Method and device for producing stoichiometric synthesis gas with reduced co2 footprint

Abstract

The present invention relates to a method for producing a product gas composition comprising carbon monoxide and hydrogen, wherein a reactant gas composition comprising hydrogen, at least one hydrocarbon-containing compound and at least one oxidizing agent is reacted in a flow reactor in a plasma at a temperature of greater than or equal to 1000 °C. The invention further relates to a device for carrying out the method.

Description

[0001] 202000196 Abroad

[0002] 1

[0003] Method and apparatus for the production of stoichiometric synthesis gas with a reduced CO2 footprint

[0004] The present invention relates to a process for producing a product gas composition comprising carbon monoxide and hydrogen by reacting a reactant gas composition comprising hydrogen, at least one hydrocarbon compound, and at least one oxidizing agent in a flow reactor in a plasma at a temperature greater than or equal to 1000 °C. An apparatus for carrying out the process is also part of the present invention.

[0005] In Germany, CO2 emissions exceeded 1 trillion tons of CO2 equivalent in the last decade, with the chemical industry contributing approximately 5% of this figure. Consequently, the chemical industry is striving to reduce CO2 emissions for both ecological and economic reasons, for example, by changing its raw material base, using low-carbon production technologies, and optimizing energy consumption. A particularly significant impact can be achieved by converting the production of large-volume basic chemicals. Suitable basic chemicals include hydrogen and synthesis gas. Global demand for hydrogen is estimated at around 50 million tons per year, and for synthesis gas at around 220 million tons per year.

[0006] Steam reforming of light hydrocarbons (short-chain hydrocarbons, typically C1 to C5 hydrocarbons) is currently the most common process for producing synthesis gas with a molar hydrogen to carbon monoxide ratio of 2.5 to 3.0. The feedstocks, such as natural gas, liquefied petroleum gas (LPG), or naphtha, are reacted endothermically with steam in catalytic tubular reactors to produce synthesis gas with a high hydrogen content. Process heat and flue gas heat are used for steam generation.

[0007] The production of synthesis gas via steam reforming becomes problematic when the synthesis gas is required to have a molar ratio of hydrogen to carbon monoxide between approximately 1.0 and 2.0. This ratio of hydrogen to carbon monoxide is, however, of particular importance in the production of fuels and chemicals. For example, significant quantities of synthesis gas are needed for the oxo synthesis of alcohols and aldehydes from olefins (hydrogen to carbon monoxide ratio of 1:1) or for Fischer-Tropsch synthesis of olefins (hydrogen to carbon monoxide ratio of 1:1). This is because steam reforming requires catalysts that exhibit exceptional resistance to coking.

[0008] Another disadvantage of catalytic steam reforming is its susceptibility to catalyst poisons, such as sulfur, which can be introduced from sulfur-containing compounds. To protect the catalyst, the feed gas must therefore undergo extensive purification in upstream process stages. For example, organic sulfur compounds, such as mercaptans or thiophenes, are removed beforehand using Co-Mo or Ni-Mo catalysts.

[0009] 2

[0010] Hydrogen sulfide is hydrogenated. For example, hydrogen sulfide reacts with ZnO, which is converted to ZnS and must be regularly replaced. Furthermore, the heat integration of steam reforming is incomplete because only about 50% of the generated heat is effectively used for the reaction. In addition, the synthesis gas produced in this way has a relatively high CO2 footprint of approximately 60 kg CO2 per 100 kg of synthesis gas.

[0011] Alternative processes for producing synthesis gas with a molar ratio of hydrogen to carbon monoxide of approximately 1.0 to 2.0 include the autothermal reforming of natural gas and partial oxidation. Both processes are used industrially, but require the use of pure oxygen, which is obtained through air separation. The energy-intensive cryogenic air separation process is a significant cost driver for these two latter processes.

[0012] The reforming of natural gas with CO2 to produce synthesis gas is an endothermic reaction. The yields in this reaction of methane with CO2 depend on various factors, such as the reaction conditions, the residence time in the reactor, and the reaction time. The yields are generally low because the endothermic nature of the reaction requires a significant amount of energy. The reaction is kinetically unfavorable due to its slow pace and high activation energy requirements. While the reaction of methane with CO2 can be improved by using catalysts, these catalysts are prone to failure due to the high process temperatures required. Furthermore, catalyst coking poses a significant problem.

[0013] The object of the present invention was therefore to provide a process and a device for producing synthesis gas with a reduced CO2 footprint. A further object was to make the process and the device available to the chemical industry under economically attractive conditions. In addition, the object was to find a process that is as catalyst-free as possible and allows synthesis gas production to be carried out at high temperatures. Likewise, the process should eliminate the need for solvents or other solids that would require processing.

[0014] The task also involved ensuring that the process could, on the one hand, produce a defined, and in particular fixed, ratio of hydrogen to carbon monoxide in the synthesis gas, and on the other hand, allow the ratio of hydrogen to carbon monoxide to be adjusted as needed. The process therefore needed to be as flexible as possible.

[0015] Furthermore, the task was to develop a device for carrying out this process to produce the desired synthesis gas. The device was to be robust against sulfur-containing substances and other impurities and exhibit a higher efficiency than known processes. Preferably, the process should allow any sulfur compounds present after the process has been carried out to be separated by suitable methods, such as thermal processes like distillation and / or absorption / desorption and / or membrane processes. 202000196 Abroad

[0016] 3

[0017] The problems could be solved by the method described in claim 1 and the apparatus described in claim 12. Preferred embodiments are specified in the dependent claims and described in detail in the description.

[0018] The present invention relates to a process for producing a product gas composition comprising at least carbon monoxide and hydrogen by reacting a reactant gas composition in a plasma at a reactant gas composition temperature of greater than or equal to 1000 °C, wherein the reactant gas composition

[0019] Hydrogen or a hydrogen-containing gas mixture; comprising at least one hydrocarbon compound selected from the group consisting of methane, ethane, ethene, propane, butane, 2-methylpropane, pentane, n-pentane, isopentane and / or neopentane, methanol, ethanol and mixtures of two or more thereof, and at least one oxidizing agent selected from the group consisting of carbon dioxide and a mixture comprising carbon dioxide and water. The water may also be used in the form of water vapor and is added in particular to control the hydrogen content of the product gas composition.

[0020] Surprisingly, the problems were solved by jointly reacting hydrogen, a hydrocarbon-containing compound, and at least one oxidizing agent, optionally containing water, in a plasma process to produce carbon monoxide and hydrogen, i.e., synthesis gas. The process according to the invention is not susceptible to sulfur compounds or other impurities and, in particular, allows for almost complete heat integration. Furthermore, the process according to the invention exhibits a higher efficiency than the individual reactions of an oxidative conversion of hydrocarbons to carbon monoxide and hydrogen. In addition, CO2 is used in the process and converted into valuable products via the synthesis gas in subsequent processes, thus reducing the CO2 footprint.

[0021] The hydrogen or hydrogen-containing gas mixture used in the plasma reaction is added primarily as an ionizable carrier gas. In addition to hydrogen, the hydrogen-containing gas mixture may contain nitrogen and / or argon, or mixtures thereof.

[0022] Suitable hydrocarbon-containing compounds are, in principle, all hydrocarbons that form gaseous hydrocarbons at temperatures above 1000 °C. According to the present invention, the hydrocarbon-containing compound is selected from the group consisting of methane, ethane, ethene, propane, butane, 2-methylpropane, pentane, n-pentane, isopentane and / or neopentane, methanol, ethanol, and mixtures of two or more thereof. In a preferred embodiment, 202000196 Foreign

[0023] Section 4 of the present invention is the hydrocarbon-containing compound methane, ethane, methanol, ethanol, or a mixture of two or more of the aforementioned compounds. The hydrocarbon-containing compound methane, methanol, or a mixture of methane and methanol is particularly preferred. The individual substances that can be used as hydrocarbon-containing compounds can, in principle, be used as pure substances or as gas mixtures. Natural gas can be used as a commercially available gas mixture containing a hydrocarbon-containing compound. Natural gas mainly contains methane.

[0024] As mentioned, the hydrocarbon-containing compound can also be a mixture of several hydrocarbons. In such a mixture, methane is preferably present in a concentration of greater than or equal to 50 to 95% by volume, within a total hydrocarbon composition of 100% by volume.

[0025] The oxidizing agent used in the process according to the invention is selected from the group consisting of carbon dioxide and a mixture comprising carbon dioxide and water.

[0026] The individual components of the feed gas composition can, in principle, be supplied separately and independently of one another and mixed before conversion to synthesis gas. It is also possible and advantageous, in principle, if individual components are already at least partially incorporated into a mixture. An example of such a feedstock is biogas, i.e., a gas mixture containing methane, carbon dioxide, and possibly also a certain amount of ammonia, hydrogen sulfide, hydrogen, and / or water or steam.

[0027] Biogas, with its main components methane and carbon dioxide, can also be produced from the anaerobic digestion of biopolymers, such as polymeric substrates comprising polysaccharides, proteins, and lipids. Suitable feedstocks for the anaerobic digestion of biopolymers include, among others, corn silage, grass silage, whole-plant rye silage (WPS), sugar beet pulp, pig manure, cow manure, fodder beets, organic waste, grain distillers' grain, pig slurry, and cattle slurry.

[0028] The reactant gas composition used in the process according to the invention preferably contains 60 to 80 vol%, preferably 65 to 75 vol% hydrogen; 10 to 20 vol%, preferably 12 to 20 vol% at least one hydrocarbon-containing compound; and 10 to 20 vol%, preferably 12 to 20 wt% at least one oxidizing agent. The total composition of the reactant gas composition is always 100 vol%. The content of sulfur-containing compounds in the reactant gas composition is preferably below 2 vol%, preferably less than or equal to 0.2 vol%, and particularly preferably less than 0.02 vol%.

[0029] The reaction of the reactant gas composition takes place in a high-temperature plasma. According to the invention, the temperature of the process gas (= reactant gas composition) during the reaction is greater than or equal to 1000 °C. In a preferred embodiment, the reaction is carried out at a temperature of greater than or equal to 1300 °C, more preferably greater than or equal to 1500 °C, and particularly [202000196 Ausland]

[0030] 5. Preferably greater than or equal to 1800 °C, preferably depending on the residence time in the reactor tube. Optical methods are suitable for temperature measurement at these high temperatures, e.g. using a glow wire as a reference, or sensors such as pyrometers. Measuring sensors up to 1800 °C, e.g. from ABB® or Endress+Hauser®, are suitable. Suitable thermocouples include those of type S (inner core / thermocouple: platinum-rhodium 10% / platinum) for temperatures up to 1600 °C, type R (inner core / thermocouple: platinum-rhodium 13% / platinum) for temperatures up to 1600 °C, type B (inner core / thermocouple: platinum-rhodium 30% / platinum-rhodium 6%) for temperatures up to 1700 °C, type C (inner core / thermocouple: tungsten-5% rhenium / tungsten-20% rhenium) for temperatures up to 2315 °C and / or type A (inner core / thermocouple: tungsten-5% rhenium / tungsten-20% rhenium) for temperatures up to 2500 °C.Preferably, and depending on the process gas composition, the thermocouple is embedded in a ceramic protective tube known to those skilled in the art, e.g., made of corundum ceramic (Al2O3 for temperatures up to 1800°C) or zirconium mixed oxide (up to 2200°C).

[0031] The plasma is preferably operated with an electrical power in the range of 500 kW to 10,000 kW, particularly preferably in the range of 6,500 to 8,000 kW. The applied voltage, which can be either direct or alternating current, is preferably in the range of 5,000 volts to 7,000 volts or 7,000 volts to 8,500 volts. The current is preferably in the range of 500 to 800 or 800 to 950 amperes.

[0032] The method according to the invention is preferably operated at a pressure of 10 mbarabs to 10 barabs, more preferably at a pressure of 500 mbarabs to 5 bar, and particularly preferably at a pressure of 1 to 3 barabs. The unit barabs means absolute bar, i.e., absolute pressure. Absolute pressure is referenced to the vacuum (= pressure of 0 bar). Absolute pressure sensors known to those skilled in the art measure the absolute pressure relative to a vacuum enclosed in the sensor element (close to approximately 0 bar).

[0033] The conversion process takes place as a gas-phase process in which energy is supplied via electrical discharge by electrons (plasma). This eliminates the need for catalysts and also eliminates the need for pre-purification of the reactant gas composition or individual components thereof. Furthermore, it was found that carbon deposits form on the inner surface of the tubular electrode (cathode) of the reactor during plasma operation. Surprisingly, it was discovered that this significantly extends the electrode's service life. Therefore, the coke formation that may occur during the reforming reaction in the plasma is desirable, as it leads to a longer electrode lifespan and improves the process's economic efficiency.

[0034] The process according to the invention produces a product gas composition containing hydrogen and carbon monoxide. Accordingly, the product gas composition preferably comprises a hydrogen content of 45 to 90 vol.%, particularly preferably 60 to 80 vol.%, and a 202000196 foreign country

[0035] 6

[0036] Carbon monoxide content preferably 10 to 55 vol.%, particularly preferably 20 to 40 vol.%. The overall composition of the product is always 100 vol.%.

[0037] The product gas composition further preferably comprises carbon monoxide and hydrogen in a molar ratio (CO : H2) of 1 : 5 to 0.5 : 1, more preferably of 1 : 2 to 1 : 4 and particularly preferably of 0.75 to 1.25 : 1.

[0038] The present process thus makes it possible to produce synthesis gas in the desired stoichiometric molar ratio of CO to H₂ of approximately 1, particularly with ±10 percent, reproducibly and economically. By adding water, especially steam, or (optionally low-emission) ammonia, or a mixture of ammonia and water, especially steam, the hydrogen content in the synthesis gas, i.e., the product gas composition, can be controlled. Therefore, the ideal stoichiometry for oxo synthesis (e.g., hydroformylation) can be set and maintained using the process according to the invention. This correspondingly reduces the carbon footprint of the oxo products produced. Consequently, further ecological and economic advantages arise for the marketing of the oxo synthesis products.An additional use of green methanol, ethanol or mixtures thereof in the gas phase, optionally with a water content, or the alternative use of methane obtained from biomass, enables a further reduction of the CO2 footprint.

[0039] The process according to the invention can, in principle, be operated continuously or in batch mode. Since processes that use synthesis gas as a raw material are generally operated continuously, it is preferred if the present process is also operated continuously.

[0040] The method according to the present invention can be carried out in any device in which such a plasma process can be performed. Preferably, the method is carried out in a flow reactor (0) comprising an anode (5), a cathode (4), a gas inlet (1), a first gas outlet (6), and a second gas outlet (8), wherein the reactant gas composition is supplied via the gas inlet (1), reacted in the flow reactor (0), and the product gas composition is discharged via the second gas outlet (8). The reactant gas composition is supplied to the flow reactor (0) via a tangential gas inlet (1, 3) on a vortex chamber (2). The anode is arranged on the vortex chamber (2) in the direction of the first gas outlet (6), and the cathode (4) is located in the reaction tube (3, 1), and the plasma (C) is formed between the anode (5) and the cathode (4). The tangential gas inlet (1, 3)3) In this preferred embodiment, the gas inlet (1) corresponds to the gas inlet. The term "tangential" here refers to the vortex chamber (2). The gas inlet (1 .3) is arranged tangentially to the vortex chamber (2). The reactant gas composition is preferably already at the gas inlet (1) of the vortex chamber (2) of the flow reactor (0) at the desired temperature of greater than or equal to 100 °C, in particular greater than or equal to 300 °C, preferably greater than or equal to 500 °C and particularly preferably greater than or equal to 800 °C 202000196 Abroad.

[0041] 7. The temperature can be measured using optical methods or suitable sensors, as described above.

[0042] The gas inlet (1) and the first gas outlet (6) are preferably arranged on the vortex chamber (2) of the flow reactor (0). The flow reactor (0) also has a reaction tube (3.1) with the second gas outlet (8). The second gas outlet (8) of the flow reactor (0) is spatially opposite the first gas outlet (1). This is illustrated in the drawings according to the invention.

[0043] The flow reactor (0) for the process according to the invention further preferably comprises an anode (5) and a cathode (4), wherein the anode is arranged at the vortex chamber (2) in the direction of the first gas outlet (6) and the cathode (4) is arranged in the reaction tube (3.1). During the process, the plasma (C) forms between the anode (5) and the cathode (4). The plasma temperature in the reaction tube (3.1) has an (arithmetically) averaged value of greater than or equal to 1000 °C, in particular greater than or equal to 1300 °C, preferably greater than or equal to 1500 °C, and particularly preferably greater than or equal to 1800 °C. At an average gas temperature of 1800 °C, the residence time of the process gas in the plasma is between 0.01 and 10 microseconds, preferably between 0.2 and 5 microseconds.

[0044] Furthermore, a heat exchanger (20), in particular a high-temperature heat exchanger, can be arranged on the flow reactor (0), especially in the region of the second gas outlet (8), with which energy in the form of thermal energy can be transferred from the product composition to the reactant gas composition. The heat exchanger (20) preferably cools the product composition and heats the reactant gas composition.

[0045] In a particularly preferred embodiment of the present invention, the method is a method for producing a product gas composition comprising at least 10 to 55 vol.% carbon monoxide and 45 to 90 vol.% hydrogen by reacting a reactant gas composition in a plasma at a reactant gas composition temperature of greater than or equal to 1300 °C, preferably greater than or equal to 1500 °C, particularly preferably greater than or equal to 1800 °C, wherein the reactant gas composition

[0046] Hydrogen or a hydrogen-containing gas mixture; comprising at least one hydrocarbon compound selected from the group consisting of methane, methanol and mixtures of methane and methanol, and at least one oxidizing agent selected from the group consisting of carbon dioxide and a mixture comprising carbon dioxide and water, wherein the process 202000196 foreign

[0047] 8 in a flow reactor (0) comprising an anode (5), a cathode (4), a vortex chamber (2), a gas inlet (1), a first gas outlet (6) and a second gas outlet (8), wherein the reactant gas composition is supplied via the gas inlet (1), reacted in the flow reactor and the product gas composition is discharged via the second gas outlet (8).

[0048] In principle, it is preferred to supply the reactant gas composition to the vortex chamber (2) in such a way that the reactant gas composition has a tangential flow velocity of greater than or equal to 20 m / s, in particular greater than or equal to 30 m / s up to 300 m / s, and particularly preferably greater than or equal to 35 m / s and less than or equal to 95 m / s within the vortex chamber (2).

[0049] Corresponding flow velocities are then also present in the tubular reactor (3) or the reaction tube (3.1). Depending on the desired electrical and process-related operating parameters, the plasma can, for example, be generated and operated with a length of approximately 1 meter in a tubular reactor with a length greater than 1 meter between the anode and the cathode.

[0050] A so-called cold gas stream can be drawn off via the first gas outlet (6), which is preferably located opposite the second gas outlet (8). This cold gas stream will correspond to a mixture of the reactant gas composition and the product gas with regard to its chemical composition, and may therefore contain hydrogen and carbon monoxide. In a preferred embodiment of the present invention, the cold gas stream drawn off at the first gas outlet (6) can be mixed with the reactant gas composition before the reactant gas composition is fed to the flow reactor (0) upstream, in, or downstream of the heat exchanger (20). Consequently, the reactant gas composition can also contain carbon monoxide due to the addition of the cold gas stream.

[0051] The present invention also relates to a device for producing a product gas composition comprising at least carbon monoxide and hydrogen, wherein the device comprises a flow reactor (0) with a first gas inlet (1), a first gas outlet (6), a second gas outlet (8), at least one anode (5) and at least one cathode (4) for generating a plasma (C) and at least one heat exchanger (20) as well as a membrane unit (not shown).

[0052] The process according to the invention for converting the reactant gas composition takes place in the flow reactor (0). The flow reactor (0) is preferably oriented in the direction of gravity or substantially perpendicular to the substrate. The reactant gas composition is supplied via the first gas inlet (1) and reacted in the plasma (C) between the at least one anode (5) and the at least one cathode (4). The product gas composition leaves the flow reactor via the second gas outlet (8). The first gas outlet (6) is the outlet for the so-called cold gas stream. The heat exchanger (20) serves to heat the reactant gas composition and (simultaneously) cool the product gas composition. The heat exchanger must be designed for the corresponding operating temperature using suitable materials (e.g., corundum ceramic - containing ALOs, boron nitride ceramic, silicon carbide ceramic, etc.).

[0053] 9

[0054] The hot side of the heat exchanger and special steels, such as heat-resistant steels according to Table 1 for the cold side, must be designed and constructed.

[0055] Table 1: Overview of suitable steel materials

[0056] The flow reactor (0) comprises at least one anode (5) and one cathode (4). Therefore, multiple anodes (5) and / or multiple cathodes (4) may also be present. In a preferred embodiment, the flow reactor (0) comprises 2 to 10 anodes (5) and / or 2 to 10 cathodes (4). The distance between the at least one anode (5) and the at least one cathode (4) is preferably 1 cm to 10 m, more preferably 20 cm to 8 m, and particularly preferably 20 cm to 2 m.

[0057] The at least one cathode (4) preferably contains iron. Particularly preferably, the at least one cathode (4) is made of iron or an iron alloy. If several cathodes (4) are present, the cathodes can each consist of the same or different materials. To increase the cathode lifetime, carbon deposition on the cathode (4) can be accelerated, or the carbon deposition or reaction on the cathode (4) can be controlled by precisely adjusting the hydrogen content in the reactant gas composition.

[0058] The at least one anode (5) preferably contains copper. The at least one anode (5) is also particularly preferably a hollow anode and preferably consists of copper or a copper alloy or a copper-silver-barium alloy. If several anodes (5) are present, the anodes can each consist of the same or different materials.

[0059] The heat exchanger (20) is preferably a high-temperature heat exchanger. In a preferred embodiment, the heat exchanger (20) comprises at least two hollow bodies that are guided inside one another, i.e., there is at least one inner hollow body and at least one outer hollow body, in particular a tube-in-tube configuration. In a preferred embodiment of the present invention, the heat exchanger (20) has a plurality of inner and outer hollow bodies. This increases the surface area for energy transfer and makes the energy transfer between the product gas composition and the reactant gas composition simpler and faster. 202000196 Foreign

[0060] 10

[0061] The at least one inner hollow body is designed for the flow of the product gas composition. For example, a ceramic material, such as aluminum oxide, particularly corundum, can be used as the material for manufacturing the at least one inner hollow body. The at least one outer hollow body is designed for the flow of the reactant gas composition. For example, steel, particularly special steel or carbon steel, can be used as the material for manufacturing the at least one outer hollow body. The heat exchanger (20) preferably operates according to the counterflow principle, i.e., the reactant and product gas compositions are guided in opposite directions through the hollow bodies of the heat exchanger (20).The length of the two hollow bodies and the wall thickness of the first hollow body can be determined at defined flow velocities and at defined pressure based on the temperature difference between product gas composition and reactant gas composition in the heat exchanger (20).

[0062] In a preferred embodiment of the present invention, the flow reactor (0) further comprises a vortex chamber (2) with a tangential gas inlet (1 .3), the first gas outlet (6) and the at least one anode (5) and a reaction tube (3.1) arranged on the vortex chamber, preferably a reaction tube (3.1) oriented in the direction of gravity or vertically to the ground, with a second gas outlet (8) and at least one cathode (4), wherein the at least one anode (5) is axially located in the vortex chamber (2) or axially in the first gas outlet (6) of the vortex chamber and the at least one cathode (4) is located in the reaction tube (3.1) is arranged, and the reactant gas composition passes through the heat exchanger (20) before being fed to the swirl chamber (2), and a discharge (11) is arranged at the second gas outlet (8) through which the product gas composition is guided through the heat exchanger (20), whereby energy in the form of heat energy is transferred from the product gas composition to the reactant gas composition in the heat exchanger (20).

[0063] The feed gas composition into the flow reactor (0) is therefore supplied via a tangential gas inlet (1, 3) into the vortex chamber (2), ensuring the necessary turbulence of the feed gas composition. In the context of the present invention, "tangential" means that the gas inlet is arranged tangentially to the vortex chamber, in particular tangentially to the outer radius of the vortex chamber (2). The tangential gas inlet (1, 3) is in particular arranged perpendicular to the longitudinal center axis of the flow reactor (0). The origin of the radius of the vortex chamber is in particular located on the longitudinal center axis of the flow reactor, and this longitudinal center axis preferably also lies on the longitudinal center axis of the tubular reactor (3) or the reaction tube (3.1). The term tubular reactor (3) is used synonymously with the term reaction tube (3.1) in this context. The tubular reactor (3) is in particular arranged in the direction of gravity.

[0064] 11

[0065] The vortex chamber (2) also comprises the first gas outlet (6) and the at least one anode (5). The anode (5) is preferably arranged on the vortex chamber in the direction of the first gas outlet (6) or in the gas outlet (6). The anode (5) can furthermore be arranged axially in the vortex chamber (2) or axially in the first gas outlet (6) of the vortex chamber (2). The anode (5) is preferably a hollow anode made of copper or a copper alloy or a copper-silver-barium alloy.

[0066] The first gas outlet (6) is preferably connected to a closed cavity, wherein the anode may be arranged in the first gas outlet (6) or in the cavity. In this embodiment, the cooler flow of the reactant gas composition is directed into the cavity, stagnated in the cavity, and returned to the vortex chamber (2). Alternatively, the first gas outlet can be designed as a nozzle, in particular as a diffuser.

[0067] The flow reactor (0) comprises, in addition to the vortex chamber (2) with tangential gas inlet (1, 3), a reaction tube (3.1) arranged on the vortex chamber (2), which, spatially speaking, is located particularly below the vortex chamber (2). The reaction tube (3.1) includes the second gas outlet (8), preferably at the base of the reaction tube (3.1), i.e., in the direction of gravity at the lower end of the reaction tube (3.1). The first gas outlet (6), which is located in the vortex chamber (2), and the second gas outlet (8) are preferably opposite each other.

[0068] The vortex chamber (2) is preferably round. The diameter of the vortex chamber (2) is preferably from 50 mm to 1000 mm. The longitudinal axes of the vortex chamber (2) and the reaction tube (3.1) preferably coincide. The ratio of the diameter of the vortex chamber (2) to the diameter of the reaction tube (3.1) is preferably from 1:1 to 1:3, particularly preferably from 1:1.1 to 1:1.5.

[0069] The reaction tube (3.1) further comprises at least one cathode (4). Multiple cathodes (4) may also be present. Between the at least one anode (5) and the at least one cathode (4), the plasma (C) required for the conversion of the reactant gas composition will then form, as mentioned. All other components of the flow reactor are grounded, in particular, independently of one another, in groups, or collectively. The at least one cathode (4) is preferably formed circumferentially in the central region of the tube reactor. The at least one cathode (4) can have a height of 800 to 1500 mm. Furthermore, a material thickness of 50 to 150 mm for the cathode (4) is preferred; a material thickness of 85 to 95 mm, including the annular gap for water cooling, is particularly preferred.

[0070] The plasma (C) is generated by applying an alternating voltage (AC) or a direct voltage (DC). The electrical power for generating and maintaining the plasma is preferably in the range of 200 kW to 10,000 kW, particularly preferably in the range of 6,500 to 8,000 kW. Core temperatures of up to 2,700 °C and higher can occur in the plasma (C). The vortex chamber (2), and in particular the arrangement of the preferably tangential gas inlet (1), serves to direct the gas flow.

[0071] 12 to impart a swirl to the reactant gas composition. The turbulence of the incoming reactant gas composition also keeps the plasma in motion, minimizing the risk of the cathode (4) burning out. Furthermore, this embodiment allows the flow reactor (0) to operate as a vortex, with the colder inner flows directed in the opposite direction to the hotter outer flows. The colder flows can cool the anode (5). The colder gas stream, consisting primarily of the reactant gas composition, can, if a cavity is arranged at the first gas outlet (6), return to the vortex chamber (2) or be discharged via a gas line through the first gas outlet (6) and optionally serve to preheat the reactant gas composition supplied to the gas inlet (1). The hotter reactant gas streams are directed into the reaction tube (3).1) are guided, reacted in the plasma, and exit the flow reactor at the second gas outlet (8) as a product gas composition. A flow resistance, in particular an impact-shaped element such as a cone or at least one plate, can preferably be arranged in the region of the second gas outlet. Alternatively or additionally, the second gas outlet can be configured as a confounder.

[0072] The product gas composition is preferably fed into the heat exchanger (20) via the second gas outlet (8), in particular to be cooled there to less than or equal to 600 °C, wherein the reactant gas composition is preferably heated to 700 °C, preferably greater than 700 °C or up to 1150 °C in the heat exchanger. A gas line leads from the heat exchanger (20) to the gas inlet (1), through which the reactant gas composition heated in the heat exchanger (20) reaches the flow reactor (0).

[0073] Due to the high temperatures, the reaction tube (3.1) may have a cooling system (9), preferably designed as a jacket cooling system. The reaction tube (3.1) is encased in an external cooling jacket. Cooling can be achieved using water, steam, oils, or coolants. The cooling is preferably carried out countercurrently to the flow of the reactant gas composition in the reaction tube. Furthermore, the reaction tube (3.1) may have an inlet for water and / or a monohydric alcohol and / or a quench before or in the region of the second gas outlet (8), which can serve to provide further cooling.

[0074] The device according to the invention can therefore be divided into at least three modules (M1, M2, M3). The device according to the invention comprises at least the following three modules M1, M2 and M3, wherein the first module (M1) comprises a mixing device (16) for producing the reactant gas composition, wherein the hydrocarbon-containing compound is supplied to the mixing device (16) via a hydrocarbon line (12), the carbon dioxide via a carbon dioxide line (13), the hydrogen via a hydrogen line (14), and optionally or additionally ammonia and water or steam via a water line (15), and mixed there, and the reactant gas composition is withdrawn from the mixing device (16) via the reactant gas line (17).

[0075] 13 wherein the first module (M1) comprises at least one first processor with which the composition or volume flow of the reactant gas composition is set, and at least one first computer interface via which the first module (M1) is integrated into a processor orchestration level (POL), wherein the at least one first processor can be controlled via the at least one first computer interface; the second module (M2) comprises the heat exchanger (20), wherein the reactant gas composition is fed to the heat exchanger (20) via the reactant gas line (17) and leaves the heat exchanger (20) via a supply line (10), and wherein the product gas composition is fed from the flow reactor (0) to the heat exchanger via the discharge (11), and energy in the form of thermal energy is transferred from the product gas composition to the reactant gas composition in the heat exchanger (20), wherein the second module (M2) comprises at least one second processor,with which the volume flow and / or the temperature of the reactant gas composition in the supply line (10) and / or the volume flow and / or the temperature of the product gas composition in the outlet (11) is controlled, and at least one second computer interface via which the second module (M2) is integrated into a processor orchestration level (POL), wherein the at least one second processor can be controlled via the at least one second computer interface; the third module (M3) comprises the flow reactor (0), wherein the reactant gas composition is supplied from the heat exchanger (20) via the supply line (10), is reacted in the flow reactor in a plasma at a gas temperature of greater than or equal to 1000 °C and a product gas composition leaves the flow reactor (0) via the outlet (11), wherein the third module comprises at least one third processor,with which the energy density of the plasma (C) and / or the residence time in the reaction tube (3.1) and optionally the cooling (9) in the flow reactor (0) is controlled as a function of the volume flow rate of the reactant gas composition in the feed line (10), the temperature of the reactant gas composition in the feed line (10) and / or the molar composition of the reactant gas composition in the feed line (10), and comprising at least one third computer interface via which the third module (M3) is integrated into a processor orchestration level (POL), wherein the at least one third processor can be controlled via the at least one third computer interface; and wherein the device comprises a processor orchestration level (POL) which serves for the integration and functional control of the at least one first module (M1), the at least one second module (M2) and / or the at least one third module (M3).

[0076] The device according to the invention further preferably comprises a fourth module M4. The optional 4th module

[0077] Module (M4) comprises a heat exchanger, wherein the product composition is supplied from the heat exchanger via the supply line from M3, in the heat exchanger at a 202000196 abroad

[0078] 14

[0079] The gas temperature of greater than 40 °C and less than or equal to 700 °C is cooled to 40 °C by means of a cooling medium and the product gas composition leaves the heat exchanger via the discharge pipe, wherein the fourth module comprises at least one fourth processor with which the energy density of the product gas composition, the temperature and / or the residence time in the heat exchanger and optionally the cooling in the heat exchanger is controlled as a function of the volume flow of the process gas composition in the supply pipe, the temperature of the reactant gas composition and / or the molar composition of the reactant gas composition in the supply pipe (10), and at least one fourth computer interface via which the fourth module (M4) is integrated into a processor orchestration level (POL), wherein the at least one fourth processor can be controlled via the at least one fourth computer interface;

[0080] According to the invention, it is preferred that the first module is connected to a gas reservoir or a pipeline, enabling a continuous supply to the hydrocarbon-containing compound. Furthermore, the individual modules are connected to one another via pipes and / or connections so that the steps of the process according to the invention can be carried out sequentially. The modular design allows the plant to be prefabricated quickly and easily in a single production facility and made available internationally. Thus, the modular plant can be prefabricated in Europe and easily installed at more distant locations with the hydrocarbon and / or carbon dioxide sources available there.

[0081] In the presence of a fourth module (M4), the device comprises a processor orchestration level (POL) which serves for the integration and functional control of the at least one first module (M1), the at least one second module (M2), the at least one third module (M3) and / or the fourth module (M4).

[0082] The first module is used to adjust or regulate the composition or volumetric flow rate of the reactant gas. This adjustment is performed via a processor. The corresponding setup and calibration are well-established in application engineering. The processor of the first module is integrated into a processor orchestration layer (POL) via a computer interface, enabling automated communication with the processors of the other modules.

[0083] The respective processor of the first, second, and / or third and / or fourth module, etc., preferably corresponds to a Module Type Package (MTP: according to VDI / VDE / NAMUR 2658) known to those skilled in the art, which defines the interfaces and functions of the automation technology and enables the integration of the module into a Processor Orchestration Level (POL). All modules can independently have control valves, so that the control valves can be actuated and regulated by the POL. 202000196 Abroad

[0084] 15

[0085] The Module Type Package (MTP) is a concept that can contribute to exploiting optimization potential in all phases from the planning to the operation of a process engineering plant.

[0086] It is preferred that each module of the system (first, second, and / or third module) has at least one processor-controlled and adjustable control valve per gas line. Advantageously, the first module includes independent control valves for adjusting the respective flow rate of the hydrocarbon line, carbon dioxide line, hydrogen line, and / or the optional water line.

[0087] The processor orchestration level (POL) therefore makes it possible to control the plant in such a way that, for example, a specified molar content and / or volume flow of carbon dioxide can be processed in the reactant gas composition, or a predetermined molar content of carbon monoxide and / or hydrogen can be achieved in the product gas composition.

[0088] Particularly preferably, the processor orchestration level (POL) is set such that in the first module the composition or the volume flow rate of the reactant gas composition, in the second module the volume flow rate of the reactant gas composition and / or the volume flow rate of the product gas composition, and in the third module the energy density of the plasma (C) and / or the residence time in the reaction tube (3.1) and optionally the cooling (9) in the flow reactor (0) are set as a function of the volume flow rate of the reactant gas composition, the temperature of the

[0089] The reactant gas composition and / or the molar composition of the reactant gas is regulated so that a predetermined content of carbon monoxide and / or hydrogen is obtained in the product gas composition. The reactant gas composition may contain other components: in the case of biogas, for example, in addition to water vapor, H₂S and NH₃.

[0090] After being removed from the second gas outlet (8) or from the heat exchanger (20), the product gas composition can be purified of acidic components such as H₂S and CO₂ and then used for further purposes. Other known uses of the produced synthesis gas or hydrogen include NH₃ synthesis, the aforementioned oxo synthesis, and / or alcohol synthesis (e.g., methanol and / or ethanol synthesis).

[0091] The device according to the invention can further comprise a plurality of flow reactors, i.e., more than one third module (M3). If several third modules (3) are present, a corresponding number of processors are available, each of which can be controlled independently of one another via the processor orchestration level (POL).

[0092] In a further preferred embodiment, the condition of the cathode can be checked and monitored by measuring resistance at regular or irregular intervals. The resistance measurement is a measure of the sooting or carbon deposits on the cathode. Depending on the sooting of the cathode, the hydrogen content in the respective reactant gas can be determined.

[0093] 16

[0094] The composition may be increased or decreased. It is possible that the resistance measurement could trigger a replacement of the cathode.

[0095] The invention is explained in more detail with reference to the embodiments shown in the figures, without limiting the invention to these embodiments. The figures show:

[0096] Fig. 1 : Flow diagram of the apparatus for producing the product gas composition comprising the first module (M1), the second module (M2) and the third module (M3).

[0097] Fig. 2: Longitudinal section of the flow reactor (0) with vortex chamber (2) and reaction tube (3.1) with cold gas outlet (A) and hot gas outlet (B).

[0098] Fig. 3: Cross-section of the vortex chamber (2) with gas inlet (1) and with flow device (21)

[0099] Fig. 4: Longitudinal section of the flow reactor (0) with vortex chamber (2) and reaction tube (3.1) with flow device (21) and formation of the plasma (C).

[0100] Figure 1 shows a flow diagram of a system with a flow reactor (0) and a heat exchanger (20). The components of the reactant gas composition, i.e., the carbon-containing compound via line (12), carbon dioxide via line (13), hydrogen via line (14), and optionally water or steam via line (15), are fed to the device (16) for the production of the reactant gas composition via lines (12, 13, 14, and 15). In the device (16), the components are mixed to form the reactant gas composition and fed via gas line (17) to the heat exchanger (20), where they are heated. After passing through the heat exchanger (20), the reactant gas composition exits via gas line (10) and is fed to the gas inlet (1) of the flow reactor (0). The reactant gas composition then advantageously already has a temperature of 1000 °C or higher.The product gas composition leaves the flow reactor (0) via gas line (11) at the second gas outlet (8, not shown) and is fed to the heat exchanger (20), where it is preferably cooled to approximately 700 °C by heat transfer to the reactant gas composition. The product gas composition then leaves the heat exchanger (20) via gas line (18). An additional cold gas stream is generated in the flow reactor (0), which is preferably only slightly cooler, i.e., by a few degrees Celsius, than the reactant gas composition at the gas inlet (1). This cold gas stream is drawn off via line (19) at the first gas outlet (6, not shown) and can be fed to the reactant gas composition for preheating, for example, in gas line (17) and / or to the reactant gas composition in gas line (10) (dashed lines originating from line (19) in Figure 1).It would also be possible for the cold gas stream in heat exchanger 20 to be mixed with the gas stream containing the reactant gas composition (not shown). Figure 1 also shows the first module (M1), the second module (M2), and the third module (M3) of the system. 202000196 Abroad.

[0101] 17

[0102] Figure 2 shows a schematic longitudinal section of the flow reactor (0). The longitudinal section cuts through the gas inlet (1). The reactant gas composition is fed as a gas stream into the vortex chamber (2) of the flow reactor (0) via the gas inlet (1). In the vortex chamber, the gas stream is swirled and from there enters the reaction chamber (3) of the reaction tube (3.1). At the lower end of the reaction tube (3.1) is a flow resistance (7), which is designed in particular as an impact-shaped body such as a conical body or consists of at least one plate. This transforms the flow reactor into a vortex tube. The gas stream forms a hot gas stream, which flows towards the second gas outlet (8) in the region of the hot gas outlet (B), and a cold gas stream, which flows in the opposite direction towards the first gas outlet (6) in the region of the cold gas outlet (A).The cold gas stream flows through the first gas outlet (6) to the at least one anode (5) and can flow around and cool it. The cold gas stream can then either flow back into the flow reactor (0) or be returned at the top of the reactor via the line (19) shown in Figure 1. A cooling system (9) is provided on the outside of the reaction tube (3.1), for example, a counter-rotating, circulating tube cooling system through which a cooling medium, such as water or oil, is passed.

[0103] Figure 3 shows a cross-section of the flow reactor (0) and the vortex chamber (2). The cross-section intersects the gas inlet (1). The reactant gas composition is supplied to the vortex chamber (2, not shown) as a gas stream via the gas inlet. The gas stream is fed tangentially to the vortex chamber (2) through at least one gas inlet (1), which is arranged perpendicular to the longitudinal center axis of the flow reactor (0) (tangential gas inlet (1.3)). From there, the gas stream enters an outer flow channel (22), from which gas channels (1.1) lead downwards in the flow direction. The gas channels (1.1) each have an inlet width (b.1) and an outlet width (b.2) and are located at the inner edge of the flow device (21) of the reaction tube (3.1). This transfers the gas stream into the inner vortex chamber (23). The gas channels (1.1) can be formed by walls (1.2) or blades.In alternative embodiments, several, for example 2 to 20, gas inlets (1) can also lead peripherally and radially, preferably symmetrically spaced, into the vortex chamber.

[0104] Figure 4 shows another schematic longitudinal section of the flow reactor (0) with its connection to the heat exchanger (20). The reactant gas composition is fed as a gas stream via the tangential gas inlet (1, 3) of the vortex chamber (2) with first gas outlet (6) and anode (5) and with flow device (21), and passes through the gas channels (1, 1, not shown here) into the inner vortex chamber (23). From the inner vortex chamber (23), the gas stream enters the reaction tube (3, 1). The vortex chamber (2) or the inner vortex chamber (23) and the reaction tube (3, 1) have a common longitudinal axis, which also forms the longitudinal axis of the entire flow reactor (0). The cathode (4), for example as a circumferential ring, is located in the reaction tube (3, 1). During operation, the plasma (C) forms between the cathode (4) and the anode (5).The resulting product gas composition is routed via the hot gas outlet (B) and the line (11) to the heat exchanger (20) and there used to heat the reactant gas composition, which is routed via the gas line (17) to the heat exchanger (20) and from there via the gas line (10) to the gas inlet 202000196 Abroad.

[0105] 18

[0106] (1) of the flow reactor (0) is used. A quench (24) may be provided in the area of ​​the hot gas outlet (B).

[0107] 202000196 Abroad

[0108] 19

[0109] Reference symbol:

[0110] A cold gas outlet

[0111] B Hot gas outlet

[0112] C Plasma (Arc)

[0113] M1 first module

[0114] M2 second module

[0115] M3 third module

[0116] 0 Flow reactor

[0117] 1 Gas inlet

[0118] 1.1 Gas channel b1 Width of inlet to gas channel b2 Width of outlet to gas channel

[0119] 1.2 Wall or shovel

[0120] 1.3 tangential gas inlet

[0121] 2 Vortex chambers, especially vortex chambers

[0122] 3. Reaction chamber, reaction chamber in tubular reactor

[0123] 3.1 Reaction tube

[0124] 4 Cathode

[0125] 5 Anode

[0126] 6 first gas outlet

[0127] 7 Flow resistance

[0128] 8 second gas outlet

[0129] 9 Cooling of the flow reactor

[0130] 10 Gas line to gas inlet (1)

[0131] 11 Gas line to heat exchanger (20)

[0132] 12. Line for the carbon-containing compound, hydrocarbon line

[0133] 13 Carbon dioxide pipeline

[0134] 14 Hydrogen pipeline

[0135] 15 optional water pipes

[0136] 16 Mixing device for producing the reactant gas composition

[0137] 17 Edult gas line for the reactant gas composition to the heat exchanger (20)

[0138] 18 Gas line product gas composition from the heat exchanger

[0139] 19 Gas line product gas composition from the first gas outlet flow reactor into heat exchanger 20,

[0140] 20 heat exchangers

[0141] 21 Flow device

[0142] 22 outer flow channel

[0143] 23 inner vertebral chamber

[0144] 24 Quench or water supply 202000196 Abroad

[0145] 20

[0146] The present invention is described with reference to the following examples.

[0147] Synthesis gas production is differentiated according to a) water gas, which is obtained from coal and steam (C + H2O) (CO + H2), b) producer gas (air gas), which is obtained from coal and air. CO), and c) cracked gas obtained from the cracking of natural gas and petroleum (CH4+ CO + 3 H2).

[0148] Depending on the intended use, a distinction is made between

[0149] 1.) Synthesis gas (CO + 2 H2) for methanol production,

[0150] 2.) Synthesis gas (N2 + 3 H2) for ammonia production and

[0151] 3.) Synthesis gas (CO + H2) for oxo synthesis.

[0152] Example 1 (not according to the invention)

[0153] One kilogram of synthesis gas is produced by steam reforming from the input of 0.47 kg of methane and 0.53 kg of steam into a heated catalytic reactor. The reaction between methane and steam takes place at high temperatures (approx. 700 to 1000°C) and high pressure (approx. 20 to 30 bar) to form synthesis gas according to the following reactions:

[0154] CH4 + H2O CO + 3H2

[0155] CO2 + H2 → CO + H2O

[0156] The synthesis gas leaving the reactor is gradually cooled in heat exchangers.

[0157] Case A)

[0158] The resulting synthesis gas consists of a mixture of 84.8 wt% carbon monoxide (CO) and 15.2 wt% hydrogen (H₂), corresponding to a ratio of approximately 1:2.5. The specific energy input for the processing is around 3 kWh / kg synthesis gas, which is provided by the oxidation of methane.

[0159] The CO2 balance of synthesis gas production via steam reforming, using 3 kWh / kg synthesis gas, results in a value of 186.9 kg CO2 / 100 kg synthesis gas. This is composed of the CO2 footprint of the carbon monoxide in the synthesis gas itself, amounting to 133.3 kg CO2 / 100 kg synthesis gas (calculated as 84.8 kg 00*44 / 28 = 133.2 kg), and 300 kWh / 100 kg synthesis gas from methane, which is converted to CO2 and water with energy release. This 300 kWh of thermal energy can be provided by 18.9 kg CH4 (300 kWh / 15.4 kWh / kg CH4 = 19.5 kg CH4). Through oxidation, the carbon is converted into 51.9 kg CO2 (19.5 kg * 44 / 16 = 53.6 kg CO2).

[0160] In case A, the CO2 footprint of 100kg synthesis gas is 186.9 kg CO2 (133.3kg + 53.6kg = 186.9kg).

[0161] Case B)

[0162] For synthesis gas with a ratio of 1:1, the calculation looks like this:

[0163] 93.5 wt% CO and 6.5 wt% H2. The CO2 footprint of CO for 100 kg of synthesis gas is then 146.9 kg CO2 (93.5 kg * 44 / 28 = 146.9 kg). An additional 53.6 kg CO2 is required for energy production. In case B, the CO2 footprint of 100 kg of synthesis gas is 200.5 kg CO2 (146.9 kg + 53.6 kg = 200.5 kg). 202000196 Abroad

[0164] 21

[0165] Due to the process, steam reforming in case B produces an excess of H2 amounting to 8.7 kg H2. Emissions can be attributed to this excess, which can be determined based on their energy value: 108.7 kg of synthesis gas has a calorific value (energy content) of 108.7 kWh / kg. This results in the following energy values: 93.5 kg CO2 + 15.2 kg H2 -> 93.5 * 2.8 kWh / kg CO2 + 15.2 kg H2 * 39.3 kWh / kg H2 = 262 kWh + 597 kWh = 859 kWh. The excess hydrogen of 8.7 kg H2 has an energy content of 346 kWh. This yields 346 kWh / 859 kWh * 200.5 kg CO2 = 81 kg CO2, weighted by the 8.7 kg excess, resulting in 8.7 / 15.2 * 80 kg CO2 = 46.2 kg CO2. Therefore, the CO2 footprint of 100kg synthesis gas (CO:H2 1 :1) is 200.5kg CO2 - 46.2kg CO2 = 154.3kg CO2.

[0166] Example 2 (according to the invention)

[0167] In the process according to the invention, synthesis gas (CO:H₂ 1:1) for oxo synthesis is produced by feeding methane and carbon dioxide into a plasma reactor. The corresponding arrangement is shown in Figure 1. The synthesis gas produced can be used as a raw material for the production of chemical products, such as those obtained through oxo synthesis.

[0168] The plasma reactor (0) according to Figure 1 is operated by a power supply with an electrical output of approximately 260 kW. The reactant gas composition (17) consists of the individual reactant partial streams (12), (13) and (14). The reactant gas composition (17) is specified by means of mass flow controllers (MFCs) (MFC-CO2 (12), MFC-CH4 (13), MFC-H2 (14); column “Reactants in g / h” in Table 2) and monitored by means of GC analysis. The individual flows are combined and mixed in the mixer (16), and the reactant gas composition (17) thus formed is passed through a variable area flow meter to determine the total volumetric flow rate. This can be determined, as is known to those skilled in the art, e.g., by summing the molar fractions. The gas chromatograph (GC) is calibrated with gas mixtures in mol% under standard conditions (e.g., two-point calibration). Two-point calibration was also performed for the temperature measurements.For process temperatures below 1000°C, standard platinum or thermocouple sensors were used. For temperatures above 1000°C, special thermocouple sensors for extreme temperatures (up to 2315°C) were used. The thermocouple itself can be made of either platinum / rhodium (types R, S, B) or tungsten / rhenium (types C, G, D). Various materials are available for the insulation and sheath, depending on the application. Depending on the sheath material, the thermocouple sensors can be used in chemically inert, oxidizing, or reducing environments, or in a vacuum. The maximum operating temperature is determined by the material with the lowest temperature limit. The temperature can also be determined using commercially available infrared sensors. 202000196 Abroad.

[0169] 22

[0170] Table 2: Molar fractions (column “Mol-%”) for the reactant gas composition (17) at room temperature and standard pressure (25°C, 1 bar absolute)

[0171] In the present example, a gas discharge with a power density of approximately 0.7 kW / cm² was generated between the electrodes in the plasma reactor (0). 3The cold reactant gas (17) was preheated to approximately 500°C in the heat exchanger (20). The preheated reactant gas stream (10) entered the plasma reactor (0), where the chemical reaction to form the products took place. The product stream (11) had a gas temperature of approximately 1500°C at the outlet of the plasma reactor (0). The product stream (11) was then directed to the hot gas side of the heat exchanger (20) and exited as a cooled product gas (18). The gas temperature of the product (18) at the outlet of the heat exchanger (20) was approximately 700°C. After further cooling of the product (18) to approximately 25°C, the mass flow rate was determined using a Coriolis mass flow meter. Correspondingly, the volumetric flow rate was determined using a variable area flow meter. The composition of the product gas composition (18) was determined by GC analysis of the process gases (see Table 3).For this purpose, the GC was calibrated with gas mixtures in mol% under standard conditions. To determine the volumetric flow rate of carbon monoxide, the total volumetric flow rate is weighted by the molar fraction from the GC analysis. The volumetric flow rate thus determined can then be converted into a corresponding mass flow rate using the molar mass.

[0172] 202000196 Abroad

[0173] 23

[0174] Table 3: Composition of the product gas stream at room temperature and normal pressure (25°C, 1 bar absolute) By subtracting the masses in Table 2 (reactant gas composition) and Table 3 (product gas composition), the mass differences in the individual substance categories (CO2, CH4, CO, H2) are obtained. The mass conversion is then calculated by quotienting the values ​​in each category. Table 4: Mass difference and mass conversion

[0175] The electrical current used for the gas discharge in the inventive example has a specific CO2 footprint between 0.025 kg CO2 / kWh and 0.0073 kg CO2 / kWh. For electricity from Norway, an official CO2 footprint of approximately 0.025 kg CO2 / kWh is reported; for offshore wind power in Germany, a specific CO2 footprint of 0.0073 kg CO2 / kWh is cited.

[0176] Based on the previously listed table values, a power consumption of 260 kWh results in an electrical energy input of 260 kW for one hour. This process converts 31.569 kg / h CO2 and 11.767 kg / h CH4 into 40.682 kg / h CO2 and 2.941 kg H2, totaling 43.336 kg / h synthesis gas.

[0177] 24. One obtains a specific value of 6 kWh of electricity per kg of synthesis gas (calculated: 260 kW / 43.336 kg / h = 6 kWh per kg of synthesis gas).

[0178] In the process according to the invention, approximately 4.4 kg CO2 / 100 kg synthesis gas is emitted per 100 kg of synthesis gas by the offshore wind power required for plasma generation (calculation: 6 kWh / kg synthesis gas * 100 kg synthesis gas * 0.0073 kg CO2 / kWh = 4.4 kg CO2), which represents a reduction of 47.5 kg CO2 / 100 kg synthesis gas compared to steam reforming (calculated: 51.9 kg CO2 / 100 kg synthesis gas - 4.4 kg CO2 / 100 kg synthesis gas = 47.5 kg CO2 / 100 kg synthesis gas). Because CO2 is used as a raw material in the process according to the invention, the CO2 footprint is further reduced by (31.569 * 2.3 =) 72.9 kg CO2 / 100 kg synthesis gas. The total savings therefore amount to (47.5 kg CO2 + 72.9 kg CO2 =) 120.4 kg CO2 / 0 kg synthesis gas. This corresponds to a percentage reduction of approximately 78%.

Claims

202000196 Abroad 25 Patent claims 1. A process for producing a product gas composition comprising at least carbon monoxide and hydrogen by reacting a reactant gas composition in a plasma at a reactant gas composition temperature of greater than or equal to 1000 °C, wherein the reactant gas composition Hydrogen or a hydrogen-containing gas mixture; comprising at least one hydrocarbon compound selected from the group consisting of methane, ethane, ethene, propane, butane, 2-methylpropane, pentane, n-pentane, isopentane and / or neopentane, methanol, ethanol and mixtures of two or more thereof, and at least one oxidizing agent selected from the group consisting of carbon dioxide and a mixture comprising carbon dioxide and water.

2. The method of claim 1, wherein the hydrocarbon-containing compound is methane, ethane, methanol, ethanol or a mixture of two or more of the aforementioned compounds.

3. The method of claim 2, wherein the hydrocarbon-containing compound is methane, methanol or a mixture of methane and methanol.

4. Method according to one of the preceding claims, wherein the method is carried out in a flow reactor (0) comprising a gas inlet (1), a first gas outlet (6) and a second gas outlet (8), wherein the reactant gas composition is supplied via the gas inlet (1), reacted in the flow reactor and the product gas composition is discharged via the second gas outlet (8).

5. Method according to claim 4, wherein the gas inlet (1) and the first gas outlet (6) are arranged on a swirl chamber (2) of the flow reactor (0), and wherein the flow reactor (0) has a reaction tube (3.1) with a second gas outlet (8) and preferably the first (6) and the second gas outlet (8) of the flow reactor (0) are opposite each other.

6. Method according to one of the preceding claims, wherein the feed gas composition is supplied to the flow reactor (0) via a tangential gas inlet (1 .3) at the vortex chamber (2).

7. A method according to any of the preceding claims, wherein the reaction of the reactant gas composition takes place at a temperature greater than or equal to 1300 °C, preferably greater than or equal to 1500 °C, particularly preferably greater than or equal to 1800 °C. 202000196 Abroad 26 8. Method according to one of the preceding claims, wherein the flow reactor (0) comprises an anode (5) and a cathode (4), wherein the anode is arranged at the vortex chamber (2) in the direction of the first gas outlet (6) and the cathode (4) is arranged in the reaction tube (3.1) and the plasma (C) is formed between the anode (5) and the cathode (4).

9. A method according to any of the preceding claims, wherein the product gas composition contains carbon monoxide and hydrogen in a molar ratio (CO : H2) of 1 : 5 to 0.5 : 1, preferably of 1 : 2 to 1 : 4, particularly preferably of 0.75 to 1.25 :

1.

10. A method according to any of the preceding claims, wherein the method is operated continuously.

11. Method according to any of the preceding claims, wherein the reactant gas composition is 60 to 80 vol.% hydrogen; 10 to 20 vol% at least one hydrocarbon-containing compound; and Contains at least one oxidizing agent in 10 to 20 vol%, wherein the total composition of the reactant gas is 100 vol%.

12. Device for producing a product gas composition comprising at least carbon monoxide and hydrogen, the device comprising a flow reactor (0) with a first gas inlet (1), a first gas outlet (6), a second gas outlet (8), at least one anode (5) and at least one cathode (4) for generating a plasma (C) and at least one heat exchanger (20), , wherein the flow reactor (0) comprises a vortex chamber (2) with a tangential gas inlet (1.3), the first gas outlet (6), and the at least one anode (5), and a reaction tube (3.1) arranged on the vortex chamber, preferably a reaction tube (3.1) oriented in the direction of gravity or vertically to the ground, with the second gas outlet (8) and the at least one cathode (4), wherein the at least one anode (5) is arranged axially in the vortex chamber (2) or axially in the first gas outlet (6) of the vortex chamber, and the at least one cathode (4) is arranged in the reaction tube (3.1), and the reactant gas composition passes through the heat exchanger (20) before being fed to the vortex chamber (2), and a discharge (1 1) is arranged at the second gas outlet (8) through which the product gas composition is guided through the heat exchanger (20), wherein in the 202000196 Abroad 27 Heat exchanger (20) Energy in the form of heat energy is transferred from the product gas composition to the reactant gas composition.

13. Device according to claim 12, wherein the reaction tube (3.1) has a cooling system (9) which is preferably designed as a jacket cooling system.

14. Device according to claim 13, wherein the device comprises at least the following three modules M1, M2 and M3, wherein the first module (M1) comprises a mixing device (16) for producing the reactant gas composition, wherein the hydrocarbon-containing compound is supplied via a hydrocarbon line (12), the carbon dioxide via a carbon dioxide line (13), the hydrogen via a hydrogen line (14) and optionally or additionally ammonia and water or steam via a water line (15) to the mixing device (16) and mixed there and out of the mixing device (16) the reactant gas composition is extracted via the reactant gas line (17), wherein the first module (M1) comprises at least one first processor with which the composition or volume flow of the reactant gas composition is set, and at least one first computer interface via which the first module (M1) is integrated into a processor orchestration level (POL), wherein the at least one first processor can be controlled via the at least one first computer interface; the second module (M2) comprises the heat exchanger (20),wherein the reactant gas composition is fed to the heat exchanger (20) via the reactant gas line (17) and leaves the heat exchanger (20) via a supply line (10) and wherein the product gas composition is fed from the flow reactor (0) to the heat exchanger via the discharge (11) and energy in the form of heat energy is transferred from the product gas composition to the reactant gas composition in the heat exchanger (20) wherein the second module (M2) has at least one second processor with which the volume flow and / or the temperature of the reactant gas composition in the supply line (10) and / or the volume flow and / or the temperature of the product gas composition in the discharge (11) is controlled, and at least one second computer interface via which the second module (M2) is integrated into a processor orchestration level (POL), wherein the at least one first processor can be controlled via the at least one second computer interface,comprising; the third module (M3) comprising the flow reactor (0), wherein the reactant gas composition is supplied from the heat exchanger (20) via the inlet (10), is reacted in the flow reactor in a plasma at a gas temperature greater than or equal to 1000 °C and a product gas composition leaves the flow reactor (0) via the outlet (11), wherein the third module includes at least a third processor with which the energy density of the plasma (C) and / or the residence time in the reaction tube (3.1) and optionally the cooling (9) in the, 202000196 Abroad 28 Flow reactor (0) is controlled as a function of the volume flow rate of the reactant gas composition in the supply line (10), the temperature of the reactant gas composition in the supply line (10) and / or the molar composition of the reactant gas composition in the supply line (10), and at least one third computer interface, via which the third module (M3) is integrated into a processor orchestration level (POL), wherein the at least one first The device comprises a processor via which at least one third computer interface can be controlled; and wherein the device comprises a processor orchestration level (POL) that serves for the integration and functional control of the at least one first module (M1), the at least one second module (M2) and / or the at least one third module (M3).

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