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Pilot plant reliability metrics for grinding and fast pyrolysis of woody residues

Here we report on the effects of loblolly pine residue variability on material throughput, pilot plant uptime, operator intervention, product yield, and product quality for grinding, fast pyrolysis, and hydrotreating operations. Preprocessing throughput using a hammer mill varied between 31-48% of nameplate capacity (5 tons/hr). Grinder overloads in the size reduction step were more prevalent for lower ash and higher moisture materials. Fast pyrolysis throughput varied between 57-72% of nameplate capacity (20 kg/hr) and bio-oil yields varied between 46-53% (feedstock carbon to oil, dry basis). During fast pyrolysis operations, downtime was caused by bridging in the feed and char removal systems and plugging in the condensation system. Cohesion of feedstock and char leading to system plugging was less frequent for higher ash feedstocks, and differences in condenser plugging behavior between high and low ash feedstocks were observed. The catalyst stability of the bio-oil stabilization step was strongly dependent on the sulfur content in the bio-oil, which was higher for the high-ash residue oils. Lower moisture content in the starting biomass was consistent with lower sulfur content in bio-oil. Yields and properties of hydrotreated fuel products showed minimal deference among the bio-oils.

Klinger, Jordan↗

Aragonite saturation horizon variability along North Pacific seamounts and implications for deep-sea coral reefs

The 2014 discovery of living deep-sea coral reefs along the Northwest Hawaiian Islands (NWHI) and lower Emperor Seamount Chain (ESC), despite the North Pacific’s shallow aragonite saturation horizon (ASH) and high CaCO3 dissolution rates, underscores the need to understand the local seawater chemistry that allows these reefs to persist. We investigated seawater carbonate chemistry using discrete samples along the NWHI and ESC from two cruises ~1 year apart (08/26/21 – 09/26/21, 09/09/22 – 10/24/22). Across the two cruises, ASH depth difference ranged from 15 to 77 m. Since the Pacific ASH shoals by 1–2 m yr?¹, this long-term trend cannot explain the magnitude of ASH change observed between cruises. Temperature-salinity plots similarly indicate no major shifts in intermediate water masses that could account for these changes. Instead, ASH depth variability was primarily governed by localized biogeochemical processes, namely changes in intermediate water respiration and CaCO3 dissolution. Indicators for dissolution (TA*) and respiration (AOU) suggest changes in ASH depth were driven by changes in dissolution at the northern- and southern-most sites, whereas respiration exerted stronger control at central sites. Combining 2021 and 2022 data with data from 2014 – 2019 (excluding 2018) revealed high interannual ASH variability, by as much as >200 m at one site. Deep-sea coral reefs across the NWHI and ESC currently reside close to the ASH depth and likely experience seasonal and interannual shifts between under- and supersaturation. As ocean acidification progresses however, persistent exposure to undersaturated seawater could further threaten these critical deep-sea ecosystems.

coral reefs↗

Acid digestion processes for recovery of rare earth elements from coal and coal byproducts

A system for recovering rare earth elements from coal ash includes a leaching reactor, an ash dryer downstream of the leaching reactor, and a roaster downstream of the ash dryer that is cooperatively connected to both the leaching reactor and the ash dryer. Coal ash is mixed with an acid stream such that rare earth elements present in the coal ash are dissolved in the acid stream, thereby creating (i) a leachate containing the rare earth elements and (ii) leached ash. The leachate is heated to obtain acid vapor and an acid-soluble rare earth concentrate. Mixing of the coal ash with the acid stream can occur in a leaching reactor and heating of the leachate can occur in a roaster. The acid-soluble rare earth concentrate can be fed to a hydrometallurgical process to separate and purify the rare earth elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Abstract for CRADA between NETL and Rivalia Chemical Co

The National Energy Technology Laboratory (NETL) will assist Rivalia Chemical Co (Participant) with system analyses to aid the Participant with setting priorities and securing funding. The Participant is an early-stage startup pioneering new chemical extraction technology to solve two important problems: critical mineral scarcity and coal ash waste management. The U.S. generates coal fly ash from coal combustion for power generation and has amassed over two billion metric tons of ash, which contains valuable rare earth elements. The ash is often stored in unlined ponds and frequently contaminates the local environment. The Participant’s patent-pending process harvests rare earths from ash, then transforms the residual ash for use in green concrete, providing an economic pathway for utilities to empty and remediate the ash ponds. Founder Laura Stoy created the company in July 2022 after developing the core intellectual property during her Ph.D. at the Georgia Institute of Technology. Stoy is currently participating in the Chain Reactions Innovations (CRI) program at the U.S. Department of Energy (DOE) Argonne National Laboratory (ANL) where she will be optimizing the core technology and scaling from bench scale to demonstration scale. The technology has been validated at bench scale (TRL3); the goal is to approach TRL5 by the conclusion of the CRI program and prepare to raise capital investment for a pilot facility. NETL and the Participant will develop an updated technoeconomic analysis (TEA) and identify key sustainability performance parameters to inform ’s research and development priorities and de-risk the technology. NETL will also provide the Participant with guidance to prepare a more detailed life cycle assessment (LCA), and a narrative on the Participant’s product markets. These tools will aid the Participant with the next steps of commercialization.

01 COAL, LIGNITE, AND PEAT↗

Post-Wildfire Mobilization of Organic Carbon

Wildfires significantly alter watershed functions, particularly the mobilization of organic carbon (OC). This study investigated OC mobility and the physicochemical characteristics of wildfire-impacted soils and ashes from the northern California and Nevada fires (Dixie, Beckworth, Caldor). Organic carbon in wildfire-derived ashes (9.2–57.3 mg/g) generally exceeded levels in the background soils (4.3–24.4 mg/g), except at the Dixie fire sites. The mobile OC fraction varied from 0.0093 to 0.029 in ashes and 0.010 to 0.065 in soils, though no consistent trend was observed between the ashes and soils. Notably, the ash samples displayed lower OC mobility compared with the soils beneath them. A negative correlation was found between the mobile OC fraction and bulk OC content. Wildfire increased the total amount of mobile OC substantially by 5.2–574% compared to the background soils. Electron paramagnetic resonance (EPR) spectra confirmed the presence of environmentally persistent free radicals (EPFRs), which correlated with observed redox reactivity. Additionally, X-ray absorption near edge structure (XANES) and X-ray fluorescence (XRF) imaging revealed that Fe(II) oxidation in soils beneath the ashes may have enhanced the OC mobility, likely driven by pyrogenic carbon and free radicals. These findings enhance our understanding of post-wildfire OC mobilization and the impact of ash–soil physicochemical properties on watershed health.

organic carbon↗

The Calipso Version 4.5 Stratospheric Aerosol Subtyping Algorithm

The accurate classification of aerosol types injected into the stratosphere is important to properly characterize their chemical and radiative impacts within the Earth climate system. The updated stratospheric aerosol subtyping algorithm used in the version 4.5 (V4.5) release of the Cloud Aerosol Lidar with Orthogonal Polarization (CALIOP) level 2 data products now delivers more comprehensive and accurate classifications than its predecessor. The original algorithm identified four aerosol subtypes for layers detected above the tropopause: volcanic ash, smoke, sulfate/other, and polar stratospheric aerosol (PSA). In the revised algorithm, sulfates are separately identified as a distinct, homogeneous subtype, and the diffuse, weakly scattering layers previously assigned to the sulfate/other class are recategorized as a fifth “unclassified” subtype. By making two structural changes to the algorithm and revising two thresholds, the V4.5 algorithm improves the ability to discriminate between volcanic ash and smoke from pyrocumulonimbus injections, improves the fidelity of the sulfate subtype, and more accurately reflects the uncertainties inherent in the classification process. The 532 nm lidar ratio for volcanic ash was also revised to a value more consistent with the current state of knowledge. This paper briefly reviews the previous version of the algorithm (V4.1 and V4.2) then fully details the rationale and impact of the V4.5 changes on subtype classification frequency for specific events where the dominant aerosol type is known based on the literature. Classification accuracy is best for volcanic ash due to its characteristically high depolarization ratio. Smoke layers in the stratosphere are also classified with reasonable accuracy, though during the daytime a substantial fraction are misclassified as ash. It is also possible for mixtures of ash and sulfate to be misclassified as smoke. The V4.5 sulfate subtype accuracy is less than that for ash or smoke, with sulfates being misclassified as smoke about one-third of the time. However, because exceptionally tenuous layers are now assigned to the unclassified subtype and the revised algorithm levies more stringent criteria for identifying an aerosol as sulfate, it is more likely that layers labeled as this subtype are in fact sulfate compared to those assigned the sulfate/other classification in the previous data release.

Jason L Tackett↗

Assessment of municipal solid waste for valorization into biofuels

Abstract Almost 36 million tons of paper and yard trimmings are not currently being recycled or composted annually and likely end up in landfills. One approach to valorize these resources would be for biofuels production. Nonrecyclable municipal solid waste (MSW) paper and yard trimmings were assessed for their suitability as feedstocks to produce biofuels from sugars. Both materials met the cost target of less than $85.51/ton ($2016) with MSW paper ranging from $36.40 to $62.18/dry ton and grass clippings from $25.64 to $45.86/dry ton. MSW paper exceeded the carbohydrate requirement of 59% while grass clippings had significantly lower amounts of carbohydrates (30%). However, both types of MSW had ash contents significantly above the required 5% total ash with paper at 22% ash and grass clippings at 16%. While neither waste material was individually found to be suitable for biofuels production based on compositional requirements, it was determined that blending either waste with corn stover would produce materials that met carbohydrate, ash, and cost targets. The higher carbohydrate and lower ash stover compensated for the lower carbohydrates and high ash of the waste materials, while the lower cost waste materials offset the higher cost of corn stover.

09 BIOMASS FUELS↗

Sulphate resistance of low‐clinker engineered cementitious composites examined by MicroXRF imaging

Abstract Engineered cementitious composites (ECC) are a class of high‐performing fibre‐reinforced cementitious materials recognised for their increased ductility and durability compared to conventional cement‐based materials, owing to their autogenously controlled tight crack widths, even when subjected to high strains. To reduce ECC's environmental impact, this research examines the use of a low‐clinker binder − limestone‐calcined clay cement (LC3) − as an alternative to portland cement (PC), along with fly ash to further reduce the clinker proportion and the embodied CO 2 of the formulations. In conventional concrete, LC3 hydrates to a denser microstructure resulting from the synergistic reaction between limestone and calcined clay. At the lower water contents typical of ECC and with the presence of fly ash, the influence of the binder composition on the microstructure is difficult to anticipate. To examine the influence of these compositional variables on microstructure, permeability and durability, the sulphate resistance of LC3‐based ECC is explored. Specifically, the ECC‐LC3 blends are designed with high clinker replacement rate of 75% by mass of binder and contain either conventional fly ash or reclaimed fly ash at 50% by mass of binder. Expansion of ECC‐LC3 samples subjected to standard sodium sulphate test conditions was measured up to 12 months and the depth of penetration of sulphates into the ECC‐LC3 of varying compositions was quantified using micro‐X‐Ray Fluorescence (microXRF) imaging and modelling. The expansion results show that the ECC‐LC3 formulations performed better than the PC samples and can provide adequate resistance to external sulphate attack, even when reclaimed fly ashes are used in place of the conventional ash. In addition, the shallow penetration of sulphate into these cementitious composites demonstrates the low diffusion coefficients values that were determined using the quantitative data from MicroXRF imaging.

Microscopy↗

Differences in urban plant community compositions across an urban-rural gradient in Knoxville, TN

Urban forests, or vegetation in areas under heavy human influence, provide many ecosystem services to urban residents such as localized cooling via evapotranspiration, shade, filtering of air pollution, and the associated health benefits of natural spaces. In order to quantify the magnitude of localized cooling by trees growing in varying levels of urbanization (based on % impervious surfaces, e.g., buildings, pavement), urban forest species composition, tree size, and tree density must be characterized. As a part of Oak Ridge National Laboratory’s (ORNL) urban forest temperature study, we conducted tree censuses in five Knoxville city parks where ORNL meteorological stations are deployed. Moreover, we measured every woody plant ≥ 5 cm diameter at breast height (DBH) within a 50 m radius of each site’s meteorological station for its DBH and species identification. When possible, individuals were identified down to species. Certain genera (Quercus spp., Carya spp., Pinus spp.) were identified down to genera in interest of time. Individual and total site basal area were calculated from measured DBH data. Results show notable differences in urban plant community compositions and total woody plant basal area across sites, with more urban sites closer to downtown (West View and SEEED) having lower tree basal area than the more suburban sites (West Hills, Cumberland Estates, and Victor Ashe). We identified 54 species across all sites, with West Hills and Victor Ashe having the highest species diversity. Our results show differences in forest compositions and sizes across Knoxville, which are currently informing ORNL’s evapotranspiration estimates for each site. Data Summary: Census data for West Hills (WH), Cumberland Estates (CE), Victor Ashe (VA), West View (WV), and Socially Equal Energy Efficient Development or SEEED (SD) urban forests in Knoxville, TN, USA, including tree size based on diameter at breast height (DBH; 1.3 m), species identification (Latin and common names), and basal area per stem (BA=π×[.5*DBH]^2). Field data are summarized in this file: “Community_Composition_Data.CSV”. Site-specific data detailing each site’s coordinates, number of stems measured at DBH, average tree DBH, α-diversity (number of species present), and total site basal area (sum of individual basal areas per site) are in this file: “Site_Comparisons.CSV”.

Warren, Jeffrey [ORNL] (ORCID:0000000206804697)↗

Slag Management of Carbon Feedstock Used in Gasification FY17 TCF between Eastman Chemical and NETL (Final Report)

NETL, in collaboration with Eastman Chemical Corp (Kingsport, TN), targeted the joint evaluation and refinement of a slag management program developed by NETL (NETL IP, patent applied for) to control gasifier slag properties formed from ash in individual or combinations of different coal-based carbon feedstock materials and specific slag modifiers used in gasification. Slag forms from mineral or organic-metallic impurities in the carbon feedstock that melt at the high temperatures of gasification, coalescing to form a liquid (slag) that must flow from the gasifier. Slag additives, also known as slag modifiers, are often added to the carbon feedstock to modify the ash chemistry and achieve desired slag flow properties at target temperatures used in gasification. If slag does not flow from a gasifier, its buildup within the gasification chamber will cause either gasifier shutdown to physically remove the slag (consuming time and damaging the protective refractory lining), or the gasification temperature must be increased to lower slag viscosity so it can flow from the gasifier, leading to greater refractory wear/corrosion, along with increased fouling and downstream component wear. Because of these issues, gasification is typically targeted at the lowest temperature possible where slag will flow in a controlled manner (a temperature range called T100 for the lowest temperature, with T250 being the highest temperature where the slag has achieved the desired fluidity). That temperature range also needs to yield a desired syngas composition, highlighting the importance of knowing and being able to control carbon feedstock slag viscosity and the temperature of thermal breakdown of the carbon feedstock. Slag viscosity varies with changes in the gasification chamber temperature, oxygen partial pressure, and slag chemistry. The slag model work with Eastman Chemical targeted predicting and controlling molten coal ash slag behavior at specific gasification conditions. The final goal of the refined model was to develop/refine the NETL slag model so a gasifier operator would be able to predict slag behavior prior to purchasing or using a carbon feedstock and control slag properties once a carbon feedstock is being gasified, allowing a gasifier user to determine what mineral additives or blends of different carbon materials would be needed to achieve desired slag properties at targeted gasification conditions. For a given carbon feedstock and desired gasification condition, the actual gasification cost and slag behavior would be able to be predicted using the slag management program in advance of purchasing or using the carbon feedstock – allowing accurate control of slag ash behavior in real time. As part of the TCF project work with Eastman Chemical, the viscosity of several ash compositions of interest to them would be measured and used to populate the slag model, along with a large database of historical slag temperature, chemistry, and viscosity information they possess – information that would in-crease the predictive accuracy of the slag management model with slag ash chemistry of interest to them. As part of the model evaluation and refinement, the predictive model and its database will be installed on computers at Eastman Chemical and used to manage slag properties in a gasifier during real-time operation of their gasifier. In summary, success of the slag management program at Eastman Chemical would support its use by other gasifier operators to manage slag chemistry and properties over other desired gasification temperature ranges, allowing greater process control and efficiency of their carbon feedstock conversion during gasification.

01 COAL, LIGNITE, AND PEAT↗

Optimal N Application Rates on Switchgrass for Producers and a Biorefinery

This study analyzes the effects of N fertilizer application rates on profitability of growing switchgrass and using the feedstock in a pyrolysis biorefinery facility to create a source of sustainable aviation fuel (SAF) supply in Tennessee. Switchgrass (Panicum virgatum L.) is a perennial bunchgrass native to North America with traits suitable for biofuel and co-product production. Previous chemical analysis has shown that ash content in switchgrass is related to the amount of nitrogen applied to the field, while at the biorefinery level, the percentage ash content reduces the biorefinery fuel output. To obtain optimal nitrogen (N) application rates for the switchgrass producers and the biorefinery, a two-part analysis is employed. First, a partial budgeting profitability analysis is conducted for this cropping enterprise at the farm-gate level without considering downstream implications of biomass quality, i.e., ash content. Second, the effects of higher ash content as a percentage of the feedstock on biorefinery output are analyzed. Results show farm-gate profit is maximized when N fertilizer is applied at 111 kg/ha, while as a result of increased production levels and decreased percentage ash content, biorefinery profit is maximized when N is applied at 157 kg/ha. Lower ash could lead to premium prices paid to switchgrass producers if higher quality feedstock were to be demanded as part of an integrated biofuel industry.

Robertson, Keven Alan↗

Incineration as a Method for Resource Recovery from Inedible Biomass in a Controlled Ecological Life Support System

Resource recovery from waste streams in a space habitat is essential to minimize the resupply burden and achieve self-sufficiency. In a Controlled Ecological Life Support System (CELSS) human wastes and inedible biomass will represent significant sources of secondary raw materials necessary for support of crop plant production (carbon, water, and inorganic plant nutrients). Incineration, pyrolysis, and water extraction have been investigated as candidate processes for recovery of these important resources from inedible biomass in a CELSS. During incineration CO2 is produced by oxidation of the organic components and this product can be directly utilized by plants. Water is concomitantly produced, requiring only a phase change for recovery. Recovery of inorganics is more difficult, requiring solubilization of the incinerator ash. The process of incineration followed by water solubilization of ash resulted in loss of 35% of the inorganics originally present in the biomass. Losses were attributed to volatilization (8%) and non-water-soluble ash (27%). All of the ash remaining following incineration could be solubilized with acid, with losses resulting from volatilization only. The recovery for individual elements varied. Elemental retention in the ash ranged from 100% of that present in the biomass for Ca, P, Mg, Na, and Si to 10% for Zn. The greatest water solubility was observed for potassium with recovery of approximately 77% of that present in the straw. Potassium represented 80% of the inorganic constituents in the wheat straw, and because of slightly greater solubility made up 86% of the water-soluble ash. Following incineration of inedible biomass from wheat, 65% of the inorganics originally present in the straw were recovered by water solubilization and 92% recovered by acid solubilization. Recovery of resources is more complex for pyrolysis and water extraction. Recovery of carbon, a resource of greater mass than the inorganic component of biomass, is more difficult following pyrolysis and water extraction of biomass. In both cases, additional processors would be required to provide products equivalent to those resulting from incineration alone. The carbon, water, and organic resources of inedible biomass are effectively separated and output in usable forms through incineration.

Bubenheim, David L.↗

Manganese Oxidation during Vegetation Burning

Redox recycling of manganese (Mn) plays a key role in organic matter decomposition and nutrient cycling in terrestrial vegetated ecosystems, and it is expected to be changed by fires. This study revealed how Mn is oxidized during vegetation burning, by characterizing the chemical speciation of Mn in fire ash from wildland fires and laboratory burning and evaluating the factors governing its average oxidation state (AOS) and speciation. Manganese in wildland fire ash from different ecosystems showed variable AOS that ranges from 2.5 to 3.3. Laboratory burning experiments showed that Mn oxidation was primarily controlled by fire thermal intensity (temperature × duration) and burning completeness. As heating time increased from 5 min to 5 h at 550 and 700 °C, Mn AOS in the lab-burned vegetation ash increased from 2.7 to 4.0 and the oxidation rate was faster at higher temperature. Diverse Mn species can present in wildland fire ash and differ structurally from biogenic Mn oxides. The oxidized Mn species enable fire ash to mediate oxidative degradation of catechol, demonstrating its potential in mediating organic matter decomposition. This study revealed a new paradigm of Mn redox recycling, as compared to the microbe-mediated Mn redox cycling in the absence of fires.

36 MATERIALS SCIENCE↗

In Situ Observations and Sampling of Volcanic Emissions with Unmanned Aircraft: A NASA/UCR Case Study at Turrialba Volcano, Costa Rica

Burgeoning new technology in the design and development of robotic aircraft-unmanned aerial vehicles (UAVs)-presents unprecedented opportunities for the volcanology community to observe, measure, and sample eruption plumes and drifting volcanic clouds in situ. While manned aircraft can sample dilute parts of such emissions, demonstrated hazards to air breathing, and most particularly turbine, engines preclude penetration of the zones of highest ash concentrations. Such areas within plumes are often of highest interest with respect to boundary conditions of applicable mass-loading retrieval models, as well as Lagrangian, Eulerian, and hybrid transport models used by hazard responders to predict plume trajectories, particularly in the context of airborne hazards. Before the 2010 Ejyafyallajokull eruption in Iceland, ICAO zero-ash-tolerance rules were typically followed, particularly for relatively uncrowded Pacific Rim airspace, and over North and South America, where often diversion of aircraft around ash plumes and clouds was practical. The 2010 eruption in Iceland radically changed the paradigm, in that critical airspace over continental Europe and the United Kingdom were summarily shut by local civil aviation authorities and EURO CONTROL. A strong desire emerged for better real-time knowledge of ash cloud characteristics, particularly ash concentrations, and especially for validation of orbital multispectral imaging. UAV platforms appear to provide a viable adjunct, if not a primary source, of such in situ data for volcanic plumes and drifting volcanic clouds from explosive eruptions, with prompt and comprehensive application to aviation safety and to the basic science of volcanology. Current work is underway in Costa Rica at Turrialba volcano by the authors, with the goal of developing and testing new small, economical UAV platforms, with miniaturized instrument payloads, within a volcanic plume. We are underway with bi-monthly deployments of tethered SO2-sondes and are in the planning stages for the deployment of the SIERRA UAV to our site in March 2013. We will be conducting in situ observations simultaneously with ASTER orbital multispectral TIR data acquisitions, in order to compare in situ measurements with estimates of SO2 mass loading and dispersion derived from ASTER data. Though small UAVs are now being considered for use in active volcanic areas for in situ sampling of emissions (e.g., efforts by our group, and by our colleagues at the INGV in Italy and the Applied Science University in Dusseldorf, Germany, and others in the United Kingdom and Iceland), and also for remote sensing, much more needs to be done in the way of instrument development, and in developing small UAVs for both low altitude (tropospheric) and high altitude (stratospheric) applications. In particular, the development of all weather and day/night operational flight capabilities in close proximity to hazardous topography is crucial to a truly responsive volcano in situ measurement system. Finally, it is imperative that national civil aviation authorities recognize the unique benefits of such platforms. It is important that authorities understand that severely restricting or not deploying such tools in airspace over restless volcanoes or within eruption plumes, ostensibly because of the perceived (small) risk that such unmanned aircraft pose to manned air operations, itself poses a bigger transcendental risk to proximal populations and particularly to the aviation community, itself.

Volcanic Ash Advisory Centers (VAACs)↗

Burn Intensity Drives the Alteration of Phenolic Lignin to (Poly) Aromatic Hydrocarbons as Revealed by Pyrolysis Gas Chromatography–Mass Spectrometry (Py-GC/MS)

High-intensity wildfires alter the chemical composition of organic matter, which is expected to be distinctly different from low-intensity prescribed fires. In this study, we used pyrolysis gas chromatography/mass spectrometry (Py-GC/MS), in conjunction with solid-state 13 C nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectroscopy, to assess chemical alterations from three wildfires and a long-term frequent prescribed fire site. Our results showed that black ash formed under moderate intensity burns contained less aromatic (ArH), polyaromatic hydrocarbon (PAH), and nitrogen-containing compounds (Ntg) but more lignin (LgC) and phenol compounds (PhC), compared to white ash formed under high intensity burns. Both 13 C NMR and FT-IR confirmed a higher relative percentage of carboxyl carbon in white ash, indicating the potential for higher water solubility and more mobile carbon, relative to black ash. Compared to wildfires, ash from low-intensity prescribed fire contained less ArH, PAH, and Ntg and more LgC and PhC. Controlled laboratory burning trials indicated that organic matter alteration was sensitive to the burn temperature, but not related to the fuel type (pine vs fir) nor oxygen absence/presence at high burn temperatures. This study concludes that higher burn temperatures resulted in higher (poly)aromatic carbon/nitrogen and lower lignin/phenol compounds.

54 ENVIRONMENTAL SCIENCES↗

Accelerated Testing of Selected Filler Compositions

The fillers R&D program, mostly experimental, is part of a broader R&D program that includes new process modeling and performance assessment of criticality effects and the overall importance of criticality to repository performance (consequence screening). A literature research and consultation effort with experts by Hardin and Brady (2018) identified several potentially effective and workable filler materials including cements (primarily phosphate based), molten-metal alloys, and low-temperature glasses. Filler attributes were defined and the preliminary lists were compared qualitatively. Further comparative analysis will be done (e.g., cost estimates) after experimental screening has narrowed the list of alternatives. The following cement filler compositions were selected for experimental development work and accelerated testing in FY19: Aluminum phosphate cements (APCs); more specifically aluminum oxide / aluminum phosphate (Al 2 O 3 / AlPO 4 ) cements in which Al 2 O 3 serves as the filler material bound by an AlPO 4 binder formed by the reaction of Al 2 O 3 with H 3 PO 4 ; Calcium phosphate cements (CPCs); more specifically composed of pure or nearly pure hydroxyapatite (Ca 5 (PO 4 ) 3 (OH)); Magnesium potassium phosphate cements (MKPs) composed of magnesium oxide / magnesium potassium phosphate (MgO / MgKPO 4 ) cements in which MgO serves as the filler and MgKPO 4 serves as the binder formed by the reaction of MgO with monopotassium phosphate (KH 2 PO 4 ) and tricalcium phosphate ((Ca 3 (PO 4 ) 2 ); Two additional potential cement materials were explored preliminarily as the result of: (1) continued literature investigations into other filler candidates (wollastonite-based phosphate ceramic) and (2) the experimental discovery of a well-consolidated fly ash phosphate cement during the evaluation of fly ash as a potential filler material with Al 2 O 3 in APCs. Fly ash phosphate cements, more specifically in which a fly ash material composed primarily of mullite and quartz serves as the filler and is reacted with H 3 PO 4 to form amorphous phosphate phase(s) as the binder; Wollastonite aluminum phosphate cements (WAPC), specifically wollastonite / aluminum phosphate (CaSiO 3 / AlPO 4 ) in which CaSiO 3 serves as the filler material and AlPO 4 serves as the binder formed by Al(OH) 3 or metakaolin as Al sources and H 3 PO 4 or ammonium dihydrogen phosphate (ADP) (NH 4 H 2 PO 4 ) as phosphate sources. The FY19 effort focused on the optimization of compositions and subsequent processing of these five materials to achieve dense and well-consolidated monolithic samples with relatively low porosity. Once these goals were met basic material properties screening evaluations were performed including an assessment of dissolution resistance in water at elevated temperature (200 °C) and mechanical testing including unconfined compressive strength (UCS) testing. To date, the aluminum phosphate cements (APCs) appear to show the most promise for continued development. They are easily prepared and form smooth pourable slurries that remain stable for days with relatively low viscosities of several thousand centipoise (cP). They are then set at elevated temperatures (e.g., 170 °C) under ambient (0.1 MPa) or elevated pressure (~1MPa). Overall, they demonstrate the best dissolution resistance in water at elevated temperature (200 °C) and good compressive strengths. However, additional effort is required to optimize the APC slurry formulations and the process used for thermal curing these materials. The calcium phosphate cements (CPCs) can be formed at room temperature to produce a well-consolidated body. However, their slurry viscosities are very high (and difficult to measure) and they exhibit relatively short cure times of 2 to 3 hours. Also, dissolution resistance is very poor, the poorest of all the cements examined The same is the case for the small number of MKP cements fabricated; they cure very quickly (10 minutes or less) and disintegrate within a few hours upon immersion in distilled water. Surprisingly, fly ash reacts with phosphoric acid to form dense and well-consolidated cements but the mixture rapidly sets at room temperature (less than 30 minutes) and the subsequent conversion of the binder to an amorphous phosphate phase(s) as a function of temperature is complicated. Finally, the wollastonite aluminum phosphate cements (WAPC) are easily prepared and form smooth pourable slurries that remain stable for several hours. They are then set at 130 °C. A WAPC sample exhibited the highest compressive strengths of all the materials we evaluated but in general their dissolution resistance to water is poor.

36 MATERIALS SCIENCE↗

Woody Feedstock 2022 State of Technology Report

The U.S. Department of Energy promotes production of advanced liquid transportation fuels from lignocellulosic biomass by funding fundamental and applied research that advances the state of technology (SOT). As part of its involvement in this mission, Idaho National Laboratory completes an annual SOT report for n th -plant and 1 st -plant woody biomass feedstock logistics. The purpose of the SOT is to provide the status of feedstock supply system technology development for woody biomass to biofuels relative to technical targets and cost goals from specific design cases, based on data and experimental results. Conventional feedstock supply systems need to be modified to meet the demands of conversion pathways, specifically to have the ability to adjust the quality of the raw biomass materials. Advanced systems incorporate innovative methods of material handling, preprocessing and supply chain configuration. In advanced designs, variability of the raw biomass can be reduced to produce feedstocks of a uniform format, moving toward biomass commoditization. Against this backdrop, the 2022 Woody SOT for low-ash woody feedstocks utilizes feedstock fractionation by incorporating technologies that can separate the biomass into its anatomical fractions (wood, bark, needle, and extrinsic ash) to reduce impurities and attempt to maximize the retention of usable fractions that satisfy downstream quality considerations. By using a series of air classification steps, this strategy can reduce the extrinsic ash in forest residues, separate out a majority of the incoming needles (which can be supplied to alternate markets), and maximize the retention of whitewood in the usable fraction. The fractionated forest residues are then mixed with clean-pine chips in a 50-50 blend to prepare the feedstock for the desired conversion pathway. The n th -plant analysis estimated the delivered cost for the feedstock at $\$$69.23/dry ton (2016$\$$) which represents a $\$$6.64/dry ton decrease compared to the cost estimate of the 2021 Woody SOT supply system for low-ash woody feedstocks. The quality requirements in the 2022 Woody SOT were identical to those of the 2021 Woody SOT at = 1.00 wt % ash and = 50.51 wt% carbon. The cost savings derive primarily from reductions in dry matter losses during air classification. The GHG emissions for the n th -plant analysis were estimated at 178.39 kg CO2e/dry ton compared to 178.71 kg CO 2 e/dry ton in the 2021 Woody SOT, a decrease of 0.32 kg CO2e/dry ton. The small change stems from an increase in emissions attributed to preprocessing and slightly larger savings in emissions from transportation. In the 1 st -plant analysis of the 2022 Woody SOT system, the average throughput was estimated to be approximately 2,128 dry tons/day or 96.51% of the name plate capacity. During the simulation the daily throughput ranged from 1,090 dry tons/day to 2,200 dry tons/day, or 49.43% to 99.75% of the daily nameplate capacity. After the year of operation 722,403 tons of processed feedstock were produced in total without regard to quality considerations (99.64% of the annual nameplate capacity). The variability in throughput was primarily caused by equipment failures in the system. Regular failures, downtime caused by routine maintenance per manufacturer guidelines, contributed to a majority 62.50% of failures and 62.60% of downtime. Failures due to wear were the other cause of disruption within the system, impacting the rotary shear and orbital screen and accounting for 37.50% of the failures and 37.40% of the total downtime. Ultimately the system was on stream for 87.84% during the simulation period, which is only 2.16 percentage points below the nth-plant assumption for on-stream time. The production cost of the system averaged $\$$71.66/dry ton. The costs ranged from a minimum of $\$$71.23/dry ton to a maximum of $\$$2,115.30/dry ton. When dry matter losses (disposed low-quality fractions as well as other losses such as in grinders) were considered the costs increased to an average of $\$$75.11/dry ton with a minimum of $\$$74.69/dry ton and a maximum of $\$$2,136.86/dry ton...

09 BIOMASS FUELS↗

Coal-Waste-Enhanced Filaments for Additive Manufacturing of High-Temperature Plastics and Ceramic Composites

In the United States, coal waste from over a century of mining and burning coal for heat and electricity has accumulated as mountains of coal fly ash and bottom ash and acre-size ponds, coal fines and gob. These materials can be a problem for local communities and water systems. A cost-effective process to utilize high volumes of these coal wastes in a high-value product would be beneficial to those communities by reducing the amount of waste and providing jobs, manufacturing components, and materials from the waste. Many coal-to-products technologies (e.g., carbon fibers, graphene, carbon foam) rely on carefully choosing the starting material and then altering it chemically or thermally to make the products work. Due to the wide variability of composition and coal content in typical coal waste streams, many high-volume coal waste streams are likely to be unsuitable for use in those technologies. Semplastics’ technology has been shown to utilize most types of coal waste successfully without any pre-selection or pre-processing requirements other than a nominal particle-size reduction for wastes like bottom ash. This characteristic of Semplastics’ solution may enable the use of much larger volumes of a wider range of coal wastes than other coal-to-products technologies. In this project, Semplastics leveraged its unique experience with both coal waste (fly ash or coal combustion residuals), resin materials, and 3D printing to develop 3D printer filaments using common coal wastes – bituminous coal fines and fly ash – and researched the feasibility of using other forms of coal waste as fillers. Simple 3D-printed parts were successfully produced from the coal waste enhanced filaments, which were found to have improved strength and stiffness.

01 COAL, LIGNITE, AND PEAT↗