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Regional Feedstock Partnership Biomass Quality Assessment Final Report

The United States (U.S.) Department of Energy (DOE) developed the Billion-Ton Vision to enable production of one-billion tons of sustainable, reliable biomass for the bioenergy industry by 2030 (Perlack et al., 2005). The Sun Grant Regional Feedstock Partnership (RFP) was organized to fill information gaps and validate biomass yield assumptions related to the Billion-Ton Study (Owens, 2018; Owens, Karlen, and Lacey, 2016). Along with the more than 130 scientific publications generated from these studies, yield and sustainability data from the RFP field trials not only validated the Billion-Ton estimates, but were critical in developing both the U.S. Billion-Ton Update report in 2011 and the 2016 Billion-Ton Report (DOE, 2011; 2016). The intention of this biomass quality assessment report is to build on these initial successes from the RFP field trials by focusing on variability in biomass quality data necessary to evaluate conversion performance. This report contains a summary of chemical quality results from samples collected as part of the RFP field trials. This report focuses on assessment of the impact of experimental agronomic designs on biomass properties followed by analyses of the impact of environmental and production variables on biomass properties. Datasets include species and other genetic variables, fertilizer treatments, harvest information, and yield, as well as other publicly available data such as precipitation, temperature, soil properties, and drought. The key outcomes from this chemical quality focused assessment have included: • Complete evaluation of the impacts of agronomic designs, genetics, and environmental conditions on chemical properties for Miscanthus, switchgrass, sorghum, energycane, mixed perennial grasses, and shrub willow short-rotation feedstocks • Over 30 peer review publications and technical reports focused on variability in quality data • Development of spatial and temporal environmental quality prediction maps for Miscanthus and switchgrass feedstocks allowing for comprehensive evaluation of variability in feedstock chemical quality across U.S. regions and over multiple harvest years

09 BIOMASS FUELS↗

Impact of irradiance and inorganic carbon availability on heterologous sucrose production in Synechococcus elongatus PCC 7942

Cyanobacteria have been proposed as a potential alternative carbohydrate feedstock and multiple species have been successfully engineered to secrete fermentable sugars. To date, the most productive cyanobacterial strains are those designed to secrete sucrose, yet there exist considerable differences in reported productivities across different model species and laboratories. In this study, we investigate how cultivation conditions (specifically, irradiance, CO 2 , and cultivator type) affect the productivity of sucrose-secreting Synechococcus elongatus PCC 7942. We find that S. elongatus produces the highest sucrose yield in irradiances far greater than what is often experimentally utilized, and that high light intensities are tolerated by S. elongatus , especially under higher density cultivation where turbidity may attenuate the effective light experienced in the culture. By increasing light and inorganic carbon availability, S. elongatus cscB / sps produced a total of 3.8 g L -1 of sucrose and the highest productivity within that period being 47.8 mg L -1 h -1 . This study provides quantitative description of the impact of culture conditions on cyanobacteria-derived sucrose that may assist to standardize cross-laboratory comparisons and demonstrates a significant capacity to improve productivity via optimizing cultivation conditions.

59 BASIC BIOLOGICAL SCIENCES↗

Inorganometallic Catalyst Design Center (ICDC) EFRC Accomplishments

The ICDC focused largely on heterogeneous catalysis of oxidative chemical transformations, especially those that came to prominence as natural gas (wet shale gas) supplanted crude oil as the primary feedstock in North America for carbon-based manufacturing of commodity chemicals. Driven by fracking-enabled access to enormous stores of shale-trapped wet gas, the feedstock change from oil to gas enabled a shift away from high-temperature catalytic breakdown of large hydrocarbons to catalytic build-up of C4, C3, C2, and C1 into desired intermediates, but now at much more modest temperatures. In turn, the much lower thermal force accompanying these kinds of reactions facilitates catalyst stabilization and characterization, including operando characterization, while slowing on-stream catalyst evolution (i.e., preserving catalyst structure), accommodating catalyst complexity, and enabling creation of uniform arrays of heterogeneous catalysts with single-atom or near-single-atom precision—at least for model systems. Together these features have proven to be a boon to hypothesis-driven catalysis science and to experimentally testable computation-based design advances and mechanism explication. The ICDC has greatly facilitated the integration of catalyst synthesis, advanced characterization, performance assessment, and computational elucidation—with advances in each of these realms spurring achievements in catalysis science and complementary realms.

03 NATURAL GAS↗

Evaluation of mixed #3–7 plastic waste from material recovery facilities (MRFs) in the United States

Plastic recycling rates are still low in the United States (U.S.), with less than 10% of municipal solid waste (MSW) plastic being recycled. Most unrecycled plastics are identified by Resin Identification Codes (RIC) from #3–7, which are commonly destined for landfill or waste-to-energy facilities (WTE). Therefore, the composition and quality of outbound bales containing #3–7 plastics were assessed to understand the potential to increase recycling rates. Three bales were sourced from three different Material Recovery Facilities (MRFs) located in the United States. Each bale was manually sorted and characterized for quality and performance via multiple plastic characterization techniques. Considerable differences in bale composition were observed between MRFs, which correlated with the technology used by each MRF in the sorting process. The differences were substantial in the residual levels of poly(ethylene terephthalate) (PET) and high-density polyethylene (HDPE), which are highly desired for mechanical recycling processes and not expected in #3–7 plastics bales. Traditional recycling processes including washing, extrusion, and injection molding of the sorted material were employed prior to the physical, thermal, and molecular characterization. Despite differences in bale composition by plastic type, some polymer properties were similar across MRFs. Here, this research suggests that landfill-diverted mixed plastic waste can be utilized in the mechanical recycling of currently unrecycled materials, as processes can be designed to work with consistent polymer properties. It also highlights the need to upgrade the sorting systems to prevent waste feedstocks, which can be recycled with current technologies, from contaminating other plastic streams or reach landfills.

36 MATERIALS SCIENCE↗

Scalable Gas Diffusion Electrode Fabrication for Electrochemical CO 2 Reduction Using Physical Vapor Deposition Methods

Electrochemical CO 2 reduction (ECR) promises the replacement of fossil fuels as the source of feedstock chemicals and seasonal storage of renewable energy. While much progress has been made in catalyst development and electrochemical reactor design, few studies have addressed the effect of catalyst integration on device performance. Using a microfluidic gas diffusion electrolyzer, we systematically studied the effect of thickness and the morphology of electron beam (EB) and magnetron-sputtered (MS) Cu catalyst coatings on ECR performance. We observed that EB-Cu outperforms MS-Cu in current density, selectivity, and energy efficiency, with 400 nm thick catalyst coatings performing the best. Additionally, the superior performance of EB-Cu catalysts is assigned to their faceted surface morphology and sharper Cu/gas diffusion layer interface, which increases their hydrophobicity. Tests in a large-scale zero-gap electrolyzer yielded similar product selectivity distributions with an ethylene Faradaic efficiency of 39% at 200 mA/cm 2 , demonstrating the scalability for industrial ECR applications.

36 MATERIALS SCIENCE↗

Boosting the performance of reversible solid oxide electrochemical cells with a novel hybrid oxygen electrode, Pr 1.39 Ba 0.14 Sr 0.53 Co 1.48 Fe 0.76 O 6- δ -Ba 0.66 Sr 0.34 CoO 3- δ

Solid oxide electrochemical cells (SOECs) stand out as a highly promising clean energy technology that offers several benefits, showing significant potential to play a pivotal role in the transition towards a sustainable and low-carbon energy future. SOECs can efficiently convert the chemical energy stored in fuels to electricity in fuel cell mode, and produce various chemicals from abundant feedstocks (e.g., CO 2 , H 2 O) and intermittent solar/wind-based renewable electricity. Despite extensive efforts that have been devoted to designing novel materials and optimizing SOEC manufacturing processes, aiming to achieve enhanced energy efficiency, the current SOECs still suffer from poor performance, which is mainly due to the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics. To address this challenge, in this work, we have successfully designed an in situ formed hybrid oxygen electrode material (Pr 1.39 Ba 0.14 Sr 0.53 Co 1.48 Fe 0.76 O 6- δ -Ba 0.66 Sr 0.34 CoO 3- δ ), which significantly improves the surface oxygen exchange coefficient and bulk oxygen-ion diffusion coefficient, enhancing the OER and ORR electrocatalytic activities. Further, the SOECs equipped with this newly developed oxygen electrode achieved exceptional performance for power generation using both hydrogen and propane as the fuels. At 750 °C, a peak power density of 2.4 W cm -2 was obtained with H 2 as the fuel. Additionally, the SOECs attain unprecedented performance in steam electrolysis mode. A current density of 4.4 A cm -2 was achieved at 1.3 V and 750 °C, which represents the highest performance among all yttria-stabilized zirconia (YSZ) electrolyte-based SOECs. The SOECs also deliver remarkable stability during the accelerated stability testing, highlighting the great potential of Pr 1.39 Ba 0.14 Sr 0.53 Co 1.48 Fe 0.76 O 6- δ -Ba 0.66 Sr 0.34 CoO 3- δ as a high-performance oxygen electrode for next generation SOECs.

08 HYDROGEN↗

Mechanical Characterization of Loblolly Pine

Biorefineries are faced with various material flow challenges during feeding and handling, due to inherent variability and inhomogeneity of biomass feedstocks. This impacts the efficiency of refinery processes and unit operations. Proper characterization of bulk properties allows for optimal process design and reduction of overall costs. This work is aimed at evaluating the physical and mechanical properties that impact bulk flow of loblolly pine. Cyclic axial compression tests are performed to elucidate consolidation behavior under different stress conditions. The results are then used to develop correlations between material parameters (particle size, tissue type, moisture content) and Elastic Modulus of bulk samples.

09 BIOMASS FUELS↗

Design and scale-up of 3D printed bat houses with biomass-derived polymer composites

Biomass (e.g., pine sawdust, especially high–ash content pine sawdust) is commonly disposed of as waste. Combining biomass with polymers to make composite feedstocks for 3D printing has been explored as a method to reduce or repurpose the biomass waste. Although not all biocomposite properties are known, the wood-based polylactic acid (PLA) composite has promising qualities for applications in ecological settings. In this work, pine wood–PLA composite feedstock was used to 3D print supplemental roost structures for endangered tree-roosting bats, which often face a paucity of suitable naturally occurring roosts. This material combination was selected because it is estimated to degrade faster than the synthetic material systems that are used widely in supplemental bat roosting structures to aid in the conservation of tree roosting bats. The layered, rough surface created by the 3D printing process serves as a surface that bats can grip while roosting. Computer-aided design (CAD) models were generated based on natural roost structures, and a full-size bat house was successfully additively manufactured using a pellet-fed large-scale 3D printing system. The 3D printed hexagon exhibited a tensile strength of 22–23 MPa and a Young’s modulus of 3202–3218 MPa in the x-direction. It has been demonstrated that the 3D printed bat house can be installed on a tree in a stable fashion. This successful demonstration of a bat roost manufactured using a bioderived composite should promote its use in other fish and wildlife structures and broader industrial applications such as construction and automobiles.

3D printing↗

Sustainable Lactic Acid Production from Lignocellulosic Biomass

Lignocellulosic biomass is a promising feedstock for sustainable biofuels and bioproducts. Among emerging bioproducts, lactic acid has attracted significant interest because of its growing application in many industries (e.g., packaging, medical, and pharmaceutical). In this study, BioSTEAM—an open-source platform—was leveraged for the design, simulation, and evaluation (via techno-economic analysis, TEA, and life cycle assessment, LCA) of lignocellulosic lactic acid biorefineries. With a minimum product selling price (MPSP) between 1.38 and 1.91 kg –1 (5th–95th percentiles, baseline at 1.57 kg –1 ), the biorefinery was capable of producing market-competitive lactic acid (market price between 1.7 and 2.1 kg –1 ), and its performance could be further enhanced (e.g., MPSP down to 1.09 kg –1 , global warming potential of 2.79 kg CO 2 -eq·kg –1 , and fossil energy consumption of 31.7 MJ·kg –1 ) with advancements in key technological parameters (fermentation yield and separation process conversions) and optimization in process operation. Sensitivity analyses focused on the fermentation unit (across titer, yield, and productivity; neutral vs low-pH fermentation) and feedstock characteristics (carbohydrate content and price) were also included to quantify their impact on the sustainability of the biorefinery. Overall, this research highlights the ability of agile TEA/LCA to screen promising biorefinery designs, prioritize research needs, and establish a road map for the continued development of bioproducts and biofuels.

09 BIOMASS FUELS↗

Annual report for DOE VTO

Carbon fiber (CF)/polymer composites are a transformative class of high-performance, lightweight material, where high aspect-ratio CFs reinforce a polymer matrix and exceed the strength of steel alloys at a fraction of the density. Despite the advantages of such a class of material, the broader implementation of CF composites in a range of automotive, aerospace, and energy applications is hindered by limitations of current manufacturing methods. These current techniques (e.g., hand lay-up, wet filament winding) are costly and impose severe limitations on fiber placement, orientation, and angle, and thus a composite’s ultimate properties. Today’s CF composites are expensive to manufacture, limited in form factor, and utilize costly and sub-optimal continuous filament CF. Advanced additive manufacturing (AM) processes, combined with computational design optimization and new approaches to resin development, offer alternative design and manufacturing paradigms that have the realistic potential to lift these constraints. Such integrated AM approaches could thus help to realize the full potential of CF composite materials. One relevant application of CF composite materials where manufacturing constraints limit the cost-benefit ratio is in the manufacture of high-performance composite pressure vessels for onboard compressed natural gas (CNG) storage. Current CNG storage vessels (Types 3–5) are made from load-bearing filament-wound carbon-fiber composite and are ~3.5 times as expensive as an all-metallic Type-1 vessel. This cost is invariably tied to the complex and labor-intensive nature of conventional filament winding processes and the large volumes of expensive high tensile-strength CF tow feedstock required in manufacture. Our proposed approach to CNG storage vessel manufacture is based on a combination of AM technologies for CF composite printing and design optimization tools that were pioneered at Lawrence Livermore National Laboratory (LLNL), with advances in resin/composite formulation enabled by chemical and nano-material modification. Through the successful development of this technology, LLNL seeks to demonstrate the capability for advanced CNG storage vessel manufacture at reduced cost with no reduction in performance versus the most advanced, extant Type-5 designs.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Production of bio-based lactones as monomers for a circular polymer economy

To create a circular plastics economy, new polymers are being developed that can be chemically recycled. Circular polyesters are of particular interest and to this end, lactones are ideal monomers. Here, this Review examines catalytic routes to convert diols, hydroxy acids, and dicarboxylic acids to lactones, focusing on the development of scalable, atom-economic, and energy-efficient conversions of bio-derived feedstocks. Free energy analysis is used to inform process choices, such as reactor type, reaction phase, and use of solvent. Catalyst design principles are summarized for both direct (bio-substrate to lactone) and indirect (bio-substrate to intermediate to lactone) routes. Finally, we summarize literature that shows that many lactone precursors are readily accessible from various metabolic and chemo-catalytic pathways. Transitioning to bio-based monomers offers an opportunity to reduce reliance on fossil carbon resources, but requires advanced catalytic processes informed by mechanistic insights.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enabling Partnership between South Carolina and NREL for Advancing Opportunities in Plastics Recycling Research (EPSCOR for Plastics Recycling)

Proposal Objectives: 1. Utilize depolymerization/fractionation techniques to recover highly processable and reactive feedstocks for polymer synthesis from lignin. 2. Synthesize lignin‐derived non‐isocyanate polyurethane, epoxy, and polyamide using non‐ toxic, biobased route designed for chemical recycling. Characterize resulting materials. 3. Design a high‐yielding chemical recycling process for as‐synthesized materials yielding usable building blocks for many generations of polymer synthesis. 4. Optimize chemical recycling of PET waste for the synthesis of lignin‐based polymers. Compare properties to commercial materials. 5. Optimize reaction conditions and recycling steps to facilitate enhanced sustainability of the synthetic steps and final properties of materials. 6. Complete a lifecycle assessment of lignin utilization and chemical recycling to compare their environmental performance to that of materials produced from virgin material. Identify hot spots and benefits using the chemical recycling process.

36 MATERIALS SCIENCE↗

Process Optimization and Real-Time Control of Synergistic Microalgae Cultivation and Wastewater Treatment (Final Technical Report)

The overarching goal of this work was to accelerate the commercialization of high productivity, mixed community microalgal treatment technologies for the synergistic treatment of wastewater and the production of biofuel feedstocks. This project addressed a critical barrier to the financial viability and energy efficiency of algal wastewater treatment: an inability to design and operate high-rate processes that reliably achieve target effluent qualities, areal productivities, and biochemical compositions (lipid, protein, carbohydrate content) despite fluctuations in wastewater composition, weather, and microbial communities. Key outcomes from this work include an optimized and controlled Advanced Biological Nutrient Recovery (ABNR) design as well as a suite of open-source tools that include a calibrated and validated algae process simulator in QSDsan and a novel low-cost, real-time microbial monitoring tool. These tools can be leveraged by other algal cultivation and wastewater treatment technology developers in future work.

09 BIOMASS FUELS↗

Opportunities for Process Intensification with Membranes to Promote Circular Economy Development for Critical Minerals

Critical minerals are essential to the future of clean energy, especially energy storage, electric vehicles, and advanced electronics. In this paper, we argue that process systems engineering (PSE) paradigms provide essential frameworks for enhancing the sustainability and efficiency of critical mineral processing pathways. As a concrete example, we review challenges and opportu-nities across material-to-infrastructure scales for process intensification (PI) with membranes. Within critical mineral processing, there is a need to reduce environmental impact, especially con-cerning chemical reagent usage. Feed concentrations and product demand variability require flex-ible, intensified processes. Further, unique feedstocks require unique processes (i.e., no one-size-fits-all recycling or refining system exists). Membrane materials span a vast design space that allows significant optimization. Therefore, there is a need to rapidly identify the best opportunities for membrane implementation, thus informing materials optimization with process and infrastructure scale performance targets. Finally, scale-up must be accelerated and de-risked across the materials-to-process levels to fully realize the opportunity presented by membranes, thereby fostering the development of a circular economy for critical minerals. Tackling these challenges requires integrating efforts across diverse disciplines. We advocate for a holistic molecular-to-systems perspective for fully realizing PI with membranes to address sustainability challenges in critical mineral processing. The opportunities for PI with membranes are excellent applications for emerging research in machine learning, data science, automation, and optimization.

Dougher, Molly↗

Process Intensification for Nanocomposite Aluminum Extrusions: CRADA 411 (Final Report)

The project evaluated the feasibility of using Shear Assisted Processing and Extrusion (ShAPE) for the fabrication of extrusions with a diameter of 0.5” and higher from an Al-alloy powder feedstock that contains nanoscale second phases for achieving enhanced elevated temperature strength. PNNL has previously extruded 0.2” diameter rods with high strength aluminum alloy powder Al-12.4TM. This project aimed to scale the process up to a diameter of 1.0” at a length of >24” while retaining the excellent mechanical properties achieved for the 0.2” diameter rods. As part of the project, extrusion dies were fabricated with various design features. As an example, scroll features on the tool die face was introduced to enhance powder mixing, and reduce extrusion load. Varying extrusion ratios were used to obtain better microstructural homogeneity. Use of tool design features together with the optimization of process parameters helped in the fabrication of extrusions that were up to 48” long with a diameter of 0.5” using Al-12.4 TM powder feedstock in a two-step process involving cold compaction followed by extrusion. Extrusions with a diameter of 1.0” could also be fabricated, but limitations on the extent of consolidation were experienced as a result of the torque and ram force capacity of the current ShAPE machine.

36 MATERIALS SCIENCE↗

BETO 2021 Peer Review - FCIC Task 5 - Preprocessing

In the study of feedstock variability, this presentation specifically looks at preprocessing processes that will created well-defined and homogenous feedstock from variable biomass resources, in the quest to produce homogeneous intermediates that will be converted into market-ready products. The objective of this stage of the project is to develop science-based design and operation principles informed by TEA/LCA that result in predictable, reliable, and scalable performance of preprocessing unit operations (comminution, fractionation, deconstruction, and real-time imaging).

biomass↗

MEASURING THERMALLY-INDUCED DISTORTION OF LARGE-SCALE COMPOSITE PRINTED STRUCTURES USING DIGITAL IMAGE CORRELATION

Additive manufacturing (AM) gives designers the ability to create complex part geometries without several of the limitations of traditional manufacturing. Large-Scale AM (LSAM) allows the creation of large composite structures and is a popular area of composite tooling research. Fiber-reinforced polymers are common feedstock for LSAM tooling but introduce anisotropic thermomechanical properties that can lead to the warpage of tools at autoclave conditions. Digital image correlation (DIC) has been used to measure the coefficient of thermal expansion (CTE) of LSAM parts using a novel DIC Oven design. This method was utilized to measure the CTE of LSAM structures printed using different fiber-reinforced materials and multiple geometries. Specifically, glass fiber ABS (GF-ABS) and carbon fiber ABS (CF-ABS) samples were compared as well as cube and plate geometries for each material. The temperature profile over time was also evaluated to determine how rapidly the strain of the sample increased as temperature of the DIC Oven was increased. A thermal model was developed to predict temperature profiles for various samples and identify when the samples had reached thermal equilibrium.

Corum, Tyler↗

BETO 2021 Peer Review - Overview of the Chemical Catalysis for Bioenergy Consortium

Catalysis plays a central role in converting biomass and carbon-rich waste feedstocks into fuels and chemicals; however, critical catalysis challenges exist that are limiting commercialization of emerging bioenergy technologies. By leveraging unique U.S. Department of Energy National Laboratory capabilities and expertise, the Chemical Catalysis for Bioenergy consortium seeks to overcome these catalysis challenges and accelerate the catalyst and process development cycle. The foundation of the consortium consists of an integrated and collaborative portfolio of catalytic technologies and enabling capabilities, which positions ChemCatBio to address both technology-specific and overarching catalysis challenges across the development cycle from discovery to scale-up. The core catalysis projects target technological advancements for specific conversion processes, such as catalytic upgrading of biochemical process intermediates, catalytic fast pyrolysis, C1 and C2 upgrading, and electrochemical CO2 reduction, while the enabling technologies provide access to world-class capabilities and expertise in computational modeling, materials synthesis, advanced in situ and in operando catalyst characterization, and catalyst design tools.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗