TY - CHAP A1 - Israel, Johannes A1 - Rachow, Fabian A1 - Schwiertz, Carola A1 - Charlafti, Evgenia A1 - Müller, Klaus A1 - Schmeißer, Dieter T1 - Self restriction oft the Sabatier reaction in large scale T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft N2 - A main goal for a sustainable energy supply is a long term energy storage system. One opportunity in this research field is the power to gas concept, where the produced gas can be fed in the existing network of natural gas. Here we show in a technical scale how the direct CO2 conversion to methane according the Sabatier reaction, CO2 + 4 H2 → CH4 + 2H2O , is self organized. At a certain limit of gas flow, a steady state equilibrium of exothermic heat production and thermal flow is reached and the reaction needs no further external annealing. We find for the maximum volume rate at the steady state equilibirum a shift of around 250 ∘C above the optimized temperature of the catalytic supported chemical equilibrium. It is shown that also with this setup the used catalyst works with a stable conversion higher than 80 % under the reached temperature and given pressure conditions. KW - methanation KW - Sabatier reaction Y1 - 2015 UR - http://www.dpg-verhandlungen.de/year/2015/conference/berlin/part/ake/session/9/contribution/4?lang=en PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - CHAP A1 - Rachow, Fabian A1 - Israel, Johannes A1 - Schwiertz, Carola A1 - Charlafti, Evgenia A1 - Müller, Klaus A1 - Schmeißer, Dieter T1 - CO2 Methanation with different gas mixtures T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft N2 - A key issue in the Energiewende in Germany is the storage of excess energy, as it enables energy management systems to react to fluctuating sources and enhances the flexibility of an energy mix. Power to Gas may be the most reasonable approach to store the energy in the form of hydrogen or synthetic natural gas. We study the direct conversion of CO2 by the Sabatier reaction to gain a methane based mixture which can replace natural gas in CHP plants and gas motors and can help to partially reduce the CO2 emission. In laboratory scale we investigated the performance (with IR and QMS) of Ni-based catalyst for different sources of CO2 like clean CO2, CO2 emitted as flue gas from an Oxyfuel power plant or a synthetic mixture with O2, N2 and SO2 in concentration typical for conventional power plants. Measurements from an up-scaled system are also presented, showing data important for a technical application. Here, we are able to convert more than 200kg CO2/day with conversion rates up to 90%. KW - methanation KW - Sabatier reaction KW - contamination KW - catalyst Y1 - 2015 SN - 0420-0195 SP - S. 539 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - CHAP A1 - Israel, Johannes A1 - Müller, Klaus A1 - Rachow, Fabian A1 - Beuckert, Guido A1 - Schmeißer, Dieter T1 - Reaction kinetics of the Sabatier Reaction in a demonstration plant T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft N2 - We currently build up a demonstration plant for the direct catalytic conversion of CO2 into methane according to the Sabatier reaction CO2+4H2→CH4+2H2O. We have already reached conversion rates higher than 90% and a selectivity close to unity in our laboratory experiments with NiO based catalysts. A good long term stability was obtained with a reactant gas flow density of 0.8 l/min cm2· at 350∘C. We will study the process now on a larger scale with a factor 10000. The process is controlled via mass flow controllers with a throughput of 20m3/h H2 and 5m3/h CO2 at an inlet gas pressure of up to 15 bar, the temperature is regulated by a PID multichannel controller. As water is a by-product we use an efficient cooling trap for its separation form the obtained methane. The reaction products are analyzed by a quadrupole mass spectrometer under reaction conditions. We start our experiments in using clean CO2 and H2. Later experiments will involve industrial quality (oxy-fuel) conditions also. Goal of this project is to determine the performance of the catalytic process under conditions which enable an industrial implementation in energy storage concepts. In this contribution we report of the design of a demonstration plant and on first experiments concerning the kinetics within the system. KW - methanation KW - Sabatier reaction KW - reaction kinetics Y1 - 2013 UR - http://www.dpg-verhandlungen.de/year/2013/conference/regensburg/part/o/session/20/contribution/5?lang=de PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - CHAP A1 - Israel, Johannes A1 - Rachow, Fabian A1 - Schwiertz, Carola A1 - Charlafti, Evgenia A1 - Müller, Klaus A1 - Schmeißer, Dieter T1 - Direct CO2-Methanation of flue gas emitted by conventional power plants T2 - Verhandlungen der Deutschen Physikalischen Gesellschaft N2 - The catalytic conversion of CO2 with H2 into CH4 is possible by the Sabatier reaction CO2+4H2→CH4+2H2O. Using excess energy from renewable electricity generation, this approach offers an opportunity for recycling of CO2 as synthetic natural gas. In a new concept, we investigate the performance of the Sabatier reaction as direct methanation of flue gas, emitted by conventional power plants. We investigate the Sabatier process in an upscaled system, with a maximum input flow rate of 45 Nm3/h Gas. The performance is investigated in a simulated composition of flue gas and under real conditions at a lignite power plant in Schwarze Pumpe, Brandenburg, Germany. We can achieve a CO2-conversion of up to 90%, with approx. 100% selectivity towards CH4. Under flue gas conditions and at a certain limit of gas flow the system is operated at an autothermal running modus, a steady state equilibrium of exothermic heat production and thermal flow that needs neither external annealing nor cooling. KW - CO2 KW - methanation KW - Sabatier reaction KW - power plant KW - Schwarze Pumpe KW - autothermal mode Y1 - 2017 UR - http://www.dpg-verhandlungen.de/year/2017/conference/muenster/part/ake/session/8/contribution/5 SP - S. 255 PB - Deutsche Physikalische Gesellschaft CY - Bad Honnef ER - TY - THES A1 - Israel, Johannes T1 - Sabatierbasierte autothermale katalytische Rauchgasmethanisierung im Technikumsmaßstab und Rückverstromung im BHKW T1 - Sabatier based autothermal catalytic methanation of flue gas in scale of a demonstration plant and reconversion in a CHP N2 - Es konnte gezeigt werden, dass die direkte Methanisierung des Kohlenstoffanteils aus Rauchgas auf Grundlage der Sabatier-Reaktion im Rahmen des Power-to-Gas Ansatzes unter realen Bedingungen im Technikumsmaßstab möglich ist. Es wurde ein Durchsatz von knapp 235 kg/d CO2 bei einer Gesamtraumgeschwindigkeit der Eduktgase von ca. 1500 h-1, was einem Durchfluss von 45 Nm³/h bei einem Reaktorvolumen von 30 dm³ entspricht, erreicht. Dabei wurde das Kohlenstoffdioxid direkt, ohne weitere Aufarbeitung des Rauchgases, mit mindestens 60% Umsatz katalytisch zu Methan reduziert. Dafür wurde ein Katalysator auf Nickelbasis verwendet. Des Weiteren hat sich gezeigt, dass für eine autotherme Betriebsweise der Methanisierung von Rauchgas der Sauerstoffanteil im Rauchgas eine notwendige Voraussetzung darstellt. Es hat sich dabei herausgestellt, dass das vorliegende Intervall von 4 - 6 Vol % Sauerstoffanteil im Rauchgas aus konventionellen Braunkohlekraftwerken genau in dem notwendigen Bereich liegt, der für eine ausgeglichene Wärmebilanz sorgt. Die bei der Wasserstoff-Sauerstoffreaktion zusätzlich frei werdende Wärme gleicht den kühlenden Effekt des mitgetragenen Stickstoffes genau aus, wodurch die für die Sabatier-Reaktion benötigte Temperatur von mindestens 300 °C aufrechterhalten werden kann. Ohne den Sauerstoff könnte die Methanisierung nicht autotherm betrieben werden. Zudem ist die Reaktion selbstregulierend, die Reaktionstemperatur läuft auf einen oberen Grenzwert von etwa 600 °C hinaus, wodurch Umsätze von 60% nicht unterschritten werden. Bei niedrigeren Temperaturen von ca. 400 °C konnten auch Ergebnisse von über 90% CO2 Umsatz im Rauchgas erreicht werden. Diese Ergebnisse konnten sowohl unter Laborbedingungen, d.h. mit aus technischen Gasen synthetisch hergestelltem Rauchgas, gemessen werden, als auch mit realem Rauchgas direkt am Kraftwerk vor Ort reproduziert werden. Das bei der Rauchgasmethanisierung entstehende Produktgas weist eine Energiedichte von ca. 5 MJ/Nm³ auf, womit es zu den Schwachgasen gezählt wird. Hier konnte der Nachweis erbracht werden, dass eine Nutzung des Produktgases in einem Rückverstromungskonzept mittels eines dezentralen Blockheizkraftwerkes, welches mit einem herkömmlichen Wankelmotor betrieben wird, möglich ist. Das "Proof of Principle" für einen geschlossenen CO2 Kreislauf unter realen Bedingungen mittels der Sabatier Reaktion wurde somit erbracht und lädt dazu ein, diesen Weg weiter zu verfolgen. N2 - It is shown, that the direct methanation of the carbon content of flue gas is possible. This was done on the basis of the Sabatier reaction and under real circumstances in a pilot plant scale. At the reactant gases hourly space velocity of approximately 1500 h-1 an output of just under 235 kg/d CO2 was reached, which corresponds to a flow-rate of 45 Nm³/h at a reactor volume of 30 dm³. Without further reprocessing of the flue gas, the carbon dioxide was directly reduced to methane via catalysis, which resulted in a conversion rate of at least 60%. A nickel based catalyst was used. Furthermore, it appeared that the flue gases oxygen content is a necessary precondition for the methanations autothermic mode of operation. Thereby the present interval of 4 - 6 vol% oxygen content of flue gas from conventional lignite power plants turned out to lie exactly in the necessary range to provide an even thermal balance. Since the additionally released heat from the hydrogen-oxygen reaction just compensates for the cooling effect of the present nitrogen, the Sabatier reaction's required temperature of at least 300 °C can be maintained. Without that oxygen the methanation could not be run autothermally. Additionally, the reaction is self-regulating. The reaction temperature results in a maximum limit value of approximately 600 °C, whereby conversion rates do not fall below 60%. At lower temperatures of about 400 °C, results of over 90% CO2 conversion from flue gas could be reached. These results could be measured under laboratory conditions, i.e. with synthetically produced flue gases mixed from industrial gases, and were reproduced with real flue gas directly from the power plant. The resulting gas from the flue gas methanation exhibits an energy density of approximately 5 MJ/Nm³, which ranks it among the lean gases. Here it could be proven that a reconversion of the produced gas into electricity is possible using a local block-type thermal power station, run with a conventional Wankel rotary engine. Thus the 'Proof of Principle' was provided for a closed CO2 circle under real conditions by means of the Sabatier reaction, which is an invitation to further pursue this path. KW - BHKW KW - Blockheizkraftwerk KW - CCU KW - Energiespeicher KW - Kohlendioxid KW - Methanisierung KW - Rauchgas KW - Sabatier KW - Wasserstoff KW - CCU KW - CHP KW - Carbon dioxid KW - Combined heat and power plant KW - Energy storage KW - Flue gas KW - Hydrogen KW - Methanation KW - Power-to-Gas KW - Sabatier Y1 - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:co1-opus4-41467 ER - TY - GEN A1 - Müller, Klaus A1 - Rachow, Fabian A1 - Israel, Johannes A1 - Charlafti, Evgenia A1 - Schwiertz, Carola A1 - Schmeißer, Dieter T1 - Direct Methanation of Flue Gas at a Lignite Power Plant T2 - International Journal of Environmental Science N2 - The combustion of fossil fuels results in CO2 emission, which is one of the primary causes of global warming. An important approach for solving this problem is the fixation, the chemical utilization and the recycling of CO2. Therefore, we investigate the catalytic conversion of CO2 with H2 into methane (CH4) with an upscaled test station at a brown coal power plant. In a completely new strategy, we realize the direct conversion of the CO2 content of the flue gas, without a cleaning process like amine scrubbing or optimized combustion like oxyfuel. Our experiments are performed in matters of catalytic performance, heat production and stability of the catalytic Sabatier process, as a function of the gas flow rate. The catalytic performance is investigated with a simulated composition of flue gas and under real conditions directly at the power plant. The CH4 production by the Sabatier process is realized with a maximum input flow rate of near 50Nm3/h, with 30Nm3/h flue gas and 20Nm3/h hydrogen. For these values, the necessary power scale for hydrogen generation by electrolysis is around 100kW. With synthetic and real flue gas, a conversion up to 99% (for hydrogen surplus) with 100% selectivity is stabilized. The reaction operates in thermal steady state equilibrium without any external energy supply. In consequence, the process of CO2 recycling could be integrated directly as a post combustion process of conventional power plants, without an expensive capturing step, for example. KW - CO2 recycling KW - Power to Gas (PtG) KW - Synthetic Natural Gas (SNG) KW - Sabatier-Reaction KW - Flue Gas Y1 - 2017 UR - http://www.iaras.org/iaras/home/caijes/direct-methanation-of-flue-gas-at-a-lignite-power-plant SN - 2367-8941 IS - 2 SP - 425 EP - 437 ER - TY - CHAP A1 - Müller, Klaus A1 - Israel, Johannes A1 - Rachow, Fabian A1 - Schmeißer, Dieter ED - Ramirez Reina, Tomas ED - Odriozola, José Antonio ED - Arellano-García, Harvey T1 - Sabatier-Based Direct Synthesis of Methane and Methanol Using CO2 from Industrial Gas Mixtures T2 - Engineering Solutions for CO2 Conversion KW - Sabatier reaction KW - CO2 emission reduction KW - industrial CO2 sources Y1 - 2021 SN - 978-3-527-34639-4 SP - 253 EP - 280 PB - Wiley-VCH CY - Weinheim ET - 1 ER - TY - GEN A1 - Richter, Jana A1 - Rachow, Fabian A1 - Israel, Johannes A1 - Roth, Norbert A1 - Charlafti, Evgenia A1 - Günther, Vivien A1 - Flege, Jan Ingo A1 - Mauß, Fabian T1 - Reaction Mechanism Development for Methane Steam Reforming on a Ni/Al2O3 Catalyst T2 - Catalysts N2 - In this work, a reliable kinetic reaction mechanism was revised to accurately reproduce the detailed reaction paths of steam reforming of methane over a Ni/Al2O3 catalyst. A steady-state fixed-bed reactor experiment and a 1D reactor catalyst model were utilized for this task. The distinctive feature of this experiment is the possibility to measure the axially resolved temperature profile of the catalyst bed, which makes the reaction kinetics inside the reactor visible. This allows for understanding the actual influence of the reaction kinetics on the system; while pure gas concentration measurements at the catalytic reactor outlet show near-equilibrium conditions, the inhere presented temperature profile shows that it is insufficient to base a reaction mechanism development on close equilibrium data. The new experimental data allow for achieving much higher quality in the modeling efforts. Additionally, by carefully controlling the available active surface via dilution in the experiment, it was possible to slow down the catalyst conversion rate, which helped during the adjustment of the reaction kinetics. To assess the accuracy of the revised mechanism, a monolith experiment from the literature was simulated. The results show that the fitted reaction mechanism was able to accurately predict the experimental outcomes for various inlet mass flows, temperatures, and steam-to-carbon ratios. KW - kinetic reaction mechanism development KW - 1D modeling KW - reaction rates KW - methane steam reforming KW - fixed-bed reactor experiments KW - nickel catalyst Y1 - 2023 U6 - https://doi.org/10.3390/catal13050884 SN - 2073-4344 VL - 13 IS - 5 ER -