Kinetic Modeling of Pt-Catalyzed Glycolaldehyde Decomposition to Syngas
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Concurrent simulation of chemical and electro-chemical processes on Sr 2 Fe 1.5 Mo 0.5 O 6-δ predicted a higher activity for CO/syngas fuels for a surface with higher Mo content.
A facile new method for the synthesis of nanostructured Cu 2 O–ZnO and Cu 2 O–ZnO–MgO catalysts has been described.
Through insights from first-principles calculations, we predict defect-laden h -BN, particularly with N vacancy, to have good propensity toward CO and CO 2 hydrogenation. Vibrational frequencies of CO and CO 2 are proposed as identifiers of defect type.
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Abstract New laminar flame speed and burned-gas Markstein length data for H2–CO–O2–CO2–He mixtures have been measured from spherically expanding flames. Experiments were conducted at 10 atm and room temperature for H2:CO ratios ranging from 2:1 to 1:4 and for overall CO2 mole fractions from 0% to 30%. CO2 dilution had little effect on Markstein length, but CO2 dilutions of 10%, 20%, and 30% caused average reductions in flame speed of 47%, 73%, and 89%, respectively, regardless of H2:CO ratio. The study was designed to isolate the dilution effect of CO2 on flame speed, and a detailed analysis using the FCO2 method was used to show that the chemical-kinetic participation of CO2 was responsible for up to 20% of the reduction in flame speed. Hence, the majority (80% or more) of the reduction in flame speed due to CO2 is from the thermal effect. Accurate flame speed predictions were produced by five different chemical kinetics mechanisms for most conditions, with the slight exception of high-CO, high-CO2 mixtures. A thorough sensitivity analysis highlighted the larger effect of CO2 dilution on the important kinetics reactions than the effect of changing H2:CO. Sensitivity analysis also showed that the chain branching reaction H2O + O ⇌ OH + OH could be modified (albeit beyond its uncertainty) to achieve more accurate flame speed predictions, but also indicated that further improvement of flame speed modeling would require changes to many lesser reactions.
Abstract not provided
18th International Symposium on Solid Oxide Fuel Cells (SOFC-XVIII), Boston, MA, May 28-June 2, 2023
This collaborative study with Toyota Research Institute of North America (TRINA), which we started in November 2010 and completed in February 2013, explored the feasibility of using carbon dioxide and water in the production of CO/H 2 gas mixtures through the utilization of transition-metal complexes as catalysts and solar energy converters.
The primary objective of this multi-year research effort was to explore the possibility of modifying turbine endwall geometries to both increase their aerodynamic performance and reduce the potential for degradation due to deposition. The effort included both experimental and computational components. The experimental work was divided between two reacting flow turbine test facilities: one at BYU and the other at OSU. The facility at BYU was used for high temperature deposition experiments, up to 1400C with film cooling capability. The effects of particle size, surface temperature, gas temperature, and particle flowrate on deposition were all studied in the course of this research program. This facility was also adapted to allow elevated diluent (water vapor) concentrations. The OSU facility provided the capability to test actual turbine vane flowpaths at operating temperatures with film cooling. Effects of film cooling, particle size, gas temperature, and ash composition were all investigated. Experimental data from both facilities provided critical validation for computational models of deposition that were developed under this same research effort. Model development included the refinement of several existing particle sticking models and their incorporation into a commercial CFD package.
The chemical looping strategy for fossil energy applications promises to achieve an efficient energy conversion system for electricity, liquid fuels, hydrogen and/or chemicals generation, while economically separate CO 2 by looping reaction design in the process. Chemical looping particle performance, looping reactor engineering, and process design and applications are the key drivers to the success of chemical looping process development. In order to better understand and further scale up the chemical looping process, issues such as cost, time, measurement, safety, and other uncertainties need to be examined. To address these uncertainties, advanced reaction/reactor modeling and process simulation are highly desired and the modeling efforts can accelerate the chemical looping technology development, reduce the pilot-scale facility design time and operating campaigns, as well as reduce the cost and technical risks. The purpose of this work is thus to conduct multiscale modeling and simulations on the key aspects of chemical looping technology, including particle reaction kinetics, reactor design and operation, and process synthesis and optimization.
An integrated and collaborative effort involving experiments and complementary chemical kinetic modeling investigated the effects of significant concentrations of water and CO 2 and minor contaminant species (methane [CH 4 ], ethane [C 2 H 6 ], NOX, etc.) on the ignition and combustion of HHC fuels. The research effort specifically addressed broadening the experimental data base for ignition delay, burning rate, and oxidation kinetics at high pressures, and further refinement of chemical kinetic models so as to develop compositional specifications related to the above major and minor species. The foundation for the chemical kinetic modeling was the well validated mechanism for hydrogen and carbon monoxide developed over the last 25 years by Professor Frederick Dryer and his co-workers at Princeton University. This research furthered advance the understanding needed to develop practical guidelines for realistic composition limits and operating characteristics for HHC fuels. A suite of experiments was utilized that that involved a high-pressure laminar flow reactor, a pressure-release type high-pressure combustion chamber and a high-pressure turbulent flow reactor.
An experimental program was undertaken to develop and demonstrate novel steam reforming catalysts for converting tars, C2+ hydrocarbons, and methane under high temperature and sulfur environments at lab scale. Several catalysts were developed and synthesized along with some catalysts based on recipes found in the literature. Of these, two had good resistance at 90 ppm H 2 S with one almost not affected at all. Higher concentrations of H 2 S did affect methane conversion across the catalyst, but performance was fairly stable for up to 200 hours. Based on the results of the experimental program, a techno-economic analysis was developed for IGCC and CTL applications and compared to DOE reference cases to examine the effects of the new technology. In the IGCC cases, the reformer/POX system produces nearly the same amount of electricity for nearly the same cost, however, the reformers/POX case sequesters a higher percentage of the carbon when compared to IGCC alone. For the CTL case the economics of the new process were nearly identical to the CTL case, but due to improved yields, the greenhouse gas emissions for a given production of fuels was approximately 50% less than the baseline case.
This report describes the second phase of a project to design, construct and commission an integrated coal/biomass-to-liquids facility at a capacity of 1 bbl. /day at the University of Kentucky Center for Applied Energy Research (UK-CAER) – specifically for construction, commissioning and operating of the downstream process units for water-gas-shift, Fischer-Tropsch synthesis and balance of plant [BOP]. The deliverables from the operation of this pilot plant is firstly the liquid F-T products and finished fuels which are of interest to UK-CAER’s academic, government and industrial research partners. Going forward the facility will produce research quantities of F-T liquids and finished fuels for subsequent Fuel Quality Testing, Performance and Acceptability. Moreover, the facility is expected to be employed for a range of research and investigations related to: Feed Preparation, Characteristics and Quality; Coal and Biomass Gasification; Gas Clean-up/ Conditioning; Gas Conversion by -F-T Synthesis; Product Work-up and Refining; Systems Analysis and Integration; and Scale-up and Demonstration. Environmental Considerations - particularly how to manage and reduce carbon dioxide emissions from CBTL facilities and from use of the fuels will be a primary research objective. The results of this second phase study include the FEED study and detailed engineering design of the downstream processing units and BOP, the selection of a range of technologies and technology vendors, the as-built plant - its equipment and capabilities, and the results of two trial production runs, one with coal only and one with a coal/biomass blend. These are described in detail in this report.
An effective strategy to design platinum group metal (PGM) free redox catalysts for “low temperature” CO 2 splitting followed with methane partial oxidation was proposed and validated. Composites of mixed ionic-electronic conductive (MIEC) oxides were found to be highly effective at relatively low temperatures (600–750 °C). Specifically, perovskite structured LaNi 0.35 Fe 0.65 O 3 and rock salt structured Ce 0.85 Gd 0.1 Cu 0.05 O 2-δ , as two compatible yet structurally distinct MIEC oxides, were integrated into composite redox catalyst particles. Resulting from the synergistic effect of the two MIEC phases, 90% CO 2 to CO conversion was demonstrated at 750 °C. Up to 90% methane conversion with 96% CO selectivity was also achieved in the methane POx step. The redox catalysts were characterized in detail to illustrate the underlying mechanisms for the synergistic effects. Electrical conductivity relaxation (ECR) measurements indicated significantly lowered activation energy for lattice oxygen (O 2- ) migration (0.43 eV). The enhanced oxygen migration in turn led to reversible exsolution of active transition metal nanoparticles (Ni–Fe alloy) from the mixed oxide, serving as active sites for methane activation while further enhancing lattice oxygen exchange, as confirmed by in situ X-ray diffraction and transmission electron microscopy. As a result, the composite redox catalysts demonstrate superior redox activity, coke resistance, and long term redox stability, making them potentially suitable for CO 2 utilization and methane partial oxidation under a hybrid redox process scheme.
This project has developed a new testing capability at PNNL and has evaluated solid oxide electrolysis cell (SOEC) materials for the ability to co-electrolyze carbon dioxide and steam to produce synthesis gas. CO 2 -H 2 O co-electrolysis, the simultaneous electrochemical reduction of carbon dioxide and steam, was performed on the porous Ni-based electrodes in high temperature SOECs. Experiments were conducted using small button cells and the rate of the electrochemical reactions was measured at 750°C for varied reactant compositions: 10-98%CO 2 and 5-50% H 2 O, also in the presence of some H 2 and CO to ensure reducing environment and avoid Ni oxidation.
This study focuses on developing a catalytic process for the aromatization of mixed olefin (comprised of C 2 -C 6 ) over various metal doped zeolites towards the formation of large aromatics (preferably C 8 -C 16 ) compliance to the sustainable aviation fuel (SAF). Experiments were carried out using model olefin feedstocks containing either ethylene (C 2 ) or mixture of C 2 and C 3+ olefins. Both the catalyst composition and process parameters were evaluated in detail to identify their impact on the formation large aromatics. We specifically focus on the aromatization of ethylene as the model reaction and evaluated the impact of C 2+ olefins and paraffins that may present in the real feedstock. In all the reaction condition, aromatization of ethylene was used as the baseline to evaluate the effect of larger olefins or paraffins. Our results show that at this reaction condition paraffins remained either inert or show positive impact on the formation of large aromatics. While C 2 and C 3 olefins are highly reactive towards aromatization during reaction condition, large olefins are less reactive and thus, strategy was developed to oligomerize these large olefins (C 4+ ) alongside the aromatization of smaller olefins (C 2 /C 3 ).
The goals of Office of Clean Coal are: (1) Improved energy security; (2) Reduced green house gas emissions; (3) High tech job creation; and (4) Reduced energy costs. The goals of the Hydrogen from Coal Program are: (1) Prove the feasibility of a 40% efficient, near zero emissions IGCC plant that uses membrane separation technology and other advanced technologies to reduce the cost of electricity by at least 35%; and (2) Develop H{sub 2} production and processing technologies that will contribute {approx}3% in improved efficiency and 12% reduction in cost of electricity.