Soot Formation in Methane Pyrolysis Reactor: Modeling Soot Growth and Particle Characterization.

Methane pyrolysis is a very attractive and climate-friendly process for hydrogen production and the sequestration of carbon as solid material. The formation of soot particles in methane pyrolysis reactors needs to be understood for technology scale-up calling for appropriate soot growth models. A monodisperse model is coupled with a plug flow reactor model and elementary-step reaction mechanisms to numerically simulate processes in methane pyrolysis reactors, namely, the chemical conversion of methane to hydrogen, formation of C-C coupling products and polycyclic aromatic hydrocarbons, and growth of soot particles. The soot growth model accounts for the effective structure of the aggregates by calculating the coagulation frequency from the free-molecular regime to the continuum regime. It predicts the soot mass, particle number, area, and volume concentration, along with the particle size distribution. For comparison, experiments on methane pyrolysis are carried out at different temperatures and collected soot samples are characterized using Raman spectroscopy, transmission electron microscopy (TEM), and dynamic light scattering (DLS).

Identification of the Reaction Sequence of the MTO Initiation Mechanism Using Ab Initio-Based Kinetics.

The initiation of the methanol-to-olefins (MTO) process is investigated using a multiscale modeling approach where more than 100 ab initio computed (MP2:DFT) rate constants for H-SSZ-13 are used in a batch reactor model. The investigated reaction network includes the mechanism for initiation (42 steps) and a representative part of the autocatalytic olefin cycle (63 steps). The simulations unravel the dominant initiation pathway for H-SSZ-13: dehydrogenation of methanol to CO is followed by CO-methylation leading to the formation of the first C-C bond in methyl acetate despite high barriers of >200 kJ/mol. Our multiscale approach is able to shed light on the reaction sequence that ultimately leads to olefin formation and strikingly demonstrates that only with a full reactor model that includes autocatalysis with olefins as cocatalysts is one able to understand the initiation mechanism on the atomic scale. Importantly, the model also shows that autocatalysis takes over long before significant amounts of olefins are formed, thus guiding the interpretation of experimental results.

Thermodynamics and reaction mechanism of urea decomposition.

The selective catalytic reduction technique for automotive applications depends on ammonia production from a urea-water solution via thermolysis and hydrolysis. In this process, undesired liquid and solid by-products are formed in the exhaust pipe. The formation and decomposition of these by-products have been studied by thermogravimetric analysis and differential scanning calorimetry. A new reaction scheme is proposed that emphasizes the role of thermodynamic equilibrium of the reactants in liquid and solid phases. Thermodynamic data for triuret have been refined. The observed phenomenon of liquefaction and re-solidification of biuret in the temperature range of 193-230 °C is explained by formation of a eutectic mixture with urea.

Iron as Recyclable Metal Fuel: Unraveling Oxidation Behavior and Cyclization Effects Through Thermogravimetric Analysis, Wide-Angle X-ray Scattering and Mössbauer Spectroscopy.

The carbon-free chemical storage and release of renewable energy is an important task to drastically reduce CO2 emissions. The high specific energy density of iron and its recyclability makes it a promising storage material. Energy release by oxidation with air can be realized by the combustion of micron-sized iron powders in retro-fitted coal fired power plants and in fixed-bed reactors under milder conditions. An experimental parameter study of iron powder oxidation with air was conducted based on thermogravimetric analysis in combination with wide-angle X-ray scattering and Mössbauer spectroscopy. In agreement with literature the oxidation was found to consist of a very fast initial oxidation of the outer particle layer followed by much slower oxidation due to diffusion of iron ions through the Fe2O3/Fe3O4 layer being the rate-limiting step. Scanning electron microscopy analysis of the iron particle before and after oxidation reveal a strong particle morphology transformation. This impact on the reaction was studied by cyclization experiments. Up to 10 oxidation-reduction cycles show that both, oxidation and reduction rates, increase strongly with cycling due to increased porosity.

Following the Structural Changes of Iron Oxides during Reduction under Transient Conditions.

Iron is considered as attractive energy carrier in a carbon-free circular energy economy. The reduction of iron oxide is crucial for its applica-tion as a metal fuel as it determines the efficiency of the cycle. Temperature programmed reduction of α-Fe2O3 was monitored by complementary X-ray absorption spectroscopy (XAS) and diffraction (XRD) to obtain the phase composition with high time resolution. Synchrotron Mössbauer spectroscopy (SMS) was additionally employed due to its high sensitivity to the different iron species. Theoretical calculations of surface and bulk adsorption processes were performed to establish the potential reaction pathways and the corresponding energy barriers. A kinetic particle model was then developed to bridge the experimental data and theoretical calculations, which reproduced the reduction onset and behavior. The reduction process was found to be strongly dependent on the heating rate in terms of the reduction window and the observed intermediate species. We propose that a core-shell mechanism determines the reaction by forming an iron layer which subsequently hinders diffusion of water out of the porous particles leading to some unreduced FeO at high temperature. This study demonstrates the need for complementary methods for describing complex heterogeneous systems and overcoming the chemical sensitivity limitations of any single method.

Hydrogen Production and Carbon Capture by Gas-Phase Methane Pyrolysis: A Feasibility Study.

Using natural gas and sustainable biogas as feed, high-temperature pyrolysis represents a potential technology for large-scale hydrogen production and simultaneous carbon capture. Further utilization of solid carbon accruing during the process (i. e., in battery industry or for metallurgy) increases the process's economic chances. This study demonstrated the feasibility of gas-phase methane pyrolysis for hydrogen production and carbon capture in an electrically heated high-temperature reactor operated between 1200 and 1600 °C under industrially relevant conditions. While hydrogen addition controlled methane conversion and suppressed the formation of undesired byproducts, an increasing residence time decreased the amount of byproducts and benefited high hydrogen yields. A temperature of 1400 °C ensured almost full methane conversion, moderate byproduct formation, and high hydrogen yield. A reaction flow analysis of the gas-phase kinetics revealed acetylene, ethylene, and benzene as the main intermediate products and precursors of carbon formation.

Hydrogen Production and Carbon Capture by Gas-Phase Methane Pyrolysis: A Feasibility Study.

Invited for this month's cover is the research group of Olaf Deutschmann and the team of Patrick Lott at the Karlsruhe Institute of Technology. The Cover image shows how an electrically heated reactor converts methane from natural gas or biogas into gaseous hydrogen and elemental carbon by means of high-temperature pyrolysis. The transfer of this technology into industrial applications can be a valuable contribution towards a decarbonization of the chemical industry and the establishment of a hydrogen economy. The Research Article itself is available at 10.1002/cssc.202201720.