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Results for “biomass catalysis”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Supercritical Methanol Solvolysis and Catalysis for the Conversion of Delignified Woody Biomass into Light Alcohol Gasoline Bioblendstock

Supercritical methanol (SCM) solvolysis and catalysis has recently emerged as a promising pathway to produce gasoline-range light alcohols from woody biomass through staged depolymerization and hydro-deoxygenation (DHDO). Here, structure-property relationships of Cu"M"AlO x catalysts (M = Mg, Zr, and Ce) are examined for upgrading delignified hybrid poplar via SCM-DHDO. CuCeAlO x displays the highest activity, increasing the C 2 -C 7 alcohol production rate and selectivity by twofold in batch reactions, and >50% in semicontinuous reactions relative to the current state-of-the-art CuMgAlO x . The performance of CuCeAlOx is correlated with its high reducibility and acidity. Cu sintering and biogenic impurity poisoning are identified as possible deactivation mechanisms over 60 h of continuous testing. The gasoline-range SCM-DHDO products are comprised of primarily aliphatic alcohols that result in improved energy density and favorably reduced vapor pressure, relative to ethanol, with the tradeoff of nonsynergistic octane blending with conventional gasoline and lower oxidation stability. Overall, this work highlights the potential to produce suitable light oxygenates by SCM-DHDO processing for gasoline bioblendstock applications.

09 BIOMASS FUELS↗
DOE OSTI2026

Final Report for Electro-oxidative valorization of biomass: design strategies for selective and stable catalysis

This project aimed to develop a fundamental understanding of the factors that dictate activity and selectivity during electrochemical partial oxidation of multi-carbon organic molecules derived from biomass. Value-adding selective conversions of alcohols to aldehydes, and aldehydes to carboxylic acids were considered, with the ultimate goal to establish general principles for controlling selectivity in organic oxidations. Specific aims involved the use of furfural (FF) and 5-hydoxymethyfurfural (HMF) as model systems and seek to develop knowledge for control of mechanisms that permit selective conversions between oxygenate functional groups with prevention or control of C-C cleavage steps. Another major focus of the work was in achieving these transformations in acidic conditions, which contrasts most existing work (done in base), but is crucial toward compatibility with common pretreatments used to generate small molecules from lignocellulose (e.g. acid hydrolysis or pyrolysis). The work involved well-defined catalyst material synthesis, comparative kinetics, and operando spectroscopies (PI Holewinski), supported by quantum chemical simulations (PI Janik), enabling progress toward efficient, acid-stable oxidation catalysis for biomass upgrading.

Holewinski, Adam [University of Colorado Boulder] ↗
DOE OSTI2025

Microwave-Assisted Catalytic Gasification of Various Biomass with Mixed Plastic Wastes for H2-Rich Syngas Production

Co-gasification of plastics mixture with biomass has shown synergistic effects in Microwave (MW) reactor resulting in higher H2-rich syngas yield and reduced char/tar. This study investigates a microwave-assisted catalytic gasification of variable feedstock such as various biomass blended with mixed plastics waste using Fe-based catalyst to produce H2 rich syngas as a primary product.

catalysis, biomass gasification↗
DOE OSTI2020

Steam-Induced Coarsening of Single-Unit-Cell MFI Zeolite Nanosheets and Its Effect on External Surface Brønsted Acid Catalysis

Commonly used methods to assess crystallinity, micro-/mesoporosity, Brønsted acid site density and distribution (in micro- vs. mesopores), and catalytic activity suggest nearly invariant structure and function for aluminosilicate zeolite MFI two-dimensional nanosheets before and after superheated steam treatment. Yet, pronounced reaction rate decrease for benzyl alcohol alkylation with mesitylene, a reaction that cannot take place in the zeolite micropores, is observed. Transmission electron microscopy images reveal pronounced changes in nanosheet thickness, aspect ratio and roughness indicating that nanosheet coarsening and the associated changes in the external (mesoporous) surface structure are responsible for the changes in the external surface catalytic activity. Finally, superheated steam treatment of hierarchical zeolites can be used to alter nanosheet morphology and regulate external surface catalytic activity while preserving micro- and mesoporosity, and micropore reaction rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Catalytic Graphitization of Biocarbon for Lithium‐Ion Anodes: A Minireview

Abstract The demand for electrochemical energy storage is increasing rapidly due to a combination of decreasing costs in renewable electricity, governmental policies promoting electrification, and a desire by the public to decrease CO 2 emissions. Lithium‐ion batteries are the leading form of electrochemical energy storage for electric vehicles and the electrical grid. Lithium‐ion cell anodes are mostly made of graphite, which is derived from geographically constrained, non‐renewable resources using energy‐intensive and highly polluting processes. Thus, there is a desire to innovate technologies that utilize abundant, affordable, and renewable carbonaceous materials for the sustainable production of graphite anodes under relatively mild process conditions. This review highlights novel attempts to realize the aforementioned benefits through innovative technologies that convert biocarbon resources, including lignocellulose, into high quality graphite for use in lithium‐ion anodes.

25 ENERGY STORAGE↗
DOE OSTI2023

Insights into Acetic Acid Binding and Ketene Formation on Anatase TiO 2 (101)

Understanding the adsorption and reactivity of carboxylic acids on oxide surfaces is of great interest in catalysis for biomass upgrading via ketonization, a carbon–carbon coupling reaction. Herein, we investigate the adsorption and reaction of acetic acid on anatase TiO 2 (101) using scanning tunneling microscopy, infrared spectroscopy, temperature programmed reaction, and density functional theory calculations. We demonstrate the adsorption of acetic acid can form two intermediates: (1) dissociated, bidentate acetate with an associated bridging hydroxyl, and (2) molecular, monodentate acetic acid. The coexistence of ordered phases with increasing monolayer (ML) saturation coverages consisting of (1) pure acetate (0.5 ML), (2) mixed acetate/acetic acid (0.67 ML), (3) mixed acetate/acetic acid (1.0 ML) and (4) pure acetic acid demonstrates similar energetics for both acetate and acetic acid species. Under ultra-high vacuum conditions, the presence of both monodentate acetic acid and bidentate acetate was observed below room temperature, while solely bidentate acetate was observed up to 575 K. The deprotonation of acetic acid produces water at 280 K, while the thermal decomposition of bidentate acetate produces ketene and acetic acid at 645 K. In conclusion, this model study provides detailed insight into the stability and reactivity of carboxylic acid surface-bound intermediates, which could participate during ketonization reactions for biomass upgrading.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Sustainable Li-ion anode material from Fe-catalyzed graphitization of paper waste

We report a novel method for the conversion of paper towel waste to biographite anode material is developed and optimized for use in Li-ion batteries. The surge in demand for Li-ion battery anode materials coupled with the unsustainable and inefficient methods of producing battery-grade graphite necessitate alternative carbon feedstocks and graphitization technologies. Paper waste (PW) is identified as a suitable carbon feedstock for iron-catalyzed graphitization due to its sustainability, low cost, low ash content, and ample supply for the intended end use. A Box Behnken experimental design for statistical optimization is pursued for untreated and pre-carbonized PW with factors of temperature (1100-1300 °C), hold time (1-5 h), and iron catalyst loading (0.5-1.5x fixed carbon content) with biographite crystal size as the primary response variable. Temperature and iron catalyst loading are found to be significant factors, whereas hold time is found to be insignificant. Reversible capacities of the biographite anodes are found to be 340-355 mAh g-1 with 99% capacity retention over 100 cycles, indicating good electrochemical performance relative to commercial graphite anodes. The initial Coulombic efficiency of untreated and pre-carbonized biographites, however, are 77% and 75%, respectively, suggesting parasitic reactions including electrolyte decomposition.

25 ENERGY STORAGE↗
DOE OSTI2022

Screening and evaluation of biomass upgrading strategies for sustainable transportation fuel production with biomass-derived volatile fatty acids

Biomass conversion to fuels and chemicals is crucial to decarbonization, but choosing an advantageous upgrading pathway out of many options is challenging. Rigorously evaluating all candidate pathways (process simulation, product property testing) requires a prohibitive amount of research effort; even simple upgrading schemes have hundreds of possible permutations. We present a method enabling high-throughput screening by approximating upgrading unit operations and drop-in compatibility of products (e.g., fuel properties) and apply it to volatile fatty acid (VFA) conversion to liquid transportation fuels via a MATLAB script, VFA Upgrading to Liquid Transportation fUels Refinery Estimation (VULTURE). VULTURE selects upgrading configurations that maximize fuel blend bio-derived content. We validate VULTURE's approximations through surrogate fuel property testing and process simulation. Techno-economic and life cycle analyses suggest that VFA upgrading processes down-selected by VULTURE are profitable and have low carbon intensities, demonstrating the potential for the strategy to accelerate process development timelines at decreased costs.

09 BIOMASS FUELS↗
DOE OSTI2019

Effect of Mixed-Solvent Environments on the Selectivity of Acid-Catalyzed Dehydration Reactions

The composition of the liquid phase can alter the rates of individual reaction steps and thus alter the selectivity of acid-catalyzed reactions, but these solvent effects are difficult to anticipate for design purposes. Herein, we report the kinetics and selectivity of Brønsted acid-catalyzed 1,2-propanediol dehydration in pure water and in aqueous mixtures of the polar aprotic cosolvents γ-valerolactone, 1,4-dioxane, tetrahydrofuran, N-methyl-2-pyrrolidone, tetramethylene sulfoxide, and dimethyl sulfoxide at 433 K. We find that the major product of 1,2-propanediol dehydration is propanal in most mixed-solvent environments with selectivities between 1 and 68 mol %. In contrast, 1,2-propanediol dehydration in aqueous mixtures of dimethyl sulfoxide affords acetone as the major product with up to 48% selectivity with minimal propanal formation. We use classical molecular dynamics simulations to probe these solvent effects by computing the difference between the solvation free energies of 1,2-propanediol and propanal in aqueous mixtures of polar aprotic cosolvents and in pure water. We find that the difference in the solvation free energies is correlated with the rates of propanal formation in all mixed-solvent environments, indicating that the solvent-mediated stabilization of the product state relative to the reactant state translates to increased selectivity toward the same product. Similar agreement between simulated solvation free energies and experimental reaction rates/selectivities is established for the acid-catalyzed dehydration of cis- and trans-1,2-cyclohexanediol and 1,3-cyclohexanediol. Finally, analysis of the solvation environment around 1,2-propanediol shows that dimethyl sulfoxide uniquely competes against water to solvate reactive hydroxyl groups, which causes a change in reaction mechanism in this solvent system that leads to the formation of acetone rather than propanal. Here, these results represent a step toward the computationally efficient screening of solvent systems for acid-catalyzed, liquid-phase processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Co(salen)-Catalyzed Oxidation of Lignin Models to Form Benzoquinones and Benzaldehydes: A Computational and Experimental Study

Lignin is a highly abundant polyphenolic polymer that imparts mechanical strength to plant biomass. Transition-metal complexes can catalyze lignin oxidation to produce value-added products, but low catalytic efficiency has hampered their use in industry. Identifying the chemical and structural factors that govern catalytic activity is a prerequisite to rational design of catalysts with improved activity. In this study, we combine computational and experimental approaches to investigate the mechanism of Co(salen)-catalyzed oxidation of the monomeric lignin models syringyl (S), vanillyl (G), and 4-hydroxybenzyl alcohol (H) to produce benzoquinone and benzaldehyde products. Experimentally, S oxidation to form dimethoxybenzoquinone proceeded efficiently with a Co(salen) catalyst coordinated by a pyridine ligand, but G and H did not undergo oxidation. Density functional theory calculations reveal that catalyst regeneration is energetically unfavorable in the presence of H, which prevents oxidation. In contrast, S readily facilitates catalyst regeneration. Formation of methoxybenzoquinone from G was achieved experimentally by adding bulky, noncoordinating bases. These findings provide a fundamental baseline for enhancing the activity of Co-Schiff base catalysts toward lignin-like molecules by adding sterically hindered nitrogenous bases or potentially by including a cocatalyst that promotes catalyst regeneration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Chemical and Biological Catalysis for Plastics Recycling and Upcycling

Plastics pollution is causing an environmental crisis, prompting the development of new approaches for recycling, and upcycling. Here, we review challenges and opportunities in chemical and biological catalysis for plastics deconstruction, recycling, and upcycling. We stress the need for rigorous characterization and use of widely available substrates, such that catalyst performance can be compared across studies. Where appropriate, we draw parallels between catalysis on biomass and plastics, as both substrates are low-value, solid, recalcitrant polymers. Innovations in catalyst design and reaction engineering are needed to overcome kinetic and thermodynamic limitations of plastics deconstruction. Either chemical and biological catalysts will need to act interfacially, where catalysts function at a solid surface, or polymers will need to be solubilized or processed to smaller intermediates to facilitate improved catalyst–substrate interaction. Overall, developing catalyst-driven technologies for plastics deconstruction and upcycling is critical to incentivize improved plastics reclamation and reduce the severe global burden of plastic waste.

28 EE - Advanced Manufacturing Office (EE-5A)↗
DOE OSTI2021

Synthesis of (hemi)cellulosic lubricant base oils via catalytic coupling and deoxygenation pathways

The past decade has witnessed a significant growth in bioproduct development due to the strong interest in creating a more diverse energy supply, environmental sustainability, and a carbon neutral bioeconomy. The initial biorefinery strategy, which focused mainly on the production of low carbon number drop-in bioproducts, has recently shifted its focus on the production of high carbon number and high performance bioproducts with unique properties and value propositions. One such product is lubricant base oil (LBO), which represents over $150 billion global lubricant market and is used for various industrial, automotive, marine, metal-working, consumer, and specialized applications. The application landscape of lubricants has changed significantly over the past decade because of environmental regulations and the growing demand for sustainable lubricants to mitigate regulatory challenges and improve carbon footprint. Currently, only 3% LBOs are produced from bio-based triglycerides/fatty acids. Because of low oxidation stability and high hydrolytic susceptibility, these bio-based LBOs have limited applications. Thus, research and development and commercialization efforts for (hemi)cellulosic LBOs to meet the market demand have received momentum over the past few years. This review describes strategies to produce (hemi)cellulosic LBOs via carbon–carbon coupling and hydrodeoxygenation chemistries. We emphasize the coupling strategies to create LBOs with a branched architecture to surrogate petroleum-based poly-α-olefins. Here, a structure–property relationship for tuning the key specifications of LBOs as a function of molecular architecture is illustrated. Mechanistic understanding and molecular interactions of multi-furan substrates with the active sites of complex multifunctional catalysts are described. Furthermore, techno-economic and life-cycle analysis is summarized along with standing challenges and future opportunities.

09 BIOMASS FUELS↗
DOE OSTI2024

The Catabolism of Lignin-Derived p-Methoxylated Aromatic Compounds by Rhodococcus jostii RHA1

Emergent strategies to valorize lignin, an abundant but underutilized aromatic biopolymer, include tandem processes that integrate chemical depolymerization and biological catalysis. To date, aromatic monomers from C-O bond cleavage of lignin have been converted to bioproducts, but the presence of recalcitrant C-C bonds in lignin limits the product yield. A promising chemocatalytic strategy that overcomes this limitation involves phenol methyl protection and autoxidation. Incorporating this into a tandem process requires microbial cell factories able to transform the p-methoxylated products in the resulting methylated lignin stream. In this study, we assessed the ability of Rhodococcus jostii RHA1 to catabolize the major aromatic products in a methylated lignin stream and elucidated the pathways responsible for this catabolism. RHA1 grew on a methylated pine lignin stream, catabolizing the major aromatic monomers: p-methoxybenzoate (p-MBA), veratrate, and veratraldehyde. Bioinformatic analyses suggested that a cytochrome P450, PbdA, and its cognate reductase, PbdB, are involved in p-MBA catabolism. Gene deletion studies established that both pbdA and pbdB are essential for growth on p-MBA and several derivatives. Furthermore, a deletion mutant of a candidate p-hydroxybenzoate (p-HBA) hydroxylase, ..delta..pobA, did not grow on p-HBA. Veratraldehyde and veratrate catabolism required both vanillin dehydrogenase (Vdh) and vanillate O-demethylase (VanAB), revealing previously unknown roles of these enzymes. Finally, a ..delta..pcaL strain grew on neither p-MBA nor veratrate, indicating they are catabolized through the ..beta..-ketoadipate pathway. This study expands our understanding of the bacterial catabolism of aromatic compounds and facilitates the development of biocatalysts for lignin valorization.

aromatic biopolymers↗
DOE OSTI2021

The Development of Catalysts for Upgrading of Pyrolysis Vapor for Refinery Feedstocks and Intermediates: Cooperative Research and Development, CRADA Number CRD-12-00497 (Final Report)

Fast pyrolysis of biomass with vapor phase upgrading (VPU) can produce refinery feedstocks or intermediates that can meet the Department of Energy’s goal of cost-competitive hydrocarbon fuels by 2017. A key technical barrier for this technology is the lack of selective, cost effective catalysts that can produce high yields of fuel-appropriate hydrocarbons from the pyrolysis vapors. In overcoming this barrier, it will be important to engage leading catalyst development companies to devote their resources and expertise to the development of these materials. Thus, we propose a Cooperative Research and Development Agreement (CRADA) between the National Renewable Energy Laboratory (NREL), a world leader in biomass pyrolysis research and Johnson Matthey (JM), a world leader in the production of advanced catalyst materials to develop and test novel catalysts for efficient VPU. Through its Intercat Inc. subsidiary in Savannah, Ga., Johnson Matthey is internationally recognized as a leader in zeolite-based vapor phase upgrading in refinery duties and an emerging developer of biomass conversion technologies. The research and development efforts described in the proposed work will build upon existing collaborations between NREL and JM and play to the strengths of both institutions. NREL will analyze the composition of pyrolysis vapors as an input to catalyst design, screen and test catalysts, characterize the resulting oil and conduct techno-economic analysis. Catalyst samples will be produced and funded by JM. JM will design and synthesize catalysts, characterize fresh and used catalysts and develop catalyst supports needed to achieve commercially meaningful lifetimes. The project will span catalyst development and testing from the fundamental stage using quantum mechanical modeling and chemical reaction analysis to catalyst screening to integrated pilot studies.

09 BIOMASS FUELS↗