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At least 253 records · Page 14

Eudicot Nutshells: Cell-Wall Composition and Biofuel Feedstock Potential

Nutshells are the recalcitrant and membranous layers that encompass and provide protection to the seed of a fruit. Rich in lignin, these are often waste products of the food industry and are a potential energy-dense feedstock for biorefineries to convert to biofuels. Here, assessing their potential requires an understanding of the relative amounts of cellulose, hemicelluloses, and lignin, the composition and structure of the lignin, and a saccharifiability assessment, all provided here. In the context of understanding the general character of phylogenetically diverse eudicot species, we provide a chemical analysis of the lignin in the shells of commonly eaten nuts and detail the chemical composition of their lignins. Particularly striking observations include the >40% levels of Klason lignins in the nutshells from macadamia, pecan, and Brazil nut and lignin compositions ranging from <1% syringyl (S) in macadamia to 77% S in pistachio and essentially 0% p-hydroxyphenyl (H) in mango to as high as 7.5% H in walnut. Novel units in the lignin polymer (such as the hydroxystilbenes recently discovered in macaúba and coconut shell lignins) were not evident in any of the samples, but the series provided such a range of compositions that it aided more detailed assignment.

NMR↗

At-Line Sampling and Characterization of Pyrolytic Vapors from Biomass Feedstock Blends Using SPME-GC/MS-PCA: Influence of Char on Fast Pyrolysis

Solid-phase microextraction (SPME) coupled with GC-MS analysis was used for at-line sampling of pyrolytic vapors produced during fast pyrolysis of biomass. The pure and binary blends of switchgrass (SWG) and pine harvest residues (PT6) were used as feedstock. Sequential SPME sampling allowed for monitoring of changes in the pyrolysis vapors as char accumulated in the fluid bed. The concentration and composition of the vapors desorbed from the SPME fibers were investigated using GC-MS, and the data sets were then analyzed using principal component analysis (PCA) to compare the composition of the pyrolysis vapors over the course of the pyrolysis run. The chemical composition of both carbohydrate and lignin fragments varied as the char builds up in the reactor bed. Fragments derived from cellulose and xylan included anhydrosugars, furans and light oxygenated compounds. Lignin fragments included methoxyphenols, phenolic ketones and aldehydes, low molecular weight aromatics. The composition of the carbohydrate fragments changed more than the lignin fragments as the char build-up in the fluid bed. This combination of SPME-GC/MS-PCA were a novel, easy and effective method for measuring the composition and changes in the composition of pyrolysis vapors during the fast pyrolysis process. Here, this work also highlighted the effect of char build-up on the composition of the overall pyrolysis vapors.

09 BIOMASS FUELS↗

Dual Feedstock Upcycling of α-Methylstyrene-Doped Poly(methyl methacrylate) and Biomass via the Telescope of Depolymerization and Diels–Alder Reaction

Nearly 90% of poly(methyl methacrylate) (PMMA) is not recycled and instead ends up in landfills. Conventional pyrolysis of PMMA recovers impure methyl methacrylate (MMA) with low economic value. Here, we present a telescoped dual upcycling strategy that integrates PMMA depolymerization, Diels–Alder cycloaddition, and aromatization to convert AMS-doped PMMA and biomass-derived 2,5-dimethylfuran (DMF) into 1,2,4-trimethylbenzene (pseudocumene), a valuable chemical feedstock. BBr 3 proved effective in promoting the challenging Diels–Alder reaction between MMA and DMF under high pressure of argon.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rare earth metals production using alternative feedstock that eliminates HF

This work reports the successful production of rare earth (RE) metal using Na-RE-F. Presently, RE metals are primarily produced using RE-fluoride due to its higher air and moisture stability compared to RE-chloride. However, its preparation requires the use of corrosive and hazardous chemicals, such as hydrofluoric acid (HF) or ammonium bifluoride (NH 4 HF 2 ). The present study demonstrates that Na-RE-F is an alternative salt to the typically used RE-fluoride. The Na-RE-F for this work is produced via a scalable hydrometallurgical approach using three different RE salts as feedstock, including acetate, nitrate, and chloride. HF is neither used nor generated during the salt preparation process. Furthermore, the Na-RE-F powder dries in air (without dry HF), and only water evolves during the drying process. Analyses of the Na-RE-F show that NaF liberates as a flux during the heating process, which lowers the salt reduction temperature to <900 °C, thus minimizing or eliminating the need for additional flux. Calciothermic reduction of the Na-RE-F salt is successfully employed to obtain RE metal. This work represents a safer, greener, and more widely deployable approach for producing the RE metals needed for permanent magnets which support the transition to a cleaner society through the decarbonization of the transportation industry.

36 MATERIALS SCIENCE↗

Expanding the use of ethanol as a feedstock for cell-free synthetic biochemistry by implementing acetyl-CoA and ATP generating pathways

Abstract Ethanol is a widely available carbon compound that can be increasingly produced with a net negative carbon balance. Carbon-negative ethanol might therefore provide a feedstock for building a wider range of sustainable chemicals. Here we show how ethanol can be converted with a cell free system into acetyl-CoA, a central precursor for myriad biochemicals, and how we can use the energy stored in ethanol to generate ATP, another key molecule important for powering biochemical pathways. The ATP generator produces acetone as a value-added side product. Our ATP generator reached titers of 27 ± 6 mM ATP and 59 ± 15 mM acetone with maximum ATP synthesis rate of 2.8 ± 0.6 mM/h and acetone of 7.8 ± 0.8 mM/h. We illustrated how the ATP generating module can power cell-free biochemical pathways by converting mevalonate into isoprenol at a titer of 12.5 ± 0.8 mM and a maximum productivity of 1.0 ± 0.05 mM/h. These proof-of-principle demonstrations may ultimately find their way to the manufacture of diverse chemicals from ethanol and other simple carbon compounds.

59 BASIC BIOLOGICAL SCIENCES↗

Spectroscopic analysis reveals that soil phosphorus availability and plant allocation strategies impact feedstock quality of nutrient-limited switchgrass

Abstract The perennial native switchgrass adapts better than other plant species do to marginal soils with low plant-available nutrients, including those with low phosphorus (P) content. Switchgrass roots and their associated microorganisms can alter the pools of available P throughout the whole soil profile making predictions of P availability in situ challenging. Plant P homeostasis makes monitoring of P limitation via measurements of plant P content alone difficult to interpret. To address these challenges, we developed a machine-learning model trained with high accuracy using the leaf tissue chemical profile, rather than P content. By applying this learned model in field trials across two sites with contrasting extractable soil P, we observed that actual plant available P in soil was more similar than expected, suggesting that adaptations occurred to alleviate the apparent P constraint. These adaptations come at a metabolic cost to the plant that have consequences for feedstock chemical components and quality. We observed that other biochemical signatures of P limitation, such as decreased cellulose-to-lignin ratios, were apparent, indicating re-allocation of carbon resources may have contributed to increased P acquisition. Plant P allocation strategies also differed across sites, and these differences were correlated with the subsequent year’s biomass yields.

59 BASIC BIOLOGICAL SCIENCES↗

Agentic workflow enables the recovery of critical materials from complex feedstocks via selective precipitation

We present a multi-agentic workflow for critical materials recovery that deploys a series of AI agents and automated instruments to recover critical materials from produced water and magnet leachates. This approach achieves selective precipitation from real-world feedstocks using simple chemicals, accelerating the development of efficient, adaptable, and scalable separations to a timeline of days, rather than months and years.

Ritchhart, Andrew J.↗

Progress and challenges in sorghum biotechnology, a multipurpose feedstock for the bioeconomy

Abstract Sorghum [Sorghum bicolor (L.) Moench] is the fifth most important cereal crop globally by harvested area and production. Its drought and heat tolerance allow high yields with minimal input. It is a promising biomass crop for the production of biofuels and bioproducts. In addition, as an annual diploid with a relatively small genome compared with other C4 grasses, and excellent germplasm diversity, sorghum is an excellent research species for other C4 crops such as maize. As a result, an increasing number of researchers are looking to test the transferability of findings from other organisms such as Arabidopsis thaliana and Brachypodium distachyon to sorghum, as well as to engineer new biomass sorghum varieties. Here, we provide an overview of sorghum as a multipurpose feedstock crop which can support the growing bioeconomy, and as a monocot research model system. We review what makes sorghum such a successful crop and identify some key traits for future improvement. We assess recent progress in sorghum transformation and highlight how transformation limitations still restrict its widespread adoption. Finally, we summarize available sorghum genetic, genomic, and bioinformatics resources. This review is intended for researchers new to sorghum research, as well as those wishing to include non-food and forage applications in their research.

59 BASIC BIOLOGICAL SCIENCES↗

Multi-feedstock Supply Chain Optimization Model

This tool can be used to determine a least-cost feedstock mix from crop residue, energy crop and MSW to meet conversion specifications, while also identifying appropriate depot locations and size, given that depot can be co-located with the biorefinery or can be located in any counties in the biofinery’s supply shed.

Roni, MohammadS↗

Manuscript Workflows from and Processed Organic Matter Composition of Experimentally Burned Open Air and Muffle Furnace Vegetation Chars across Differing Burn Severity and Feedstock Types from Pacific Northwest, USA (v3)

This dataset includes processed organic matter chemistry data from an experimental study designed to compare how the chemical composition of organic matter changes across different burn conditions and vegetation materials representative of major land cover types of the Pacific Northwest, USA. Chars were created in a closed muffle furnace or on an open burn table from four different feedstock species representing vegetation commonly impacted by fire regimes across the Pacific Northwest, USA. Source data and associated metadata (including methods and geospatial information) can be found at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1894135 (Grieger et al. 2022). This dataset provides processing scripts and processed data for both solid and dissolved phase organic matter characterization data from experimentally generated chars. These processed data can be used to compare how different burn conditions may influence resultant organic matter chemistry and help further our understanding of potential biogeochemical impacts on river corridors post-fire. The processed data were subsequently analyzed; and the results and ecological implications of the findings were published in peer-reviewed manuscripts. The scripts and workflows used to develop the manuscripts are also included in this data package.This data package was originally published June 2024. It was updated September 2024 (new and modified files) and in January 2025 (modified files). See the change history section in the readme for more details.This dataset is comprised of one data package readme, one data dictionary (dd), one file level metadata (flmd), and folders containing (A) processed data; (B) general processing scripts; and (C) additional folders with specific manuscript analysis scripts and processed data. Step-by-step instructions to assist the user in recreating the workflow used to generate the results in the manuscripts is also provided. The processed data folder includes (1) a folder of processed Parallel Factor Analysis (PARAFAC) and spectra indices outputs from excitation emissions matrix (EEM) fluorescence and absorbance data; (2) a folder of processed solid state carbon-13 (13-C NMR) integrals; (3) folder of high resolution characterization of organic matter via 21 Tesla Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) generated through the Environmental Molecular Sciences Laboratory (EMSL; https://www.pnnl.gov/environmental-molecular-sciences-laboratory) processed data outputs from Formultitude (https://github.com/PNNL-Comp-Mass-Spec/Formultitude), blank corrections and data aggregation, and calculated molecular indices. All files are .pdf, .csv, .html, .Rmd, .R, or .RData.

54 ENVIRONMENTAL SCIENCES↗

Investigation of Rare Earth Element Extraction from North Dakota Coal-Related Feedstocks (Phase 2 Final Technical Report)

There were four major goals of this project: i) identify promising lignite or lignite-related feedstocks with total rare earth element content above 300 parts per million (ppm), ii) evaluate at the lab and bench-scale the extractability of the REE from the material, iii) determine the processing required to generate REE concentrates in excess of 2 wt%, iv) evaluate the economic feasibility of the process and develop a pathway for commercialization. In the Phase 1 study, work was primarily focused upon resource evaluation and labscale extractability of the REE, with a preliminary techno-economic assessment (TEA) conducted, whereas in the Phase 2 work, the extraction process was conducted at the bench scale, a method for cost-effective generation of higher purity mixed REE concentrates (up to 65%) was developed, and a refined TEA on the bench-scale data for a 1,000 kg coal processing test was conducted.

01 COAL, LIGNITE, AND PEAT↗

Rheological Characterization of Biomass Feedstock for Alternative Energy Applications

With the increased necessity of alternative energy resources, bulk feedstock biomass materials were characterized with the purpose of replacing depleting energy supplies such as fossil fuels and other nonrenewable energy sources. Residual organic waste material (biomass) left over from agricultural processing and handling systems was recycled, and further investigated for renewable energy use. Understanding the scope of flowability for biomass material yielded more efficient, and economical crop harvesting, transporting, and storing method design for the agricultural industry. The effects of moisture on bulk solid flowability was investigated using a variety of parametric testing methods that measure basic flowability energy, and other properties such as compressibility and material resistance. In an industry where organic material is a wasteful byproduct, converting this biomass material into a new energy source and streamlining efficiently for innovative agricultural development supports a clean, renewable energy approach to everyday nonrenewable energy uses, such as oil, propane, and coal. As observed from the repeatable results from the investigated rheological material properties, biomass is an incredibly diverse material that requires modern engineering solutions to revolutionize biomass into a renewable energy source. Biomass will decarbonize petroleum (nonrenewable) derived fuels and chemicals, yielding recyclable carbon. This push to replace fossil fuels with recycled carbon is ideal because of the abundant, renewable, and otherwise agricultural waste of corn stover material. Decarburization, and reduction of C0 2 emissions reduces the effects of global warming.

09 BIOMASS FUELS↗

An Abrasion Wear Model of Rotary Shear Comminution of Biomass Feedstock

The research team formulated a workable analytical abrasion model that relates critical rotary shear process parameters (shear geometry and rotational speed) to critical material attributes of inorganic mineral species in feedstock (density, size, and aspect ratio) and substrate (hardness and elastic modulus) that enabled us to model the wear of shear cutters in a rotary shear milling system developed by Forest Concepts. We compared results of the model to experimental observations of the shape of rotary shear cutters used in a Forest Concept Crumbler® shear mill. Results showed good agreement between the predicted and measured shape of a worn cutter; thus, a quality-by-design (QbD) approach can be developed to predict component reliability based on scientific engineering principles in lieu of trial-and-error approaches.

42 ENGINEERING↗

Next Generation Logistics Systems for Delivering Optimal Biomass Feedstocks to Biorefining Industries in the Southeastern U.S.

The diverse portfolio of biomass sources that is available in the Southeastern U.S., including a significant supply of pine “residue”, represents a valuable strategic position for the region. Through blends formulated based on critical properties, this project will take full advantage of the range in biomass properties afforded by the portfolio to produce a consistent, high-performance feedstock for the industry, while lowering cost. Key developments being targeted to enable this potential include whole-tree transport to a state-of-the-art merchandising depot that will further access biomass from ongoing, forest industry operations. The approach will more effectively utilize the tree and distribute cost, while minimizing in-woods contamination of the woody biomass component. To implement this vision, information on the chemical composition and changes that are induced during multiple preprocessing steps (size reduction, moisture removal, densification, etc.) is needed. New NIR sensor technology will be developed for online monitoring of important biomass properties. The data will be incorporated into a statistical process control platform to improve process efficiency and meet required specifications. Advanced process models are being developed to inform the techno-economic and life-cycle assessment of the program’s impact. The new system will ultimately reduce operational risks from supply chain disruptions, and allow operation of larger-scale biorefineries.

09 BIOMASS FUELS↗

Using Chemical Reactor Models to Predict Fluidized Bed Pyrolysis Yields of Biomass Feedstocks

A detailed biomass pyrolysis kinetics scheme is implemented in reduced-order reactor models to predict chemical species yields from a fluidized bed reactor. The biomass composition in terms of cellulose, hemicellulose, lignins, and extractives are determined for several biomass feedstocks. Model results are compared to yields measured from a two-inch diameter bench-scale fluidized bed reactor operating at fast pyrolysis conditions. The reduced-order chemical reactor models compare favorably with the experimental measurements and capture trends in product yields due to biomass compositional effects such as high ash content. This work offers a computationally inexpensive approach to predict the quality of biomass pyrolysis products in a timely manner. Source code for the reactor models along with a biomass composition web tool are made available online for future scientific research efforts.

09 BIOMASS FUELS↗

The Role of Biofuels and Biomass Feedstocks for Decarbonizing the U.S. Economy by 2050 - (DECARB) Decarbonizing Energy Through Collaborative Analysis of Routes and Benefits

Utilizing biomass resources, such as cellulosic biomass and waste, can greatly contribute to decarbonization efforts in the U.S. economy. The U.S. bioenergy sector includes corn ethanol production, biodiesel, renewable diesel production, and the utilization of biomass wastes for electricity generation being the primary applications. Within the electricity sector, biopower can play a crucial role as a stable low-carbon resource. Enhancing the electricity mix's diversity could enhance grid reliability. If the issues regarding hot gas cleanup can be resolved, flexible biopower resources like biomass gasification facilities could complement the integration of variable renewable energy sources due to their quick ramp-up and ramp-down times. The criticality of bioenergy deployment lies in its ability to decarbonize hard-to-electrify sectors, such as aviation, where alternative decarbonization options may not be viable in the short term. Moreover, bioenergy has the potential to be converted into process heating, building materials, and plastics, which are not considered in this study. A set of pathways was carefully chosen to represent viable options for converting ample herbaceous and woody cellulosic feedstocks into fuels, chemicals, and electricity in this study. In conclusion, biomass pathways provide flexibility by generating various types of bioenergy and bioproducts, including electricity, hydrogen, liquid fuels, biochemicals, and bioplastics. When paired with carbon dioxide capture and storage (CCS), specific bioenergy approaches can effectively extract carbon dioxide from the atmosphere, thus providing an effective decarbonization option for the transportation sector.

09 BIOMASS FUELS↗