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  • C25B1/00—Electrolytic production of inorganic compounds or non-metals
  • C25B1/01—Products
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  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology

Definitions

• the present invention includes a process for the production of hydrogen, which is characterized in that in a first stage hydrocarbons are decomposed into solid carbon and into a hydrogen-containing, gaseous product mixture, the hydrogen-containing, gaseous product mixture, which has a composition with regard to the main components CH4 , N2 and H2 from 20 to 95% by volume of H2 and 80 to 5% by volume of CH4 and / or N2, is discharged from the first stage at a temperature of 50 to 300 ° C and at a temperature, which differs from this outlet temperature by a maximum of 100 ° C, is fed into an electrochemical separation process and in this second stage the hydrogen-containing product mixture in the electrochemical separation process at a temperature of 50 to 200 ° C in hydrogen with a purity of> 99 , 99 vol .-% and a remaining residual gas mixture is separated.
• Hydrogen offers the desired prerequisites to become a key factor for the energy supply of the future.
• the transport sector in particular is facing the great challenge of becoming more climate-friendly. In Germany, traffic is responsible for almost 20 percent of total CO2 emissions, a good half of which is accounted for by private transport.
• the transport sector can reduce its dependence on petroleum-based fuels.
• hydrogen is being introduced as a new fuel that does not produce any local pollutants when used with fuel cell technology.
• Hydrogen is currently mainly produced locally in comparatively large Steam-Methane Reforming (SMR) production units and the hydrogen is separated from the gas mixtures produced by means of pressure swing adsorption.
• the pressure swing adsorption technology is limited to hydrogen-rich gases (depending on the accompanying gases, preferably> 50% by volume); Furthermore, only 70 to 85% of the hydrogen is separated off, the remaining hydrogen being required for the desorption of the accompanying components.
• the separated hydrogen is liquefied or compressed and by means of appropriate Transport vehicles with high pressure tanks (500 bar) brought to the place where it is needed, for example a hydrogen filling station.
• electrolysis is a membrane process and, because of its low economy-of-scale (cost advantages due to the size of the company), is more suitable for small systems than for large ones.
• the reason for the limited economy-of-scale is the direct dependence of the capacity on the electrochemically active surface, which in turn translates into a corresponding number of membrane-electrode units and stacks.
• the electrolytic splitting of water into hydrogen and oxygen requires at least 6 times as much energy as the thermal splitting of hydrocarbons into hydrogen and carbon. In the case of electrolysis, this energy must be made available in the form of electricity. Even with a small carbon footprint of the electricity generated, electrolysis hydrogen is associated with a higher carbon footprint than pyrolysis hydrogen [O. Machhammer, A. Bode, W. Hormuth, “Financial and Ecological Evaluation of Hydrogen Production Processes on Large Scale”, Chem. Ing. Tech. 2015, 87, no. 4, 409]
• system factor In world-scale systems, the system factor is in the order of three. Will the production capacity be reduced by the If the system concept remains the same and smaller machines and devices are used, the system factor can increase to 10.
• Pyrolysis is a thermal process with the help of which hydrogen and high-purity carbon can be produced from hydrocarbons (e.g. from natural gas) with a low carbon footprint. Pyrolysis is a thermal equilibrium process that requires energy. Since the number of moles in the gas phase increases with the conversion, the conversion is higher the higher the temperature and the lower the H2 partial pressure. The pyrolysis of hydrocarbons therefore takes place at high temperatures in the range of 800 and 1600 ° C; in the case of high-temperature plasma processes even more.
• the carbon (pyrolysis carbon) is obtained in a highly pure form and can be used in high-price segments, e.g. as electrode material or as a preliminary product for the production of graphite for Li-ion batteries.
• a gaseous heat transfer medium is proposed in WO2013 / 004398A2. This is preferably an H2 or N2-rich gas that is heated in an external combustion chamber and introduced into the pyrolysis zone.
• US2982622 describes a resistance heated fluidized bed process.
• the electrical conductivity of carbon is used to resistively heat a fluidized bed made of carbon particles.
• the process is implemented in a moving bed reactor, with the solid particles following gravity from top to bottom and the natural gas to be split being passed through the reactor from bottom to top.
• WO2018 / 083002 A1 describes a cyclical mode of operation with a combination of a reactor and a regenerator. Carrier particles are cycled through the reactor.
• the regenerator is filled with inert material.
• the reactor and regenerator are connected to one another via a combustion chamber in which part of the pyrolytically generated hydrogen is burned with air or O2 to cover the required energy. With this current conduction, all products leave the apparatus in a cooled state.
• thermocatalytic decomposition of methane [Smolinka, T .; Günther, M. (Fraunhofer ISE); Garche, J. (FCBAT): NOW study “Stand und Development potential of water electrolysis for the production of hydrogen from renewable energies ", revision of 05.07.2011], the purely thermal decomposition of methane in liquid metals [AM Bazzanella, F. Ausfelder," Low carbon energy and feedstock for the European chemical industry ”, DECH EM A-Technology study, June 20172]
• the electrochemical hydrogen separation (EHS) is an electrochemical process that relies on the transport of protons (H + ions) through ion-conductive membranes and represents a new application of fuel cell technology (see WO 2016/50500 and WO 2010/115786).
• the hydrogen-containing mixture enters the anodic chamber, where it is oxidized to protons and electrons.
• An electrical power supply provides the driving force to transport the protons through the catalyzed membrane, where they combine to form "new" hydrogen at the cathode (also known as "developing the hydrogen” at the electrode) Protons are transported, the other components of the gas mixture remain in the exhaust system.
• the EHS is therefore able to produce hydrogen with a high degree of purity (> 99.99% H2).
• This high degree of purity as is necessary for fuel cells, for example other H2 separation processes, e.g. cryogenic gas separation (cold box), pressure swing adsorption (PSA), temperature swing adsorption (TSA) and conventional membrane separation technology with hydrogen-selective metal membranes (e.g. palladium, palladium alloys), only with very expensive.
• Adsorption processes such as PSA or TSA are based, among other things, on the effect that substances can be adsorbed better the easier they condense. Since hydrogen has the lowest tendency to condense of all gases, all gas components are adsorbed in front of it, i.e. separated from the gas flow. This relationship between condensation or temperature and adsorption tendency explains why it is easier to separate C02 or CH4 from H2 than 02 or N2.
• the sequence of the boiling temperatures at ambient pressure is: C02 (-78 ° C), CH4 (-162 ° C), 02 (-183 ° C), N2 (-196 ° C), H2 (-252 ° C).
• the concentration of the accompanying hydrogen components in the pyrolysis product flow is low (e.g. ⁇ approx. 25 mol%) and the accompanying components are easily adsorbed in the product flow (eg CH4), hydrogen can then be obtained economically from this product stream with the help of the two separation technologies PSA or TSA in a purity of up to 99.9%.
• the EHS is the more economical separation method.
• the EHS process is a surface process, as the membrane area of a single cell is limited to 25 to 3000 cm 2 .
• An increase in capacity can only be achieved by increasing the number of cells. This means that a plant with a large capacity is specifically not significantly cheaper than a plant with a small capacity. In other words: the EHS only has a small economy-of-scale. For the profitability of the EHS, it is also irrelevant how well the accompanying components can be condensed.
• the challenge for the future lies, among other things, in the development of small, flexible and cost-effective systems that can be installed directly on site, e.g. B. installed at the hydrogen filling station, short-term and possibly transient high-purity hydrogen, especially with a low CO2 footprint, can be generated.
• a process concept is therefore sought that, despite a small production capacity, has a small system factor and thus has a low specific investment. Furthermore, the process concept should accommodate as many process steps as possible in a few apparatuses and have the lowest possible specific heat transfer capacity.
• Process for the production of hydrogen characterized in that in a first stage hydrocarbons are decomposed into solid carbon and into a hydrogen-containing, gaseous product mixture, the hydrogen-containing, gaseous product mixture, which has a composition with regard to the main components CH4, N2 and H2 from 20 to 95% by volume of H2 and 80 to 5% by volume of CH4 and / or N2, is discharged from the first stage at a temperature of 50 to 300 ° C and at a temperature that is at most 100 ° C from This exit temperature differs, is fed into an electrochemical separation process and in this second stage the hydrogen-containing product mixture in the electrochemical hydrogen separation membrane process at a temperature of 50 to 200 ° C in hydrogen with a purity of> 99.99% and a remaining residual gas mixture is separated.
• the hydrogen-containing product mixture is advantageously fed to the anodic side of a membrane-electrode arrangement, then at least part of the hydrogen contained in the product gas is electrochemically separated by means of the membrane-electrode arrangement, with at least one on the anodic side of the membrane Part of the hydrogen is oxidized to protons on an anode catalyst and the protons are reduced to hydrogen after crossing the membrane on the cathode side on the cathode catalyst.
• Low-cost methane pyrolysis is more productive than the use of decentralized electrolysis, mini-SMR or central H2 production in world-scale systems in conjunction with transport to the gas station.
• Low-cost pyrolysis is to be understood as a pyrolysis which, due to the combination with an EHS, is subject to lower process-related constraints than a stand-alone pyrolysis.
• the methane conversion can be lower, preferably 30% to 99.9%, particularly preferably 65% to 99.0%, in particular 85% to 98%.
• the pyrolysis can be carried out at lower temperatures, preferably from 650 to 1200 °, particularly preferably from 750 to 1100 ° C., preferably from 800 to 1100 ° C., preferably from 900 to 1050 ° C., in particular from 950 to 1050 ° C., higher pressures , preferably at 1 to 30 bar, particularly preferably at 1 to 10 bar, in particular at 1 to 5 bar and / or with shorter residence times of advantageously 1 s-5 min, preferably 1-30 s, in particular 1-5 s become.
• the reaction temperature is preferably from 1100 to 1200 ° C and the residence time from 1 to 5 s or the reaction temperature from 1000 to 1100 ° C and the residence time from 5 s to 30 s or the reaction temperature from 900 to 1000 ° C and the Residence time at 30 s to 1 minute or the reaction temperature at 750 to 900 ° C and the residence time at 1 to 5 minutes.
• methane content in the product gas of the pyrolysis has no major influence on the economic efficiency makes it easier to promote the cycle for the pyrolysis carbon, which is necessary for the integration of heat.
• Methane natural gas
• leaks between the process areas in the pyrolysis apparatus only play a subordinate role.
• EHS electrochemical hydrogen separation membrane process
• the (thermal) decomposition of hydrocarbons to solid carbon and hydrogen-containing, gaseous product mixture all pyrolysis processes known to those skilled in (thermal) decomposition technology can be used.
• the energy required for the decomposition is preferably made available autothermally, via low-temperature plasma and / or with the aid of electrical resistance heating.
• the form of the energy input is responsible for the variable costs of thermal decomposition.
• the sub-stoichiometric combustion of hydrocarbons with air is more favorable in this context than the sub-stoichiometric combustion with pure oxygen or the use of electric current, since some of the hydrocarbons are reformed to CO and not pyrolyzed to carbon.
• atmospheric nitrogen (N2) in the gas flow lowers the partial pressure of the hydrogen and thereby increases the equilibrium conversion.
• the hydrogen-containing, gaseous product mixture formed during the decomposition of hydrocarbons advantageously has the following composition with regard to the two main components CH4, N2 and H2 in% by volume: 10 to 99% by volume of H2 and 90 to 1% by volume are advantageous CH4 and / or N2, preferably 20 to 95% by volume of H2 and 80 to 5% by volume of CH4 and / or N2, preferably 40 to 90% by volume of H2 and 60 to 10% by volume of CH4 and / or N2, preferably 65 to 90% by volume of H2 and 35 to 10% by volume of CH4 and / or N2, preferably 80 to 90% by volume of H2 and 20 to 10% by volume of CH4 and / or N2.
• the pyrolysis carbon is mainly deposited as a compact layer on the carrier surface. If the carrier surface is hotter than the gas volume, this mechanism is reinforced.
• soot is formed, i.e. a large number of very small pyrolysis carbon particles that can block the entire reactor volume in extreme cases. Soot formation is increased by high gas temperatures and pressures. If soot is formed, for reasons of good heat integration it should be separated from the gas stream at the reaction temperature if possible, for example by: cyclones, filters and / or beds.
• debris acts like depth filters.
• the pyrolysis carbon covers the surfaces of the bulk particles and closes the intermediate volumes over time. If the pressure loss over the bed becomes too great, the bed must be replaced with fresh, unoccupied particles.
• a thermal decomposition of hydrocarbons operated with the aid of low-temperature plasma is known to the person skilled in the art of low-temperature plasma technology and, for example, in “Methane Conversion in Low-Temperature Plasma” by Pushkarev et al in High Energy Chemistry, 2009, Vol. 43, No. 3, pages 156-162.
• thermal pyrolysis requires high reaction temperatures (> 1000 ° C).
• the energy required to warm up the gas flow used is in the order of magnitude of the pyrolysis reaction enthalpy. Therefore, the highest possible heat integration is advantageous, so that, for example, the cooling of the hot product streams is used to heat the feed streams.
• a regenerative heat exchange is advantageous because it opens up the possibility of removing the pyrolysis carbon from the process at the same time as the heat exchange.
• the temperatures of the pyrolysis process are advantageously between 1000 and 1600.degree. C., in particular between 1100 and 1300.degree.
• the pressure of the pyrolysis process is preferably 1 to 10 bar, in particular 1 to 5 bar.
• the thermal conversion is advantageously carried out in the presence of solid support materials, preferably heat transfer materials, on which the carbon formed in the splitting reaction of the hydrocarbons is mainly deposited, in particular greater than 90% of the maximum pyrolysable carbon content.
• solid supports can be used for regenerative heat integration.
• the thermal decomposition can advantageously be carried out in a fixed bed, fluidized bed or moving bed reactor, the term “fluidized bed” also being understood to mean a production bed if the solid reactor contents in the reaction zone are at least partially fluidized and above and / or below the Reaction zone the solid contents of the reactor are moving, but no longer fluidized.
• the carrier is preferably passed through the reaction space as a moving bed, the hydrocarbons to be decomposed being passed in countercurrent to the carrier.
• the reaction space is advantageously designed as a vertical shaft, possibly as a conical shaft, so that the Movement of the moving bed comes about solely under the action of gravity.
• the Wan derbett is advantageously homogeneous and evenly flow through.
• the support materials of this reaction bed are advantageously temperature-resistant in the range from 1000 to 1800.degree. C., preferably from 1300 to 1800.degree. C., particularly preferably from 1500 to 1800.degree. C., in particular from 1600 to 1800.degree.
• Ceramic carrier particles in particular materials according to DIN EN 60 672-3 such as alkali aluminum silicates, magnesium silicates, titanates, alkaline earth aluminum silicates, aluminum and magnesium silicates, mullite, aluminum oxide, magnesium oxide and / or zirconium oxide are advantageous as temperature-resistant carrier materials .
• non-standardized ceramic high-performance materials such as quartz glass, silicon carbide, boron carbide and / or nitrides can serve as temperature-resistant carrier materials. These heat transfer materials can have different expansion capacities compared to the carbon deposited on them.
• a carbon-containing granulate is understood to mean a material which advantageously consists of solid grains.
• the carbon-containing granules are advantageously spherical.
• the granulate advantageously has a grain size, ie an equivalent diameter, which can be determined by sieving with a certain mesh size, of 0.05 to 100 mm, preferably 0.1 to 50 mm, more preferably 0.2 to 10 mm, in particular 0, 5 to 5 mm.
• a large number of different carbon-containing granules can be used.
• Such granules can consist predominantly of coal, coke, coke breeze and / or mixtures thereof, for example.
• the carbon-containing granulate can contain 0 to 15% by weight based on the total mass of the granulate, preferably 0 to 5% by weight, of metal, metal oxide and / or ceramic.
• the ATP is advantageously carried out at temperatures between 500.degree. C. and 1500.degree. C., preferably between 600.degree. C. and 1300.degree. C., particularly preferably between 700.degree. C. and 1200.degree.
• the pressures are advantageously between 1 and 10 bar, preferably between 1 and 5 bar and particularly preferably between 1 and 3 bar.
• the temperature can advantageously be lower and thus the turnover can be lower and air can advantageously be used instead of expensive pure oxygen, because neither a high methane content nor a high N2 content in the pyrolysis product gas reduces the profitability of the EHS in contrast to PSA.
• the temperature is from 650 to 1200 °, preferably from 750 to 1100 ° C, in particular from 800 to 1000 ° C.
• the pressure is from 1 to 30 bar, particularly preferably from 1 to 10 bar, in particular from 1 to 5 bar.
• Suitable carrier materials are e.g. ceramic carrier particles, in particular materials according to DIN EN 60 672-3 such as alkali aluminum silicates, magnesium silicates, titanates, alkaline earth aluminum silicates, aluminum and magnesium silicates, mullite, aluminum oxide, magnesium oxide and / or zirconium oxide.
• non-standardized high-performance ceramic materials such as quartz glass, silicon carbide, boron carbide and / or nitrides can serve as temperature-resistant carrier materials. These heat transfer materials can have different expansion capacities compared to the carbon deposited on them.
• the use of carbonaceous material as granules is particularly preferred.
• a carbon-containing granulate is to be understood as a material which advantageously consists of solid grains.
• the carbon-containing granules are advantageously spherical.
• the granulate advantageously has a grain size, ie an equivalent diameter, which can be determined by sieving with a certain mesh size, of 0.05 to 100 mm, preferably 0.1 to 50 mm, more preferably 0.2 to 10 mm, in particular 0, 5 to 5 mm.
• a large number of different carbon-containing granules can be used.
• Such granules can consist predominantly of coal, coke, coke breeze and / or mixtures thereof, for example.
• the carbon-containing granulate can contain 0 to 15% by weight based on the total mass of the granulate, preferably 0 to 5% by weight, of metal, metal oxide and / or ceramic.
• the ATP offers the best prerequisites for low-cost pyrolysis in combination with the EHS:
• the energy input takes place advantageously through combustion of the educt or product gases with air. This means that neither expensive electricity nor expensive pure oxygen is required for the input of energy needed.
• a reactor concept is proposed that is based on a revolver principle (FIG. 2).
• a vertically standing drum (1) which continues to rotate in sections in cycles, is divided into 4 segments (2a-d), for example, by dividing walls that are arranged in a star shape and have good heat-insulating properties.
• the segments are advantageously open at the bottom and closed at the top by a plate (3) which contains one hole per segment (3a-d).
• a stationary plate 4 with only 3 holes (4a-c) in the same shape and position as (3a-c) is advantageously located above plate 3.
• Segment (2d) is advantageously closed at the top because a hole (4d) is missing in this cycle.
• the holes (4c) and (4b) are advantageously connected via a tube (5, shown dotted), in which the device for the energy input (6c, shown as a lightning bolt) can advantageously be located.
• the energy input can alternatively also take place in that a hot gas is generated outside the tube in, for example, a burner (6a) or in a plasma generator (6b), which gas is then advantageously introduced into the tube 5.
• a tube (7, also shown dotted) advantageously opens into hole (4a) which is above hole (3a).
• Particles (P1) also called carrier material, are advantageously fed to segment (2a) through pipe (7), which act as depth filters for separating the pyrolysis carbon and / or as regenerators for heat integration.
• the segments (2a-c), which are advantageously open at the bottom and rotate in sections, are advantageously closed at the bottom by a fixed plate (8) to such an extent that advantageously no particles can get into the space (9) below.
• Plate (8) advantageously only has a corresponding opening (8d) for segment (2d).
• the particles (P2) can advantageously pass from segment (2d) into the space (9) below.
• Plate (8) advantageously has pipe feeds (10b and 10c, shown dotted) under the two segments (2b) and (2a). These pipe feeds are advantageously designed in such a way that, although gases can flow into the segments, no particles can get into the pipes from the segments. This can be achieved, for example, with a close-meshed screen mesh. From pipe (10b) cold pyrolysis product gas (G4) is advantageously withdrawn from segment (2b) and cold feed gas (G1) advantageously flows through pipe (10c) into segment (2c).
• the individual segments (2a-d) are drawn in a linear row in order to illustrate what is happening in the individual segments at any point in time.
• a dark background means that the segment or the particles in it are cold.
• a light background means that the segment or the particles in it are hot.
• the transitions from dark to light or light to dark represent moving temperature fronts.
• the arrows (Tb) and (Tc) indicate the direction of migration of the temperature fronts.
• Segment (2a) is located under the pipe (7) and is filled with fresh particles (P1). • In segment (2b) the hot reaction gas (G3) is passed from the pipe (5), which heats the fresh and still cold particles to the reaction temperature.
• the hot reaction gas (G3) can contain pyrolysis soot formed as soon as it enters segment (2c). According to the invention, the greater part of the pyrolysis reaction takes place in segment (2b).
• Segment (2d) is located above the opening (8d) so that the cooled particles (P2) loaded with pyrolysis C can fall into the chamber (9) below in order to be discharged from there.
• the drum remains in one position as long as the particle bed in segment (2c) needs to be cooled down. Then one cycle is over and the drum rotates one segment further. The segment that was in the previous cycle (2a) becomes segment (2b) etc. in the new cycle. It is assumed that the time for filling segment (2a) and emptying segment (2d) is shorter than cooling the particle bed in the segment (2c).
• reaction heat input to cover the heat of reaction
• separation of the pyrolysis carbon heat recovery (heating of the natural gas and cooling of the pyrolysis carbon) .
• a thermal decomposition of hydrocarbons operated with the aid of resistance heating is known to those skilled in the art of thermal decomposition technology and, for example, in CH 409890, US 2982622, the international patent application No.
• two electrodes are installed in the beds, between which the beds act as an electrical resistor and heat up when the current is passed through due to the electrical transmission losses.
• the flow of current can take place both transversely to the directions of flow of the beds as well as along them. Since all conversion processes require energy, it can be advantageous to design the pyrolysis stage of the process according to the invention as a hybrid process so that it can also be operated with excess electricity obtained from renewable sources (see WO 2014/090914, European patent application with the number 19178437.0).
• the technology of electrochemical hydrogen separation is based on ion transport membranes that selectively conduct protons (H +). These membranes are known from other applications such as electrodialysis, fuel cells and water electrolysis.
• the structure for hydrogen separation is largely identical to a fuel cell structure.
• the core of the EHS system is the membrane electrode assembly (MEA).
• MEA membrane electrode assembly
• the EHS system separates the hydrogen from gas mixtures.
• the technology of electrochemical hydrogen separation is described, for example, in WO 2016/50500 and WO 2010/115786.
• the usual compounds and elements known to the person skilled in the art can be used as the catalytically active material, which can catalyze the dissociation of molecular hydrogen in atomic hydrogen, the oxidation of hydrogen to protons and the reduction of protons to hydrogen.
• the catalytically active material can catalyze the dissociation of molecular hydrogen in atomic hydrogen, the oxidation of hydrogen to protons and the reduction of protons to hydrogen.
• Pd, Pt, Cu, Ni, Ru, Fe, Co, Cr, Mn, V, W, tungsten carbide, Mo, molybdenum carbide, Zr, Rh, Ru, Ag, Ir, Au, Re, Y, Nb and alloys are suitable and mixtures thereof, Pt is preferred according to the invention.
• the catalytically active materials can also be in a supported form; carbon is preferably used as the support.
• the amount of the catalytically active material of the cathode catalyst is 0.1 mg / cm2 to 2.00 mg / cm2, preferably 0.1 mg / cm2 to 1 mg / cm2, based on the total area of the anode and cathode.
• the membrane used according to the invention selectively conducts protons, that is to say in particular that it is not electron-conducting.
• all materials known to the person skilled in the art can be used for the membranes, from which proton-conducting membranes can be formed.
• selectively proton-conducting membranes, as they are known from fuel cell technology, can be used according to the invention.
• Suitable polymers are sulfonated polyether ketones (S-PEEK), sulfonated polybenzoimidazoles (S-PBI) and sulfonated fluorocarbon polymers (e.g. NAFION®). Furthermore, perforated polysulfonic acids, styrene-based polymers, poly (arylene ethers), polyimides and polyphosphazenes can be used.
• Membranes made from polybenzamidazoles are very particularly preferably used, in particular MEAs based on polybenzimidazole and phosphoric acid, such as those marketed, for example, under the name Celtec-P® by BASF SE.
• the operating conditions of the EHS system depend heavily on the MEA selected.
• Celtec ® technology it is advantageous to use a voltage of 0.1 to 0.4V and a current of 0.2 to 1 A / cm 2 .
• the separation of the H2 is not based on differential pressure, but on electrochemistry.
• the EHS can therefore advantageously be operated without pressure. As long as there is no differential pressure between anode and cathode, a higher pressure is advantageous, which leads to a higher separation rate.
• the hydrogen content in the hydrogen-containing product gas from stage 1, the pyrolysis stage is advantageously in the range from 1% by volume to 99% by volume, preferably 5% to 95% by volume, preferably 10 to 95% by volume , preferably 20 to 95% by volume, preferably 40 to 90% by volume, in particular 65 to 90% by volume, hydrogen.
• the hydrogen separation rate is typically between 60% and 99%, preferably 70 to 95%, in particular 80% to 90%, the higher the separation rate, the higher the electrical energy requirement of an EHS.
• the water content in the hydrogen-containing feed gas is advantageously in the range from 0.5 to 50%, preferably 0.5 to 5%, in particular 0.5 to 1%.
• the current density is advantageously 0.1 to 1 A / cm 2 , preferably 0.2 to 0.7 A / cm 2 , in particular 0.2 to 0.5 A / cm 2 .
• the voltage is advantageously 1 to 1000 mV, preferably 100 to 800 mV, in particular 150 to 350 mV.
• These electrochemical hydrogen separation systems are operated at temperatures advantageously from 50 to 200.degree. C., preferably from 120 to 200.degree. C., preferably from 150 to 180.degree. C., in particular from 160 to 175.degree.
• the pressure is advantageously from 0.5 to 40 bar, preferably from 1 to 10 bar, in particular from 1 to 5 bar.
• the pressure difference between the anodic and the cathodic side is advantageously less than 1 bar, preferably less than 0.5 bar.
• This mode of operation enables a high tolerance to gas contamination, e.g. CO (3%) and H2S (15 ppm) to be achieved.
• This comparatively low temperature enables relatively quick and material-friendly switching on and off, an advantage especially for non-continuous operation in decentralized systems with fluctuating hydrogen sales, e.g. B. in gas stations.
• the active area of the membrane electrode unit is advantageously in the range from 5 cm 2 to 20,000 cm 2 , preferably 25 to 10,000 cm 2 , in particular 150 to 1000 cm 2
• the thickness of the membrane-electrode unit is advantageously in the range from 250 to 1500 ⁇ m, preferably 600 to 1000 ⁇ m.
• a hydrogen separation stack consisting of end plates, bipolar plates, seals and membrane-electrode units separates with a volume of 1 m 3 advantageously separates 100 to 200 Nm 3 / h hydrogen and is therefore significantly smaller than systems with physical hydrogen separation.
• the energy consumption is typically between 3 and 7 kWh / kg H2 - depending on the gas composition and the selected separation rate.
• the purity of the hydrogen generated can be very high, typically greater than 99.9%, preferably greater than 99.95%, in particular greater than 99.99%.
• the decomposition of the hydrocarbons and the electrochemical separation are advantageously carried out at the same pressure level. Both stages, thermal decomposition and electrochemical separation, are advantageously carried out at an absolute pressure of 1 bar to 30 bar. The pressure difference between the two stages is advantageously in the range from 0.001 bar to 5 bar.
• the hydrogen-containing product mixture is advantageously introduced into the process stage of electrochemical separation at the same temperature level that it has after the process stage of decomposition.
• the hydrogen-containing product mixture advantageously has a temperature of from 20 to 400 ° C., preferably from 50 to 300 ° C., preferably from 80 to 250 ° C., preferably from 100 to 200 ° C., in particular from 120 to 180 ° C., after the decomposition process stage ° C and is advantageously discharged from the first stage at this temperature (exit temperature).
• the cooling of the hot product-containing gas from the reaction temperature to these exit temperatures can take place, for example, in a fixed bed.
• the hydrogen-containing product mixture is fed into the electrochemical separation process at a temperature which advantageously differs by a maximum of 100 ° C., preferably a maximum of 50 ° C., in particular a maximum of 25 ° C., from this outlet temperature.
• the residual gas mixture remaining after the electrochemical separation process is advantageously at least partially recirculated into the first stage, the pyrolysis reaction.
• 99.99 to 90%, preferably 99.95 to 95%, preferably 99.9 to 98%, in particular 99.8 to 99% of the remaining residual gas amount is recirculated into the first stage.
• the residual gas that is not recirculated is advantageously discharged as purge gas.
• 0.01 to 10%, preferably 0.05 to 5%, particularly preferably 0.1 to 2%, in particular 0.2 to 1% of the remaining amount of gas are discharged as purge gas.
• the ratio of feed (hydrocarbons) to cycle gas (residual gas mixture) in the first stage in kg / kg is advantageously 0.01: 1 to 1: 5, preferably 0.03: 1 to 1: 2, in particular 0.05: 1 to 1 :1.
• One or more of the following process steps can optionally precede the EHS: heat integration, reforming of NH3 to N2 and H2, hydrogenation of multiple bonds, water gas shift (WGS). If several of the intermediate steps mentioned are installed, the hydrogen-containing, gaseous product mixture from the thermal decomposition is advantageously first reformed before the hydrogenation and / or the water-gas shift takes place.
• a process stage is advantageously installed upstream of the EHS, in which the basic components are removed from the product gas stream.
• NH3 can be reformed using catalysts known to those skilled in the art.
• This selective ammonia reforming (SAR) can be designed very easily in terms of equipment (see e.g. NOx reduction in car exhaust with AdBlue).
• the removal of ammonia is recommended for values of typically above 1 ppm, preferably above 10 ppm and in particular above 25 ppm.
• CH compounds with multiple bonds are adsorbed by the EHS catalyst and thereby reduce its activity.
• the pyrolysis product gas contains more than 10 mol ppm CH compounds with multiple bonds
• a hydrogenation process is preferred in which the multiple bonds with part of the water hydrogen contained in the product gas is hydrogenated to single bonds with catalysts known to those skilled in hydrogenation technology, which are no longer a catalyst poison for the EHS.
• CH multiple bonds are recommended for values of typically over 1000 ppm, preferably over 5000 ppm and in particular over 10000 ppm.
• Carbon monoxide is also adsorbed by the EHS catalyst, thereby reducing its activity. So if carbon monoxide is formed during the energy input for the pyrolysis and the pyrolysis product gas contains more than 3% CO, then this carbon monoxide, which is harmful to the EHS catalyst, is advantageous before entering the EHS at low temperatures ( ⁇ 400 ° C) with the help of the also im Combustion water present in the product gas stream - or if required - can be converted to further hydrogen and carbon dioxide with the aid of externally supplied water vapor and a WGS catalyst known to those skilled in the water gas shift technology. In contrast to carbon monoxide, carbon dioxide is not a catalyst poison for the EHS.
• the removal of CO is recommended when the proportion in the gas stream is typically more than 0.5% by volume and particularly preferably more than 1% by volume, in particular more than 3% by volume.
• the hydrogen present after the electrochemical separation can be fed to a hydrogen car in accordance with the current state of the art.
• the process was calculated for an H2 capacity of 1000 kg / d or 42 kg / h.
• the value is based on the currently discussed the largest H2 filling stations.
• the future-oriented electricity mix forecast for 2030 for the EU27 was used with 19% nuclear, 33% fossil and 48% renewable energy.
• the data are taken from [7] and represent a European average. This results in a carbon footprint of 190 kg C02 / MWh ei. for the electricity mix in EU 27 in 2030.
• the filling station is connected to a 25 bar natural gas network.
• the efficiency of the overall system which works at atmospheric pressure and 80 ° C, is 68%. This corresponds to a specific electrical energy consumption of 48.4 kWh / kg H2. If the H2 is compressed from 1 bar to 20 bar, there is another 1.6 kWh / kg H2.
• the specific electrical energy requirement is therefore a total of 50.0 kWIWkg H2.
• the specific carbon footprint is then 9.50 kg C02 / kg H2.
• the specific investment is € 3070 a / 1 H2.
• the natural gas has the following composition in% by weight: 88.7% CH4, 4.7% C2H6, 3.9% C3H8, 1.3% N2 and 1.3% C02.
• the specified electricity requirement not only covers the actual requirement of the process, but also the natural gas compression from 7 to 22 bar before the process and the H2 compression after the process from 21 bar to 207 bar.
• the data given results in an electricity requirement of 0.2 kWh ei / kg H2.
• the specific investment of a mini-SMR is 12,100 € a / 1 H2.
• the numbers given in [9] were used; Operating parameters and heat transfer rates are specified and the unknown heat transfer rate for the reformer is thus determined. It is then 8.9 kW per kg H2 / h.
• the Mini-SMR therefore needs per kg H2:
• the H2 is brought in 500 bar containers on trailers across the street to the petrol stations and these containers are emptied at the petrol station to 21 bar before they are transported back to the world-scale facility.
• the H2 must be compressed from 20 to 500 bar at the world-scale system [5]. 1.6 kWh / kg H2 must be used for this.
• this high pressure in the container has an advantageous effect when compressing at the gas station to the final pressure of, for example, 950 bar the refueling of the cars.
• the specific investment for compression is 430 € a / 1 H2.
• a 401 tanker truck can transport a maximum of 1344 kg H2 [5] which are emptied at the filling station up to a pressure of 21 bar. 54 kg of H2 then remain in the container and are then returned to the world-scale plant.
• the tube trailer variant requires per kg H2:
• a combination of an autothermally operated pyrolysis (ATP) and an EHS was calculated as an example.
• the advantage of this combination is a low consumption of electricity and natural gas as well as a low heat transfer rate.
• Natural gas is pre-cleaned. This can be done, for example, as described in [9], by catalytic desulphurisation.
• the rest of the natural gas is mixed with 227 kg / h of cycle gas in a jet pump.
• the pre-pressure of the natural gas is used in the jet pump to compress the cycle gas from 1.0 to 1.5 bar.
• the feed gas enters the bed of segment (2c) at 28 ° C and is heated to 1000 ° C therein.
• the bulk cools down in the process.
• a temperature front is created that moves from bottom to top. 199 kW are transferred thermally.
• the hot reaction gas heats the bed in segment (2b) and cools down in the process. 199 kW are also thermally transferred there.
• a combination of pyrolysis operated with a low temperature plasma (NT plasma) and an EHS was calculated as an example.
• the task of the plasma is to increase the reaction speed.
• the advantage of this combination lies in the relatively low process temperatures and the absence of CO, which has a positive effect on the energy requirements of the EHS.
• Natural gas is pre-cleaned. This can be done, for example, as described in [9], by catalytic desulphurisation.
• the feed gas (373 kg / h) enters the bed of segment (2c) at 28 ° C and is heated to 700 ° C therein.
• the bulk cools down in the process. This creates a temperature front that moves from bottom to top. Thereby 244 kW are thermally transferred.
• segment (2c) After exiting segment (2c), the gas molecules are excited e.g. by pulsed microwaves in a low-temperature plasma device and then passed into segment (2b).
• the hot reaction gas heats the bed in segment (2b) and cools down to 160 ° C. in the process. Thereby, 244 kW are also transferred thermally.
• the cooled product gas to 160 ° C (248 kg / h) is passed into a EHS, s are separated from the product gas electrochemically in the 91% of the ge formed H2 '. This requires an electrical output of 102 kW.
• the NT plasma & EHS process produces 3.0 kg of high-purity pyrolysis C per kg of H2 and requires:
• a combination of electrically heated pyrolysis, in which the pyrolysis C bed acts as resistance heating (WH pyrolysis) and an EHS was calculated as an example.
• the principle of WH pyrolysis is described in US2982622, for example.
• the advantage of this combi nation lies in the simplicity of the reactor and the design-related possible higher operating pressures, which leads to smaller reactor dimensions and a subsequent lower compression effort for H2.
• the absence of CO has a positive effect on the energy requirements of the EHS.
• WH pyrolysis with EHS a gas circuit with a high proportion of H2 can be built up.
• the higher H2 level reduces soot formation and also lowers the energy requirement in the EHS.
• the circulation of gas opens up new possibilities for conveying the pyrolysis C circuit (e.g. pneumatic conveyance) and enables better heat integration.
• Natural gas is pre-cleaned. This can be done, for example, as described in [9], by catalytic desulphurisation.
• 167 kg / h of purified natural gas at a pressure level of 25 bar are fed to the process at ambient temperature (25 ° C) and mixed with 68 kg / h of cycle gas in a jet pump.
• the pre-pressure of the natural gas is used in the jet pump to compress the cycle gas from 5.0 to 5.2 bar.
• the methane fission product gas flows upwards and warms up the recirculated particles that slide downwards. In return, the product gas cools down.
• the degree of heat integration can be controlled by the amount of cycle gas. With this countercurrent heat exchange, 315 kW are thermally transferred
• the cooled product gas to 160 ° C (110 kg / h) is passed into a EHS, s are separated from the product gas electrochemically in the 50% of the ge formed H2 '. For this, a specific electrical power of 63 kW is ei necessary.
• the remaining anode off-gas (68 kg / h) is recirculated. In order to prevent a build-up of inert components, 0.1 kg / h are withdrawn from the cycle gas.
• the WH pyrolysis & EHS process produces 3.0 kg of high-purity pyrolysis C per kg of H2 and therefore requires:
• the increased consumption of natural gas in the process concepts according to the invention is offset by the additional extraction of high-purity carbon. This increases the raw material yield and thus added value.
• the process concepts according to the invention also have only 1/5-el to 1/9-el of the power requirement of a water electrolysis.
• a small amount of electricity is particularly important with regard to the expansion of renewable energies that will be necessary in the future, as mobility here is in competition with other energy consumers.

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