. Zusätzliches Wasser kann nach Bedarf als Kühlfluid in den Rohrreaktor geführt werden. Das Wasser sollte dampfförmig vorliegen, um die Stabilität des Katalysatorbetts zu erhalten.
In einer vorteilhaften Ausgestaltung und Weiterbildung der Erfindung umfassen das erste, das zweite und/oder das dritte Katalysatorbett eine poröse Metallstruktur zur Aufnahme des Katalysators. Die Metallstruktur ist vorteilhaft elektrisch leitend. Vorteilhaft weisen solche metallischen Grundstruktu ren eine hohe Wärmeleitfähigkeit und eine hohe elektrische Leitfähigkeit auf. Weiterhin ermöglichen diese Strukturen ein hohes Oberflächen zu Volumenverhältnis, was einen effektiven Wärmeeintrag in den Reaktor ermöglicht. Der Wärmeeintrag kann über eine Beheizung der Reaktorwand, welche mit der Metall struktur in direktem Kontakt steht, erfolgen. Dies ermöglicht einen im Vergleich zu herkömmlichen Katalysatorpellets besse ren Wärmeeintrag. Dies ist insbesondere in der ersten Reakti onszone vorteilhaft. Alternativ kann die Metallstruktur mit Elektroden verbunden sein. Durch Anlegen einer Spannung an die Elektroden und den elektrischen Widerstand in der Metall struktur kann ein Temperaturanstieg der Metallstruktur er reicht werden. Das Kontaktieren der Metallstruktur mit Elekt roden ermöglicht einen noch schnelleren Wärmeeintrag im Ver gleich zur Kontaktierung der Metallstruktur mit einer Hei zung. Das schnelle Beheizen der ersten Reaktionszone ist be sonders dann vorteilhaft, wenn der Reaktor bei einer Unter brechung der Eduktzufuhr unterhalb einer Minimaltemperatur abgekühlt ist und daher bei erneutem Einsatz des Reaktors schnell beheizt werden muss, um die Anfahrtstemperatur zu er reichen . In a further advantageous embodiment and further development of the invention, the first reaction zone comprises a Hei tion. This heater advantageously ensures that the mini maltemperatur is reached for the reaction start. Furthermore, the heater ensures that the temperature is above the condensation temperature of the water. Water is produced as a product during the conversion of the hydrogen with carbon dioxide to methane. Additional water can be fed into the tubular reactor as cooling fluid as needed. The water should be in vapor form to maintain the stability of the catalyst bed. In an advantageous embodiment and development of the invention, the first, the second and / or the third catalyst bed comprise a porous metal structure for accommodating the catalyst. The metal structure is advantageously electrically conductive. Advantageously, such metallic Grundstruktu ren a high thermal conductivity and high electrical conductivity. Furthermore, these structures allow a high surface area to volume ratio, allowing for efficient heat input into the reactor. The heat input can via a heating of the reactor wall, which is in direct contact with the metal structure, take place. This allows a better heat input compared to conventional catalyst pellets. This is particularly advantageous in the first reaction zone. Alternatively, the metal structure may be connected to electrodes. By applying a voltage to the electrodes and the electrical resistance in the metal structure, a temperature increase of the metal structure, it can be sufficient. The contacting of the metal structure with Elekt roden allows even faster heat input in the United equal to the contacting of the metal structure with a Hei tion. The rapid heating of the first reaction zone is particularly advantageous if the reactor is cooled at an interruption of the Eduktzufuhr below a minimum temperature and therefore must be heated quickly when re-use of the reactor to reach the starting temperature to it.
In einer vorteilhaften Ausgestaltung und Weiterbildung der Erfindung wird der Katalysator als poröses Schüttgut in den Rohrreaktor eingebracht. In an advantageous embodiment and development of the invention, the catalyst is introduced as a porous bulk material in the tubular reactor.
Eine alternative Ausgestaltung und Weiterbildung der Erfin dung besteht darin, eine Metallstruktur mit Katalysator zu beschichten . An alternative embodiment and development of the inven tion is to coat a metal structure with catalyst.
Besonders vorteilhaft ist die Kombination einer mit Katalysa tor beschichteten Metallstruktur, welche mit Elektroden ver-
bunden ist, um eine direkte und damit auch vorteilhaft schnelle Heizung der Metallstruktur und somit des Katalysa tors zu erreichen. Particularly advantageous is the combination of a metal-coated catalyst structure, which is coated with electrodes. is bound to achieve a direct and therefore advantageous fast heating of the metal structure and thus of the cata- gate.
In einer weiteren vorteilhaften Ausgestaltung und Weiterbil dung der Erfindung stammt der Wasserstoff aus der Elektrolyse von Wasser. Besonders vorteilhaft kann der Rohrreaktor mit den drei Reaktionszonen mit dem fluktuierenden Wasserstoff strom aus der Elektrolyse in Abhängigkeit der zur Verfügung stehenden elektrischen Energie dynamisch betrieben werden. In a further advantageous embodiment and weitererbil tion of the invention, the hydrogen comes from the electrolysis of water. Particularly advantageous, the tubular reactor with the three reaction zones with the fluctuating hydrogen flow from the electrolysis in dependence on the available electrical energy can be operated dynamically.
Weitere Merkmale, Eigenschaften und Vorteile der vorliegenden Erfindung ergeben sich aus der nachfolgenden Beschreibung un ter Bezugnahme auf die beiliegende Figuren. Darin zeigen schematisch : Further features, properties and advantages of the present invention will become apparent from the following description un ter reference to the accompanying figures. In it show schematically:
Figur 1 einen Rohrreaktor mit drei Reaktionszonen; 1 shows a tubular reactor with three reaction zones;
Figur 2 einen Rohrreaktor mit drei Reaktionszonen, Reakti onsumsatz und drei Temperaturbereichen; FIG. 2 shows a tube reactor with three reaction zones, reaction onsumsatz and three temperature ranges.
Figur 3 eine Metallstruktur eines Katalysatorbetts des FIG. 3 shows a metal structure of a catalyst bed of the
Rohrreaktors ; Tubular reactor;
Figur 4 ein Verfahrensschema der Methanisierung des Wasser stoffs mittels des Rohrreaktors. FIG. 4 shows a process diagram of the methanation of the hydrogen by means of the tubular reactor.
Figur 1 zeigt einen Rohrreaktor 1 mit einer ersten Reaktions zone 11, einer zweiten Reaktionszone 12 und einer dritten Reaktionszone 13. Die erste Reaktionszone 11 umfasst ein ers tes Katalysatorbett 14 mit einer ersten Dichte. Die zweite Reaktionszone 12 umfasst ein zweites Katalysatorbett 15 mit einer zweiten Dichte. Die dritte Reaktionszone 13 umfasst ein drittes Katalysatorbett 16 mit einer dritten Dichte. Die Reaktionszonen sind im Rohrreaktor 1 hintereinander hinsicht lich der Strömungsrichtung des Eduktgases umfassend Wasser stoff 2 und Kohlenstoffdioxid 3 angeordnet. Zwischen der zweiten Reaktionszone 12 und der dritten Reaktionszone 13 be-
findet sich eine Zuführvorrichtung 9 für ein Kühlfluid. Am Ende des Rohrreaktors 1 verlassen Methan 4 und Wasser 5 als Produktstrom den Rohrreaktor 1. FIG. 1 shows a tube reactor 1 having a first reaction zone 11, a second reaction zone 12 and a third reaction zone 13. The first reaction zone 11 comprises a first catalyst bed 14 having a first density. The second reaction zone 12 comprises a second catalyst bed 15 having a second density. The third reaction zone 13 comprises a third catalyst bed 16 having a third density. The reaction zones are in the tubular reactor 1 in a row Lich respect of the flow direction of the educt gas including hydrogen material 2 and carbon dioxide 3 is arranged. Between the second reaction zone 12 and the third reaction zone 13 there is a supply device 9 for a cooling fluid. At the end of the tubular reactor 1, methane 4 and water 5 leave the tubular reactor 1 as product stream.
Die Dichte des Katalysatorbetts in der jeweiligen Reaktions zone nimmt in Richtung der Strömung des Eduktgases zu. D. h., die erste Reaktionszone weist das Katalysatorbett mit der niedrigsten Dichte auf, die dritte Reaktionszone das Kataly satorbett mit der höchsten Dichte. The density of the catalyst bed in the respective reaction zone increases in the direction of the flow of educt gas. That is, the first reaction zone has the catalyst bed with the lowest density, the third reaction zone, the catalyst bed with the highest density.
Der Katalysator ist insbesondere vorteilhaft in einer Metall struktur 30 angeordnet. Diese Metallstruktur wird in Figur 3 näher erläutert. The catalyst is particularly advantageously arranged in a metal structure 30. This metal structure is explained in more detail in FIG.
Figur 2 zeigt ebenfalls den Rohrreaktor 1 mit der ersten Reaktionszone 11, der zweiten Reaktionszone 12 und der drit ten Reaktionszone 13. Weiterhin zeigt Figur 2 in Längsrich tung des Rohrreaktors 1, also in Strömungsrichtung des Edukt gases, eine y-Achse 8, welche die Länge des Rohrreaktors 1 beschreibt. Figur 2 zeigt quer zur Strömungsrichtung der Eduktgase eine x-Achse 7, welche sowohl den Reaktionsumsatz als auch die Temperaturbereiche beschreibt. FIG. 2 also shows the tubular reactor 1 with the first reaction zone 11, the second reaction zone 12 and the third reaction zone 13. Furthermore, FIG. 2 shows a y-axis 8 in the longitudinal direction of the tubular reactor 1, ie in the flow direction of the educt gas Length of the tubular reactor 1 describes. FIG. 2 shows, transversely to the flow direction of the educt gases, an x-axis 7 which describes both the reaction conversion and the temperature ranges.
Die Methanisierungs-Reaktion kann mit Gleichung 1 beschrieben werden . The methanation reaction can be described by Equation 1.
4 H2+C02 CH4+ 2 H20 Gleichung 1 4 H 2 + C0 2 CH 4 + 2 H 2 0 Equation 1
Aus Figur 2 wird deutlich, dass die erste Reaktionszone 11 mit dem ersten Katalysatorbett 14 mit einer ersten Dichte ei ne Anfahrzone für die Methanisierungs-Reaktion nach Gleichung 1 darstellt. In dieser ersten Reaktionszone herrscht eine erste Temperatur in einem ersten Temperaturbereich zwischen 100 °C und 400 °C, besonders bevorzugt zwischen 150 °C und 250 °C. Dieser Temperaturbereich ist in Figur 2 als Band dar gestellt. Die Temperatur muss zweckmäßigerweise die Reakti onsstart-Temperatur überschreiten. Außerdem sollte die Tempe ratur oberhalb von 100 °C liegen, damit das während der Reak-
tion entstehende Wasser dampfförmig vorliegt. Weiterhin zeigt Figur 2 anhand des Umsatzes, dass die Reaktion in dieser ers ten Reaktionszone startet. Die Dichte des Katalysatorbetts 14 in dieser ersten Reaktionszone 11 ist gering, um ausgeprägte Temperaturspitzen aufgrund der exothermen Reaktion zu vermei den. Auf der anderen Seite muss die Dichte des Katalysator betts 14 ausreichend hoch sein, um so viel Wärme zu produzie ren, dass die Beheizung der folgenden zweiten Reaktionszone 12 gewährleistet werden kann. Die in der ersten Reaktionszone 11 entstandene Wärmemenge wird verwendet, um die zweite Reak tionszone 12 mittels Konvektion zu beheizen. From Figure 2 it is clear that the first reaction zone 11 with the first catalyst bed 14 with a first density ei ne start-up zone for the methanation reaction of Equation 1 represents. In this first reaction zone, a first temperature prevails in a first temperature range between 100 ° C and 400 ° C, more preferably between 150 ° C and 250 ° C. This temperature range is set in Figure 2 as a tape is. The temperature must suitably exceed the reaction onset temperature. In addition, the temperature should be above 100 ° C, so that during the reaction tion resulting vapor water. Furthermore, FIG. 2 shows on the basis of the conversion that the reaction starts in this first reaction zone. The density of the catalyst bed 14 in this first reaction zone 11 is low in order to avoid pronounced temperature peaks due to the exothermic reaction. On the other hand, the density of the catalyst bed 14 must be sufficiently high to produce so much heat that the heating of the following second reaction zone 12 can be ensured. The amount of heat generated in the first reaction zone 11 is used to heat the second reaction zone 12 by convection.
Figur 2 zeigt weiterhin, dass die zweite Reaktionszone 12 ein höheres Temperaturniveau als die erste Reaktionszone 11 auf weist. Die Temperatur in der zweiten Reaktionszone 12 liegt typischerweise maximal bei 600 °C, insbesondere maximal bei 500 °C. Diese maximale Temperatur darf nicht überschritten werden, damit die Festigkeit des Reaktormaterials und die Stabilität des Katalysators bestehen bleibt. Figur 2 zeigt auch, dass in dieser zweiten Reaktionszone 12 der größte Reaktionsumsatz stattfindet. Aufgrund der höheren Katalysa tordichte ist dieser hohe Umsatz möglich. Allerdings wird der Umsatz in dieser zweiten Reaktionszone 12 durch die Tempera tur begrenzt, da die maximale Temperatur trotz der exothermen Reaktion nicht überschritten werden darf. FIG. 2 further shows that the second reaction zone 12 has a higher temperature level than the first reaction zone 11. The temperature in the second reaction zone 12 is typically at most 600 ° C, especially at most 500 ° C. This maximum temperature must not be exceeded in order to maintain the strength of the reactor material and the stability of the catalyst. FIG. 2 also shows that the greatest reaction conversion takes place in this second reaction zone 12. Due to the higher catalyst tordichte this high turnover is possible. However, the conversion in this second reaction zone 12 is limited by the temperature, since the maximum temperature must not be exceeded despite the exothermic reaction.
Figur 2 zeigt weiterhin, dass die Temperatur in der dritten Reaktionszone 13 unterhalb der Temperatur in der zweiten Reaktionszone 12 liegt. Die Temperatur in der dritten Reakti onszone 13 liegt typischerweise in einem Bereich von 200 °C bis 400 °C, insbesondere in einem Bereich von 250 °C bis 350 °C. Um diese Temperaturunterschiede von der zweiten Reakti onszone 12 in die dritte Reaktionszone 13 zu erreichen, be darf es einer Kühlung entweder zwischen den beiden Reaktions zonen, oder innerhalb der dritten Reaktionszone 13. FIG. 2 further shows that the temperature in the third reaction zone 13 is below the temperature in the second reaction zone 12. The temperature in the third reaction zone 13 is typically in a range of 200 ° C to 400 ° C, more preferably in a range of 250 ° C to 350 ° C. In order to achieve these temperature differences from the second reaction zone 12 into the third reaction zone 13, it may be necessary for cooling to take place either between the two reaction zones or within the third reaction zone 13.
In diesem Ausführungsbeispiel wird mittels der Zuführvorrich tung 9 als Kühlmittel Wasser 5 hinzugegeben. Es handelt sich
in diesem Beispiel also um eine direkte Kühlung. Alternativ, aber hier nicht gezeigt, ist es möglich, dass die dritte Reaktionszone 13 mittels Wärmetauscherstrukturen indirekt ge kühlt wird. Wasser als Kühlmittel ist insbesondere bei der direkten Kühlung vorteilhaft, da es einerseits, insbesondere aufgrund der Verdampfungsenthalpie, eine ausreichend große Kühlwirkung erzielen kann und andererseits bereits als Pro dukt im Rohrreaktor 1 vorhanden ist, sodass keine zusätzli chen Komponenten in das System geführt werden müssen. Die dritte Katalysatordichte 16 sollte höher sein als die ersten beiden Katalysatorbettdichten, um eine ausreichende Reakti onsgeschwindigkeit bei geringen Temperaturen und geringen Eduktkonzentrationen zu erreichen. Wie auch in der ersten Reaktionszone 11 wird der Temperaturbereich nach unten durch die Reaktionsstarttemperatur und die Kondensationstemperatur des Wassers 5 begrenzt. Figur 2 verdeutlicht, dass nach der dritten Reaktionszone 13 nahezu Vollumsatz erreicht wird. In this embodiment, 9 is added by means of Zuführvorrich device as coolant water 5. It is about in this example, therefore, a direct cooling. Alternatively, but not shown here, it is possible that the third reaction zone 13 is ge indirectly cooled by means of heat exchanger structures. Water as a coolant is particularly advantageous in the direct cooling, since it on the one hand, in particular due to the enthalpy of vaporization, can achieve a sufficiently large cooling effect and on the other hand already as Pro product in the tubular reactor 1 is present, so that no addi tional components must be performed in the system. The third catalyst density 16 should be higher than the first two catalyst bed densities in order to achieve a sufficient reaction rate at low temperatures and low educt concentrations. As in the first reaction zone 11, the temperature range is limited downwards by the reaction start temperature and the condensation temperature of the water 5. Figure 2 illustrates that after the third reaction zone 13 almost full conversion is achieved.
Die drei Reaktionszonen 11, 12, 13 ermöglichen durch die un terschiedlichen Dichten der drei Katalysatorbetten 14, 15 undThe three reaction zones 11, 12, 13 allow by the un ferent densities of the three catalyst beds 14, 15 and
16 den Betrieb für unterschiedliche Wasserstoff-Eingangskon- zentrationen . Aufgrund der für jede Reaktionszone festgeleg ten Temperaturbänder ist es möglich, den Reaktor dynamisch zu betreiben. Insbesondere das Kühlfluid Wasser 5 kann über die Zuführvorrichtung 9 flexibel in unterschiedlichen Mengen hin zu geführt werden und so die dritte Reaktionszone entspre chend des Umsatzes und der Temperatur der ersten beiden Reak tionszonen derart temperieren, dass das Eduktgas Wasserstoff 2 mit Kohlenstoffdioxid 3 nahezu vollständig zu Methan umge setzt wird. Ein großer WasserstoffSpeicher zum Speichern des Wasserstoffs in Zeiten von hoher Wasserstoffproduktion ist vorteilhaft nicht nötig. 16 operation for different hydrogen input concentrations. Due to the festgeleg for each reaction zone th temperature bands, it is possible to operate the reactor dynamically. In particular, the cooling fluid water 5 can be guided flexibly in different amounts through the supply device 9 and so the third reaction zone accordingly the conversion and the temperature of the first two reac tion zones temperature such that the educt gas hydrogen 2 with carbon dioxide 3 almost completely to methane vice versa. A large hydrogen storage for storing the hydrogen in times of high hydrogen production is advantageously not necessary.
Sowohl Figur 1 als auch Figur 2 zeigen beispielhaft, dass die zweite Reaktionszone die größte Länge aufweist. In dieser zweiten Reaktionszone wird der größte Umsatz erreicht. Sowohl in Figur 1 als auch in Figur 2 sind drei Reaktionszonen dar gestellt. Es ist aber insbesondere möglich, dass mehrere
zweite Reaktionszonen 12 hintereinander angeordnet sind. Dann kann auch die Länge der zweiten Reaktionszone 12 geringer sein. In diesem Fall ist es zweckmäßig, dass zwischen diesen zweiten Reaktionszonen 12 Zuführvorrichtungen für das Kühl mittel Wasser vorhanden sind, um eine Temperierung unterhalb der maximalen Temperatur für jede der zweiten Reaktionszonen 12 zu erreichen. Both FIG. 1 and FIG. 2 show by way of example that the second reaction zone has the greatest length. In this second reaction zone, the highest conversion is achieved. Both in Figure 1 and in Figure 2, three reaction zones are provided. But it is especially possible that several second reaction zones 12 are arranged one behind the other. Then, the length of the second reaction zone 12 may be smaller. In this case, it is expedient that water supply means for the coolant are present between these second reaction zones 12 in order to achieve a temperature below the maximum temperature for each of the second reaction zones 12.
Figur 3 zeigt eine Metallstruktur 30, auf welche der Kataly sator aufgebracht werden kann. Diese Metallstruktur 30 weist insbesondere eine Diamanteinheitszelle auf, welche Zwischen räume aufweist. In diesem Ausführungsbeispiel wurde die Me tallstruktur mit Katalysator beschichtet, sodass eine Kataly satorschicht 32 auf dem Metallträger 33 entsteht. Vorteilhaft weist diese metallische Grundstruktur eine hohe Wärmeleitfä higkeit und eine hohe elektrische Leitfähigkeit auf. Zudem weist diese Struktur ein hohes Oberflächen- zu Volumenver hältnis auf, was einen effektiven Wärmeeintrag in den Reaktor 1 ermöglicht. FIG. 3 shows a metal structure 30 on which the cata- capacitor can be applied. This metal structure 30 has in particular a diamond unit cell, which has spaces between. In this embodiment, the Me tallstruktur was coated with catalyst, so that a cata- satorschicht 32 is formed on the metal substrate 33. Advantageously, this metallic basic structure has a high heat conductivity and a high electrical conductivity. In addition, this structure has a high surface to Volumenver ratio, which allows effective heat input into the reactor 1.
Der Wärmeeintrag in den Rohrreaktor 1 kann über die Beheizung einer Reaktorwand des Rohrreaktors 1 erfolgen. Dann ist es zweckmäßig wenn die Reaktorwand des Rohrreaktors 1 die Me tallstruktur 30 direkt kontaktiert. The heat input into the tubular reactor 1 can take place via the heating of a reactor wall of the tubular reactor 1. Then it is useful if the reactor wall of the tube reactor 1, the tall tall structure 30 Me directly contacted.
Alternativ ist es besonders bevorzugt, dass die Metallstruk tur 30 von Elektroden kontaktiert wird und bei Anlegen einer Spannung aufgrund des elektrischen Widerstands erhitzt wird. Dies ermöglicht eine sehr effiziente und schnelle Erwärmung der Metallstruktur 30, was den Wärmeeintrag in den Rohrreak tor 1 energieeffizient gestaltet. Vorteilhaft kann weiterhin bei der Unterbrechung der Eduktzufuhr der abgekühlte Rohrre aktor 1 schnell elektrisch beheizt werden und somit schnell wieder die Betriebstemperatur der ersten Reaktionszone 11 er zeugt werden. Diese beschichtete Metallstruktur 30 liegt be sonders vorteilhaft in der ersten Reaktionszone 11 vor. Es ist aber auch möglich, dass die Metallstruktur 30 auch in der
zweiten Reaktionszone 12 und in der dritten Reaktionszone 13 angeordnet ist. Alternatively, it is particularly preferred that the metal structure 30 is contacted by electrodes and heated when a voltage is applied due to the electrical resistance. This allows a very efficient and rapid heating of the metal structure 30, which makes the heat input into the Rohrreak gate 1 energy-efficient. Advantageously, in the interruption of Eduktzufuhr the cooled Rohrre actuator 1 can be heated electrically quickly and thus quickly return the operating temperature of the first reaction zone 11 he testifies. This coated metal structure 30 is particularly advantageous in the first reaction zone 11 before. But it is also possible that the metal structure 30 in the second reaction zone 12 and in the third reaction zone 13 is arranged.
Figur 4 zeigt schematisch die Verschaltung des Rohrreaktors 1, also der Methanisierung 10, mit der Elektrolyse 40, einer Aufbereitungsanlage 50 und dem Erdgasnetz 60. FIG. 4 schematically shows the interconnection of the tubular reactor 1, ie the methanation 10, with the electrolysis 40, a treatment plant 50 and the natural gas network 60.
Wasser 5 wird mittels elektrischer Energie, insbesondere wenn Überschussenergie bei viel Wind und Sonne vorhanden ist, zu Wasserstoff 2 und Sauerstoff 17 gespalten. Der Wasserstoff 2 wird in den Rohrreaktor 1 zu Methanisierung 10 geführt. Au ßerdem wird Kohlenstoffdioxid 3 zugeführt. Während der Metha nisierung 10 wird aus dem Kohlenstoffdioxid 3 und dem Wasser stoff Methan 4 und Wasser 5 hergestellt. Das Methan 4 wird anschließend in eine Methanaufbereitungsanlage 50 geführt, wo es so aufgearbeitet wird, dass es in das Erdgasnetz 60 gelei tet werden kann. Alternativ zu dem Führen in die Erdgaslei tung ist es denkbar, dass das Methan 4 für Folgereaktionen verwendet wird. Eine weitere Alternative ist das Einsetzen des Methans als Treibstoff, insbesondere für Fortbewegungs mittel, insbesondere Fahrzeuge.
Water 5 is split into hydrogen 2 and oxygen 17 by means of electrical energy, in particular if excess energy is present in a large amount of wind and sun. The hydrogen 2 is fed into the tubular reactor 1 to methanation 10. In addition, carbon dioxide 3 is supplied. During the metha nization 10 is made of the carbon dioxide 3 and the water methane 4 and water 5 produced. The methane 4 is then fed into a methane treatment plant 50, where it is worked up so that it can be Gelei tet in the natural gas network 60. As an alternative to driving into the natural gas line, it is conceivable that the methane 4 is used for subsequent reactions. Another alternative is the onset of methane as a fuel, especially for locomotion means, especially vehicles.
Claims
1. Rohrreaktor (1) zum Umsetzen von Wasserstoff (2) zu Methan (4) umfassend 1. tube reactor (1) for converting hydrogen (2) to methane (4) comprising
- eine erste Reaktionszone (11) mit einem erstes Katalysator bett (14) mit einer ersten Dichte mit einer Temperatur in einem ersten Temperaturbereich (21), a first reaction zone (11) having a first catalyst bed (14) having a first density at a temperature in a first temperature range (21),
- eine zweite Reaktionszone (12) mit einem zweiten Katalysa torbett (15) mit einer zweiten Dichte mit einer Temperatur in einem zweiten Temperaturbereich (22), a second reaction zone (12) having a second catalyst bed (15) with a second density having a temperature in a second temperature range (22),
- eine dritte Reaktionszone (13) mit einem dritten Katalysa torbett (16) mit einer dritten Dichte mit einer Temperatur in einem dritten Temperaturbereich (23) , wobei die erste Dichte unterhalb der zweiten Dichte und die zweite Dichte unterhalb der dritten Dichte liegen. - A third reaction zone (13) with a third cata torbett (16) having a third density with a temperature in a third temperature range (23), wherein the first density below the second density and the second density below the third density.
2. Rohrreaktor (1) nach Anspruch 1, wobei zwischen der zweiten Reaktionszone (12) und der dritten Reaktionszone (13) eine Zuführvorrichtung (9) für ein Kühlfluid angeordnet ist 2. tube reactor (1) according to claim 1, wherein between the second reaction zone (12) and the third reaction zone (13) a supply device (9) is arranged for a cooling fluid
3. Rohrreaktor (1) nach Anspruch 1 oder 2, wobei der dritte Temperaturbereich (23) unterhalb des zweiten Temperaturbe reichs (22) liegt. 3. tubular reactor (1) according to claim 1 or 2, wherein the third temperature range (23) below the second Temperaturbe range (22).
4. Rohrreaktor (1) nach einem der vorhergehenden Ansprüche, wobei der zweite Temperaturbereich (22) oberhalb des ersten Temperaturbereichs (21) liegt. 4. tubular reactor (1) according to any one of the preceding claims, wherein the second temperature range (22) above the first temperature range (21).
5. Rohrreaktor (1) nach einem der vorhergehenden Ansprüche, wobei der erste Temperaturbereich (21) von 100 °C bis 400 °C reicht . 5. tubular reactor (1) according to any one of the preceding claims, wherein the first temperature range (21) of 100 ° C to 400 ° C.
6. Rohrreaktor (1) nach einem der vorhergehenden Ansprüche, wobei der zweite Temperaturbereich (22) maximal bis zu 600 °C reicht.
6. tubular reactor (1) according to one of the preceding claims, wherein the second temperature range (22) reaches a maximum of up to 600 ° C.
7. Rohrreaktor (1) nach einem der vorhergehenden Ansprüche, wobei der dritte Temperaturbereich (23) von 200 °C bis 400 °C reicht . 7. tubular reactor (1) according to any one of the preceding claims, wherein the third temperature range (23) of 200 ° C to 400 ° C.
8. Rohrreaktor (1) nach einem der vorhergehenden Ansprüche, wobei die erste Reaktionszone (11) eine Heizung umfasst. 8. tubular reactor (1) according to any one of the preceding claims, wherein the first reaction zone (11) comprises a heater.
9. Rohrreaktor (1) nach einem der vorhergehenden Ansprüche, wobei die erste (11), die zweite (12) und/oder die dritte Reaktionszone (13) eine poröse Metallstruktur (30) zum Auf nehmen des Katalysators umfassen. 9. tubular reactor (1) according to any one of the preceding claims, wherein the first (11), the second (12) and / or the third reaction zone (13) comprise a porous metal structure (30) to take on the catalyst.
10. Rohrreaktor (1) nach Anspruch 9, wobei der Katalysator als eine Schüttung in die Poren der Metallstruktur (30) ein gebracht ist. 10. tubular reactor (1) according to claim 9, wherein the catalyst is brought as a bed in the pores of the metal structure (30).
11. Rohrreaktor (1) nach Anspruch 9, wobei der Katalysator als eine Schicht (32) auf der porösen Metallstruktur (30) aufgebracht ist. 11. tubular reactor (1) according to claim 9, wherein the catalyst is applied as a layer (32) on the porous metal structure (30).
12. Rohrreaktor (1) nach einem der Ansprüche 9 bis 11, wobei die poröse Metallstruktur (30) in direktem Kontakt mit der Heizung steht. 12. tubular reactor (1) according to any one of claims 9 to 11, wherein the porous metal structure (30) is in direct contact with the heater.
13. Rohrreaktor (1) nach einem der Ansprüche 9 bis 11, wobei die poröse Metallstruktur (30) zum direkten Aufheizen der Me tallstruktur (30) mit einem Elektrodenpaar verbunden ist. 13. tubular reactor (1) according to any one of claims 9 to 11, wherein the porous metal structure (30) for direct heating of Me tallstruktur (30) is connected to a pair of electrodes.
14. Verfahren zum Betreiben eines Rohrreaktors (1) mit fol genden Schritten: 14. A method for operating a tubular reactor (1) with fol lowing steps:
- Bereitstellen eines Rohrreaktors (1) mit einer ersten Reak tionszone (11) mit einem erstes Katalysatorbett (14) mit einer ersten Dichte mit einer Temperatur in einem ersten Temperaturbereich (21), mit einer zweiten Reaktionszone (12) mit einem zweiten Katalysatorbett (15) mit einer zwei ten Dichte mit einer Temperatur in einem zweiten Tempera turbereich (22), mit einer dritten Reaktionszone (13) mit einem dritten Katalysatorbett (16) mit einer dritten Dichte
mit einer Temperatur in einem dritten Temperaturbereich (23) , wobei die erste Dichte unterhalb der zweiten Dichte und die zweite Dichte unterhalb der dritten Dichte liegt,- Providing a tubular reactor (1) with a first reac tion zone (11) with a first catalyst bed (14) having a first density at a temperature in a first temperature range (21), with a second reaction zone (12) with a second catalyst bed (15 ) having a second density at a temperature in a second temperature range (22), a third reaction zone (13) having a third catalyst bed (16) having a third density having a temperature in a third temperature range (23), wherein the first density is below the second density and the second density is below the third density,
- Zuführen eines Eduktgases umfassend Wasserstoff (2) in die erste Reaktionszone (11), Feeding a starting gas comprising hydrogen (2) into the first reaction zone (11),
- Umsetzen eines ersten Anteils des Wasserstoffs (2) zu einem ersten Anteil Methan (4), Reacting a first portion of the hydrogen (2) to a first portion of methane (4),
- Führen des nicht reagierten Wasserstoffs (2) und des ersten Anteils Methan (4) in die zweite Reaktionszone (12), Passing the unreacted hydrogen (2) and the first portion of methane (4) into the second reaction zone (12),
- Umsetzen eines zweiten Anteils des Wasserstoffs (2) zu ei nem zweiten Anteil Methan (4) in der zweiten Reaktionszone - reacting a second portion of the hydrogen (2) to a second portion of methane (4) in the second reaction zone
(12), wobei der zweite Anteil Methan (4) größer als der erste Anteil Methan (4) ist, (12), wherein the second portion of methane (4) is greater than the first portion of methane (4),
- Führen des nicht reagierten Wasserstoffs (2), des ersten und des zweiten Anteils an Methan (4) aus der zweiten in die dritte Reaktionszone (13), Leading the unreacted hydrogen (2), the first and the second portion of methane (4) from the second to the third reaction zone (13),
- Umsetzen eines dritten Anteils Wasserstoff (2) zu einem dritten Anteil Methan (4) in der dritten Reaktionszone - Reacting a third portion of hydrogen (2) to a third portion of methane (4) in the third reaction zone
(13) . (13).
15. Verfahren nach Anspruch 14, wobei der Wasserstoff (2) mittels Elektrolyse (40) von Wasser (5) hergestellt wird.
15. The method of claim 14, wherein the hydrogen (2) by means of electrolysis (40) of water (5) is produced.
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