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At least 451 records · Page 25

Numerical Prediction of Radiation Measurements Taken in the X2 Facility for Mars and Titan Gas Mixtures

Thermochemical relaxation behind a normal shock in Mars and Titan gas mixtures is simulated using a CFD solver, DPLR, for a hemisphere of 1 m radius; the thermochemical relaxation along the stagnation streamline is considered equivalent to the flow behind a normal shock. Flow simulations are performed for a Titan gas mixture (98% N2, 2% CH4 by volume) for shock speeds of 5.7 and 7.6 km/s and pressures ranging from 20 to 1000 Pa, and a Mars gas mixture (96% CO2, and 4% N2 by volume) for a shock speed of 8.6 km/s and freestream pressure of 13 Pa. For each case, the temperatures and number densities of chemical species obtained from the CFD flow predictions are used as an input to a line-by-line radiation code, NEQAIR. The NEQAIR code is then used to compute the spatial distribution of volumetric radiance starting from the shock front to the point where thermochemical equilibrium is nominally established. Computations of volumetric spectral radiance assume Boltzmann distributions over radiatively linked electronic states of atoms and molecules. The results of these simulations are compared against experimental data acquired in the X2 facility at the University of Queensland, Australia. The experimental measurements were taken over a spectral range of 310-450 nm where the dominant contributor to radiation is the CN violet band system. In almost all cases, the present approach of computing the spatial variation of post-shock volumetric radiance by applying NEQAIR along a stagnation line computed using a high-fidelity flow solver with good spatial resolution of the relaxation zone is shown to replicate trends in measured relaxation of radiance for both Mars and Titan gas mixtures.

Palmer, Grant↗

Redox-active oxide materials for thermal energy storage

Thermochemical storage materials having the general formula A x A′ 1-x B y B′ 1-y O 3-δ , where A=La, Sr, K, Ca, Ba, Y and B=Mn, Fe, Co, Ti, Ni, Cu, Zr, Al, Y, Cr, V, Nb, Mo, are disclosed. These materials have improved thermal storage energy density and reaction kinetics compared to previous materials. Concentrating solar power thermochemical systems and methods capable of storing heat energy by using these thermochemical storage materials are also disclosed.

14 SOLAR ENERGY↗

Redox-active oxide materials for thermal energy storage

Thermochemical storage materials having the general formula AxA′1-xByB′1-yO3-δ, where A=La, Sr, K, Ca, Ba, Y and B=Mn, Fe, Co, Ti, Ni, Cu, Zr, Al, Y, Cr, V, Nb, Mo, are disclosed. These materials have improved thermal storage energy density and reaction kinetics compared to previous materials. Concentrating solar power thermochemical systems and methods capable of storing heat energy by using these thermochemical storage materials are also disclosed.

14 SOLAR ENERGY↗

Developing a High Value Chemical Coproduct: Bio-Base Insecticides from Catalytic Fast Pyrolysis

Coproduction of biochemicals from the thermochemical conversion of biomass is a strategy to reduce biofuel costs and improve bio-oil quality in an integrated biorefinery. (Challenge) Cost effective separations of coproducts from thermochemical conversion streams remains a challenge largely due to the heterogenous nature and stability of thermochemical conversion streams. (Solution) Bio-based insecticides isolated from catalytic fast pyrolysis (CFP) oils are a viable coproduct that can overcome the oil is more stable, they are a high value product, and they can remain a mixture of components. (Approach) This work focuses on the development of a bio-based insecticide coproduct that is distilled from a catalytic fast pyrolysis bio-oil produced using a platinum on titanium dioxide (Pt/TiO2) catalyst to upgrade pyrolysis vapors.

BIOMASS FUELS↗

Redox-active oxide materials for thermal energy storage

Thermochemical storage materials having the general formula AxA′1-xByB′1-yO3-δ, where A=La, Sr, K, Ca, Ba, Y and B=Mn, Fe, Co, Ti, Ni, Cu, Zr, Al, Y, Cr, V, Nb, Mo, are disclosed. These materials have improved thermal storage energy density and reaction kinetics compared to previous materials. Concentrating solar power thermochemical systems and methods capable of storing heat energy by using these thermochemical storage materials are also disclosed.

Babiniec, Sean M.↗

Using Co-Optimized Machine Learned Manifolds for Modeling Chemically Reacting Flows

Chemically reacting flows play a key role in a wide range of engineered systems, from chemical and polymer processing to combustion-based energy conversion technologies. Simulations of these flows involve solving a coupled set of partial differential equations for mass, momentum, energy, and all relevant chemical species in the system. Chemical reaction pathways may be extremely complex and involve hundreds or more intermediate species, with reactions that occur over timescales varying by several orders of magnitude - presenting a significant numerical stiffness challenge. The combination of these factors makes simulation of chemically reacting flows vastly more expensive than nonreactive simulations, and often makes direct solution of the governing equations intractable. It is necessary to apply lower-fidelity models in place of the detailed governing equations in order to reduce computational cost to enable reacting flow simulation tools to be used in the engineering design process. Many of the models employed for this purpose are based on reducing the dimension of the thermochemical state, motivated by the observation that the observed thermochemical states in a system lie on a low-dimensional manifold in thermochemical state space. This behavior occurs due to the fast equilibration of certain reactive and transport processes, and physics-based manifold models rely on idealized assumptions about the balance of timescales and the way in which chemistry and transport are coupled. In this work, we apply a novel method for data-driven manifold-based modeling that can leverage data from high-fidelity reacting flow simulations to improve model accuracy in cases where the physics-based modeling assumptions break down. The approach is designed to be broadly applicable across chemically reacting flow systems but is applied here to turbulent combustion modeling.

machine learning↗

Hydrogen-Steam Separation Using Mechanical Vapor Recompression Cycle

Solar thermochemical hydrogen and fuel production is a promising pathways for producing sustainable fuels and chemicals. One of the main challenges in the development of these systems is their low steam conversion extent, dictated by its restrictive thermodynamics requiring extremely high temperatures and low oxygen partial pressure to obtain conversions over 10 \%. While condensing the unreacted steam is technically simple, the latent heat is thus lost, which can be larger than the producd hydrogen higher heating value. We propose to use a modified mechanical vapor recompression cycle, allowing to recover the latent heat by compressing the steam-hydrogen mixture prior to the condensation process, thus creating a temperature different between the hot exhaust and cold inlet streams. We show that this method can recover over 90 % of the latent heat, thus increasing the viability of solar thermochemical hydrogen production cycles even under limited conversion conditions.

hydrogen technology↗

Zero carbon solid-state rechargeable redox fuel for long duration and seasonal storage

Here, this work presents a unique thermochemical process for charging magnesium-manganese-oxide-based solid-state rechargeable redox fuel. High-temperature heating of the processing furnace can be driven by either renewable electricity or concentrated solar power. The simple recyclable fuel charging concept is based on a tubular falling bed reactor with countercurrent oxygen-depleted gas flow for complete heat recuperation. The main focus of this work is achieving solid flowability at high temperatures (1,450°C) and extracting chemically charged solid at ambient temperature with minimal energy loss. The operation strategies described in this work have enabled consistent magnesium-manganese-oxide particle flow up to 1,450°C. The measured extent of the thermal reduction reaction after cooling the particles is more than 90% of the fully reduced state at equilibrium. The thermal-to-chemical efficiency and overall system efficiency are 96% and 35% respectively, which are the highest reported for thermochemical fuels to date.

25 ENERGY STORAGE↗

Discrepancies between Theory and Experiment in Determining the Ionization Energy of NF 3

High-accuracy ab initio thermochemical predictions for the ionization energy of NF 3 , the barrier height (to inversion) of NF 3 + , and the dissociative ionization threshold of NF 3 to NF 2 + + F are presented and incorporated into Active Thermochemical Tables. The adiabatic ionization energy of the first ionization band of NF 3 , calculated at 12.647 ± 0.010 eV, is at odds with previous experimental interpretations by nearly 0.36 eV due to unfavorable Franck-Condon factors associated with this transition. The barrier (to inversion) height is calculated to be about 0.6 eV lower in energy than the prior interpretation, which instigates a discussion of the supposed vibrational structure of the first ionization band of NF 3 . Updated assignments of the photoelectron spectrum are proposed, and the loss in vibrational spacing on the high-energy side of the experimental ionization band is discussed. Rudimentary anharmonic Franck-Condon simulations qualitatively reproduce the broad spectral features observed in experiment.

Active Thermochemical Tables↗

Factors Governing Oxygen Vacancy Formation in Oxide Perovskites

The control of oxygen vacancy (V O ) formation is critical to advancing multiple metal-oxide-perovskite-based technologies. In this work, we report the construction of a compact linear model for the neutral V O formation energy in ABO 3 perovskites that reproduces, with reasonable fidelity, Hubbard-U-corrected density functional theory calculations based on the state-of-the-art, strongly constrained and appropriately normed exchange-correlation functional. We obtain a mean absolute error of 0.45 eV for perovskites stable at 298 K, an accuracy that holds across a large, electronically diverse set of ABO 3 perovskites. Our model considers perovskites containing alkaline-earth metals (Ca, Sr, and Ba) and lanthanides (La and Ce) on the A-site and 3d transition metals (Ti, V, Cr, Mn, Fe, Co, and Ni) on the B-site in six different crystal systems (cubic, tetragonal, orthorhombic, hexagonal, rhombohedral, and monoclinic) common to perovskites. Physically intuitive metrics easily extracted from existing experimental thermochemical data or via inexpensive quantum mechanical calculations, including crystal bond dissociation energies and (solid phase) reduction potentials, are key components of the model. Beyond validation of the model against known experimental trends in materials used in solid oxide fuel cells, the model yields new candidate perovskites not contained in our training data set, such as (Bi,Y)(Fe,Co)O 3 , which we predict may have favorable thermochemical water-splitting properties. The confluence of sufficient accuracy, efficiency, and interpretability afforded by our model not only facilitates high-throughput computational screening for any application that requires the precise control of V O concentrations but also provides a clear picture of the dominant physics governing V O formation in metal-oxide perovskites.

08 HYDROGEN↗

Sub 20 cm -1 computational prediction of the CH bond energy – a case of systematic error in computational thermochemistry

Here, the bond dissociation energy of methylidyne, D 0 (CH), is studied using an improved version of the High-Accuracy Extrapolated ab initio Thermochemistry (HEAT) approach as well as the Feller–Peterson–Dixon (FPD) model chemistry. These calculations, which include basis sets up to nonuple (aug-cc-pCV9Z) quality, are expected to be capable of providing results substantially more accurate than the ca. 1 kJ mol -1 level that is characteristic of standard high-accuracy protocols for computational thermochemistry. The calculated 0 K CH bond energy (27 954 ± 15 cm -1 for HEAT and 27 956 ± 15 cm -1 for FPD), along with equivalent treatments of the CH ionization energy and the CH + dissociation energy (85 829 ± 15 cm -1 and 32 946 ± 15 cm -1 , respectively), were compared to the existing benchmarks from Active Thermochemical Tables (ATcT), uncovering an unexpected difference for D 0 (CH). This has prompted a detailed reexamination of the provenance of the corresponding ATcT benchmark, allowing the discovery and subsequent correction of a systematic error present in several published high-level calculations, ultimately yielding an amended ATcT benchmark for D 0 (CH). Finally, the current theoretical results were added to the ATcT Thermochemical Network, producing refined ATcT estimates of 27 957.3 ± 6.0 cm -1 for D0(CH), 32 946.7 ± 0.6 cm -1 for D 0 (CH + ), and 85 831.0 ± 6.0 cm -1 for IE(CH).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Perspective on Solar Energy Materials, Design and Discovery, Defects, Disorder, and Interfaces

The energy transition still faces a daunting math. Currently, more than three quarters of final energy consumption occurs in form of fuels vs less than one quarter in electricity. On the other hand, renewable energy additions come almost exclusively in the form of electricity (dominantly photovoltaics and wind). Thus, meeting the terawatt challenge requires enormous growth in renewables, sufficient to convert excess electricity into fuels, as well as the development of non-electricity based solar fuel technologies, for example via solar thermochemical routes. In this presentation, we will review successes and challenges in photovoltaic materials from silicon to CdTe to halide perovskites and potential emerging materials, with a particular perspective on the role of first principles calculations and predictions. Materials design and discovery is evolving to incorporate defects, disorder, and interfaces. These phenomena play also an important role in the thermochemical generation of hydrogen, allowing to utilize synergies between renewable electricity and fuels in computational research. At the same time, machine learning approaches are increasingly geared toward properties of non-ideal materials, for example defect formation, allowing the screening for more complex material behavior as needed for the respective applications.

fuels↗

Hydrogen and its Vital Role in a Clean Energy Future

Large-scale, low -cost hydrogen production can enable an economically competitive, secure, and environmentally beneficial future energy system across multiple sectors. Furthermore, clean hydrogen can address specific sectors that are hard to decarbonize (e.g., heavy-duty trucking, load-following electricity, iron, steel, and cement) and can help the U.S. meet the net zero carbon goal by 2050. To achieve this goal, tens of millions of metric tons of clean, reliable, and affordable hydrogen will be needed annually1. In 2021, the Hydrogen Energy Earthshot was launched, and its goal is to reduce the cost of clean hydrogen to $1 per $1 kilogram in 1 decade (1 1 1) 2. One very promising pathway for large-scale hydrogen production is water splitting. Water splitting technologies range from commercial technologies such as electrolyzers to approaches that are at a much earlier stage of development, such as photoelectrochemical (PEC) and thermochemical (TCH) processes. All these water splitting pathways offer diverse benefits in energy storage, grid services, and cross-sector emissions reductions while taking advantage of the diverse domestic resources. However, critical materials-, component- and system-level challenges must be addressed to improve efficiency and durability and reduce cost. To address these barriers and move these promising and high impact technologies forward, the HydroGEN Advanced Water Splitting Materials (AWSM) and the H2 from the Next-generation of Electrolyzers of Water (H2NEW) consortia were formed and supported by the Department of Energy (DOE) EERE Hydrogen and Fuel Cell Technologies Office (HFTO). HydroGEN (https://www.energy.gov/eere/h2awsm/) consortium, established in 2016, is an Energy Materials Network (EMN) that aims to accelerate the materials R&D of low technology readiness level (TRL) advanced water splitting (AWS) technologies. The consortium comprises five core national laboratories and focuses on four early-stage AWS pathways: alkaline exchange membrane (AEM) electrolysis, proton conducting solid oxide electrolysis (p-SOEC), photoelectrochemical, and thermochemical water splitting. Liquid alkaline and PEM electrolyzers are already commercial and significant advancements in oxygen conducting solid oxide electrolysis cells (o-SOECs) have been realized. Yet, these systems are still too expensive and not sufficiently durable for wide-scale commercialization. To enable high-volume manufacturing of affordable, durable, efficient electrolyzers, H2NEW (https://h2new.energy.gov/), another multi-lab consortium, was established in 2020. This comprehensive, concerted effort is focused on overcoming barriers related to components and materials integration and scale-up to achieve performance, durability, with an initial focus to achieve $2/kg H2 by 2026.

AEM↗

High-Throughput Analysis of Materials for Chemical Looping Processes

Chemical looping is a promising approach for improving the energy efficiency of many industrial chemical processes. However, a major limitation of modern chemical looping technologies is the lack of suitable active materials to mediate the involved subreactions. Identification of suitable materials has been historically limited by the scarcity of high-temperature (>600 °C) thermochemical data to evaluate candidate materials. An accuratethermodynamic approach is demonstrated here to rapidly identify active materials which is applicable to a wide variety of chemical looping chemistries. Application of this analysis to chemical looping combustion correctly classifies 17/17 experimentally studied redox materials by their viability and identifies over 1300 promising yet previously unstudied active materials. This approach is further demonstrated by analyzing redox pairs for mediating a novel chemical looping process for producing pure SO2 from raw sulfur and air which could provide a more efficient and lower emission route to sulfuric acid. 12 promising redox materials for this process are identified, two of which are supported by previous experimental studies of their individual oxidation and reduction reactions. This approach provides the necessary foundation for connecting process design with high-throughput material discovery to accelerate the innovation and development of a wide range of chemical looping technologies.

chemical looping↗

Oxidation and pyrolysis of methyl propyl ether

The ignition, oxidation, and pyrolysis chemistry of methyl propyl ether (MPE) was probed experimentally at several different conditions, and a comprehensive chemical kinetic model was constructed to help understand the observations, with many of the key parameters computed using quantum chemistry and transition state theory. Experiments were carried out in a shock tube measuring time variation of CO concentrations, in a flow tube measuring product concentrations, and in a rapid compression machine (RCM) measuring ignition delay times. The detailed reaction mechanism was constructed using the Reaction Mechanism Generator software. Sensitivity and flux analyses were used to identify key rate and thermochemical parameters, which were then computed using quantum chemistry to improve the mechanism. Validation of the final model against the 1-20 bar 600-1500 K experimental data is presented with a discussion of the kinetics. The model is in excellent agreement with most of the shock tube and RCM data. Strong non-monotonic variation in conversion and product distribution is observed in the flow-tube experiments as the temperature is increased, and unusually strong pressure dependence and significant heat release during the compression stroke is observed in the RCM experiments. These observations are largely explained by a close competition between radical decomposition and addition to O2 at different sites in MPE; this causes small shifts in conditions to lead to big shifts in the dominant reaction pathways. The validated mechanism was used to study the chemistry occurring during ignition in a diesel engine, simulated using Ignition Quality Test (IQT) conditions. At the IQT conditions, where the MPE concentration is higher, bimolecular reactions of peroxy radicals are much more important than in the RCM.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermodynamic modeling of KCl-PrCl 3 and KCl-LiCl-PrCl 3 systems

Molten salt electrolysis can recover the actinides from spent nuclear fuels, and it involves a eutectic LiCl-KCl in molten form as an electrolyte. During reprocessing, the concentration of fission products such as La, Nd, Pr, etc., increases and affects the recovery efficiency of the electrolyte. In this work, thermodynamic modeling of KCl-PrCl 3 and KCl-LiCl-PrCl 3 systems was carried out using the CALPHAD (Calculation of Phase Diagrams) approach for the first time. The thermodynamic functions for the pure salts were taken from the SGTE (Scientific Group Thermodata Europe) Substances (SSUB) database. The experimental thermochemical and phase equilibria data available in the literature were used as input for the assessment of KCl-PrCl 3 and KCl-LiCl-PrCl 3 systems. The model parameters for the KCl-LiCl system were adjusted to include the new Gibbs energy descriptions for the pure salts. In addition, the sublattice model for the liquid phase in the LiCl-PrCl 3 system was modified and reassessed to ensure the model compatibility for higher-order extrapolation. There is a good agreement between the experimental and calculated thermochemical and phase diagram data for all the optimized constituent binaries and the ternary system. Furthermore, this work will be beneficial for determining the solubility limit of PrCl 3 in molten LiCl-KCl electrolytes and their thermodynamic properties for improving the efficiency of the pyrochemical process.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Sorbent-based oxygen separation with YBC114 for energy storage systems

In our report we aimed to design, build, and evaluate an oxygen separation system to provide an inert sweep gas with low oxygen partial pressure (pO2) to redox-active thermochemical energy conversion reactors for a range of applications, including two-step redox cycles for thermochemical energy storage, water splitting, and carbon-dioxide splitting. The separation is based on an oxygen-selective sorbent, YBaCo4O7+δ (YBC114), which has excellent oxygen sorption and desorption properties demonstrated in our previous work. The oxygen separation performance of YBC114 was comprehensively studied by thermogravimetric analysis, sorption breakthrough experiments, and temperature swing sorption - desorption cycles. The results reveal that YBC114 can produce inert sweep gas with an oxygen concentration of less than 100 ppmv for at least 20 min during the thermal swing adsorption (TSA) cycle with the current sorption bed configuration, and the performance is consistent from cycle to cycle. The optimal sorption and desorption temperatures for the TSA process with YBC114 are determined to be 300 °C and 500 °C, respectively. Although challenges remain for the current separation system (e.g., high sorption temperature and slow kinetics), this study demonstrates the potential to use the oxygen-selective sorbent to produce an inert sweep gas, the feasibility of the oxygen separation concept, and guides new sorbent material development to make this application economically practical. A simple procedure is described for designing the YBC114 oxygen separation process.

42 ENGINEERING↗

Boosting the use of bauxite residue (red mud) in cement - Production of an Fe-rich calciumsulfoaluminate-ferrite clinker and characterisation of the hydration

Highlights: • Incorporation of 35 wt% of bauxite residue for production of CSAF clinker • Thermochemical calculations as suitable tool for predicting phase assemblage • Hydration of the cement was found to be accelerated in contrast to other CSA cements. • High early compressive strengths of 40 MPa In the present work, calciumsulfoaluminate-ferrite clinker was produced using 35 wt% of bauxite residue in combination with alumina, clay, limestone and gypsum. At a temperature of 1300 °C, the hydraulic phases ye'elimite, ferrite and C{sub 2}S were formed. Computed thermochemical predictions were a significantly better match for the real mineralogy than modified Bogue equations. Hydration of the clinker led to the formation of ettringite and monosulfate, resulting in compressive strengths of 17 MPa after 28d. Compressive strengths of 40 MPa after 2d, and 28d-strengths exceeding 50 MPa, were reached in blends with 10 wt% of anhydrite. The strength development was due to the rapid formation of ettringite, mainly originating from ye'elimite, which did not convert to AFm phases and led to a compact microstructure. Only when the ye'elimite dissolution decreased, did the ferrite phase react. In pastes with additional sulfates, ferrite hydration led to the formation of ettringite and to hydrogarnet. Cement nomenclature is used in this work.{sup 1}.

36 MATERIALS SCIENCE↗