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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 613 records · Page 34

Techno-Economic Analysis and Life-Cycle Assessment of Emerging Technologies for Bioprocessing Separations

Limited availability, rising costs, and environmental concerns about fossil fuels have generated considerable interest in finding alternative, renewable sources including biomass, which can be converted into a number of biofuels and bioproducts. In comparison to petroleum-based products, high processing costs, mainly associated with bioprocessing separations, limit widespread implementation of biofuels and bioproducts. Bioprocess-related separations are also complicated, regardless of the conversion pathway, due to the dilute nature of products and the chemically complex mixtures that result from biomass deconstruction. In many cases, bioprocessing separation approaches lack a technology baseline, or definition of the state of technology (SOT). This work focuses on evaluating the technology readiness of novel separations technologies for the conversion of biomass into biofuels and bioproducts and will address three key topics: 1) SOT description, 2) economic viability analysis of both SOT and innovative separations, and 3) environmental impact assessment of both SOT and novel processes. The current SOT for lignin valorization, dilute carbon recovery, and impurity removal is used to identify potential opportunities for improvement and provide a baseline for comparison with the emerging technologies. Detailed techno-economic analysis (TEA) and life cycle assessment (LCA) are applied to understand the key drivers and challenges related to the economic feasibility and environmental impacts, respectively.

BASIC BIOLOGICAL SCIENCES,BIOMASS FUELS↗

Cross-Kingdom Comparative Genomics of Aromatic Catabolic Pathways in Fungi and Bacteria

The overall goal of this project is to test the hypothesis that white-rot fungi can simultaneously depolymerize lignin extracellularly and catabolize depolymerization products intracellularly as carbon and energy sources. The results from this project will lead to improved understanding of lignin utilization by white-rot fungi, and enable identification of promising fungal strains for lignin catabolism and valorization. As part of this effort, we have conducted a comparative genomic study to investigate a diversity of aromatic catabolic pathways in the fungal and bacterial kingdoms. Furthermore, we have combined genomic and phylogenetic approaches to decipher the evolution of certain aromatic catabolic enzymes and discover new classes of enzymes, which represents a foundation for future biochemical and molecular genetic studies.

aromatic compounds↗

Simulation and Optimization of Volatile Fatty Acid Upgrading Strategies for Sustainable Transportation Fuel Production

The multicomponent nature of and variability of biomass makes chemical upgrading via a single process stream to a single end use infeasible for most feedstocks. A more promising approach is to identify upgrading strategies (encompassing bioprocessing, catalysis, and separations) which valorize varied biomass fractions to distinct products to which each is best suited. A robust procedure to carry out this goal should incorporate comparison of various upgrading procedures as well as suitability of products to a slate of identified end uses. We applied this strategy to one biomass-derived feedstock, volatile fatty acids (VFAs) derived from wet waste arrested anaerobic digestion, by developing a computer program, VFA Upgrading to Liquid Transportation fUels Refinery Estimation (VULTURE) which evaluates VFA catalytic upgrading to liquid transportation fuels. VULTURE considers multiple separations, catalysis (ketonization, hydrogenation), and fuel application options, generating hundreds of candidate scenarios for a given VFA stream, then selects several promising strategies that optimize bio-content of products with properties best suited for target fuel types. We find that VFAs are upgraded most efficiently when separate light alcohol (C3-6) and heavy hydrocarbon or alcohol (C7-13) fractions are targeted to create gasoline and heavy-duty (diesel or jet) fuels or fuel blends. Surrogate property testing of VULTURE-recommended fuels reveals that most predictive models employed are robust, while rigorous process simulation shows that the simple unit operation assumptions used in VULTURE are largely accurate, especially for heavy-duty fuel synthesis. Techno-economic and life-cycle analyses show that VFA-derived fuels are profitable and have dramatically (=57%) lower carbon intensities than fossil analogs.

BIOMASS FUELS↗

Reversibly soluble bases for lignin oxidative depolymerization

Disclosed herein are lignin valorization strategies that integrate thermochemical pretreatment strategies. Using methods disclosed herein, yields of greater than 40% of usable monomers are obtained from lignin in biomass. The monomers can be assimilated by strains of Pseudomonas putida.

Kruger, Jacob S.↗

Extraction of Value-Added Products from Food Processing Waste Using Dimethyl Ether

Poster for 2024 Intern Poster Session. Food production waste can be valorized to create a circular economy. Traditional extraction methods require pretreatment of the sample through heating or cell disruption, but this contributes to a majority of the process's energy usage for wet biomass. Using dimethyl ether extraction can combine the dewatering and extraction processes into one to skip the pretreatment step while still maintaining similar extraction rates.

09 BIOMASS FUELS↗

Extraction of Value-Added Products From Food Processing Waste Using Liquid Dimethyl Ether

Technical presentation for 2024 Intern Poster Session. Food production waste can be valorized to create a circular economy. Traditional extraction methods require pretreatment of the sample through heating or cell disruption, but this contributes to a majority of the process's energy usage for wet biomass. Using dimethyl ether extraction can combine the dewatering and extraction processes into one to skip the pretreatment step while still maintaining similar extraction rates.

09 BIOMASS FUELS↗

LDRD Macromolcule Radiolysis Poster

Moving toward a circular carbon economy depends on enabling reuse of carbon-based macromolecules and increased recycling of waste products into higher value products. Macromolecules are challenging to valorize into products easily converted into liquid fuel or chemical feedstocks, due to their large and sometimes heterogeneous network of polymeric bonds. The novel aspect of this project is to show a proof of principle that radiolysis of macromolecules using “waste” radiation from energy production in the presence of radical capping donors presents an attractive opportunity to break down complex macromolecules into smaller molecules while controlling re-polymerization. This approach offers a new, cost-efficient way to utilize “waste” radiation and heat byproducts of nuclear energy production to convert a simple mixture of complex molecules into a complex mixture of small molecules, to be utilized as an energy source by the fuel industry, or to create value-added feedstocks for new polymers or commodity chemicals. Ionizing radiation can be harnessed to convert energy to molecules, adding value to low-value macromolecules as they are broken down into smaller, more easily separated feedstocks or fuels to be converted to a value-added product. This project will test 2 hypotheses. Hypothesis 1: Macromolecular materials that comprise biomass and coal or other macromolecules can be infused with radical capping donors (RCDs), and gamma irradiation of the resulting mixtures will produce ensembles of lower-molecular weight chemicals that can be more easily separated. If this expectation is realized, the conversion chemistry can be optimized by adjusting the feedstock composition, irradiation time, and choice of RCD.

02 - PETROLEUM↗

Techno-economic analysis of biomass value-added processing informed by pilot scale de-ashing of paper sludge feedstock

Paper sludge biomass represents an underutilized feedstock rich in pulped and processed cellulose which is currently a waste stream with significant disposal cost to industry for landfilling services. Effective fractionation of the cellulose from paper sludge presents an opportunity to yield cellulose as feedstock for value-added processes. A novel approach to cellulose fractionation is the sidehill screening system, herein studied at the pilot-plant scale. Composition analysis determined ash removal and carbohydrate retention of both sidehill and high-performance benchtop screening systems. Sidehill screening resulted in greater carbohydrates retention relative to benchtop screening (90% vs 66%) and similar ash removal (95% vs 98%). Techno-economic analysis for production of sugar syrup yielded a minimum selling price of $331/metric ton of sugar syrup including disposal savings, significantly less than a commercial sugar syrup without fractionation. Furthermore, sensitivity analysis showed that screening conditions played a significant role in economic feasibility for cellulosic yield and downstream processes.

09 BIOMASS FUELS↗

Eliminating a global regulator of carbon catabolite repression enhances the conversion of aromatic lignin monomers to muconate in Pseudomonas putida KT2440

Carbon catabolite repression refers to the preference of microbes to metabolize certain growth substrates over others in response to a variety of regulatory mechanisms. Such preferences are important for the fitness of organisms in their natural environments, but may hinder their performance as domesticated microbial cell factories. In a Pseudomonas putida KT2440 strain engineered to convert lignin-derived aromatic monomers such as p -coumarate and ferulate to muconate, a precursor to bio-based nylon and other chemicals, metabolic intermediates including 4-hydroxybenzoate and vanillate accumulate and subsequently reduce productivity. We hypothesized that these metabolic bottlenecks may be, at least in part, the effect of carbon catabolite repression caused by glucose or acetate, more preferred substrates that must be provided to the strain for supplementary energy and cell growth. Using mass spectrometry-based proteomics, we have identified the 4-hydroxybenzoate hydroxylase, PobA, and the vanillate demethylase, VanAB, as targets of the Catabolite Repression Control (Crc) protein, a global regulator of carbon catabolite repression. By deleting the gene encoding Crc from this strain, the accumulation of 4-hydroxybenzoate and vanillate are reduced and, as a result, muconate production is enhanced. In cultures grown on glucose, the yield of muconate produced from p-coumarate after 36 h was increased nearly 70% with deletion of the gene encoding Crc (94.6 ± 0.6% vs. 56.0 ± 3.0% (mol/mol)) while the yield from ferulate after 72 h was more than doubled (28.3 ± 3.3% vs. 12.0 ± 2.3% (mol/mol)). The effect of eliminating Crc was similar in cultures grown on acetate, with the yield from p -coumarate just slightly higher in the Crc deletion strain after 24 h (47.7 ± 0.6% vs. 40.7 ± 3.6% (mol/mol)) and the yield from ferulate increased more than 60% after 72 h (16.9 ± 1.4% vs. 10.3 ± 0.1% (mol/mol)). In conclusion, these results are an example of the benefit that reducing carbon catabolite repression can have on conversion of complex feedstocks by microbial cell factories, a concept we posit could be broadly considered as a strategy in metabolic engineering for conversion of renewable feedstocks to value-added chemicals.

09 BIOMASS FUELS↗

Design and Validation of a High-Throughput Reductive Catalytic Fractionation Method

Reductive catalytic fractionation (RCF) is a promising method to extract and depolymerize lignin from biomass, and bench-scale studies have enabled considerable progress in the past decade. RCF experiments are typically conducted in pressurized batch reactors with volumes ranging between 50 and 1000 mL, limiting the throughput of these experiments to one to six reactions per day for an individual researcher. Here, we report a high-throughput RCF (HTP-RCF) method in which batch RCF reactions are conducted in 1 mL wells machined directly into Hastelloy reactor plates. The plate reactors can seal high pressures produced by organic solvents by vertically stacking multiple reactor plates, leading to a compact and modular system capable of performing 240 reactions per experiment. Using this setup, we screened solvent mixtures and catalyst loadings for hydrogen-free RCF using 50 mg poplar and 0.5 mL reaction solvent. The system of 1:1 isopropanol/methanol showed optimal monomer yields and selectivity to 4-propyl substituted monomers, and validation reactions using 75 mL batch reactors produced identical monomer yields. To accommodate the low material loadings, we then developed a workup procedure for parallel filtration, washing, and drying of samples and a 1H nuclear magnetic resonance spectroscopy method to measure the RCF oil yield without performing liquid-liquid extraction. As a demonstration of this experimental pipeline, 50 unique switchgrass samples were screened in RCF reactions in the HTP-RCF system, revealing a wide range of monomer yields (21-36%), S/G ratios (0.41-0.93), and oil yields (40-75%). These results were successfully validated by repeating RCF reactions in 75 mL batch reactors for a subset of samples. We anticipate that this approach can be used to rapidly screen substrates, catalysts, and reaction conditions in high-pressure batch reactions with higher throughput than standard batch reactors.

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

A distinct subpopulation of membrane vesicles in Pseudomonas putida is enriched in enzymes for lignin catabolism

Bacterial membrane vesicles (MVs) mediate diverse microbial processes and are emerging as powerful biomedical tools, but MV population heterogeneity remains an open question. Here, we separate, enumerate, and characterize two MV populations from the soil bacterium Pseudomonas putida during growth with or without lignin-derived carbon, a major carbon source from plant cells in the rhizosphere. Small MVs (MV-S, diameter ~100 nm) were produced from all cultures, whereas large MVs (MV-L, diameter ~300 nm) were observed during the late stationary phase of lignin cultivations. MV-S contained selectively packaged proteins with diverse physiological functions, whereas the MV-L proteome was smaller and largely enriched in outer membrane proteins. Interestingly, enzymes known to mediate the catabolism of lignin-derived aromatic compounds were enriched in MV-S. Overall, this study highlights the need for careful consideration of MV populations in microbial systems.

59 BASIC BIOLOGICAL SCIENCES↗

Increased triacylglycerol production in Rhodococcus opacus by overexpressing transcriptional regulators

Lignocellulosic biomass is currently underutilized, but it offers promise as a resource for the generation of commercial end-products, such as biofuels, detergents, and other oleochemicals. Rhodococcus opacus PD630 is an oleaginous, Gram-positive bacterium with an exceptional ability to utilize recalcitrant aromatic lignin breakdown products to produce lipid molecules such as triacylglycerols (TAGs), which are an important biofuel precursor. Lipid carbon storage molecules accumulate only under growth-limiting low nitrogen conditions, representing a significant challenge toward using bacterial biorefineries for fuel precursor production. In this work, we screened overexpression of 27 native transcriptional regulators for their abilities to improve lipid accumulation under nitrogen-rich conditions, resulting in three strains that accumulate increased lipids, unconstrained by nitrogen availability when grown in phenol or glucose. Transcriptomic analyses revealed that the best strain (#13) enhanced FA production via activation of the β-ketoadipate pathway. Gene deletion experiments confirm that lipid accumulation in nitrogen-replete conditions requires reprogramming of phenylalanine metabolism. By generating mutants decoupling carbon storage from low nitrogen environments, we move closer toward optimizing R. opacus for efficient bioproduction on lignocellulosic biomass.

09 BIOMASS FUELS↗

Lignin Bioproducts to Enable Biofuels

Here we report that today's and tomorrow's biofuels production facilities could benefit tremendously from increasing the value from the large amount of lignin that results from biofuels operations. Certainly, the scientific community, and biofuels industry has begun to recognize the challenges and opportunities associated with lignin.

09 BIOMASS FUELS↗

Effects of Sugars, Furans, and their Derivatives on Hydrodeoxygenation of Biorefinery Lignin-Rich Wastes to Hydrocarbons

Hydrodeoxygenation of biorefinery lignin–rich wastes to jet fuel hydrocarbons offers a significant opportunity for enhancing the overall operational efficiency, carbon conversion efficiency, economic viability, and sustainability of biofuels production. However, these wastes usually mainly contain lignin with sugars, furans, and their derivatives as “impurities”. Although several factors, including reactant structure, solvents, or the decreased ratio of catalyst to reactant, could be responsible for the jet fuel hydrocarbons yield loss, we found evidence that glucose, xylose, and 5–hydroxymethylfurfural dramatically decreased conversion yields. For example, xylose and glucose lowered the final hydrocarbon yield by 78 and 63 %, respectively. The results revealed that these compounds could suppress metal catalysts and inhibit lignin depolymerization and hydrodeoxygenation (HDO) reactions thus decrease yields of jet fuel range hydrocarbons from biomass–derived lignin. As a result, the first–principles calculations and TGA results from spent catalysts validated these findings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Emerging Modification Technologies of Lignin-based Activated Carbon toward Advanced Applications

Lignin-based activated carbon (LAC) is a promising high-quality functional material due to high surface area, abundant porous structure, and various functional groups. Modification is the most important step to functionalize LAC by altering its porous and chemical properties. Here, this Review summarizes the state-of-the-art modification technologies of LAC toward advanced applications. Promising modification approaches are reviewed to display their effects on the preparation of LAC. The multiscale changes in the porosity and the surface chemistry of LAC are fully discussed. Advanced applications are then introduced to show the potential of LAC for supercapacitor electrode, catalyst support, hydrogen storage, and carbon dioxide capture. Finally, the mechanistic structure-function relationships of LAC are elaborated. These results highlight that modification technologies play a special role in altering the properties and defining the functionalities of LAC, which could be a promising porous carbon material toward industrial applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogenolysis of Poly(Ethylene–co–Vinyl Alcohol) and Related Polymer Blends over Ruthenium Heterogeneous Catalysts

The hydrogenolysis of polymers is emerging as a promising approach to deconstruct plastic waste into valuable chemicals. Yet, the complexity of plastic waste, including multilayer packaging, is a significant barrier to handling realistic waste streams. Herein, we reveal fundamental insights into a new chemical route for transforming a previously unaddressed fraction of plastic waste – poly(ethylene–co­­–vinyl alcohol) (EVOH) and related polymer blends – into alkane products. Additionally, we report that Ru/ZrO2 is active for the concurrent hydrogenolysis, hydrogenation, and hydrodeoxygenation of EVOH and its thermal degradation products into alkanes (C1–C35) and water. Detailed reaction data, product analysis, and catalyst characterization reveal that the in–situ thermal degradation of EVOH forms aromatic intermediates that are detrimental to catalytic activity. Increased hydrogen pressure promotes hydrogenation of these aromatics, preventing catalyst deactivation and improving alkane product yields. Calculated apparent rates of C–C scission reveal that the hydrogenolysis of EVOH is slower than low–density polyethylene. We apply these findings to achieve hydrogenolysis of EVOH/polyethylene blends and elucidate the sensitivity of hydrogenolysis catalysts to such blends. Overall, we demonstrate progress towards efficient catalytic processes for the hydroconversion of waste multilayer film plastic packaging into valuable products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗