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At least 307 records · Page 17

Catalytic ignition model in monolithic reactor with in-depth reaction

A transient model has been developed to study ignition in a monolithic catalytic reactor. Special features are the inclusion of thermal and species structures in the porous catalytic layer and the resolution of small-time-scale events. Catalyst loading is used as a parameter to study these structure variations before and after ignition. Regions where the catalytic reaction is kinetically controlled and regions where the reaction is diffusionally controlled are identified in both steady and transient states.

Tien, Ta-Ching↗

Destruction of problematic airborne contaminants by hydrogen reduction using a Catalytically Active, Regenerable Sorbent (CARS)

Thermally regenerable sorbent beds were demonstrated to be a highly efficient means for removal of toxic airborne trace organic contaminants aboard spacecraft. The utilization of the intrinsic weight savings available through this technology was not realized since many of the contaminants desorbed during thermal regeneration are poisons to the catalytic oxidizer or form highly toxic oxidation by-products in the Trace Contaminant Control System (TCCS). Included in this class of compounds are nitrogen, sulfur, silicon, and halogen containing organics. The catalytic reduction of these problematic contaminants using hydrogen at low temperatures (200-300 C) offers an attractive route for their destruction since the by-products of such reactions, hydrocarbons and inorganic gases, are easily removed by existing technology. In addition, the catalytic oxidizer can be operated more efficiently due to the absence of potential poisons, and any posttreatment beds can be reduced in size. The incorporation of the catalyst within the sorbent bed further improves the system's efficiency. The demonstration of this technology provides the basis for an efficient regenerable TCCS for future NASA missions and can be used in more conventional settings to efficiently remove environmental pollutants.

Thompson, John O.↗

Fuel-rich catalytic combustion of a high density fuel

Fuel-rich catalytic combustion (ER is greater than 4) of the high density fuel exo-tetrahydrocyclopentadiene (JP-10) was studied over the equivalence ratio range 5.0 to 7.6, which yielded combustion temperatures of 1220 to 1120 K. The process produced soot-free gaseous products similar to those obtained with iso-octane and jet-A in previous studies. The measured combustion temperature agreed well with that calculated assuming soot was not a combustion product. The process raised the effective hydrogen/carbon (H/C) ratio from 1.6 to over 2.0, thus significantly improving the combustion properties of the fuel. At an equivalence ratio near 5.0, about 80 percent of the initial fuel carbon was in light gaseous products and about 20 percent in larger condensable molecules. Fuel-rich catalytic combustion has now been studied for three fuels with H/C ratios of 2.25 (iso-octane), 1.92 (jet-A), and 1.6 (JP-10). A comparison of the product distribution of these fuels shows that, in general, the measured concentrations of the combustion products were monotonic functions of the H/C ratio with the exception of hydrogen and ethylene. In these cases, data for JP-10 fell between iso-octane and jet-A rather than beyond jet-A. It is suggested that the ring cross-linking structure of JP-10 may be responsible for this behavior. All the fuels studied showed that the largest amounts of small hydrocarbon molecules and the smallest amounts of large condensable molecules occurred at the lower equivalence ratios. This corresponds to the highest combustion temperatures used in these studies. Although higher temperatures may improve this mix, the temperature is limited. First, the life of the present catalyst would be greatly shortened when operated at temperatures of 1300 K or greater. Second, fuel-rich catalytic combustion does not produce soot because the combustion temperatures used in the experiments were well below the threshold temperature (1350 K) for the formation of soot. Increasing the temperature above this value would remove the soot-free nature of the process. Since all the fuels studied show a similar breakdown of the primary fuel into smaller molecular combustion products, this technique can be applied to all hydrocarbon fuels.

Brabbs, Theodore A.↗

Catalytic methods using molecular oxygen for treatment of PMMS and ECLSS waste streams, volume 2

Catalytic oxidation has proven to be an effective addition to the baseline sorption, ion exchange water reclamation technology which will be used on Space Station Freedom (SSF). Low molecular weight, polar organics such as alcohols, aldehydes, ketones, amides, and thiocarbamides which are poorly removed by the baseline multifiltration (MF) technology can be oxidized to carbon dioxide at low temperature (121 C). The catalytic oxidation process by itself can reduce the Total Organic Carbon (TOC) to below 500 ppb for solutions designed to model these waste waters. Individual challenges by selected contaminants have shown only moderate selectivity towards particular organic species. The combined technology is applicable to the more complex waste water generated in the Process Materials Management System (PMMS) and Environmental Control and Life Support System (ECLSS) aboard SSF. During the phase 3 Core Module Integrated Facility (CMIF) water recovery tests at NASA MSFC, real hygiene waste water and humidity condensate were processed to meet potable specifications by the combined technology. A kinetic study of catalytic oxidation demonstrates that the Langmuir-Hinshelwood rate equation for heterogeneous catalysts accurately represent the kinetic behavior. From this relationship, activation energy and rate constants for acetone were determined.

Akse, James R.↗

Heat Transfer to Surfaces of Finite Catalytic Activity in Frozen Dissociated Hypersonic Flow

The heat transfer due to catalytic recombination of a partially dissociated diatomic gas along the surfaces of two-dimensional and axisymmetric bodies with finite catalytic efficiencies is studied analytically. An integral method is employed resulting in simple yet relatively complete solutions for the particular configurations considered. A closed form solution is derived which enables one to calculate atom mass-fraction distribution, therefore catalytic heat transfer distribution, along the surface of a flat plate in frozen compressible flow with and without transpiration. Numerical calculations are made to determine the atom mass-fraction distribution along an axisymmetric conical body with spherical nose in frozen hypersonic compressible flow. A simple solution based on a local similarity concept is found to be in good agreement with these numerical calculations. The conditions are given for which the local similarity solution is expected to be satisfactory. The limitations on the practical application of the analysis to the flight of the blunt bodies in the atmosphere are discussed. The use of boundary-layer theory and the assumption of frozen flow restrict application of the analysis to altitudes between about 150,000 and 250,000 feet.

Chung, Paul M.↗

Demonstration of an Ultra-Short Channel Metal Monolith Catalytic Reactor for Trace Contaminant Control Applications

The International Space Station (ISS) Trace Contaminant Control Subassembly (TCCS) design is based upon proven, highly reliable technology. However, because its core unit operations rely upon expendable activated charcoal and an indirectly heated high temperature catalyst, annual logistics mass, crew time, and power consumption requirements are significant. To address this situation, a unique catalytic reactor design has been developed which is suitable for retrofit into the TCCS's high temperature catalytic oxidizer (HTCO) assembly. The unique design, which employs a metallic, ultra-short channel length monolith (USCM) catalyst substrate, was tested in a flight-like TCCS HTCO assembly to investigate its performance characteristics. Test results indicate that retrofitting the TCCS with a USCM-based catalytic reactor is feasible and that it may provide significant reductions in logistics mass, crew time, and power consumption. Savings indicated by test results are up to 81% for annual logistics, 56% for crew time, and 77% for startup transient duration. In addition, its demonstrated ability to operate in a power saving mode provides up to a 43% savings in average power consumption. A summary of the USCM demonstration test objectives, approach, results, and specific benefits to the TCCS's process economics are presented,

Perry, J. L↗

Effect of Porosity on Surface Catalytic Efficiency

This paper describes the effect of surface porosity of thermal protection materials on surface catalytic efficiency using test data taken from both arc-jet and side-arm reactor facilities. Relative surface porosity of the samples varied from 6% to 50%. Surface porosity was measured using a flow apparatus and Bernoulli equation. The surface catalytic efficiency of the materials was calculated using aerothermodynamic, and kinetic theories. The catalytic efficiency of the materials are compared at surface temperatures between room temperature and 2500 F. The data are presented in the form of graphs and tables.

Stewart, David A.↗

Structural Basis for the Catalytic Activity of Human Serine/Threonine Protein Phosphatase-5

Serinehhreonine protein phosphatase-5 (PP5) affects many signaling networks that regulate cell growth and cellular responses to stress. Here we report the crystal structure of the PP5 catalytic domain (PP5c) at a resolution of 1.6 A. From this structure we resolved the mechanism for PP5-mediated hydrolysis of phosphoprotein substrates, which requires the precise positioning of two metal ions within a con served Aspn-271-M(sub 1):M(sub 2)-W(sup 1)-His-427-His-304-Asp-274 catalytic motif. The structure of PPSc provides a structural basis for explaining the exceptional catalytic proficiency of protein phosphatases, which are among the most powerful known catalysts. Resolution of the entire C-terminus revealed a novel subdomain, and the structure of the PP5c should also aid development of type-specific inhibitors.

Swingle, M. R.↗

Structural Basis for the Catalytic Activity of Human SER/THR Protein Phosphatase-5

Serinekhreonine protein phosphatase-5 (PP5) affects many signaling networks that regulate cell growth. Here we report the 1.6 Angstrom resolution crystal structure of PP5 catalytic domain with metal and phosphate ions in the active site. The structure reveals a mechanism for PPS-mediated catalysis that requires the precise positioning of two metal ions within a conserved Asp(sup 271)-M(sub 1),-M(sub 2)-His(sup 427)-W(sup 2)-His(sup 304)-Asp(sup 274) catalytic motif, and provides a structural basis for the exceptional catalytic proficiency of protein phosphatases placing them among the most powerful catalysts. Resolution of the entire C-terminus revealed a novel subdomain, and the structure of PP5 should aid development of specific inhibitors.

Swingle, M. R.↗

Characterization and distribution of a maize cDNA encoding a peptide similar to the catalytic region of second messenger dependent protein kinases

Maize (Zea mays) roots respond to a variety of environmental stimuli which are perceived by a specialized group of cells, the root cap. We are studying the transduction of extracellular signals by roots, particularly the role of protein kinases. Protein phosphorylation by kinases is an important step in many eukaryotic signal transduction pathways. As a first phase of this research we have isolated a cDNA encoding a maize protein similar to fungal and animal protein kinases known to be involved in the transduction of extracellular signals. The deduced sequence of this cDNA encodes a polypeptide containing amino acids corresponding to 33 out of 34 invariant or nearly invariant sequence features characteristic of protein kinase catalytic domains. The maize cDNA gene product is more closely related to the branch of serine/threonine protein kinase catalytic domains composed of the cyclic-nucleotide- and calcium-phospholipid-dependent subfamilies than to other protein kinases. Sequence identity is 35% or more between the deduced maize polypeptide and all members of this branch. The high structural similarity strongly suggests that catalytic activity of the encoded maize protein kinase may be regulated by second messengers, like that of all members of this branch whose regulation has been characterized. Northern hybridization with the maize cDNA clone shows a single 2400 base transcript at roughly similar levels in maize coleoptiles, root meristems, and the zone of root elongation, but the transcript is less abundant in mature leaves. In situ hybridization confirms the presence of the transcript in all regions of primary maize root tissue.

NASA Program Space Biology↗

The Conservation of Structure and Mechanism of Catalytic Action in a Family of Thiamin Pyrophosphate (TPP)-dependent Enzymes

Thiamin pyrophosphate (TPP)-dependent enzymes are a divergent family of TPP and metal ion binding proteins that perform a wide range of functions with the common decarboxylation steps of a -(O=)C-C(OH)- fragment of alpha-ketoacids and alpha- hydroxyaldehydes. To determine how structure and catalytic action are conserved in the context of large sequence differences existing within this family of enzymes, we have carried out an analysis of TPP-dependent enzymes of known structures. The common structure of TPP-dependent enzymes is formed at the interface of four alpha/beta domains from at least two subunits, which provide for two metal and TPP-binding sites. Residues around these catalytic sites are conserved for functional purpose, while those further away from TPP are conserved for structural reasons. Together they provide a network of contacts required for flip-flop catalytic action within TPP-dependent enzymes. Thus our analysis defines a TPP-action motif that is proposed for annotating TPP-dependent enzymes for advancing functional proteomics.

Dominiak, P.↗

Catalytic Ignition and Upstream Reaction Propagation in Monolith Reactors

Using numerical simulations, this work demonstrates a concept called back-end ignition for lighting-off and pre-heating a catalytic monolith in a power generation system. In this concept, a downstream heat source (e.g. a flame) or resistive heating in the downstream portion of the monolith initiates a localized catalytic reaction which subsequently propagates upstream and heats the entire monolith. The simulations used a transient numerical model of a single catalytic channel which characterizes the behavior of the entire monolith. The model treats both the gas and solid phases and includes detailed homogeneous and heterogeneous reactions. An important parameter in the model for back-end ignition is upstream heat conduction along the solid. The simulations used both dry and wet CO chemistry as a model fuel for the proof-of-concept calculations; the presence of water vapor can trigger homogenous reactions, provided that gas-phase temperatures are adequately high and there is sufficient fuel remaining after surface reactions. With sufficiently high inlet equivalence ratio, back-end ignition occurs using the thermophysical properties of both a ceramic and metal monolith (coated with platinum in both cases), with the heat-up times significantly faster for the metal monolith. For lower equivalence ratios, back-end ignition occurs without upstream propagation. Once light-off and propagation occur, the inlet equivalence ratio could be reduced significantly while still maintaining an ignited monolith as demonstrated by calculations using complete monolith heating.

Struk, Peter M.↗

Catalytic Microtube Rocket Igniter

Devices that generate both high energy and high temperature are required to ignite reliably the propellant mixtures in combustion chambers like those present in rockets and other combustion systems. This catalytic microtube rocket igniter generates these conditions with a small, catalysis-based torch. While traditional spark plug systems can require anywhere from 50 W to multiple kW of power in different applications, this system has demonstrated ignition at less than 25 W. Reactants are fed to the igniter from the same tanks that feed the reactants to the rest of the rocket or combustion system. While this specific igniter was originally designed for liquid methane and liquid oxygen rockets, it can be easily operated with gaseous propellants or modified for hydrogen use in commercial combustion devices. For the present cryogenic propellant rocket case, the main propellant tanks liquid oxygen and liquid methane, respectively are regulated and split into different systems for the individual stages of the rocket and igniter. As the catalyst requires a gas phase for reaction, either the stored boil-off of the tanks can be used directly or one stream each of fuel and oxidizer can go through a heat exchanger/vaporizer that turns the liquid propellants into a gaseous form. For commercial applications, where the reactants are stored as gases, the system is simplified. The resulting gas-phase streams of fuel and oxidizer are then further divided for the individual components of the igniter. One stream each of the fuel and oxidizer is introduced to a mixing bottle/apparatus where they are mixed to a fuel-rich composition with an O/F mass-based mixture ratio of under 1.0. This premixed flow then feeds into the catalytic microtube device. The total flow is on the order of 0.01 g/s. The microtube device is composed of a pair of sub-millimeter diameter platinum tubes connected only at the outlet so that the two outlet flows are parallel to each other. The tubes are each approximately 10 cm long and are heated via direct electric resistive heating. This heating brings the gasses to their minimum required ignition temperature, which is lower than the auto-thermal ignition temperature, and causes the onset of both surface and gas phase ignition producing hot temperatures and a highly reacting flame. The combustion products from the catalytic tubes, which are below the melting point of platinum, are injected into the center of another combustion stage, called the primary augmenter. The reactants for this combustion stage come from the same source but the flows of non-premixed methane and oxygen gas are split off to a secondary mixing apparatus and can be mixed in a near-stoichiometric to highly lean mixture ratio. The primary augmenter is a component that has channels venting this mixed gas to impinge on each other in the center of the augmenter, perpendicular to the flow from the catalyst. The total crosssectional area of these channels is on a similar order as that of the catalyst. The augmenter has internal channels that act as a manifold to distribute equally the gas to the inward-venting channels. This stage creates a stable flame kernel as its flows, which are on the order of 0.01 g/s, are ignited by the combustion products of the catalyst. This stage is designed to produce combustion products in the flame kernel that exceed the autothermal ignition temperature of oxygen and methane.

Schneider, Steven J.↗

Peptide conjugates with polyaromatic hydrocarbons can benefit the activity of catalytic RNAs

Early stages of life likely employed catalytic RNAs (ribozymes) in many functions that are today filled by proteins. However, the earliest life forms must have emerged from heterogenous chemical mixtures, which included amino acids, short peptides, and many other compounds. Here we explored whether the presence of short peptides can help the emergence of catalytic RNAs. To do this, we conducted an in vitro selection for catalytic RNAs from randomized sequence in the presence of ten different peptides with a prebiotically plausible length of eight amino acids. This in vitro selection generated dozens of ribozymes, one of them with ∼900-fold higher activity in the presence of one specific peptide. Unexpectedly, the beneficial peptide had retained its N-terminal Fmoc protection group, and this group was required to benefit ribozyme activity. The same, or higher benefit resulted from peptide conjugates with prebiotically plausible polyaromatic hydrocarbons (PAHs) such as fluorene and naphthalene. This shows that PAH-peptide conjugates can act as potent cofactors to enhance ribozyme activity. The results are discussed in the context of the origin of life.

Kevin J. Sweeney↗

Catalytic membrane reactor, methods of making the same and methods of using the same for dehydrogenation reactions

A catalytic membrane reactor and methods of operating and producing the same are provided that efficiently produces highly pure hydrogen (H2) from ammonia (NH3) as well as operates according to other chemical conversion processes. In one embodiment, a tubular ceramic support made from porous yttria-stabilized zirconia has an outer surface that is impregnated with a metal catalyst such as ruthenium and then plated with a hydrogen permeable membrane such as palladium. An inner surface of the ceramic support is impregnated with cesium to promote conversion of ammonia to hydrogen and nitrogen (N2). The resulting catalytic membrane reactor produces highly pure hydrogen at low temperatures and with less catalytic loading. Therefore, ammonia can be used to effectively transport hydrogen for use in, for example, fuel cells in a vehicle.

Way, James Douglas↗

Conversion of Wet Waste to Sustainable Aviation Fuel and Chemical Intermediates via Catalytic Upgrading

Wet waste is a low-cost, abundant feedstock capable of displacing significant amounts of domestic petrofuel and petrochemical consumption. We present a sequential biochemical-thermochemical pathway to upgrade wet waste into hydrocarbon sustainable aviation fuel blendstock and chemical intermediates with near-zero or net-negative life-cycle CO2 emissions. Waste is initially upgraded to carboxylic acids via arrested anaerobic digestion, then catalytically converted to hydrocarbons via sequential heterogeneous catalytic ketonization, cyclization, and hydrodeoxygenation. We will discuss kinetics, durability, and reactor design of key catalytic processes, as well as applicability of final products to targeted applications.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

Methanol mixing−controlled compression ignition enabled via homogeneous charge compression ignition of dimethyl ether through catalytic decomposition of methanol

Methanol is a potentially attractive fuel for marine and off−road engines owing to its availability at bunkering and global distribution locations. Although methanol is well−distributed worldwide, its fuel chemistry and ignition properties make it poorly suited as a direct drop−in replacement for diesel fuel in compression−ignition engines. However, industrial processes are regularly used to convert methanol, via catalytic dehydration, to dimethyl ether (DME) over nonprecious metal catalysts. This chemical conversion can occur at relatively low pressures, temperatures, and catalyst space velocities, highlighting a potential opportunity to generate DME via onboard catalytic dehydration of methanol. DME’s fuel kinetic and ignition properties for compression ignition are much more favorable than those of methanol or even diesel fuel, but DME is more challenging than diesel fuel or methanol to pump, store, and deliver through conventional diesel fueling injection hardware. Thus, a potential opportunity exists to use the ignition and kinetic properties of DME, with the transportation and delivery advantages of methanol, in a methanol−fueled mixing−controlled compression−ignition engine. The present work explores performance, combustion behavior, and emissions reduction opportunities for methanol mixing−controlled combustion, enabled by a HCCI of DME that represents a small fraction of the total fuel energy that can be generated onboard via catalytic dehydration of methanol.

Splitter, Derek [ORNL] (ORCID:0000000174044047)↗

Intercalation-Activated Layered MoO 3 Nanobelts as Biodegradable Nanozymes for Tumor-Specific Photo-Enhanced Catalytic Therapy

The existence of natural van der Waals gaps in layered materials allows them to be easily intercalated with varying guest species, offering an appealing strategy to optimize their physicochemical properties and application performance. Herein, we report the activation of layered MoO 3 nanobelts via aqueous intercalation as an efficient biodegradable nanozyme for tumor-specific photo-enhanced catalytic therapy. In this work, the long MoO 3 nanobelts are grinded and then intercalated with Na + and H 2 O to obtain the short Na + /H 2 O co-intercalated MoO 3–x (NH–MoO 3–x ) nanobelts. In contrast to the inert MoO 3 nanobelts, the NH–MoO 3–x nanobelts exhibit excellent enzyme-mimicking catalytic activity for generation of reactive oxygen species, which can be further enhanced by the photothermal effect under a 1064 nm laser irradiation. Thus, after bovine serum albumin modification, the NH–MoO 3–x nanobelts can efficiently kill cancer cells in vitro and eliminate tumors in vivo facilitating with 1064 nm laser irradiation.

36 MATERIALS SCIENCE↗