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At least 865 records · Page 48

Plant physical defenses contribute to a latitudinal gradient in resistance to insect herbivory within a widespread perennial grass

Premise: Herbivore pressure can vary across the range of a species, resulting in different defensive strategies. If herbivory is greater at lower latitudes, plants may be better defended there, potentially driving a latitudinal gradient in defense. However, relationships that manifest across the entire range of a species may be confounded by differences within genetic subpopulations, which may obscure the drivers of these latitudinal gradients. Methods: We grew plants of the widespread perennial grass Panicum virgatum in a common garden that included genotypes from three genetic subpopulations spanning an 18.5° latitudinal gradient. We then assessed defensive strategies of these plants by measuring two physical resistance traits—leaf mass per area (LMA) and leaf ash, a proxy for silica—and multiple measures of herbivory by caterpillars of the generalist herbivore fall armyworm (Spodoptera frugiperda). Results: Across all genetic subpopulations, low-latitude plants experienced less herbivory than high-latitude plants. Within genetic subpopulations, however, this relationship was inconsistent—the most widely distributed and phenotypically variable subpopulation (Atlantic) exhibited more consistent latitudinal trends than either of the other two subpopulations. The two physical resistance traits, LMA and leaf ash, were both highly heritable and positively associated with resistance to different measures of herbivory across all subpopulations, indicating their importance in defense against herbivores. Again, however, these relationships were inconsistent within subpopulations. Conclusions: Defensive gradients that occur across the entire species range may not arise within localized subpopulations. Thus, identifying the drivers of latitudinal gradients in herbivory defense may depend on adequately sampling the diversity within a species.

09 BIOMASS FUELS↗

Optimal blending management of biomass resources used for biochemical conversion

This research develops an optimization model to describe the tradeoff among blend components in the least-cost biomass blend, based on resource availability, quality requirements, and logistics cost for a biochemical conversion. A mixed-integer linear programming model is developed to determine the least-cost blend from a set of candidate feedstocks. A case study – based on a biorefinery located in western Kansas that uses three-pass corn stover, two-pass corn stover, switchgrass, miscanthus, and municipal solid waste fractions to meet biochemical conversion specifications and feedstock demand – shows that the delivered cost of an optimal blend that meets carbohydrate and ash specifications is 12.12% higher than the delivered cost of optimal blend that meets a carbohydrate specification only. The results indicate that a least-cost blend that meets both carbohydrate and ash specifications consists of miscanthus (48.2%) and switchgrass (29.4%) whereas the least-cost blend meeting carbohydrate specification only comprises three-pass corn stover (55.4%) and two-pass corn stover (20.4%). Here an optimal blend uses a low-cost municipal solid waste fraction in all cases, implying that blending could be a potential strategy to reduce delivered feedstock cost.

09 BIOMASS FUELS↗

Influence of the Feedstock on Catalytic Fast Pyrolysis with a Solid Acid Catalyst

Abstract At RTI, we are developing a catalytic fast pyrolysis process with a new solid acid catalyst, the performance of which has been evaluated in a pilot‐scale reactor using loblolly pine. More robust technology development requires a deeper understanding of the influence of the feedstock properties of process performance defined by the organic liquid yield and composition. Seven types of woody and herbaceous biomass were tested in a 2.54 cm diameter fluidized‐bed reactor. This study shows that the product distribution and biocrude composition vary widely with different feedstocks. The yield of organic biocrude is in the range of 14.0–20.8 wt % for the tested feedstocks. The yields of incondensable gases and carbonaceous solids vary significantly from feedstock to feedstock, which may be because of the variation of the ash content in the feedstock. A feedstock with a higher ash content generates more gases; specifically more CO 2 but not necessarily more CO. The chemical composition, which includes lignin, hemicellulose, and cellulose, also affects the biocrude composition and the yield of gases. We also demonstrated a positive correlation between the cellulose content and CO yield and a negative correlation between the hemicellulose content and CO yield.

Wang, Kaige↗

Assaying Sorghum for Fuel Production

The publicly available NREL suite of laboratory analytical procedures (LAPs) provides researchers with the analytical tools to determine the composition of woody and herbaceous feedstocks. Feedstock characterization includes several steps: sample preparation, starch determination, moisture analysis, ashing, extraction, and hydrolysis. These steps provide information on specific compounds and classes of compounds such as ash, protein, moisture, extractives, sucrose, starch, glucan, xylan, galactan, arabinan, acetate and lignin. Here, we describe the use of these procedures to characterize sorghum [Sorghum bicolor (L.) Moench] with specific consideration of four main sorghum types: grain, forage, sweet, and biomass, which can vary significantly in composition. Special attention is paid to the extraction and the differentiation of glucose from starch and glucan from cellulose in the hybrids with significant amounts of nonstructural carbohydrates.

09 BIOMASS FUELS↗

Development of Biocomposites from Agro Wastes for Low Dielectric Applications

The present work is attempting to synthesize and characterizations of a novel carbazole core containing cardanol based benzoxazine monomer from carbazole core containing aromatic diamine, cardanol and paraformaldehyde. In addition, carbazole core containing cardanol based benzoxazine polymer and various weight percentages of amine functionalized rice husk ash incorporated carbazole core containing cardanol based polybenzoxazine composites were prepared. The prepared polymer and its composites were characterized by FTIR, XRD, DSC, TGA and dielectric studies. The various studies confirm that the composites show increased Tg, higher char yield and better thermal stability compared to carbazole core containing cardanol based benzoxazine polymer. In addition to that the composites show significant decrease in the dielectric constant values than the neat cardanol based polybenzoxazine. The surface morphology and the distribution of rice husk ash in carbazole core containing cardanol based polybenzoxazine composites are confirmed by SEM and TEM analysis. Hence, the present study has attempted to prepared eco-friendly value added carbazole core containing cardanol based polybenzoxazine products for low dielectric constant applications by making use of biowaste for both matrix and reinforcement preparation to form biowaste based composites. Graphical Abstract: Schematic representation for the preparation of carbazole core containing cardanol based benzoxazine monomer, polybenzoxazine and biobased polybenzoxazine composites .

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Petrology and geochemistry of the Middle Pennsylvanian (Langsettian) Clintwood coalbed, Pike County, Kentucky

Abstract The Middle Pennsylvanian, Langsettian sub-stage Clintwood coal, along with its correlatives, was one of the more important energy resources in eastern Kentucky. The coal thickens from the NE-SW-trending Belfry anticline in central Pike County to the southeast, towards the Virginia-Kentucky border. Much of the thickness increase is in the bright lithotypes below a dull lithology. The bright lithologies transition from a bright clarain + vitrain + fusain lithology to a clarain + fusain lithology to the southeast. Half of the lithotypes in the three analyzed sections exceed 1000-µg/g Rare earth elements + Y + Sc (REYSc) (ash basis). The La N /Sm N vs. Gd N /Yb N and La N /Sm N vs. Ce N /Ce N * plots suggest that the top lithotype may have had best indication of an oxidizing environment. Positive Gd N /Gd N * and Eu N /Eu N * in some of the lithologies suggests that there may have been a hydrothermal influence in the sediment sources and/or in the diagenesis of the coal. Consideration of La N /Sm N and Zr (µg/g; ash basis), Zr vs. Sr, and V/Cr vs. inertinite/(inertinite + vitrinite) indicates that the dull lithotypes existed in a distinct geochemical environment compared to the brighter lithotypes. The isolation of the dull lithotypes from the bright lithotypes is supported by principal components analysis on inertinite/(inertinite + vitrinite), La N /Sm N , V/Cr, Sr, and either Zr or Ln(100(TiO 2 )/Al 2 O 3 ).

Hower, James C. (ORCID:0000000346942776)↗

Experimental study and demonstration of pilot-scale oxy-coal combustion at elevated temperatures and pressures

High pressure oxy-fuel firing is a promising next-generation combustion technology for electricity generation, allowing net efficiency improvement compared to traditional oxy-fuel firing systems. Oxy-coal combustion has been extensively investigated at ambient pressure, but limited experimental data is available regarding this combustion method at elevated pressures at pilot or full scale. The study presented here investigates the operational performance of a high pressure, high temperature pilot-scale oxy-fuel combustor. Pulverized Utah bituminous coal in form of coal-water slurry was combusted at pressures up to 14 bar, temperatures up to 1600 °C and firing rates up to 300 kW. Eight different runs were selected for presentation and the measurements include flue gas composition (CO, CO 2 , CH 4 , SO 2 , O 2 ), carbon and sulfur content of fly ash, combustor temperature profile and flame radiation profile. The flame radiation measurements were carried out with a novel narrow beam radiometer which measures local radiant heat flux at a specific location in the combustor. The radiation ranged from 108 to 279 kW/m 2 depending mainly on combustor temperature. Additionally, the temperature significantly impacted the carbon content of fly ash: 2.66% was measured near 1600 °C, while the concentration increased to 36.7% when the temperature was decreased to 1300°C. Furthermore, the successful experimental demonstrations showed that increasing pressure is a viable combustion method and a step towards enhancing the efficiency in oxy-fuel firing based power plants.

01 COAL, LIGNITE, AND PEAT↗

Investigation of the Effects of Biodiesel-based Na on Emissions Control Components

A single-cylinder diesel engine was used to investigate the impact of biodiesel-based Na on emissions control components using specially blended 20% biodiesel fuel (B20). The emissions control components investigated were a diesel oxidation catalyst (DOC), a Cu-zeolite-based NH{sub 3}-SCR (selective catalytic reduction) catalyst, and a diesel particulate filter (DPF). Both light-duty vehicle, DOC-SCR-DPF, and heavy-duty vehicle, DOC-DPF-SCR, emissions control configurations were employed. The accelerated Na aging is achieved by introducing elevated Na levels in the fuel, to represent full useful life exposure, and periodically increasing the exhaust temperature to replicate DPF regeneration. To assess the validity of the implemented accelerated Na aging protocol, engine-aged lean NO{sub x} traps (LNTs), DOCs and DPFs are also evaluated. To fully characterize the impact on the catalytic activity the LNT, DOC and SCR catalysts were evaluated using a bench flow reactor. The evaluation of the aged DOC samples and LNT show little to no deactivation as a result of Na contamination. However, the SCR in the light-duty configuration (DOC-SCR-DPF) was severely affected by Na contamination, especially when NO was the only fed NO{sub x} source. In the heavy-duty configuration (DOC-DPF-SCR), no impact is observed in the SCR NO{sub x} reduction activity. Electron probe micro-analysis (EPMA) reveals that Na contamination on the LNT, DOC, and SCR samples is present throughout the length of the catalysts with a higher concentration on the washcoat surface. In both the long-term engine-aged DPF and the accelerated Na-aged DPFs, there is significant Na ash present in the upstream channels; however, in the engine-aged sample lube oil-based ash is the predominant constituent.

33 ADVANCED PROPULSION SYSTEMS↗

Oxidation kinetics of biochar from woody and herbaceous biomass

The goal of this study was to determine oxidation kinetics for biochar produced from fast pyrolysis of various biomass feedstocks. In particular, the role of inherent ash content on the oxidation rate was evaluated. Thermogravimetric analysis (TGA) and fluidized bed combustion experiments were used to explore oxidation kinetics of six fast pyrolysis produced biochars with diverse ash content. Here, the reaction rates varied by a factor of three under chemical kinetic-limited conditions, demonstrating inorganic content impacts oxidation rate. Chemical kinetic rate coefficients were proposed as a function of compositional parameters to determine overall fit and impact. Potassium content was found to have a positive correlation, best describing the differences in the oxidation kinetic rate coefficients. Additionally, feedstocks were subjected to a 1 M HCl acid wash mitigating the catalytic activity of the metals. Acid washed biochars had lower oxidation kinetic rates compared to their unwashed counterparts, indicating the removal of catalytically active metals reduced oxidation rate. Gas composition (CO/CO 2 ) was measured during fluidized bed experiments for both acid-washed and unwashed biochars, which varied between the six biochars. Formation of CO 2 was greatly affected by catalytic metals, finding potassium content to correlate well with a higher percentage of CO 2 formation as compared to CO. Comparison of oxidation rates were made between the two experimental apparatuses to measure the effect of attrition on biochar oxidation.

09 BIOMASS FUELS↗

The role of catalytic iron in enhancing volumetric sugar productivity during autothermal pyrolysis of woody biomass

Passivation of naturally occurring AAEM in biomass enhances sugar yields from the fast pyrolysis of biomass by preventing these metals from catalyzing the fragmentation of pyranose rings in cellulose and hemicellulose. However, because AAEM also catalyzes lignin depolymerization, its passivation can be accompanied by undesirable char agglomeration. Pretreatment of biomass with ferrous sulfate both passivates AAEM and substitutes ferrous ions as lignin depolymerization catalysts. This pretreatment has been particularly successful for high ash biomass like corn stover, but of limited value for low ash biomass like wood. This study explores the reasons for this discrepancy and offers a combined pretreatment of ferrous sulfate and ferrous acetate pretreatment to overcome char agglomeration in wood. Furthermore, this new pretreatment increased sugar yields from 4.4 wt% to 15.5 wt% and 5.4 wt% to 19.0 wt% for hardwood and softwood biomasses, respectively. This pretreatment produces an iron-rich biochar that catalyzes oxidation of the biochar under the oxygen-rich conditions of autothermal pyrolysis, which is preferentially consumed to provide the enthalpy for pyrolysis, preserving bio-oil as a more desirable energy product. Instead of producing carbon monoxide, which dominates oxidation of biochar from untreated biomass, the iron catalyzes oxidation to carbon dioxide, producing more energy per mole of oxygen consumed. In fact, oxygen demand to support autothermal pyrolysis of red oak and southern yellow pine was reduced 15% by the presence of iron in the biochar.

42 ENGINEERING↗

CFD-DEM Modeling of Autothermal Pyrolysis of Corn Stover with a Coupled Particle- and Reactor-Scale Framework

Autothermal operation of fast pyrolysis is an efficient process-intensification technique wherein exothermic oxidation reactions are used to overcome the heat-transfer bottleneck of conventional pyrolysis. The development of accurate, reliable modeling toolsets is imperative to generating a deeper understanding of biomass autothermal pyrolysis systems to support scale-up and industrial deployment. This modeling effort describes the development of single-particle and reactor models which incorporate detailed reaction schemes and simultaneous exothermic oxidation reactions. The particle-scale model was parameterized for corn stover feedstock with particle morphology, density, ash content, and biopolymer composition, all of which impact the emergent conversion characteristics during pyrolysis. Results were then used to parameterize a reactor-scale autothermal pyrolysis model, which was developed using a coarse-grained computational fluid dynamic-discrete element method. The simulation results compared well with experimental results, with the predicted bio-oil, light gas, and biochar yield within 3.0 wt% of the experimental yields. Further analyses were performed to test the influence of equivalence ratio, biomass injection position, and particle size distribution on autothermal pyrolysis. The analysis of the physio-chemical properties of the fluid and solid phase inside the reactor and at the reactor outlet help reveal important process interactions of autothermal pyrolysis.

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

PERFORMANCE ANALYSIS OF AN ENGINEERING SCALE HYDROTHERMAL LIQUEFACTION SYSTEM

This work evaluates the Modular Hydrothermal Liquefaction System (MHTLS), an engineering-scale, integrated continuous HTL plant operated at the Pacific Northwest National Laboratory (PNNL), for converting realistic wet wastes into energy-dense biocrudes. The production campaigns discussed here processed algae, sewage sludges, lignocellulosic blends, Industrial food waste, and engineered food-waste slurries at 350?°C and around 200?bar, with nominal feed rates of ~12?L?h?¹. We report biocrude yields and composition, establish mass and elemental (C, N) balances, and quantify energy performance via heater duties, heat-exchanger behavior, and system-level efficiencies. Biocrudes contained 76–80?wt?% C (dry, ash-free) with HHVs of 38-41?MJ?kg?¹, substantially higher than feed materials HHVs of 16.6–26.1?MJ?kg?¹ and approaching petroleum fuels. Dry, ash-free biocrude yields of 32–53?wt?% corresponded to 43–71?wt?% carbon yields, with 18–40?wt?% of feed carbon routed to the aqueous phase. Thermal efficiencies were 50-65%, and total energy efficiencies, including reactor heat input, were 35-55%. A counter-current tube-in-tube heat exchanger delivered U values of 200–450?W?m?²?K?¹, with fouling-induced declines impacting heat recovery and heater duty. The analysis highlights three priorities for the process intensification of HTL: robust, fouling-resistant heat recovery, hydrodynamically suitable reactor and heat-exchanger designs, simplified and predictable solids management, and biocrude-water separation.

Biocrude production↗

Distribution and speciation of rare earth elements in coal combustion by-products via synchrotron microscopy and spectroscopy

Rare earth element (REE) binding environments and associated mineral phases in coal and coal combustion byproducts (CCBs) are not well understood. Advanced characterization of REEs' binding environments before, during, and after production can be vital in establishing an economically viable recovery method for REEs from these materials. Here, this study characterized different REE distributions, cerium (Ce) oxidation states, and Ce binding environments in 11 CCBs collected from various locales via X-ray fluorescence (XRF) elemental mapping and X-ray absorption near edge structure (XANES) at Stanford Synchrotron Radiation Lightsource (SSRL). Bulk Ce LIII edge XANES identified Ce(III) (>85%) as the predominant Ce oxidation state in all studied samples. Ce speciation and XRF elemental map analyses further reveal the REEs in studied samples can be (1) dispersed throughout the aluminosilicate glass phase, (2) as micro-particles in large glass grain, or (3) as independent trace phases in studied samples. Both fly ash and bottom ash contain mainly Ce(III) micro-hotspots (<40 μm), co-localization with a range of elements, including, but not limited to: P, S, Ca, Ti, and Mn. At microscale, Ce can change from Ce(III) to mixture of Ce(III) and Ce(IV) and to 100% Ce(IV) oxide, revealing potential REE-phase decomposition and oxidation in coal and coal combustion process. Our study also observed intraparticle and interparticle distribution difference between light REEs and heavy REEs. Finally, the synchrotron-based characterization confirmed the presence of these trace, previously only theorized, phases during the combustion process and ultimately may inform the simplification of separation and extraction processes for REE from different CCBs.

36 MATERIALS SCIENCE↗

Silicate weathering in anoxic marine sediment as a requirement for authigenic carbonate burial

We emphasize the importance of marine silicate weathering (MSiW) reactions in anoxic sediment as fundamental in generating alkalinity and cations needed for carbonate precipitation and preservation along continental margins. We use a model that couples thermodynamics with aqueous geochemistry to show that the CO 2 released during methanogenesis results in a drop in pH to 6.0; unless these protons are buffered by MSiW, carbonate minerals will dissolve. We present data from two regions: the India passive margin and the active subduction zone off Japan, where ash and/or rivers supply the reactive silicate phase, as reflected in strontium isotope data. Offshore India and Korea, alteration of continent-derived silicates results in pore water enriched in radiogenic 87 Sr, with 87 Sr/ 86 Sr ratios as high as 0.7095 and 0.7104, respectively. Off Japan, strontium in pore water influenced by ash alteration is depleted in 87 Sr, with 87 Sr/ 86 Sr as low as 0.7065. Carbonate minerals formed by alkalinity and cations generated through MSiW carry these strontium isotopic signals, and are typically dolomite, siderite, and Fe-rich calcite. These contrast with the aragonite and high-magnesium calcite that form during anaerobic oxidation of methane and incorporate the coeval seawater 87 Sr/ 86 Sr signal. We show that MSiW is necessary for authigenic carbonate formation and preservation along continental margins, which remove carbon from Earth’s surface at rates previously estimated to be at least 10 12 mol yr -1 . In addition, these authigenic carbonates are of relevance to studies of the deep biosphere, fluid flow, seismogenesis, slope stability, and reservoir characteristics.

54 ENVIRONMENTAL SCIENCES↗

Distribution of rare earth elements and other critical elements in beneficiated Pennsylvania anthracites

The Pennsylvania Anthracite Fields are in a complex tectonic and metamorphic terrain, historically hosting one of the largest concentrations of coal mining in the USA. Anthracite mining now largely consists of the surface mining of the pillars remaining from the prime years of underground mining. The geochemical study of the sized coal products and the refuse (largely rock) from three preparation plants (breakers) demonstrates that Principal components analysis (PCA) of select major oxide, minor element, and rare earth elements illustrates some differentiation among the products from the individual plants. The rock samples, with abundant quartz and metamorphic Al-Si minerals and with a lower ash-basis REE concentration than the coals, were distinctly separated from the coal samples on the PCA plots. Plots of Gd N /Gd N * vs. Eu N /Eu N * and Ce N /Ce N * vs. Eu N / Eu N * showed differentiation between the individual suites of coals showed that the refuse samples had distinct REE distributions compared to the associated coals. Further, several minor and trace elements show enrichments in the coal samples. Lithium, with concentrations of up to 314 ppm on an ash basis, is among the most promising of the critical elements, exceeding the enrichment of the REY and Sc.

58 GEOSCIENCES↗

Comparative Evaluation of Microwave and Conventional Gasification of Different Coal Types: Experimental Reaction Studies

Here, effects of gasifier conditions (microwave or conventional) on the gasification characteristics of four different types of coal are evaluated by analysis of gaseous species generated during pyrolysis and gasification reactions. Four different coal samples are tested: a lignite (Mississippi), a low-ash subbituminous (Wyodak), a high-ash subbituminous (Usibelli), and a low volatile bituminous (Pocahontas #3). Gas composition, overall yields, carbon conversion efficiency, and cold gas efficiency are evaluated to compare gasification reactivity of the different coal types under microwave and conventional heating. During microwave pyrolysis (Ar atmosphere), greater selectivity of syngas species (H2 + CO) and greater overall non-condensable gas yields are observed, compared to conventional pyrolysis for all coals tested. The high yield of syngas during microwave pyrolysis is attributed to primary pyrolysis gases subsequently gasifying the char of the same sample to produce greater amounts of H2 and CO. During microwave gasification (CO2 atmosphere), selective heating and formation of hotspots within the coal enable the reverse Boudouard reaction to occur at a low bulk gasification temperature of 700 °C, which is less favorable under thermal gasification at this temperature. Yields of syngas are much higher under microwave gasification of all coals. Carbon conversion is found to have a linear correlation with volatile matter of the parent coal. Carbon conversion and cold gas efficiency are highest for coals gasified under microwave irradiation, and gasification reactivity of the four coals was determined to be dependent on the coal type.

01 COAL, LIGNITE, AND PEAT↗

Thermal Pretreatment of a High Lignin SSF Digester Residue to Increase its Softening Point

Residues high in lignin and ash generated from the simultaneous saccharification and fermentation of corn stover were thermally pretreated in an inert (N2) atmosphere to study the effect of time and temperature on its softening point. These residues are difficult to feed into gasifiers due to premature thermal degradation and formation of reactive liquids in the feed lines, leading to plugging. The untreated and treated residues were characterized by proximate and ultimate analysis, and then analyzed via TGA, DSC, 13C NMR, Py-GC-MS, CHNO/S, and TMA. Interpretation of the compositional analysis indicates that the weight loss observed during pretreatment is mainly due to the thermal decomposition and volatilization of the hemicelluloses and amorphous cellulose fractions. Fixed carbon increases in the pretreated material, mostly due to a concentration effect rather than the formation of new poly-aromatic material. The optimal processing time and temperature to minimize the production of carbonyl groups in the pretreated samples was 300°C at a time of 30 minutes. Results showed that the softening point of the material could be increased from 187°C to 250°C, and that pretreatment temperature plays a more important role than time. The increase in softening point was mainly due to the formation of covalent bonds in the lignin structures and the removal of low molecular weight volatile intermediates.

Gasification, Lignin rich feedstocks, high lignin ↗