Method and apparatus for the production of synthesis gas

Abstract

A process for producing synthesis gas comprising the following steps: splitting a hydrocarbon fluid, in particular a first gas with the composition CnHm, into carbon and hydrogen in a reaction chamber of a hydrocarbon converter with the addition of heat, wherein the carbon and hydrogen have a temperature of at least 800°C after the splitting; directing the carbon and hydrogen obtained from the splitting into a reaction chamber of a CO2 converter; mixing CO2 from an external source with the carbon and hydrogen in the CO2 converter; converting the CO2 and the carbon obtained by the splitting into CO at a temperature of 800 to 1700°C, so that a first synthesis gas mixture is formed; mixing the first synthesis gas mixture with additional hydrogen, so that a second synthesis gas mixture is formed, which has a higher hydrogen content than the first synthesis gas mixture;wherein the additional hydrogen is produced by the following steps: passing a second gas with the composition CnHmin into a reaction chamber of a solid-state converter containing a solid bed of carbon-containing granules, in particular a moving bed guided through the reaction chamber, wherein the solid bed has at least locally a temperature of 800 to 1700°C, wherein the energy required to generate the temperature of 800 to 1700°C of the solid bed is introduced into the reaction chamber of the solid-state converter via a hot hydrogen gas heated by means of an electric arc of a plasma torch; splitting the second gas with the composition CnHm into carbon and hydrogen, which forms the additional hydrogen; separating the carbon obtained by the splitting and the additional hydrogen by depositing the carbon onto the carbon-containing granules.

Description

[0001] The present application relates to a method and a device for producing synthesis gas with a variable H2 / CO ratio.

[0002] Large quantities of carbon dioxide, a greenhouse gas, are produced as emissions from energy generation and other industrial processes. Significant efforts are being made to prevent carbon dioxide emissions. Another approach is to bind carbon dioxide in useful substances. For example, EP 2 729 405 B1 discloses a process that uses methane and carbon dioxide as feedstocks to produce synthesis gas. However, a disadvantage of this process is that the composition of the synthesis gas, and in particular the H₂ / CO ratio, is difficult to control.

[0003] The present invention therefore aims to provide a method and a device for producing synthesis gas with a variable H2 / CO ratio.

[0004] This problem is solved by a process for the production of synthesis gas, which comprises the following steps: splitting a hydrocarbon fluid, in particular a first gas with the composition C n H m, to carbon and hydrogen in a reaction chamber of a hydrocarbon converter with the addition of heat, wherein the carbon and hydrogen have a temperature of at least 800°C after the decomposition; passing the carbon and hydrogen obtained from the decomposition into a reaction chamber of a CO2 converter; mixing CO2 from an external source with the carbon and hydrogen in the CO2 converter; converting the CO2 and the carbon obtained by the decomposition into CO at a temperature of 800 to 1700°C, so that a first synthesis gas mixture is formed; mixing the first synthesis gas mixture with additional hydrogen, so that a second synthesis gas mixture is formed which has a higher hydrogen content than the first synthesis gas mixture. The additional hydrogen is generated by the following steps: passing a second gas with the composition C n H minto a reaction chamber of a solid-state converter containing a solid bed of carbon-containing granules, in particular a moving bed guided through the reaction chamber, wherein the solid bed has a temperature of at least locally 800 to 1700°C; splitting of the second gas with composition C n H m Carbon and hydrogen, which forms the additional hydrogen, are broken down; the carbon obtained through this process and the additional hydrogen are separated by depositing the carbon onto the carbon-containing granules. The additional hydrogen is then added to the first synthesis gas mixture, allowing the H₂ / CO ratio of the resulting second synthesis gas mixture to be variably controlled and adapted to subsequent processes. If not all of the available hydrogen is needed to control the H₂ / CO ratio, it can be sold.

[0005] Preferably, heat is supplied to split the hydrocarbon fluid (the first gas with composition C). n H m The splitting process in the hydrocarbon converter is primarily carried out via a plasma. This is a particularly direct and therefore efficient form of energy input and enables the continuous splitting of a stream of hydrocarbons. The splitting is preferably performed in a Kvaerner reactor.

[0006] In the process described above, the hydrocarbon fluid is split and the CO2 and carbon are converted into CO without a catalyst. This avoids costs, as catalysts are expensive. Furthermore, it enables a trouble-free process with a long operating time, since no catalysts need to be replaced or cleaned.

[0007] The energy required to reach the temperature of 800 to 1700°C for CO2 conversion in the CO2 converter comes essentially entirely from the heat provided for splitting the hydrocarbon fluid. "Essentially" here means that at least 80%, and in particular at least 90%, of the required heat originates from the splitting step. This ensures optimal utilization of the input energy.

[0008] In the process described above, CO2 is supplied from an external source, either as exhaust gas from a power plant or as blast furnace gas, which is generated by the reduction of a metal ore in a blast furnace shaft and contains CO2. Since carbon adheres to the granules in the solid converter, these granules can be used for metal production in a blast furnace shaft after removal from the converter. Therefore, a particular advantage arises when the process is used near a steelworks and utilizes CO2 generated in the blast furnace shaft through the reduction of metal oxides or in combustion plants. If not all of the available hydrogen is required to control the H2 / CO ratio, it can be used as a reducing agent in the blast furnace shaft. Similarly, unused CO from the initial synthesis gas mixture can be used as a reducing agent in the blast furnace shaft.

[0009] Carbon-containing granules are understood here to be a material that advantageously consists of solid grains containing at least 50 wt.%, in particular at least 80 wt.%, and more preferably at least 90 wt.% carbon. The carbon-containing granules preferably have a particle size (equivalent diameter) of 0.5 to 100 mm, in particular 1 to 80 mm, which can be determined by sieving with a specific mesh size. The carbon-containing granules may be spherical. A variety of different carbon-containing granules can be used in the process described here, for example, coal, coke, coke dust, and / or mixtures thereof. Coke dust generally has a particle size of less than 20 mm. Furthermore, the carbon-containing granules may contain 0 to 15 wt.%, based on the total mass of the granules, preferably 0 to 5 wt.%, of metal, metal oxide, and / or ceramic.Particular consideration is being given to using granules containing coke dust and / or low-grade coke, i.e., coke not directly suitable for the smelting process; coke oven coke based on lignite or bituminous coal; and / or coke derived from biomass. The carbon-containing granules are upgraded for use in a blast furnace shaft using the process and equipment described here.

[0010] The energy required to generate the temperature of 800 to 1700°C for the solid bed of carbon-containing granules can be produced by thermal energy within the reaction chamber of the solid-state converter. This can be achieved through partial oxidation / combustion of the carbon-containing granules using injected air. Alternatively, the required energy can be introduced into the reaction chamber of the solid-state converter via a hot gas.

[0011] One possible design involves generating the thermal energy required in the solid-state converter through the oxidation or partial oxidation of a fuel containing hydrocarbons and / or hydrogen. Air, oxygen-enriched air, or pure oxygen, for example, can be used as the oxidizing agent. This oxidation can be carried out outside the reaction chamber, with the resulting hot gas then being introduced into the reaction chamber and passed over the carbon-containing solid, transferring thermal energy to the carbon-containing granules and / or the gases to be converted. Alternatively, the oxidizing agent can be introduced into the reaction chamber, mixed with the existing fuel, and reacted there.If the carbon-containing granules consist of low-grade coke ovens based on lignite, hard coal, or biomass, from which pyrolysis gases can escape at elevated temperatures, a pyrolysis zone is provided. To generate energy, oxygen or air is then introduced downstream of the pyrolysis zone to at least partially oxidize the pyrolysis gases. Another possible design involves generating the thermal energy required in the solid-state converter by an electric heater, in which a gas (especially hydrogen) is heated by an electric heating device (especially a plasma burner) and introduced into the reaction chamber. The possible design with electric heating is described below with reference to [reference missing]. Fig. 2 described.

[0012] In the process described here, the solid bed of carbon-containing granules is preferably conveyed continuously as a moving bed, particularly with the aid of gravity. The carbon-containing granules, at ambient temperature, are introduced into the reaction chamber of the solid-state converter in a first conveying direction (preferably from top to bottom in the direction of gravity). The second gas (e.g., methane or natural gas) is conveyed through the solid bed of carbon-containing granules in a second conveying direction, opposite to the first, and is split into carbon and "additional" hydrogen by the high temperature of the carbon-containing granules. The additional hydrogen obtained from the splitting of the second gas is cooled by contact with the carbon-containing granules.The reaction chamber of the solids converter is preferably designed as a vertical shaft, so that the movement of the moving bed can occur solely under the influence of gravity. A moving bed allows for continuous or quasi-continuous operation and can be designed to ensure homogeneous and uniform flow.

[0013] Even better control of the H2 / CO ratio of the ultimately produced second synthesis gas mixture can be achieved if H2O is introduced into the reaction chamber of the CO2 converter to control the H2 content of the first synthesis gas mixture.

[0014] The above-mentioned problem is also solved by a device for producing synthesis gas, comprising: a hydrocarbon converter for splitting a hydrocarbon fluid into carbon and hydrogen, comprising at least one process chamber with at least one inlet for a hydrocarbon fluid and at least one outlet for carbon and hydrogen, and at least one unit for introducing energy into the process chamber; a CO2 converter for converting CO2 into CO, comprising at least one further process chamber with at least one inlet for CO2 for introducing CO2 from an external source into the CO2 converter, at least one inlet for carbon and hydrogen, and at least one outlet for synthesis gas (first synthesis gas mixture), wherein the inlet for carbon and hydrogen is directly connected to the at least one outlet of the hydrocarbon converter;a solid-state converter with a reaction chamber containing a solid bed of carbon-containing granules, in particular a moving bed guided through the reaction chamber, which has an inlet for a second gas with composition C; n H mThe device comprises a solid bed with an inlet for carbon-containing granules, a heating device capable of generating at least a local temperature of 800 to 1700°C for the solid bed of carbon-containing granules, and a hydrogen outlet. The synthesis gas outlet of the CO2 converter and the hydrogen outlet of the solid converter are connected to a mixing device and / or a CO converter. This device is designed to carry out the process described above and allows additional hydrogen to be added to the first synthesis gas mixture. This makes it possible to variably control the H2 / CO ratio of the resulting second synthesis gas mixture and adapt it to subsequent processes.

[0015] The at least one unit for introducing energy into the process chamber of the hydrocarbon converter is advantageously designed to generate temperatures above 1000°C, at least locally. Preferably, it comprises a plasma unit, which enables a particularly direct and efficient form of energy input and continuous splitting of a stream of hydrocarbons. The splitting is preferably carried out in a Kvaerner reactor.

[0016] Even better control of the H2 / CO ratio of the ultimately produced second synthesis gas mixture can be achieved if the CO2 converter has an inlet for H2O into the reaction chamber, so that H2O can be introduced into the reaction chamber of the CO2 converter to control the H2 content of the first synthesis gas mixture.

[0017] The external source of CO2 is preferably formed by a combustion power plant or a blast furnace shaft, as this results in advantageous synergy effects, as described in more detail above.

[0018] If the device described above comprises only a mixing device, a synthesis gas with any desired H₂ / CO ratio can be produced and, for example, sold. If the device described above includes a CO converter, the CO converter preferably comprises one of the following: a Fischer-Tropsch converter, an SMDS converter, a Bergius-Pier converter, a Pier converter, or a combination of a Pier converter with an MtL converter. Since the H₂ / CO ratio of the second synthesis gas mixture can be very precisely adjusted, these CO converters can operate particularly efficiently. A combination of a mixing device with a downstream CO converter is also being considered. The mixing device can also be part of the CO converter.

[0019] The invention, as well as further details and advantages thereof, will be explained below with reference to preferred embodiments and the figures.

[0020] Fig. Figure 1 shows an embodiment of the device described here, from which the process becomes clear.

[0021] Fig. Figure 2 is a schematic representation of the solids converter.

[0022] Fig. Figure 3 is a schematic representation of the hydrocarbon converter, the CO2 converter, and the CO converter, with the left side in Fig. 3 the supply line for additional hydrogen from the solid-state converter is indicated.

[0023] In the following description, the terms top, bottom, right, and left, as well as similar terms, refer to the orientations or arrangements shown in the figures and serve only to describe exemplary embodiments. These terms may indicate preferred arrangements but are not to be understood in a restrictive sense. The phrase "essentially" and similar terms relating to parallel, perpendicular, or angular specifications are intended to include deviations of ±3 degrees, and with respect to other specifications and quantities, deviations of 5% are intended to include deviations. The following description also includes processes and devices that perform "hot" substances or "hot" processes. In the context of this description, the term "hot" is intended to describe a temperature above 300°C.

[0024] Fig. Figure 1 schematically depicts a device for the production of synthesis gas. From the Fig. The basic procedure also becomes clear in section 1. Fig. Figure 1 uses arrows to represent the flows of the various substances and materials, but the arrows do not represent precise inlets into or outlets from the individual converters or plant components.

[0025] The device 1 for the production of synthesis gas has a solid-state converter 2 and a hydrocarbon converter 3 on (see Fig. 1 and Fig. 3), which has a hydrocarbon inlet 4 for a hydrocarbon fluid and an output 5 for carbon and hydrogen. The device 1 for the production of synthesis gas also includes a CO2 converter 7 with a CO2 input 8 for CO2 from an external source, an input 9 for carbon and hydrogen and an output 10 for synthesis gas. The hydrocarbon converter3 and the CO2 converter 7 are arranged in such a way that the exit 5 of the hydrocarbon converter 3 via a direct connection to the entrance 9 of the Ca2 converter 7 is connected, with the output 5 of the hydrocarbon converter 3 also directly the 9 Inlet of the CO2 converter 7 can form. This allows carbon and hydrogen to be extracted from the hydrocarbon converter. 3 directly into the CO2 converter 7 be transported.

[0026] The hydrocarbon converter 3 A hydrocarbon converter is any device that can convert or split incoming hydrocarbons into carbon and hydrogen. The hydrocarbon converter 3 It can be thermally operated or operated with a plasma. In a thermally operated hydrocarbon converter 3A hydrocarbon fluid introduced into a reaction chamber is heated to its decomposition temperature by an arbitrary heat source. In a plasma-driven hydrocarbon converter, the energy is supplied via a plasma arc. At the decomposition temperature, the introduced hydrocarbon fluid decomposes into carbon and hydrogen. The separation of the hydrocarbons should ideally be carried out in the absence of oxygen to prevent the undesired formation of carbon oxides or water. However, small amounts of oxygen, introduced along with the hydrocarbons, are not detrimental to the process. Catalysts are neither used nor necessary.

[0027] The hydrocarbon converter 3 features a process room with an entrance 4 for a hydrocarbon fluid, at least one unit 12The hydrocarbon converter is designed to introduce splitting energy into the hydrocarbon fluid and has at least one outlet. The splitting energy is provided at least partially by heat, which is generated, for example, by a plasma (plasma reactor). However, it can also be provided in other ways (thermal reactor). Splitting primarily occurs via heat. The hydrocarbon fluid should be heated to over 1000°C, and ideally to a temperature above 1500°C. In the case of a plasma-operated hydrocarbon converter, any suitable gas can be selected as the plasma gas, whether supplied externally or generated within the converter. Suitable plasma gases include inert gases such as argon or nitrogen. Alternatively, hydrogen gas (H₂), carbon monoxide (CO), or synthesis gas are also suitable, as these gases are produced during the splitting of the hydrocarbons anyway.

[0028] In the illustrated embodiment, a plasma reactor is used as a hydrocarbon converter. 3 used, which is powered by a plasma arc in a plasma burner 12The necessary heat is provided. An advantageous embodiment of a plasma reactor is a Kvaerner reactor. However, other plasma reactors are also known that operate at lower temperatures, particularly below 1000°C, and introduce additional energy into the hydrocarbon besides heat, such as via a microwave plasma. As will be explained in more detail below, the invention considers both reactor types (and also those that operate without a plasma), especially in combination with each other. Hydrocarbon converters that operate at a process chamber temperature of more than 1000°C are hereinafter referred to as high-temperature reactors, while those that operate at temperatures below 1000°C, particularly at temperatures between 200°C and 1000°C, are referred to as low-temperature reactors.

[0029] In the hydrocarbon converter 3Hydrogen and carbon are generated from hydrocarbons (CnHm) using heat and / or a plasma. The hydrocarbons are preferably introduced into the process chamber in gaseous form (first gas). If the hydrocarbons are liquid under normal conditions, they can be heated before being introduced into the hydrocarbon converter. 3 They can be brought into gaseous form, or they could also be introduced in finely atomized form. All these forms are referred to here as fluids. The hydrocarbon fluid preferably consists of a stream of natural gas, methane, liquefied gases, or heavy oil, and particularly preferably of a stream of conventional or unconventional natural gas as well as liquefied gases ("wet gases"). In the hydrocarbon converter 3Introduced hydrocarbon fluids are split at high temperature into a mixture of carbon (C particles) and hydrogen (H2), also known as an H2 / C aerosol. This mixture of C particles and hydrogen remains separate even after cooling.

[0030] The CO2 converter 7 Any suitable CO2 converter can be used, capable of producing carbon monoxide (CO) from carbon (C) and carbon dioxide (CO2). This is where the CO2 converter works. 7 This process involves a portion of the blast furnace reaction known in engineering, which occurs at temperatures between approximately 750°C and 1200°C without the need for a catalyst. The CO2 converter preferably operates in this manner. 7 at a temperature between 800°C and 1000°C, the heat required to reach this temperature being primarily supplied by the feedstock of the hydrocarbon converter, as will be explained in more detail below. In the CO2 converter7 CO2 is passed over hot carbon or mixed with it (and possibly hydrogen) to be converted according to the chemical equation CO2 + C → 2CO. The CO2 converter 7 It works best at Boudouard equilibrium and a temperature of 1000°C. At temperatures of 800°C, approximately 94% carbon monoxide is produced, and at temperatures around 1000°C, approximately 99% carbon monoxide is produced. Further temperature increases do not produce any significant changes.

[0031] Fig. Figure 2 shows the solids converter in more detail. 2 . About the feed 13A carbon-containing granulate (e.g., coke dust) at ambient temperature is introduced from above into the reaction chamber R. The granulate is then guided downwards through reaction chamber R in a moving bed W under the influence of gravity. Simultaneously, a second gas containing methane (e.g., natural gas or methane) is introduced from below via a feeder. 15 The gas is directed into the reaction chamber R and guided upwards through the moving bed W in the opposite direction to the granules. The second gas, which is at ambient temperature when it enters the reaction chamber R, is heated on its way upwards through heat exchange with the granules (moving bed W).

[0032] In a high-temperature zone H (temperature above 1000°C), the second gas is split into carbon and hydrogen, with more than 95% of the carbon being deposited onto the granules of the carbon-containing material. The hydrogen produced during this splitting process flows against the conveying direction of the granules and ultimately exits the solid-state converter as "additional" hydrogen. More precisely, after splitting in the high-temperature zone H, the hydrogen continues to flow upwards, where it is cooled through heat exchange with the cooler granules of the moving bed W, so that the additional hydrogen is released via an outlet. 17 Hydrogen can be extracted at a temperature above ambient temperature but at least 500 K below the temperature at which the second gas splits. The additional hydrogen is used in a mixing device. 19 piped and mixed with the synthesis gas from the CO2 converter7 (first synthesis gas mixture) mixed to achieve a desired mixing ratio of H2 to CO in the ultimately produced second synthesis gas mixture.

[0033] The following describes a method for heating the granules and moving bed. In an optional separation unit T, a portion of the hydrogen is separated and then heated to hot hydrogen gas in an optional electric heating device PH using an electric arc (plasma burner). At a temperature of 3000 to 10000 K, the hot hydrogen gas is introduced into the high-temperature zone H, where it provides the energy required for the splitting of the second gas. At the lower end of the reaction chamber R, the granules with deposited carbon are removed. Due to their high carbon content and low ash and sulfur content, these granules with deposited carbon can be used, for example, as a coke oven additive or carburizing agent in foundries.

[0034] Components of the granules containing deposited carbon that do not meet the quality requirements for use in the blast furnace shaft or as a carburizing agent because they have a diameter that is too large or too small, or, for example, a density that is too low, are separated in a separation unit S (e.g., by sieving). Optionally, oversized granules can be conveyed via a pipe after crushing (not shown). 21 The remainder is returned to the reaction chamber R of the solid-state converter. 23 The granules with deposited carbon can be sold as blast furnace coke (i.e., as a high-quality product) or directly in a blast furnace shaft. 25 to be used, which is arranged next to the device described here for the production of synthesis gas and serves as an external CO2 source for the operation of the CO2 converter. 7 serves.

[0035] The second synthesis gas mixture is mixed in the mixing device. 19 adjusted to a desired H2 / CO ratio, and it consists of the first synthesis gas mixture (from the CO2 converter) and the additional hydrogen from the solid-state converter 2 . Fine-tuning of the H2 / CO ratio and also the temperature of the first synthesis gas mixture can be achieved by adding a lower proportion of CO2 but additional H2O to the CO2 converter. 7 Additional H2O can also be added at a point between the CO2 converter and the CO2 converter. 7 and the mixing device 19 CO is added as long as the remaining temperature is sufficient to achieve the conversion of hot carbon particles with H₂O (C + H₂O → H₂ + CO). The H₂ / CO ratio of the ultimately produced second synthesis gas mixture is determined to meet the requirements of a customer or a subsequent process step in a CO converter.

[0036] The device1 for the production of synthesis gas, it also features an optional CO converter. 27 up. The CO converter 27 Any CO converter can be used to produce synthetic hydrocarbons (with or without a functional group). In the embodiment shown, the CO converter is... 27Preferably a Fischer-Tropsch converter, an SMDS converter, a Bergius-Pier converter, a Pier converter, or a combination of a Pier converter with an MtL converter, with a suitable catalyst and a temperature and / or pressure control unit. In a Bergius-Pier converter, the Bergius-Pier process, well known to those skilled in the art, takes place, in which hydrocarbons are produced by hydrogenation of carbon with hydrogen in an exothermic chemical reaction. The range of starting materials from the Bergius-Pier process depends on the reaction conditions and the reaction control. Mainly liquid end products are obtained, which can be used as fuels, for example, heavy and medium oils. Well-known developments of the Bergius-Pier process include, for example, the Konsol process and the H-Coal process.

[0037] In a preferred embodiment, the CO converter 27A Fischer-Tropsch converter is used. A Fischer-Tropsch converter catalytically converts synthesis gas into hydrocarbons and water. Various designs of Fischer-Tropsch reactors and Fischer-Tropsch processes are known to those skilled in the art, which will not be described in detail here. The main reaction equations are as follows: nCO + (2n + 1)H2 → CnH 2n+2 + nH2O for alkanes nCO + (2n)H2 → C n H 2n + nH2O for alkenes nCO + (2n)H2 → C n H 2n+1 OH + (n – 1)H2O for alcohols

[0038] Fischer-Tropsch processes can be carried out as high-temperature or low-temperature processes, with process temperatures generally ranging between 200 and 400°C. Well-known variants of the Fischer-Tropsch process include high-load synthesis, Synthol synthesis, and Shell's SMDS process (SMDS = Shell Middle Distillate Synthesis). A Fischer-Tropsch converter typically produces a hydrocarbon compound from liquefied gases (propane, butane), gasoline, kerosene (diesel oil), soft paraffin, hard paraffin, methanol, methane diesel fuel, or a mixture of several of these. As is known to those skilled in the art, Fischer-Tropsch synthesis is exothermic. The heat of reaction from the Fischer-Tropsch process can be used, for example, to preheat CO2 by means of a heat exchanger (not shown in the figures).For example, a two-stage preheating of the CO2 introduced into the CO2 converter is being considered, with a first preheating using the waste heat of the CO converter. 27 (in the form of a Fischer-Tropsch converter) and then further heating of the CO2 using heat from one or more heat exchangers (not shown). In the context of metal production in a steelworks, waste heat generated during the operation of a Fischer-Tropsch converter can be used to preheat air or oxygen, as well as to dry ore or additives before they enter the blast furnace shaft. 25 be initiated and blown in.

[0039] In all embodiments, the hydrocarbon fluid to be split is, for example, natural gas, methane, liquefied petroleum gas, heavy oil, or a mixture thereof. Preferably, the hydrocarbon fluid to be split is natural gas or methane (the first gas having the composition C).n H m However, other hydrocarbon fluids can also be processed. The second gas introduced into the solid-state converter is natural gas or methane (second gas).

[0040] The invention has been described with reference to preferred embodiments, whereby the individual features of the described embodiments can be freely combined and / or exchanged, provided they are compatible. Likewise, individual features of the described embodiments can be omitted if they are not essential. Further information on the design and function of the individual converters mentioned here can be found, for example, in WO 2013 / 091878 A1, in EP 2 729 405 B1, and in the technical literature on plasma reactors published by Kvaerner. Numerous modifications and embodiments are possible and obvious to those skilled in the art without departing from the inventive concept. QUOTES INCLUDED IN THE DESCRIPTION

[0041] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0042] EP 2729405 B1 [0002, 0040] WO 2013 / 091878 A1

[0040]

Claims

[1] Process for the production of synthesis gas comprising the following steps: Splitting of a hydrocarbon fluid, in particular a first gas with composition C n H m , to carbon and hydrogen in a reaction chamber of a hydrocarbon converter with the addition of heat, wherein the carbon and hydrogen have a temperature of at least 800°C after the splitting; Directing the carbon and hydrogen obtained from the splitting process into a reaction chamber of a CO2 converter; Mixing CO2 from an external source with the carbon and hydrogen in the CO2 converter; Converting the CO2 and the carbon obtained through splitting into CO at a temperature of 800 to 1700°C, so that a first synthesis gas mixture is produced; Mixing the first synthesis gas mixture with additional hydrogen to create a second synthesis gas mixture with a higher hydrogen content than the first synthesis gas mixture; the additional hydrogen is produced through the following steps: Conducting a second gas with composition C n H m into a reaction chamber of a solid-state converter containing a solid bed of carbon-containing granules, in particular a moving bed guided through the reaction chamber, wherein the solid bed has a temperature of 800 to 1700°C at least locally; Splitting of the second gas with composition C n H m to carbon and hydrogen, which forms the additional hydrogen; Separation of the carbon obtained through splitting and the additional hydrogen by depositing the carbon onto the carbon-containing granules. [2] Method according to claim 1, wherein the supply of heat for splitting the hydrocarbon fluid in the hydrocarbon converter is primarily via a plasma. [3] Method according to claim 1 or 2, wherein the splitting of the hydrocarbon fluid and the conversion of the CO2 and the carbon to CO are carried out without a catalyst. [4] Method according to any of the preceding claims, wherein the energy required to reach the temperature of 800 to 1700°C for the CO2 conversion is substantially entirely derived from the heat provided for the splitting of the hydrocarbon fluid. [5] Method according to one of the preceding claims, wherein the CO2 is provided from an external source by exhaust gas of a combustion power plant or by blast furnace gas which is produced by the reduction of a metal ore in a blast furnace shaft and contains CO2. [6] Method according to one of the preceding claims, wherein the energy required to generate the temperature of 800 to 1700°C of the solid bed of carbon-containing granules is generated by thermal energy in the reaction chamber of the solid converter and / or is introduced into the reaction chamber of the solid converter via a hot gas. [7] Method according to one of the preceding claims, wherein the solid bed of carbon-containing granules is guided continuously as a moving bed and preferably with the aid of gravity; wherein the carbon-containing granules are introduced into the reaction chamber of the solid-state converter at ambient temperature in a first conveying direction; wherein the second gas is guided through the solid bed of carbon-containing granules in a second conveying direction opposite to the first conveying direction, and wherein the additional hydrogen obtained by splitting the second gas is cooled by contact with the carbon-containing granules. [8] Method according to one of the preceding claims, wherein H2O is introduced into the reaction chamber of the CO2 converter to control the H2 content of the first synthesis gas mixture. [9] Apparatus for the production of synthesis gas comprising the following: a hydrocarbon converter for splitting a hydrocarbon fluid into carbon and hydrogen, comprising at least one process chamber with at least one inlet for a hydrocarbon fluid and at least one outlet for carbon and hydrogen, and at least one unit for introducing energy into the process chamber; a CO2 converter for converting CO2 into CO, which has at least one further process chamber with at least one inlet for CO2 for introducing CO2 from an external source into the CO2 converter, at least one inlet for carbon and hydrogen and at least one outlet for synthesis gas, wherein the inlet for carbon and hydrogen is directly connected to the at least one outlet of the hydrocarbon converter; a solid-state converter with a reaction chamber containing a solid bed of carbon-containing granules, in particular a moving bed guided through the reaction chamber, which has an inlet for a second gas with the composition C n H minto the solid bed, which has an inlet for carbon-containing granules, which has a heating device that can generate at least locally a temperature of 800 to 1700°C of the solid bed of carbon-containing granules, and which has an outlet for hydrogen; wherein the output for synthesis gas of the CO2 converter and the output for hydrogen of the solid converter are connected to a mixing device and / or a CO converter. [10] Device according to claim 9, wherein the at least one unit for introducing energy into the process chamber of the hydrocarbon converter is designed to generate temperatures above 1000°C at least locally, and preferably comprises a plasma unit. [11] Device according to claim 9 or 10, wherein the CO2 converter has an inlet for H2O into the reaction chamber. [12] Device according to one of claims 9 to 11, wherein the external source for CO2 is formed by a combustion power plant or a blast furnace shaft.

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