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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Graphene Wrapped FeSe 2 Nano–Microspheres with High Pseudocapacitive Contribution for Enhanced Na–Ion Storage

Pseudocapacitance is a Faradaic process that involves surface or near surface redox reactions. Increasing the pseudocapacitive contribution is one of the most effective means to improve the rate performance of electrode materials. In this study, graphene oxide is used as a template to in situ synthesize burr globule–like FeSe 2 /graphene hybrid (B–FeSe 2 /G) using a facile one–step hydrothermal method. Structural characterization demonstrates that graphene layers not only wrap the surfaces of FeSe 2 particles, but also stretch into the interior of these particles, as a result of which the unique nano–microsphere structure is successfully established. When serving as anode material for Na–ion batteries, B–FeSe 2 /G hybrid displays high electrochemical performance in the voltage range of 0.5–2.9 V. The B–FeSe 2 /G hybrid has high reversible capacity of 521.6 mAh·g –1 at 1.0 A g –1 . Meanwhile, after 400 cycles, high discharge capacity of 496.3 mAh g –1 is obtained at a rate of 2.5 A g –1 , with a high columbic efficiency of 96.6% and less than 1.0% loss of discharge capacity. Even at the ultrahigh rate of 10 A g –1 , a specific capacity of 316.8 mAh g –1 can be achieved. Furthermore, kinetic analyses reveal that the excellent performance of the B–FeSe 2 /G hybrid is largely attributed to the high pseudocapacitive contribution induced by the special nano–micro structure.

25 ENERGY STORAGE↗
DOE OSTI2025

A Methodology for the Analysis of Water Oxidation Electrocatalysts in the Absence of Limiting Current that Avoids the Pitfalls of Existing Methods

Water oxidation is an important reaction studied as a way to generate electrons from water, to promote water splitting and the formation of green hydrogen. When using electrodes to drive homogeneous water oxidation catalysis, cyclic voltammograms are analyzed to provide catalytic rate constants. There are two main methods, foot-of-the-wave analysis (FOWA) and limiting current analysis. FOWA relies on approximations inherent to analyzing water oxidation catalysis, such as determining the formal potential of the catalytic intermediate, E 0 cat . Limiting current methods are the optimal way to analyze catalyst performance but rely on observable limiting current, which is virtually never seen in water oxidation. To avoid those issues, a method is proposed for analyzing nonideal cyclic voltammetry waveshapes in water oxidation: by analyzing rate data across a large range of potentials, an optimal potential, E 0 cat , can be obtained, where catalytic current, i cat , is nearly independent of scan rate and has a linear dependency on buffer concentration. Here, the method is applied to four homogeneous water oxidation catalysts with prior extensive electrochemical elucidation, all of which lack an ideal, purely kinetic waveshape in cyclic voltammetry. Application of the method avoids the biases of the other methods cited for the kinetic analyses of water oxidation catalysts.

14 SOLAR ENERGY↗
DOE OSTI2021

Oxidation of an iso-paraffinic alcohol-to-jet fuel and n-heptane mixture: an experimental and modelling study

Oxidation of ATJ/n-heptane blends was studied over a wide range of test conditions, using single pulse shock tubes. Test conditions were designed to study the effect of pressure (4 and 50 bar), and fuel loading (~100-1400 ppm) on the oxidation of the blends across a wide range of temperatures (800-1300 K). These effects were observed by measuring concentrations of intermediate species formed using in-line Gas Chromatography (GC) and GCxGC TOF-MS. Results showed that increasing the initial fuel load does not have a significant impact on the results. However, increasing the pressure shifts the mixture reactivity to a lower temperature by about 150 K and causes the fuel to be oxidized instead of decomposing pyrolytically as at lower pressures. Additional experiments for pure ATJ and pure n-heptane were performed at conditions matching the ATJ/n-heptane 50 bar experiments to analyze the differences between the pure and mixed fuels. Speciation measurements were compared against predictions from a detailed kinetic model. The ability of the kinetic model to capture the effects of varying experimental test conditions on the evolution of intermediate species is discussed and kinetic analyses have been conducted to identify the important reaction pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Comparison of native and non-native ubiquitin oligomers reveals analogous structures and reactivities: Comparison of Native and Non-Native Ubiquitin Oligomers

Ubiquitin (Ub) chains regulate a wide range of biological processes, and Ub chain connectivity is a critical determinant of the many regulatory roles that this post-translational modification plays in cells. To understand how distinct Ub chains orchestrate different biochemical events, we and other investigators have developed enzymatic and non-enzymatic methods to synthesize Ub chains of well-defined length and connectivity. A number of chemical approaches have been used to generate Ub oligomers connected by non-native linkages; however, few studies have examined the extent to which non-native linkages recapitulate the structural and functional properties associated with native isopeptide bonds. Here, we compare the structure and function of Ub dimers bearing native and non-native linkages. Using small-angle X-ray scattering (SAXS) analysis, we show that scattering profiles for the two types of dimers are similar. Moreover, using an experimental structural library and atomistic simulations to fit the experimental SAXS profiles, we find that the two types of Ub dimers can be matched to analogous structures. An important application of non-native Ub oligomers is to probe the activity and selectivity of deubiquitinases. Through steady-state kinetic analyses, we demonstrate that different families of deubiquitinases hydrolyze native and non-native isopeptide linkages with comparable efficiency and selectivity. Considering the significant challenges associated with building topologically diverse native Ub chains, our results illustrate that chains harboring non-native linkages can serve as surrogate substrates for explorations of Ub function.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

The structural basis for the broad aldehyde specificity of the aminoaldehyde dehydrogenase PauC from the human pathogen Pseudomonas aeruginosa

Abstract Despite significant differences in size and formal charge, the aldehyde dehydrogenasePaPauC (PA5312) fromPseudomonas aeruginosaPAO1 efficiently catalyzes the NAD + ‐dependent oxidation of the aminoaldehydes formed in polyamines degradation. We report here thatPaPauC also oxidizes 4‐guanidinebutyraldehyde, formed in one arginine degradation pathway, trimethylaminobutyraldehyde, of unknown metabolic origin, and indole‐3‐acetaldehyde, a precursor of the plant growth‐promoting hormone indoleacetic acid.PaPauC has been proposed as a potential target for combatingP. aeruginosa. However, understanding its structure–function relationships, crucial for developing specific inhibitors, is lacking. Using X‐ray crystallography, we identified the structural characteristics that determinePaPauC broad aldehyde specificity: a spacious aldehyde‐entrance tunnel and six active‐site residues. Docking simulations, site‐directed mutagenesis, and kinetic analyses support the interactions of Lys479 with glutamylated aminoaldehydes; Phe169, Trp176, and Phe467 with amino and guanidinium groups through cation–π interactions and with the indole group via NH–π and CH–π interactions; Asp459 with amino and indole groups; and Thr303 with amide and guanidinium groups. Exploiting the distinctive structural features of thePaPauC active site could aid in developing specific inhibitors to combatP. aeruginosainfections in humans and animals, as well as in preventing its colonization of plants, which are abundantP. aeruginosareservoirs and, therefore, a significant source of human infections.

Biochemistry & Molecular Biology↗
DOE OSTI2017

High purity Mn 5 O 8 nanoparticles with a high overpotential to gas evolution reactions for high voltage aqueous sodium-ion electrochemical storage

Here, developing electrodes with high specific energy by using inexpensive manganese oxides is of great importance for aqueous electrochemical energy storage (EES) using non-Li charge carriers such as Na-or K-ions. However, the energy density of aqueous EES devices is generally limited by their narrow thermodynamic potential window (~1.23 V). In this paper, the synthesis of high purity layered Mn 5 O 8 nanoparticles through solid state thermal treatment of Mn3O4 spinel nanoparticles, resulting in a chemical formula of [Mn 2 2+ ] [Mn 3 4+ O 8 2– ], evidenced by Rietveld refinement of synchrotron- based X-ray diffraction, has been reported. The electro-kinetic analyses obtained from cyclic voltammetry measurements in half-cells have demonstrated that Mn5O8 electrode has a large overpotential (~ 0.6 V) towards gas evolution reactions, resulting in a stable potential window of 2.5 V in an aqueous electrolyte in half-cell measurements. Symmetric full-cells fabricated using Mn5O8 electrodes can be operated within a stable 3.0 V potential window for 5000 galvanostatic cycles, exhibiting a stable electrode capacity of about 103 mAh/g at a C-rate of 95 with nearly 100% coulombic efficiency and 96% energy efficiency.

25 ENERGY STORAGE↗
DOE OSTI2018

Engineering of Escherichia coli β-lactamase TEM-1 variants showing higher activity under acidic conditions than at the neutral pH

Highlights: • Genetic screening is useful for obtaining β-lactamases with altered pH dependency. • A few mutations each suppress the activity of a β-lactamase at pH 7.0. • The engineered β-lactamase variants are more active under the acidic conditions. • The relevant amino acid substitutions are located far from the catalytic site. Escherichia coli β-lactamase TEM-1 is potentially useful in the antibody-directed enzyme/prodrug therapy (ADEPT), converting nontoxic prodrugs to toxic agents. The produced toxin would kill cancer cells, when the enzyme is attached to a tumor-antigen-specific antibody. However, the off-site reaction possibly occurring in the blood or normal tissues raises safety concern. In the present study, we engineered TEM-1 variants preferentially active at pH 5.8–6.2, near the pH of the acidic microenvironment of tumor. A library of randomly mutagenized variants was screened for the ability to confer an antibiotic resistance on E. coli cells in acidic growth media and not in neutral media, to isolate a variant with a Thr-to-Ile substitution at position 160. An extensive mutagenesis study was then conducted in the proximity of this position, to show that a Leu162Glu mutation also causes the acid preference. Kinetic analyses indicated that the overall activity of the wild-type TEM-1 hardly changes over a pH range from 5.8 to 7.0, whereas TEM-1(T160I) is 1.5-times as active at pH 6.2 than pH 7.0, and TEM-1(T160I) is 3.1-fold as active at pH 5.8 than pH 7.0. A further mutagenesis study suggested that a change in the overall structure of the enzyme underlies the pH dependency of the variants.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Design of light- and chemically responsive protein assemblies through host-guest interactions

Host-guest (HG) interactions have been widely used to build responsive materials and molecular machines owing to their inherently dynamic nature, interaction specificity, and responsiveness to diverse stimuli. Here, in this work, we have set out to exploit these advantages of HG chemistry in the design of dynamic protein assemblies, using a C 4 symmetric protein, C98 RhuA, as a building block. We show that a C98 RhuA variant individually modified with β-cyclodextrin (βCD) (host) or azobenzene (guest) functionalities can specifically pair with each other to form highly ordered 1D and 2D assemblies. Association and dissociation of βCD RhuA- azo RhuA assemblies can be controlled by UV and visible light as well as by small-molecule modulators of βCD-azobenzene interactions. Kinetics analyses reveal that βCD RhuA- azo RhuA nanotubes assemble without a nucleation barrier, a highly unusual occurrence for helical supramolecular systems. Taken together, our findings provide a compelling example for achieving complex structural and dynamic outcomes in protein assembly through simple chemical design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Autoignition study of binary blends of n- dodecane/1-methylnaphthalene and iso- cetane/1-methylnaphthalene

An experimental study on autoignition of two binary blends, n-dodecane/1-methylnaphthalene and iso-cetane/1-methylnaphthalene, has been conducted using a rapid compression machine. Specifically, the ignition delays of the stoichiometric blend+air mixtures were measured at elevated pressures of P C = 15 bar and 30 bar, compressed temperatures of T C = 626–944 K, and varying blending ratios of the constituents. For a given set of P C and T C , a nonlinear response of the blend reactivity with respect to the relative amount of the constituents was observed. Since a comprehensive chemical kinetic model for the blends investigated here is under development, the current ignition delay datasets serve as the needed targets for model validation. For selected conditions, ignition delay simulations were conducted to highlight and discuss the deficiencies of the literature models and the potential areas for model improvements, especially at low temperatures. In conclusion, further chemical kinetic analyses were conducted to gain understanding of the blending behavior predicted by the available model.

1-methylnaphthalene↗
DOE OSTI2018

Autoignition of trans -decalin, a diesel surrogate compound: Rapid compression machine experiments and chemical kinetic modeling

Decahydronaphthalene (decalin), with both cis and trans isomers, is a bicyclic alkane that is found in aviation fuels, diesel fuels, and alternative fuels from tar sands and oil shales. Between the two decalin isomers, trans-decalin has a lower cetane number, is energetically more stable, and has a lower boiling point. Moreover, trans-decalin has often been chosen as a surrogate component to represent two-ring naphthenes in transportation fuels. Recognizing the importance of understanding the chemical kinetics of trans-decalin in the development of surrogate models, an experimental and modeling study has been conducted. Experimentally, the autoignition characteristics of trans-decalin were investigated using a rapid compression machine (RCM) by using trans-decalin/O2/N2 mixtures at compressed pressures of PC=10–25 bar, low-to-intermediate compressed temperatures of TC=620–895 K, and varying equivalence ratios of Φ=0.5, 1.0, and 2.0. These new experimental data demonstrate the effects of pressure, fuel loading, and oxygen concentration on autoignition of trans-decalin. The current RCM data of trans-decalin at lower temperatures were also found to complement well with the literature shock tube data of decalin (mixture of cis+trans) at higher temperatures. Furthermore, a chemical kinetic model for the oxidation of trans-decalin has been developed with new reaction rates and pathways, including, for the first time, a fully-detailed representation of low-temperature chemical kinetics for transdecalin. This model shows good agreement with the overall ignition delay results of the current RCM experiments and the literature shock tube studies. Chemical kinetic analyses of the developed model were further conducted to help identify the fuel decomposition pathways and the reactions controlling the autoignition at varying conditions.

10 SYNTHETIC FUELS↗
DOE OSTI2020

Fuel molecular structure effect on autoignition of highly branched iso-alkanes at low-to-intermediate temperatures: Iso-octane versus iso-dodecane

Highly branched iso-alkanes are an important class of hydrocarbons found in conventional petroleum-derived and alternative renewable fuels used for combustion applications. Recognizing that chemical kinetics for most of these iso-alkanes, especially at low-to-intermediate temperatures, has not been well studied, an experimental and modeling investigation of two selected iso-alkanes, iso-octane (2,2,4-trimethylpentane, iC8) and iso-dodecane (2,2,4,6,6-pentamethylheptane, iC12), is conducted to understand the fuel molecular structure effect on their autoignition characteristics. Using a rapid compression machine (RCM), the ignition responses of iC8 and iC12 at varying pressures, temperatures, and equivalence ratios are characterized and compared. The newly-acquired experimental ignition delay times have been compared with the literature RCM and shock tube data, demonstrating the complementary nature of the current dataset. Further comparison of the experimental pressure traces and ignition delay times illustrates the reactivity crossover between iC8 and iC12. Namely, there exists a temperature window in the negative temperature coefficient regime within which iC12 is less reactive than iC8, but iC12 becomes more reactive outside this temperature window. Furthermore, a chemical kinetic model of iso-alkanes including both iC8 and iC12 is developed. Simulated results using this model are then compared to the experimental data obtained in this study and available in the literature, showing its ability to predict the experimental trends. Chemical kinetic analyses have also been conducted to identify the important reaction pathways controlling autoignition at varying conditions, and to elucidate the underlying mechanism leading to different reactivity trends between iC8 and iC12.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Consequences of product inhibition in the quantification of kinetic parameters

While the potential for product inhibition in catalytic reactions is well known, the impact of neglected inhibition on measured kinetic parameters is often overlooked. The presence of product inhibition, most often caused by the competitive adsorption of products with reactants on catalytic active sites, is difficult to determine a priori for an arbitrary catalytic system. The significance of product inhibition relies on the concentration of the products, their adsorption thermodynamics on catalytically relevant sites, and process parameters such as temperature and pressure. When inhibition is significant, however, apparent activation energies and reaction orders vary from the differential-reactor apparent activation energy by a factor of 1/(1 - δ), where δ is the total inhibition order (e.g., the factor (1 - δ) = 1.6 for a system with product inhibition of -0.6 order). This is illustrated here with the kinetics of NO oxidation over Cu ion clusters (Cu x O y ) in Cu-SSZ-13, for which the product NO 2 inhibits the forward reaction. Furthermore, in the presence of inhibition, when only reactants are fed to a flow reactor or placed in a batch reactor, there is often no practical conversion that is low enough to guarantee differential behavior. Inclusion of products in the feed solves this problem, allowing accurate determination of kinetic parameters such as apparent reaction orders and activation energies. We also demonstrate that evaluation of the necessity of co-feeding products to assure measurement of differential-reactor data in a given catalytic system is straightforward from a plot of the log of the rate (or conversion) versus the log of the space time in a flow reactor or elapsed time in a batch reactor. We encourage inclusion of this test in all kinetic analyses that are reasonably approximated by power law rate expressions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Metal-organic framework supported single-site nickel catalysts for butene dimerization

Homotopic sites in a well-controlled environment are not only ideal systems for mechanistic studies, but also allow optimal control of catalytic transformations. Sites having only a single metal cation and sites consisting of metal oxo complexes with few nickel (Ni) cations supported on the nodes of UiO-66 metal-organic framework (Ni-UiO-66) are studied for 1-butene dimerization. Monomeric Ni sites, which bind to the Zr 6 node via two Zr-OH(µ3) linkages, are active and selective for the dimerization of 1-butene to linear and mono-branched C 8 isomers. Ni oxo complexes with few Ni cations show lower activity and promote the oligomerization of transiently formed C 8 isomers. In conclusion, Kohn-Sham density function theory calculations combined with spectroscopic measurements and kinetic analyses indicate that dimerization follows a Cossee-Arlman reaction mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Molecular Mechanism and Evolution of Guanylate Kinase Regulation by (p)ppGpp

The nucleotide (p)ppGpp mediates bacterial stress responses, but its targets and underlying mechanisms of action vary among bacterial species and remain incompletely understood. Here, we characterize the molecular interaction between (p)ppGpp and guanylate kinase (GMK), revealing the importance of this interaction in adaptation to starvation. Combining structural and kinetic analyses, we show that (p)ppGpp binds the GMK active site and competitively inhibits the enzyme. The (p)ppGpp-GMK interaction prevents the conversion of GMP to GDP, resulting in GMP accumulation upon amino acid downshift. Abolishing this interaction leads to excess (p)ppGpp and defective adaptation to amino acid starvation. A survey of GMKs from phylogenetically diverse bacteria shows that the (p)ppGpp-GMK interaction is conserved in members of Firmicutes, Actinobacteria, and Deinococcus-Thermus, but not in Proteobacteria, where (p)ppGpp regulates RNA polymerase (RNAP). We propose that GMK is an ancestral (p)ppGpp target and RNAP evolved more recently as a direct target in Proteobacteria.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

Molecular cloning and functional characterization of a rainbow trout liver Oatp

Cyanobacterial blooms have an impact on the aquatic ecosystem due to the production of toxins (e.g. microcystins, MCs), which constrain fish health or even cause fish death. However the toxicokinetics of the most abundant toxin, microcystin-LR (MC-LR), are not yet fully understood. To investigate the uptake mechanism, the novel Oatp1d1 in rainbow trout (rtOatp1d1) was cloned, identified and characterized. The cDNA isolated from a clone library consisted of 2772 bp containing a 2115 bp open reading frame coding for a 705 aa protein with an approximate molecular mass of 80 kDa. This fish specific transporter belongs to the OATP1 family and has most likely evolved from a common ancestor of OATP1C1. Real time PCR analysis showed that rtOatp1d1 is predominantly expressed in the liver, followed by the brain while expression in other organs was not detectable. Transient transfection in HEK293 cells was used for further characterization. Like its human homologues OATP1A1, OATP1B1 and OATP1B3, rtOatp1d1 displayed multi-specific transport including endogenous and xenobiotic substrates. Kinetic analyses revealed a K{sub m} value of 13.9 μM and 13.4 μM for estrone-3-sulfate and methotrexate, respectively and a rather low affinity for taurocholate with a K{sub m} value of 103 μM. Furthermore, it was confirmed that rtOatp1d1 is a MC-LR transporter and therefore most likely plays a key role in the susceptibility of rainbow trout to MC intoxications. - Highlights: • A new Oatp1d1 in rainbow trout (rtOatp1d1) was cloned, identified and characterized. • rtOatp1d1 is predominantly expressed in the liver. • rtOatp1d1 displays multi-specific transport of endogenous and xenobiotic substrates. • rtOatp1d1 is a homologue of the OATP1A1, OATP1B1 and OATP1B3. • rtOatp1d1 is a microcystin (MC) transporter.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2016

Structural Studies on a Glucosamine/Glucosaminide N -Acetyltransferase

Glucosamine/glucosaminide N-acetyltransferase or GlmA catalyzes the transfer of an acetyl group from acetyl CoA to the primary amino group of glucosamine. The enzyme from Clostridium acetobutylicum is thought to be involved in cell wall rescue. In addition to glucosamine, GlmA has been shown to function on di- and trisaccharides of glucosamine as well. Here we present a structural and kinetic analysis of the enzyme. For this investigation, eight structures were determined to resolutions of 2.0 Å or better. The overall three-dimensional fold of GlmA places it into the tandem GNAT superfamily. Each subunit of the dimer folds into two distinct domains which exhibit high three-dimensional structural similarity. Whereas both domains bind acetyl CoA, it is the C-terminal domain that is catalytically competent. On the basis of the various structures determined in this investigation, two amino acid residues were targeted for further study: Asp 287 and Tyr 297. Although their positions in the active site suggested that they may play key roles in catalysis by functioning as active site bases and acids, respectively, this was not borne out by characterization of the D287N and Y297F variants. The kinetic properties revealed that both residues were important for substrate binding but had no critical roles as acid/base catalysts. Kinetic analyses also indicated that GlmA follows an ordered mechanism with acetyl CoA binding first followed by glucosamine. Here, the product N-acetylglucosamine is then released prior to CoA. The investigation described herein provides significantly new information on enzymes belonging to the tandem GNAT superfamily.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Structural and Biochemical Investigation of PglF from Campylobacter jejuni Reveals a New Mechanism for a Member of the Short Chain Dehydrogenase/Reductase Superfamily

Within recent years it has become apparent that protein glycosylation is not limited to eukaryotes. Indeed, in Campylobacter jejuni, a Gram-negative bacterium, more than 60 of its proteins are known to be glycosylated. One of the sugars found in such glycosylated proteins is 2,4-diacetamido-2,4,6-trideoxy-α-d-glucopyranose, hereafter referred to as QuiNAc4NAc. The pathway for its biosynthesis, initiating with UDP-GlcNAc, requires three enzymes referred to as PglF, PglE, and PlgD. The focus of this investigation is on PglF, an NAD+-dependent sugar 4,6-dehydratase known to belong to the short chain dehydrogenase/reductase (SDR) superfamily. Specifically, PglF catalyzes the first step in the pathway, namely, the dehydration of UDP-GlcNAc to UDP-2-acetamido-2,6-dideoxy-α-d-xylo-hexos-4-ulose. Most members of the SDR superfamily contain a characteristic signature sequence of YXXXK where the conserved tyrosine functions as a catalytic acid or a base. Strikingly, in PglF, this residue is a methionine. Here we describe a detailed structural and functional investigation of PglF from C. jejuni. For this investigation five X-ray structures were determined to resolutions of 2.0 Å or better. In addition, kinetic analyses of the wild-type and site-directed variants were performed. Furthermore, on the basis of the data reported herein, a new catalytic mechanism for a SDR superfamily member is proposed that does not require the typically conserved tyrosine residue.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Effect of Char Loading on Reduction Kinetics of Cu-Based Oxygen Carriers in a Drop-Tube Fluidized-Bed Reactor at Temperatures from 850 to 1100 °C: Experiment and CFD Modeling

Chemical-looping combustion with oxygen uncoupling (CLOU) is a process using gaseous or solid hydrocarbon fuels and is a promising carbon capture and storage (CCS) technology. In CLOU, combustion of the fuel is achieved through the release of gaseous O 2 from an oxygen carrier material such as CuO and is favored at high temperatures and low O 2 partial pressures. The primary objectives of this study were to (1) compare values for the apparent rate constant k ov ( T ) for the overall rate of reduction of a CuO carrier, either alone or in the presence of coal char obtained from the pyrolysis of Powder River Basin (PRB) coal, and (2) develop and validate a computational fluid dynamics (CFD) model for the CuO/PRB coal char system based on known kinetics of the individual CuO and Cu 2 O reduction, combustion, and gasification reactions. Two oxygen carriers consisting of 20 wt % CuO/Al 2 O 3 and 9 wt % CuO/Al 2 O 3 were prepared by physical mixing and by incipient wetness impregnation (IWI), respectively. Kinetic analyses were conducted in the temperature range of 850–1100 °C. The CFD model typically reproduced experimental values of k ov ( T ) to within ±10%. We note the increase in k ov ( T ) caused by addition of only 0.075 g of PRB char per gram of CuO was modest at 1100 °C, but was more than 3-fold at 850 °C. Combustion and gasification of the coal char not only produced CO, opening another pathway for CuO reduction in addition to the CLOU reaction, but also resulted in the over-reduction of Cu 2 O to the undesired metallic Cu. Production of Cu metal increased with respect to char loading.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗