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At least 163 records · Page 9

How is Rational Design of Electrocatalysts Crucial for Maximizing CO2 Electroreduction Performance?

The invited talk "How is Rational Design of Electrocatalysts Crucial for Maximizing CO2 Electroreduction Performance?” was presented in the symposium "Electrocatalysis for Sustainable Energy and Biomass Conversion: Fundamentals, Applications, and Perspectives”, Division of Catalysis Science and Technology, 2024 ACS Fall Meeting. The presentation briefly introduces NETL facilities and our Electrochemical Carbon Conversion portfolio to audiences. The talk primarily discusses how the geometry and surface composition of copper- and tin-based electrocatalysts would maximize the CO2 conversion to sustainable, carbon-neutral gas and liquid products in different device configurations. Ex situ and in situ characterization results are additionally discussed to correlate the structural, physico-chemical, and electronic properties with CO2 reduction activity and selectivity.

Nguyen Phan, Thuy Duong↗

Quantitation of olefins in sustainable aviation fuel intermediates using principal component analysis coupled with vacuum ultraviolet spectroscopy

Olefins, a common intermediate from biomass conversion processes, are undesirable in jet fuel because of their poor thermal stability. This paper presents an approach for olefin quantitation using 2D gas chromatography coupled with vacuum ultraviolet spectroscopy. Principal component analysis was used to reduce the dimensionality of the spectroscopic data from a highly olefinic fuel intermediate. A principal component template was created that enabled olefin quantitation, which was compared to the existing GCxGC-VUV approach from the literature. The principal component method was able to identify and quantify trace amounts of cyclodienes, which were present at only 0.01 wt% in the fuel sample. The principal component approach also identifies species that fall outside of the GCxGC template. For instance, quantitation with the literature method resulted in an olefin concentration of 0.95 times that of the principal component method due to olefins falling outside of the expected GCxGC regions. The principal component results were compared with 13 C and 1 H NMR data, which confirmed that the fuel had a high concentration of olefins and alkanes with little aromatic content.

Kosir, Shane↗

Virulence and Genetic Diversity of Puccinia spp., Causal Agents of Rust on Switchgrass (Panicum virgatum L.) in the USA

Switchgrass (Panicum virgatum L.) is an important cellulosic biofuel grass native to North America. Rust, caused by Puccinia spp. is the most predominant disease of switchgrass and has the potential to impact biomass conversion. In this study, virulence patterns were determined on a set of 38 switchgrass genotypes for 14 single-spore rust isolates from 14 field samples collected in seven states. Single nucleotide polymorphism (SNP) variation was also assessed in 720 sequenced cloned amplicons representing 654 base pairs of the elongation factor 1-α gene from the field samples. Five major haplotypes were identified differing by 11 out of the 39 SNP positions identified. STRUCTURE, Principal Coordinate Analysis, and phylogenetic analyses divided the rust population into two genetic clusters. Virginia and Georgia had the highest and lowest rust genetic diversity, respectively. Only nine accessions showed a differential disease response between the 14 isolates, allowing the identification of eight races, differing by 1–3 virulence factors. Overall, the results suggested clonal reproduction of the pathogen and a North–South differentiation via local adaptation. However, similar haplotypes and races were also recovered from several states, suggesting migration events, and highlighting the need to further investigate the switchgrass rust population structure and evolution in the USA.

Bahri, Bochra A. (ORCID:0000000159055880)↗

BETO 2021 Peer Review - Strategic Analysis Support WBS 4.1.1.30

Strategic Analysis Support. The objective of the NREL strategic support project is to provide sound, unbiased, and consistent analyses to inform the strategic direction of the DOE BETO office. This project addresses key technological questions, provides critical data needed to inform strategy, and highlights barriers, gaps and data needs in support of the DOE BETO's mission to improve the affordability of bio-based fuels and products. This task employs various quantitative (techno-economic analysis, TEA) and qualitative (gap analysis) approaches to allow for direct comparisons of biomass conversion technologies across a wide slate of processing platforms and products. Furthermore, this project develops and utilizes novel analyses beyond traditional biorefinery focused TEA/LCAs to identify both technical (e.g., in sustainable design) and non-technical (e.g., in value proposition) barriers, as well as to outline mitigation strategies and R&D needs for emerging technologies. Additionally, the project is tasked with evaluating drivers that support the growing bio-economy, which is achieved by the development and public release of tools to advance the understanding and facilitate comparisons of socio-economic impacts along the supply chain. Critical to the success of this project is the development of defensible methodologies, analyses, and tools that are publicly available to support stakeholders and bioeconomy growth. To develop such high-quality analyses, the biggest challenge to this project, as with most analysis focused projects, is the availability and reliability of the underlying data. Therefore, the project team works extensively with key stakeholders (e.g., policy makers, bioenergy technology developers, and investors) in developing and reviewing the results of these analyses to overcome this challenge. Any remaining uncertainties associated with the analysis efforts are clearly defined and quantified.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Metal complexes and methods of making the same

Disclosed herein are embodiments of metal complexes and methods of making the same. The disclosed method embodiments provide a one-step approach to making metal complexes, such as complexes comprising lanthanide metals, rare earth metals, transition metals, main group metals, and/or actinide metals that can be used various applications, such as in separations technology, catalysis (e.g., catalysts for pharmaceutical synthesis and/or catalysts for biomass conversion), nuclear chemistry, LED phosphors, scintillator materials, magnetic materials, and nuclear fuels.

Kiplinger, Jaqueline↗

Opening pathways for the conversion of woody biomass into sustainable aviation fuel via catalytic fast pyrolysis and hydrotreating

Meeting aggressive decarbonization targets set by the International Civil Aviation Organization (ICAO) will require the rapid development of technologies to produce sustainable aviation fuel (SAF). Catalytic fast pyrolysis (CFP) can support these efforts by opening pathways for the conversion of woody biomass into an upgraded biogenic oil that can be further processed to SAF and other fuels. However, the absence of end-to-end experimental data for the process leads to uncertainty in the yield, product quality, costs, and sustainability of the pathway. The research presented here serves to address these needs through a series of integrated experimental campaigns in which real biomass feedstocks are converted to a final SAF product using large bench-scale continuous reactor systems. For these campaigns, the degree of catalytic upgrading during CFP was varied to produce CFP-oils with oxygen contents of 17 and 20 wt% on a dry basis. The CFP-oils were then hydrotreated and distilled into gasoline, diesel, and SAF fractions. Detailed yield and compositional data were obtained for each step of the process to inform technoeconomic and lifecycle analyses, and the fuel properties of the SAF fraction were evaluated to provide first-of-its-kind insight into the quality of the final product. This research reveals opportunities to optimize process carbon efficiency by tuning the degree of catalytic upgrading during the CFP step and highlights routes to produce a high-quality cycloalkane-rich SAF with 85–92% reduction in greenhouse gas emissions compared to fossil-based pathways.

09 BIOMASS FUELS↗

Biochemical Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels and Products (2021 State of Technology and Future Research)

The annual State of Technology (SOT) assessment is an essential activity for biochemical platform research. It allows the impact of research progress to be quantified in terms of economic improvements in the overall cellulosic biofuel production process for a particular conversion pathway. As such, initial benchmarks can be established for currently demonstrated performance and progress can be tracked towards out-year goals to ultimately demonstrate cost-competitive cellulosic biofuel technology. The purpose of this report is to benchmark the latest experimental developments across a number of potential bioconversion pathways as quantified by modeled minimum fuel selling prices (MFSPs), as a measure of current status relative to those final targets. For this state of technology, TEA models were run for two separate biological conversion pathways to fuels, based on available data for integrated biomass deconstruction and hydrolysate processing; namely carboxylic acids (primarily butyric acid) and diols (2,3-butanediol [BDO]), reflecting NREL's recently-published 2018 biochemical design report focused on those two pathways. The models were run across three scenarios for lignin utilization, namely combustion, conversion to coproducts based on "base case" performance with biomass hydrolysate, and conversion to coproducts based on "high" performance demonstrated with model lignin monomer components. A key improvement reflected in the 2021 SOT is centered around making use of the latest lignin conversion data, which over the past year focused primarily on production of ß-ketoadipate (BKA) as a more optimal molecule compared to the closely-related adipic acid coproduct of prior recent focus, both in terms of superior product properties and biology, as well as reduced processing complexity (reducing two steps for sequential production of muconate followed by hydrogenation to adipic acid down to a single step for direct production of BKA). This update translated to a roughly 17% increase in mass yield of final coproduct output at a nearly four-fold increase in fermentation productivity on lignin monomers relative to prior 2020 SOT benchmarks for muconic/adipic acid production.

09 BIOMASS FUELS↗

Biochemical Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels and Products: 2020 State of Technology and Future Research

The annual State of Technology (SOT) assessment is an essential activity for biochemical platform research. It allows the impact of research progress to be quantified in terms of economic improvements in the overall cellulosic biofuel production process for a particular conversion pathway. As such, initial benchmarks can be established for currently demonstrated performance and progress can be tracked towards out-year goals to ultimately demonstrate cost-competitive cellulosic biofuel technology. The purpose of this report is to benchmark the latest experimental developments across a number of potential bioconversion pathways as quantified by modeled minimum fuel selling prices (MFSPs), as a measure of current status relative to those final targets. For this state of technology, TEA models were run for two separate biological conversion pathways to fuels, based on available data for integrated biomass deconstruction and hydrolysate processing; namely carboxylic acids (primarily butyric acid) and diols (2,3-butanediol [BDO]), reflecting NREL's recently-published 2018 biochemical design report focused on those two pathways. The models were run across three scenarios for lignin utilization, namely combustion, conversion to coproducts based on "base case" performance with biomass hydrolysate, and conversion to coproducts based on "high" performance demonstrated with model lignin monomer components. Relative to prior 2019 benchmarks, the 2020 SOT achieved further MFSP reductions of approximately $1/gallon gasoline equivalent, primarily attributed to improvements in pretreatment that led to both cost reductions and yield improvements.

09 BIOMASS FUELS↗

Strategies to achieve high productivity, high conversion, and high yield in yeast fermentation of algal biomass hydrolysate

The conversion of carbohydrates in biomass via fermentation is an important component of an overall strategy to decarbonize the production of fuels and chemicals. Owing to the cost and resources required to produce biomass hydrolysates, the economic and environmental sustainability of these fermentation processes requires that they operate with high yields, sugar conversion, and productivity. Immobilized-cell technology in a continuous bioprocess can achieve significantly higher volumetric productivities than is possible from standard batch fermentation using free cells. Here, we demonstrate approaches for improvement of ethanol yield from algal hydrolysates and a mock hydrolysate medium. Saccharomyces cerevisiae was immobilized in alginate and incorporated into a two-column immobilized cell reactor system. Furthermore, the yeast quorum-sensing molecule, 2-phenylethanol, was added to improve ethanol yield by restricting growth and diverting sugar to ethanol. The bioreactor system could achieve high ethanol volumetric productivity (>20 g/ Lreactor ·h) and high glucose conversion (>99%) in mock hydrolysate, while the addition of 0.2% 2-phenylethanol resulted in 4.9% higher ethanol yield. With an algal hydrolysate of <10 g/L sugar, the ethanol volumetric productivity reached 9.8 g/ Lreactor ·h, and the addition of 0.2% 2-phenylethanol increased the ethanol yield by up to 7.4%. These results demonstrate the feasibility of novel strategies to achieve sustainability goals in biomass conversions.

59 BASIC BIOLOGICAL SCIENCES↗

Biochemical Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels and Products: 2019 State of Technology and Future Research

The purpose of this report is to benchmark the latest experimental developments across a number of potential bioconversion pathways as quantified by modeled minimum fuel selling prices (MFSPs), as a measure of current status relative to those final targets. For this state of technology, TEA models were run for two separate biological conversion pathways to fuels, based on available data for integrated biomass deconstruction and hydrolysate processing; namely carboxylic acids (primarily butyric acid) and diols (2,3-butanediol [BDO]), reflecting NREL’s recently-published 2018 biochemical design report focused on those two pathways. The models were run across three scenarios for lignin utilization, namely combustion, conversion to coproducts based on “base case” performance with biomass hydrolysate, and conversion to coproducts based on “high” performance demonstrated with model lignin monomer components.

09 BIOMASS FUELS↗

Characterization of the Biomass Degrading Enzyme GuxA from Acidothermus cellulolyticus

Microbial conversion of biomass relies on a complex combination of enzyme systems promoting synergy to overcome biomass recalcitrance. Some thermophilic bacteria have been shown to exhibit particularly high levels of cellulolytic activity, making them of particular interest for biomass conversion. These bacteria use varying combinations of CAZymes that vary in complexity from a single catalytic domain to large multi-modular and multi-functional architectures to deconstruct biomass. Since the discovery of CelA from Caldicellulosiruptor bescii which was identified as one of the most active cellulase so far identified, the search for efficient multi-modular and multi-functional CAZymes has intensified. One of these candidates, GuxA (previously Acel_0615), was recently shown to exhibit synergy with other CAZymes in C. bescii, leading to a dramatic increase in growth on biomass when expressed in this host. GuxA is a multi-modular and multi-functional enzyme from Acidothermus cellulolyticus whose catalytic domains include a xylanase/endoglucanase GH12 and an exoglucanase GH6, representing a unique combination of these two glycoside hydrolase families in a single CAZyme. These attributes make GuxA of particular interest as a potential candidate for thermophilic industrial enzyme preparations. Here, we present a more complete characterization of GuxA to understand the mechanism of its activity and substrate specificity. In addition, we demonstrate that GuxA exhibits high levels of synergism with E1, a companion endoglucanase from A. cellulolyticus. We also present a crystal structure of one of the GuxA domains and dissect the structural features that might contribute to its thermotolerance.

09 BIOMASS FUELS↗

Maximizing long-term biohydrogen production with Clostridium thermocellum for high solids conversion of lignocellulosic biomass

Biological hydrogen production from lignocellulosic biomass sustainably couples organic waste reduction with renewable energy generation. Efficient conversion is challenged by the structural complexity of lignocellulose and resulting recalcitrance to enzymatic degradation. Clostridium thermocellum natively breaks down biomass with highly effective hemi-/cellulases systems (i.e., cellulosomes) and generates hydrogen in anaerobic cultivation, creating a compelling platform for lignocellulosic biohydrogen production. Achieving commercially viable production rates requires balancing high biomass loading and throughput against uniform mixing conditions required for enzyme dispersion, pH and temperature control, and efficient hydrogen and metabolite removal in continuous operation. To address these barriers to process intensification, we implemented novel reactor and process designs for high-solids lignocellulosic biomass fermentations using the C. thermocellum KJC19-9 strain, genetically engineered for co-utilization of cellulose and hemicellulose sugars (i.e., xylose). Via computational fluid dynamics (CFD) modeling and experimental validation, we achieved a >50% improvement in biohydrogen production with an improved anchor-type impeller morphology, coupled to a threefold reduction in agitation rate. To further reduce rheological constraints and accumulation of toxic metabolites, we then transitioned the process to sequencing fed-batch operation. The resulting process generated 24.87 L H 2 L −1 from 160 g L −1 of deacetylated and mechanically refined (DMR)-pretreated corn stover biomass over 16 days while solubilizing >95% of influent cellulose and hemicellulose, setting a new performance benchmark for continuous production of biohydrogen from lignocellulose.

08 HYDROGEN↗

Biochemical Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels and Products: 2022 State of Technology and Future Research

The annual State of Technology (SOT) assessment is a key activity for biochemical platform research. It allows the impact of research progress (both directly achieved in-house at the National Renewable Energy Laboratory [NREL] and indirectly extrapolated from available public data) to be quantified in terms of economic improvements in the overall cellulosic biofuel production process for a particular conversion pathway. As such, initial benchmarks can be established for currently demonstrated performance and progress can be tracked toward out-year goals to ultimately demonstrate cost-competitive biofuel technology. Building upon efforts to progress NREL's biochemical platform R&D work toward ultimate 2030 goals to demonstrate less than $2.50/gallon gasoline equivalent (GGE) fuel selling prices, experimental and techno-economic analysis (TEA) activities have primarily focused on "advanced" biochemical processing strategies to fuels and coproducts, guided by TEA modeling to highlight key barriers and priorities toward achieving this goal across a number of potential bioconversion pathways. The purpose of the present effort is to benchmark the latest experimental developments for these pathways as quantified by modeled minimum fuel selling prices (MFSPs), as a measure of current status relative to those final targets. For this SOT, TEA models were run for two separate biological conversion pathways to fuels, based on available data for integrated biomass deconstruction and hydrolysate processing; namely carboxylic acids (primarily butyric acid) and diols (2,3-butanediol [BDO]), reflecting NREL's recently published 2018 biochemical design report focused on those two pathways. The models were run across two scenarios for lignin utilization, namely combustion and conversion to value-added coproducts.

09 BIOMASS FUELS↗

Biochemical Conversion of Herbaceous Biomass to Renewable Diesel: Net Greenhouse Gas and Air Pollutant Trade-offs

This study examines greenhouse gas (GHG) and criteria air pollutant (CAP) emissions trade-offs for renewable diesel across 12 scenarios, involving different biochemical conversion designs, biorefinery scales, and feedstocks. A conventional design uses lignin for on-site heat and power, which exports excess power to the grid. An alternative design exports lignin pellets, offsetting other pellet production methods but requiring grid electricity to meet biorefinery power demands. Net emissions were quantified in Iowa and Georgia, selected considering feedstock availability, coproduct displacement, and regional power grids, assuming grid-exported power avoids coal or low-carbon electricity. Results for the conventional design remained consistent across the electricity displacement scenarios. When comparing lignin utilization strategies, pelletizing lignin reduces sulfur dioxide, carbon monoxide, nitrogen oxides, and volatile organic compounds (net emissions –0.66 mg MJ –1 , 25 mg MJ –1 , 25 mg MJ –1 , 7.8 mg MJ –1 , respectively). However, lignin pelletization increases net particulate matter (fine and coarse) and ammonia (net emissions of 4.7 mg MJ –1 , 13 mg MJ –1 , and 0.26 mg MJ –1 , respectively), alongside indirect GHG emissions due to grid electricity dependence. Additionally, processing 2000 tonnes corn stover daily minimizes emissions for both designs. Only lignin pelletization with renewable electricity and additional particulate matter and ammonia controls reduces all CAP and GHG emissions simultaneously.

09 BIOMASS FUELS↗

Integration of IH 2 ® with Cool Reformer for the Conversion of Cellulosic Biomass to Drop In Fuels

GTI Energy has integrated the Cool Reformer technology with the IH 2® -50 pilot plant (which can process a maximum of 50kg/day of biomass feed) to demonstrate the suitability of this new reforming technology for producing hydrogen within IH 2 ® process. As part of this study, we showed that all of the hydrogen required for the IH 2® process could be produced from steam reforming the IH 2® light gas generated within the process and the system can be integrated in a cost-effective way compared to the use of standard SMRs.

08 HYDROGEN↗

Biochemical Conversion of Herbaceous Biomass to Renewable Diesel: Biorefinery Marginal Air Quality Impacts and Comparison to Feedstock Production

This study assesses the air quality impacts of an advanced biorefinery that produces renewable diesel blendstock (RDB) from lignocellulosic biomass via aerobic respiration (Davis et al. 2022) by estimating fine particulate matter (PM2.5) impacts from biorefinery emissions. It continues a prior analysis that used a geospatial assessment to identify source regions for biomass feedstocks and studied the impact of feedstock production emissions on air quality (Thind et al. 2022). Thind et al. (2022) identified RDB biorefineries that can use corn stover feedstocks of 2,000; 5,200; and 9,100 dry metric tons per day (DMT/day), based in Iowa, and suggested 7 unique counties can serve as hosts for a biorefinery that draws biomass feedstock from neighboring counties. Given 13 unique county-biorefinery size combinations and two waste lignin end uses at the biorefinery (lignin as a fuel for electricity generation and lignin for pellet production), the air-quality-related sustainability aspects of each of these 26 scenarios are assessed by estimating the annual average impacts of biorefinery emissions on the dispersion and formation of secondary PM2.5 in the atmosphere using a novel reduced-complexity air quality model called the Intervention Model for Air Pollution (InMAP). The 26 biorefinery design combinations help capture how a biorefinery's emissions of air pollutants and their resulting impact on local and regional air quality are influenced by the magnitude of production scale, lignin utilization strategy, and location of a proposed biorefinery. Methods developed in Thind et al. (2022) are applied to estimate the constraints on primary PM2.5 and secondary PM2.5 precursor emissions based on compliance with U.S. Environmental Protection Agency's (EPA's) annual primary National Ambient Air Quality Standard (NAAQS) of PM2.5 (i.e.12.0 micrograms per cubic meter (microgram/m3)) at downwind receptors of a biorefinery. Incremental PM2.5 concentrations caused by the emission of biorefining corn stover into RDB are assessed and compared to those of corn stover production. To illuminate which upstream supply chain stage of renewable diesel production contributes most to air quality impacts, marginal PM2.5 concentrations are compared between both stages at multiple downwind air quality monitor locations. In addition, through a hotspot analysis, we identify the primary contributing factors of emissions within the feedstock production and biorefinery stage operations. In doing so, we provide insights for improving the air pollutant emission-related sustainability of advanced lignocellulosic biofuel production.

09 BIOMASS FUELS↗

Direct Conversion of Delignified Biomass into Non-Volatile Products Using Thermophilic Bacteria

Butyric acid (BA) can be used as a platform intermediate for diesel and sustainable aviation fuels (SAFs) as well as a precursor for diverse commodity chemicals for the production of polymers, fibers, solvents, and preservatives. This work presents a co-culture-based bioprocess for the production of BA from corn stover by two thermophilic bacteria, Clostridium thermocellum, a well-known efficient degrader of insoluble and oligomeric cellulosic substrates, and Clostridium thermobutyricum, a highly efficient BA producer from monomeric sugars. First, we tested the capability of C. thermocellum to deconstruct three different biomass streams from the NREL pilot plant pretreatment process -raw, deacetylated, and deacetylated and mechanically refined corn stover (DMR)-, and up to 82% solids deconstruction and 91% carbohydrate utilization were obtained when using DMR solids. Then, the sugar utilization and by-product formation capabilities on various substrates by C. thermobutyricum were compared to evaluate its potential as a co-culture partner for C. thermocellum. Model carbon sources -glucose and xylose- were compared to a mixture of substrates present in soluble DMR hydrolysate streams, and the highest cell density as well as the maximum BA titer (8.3 g/L) were observed on DMR hydrolysate. Finally, clostridial co-cultivations on DMR solids were performed to investigate the inoculation time for both organisms that enhances BA production; while C. thermocellum was always inoculated at the beginning of the cultivation, C. thermobutyricum was inoculated at 0, 36, or 72h. It was found that BA production begins immediately upon inoculation of C. thermobutyricum regardless of the inoculation time. However, higher solids deconstruction and carbohydrate utilization results (83.7 and 95.6%, respectively) were obtained when both organisms were inoculated at the beginning of the fermentation. Under those conditions, up to 2.6 g/L of BA were obtained from DMR solids after 120h of cultivation. This work provides relevant information for the sustainable production of BA using thermophilic bacteria.

bacterial co-culture↗