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The Aviation System Analysis Capability Noise Impact Model

To meet its objective of assisting the US aviation industry with the technological challenges of the future, NASA must identify research areas that have the greatest potential for improving the operation of the air transportation system. To accomplish this, NASA is building an Aviation System Analysis Capability (ASAC). The Noise Impact Model (NIM) has been developed as part of the ASAC. Its primary purpose is to enable users to examine the impact that quieter aircraft technologies and/or operation might have on community noise impact and air carrier operating efficiency at any of 16 large and medium size US airports. The analyst chooses an airport and case year for study, selects a runway use configuration and set of flight tracks for the scenario, and has the option of reducing the noise of the aircraft that operate at the airport by 3, 6, and 10 decibels, NIM computes the resultant noise impact and estimates any airline operational improvements. Community noise impact is characterized in three ways: the size of the noise contour footprint, the number of people living within the contours, and the number of homes located in the same contours. Distance and time savings are calculated by comparing the noise abatement flight path length to a less circuitous alternated routing. For a more efficient runway use configuration, the increase in capacity and reduction in delay are shown.

Ege, Russell A.↗

Analysis of an algae-based CELSS. Part 2: options and weight analysis

Life support components are evaluated for application to an idealized closed life support system which includes an algal reactor for food production. Weight-based trade studies are reported as "break-even" time for replacing food stores with a regenerative bioreactor. It is concluded that closure of the life support gases (oxygen recovery) depends on the carbon dioxide reduction chemistry and that an algae-based food production can provide an attractive alternative to re-supply for longer duration missions.

Bioreactors↗

Contribution of Chlorophyll Fluorescence to the Apparent Reflectance of Vegetation

Current strategies for monitoring the physiologic status of terrestrial vegetation rely on remote sensing reflectance (R) measurements, whi ch provide estimates of relative vegetation vigor based primarily on chlorophyll content. Vegetation chlorophyll fluorescence (CF) offers a non-destructive alternative and a more direct approach for diagnosis of vegetation stress before a significant reduction in chlorophyll content has occurred. Thus, monitoring of vegetation vigor based on CF may allow earlier stress detection and more accurate carbon sequestra tion estimates, than is possible using R data alone. However, the observed apparent vegetation reflectance (Ra) in reality includes contrib utions from both the reflected and fluoresced radiation. The aim of t his study is to determine the relative R and CF fractions contributing to Ra from the vegetation in the red to near-infrared region of the spectrum. The practical objectives of the study are to: 1) evaluate t he relationship between CF and R at the foliar level for corn, soybean, maple; and 2) for corn, determine if the relationship established f or healthy (optimal N) vegetation changes under N defiiency. To obtai n generally applicable results, experimental measurements were conducted on unrelated crop and tree species (maple, soybean and corn), unde r controlled conditions and a gradient of inorganic N fertilization l evels. Optical R spectra and actively induced CF emissions were obtained on the same foliar samples, in conjunction with measurements of p hotosynthetic function, pigment levels, and C and N content. The comm on spectral trends or similarities were examined. On average, 10-20% of apparent R at 685 nm was actually due to CF. The spectral trends in steady and maximum F varied significantly, with Fs (especially red) showing higher ability for species and treatment separation. The relative contribution of ChF to R varied significantly among species, with maple emitting much higher F amounts, as compared to corn and soybea n. Fs individual red and far-red bands and their ratio exhibited consistent species separations. For corn, the relative CF fraction increased in concert with the nutrient stress levels from <2% for non-stressed foliage to >7% for severely nutrient deficient plants. F685s provide d optimal treatment separation. This study confirms the trends in F68 5sE740s associated with N deficiency and vegetation stress, established usmg single narrow band excitation.

Campbell, P. K. Entcheva↗

Alternate Methods in Refining the SLS Nozzle Plug Loads

Numerical analysis has shown that the SLS nozzle environmental barrier (nozzle plug) design is inadequate for the prelaunch condition, which consists of two dominant loads: 1) the main engines startup pressure and 2) an environmentally induced pressure. Efforts to reduce load conservatisms included a dynamic analysis which showed a 31% higher safety factor compared to the standard static analysis. The environmental load is typically approached with a deterministic method using the worst possible combinations of pressures and temperatures. An alternate probabilistic approach, utilizing the distributions of pressures and temperatures, resulted in a 54% reduction in the environmental pressure load. A Monte Carlo simulation of environmental load that used five years of historical pressure and temperature data supported the results of the probabilistic analysis, indicating the probabilistic load is reflective of a 3-sigma condition (1 in 370 probability). Utilizing the probabilistic load analysis eliminated excessive conservatisms and will prevent a future overdesign of the nozzle plug. Employing a similar probabilistic approach to other design and analysis activities can result in realistic yet adequately conservative solutions.

Burbank, Scott↗

Composites Materials and Manufacturing Technologies for Space Applications

Composite materials offer significant advantages in space applications. Weight reduction is imperative for deep space systems. However, the pathway to deployment of composites alternatives is problematic. Improvements in the materials and processes are needed, and extensive testing is required to validate the performance, qualify the materials and processes, and certify components. Addressing these challenges could lead to the confident adoption of composites in space applications and provide spin-off technical capabilities for the aerospace and other industries. To address the issues associated with composites applications in space systems, NASA sponsored a Technical Interchange Meeting (TIM) entitled, "Composites Materials and Manufacturing Technologies for Space Applications," the proceedings of which are summarized in this Conference Publication. The NASA Space Technology Mission Directorate and the Game Changing Program chartered the meeting. The meeting was hosted by the National Center for Advanced Manufacturing (NCAM)-a public/private partnership between NASA, the State of Louisiana, Louisiana State University, industry, and academia, in association with the American Composites Manufacturers Association. The Louisiana Center for Manufacturing Sciences served as the coordinator for the TIM.

Vickers, J. H.↗

Predicting Maximum Temperatures of a Li-ion Battery on a Simulated Flight Profile using a Model-based Prognostics

One of the challenges in using Li-ion packs in aeronautics is their safety, and thermal runaway (TR) is a major concern. The current engineering solutions to prevent a Li-ion pack from a catastrophic TR require additional mass and volume to isolate cells. The excess mass could be reduced by improving detection and, thus, preventing a TR event. One of the possible early warning indicators of a TR is crossing a threshold temperature. We have developed an approach, based on the Unscented Kalman Filter (UKF), to predict the likelihood of reaching the threshold temperature for simulated flight profiles. The current battery prognostics algorithms for aerospace predict state-of-charge (SOC) and end-of-life (EOL) [1]. We extended this two-level algorithm to predict the maximum temperature during discharge. The amount of heat generated in a cell depends on factors such as cell chemistry, cell packaging, total cycles, operating temperature, and abuse history [2]. Our semi-empirical thermal model depends on three phenomenological parameters which account for those factors. In addition, a two-parameter reduced-order model is developed to predict the temperature rise for short bursts of “random-walk” (RW) discharge current sequence, which simulates a flight's current-loading profile. The performance of these models on different datasets and types of current loading will be presented. To predict the maximal temperatures for future cycles we must estimate the evolution of thermal parameters as the batteries age. It is found that the parameters of the 3-parametric thermal model cannot be estimated only from the RW data. To address the issue, we will present two alternative approaches: i) expanding the datasets to include discharge profiles beyond RWs; ii) model reduction to a two-parametric model. The two approaches will be illustrated by an application to the cycling data from a commercial LG 18650 cell. References: 1. M. Daigle, C.S. Kulkarni, End-of-discharge and End-of-life Prediction in Lithium-ion Batteries with Electrochemistry-based Aging Models, in: AIAA Infotech @ Aerospace, American Institute of Aeronautics and Astronautics, San Diego, California, USA, 2016. 2. M. Börner, et. al, Correlation of aging and thermal stability of commercial 18650-type lithium ion batteries, Journal of Power Sources. 342 (2017) 382–392.

Thermal runaway↗

A Low-Tech, Low-Budget Storage Solution for High Level Radioactive Sources

The need for safe, secure, and economical storage of radioactive material becomes increasingly important as beneficial uses of radioactive material expand (increases inventory), as political instability rises (increases threat), and as final disposal and treatment facilities are delayed (increases inventory and storage duration). Several vendor-produced storage casks are available for this purpose but are often costly — due to the required design, analyses, and licensing costs. Thus the relatively high costs of currently accepted storage solutions may inhibit substantial improvements in safety and security that might otherwise be achieved. This is particularly true in areas of the world where the economic and/or the regulatory infrastructure may not provide the means and/or the justification for such an expense. This paper considers a relatively low-cost, low-technology radioactive material storage solution. The basic concept consists of a simple shielded storage container that can be fabricated locally using a steel pipe and a corrugated steel culvert as forms enclosing a concrete annulus. Benefits of such a system include 1) a low-tech solution that utilizes materials and skills available virtually anywhere in the world, 2) a readily scalable design that easily adapts to specific needs such as the geometry and radioactivity of the source term material), 3) flexible placement allows for free-standing above-ground or in-ground (i.e., below grade or bermed) installation, 4) the ability for future relocation without direct handling of sources, and 5) a long operational lifetime . ‘Le mieux est l’ennemi du bien’ (translated: The best is the enemy of good) applies to the management of radioactive materials – particularly where the economic and/or regulatory justification for additional investment is lacking. Development of a low-cost alternative that considerably enhances safety and security may lead to a greater overall risk reduction than insisting on solutions that remain economically and/or politically ‘out of reach’.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Heat pumps in the United States: Market potentials, challenges and opportunities, technology advances

The US heat pump market has been affected by the socioeconomic impacts of the COVID-19 pandemic. However, the Biden administration’s goal of net-zero greenhouse gas emissions by 2050 through electrification and clean energy technologies is accelerating the research, development, and deployment of heat pumps in the United States for improved energy performance, reduced greenhouse gas emissions, and wider adoption. The US heat pump market has experienced steady growth since 2010. In 2020, heat pumps surpassed gas furnace shipments for the first time, and the trend maintains through 2022. The current priority is to improve the affordability of energy and equitable access to heat pump technologies through cost reductions and further accelerate this trend. In addition, current R&D includes emphases on alternative refrigeration technology and lower–global warming potential refrigerants to reduce direct emissions. Heat pump market share is expected to grow as regulatory policies and financial incentives steer the building sector toward decarbonization. This paper reviews policies and market trends, discusses the challenges and opportunities in the current policy landscape, and reviews current research in the United States.

Malhotra, Mini↗

A GIS-Based Suitability Analysis of a Phytomanagment Strategy for TCE in Groundwater and Soil Niagara Falls Storage Site, New York - 19385

The large number of complexly contaminated sites throughout the nation has propagated the application of phytoremedial techniques in a wide array of environmental remediation strategies. The use and breeding of vegetation for the in-situ treatment of environmental media (soil, groundwater, sediment) contaminated with organic or inorganic contaminants has shown to provide a low-cost alternative to conventional means of remediating contaminated sites (e.g., groundwater extraction, chemical oxidation or reduction, bioremediation, excavation, etc.). One impediment to effective phytoremediation is the selection of proper plant-species, which is complicated due to the many variables that are required for plant-species viability (i.e. range of soil pH, annual precipitation values, depth to groundwater table, etc.). This study employed the use of a Geographic Information Systems (GIS) to first define the spatial extent of contaminated media (soil and groundwater) at a project site and then support an effective means to optimize phytoremediative techniques to manage these impacts prior to final remediation. Spatial analyses and analytical calculations were coupled to determine an optimal plant species and spacing to maximize the effectiveness of a phytomanagement plan. The incorporation of fuzzy membership functions and fuzzy overlay provide an innovative method to help select the optimal plant-species for phytomanagement planning. Fuzzy membership functions were used to represent the plant growth requirements and provided an intuitive method to represent the uncertainty associated with plant-growth requirements. The fuzzy overlay function then employed a raster-based suitability analysis that together provided decision makers with a scientific solution to optimally design a phytomanagement strategy for site-related volatile organic compound (VOC) impacts. The Niagara Falls Storage Site (NFSS) VOC-impacted groundwater is contained in clayey glacial sediments, which commonly are technically impractical to remediate. Prior on-site studies show that native poplar (cottonwood variants) preferentially translocate or phytoextract the VOCs from the site soils and thus provide a proven mechanism to manage the multi-media impacts. Consequently, the Army Corps of Engineers Buffalo District evaluated phytoremediative approaches as a passive tool to manage the VOCs during the project life cycle prior to final remediation. The fuzzy membership functions and fuzzy overlay modeling of candidate species narrowed the selection to an optimal species and subsequent transpiration modeling estimated the plant spacing for the overall phytomanagement plan. The method employed for this study is easy applied to other phytoremediative and phytomanagement actions derived from hazardous waste decision making. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Planetary Protection Concerns During Pre-Launch Radioisotope Power System Final Integration Activities

The Advanced Stirling Radioisotope Generator (ASRG) is a next-generation radioisotope-based power system that is currently being developed as an alternative to the Multi-Mission Radioisotope Thermoelectric Generator (MMRTG). Power sources such as these may be needed for proposed missions to solar system planets and bodies that have challenging Planetary Protection (PP) requirements (e.g. Mars, Europa, Enceladus) that may support NASA s search for life, remnants of past life, and the precursors of life. One concern is that the heat from the ASRG could potentially create a region in which liquid water may occur. As advised by the NASA Planetary Protection Officer, when deploying an ASRG to Mars, the current COSPAR/NASA PP policy should be followed for Category IVc mission. Thus, sterilization processing of the ASRG to achieve bioburden reduction would be essential to meet the Planetary Protection requirements. Due to thermal constraints and associated low temperature limits of elements of the ASRG, vapor hydrogen peroxide (VHP) was suggested as a candidate alternative sterilization process to complement dry heat microbial reduction (DHMR) for the assembled ASRG. The following proposed sterilization plan for the ASRG anticipates a mission Category IVc level of cleanliness. This plan provides a scenario in which VHP is used as the final sterilization process. Keywords: Advanced Stirling Radioisotope Generator (ASRG), Planetary Protection (PP), Vapor hydrogen peroxide (VHP) sterilization.

Chen, Fei↗

8760-Based Method for Representing Variable Generation Capacity Value in Capacity Expansion Models: Preprint

Capacity expansion models (CEMs) are widely used to evaluate the least-cost portfolio of electricity generators, transmission, and storage needed to reliably serve demand over the evolution of many years or decades. Various CEM formulations are used to evaluate systems ranging in scale from states or utility service territories to national or multi-national systems. CEMs can be computationally complex, and to achieve acceptable solve times, key parameters are often estimated using simplified methods. In this paper, we focus on two of these key parameters associated with the integration of variable generation (VG) resources: capacity value and curtailment. We first discuss common modeling simplifications used in CEMs to estimate capacity value and curtailment, many of which are based on a representative subset of hours that can miss important tail events or which require assumptions about the load and resource distributions that may not match actual distributions. We then present an alternate approach that captures key elements of chronological operation over all hours of the year without the computationally intensive economic dispatch optimization typically employed within more detailed operational models. The updated methodology characterizes the (1) contribution of VG to system capacity during high load and net load hours, (2) the curtailment level of VG, and (3) the potential reductions in curtailments enabled through deployment of storage and more flexible operation of select thermal generators. We apply this alternate methodology to an existing CEM, the Regional Energy Deployment System (ReEDS). Results demonstrate that this alternate approach provides more accurate estimates of capacity value and curtailments by explicitly capturing system interactions across all hours of the year. This approach could be applied more broadly to CEMs at many different scales where hourly resource and load data is available, greatly improving the representation of challenges associate with integration of variable generation resources.

14 SOLAR ENERGY↗

The Challenge for Arms Control Verification in the Post-New START World

Nuclear weapon arms control treaty verification is a key aspect of any agreement between signatories to establish that the terms and conditions spelled out in the treaty are being met. Historically, arms control negotiations have focused more on the rules and protocols for reducing the numbers of warheads and delivery systems - sometimes resorting to complex and arcane procedures for counting forces - in an attempt to address perceived or real imbalances in a nation's strategic posture that could lead to instability. Verification procedures are generally defined in arms control treaties and supporting documents and tend to focus on technical means and measures designed to ensure that a country is following the terms of the treaty and that it is not liable to engage in deception or outright cheating in an attempt to circumvent the spirit and the letter of the agreement. As the Obama Administration implements the articles, terms, and conditions of the recently ratified and entered-into-force New START treaty, there are already efforts within and outside of government to move well below the specified New START levels of 1550 warheads, 700 deployed strategic delivery vehicles, and 800 deployed and nondeployed strategic launchers (Inter-Continental Ballistic Missile (ICBM) silos, Submarine-Launched Ballistic Missile (SLBM) tubes on submarines, and bombers). A number of articles and opinion pieces have appeared that advocate for significantly deeper cuts in the U.S. nuclear stockpile, with some suggesting that unilateral reductions on the part of the U.S. would help coax Russia and others to follow our lead. Papers and studies prepared for the U.S. Department of Defense and at the U.S. Air War College have also been published, suggesting that nuclear forces totaling no more than about 300 warheads would be sufficient to meet U.S. national security and deterrence needs. (Davis 2011, Schaub and Forsyth 2010) Recent articles by James M. Acton and others suggest that the prospects for maintaining U.S. security and minimizing the chances of nuclear war, while deliberately reducing stockpiles to a few hundred weapons, is possible but not without risk. While the question of the appropriate level of cuts to U.S. nuclear forces is being actively debated, a key issue continues to be whether verification procedures are strong enough to ensure that both the U.S. and Russia are fulfilling their obligations under the current New Start treaty and any future arms reduction treaties. A recent opinion piece by Henry Kissinger and Brent Scowcroft (2012) raised a number of issues with respect to governing a policy to enhance strategic stability, including: in deciding on force levels and lower numbers, verification is crucial. Particularly important is a determination of what level of uncertainty threatens the calculation of stability. At present, that level is well within the capabilities of the existing verification systems. We must be certain that projected levels maintain - and when possible, reinforce - that confidence. The strengths and weaknesses of the New START verification regime should inform and give rise to stronger regimes for future arms control agreements. These future arms control agreements will likely need to include other nuclear weapons states and so any verification regime will need to be acceptable to all parties. Currently, China is considered the most challenging party to include in any future arms control agreement and China's willingness to enter into verification regimes such as those implemented in New START may only be possible when it feels it has reached nuclear parity with the U.S. and Russia. Similarly, in keeping with its goals of reaching peer status with the U.S. and Russia, Frieman (2004) suggests that China would be more willing to accept internationally accepted and applied verification regimes rather than bilateral ones. The current verification protocols specified in the New START treaty are considered as the baseline case and are contrasted with possible alternative verification protocols that could be effective in a post-New START era of significant reductions in U.S. and other countries nuclear stockpiles. Of particular concern is the possibility of deception and breakout when declared and observed numbers of weapons are below the level considered to pose an existential threat to the U.S. In a regime of very low stockpile numbers, 'traditional' verification protocols as currently embodied in the New START treaty might prove less than adequate. I introduce and discuss a number of issues that need to be considered in future verification protocols, many of which do not have immediate solutions and so require further study. I also discuss alternatives and enhancements to traditional verification protocols, for example, confidence building measures such as burden sharing against the common threat of weapon of mass destruction (WMD) terrorism, joint research and development.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Perspectives on Low-Temperature Electrolysis and Potential for Renewable Hydrogen at Scale

Hydrogen is an important part of any discussion on sustainability and reduction in emissions across major energy sectors. In addition to being a feedstock and process gas for many industrial processes, hydrogen is emerging as a fuel alternative for transportation applications. Renewable sources of hydrogen are therefore required to increase in capacity. Low-temperature electrolysis of water is currently the most mature method for carbon-free hydrogen generation and is reaching relevant scales to impact the energy landscape. However, costs still need to be reduced to be economical with traditional hydrogen sources. Operating cost reductions are enabled by the recent availability of low-cost sources of renewable energy, and the potential exists for a large reduction in capital cost withmaterial and manufacturing optimization. This article focuses on the current status and development needs by component for the low-temperature electrolysis options.

08 HYDROGEN↗

Lightweight Materials for Automotive Application: An Assessment of Material Production Data for Magnesium and Carbon Fiber

The use of lightweight materials in vehicle components, also known as “lightweighting,” can result in automobile weight reduction, which improves vehicle fuel economy and generally its environmental footprint. Materials often used for vehicle lightweighting include aluminum, magnesium, and polymers reinforced with either glass or carbon fiber. However, because alternative materials typically used for vehicle lightweighting require more energy to make on a per part basis than the material being replaced (often steel or iron), the fuel efficiency improvement induced by a weight reduction is partially offset by an increased energy for the vehicle material production. To adequately quantify this tradeoff, reliable and current values for life-cycle production energy are needed for both conventional and alternative materials. Our focus here is on the production of two such alternative materials: magnesium and carbon fibers. Both these materials are low density solids with good structural properties. These properties have enabled their use in applications where weight is an issue, not only for automobiles but also for aerospace applications. This report addresses the predominant production methods for these materials and includes a tabulation of available material and energy input data necessary to make them. The life cycle inventory (LCI) information presented herein represents a process chain analysis (PCA) approach to life cycle assessment (LCA) and is intended for evaluation as updated materials production data for magnesium and carbon fiber for inclusion into the Greenhouse gases, Regulated Emissions, and Energy use in Transportation model (GREET2_2012). The summary life-cycle metrics used to characterize the cradle-to-gate environmental performance of these materials are the cumulative energy demand (CED) and greenhouse gas emissions (GHG) per kilogram of material.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Constructing a Simulation Surrogate with Partially Observed Output

Gaussian process surrogates are a popular alternative to directly using computationally expensive simulation models. When the simulation output consists of many responses, dimension-reduction techniques are often employed to construct these surrogates. However, surrogate methods with dimension reduction generally rely on complete output training data. This article proposes a new Gaussian process surrogate method that permits the use of partially observed output while remaining computationally efficient. The new method involves the imputation of missing values and the adjustment of the covariance matrix used for Gaussian process inference. The resulting surrogate represents the available responses, disregards the missing responses, and provides meaningful uncertainty quantification. In conclusion, the proposed approach is shown to offer sharper inference than alternatives in a simulation study and a case study where an energy density functional model that frequently returns incomplete output is calibrated.

42 ENGINEERING↗

Impact of lowering potassium contamination in liquid scintillation cocktails for ultra-sensitive radiation detection

Intrinsic 40 K radioactive backgrounds from impurities of natural K in liquid scintillation cocktails have previously been demonstrated to limit their use in ultra-sensitive applications. Here, this work explores two methodologies in parallel for the reduction of 40 K backgrounds in the cocktails, and lays the groundwork for use in ultra-sensitive applications. In one method, alternative low-K liquid scintillation matrix constituents were identified and in the other, a simple purification method for single components and finished cocktails was developed. Both methods were verified via ICP-MS analysis. Liquid scintillation counting of selected purified cocktails demonstrated background reduction, improved stability, and enhanced performance. The best performing purified cocktail was also counted on a custom-built ultra-low background liquid scintillation counter, with results below the detector background.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Quantifying the Impact of Metal Population Distribution in MFI-Supported Mo Catalysts for Methane Dehydroaromatization

Precise evaluation of intrinsic kinetic behavior in Mo/MFI catalysts for methane dehydroaromatization (MDA) is confounded by variations in Mo dispersion and speciation, which are influenced by metal loading and zeolite acidity. This work advances the utility of H 2 -temperature programmed reduction (H 2 -TPR) for characterizing Mo/MFI catalysts by enabling quantitative comparison of MoO x populations distinguished by reduction behavior and linked to initial catalytic performance. A comprehensive H 2 reduction pathway is established through systematic H 2 - TPR studies varying catalyst composition (1–10 wt % Mo, Si/Al = 15, 40, ∞), supplemented by UV-Raman spectroscopy, X-ray powder diffraction, N 2 physisorption, NH 3 -TPD, and advanced spectroscopic analysis (in situ XAS with principal component analysis/multivariate curve resolution—alternating least squares). Two low-temperature H 2 -TPR regions capture distinct Mo populations undergoing initial Mo(VI)→Mo(IV) reduction: a lower-temperature population (Mo-RI) associated primarily with highly dispersed, anchored MoO x species expected to predominantly reside within MFI channels, and a higher-temperature population (Mo-RII) corresponding to a broader set of MoO x species that becomes increasingly bulk-like/extrazeolitic at higher Mo loading. Quantification of these populations provides practical, kinetically relevant descriptors for comparing initial MDA rates across catalysts with varying Mo loading, Si/Al ratio, and MoO x heterogeneity. Application of lower-temperature Mo-RI estimates to kinetic measurements reveals a minimum threshold of ∼0.12 × 10 –3 mol Mo-RI/g cat , above which initial forward benzene rates normalized to this population converge despite differences in metal loading and zeolite Brønsted acidity. This threshold coincides with a transition toward a common C 2 -mediated benzene-forming regime, as indicated by approach-to-equilibrium analysis of methane-to-ethane, ethane-to-ethylene, and ethylene-to-benzene reaction steps. Above this threshold, normalized initial benzene rates are nearly invariant with increasing Mo-RII/Mo-RI population ratio, indicating that excess Mo-RII populations, including bulk-like/extrazeolitic MoO x domains present at higher loading, do not measurably suppress benzene formation associated with anchored and mostly channel-confined Mo population under the initial-rate conditions examined.

Mo/MFI↗

Catalytic Reduction of Residual Oxygen for the Purification of Carbon Dioxide Streams from Pressurized Oxy-Combustors

Pressurized oxy-combustion (OC) is regarded as an energy-efficient alternative to atmospheric OC. To utilize the captured carbon dioxide (CO2) from pressurized OC for enhanced oil recovery or carbon storage in geological formations, the CO2 product stream must meet the required purity specifications. One major impurity in OC flue gases is residual O2 (e.g., 3 vol%). In this study, a catalytic approach has been investigated to remove the residual O2 through a reduction reaction with injected methane (CH4) in a reverse-flow fixed-bed (RFFB) reactor. The performance was tested for a supported copper (Cu)-based catalyst synthesized by incipient wetness impregnation and a cobalt-manganese (CoMn) oxide catalyst synthesized by a coprecipitation method. A commercial Cu-based catalyst was also studied as the reference. Experimental results revealed that under the reverse-flow operation, the temperature profiles in the reactor were symmetrical on both sides of the catalyst zone and were more homogenous than those under the conventional one-direction-flow operation. Among the tested catalysts, the CoMn catalyst was the most reactive for promoting the reduction of O2 with CH4, able to attain >95% O2 removal at 475 °C and a gas hourly space velocity (GHSV) of 18,000 h-1 with a feed gas containing 3 vol% O2. Under all experiments, the concentrations of carbon monoxide (CO) were lower than 30 ppmv in the effluent gas streams. The reaction between O2 and CH4 could be depicted by using the Mars–van Krevelen redox mechanism based on a two-step reduction–oxidation reaction pathway.

36 MATERIALS SCIENCE↗