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We developed a single-phase Pd/NbOPO 4 catalyst for reductive etherification that displays high catalytic activity, product selectivity, and regeneration stability.
Catalytic Fast Pyrolysis (CFP) is a process that converts biomass into liquid intermediates suitable for transportation fuels by rapidly heating it in the presence of a catalyst, aiming to produce stable oils with reduced oxygen content. During CFP, the catalyst can become deactivated by the accumulation of coke, a carbon-rich deposit formed from the decomposition of biomass components. Unlike in petroleum refining, regenerating coked catalysts from biomass pyrolysis requires specific approaches due to the different chemical nature of the coke formed. An experimental technique, Temperature Programmed Oxidation (TPO), was used to study the de-coking process by gradually increasing temperature while monitoring the production of CO and CO2, which provides data for kinetic modeling. Utilizing data from TPO experiments, coke combustion kinetic model was developed to describe the rate of coke removal at different temperatures, allowing for simulation of regeneration processes. Then kinetic model is integrated into MFIX-Exa for the simulation of Biogenic Fluid Catalytic Cracker (BFCC) regenerator at different scales, enabling analysis of catalyst flow, temperature distribution, and regeneration efficiency under various operating conditions.
OTIS is an on-line communication platform designed for smooth flow of technology information between advanced life support (ALS) technology developers, researchers, system analysts, and managers. With pathways for efficient transfer of information, several improvements in the ALS Program will result. With OTIS, it will be possible to provide programmatic information for technology developers and researchers, technical information for analysts, and managerial decision support. OTIS is a platform that enables the effective research, development, and delivery of complex systems for life support. An electronic data collection form has been developed for the solid waste element, drafted by the Solid Waste Working Group. Forms for other elements (air revitalization, water recovery, food processing, biomass production and thermal control) will also be developed, based on lessons learned from the development of the solid waste form. All forms will be developed by consultation with other working groups, comprised of experts in the area of interest. Forms will be converted to an on-line data collection interface that technology developers will use to transfer information into OTIS. Funded technology developers will log in to OTIS annually to complete the element- specific forms for their technology. The type and amount of information requested expands as the technology readiness level (TRL) increases. The completed forms will feed into a regularly updated and maintained database that will store technology information and allow for database searching. To ensure confidentiality of proprietary information, security permissions will be customized for each user. Principal investigators of a project will be able to designate certain data as proprietary and only technical monitors of a task, ALS Management, and the principal investigator will have the ability to view this information. The typical OTIS user will be able to read all non-proprietary information about all projects.Interaction with the database will occur over encrypted connections, and data will be stored on the server in an encrypted form. Implementation of OTIS will initiate a community-accessible repository of technology development information. With OTIS, ALS element leads and managers will be able to carry out informed technology selection for programmatic decisions. OTIS will also allow analysts to make accurate evaluations of technology options. Additionally, the range and specificity of information solicited will help educate technology developers of program needs. With augmentation, OTIS reporting is capable of replacing the current fiscal year-end reporting process. Overall, the system will enable more informed R&TD decisions and more rapid attainment of ALS Program goals.
The wheat straw, an inedible biomass that can be continuously produced in a space vehicle has been used to produce activated carbon for effective control of NOx emissions from the incineration of wastes. The optimal carbonization temperature of wheat straw was found to be around 600 degrees C when a burnoff of 67% was observed. The BET surface area of the activated carbon produced from the wheat straw reached as high as 300 m2/g. The presence of oxygen in flue gas is essential for effective adsorption of NO by activated carbon. On the contrary, water vapor inhibits the adsorption efficiency of NO. Consequently, water vapor in flue gas should be removed by drying agents before adsorption to ensure high NO adsorption efficiency. All of the NO in the flue gas was removed for more than 2 h by the activated carbons when 10% oxygen was present and the ratio of carbon weight to the flue gas flow rate (W/F) was 30 g min/L, with a contact time of 10.2 s. All of NO was reduced to N2 by the activated carbon at 450 degrees C with a W/F ratio of 15 g min/L and a contact time of 5.1 s. Reduction of the adsorbed NO also regenerated the activated carbon, and the regenerated activated carbon exhibited an improved NO adsorption efficiency. However, the reduction of the adsorbed NO resulted in a loss of carbon which was determined to be about 0.99% of the activated carbon per cycle of regeneration. The sufficiency of the amount of wheat straw in providing the activated carbon based on a six-person crew, such as the mission planned for Mars, has been determined. This novel approach for the control of NOx emissions is sustainable in a closed system such as the case in space travel. It is simple to operate and is functional under microgravity environment.
Plankton community models are critical tools for understanding the processes that shape marine plankton communities, how plankton communities impact biogeochemical cycles, and the feedbacks between community structure and function. Here, using the flexible Marine Biogeochemistry Library (MARBL), we present the Size-based Plankton ECological TRAits (MARBL-SPECTRA) model, which is designed to represent a diverse plankton community while remaining computationally tractable. MARBL-SPECTRA is composed of nine phytoplankton and six zooplankton size classes represented using allometric scaling relationships for physiological traits and interactions within multiple functional types. MARBL-SPECTRA is embedded within the global ocean component of the Community Earth System Model (CESM) and simulates large-scale, emergent patterns in phytoplankton growth limitation, plankton phenology, plankton generation time, and trophic transfer efficiency. The model qualitatively reproduces observed global patterns of surface nutrients, chlorophyll biomass, net primary production, and the biogeographies of a range of plankton size classes. In addition, the model simulates how predator:prey dynamics and trophic efficiency vary across gradients in total ecosystem productivity. Shorter food chains that export proportionally more carbon from the surface to the ocean interior occur in productive, eutrophic regions, whereas in oligotrophic regions, the food chains are relatively long and export less organic matter from the surface. The union of functional type modeling with size-resolved, trait-based modeling approaches allows MARBL-SPECTRA to capture both large-scale elemental cycles and the structure of planktonic food webs affecting trophic transfer efficiency.
Establishing an inexpensive and environmentally friendly scandium (Sc) supply is critical for the development of clean energy technologies. However, refining Sc from Sc-bearing sources using current technologies poses economic and environmental challenges due to its low concentration relative to base metals and chemically similar lanthanides. In this work, we developed a biosorption-based flow-through process for extraction of Sc from low-grade feedstocks. A novel biosorbent material was synthesized by encapsulating Arthrobacter nicotianae, a bacterium that selectively adsorbs Sc, within a porous silica matrix. Through the use of several complementary microscopy techniques, we demonstrated a highly porous biosorbent structure with a high cell-loading density and a homogenous cell distribution. Batch adsorption assays revealed selective Sc adsorption over lanthanides and common based metals, with the exception of Fe(III), as evidenced by separation factors greater than 50. The MESG particles were packed into fixed-bed columns to enable adsorption under flow-through conditions, which demonstrated effective Sc extraction at flow rates up to 0.08 cm/s and high stability for reuse; greater than 95% of the adsorption capacity was maintained after 10 consecutive adsorption/desorption cycles. When applied to a lignite coal leachate, whose Fe content was depleted through pH-mediated precipitation, the MESG particles yielded Sc breakthrough at 30 bed volumes, whereas all other metals broke through after only a few bed volumes. Following desorption, an eluate with a 124-fold increase in Sc purity was achieved relative to the lignite leachate with Sc constituting 96.4% of the total REEs. This study established a rapid, facile, and scalable cell immobilization approach that enables the use of microbial biomass for Sc recovery from low-grade sources.
Here, this study focuses on the economic value and carbon benefits of riparian buffers in urban drinking water production. The impact of riparian buffers on the waterworks operation in the Raccoon River watershed was quantified using the following metrics: nitrate concentration, days of nitrate removal operation, material and energy cost (based on 17 years of historical records with a watershed model), regression, and cost analysis. The findings indicate that the presence of riparian buffers in agricultural land can substantially decrease nitrate concentration in the water intake of the waterworks during the crop-growing season: 19% in April, 9% in May, and 11% in June. These reductions mean less nitrate treatment of the plant intake flow: 23% in April, 12% in May, and 3% in June. These changes lead to significant resource savings: 425 metric tons of sodium chloride (NaCl), 147 810 kWh of electricity, 253 metric tons of powdered activated carbon, and 20.8 million liters of fresh water. The buffers would also reduce greenhouse gas emissions by 86.9 metric tons (CO 2 equivalent) in 17 years. The total cost saving was estimated at $\$$327 326, with the highest potential savings in May ($\$$215 100), followed by April ($\$$65 465), and June ($\$$46 761). When factoring in buffer installation, cropland loss, nitrate removal, and cost associated with buffer harvest for biofuel in an established biomass market, the benefit to the entire watershed community would be $\$$2.63 million annually. The results underscore the significant cost benefits and environmental benefits associated with cropland riparian buffers in a watershed community. The approach employed in this study holds promise for assessing riparian buffer benefits in other watersheds, contributes to an understanding of sustainable water management practices, and provides a basis for decision making in a wide range of agricultural regions.
The goal of this project is to develop a prototype system that integrates the capture and catalytic hydrogenation of CO 2 into methanol in the same solvent. Ultimately, this integrated approach could provide a technology with projected reductions to capital and operating costs by at least 20% relative to a benchmark methanol synthesis via gas-phase CO 2 hydrogenation. There were five primary objectives for the project: 1. Optimize the selections of both the catalysts and the CO 2 capture solvents to achieve high conversion (>80%) and high selectivity (>90%) toward methanol in the targeted processing ranges (100-180°C, 1-60 bar). 2. Design a reactor system that provides a fixed catalyst surface area and high-efficiency heat exchange to assure compact modular processing. 3. Build and test a reactor system and demonstrate in a bench scale continuous flow system, and use the operating data to refine the comparison to existing conversion technologies. 4. Refine techno economic (TEA) and Tech-to-Market (TTM) analyses using the experimental data obtained from the bench-scale system. 5. Use the experimental data and TEA/TTM projections to develop a conceptual design for a pre-commercial system that targets a specific market opportunity.
Meteorological highlights from the third NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation (GTE/CITE 3) are presented. During August and September 1989, research flights were conducted from Wallops Island, Virginia, and Natal, Brazil, and included airborne sampling of air masses over adjacent regions of the Atlantic Ocean. Isentropic backward trajectory calculations, wind vector/streamline fields, rawinsonde data, and GOES and METEOSAT satellite imagery are utilized to examine the meteorological conditions for each flight and to determine the transport paths of the sampled air masses. Some aspects of the chemical signatures of the sampled air are also discussed. During the series of flights based at Wallops Island, Virginia, the flow into the experiment area was governed primarily by the position of the North Atlantic subtropical anticyclone. The large-scale tropospheric circulation switched from primarily a marine flow during flights 1-4, to a predominantly offshore mid-latitude continental flow during flights 5-10. During these later flights, the regional influences of large eastern U.S. cities along with vertical mixing by typical summertime convective activity strongly influenced the chemical characteristics of the sampled air. During the series of flights based at Natal, Brazil, the dominant synoptic feature was the South Atlantic subtropical anticyclone which generally transported air across the tropical Atlantic toward eastern Brazil. Pronounced subsidence and a well-defined trade wind inversion often characterized the lower and middle troposphere over the Natal region. Some high-altitude recirculation of air from South America was observed, as was cross-equatorial transport which had come from northern Africa. Biomass burning plumes were observed on segments of all of the flights, the source region being the central and southern savannah regions of Africa.
Observation of oscillation decay in droplets has been shown to be an effective approach in determining physical properties such as viscosity and surface tension for emerging biofuels using μl quantities. Herein this work extends the approach to higher temperatures relevant to fuel injection conditions for internal combustion engines. Experiments are conducted that use high-resolution strobed imaging of moving, heated, μm-sized, fuel droplets to capture shape oscillation decay through image processing and analysis. Two fuels are investigated, iso-butanol and a primary reference fuel (PRF 84), which is a mixture of iso-octane and n-heptane. A piezoelectric droplet generator is used to generate a continuous train of single droplets, which are given an initial perturbation and subsequently undergo damped oscillations, captured using strobed imaging. Surface tension and viscosity calculated at four different temperatures ranging from 30°C-55°C using the frequency and decay time associated with the fundamental mode are found to be within ~ 10% of reference values obtained from the literature. Complementary numerical simulations are performed that utilize a volume-of-fluid approach to track transient droplet oscillation phenomena along with heat and mass transfer in a 2D axisymmetric domain. Simulations, where droplet size and temperature can be independently varied, capture an expected decrease in oscillation frequency and increase in decay time, with increase in fuel temperature. The simulations are further used to study the relative contribution to deviations in surface tension and viscosity predictions due to heat and mass transfer from the droplet, as well as viscous effects violating the inviscid flow assumption in the droplet oscillation theory. Mass loss effects are found to be negligible. Temperature change due to heat transfer is found to have the next highest sensitivity, particularly for the more volatile PRF 84, which has a lower viscosity and associated Ohnesorge number. For isobutanol, which has a higher viscosity and Ohnesorge number, viscous effects contribute the most to deviation in fuel property predictions.
Electrochemical technologies have garnered intense interest in both academic research and industrial applications due to their potential to increase energy efficiency and reduce carbon footprint. However, electrochemical process fundamentals have been absent from the chemical process simulators available to millions of chemical engineers worldwide. To expedite process research and development of electrochemical technologies in the chemical industry, it is imperative that essential electrochemical process fundamentals be incorporated into process simulators to support modeling and simulation of electrochemical processes. Here, this study examines three process fundamentals key to the research and development of electrochemical processes: electrochemical reaction kinetics, electrolyte thermodynamics, and heat and mass transfer. It further illustrates application of these process fundamentals with a case study modeling an electrochemical process for the conversion of acrylonitrile to adiponitrile. The modeling example highlights the roles of applied voltage on reaction rates, and electron flow rates on the performance of electrochemical processes. It suggests that the applied voltage and electron flow rates are two unique concepts that should be included in simulators for electrochemical processes.
The One Earth Energy (OEE) plant in Gibson City, Illinois produces ethanol through a corn fermentation process. For this project, the maximum possible ethanol production rate for this facility is 160 million gallons per year (MMgal/yr) based on discussions with plant personnel regarding recent annual production rates and any foreseeable plans or possibilities to increase ethanol production at this facility. Yeast ferments the corn mash to produce ethanol and produces carbon dioxide (CO 2 ) as a by-product at the same time. The CO 2 bubbles out of the mash and flows through a packed bed water scrubber to remove volatile organic compounds before the gas vents to atmosphere. CO 2 will be captured after it has passed through the existing scrubber.
Tropical forests cycle a large amount of CO 2 between the land and atmosphere, with a substantial portion of the return flux due tree respiratory processes. However, in situ estimates of woody tissue respiratory fluxes and carbon use efficiencies (CUEW) and their dependencies on physiological processes including stem wood production (Pw) and transpiration in tropical forests remain scarce. In this work, we synthesize monthly Pw and daytime stem CO 2 efflux (ES) measurements over one year from 80 trees with variable biomass accumulation rates in the central Amazon. On average, carbon flux to woody tissues, expressed in the same stem area normalized units as ES, averaged 0.90 ± 1.2 µmol m -2 s -1 for Pw, and 0.55 ± 0.33 µmol m -2 s -1 for daytime ES. A positive linear correlation was found between stem growth rates and stem CO 2 efflux, with respiratory carbon loss equivalent to 15 ± 3% of stem carbon accrual. CUEW of stems was non-linearly correlated with growth and was as high as 77-87% for a fast-growing tree. Diurnal measurements of stem CO 2 efflux for three individuals showed a daytime reduction of ES by 15-50% during periods of high sap flow and transpiration. The results demonstrate that high daytime ES fluxes are associated with high CUE W during fast tree growth, reaching higher values than previously observed in the Amazon Basin (e.g. maximum CUEW up to 77-87%, versus 30-56%). The observations are consistent with the emerging view that diurnal dynamics of stem water status influences growth processes and associated respiratory metabolism.
Nonmethane hydrocarbons (NMHCs) and halocarbons were measured in the troposphere over the northwestern Pacific as part of the airborne component of NASA's Pacific Exploratory Mission-West Phase B (PEM-West B). This study took place in late winter of 1994, a period characterized by maximum outflow from the Asian continent. The results are compared to those from Pacific Exploratory Mission-West Phase A (PEM-West A), which was flown in the same region during late summer of 1991, when flow from the subtropical western Pacific dominated the lower troposphere. Mixing ratios of NMHCS, tetrachloroethene (C2Cl4), and methyl bromide (CH3Br) were significantly higher during PEM-West B than during PEM-West A, particularly at latitudes north of 25 N and altitudes lower than 6 km. The primary reasons for these higher ambient concentrations were the seasonal increase in the atmospheric lifetimes of trace gases controlled by HO radical reactions, and the more frequent input of continental air masses. During PEM-West B, air masses of continental origin observed north of 25 N latitude were augmented with urban signature gases such as C2Cl4. By contrast, more southerly continental outflow had characteristics associated with combustion sources such as biomass burning, including wood fuel burning. During the summer PEM-West A period, the spatial distribution of methyl iodide (CH3I) was consistent with effective oceanic sources at all latitudes, being especially strong in tropical and subtropical regions. At low latitudes, PEM-West B CH3I mixing ratios in the lower troposphere were similar to PEM-West A, but at latitudes greater than about 25 N PEM-West B concentrations were significantly reduced. Equatorial regions exhibited enhanced CH3I mixing ratios extending into the upper tropical troposphere, consistent with fast vertical transport of air from the tropical marine boundary layer.
Nonmethane hydrocarbons (NMHCs) and halocarbons were measured in the troposphere over the northwestern Pacific as part of the airborne component of NASA's Pacific Exploratory Mission-West Phase B (PEM-West B). This study took place in late winter of 1994, a period characterized by maximum outflow from the Asian continent. The results are compared to those from Pacific Exploratory Mission-West Phase A (PEM-West A), which was flown in the same region during late summer of 1991, when flow from the subtropical western Pacific dominated the lower troposphere. Mixing ratios of NMHCs, tetrachloroethene (C2Cl4), and methyl bromide (CH3Br) were significantly higher during PEM-West B than during PEM-West A, particularly at latitudes north of 25 deg N and altitudes lower than 6 km. The primary reasons for these higher ambient concentrations were the seasonal increase in the atmospheric lifetimes of trace gases controlled by HO radical reactions, and the more frequent input of continental air masses. During PEM-West B, air masses of continental origin observed north of 25 deg N latitude were augmented with urban signature gases such as C2Cl4. By contrast, more southerly continental outflow had characteristics associated with combustion sources such as biomass burning, including wood fuel burning. During the summer PEM-West A period, the spatial distribution of methyl iodide (CH3I) was consistent with effective oceanic sources at all latitudes, being especially strong in tropical and subtropical regions. At low latitudes, PEM-West B CH3I mixing ratios in the lower troposphere were similar to PEM-West A, but at latitudes greater than about 25 deg N PEM-West B concentrations were significantly reduced. Equatorial regions exhibited enhanced CH3I mixing ratios extending into the upper tropical troposphere, consistent with fast vertical transport of air from the tropical marine boundary layer.
To reduce emissions from combustion of fossil fuels, sustainable aviation fuels (SAFs) have the potential to decarbonize the aviation sector. Redirecting wastes from conventional waste management practices and using them as cost-effective feedstocks for low-carbon fuels can reduce emissions from both waste disposal and fuel combustion. One approach is to upgrade wet wastes to SAF precursors, such as volatile fatty acids (VFAs). Here, in this study, novel membrane-assisted arrested methanogenesis was developed to convert high-strength wastewater to VFAs. Based on experimental results of VFA production, techno-economic and life-cycle analyses were conducted to estimate the potential economic and environmental benefits of SAF production from high-strength wastewater via VFAs. By evaluating three proposed scenarios for VFA production, a minimum production cost of VFA is achieved at $\$$0.60/kg VFA at a wastewater flow rate of 1100 MT/d. For the corresponding VFA-derived SAF, the estimated minimum fuel selling price is $\$$4.64/gasoline gallon equivalent. The life-cycle analysis shows that up to a 71% reduction in greenhouse gas emissions can be achieved relative to its fossil-counterpart along with lower water and fossil-fuel consumption.
The increased accessibility of commercial aviation to the general population has in-creased the conventional jet fuel consumption, thereby causing increased CO2emissions. One of the strategies to reduce the environmental impact is to use sustainable aviation fuels (SAFs). SAFs are jet fuels obtained from renewable resources such as biomass and waste streams such as plastics/municipal solid wastes. Even though the use of SAFs has been gaining importance over the last two decades, only a few numerical studies on their usage have been reported so far. In this study, two SAFs namely, alcohol to jet (ATJ) and hydrotreated esters and fatty acids (HEFA), are chosen and their use in a simple, lead direct injection (LDI) combustor is studied. The focus of this study is limited to the thermo-chemical properties of the fuels and their impact on fuel distribution and evaporation. Hence, only non-reactive simulations are performed. A high accuracy, adaptive mesh refinement based low-Mach solver, PeleLMeX, is used for performing the simulations. The time-averaged flow results indicate faster evaporation of HEFA when compared to ATJ and Jet-A. The difference in fuel evaporation rates is attributed to the differences in fuel viscosity and surface tension properties and the concomitant variations in the fuel droplet size distributions.
Management of aquatic weeds in complex watersheds and river systems present many challenges to assessment, planning and implementation of management practices for floating and submerged aquatic invasive plants. The Delta Region Areawide Aquatic Weed Project (DRAAWP), a USDA sponsored area-wide project, is working to enhance planning, decision-making and operational efficiency in the California Sacramento-San Joaquin Delta. Satellite and airborne remote sensing are used map (area coverage and biomass density), direct operations, and assess management impacts on plant communities. Archived satellite records enable review of results following previous climate and management events and aide in developing long-term strategies. Examples of remote sensing aiding effectiveness of aquatic weed management will be discussed as well as areas for potential technological improvement. Modeling at local and watershed scales using the SWAT modeling tool provides insight into land-use effects on water quality (described by Zhang in same Symposium). Controlled environment growth studies have been conducted to quantify the growth response of invasive aquatic plants to water quality and other environmental factors. Environmental variability occurs across a range of time scales from long-term climate and seasonal trends to short-term water flow mediated variations. Response time for invasive species response are examined at time scales of weeks, day, and hours using a combination of study duration and growth assessment techniques to assess water quality, temperature (air and water), nitrogen, phosphorus, and light effects. These provide response parameters for plant growth models in response to the variation and interact with management and economic models associated with aquatic weed management. Plant growth models are to be informed by remote sensing and applied spatially across the Delta to balance location and type of aquatic plant, growth response to altered environments and phenology. Initial utilization of remote sensing tools developed for mapping of aquatic invasive plants improved operational efficiency in management practices. These assessment methods provide a comprehensive and quantitative view of aquatic invasive plants communities in the California Delta.