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At least 19 records
All sourcesNASA NTRSDOE OSTI
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 OSTI2021

Assessing the Role of Interfacial and Metal Sites in Pt/TiO2-Catalyzed Acetic Acid Hydrodeoxygenation

The work summarized in this presentation builds off of these studies, utilizing atomic-scale modeling to discern the role of Pt-metal and Pt-TiO2-interfacial sites in promoting key C-C bond-breaking, C-O bond-breaking, and (de)hydrogenation steps in acetic acid HDO. By considering Pt(111) and Pt-TiO2-interface surface models, adsorption and reaction energetics calculated by density funcational theory provide fundamental insights into the role of both interfacial sites and oxygen vacancies in promoting desired deoxygenation pathways over undesired decarboxylation/decarbonylation pathways.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2022

Assessing the Role of Interfacial and Metal Sites in Pt/TiO2-Catalyzed Acetic Acid Hydrodeoxygenation

Thermochemical conversion of biomass to produce drop-in quality biofuels typically involves hydrodeoxygenation (HDO) steps following catalytic fast pyrolysis (CFP) to remove excess oxygen and create a more stable bio-oil product. HDO involves co-feeding the CFP vapor-phase product and H2 gas over a bi-functional catalyst. Reducible metal oxide-supported noble-metal catalysts (e.g., Pt/TiO2) are promising materials for HDO chemistry, with recent work aiming to elucidate the role of various Pt/TiO2 actives sites (i.e., Pt-metal, TiO2-support, Pt-TiO2-interfacial sites) in the competing desired deoxygenation and undesired decarboxylation/decarbonylation reactions for important classes of CFP vapor model compounds. Carboxylic acids are one important class of bio-derived compounds that has not been studied extensively for HDO on Pt/TiO2, particularly at the atomic level. Past experimental work evaluating Pt/C and Pt/TiO2 catalysts for acetic acid HDO (AA-HDO) demonstrated selectivity toward C-C and C-O bond-dissociation products, respectively. This work utilizes atomic-scale modeling to discern the role of Pt-metal and Pt-TiO2-interfacial sites in promoting key C-C bond-breaking, C-O bond-breaking, and (de)hydrogenation steps in AA-HDO. Using Pt(111) and Pt-TiO2-interface surface models, adsorption and reaction energetics calculated by density functional theory provide fundamental insights into the role of interfacial sites and oxygen vacancies in promoting desired deoxygenation pathways over undesired decarboxylation/decarbonylation pathways.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗
DOE OSTI2024

Biofuel production from palm oil deoxygenation using nickel-molybdenum on zirconia catalyst using glycerol as a hydrogen donor

The growing demand for renewable energy has generated interest in biofuels as alternatives to fossil fuels. Second-generation biofuels, derived from deoxygenating fats and oils, have garnered a higher level of interest from industry and academia due to their potential for direct replacement of diesel and jet fuels. Palm oil, mostly cultivated in Thailand and composed of C16 and C18 fatty acids, is a primary feedstock sought for biofuel production. Palm oil deoxygenation contains several pathways that may or may not require hydrogen gas. This study aimed to produce biofuels in different fuel ranges, such as gasoline, jet fuel, and diesel, through palm oil deoxygenation using glycerol as a hydrogen source. Glycerol, a low-value byproduct, was used as a hydrogen donor, whereas nickel-molybdenum-supported catalysts were chosen for their high efficiency in deoxygenation and cost-effectiveness. The study investigated the impact of reaction time, temperature, and catalyst activation method on palm oil deoxygenation. Catalyst characterization methods, including XRD, SEM, TEM, XPS, FTIR, TGA, and nitrogen-sorption, were employed to understand the role of catalysts’ activity during palm oil upgrading. Findings indicated that alkane hydrocarbons are the major components in liquid products. The presence of excess hydrogen in post reaction gaseous phase proves the hydrogen donation capability of glycerol. Increased reaction time and temperature facilitated the removal of oxygen from palm oil. Nickel-molybdenum on zirconia activated by sulfidation demonstrated higher stability than by reduction activation.

09 BIOMASS FUELS↗
DOE OSTI2019

A comprehensive state-of-technology review for upgrading bio-oil to renewable or blended hydrocarbon fuels

Bioenergy sources are being advanced as a meaningful environmental solution and a substitute for conventional energy sources. Bioenergy from biomass feedstocks currently comprises the largest portion of renewables in the United States. Thus, more effective process-level solutions can result in scaling-up biomass-derived energy production (e.g., biofuels). Pyrolysis, a thermochemical conversion technology, offers a commercially viable pathway to produce bio-oil from a wide range of biomass feedstocks (e.g., algae and terrestrial). Bio-oil requires further upgrading for producing final bio-products (e.g., transportation fuels and biochemicals). This article focuses on upgrading bio-oil to transportation fuels (liquid hydrocarbons), highlights the critical challenges of existing upgrading technologies, and identifies the potential research directions to meet the market needs. A comprehensive overview and classification of bio-oil upgrading pathways and their competencies are presented through both comparative and systematic literature reviews. It is concluded that the biofuel production cost is highly dependent on post-conversion pathways, particularly their hydrogenation and deoxygenation capacity. Thermochemical treatments are effective, but less cost-competitive due to the intensive process requirements (e.g., heat or pressure). Physicochemical treatments are less effective, however, they operate under mild process conditions and could be integrated with other treatments. Biochemical treatments are inadequate as a standalone process for upgrading bio-oil. It is further concluded that the electrochemical approach can be effective due to the retention of hydrogen from bio-oil water content during deoxygenation.

09 BIOMASS FUELS↗
DOE OSTI2022

Swinging Hydrogen Evolution to Nitrate Reduction Activity in Molybdenum Carbide by Ruthenium Doping

A common challenge for electrochemical ammonia synthesis in an aqueous phase is the consumption of Faradaic charge by the competing hydrogen evolution reaction (HER), which reduces the Faradaic efficiency for the desired conversion, i.e., the nitrate reduction reaction (NO 3 RR) to ammonium. This problem is particularly severe when a single-phase catalyst is operated at high current limits, thus a cocatalyst system that works synergistically for hydrogen acquisition and deoxygenation is needed to promote NO 3 RR over HER. For this study, we select a well-known HER catalyst Mo 2 C and investigate how metal doping can switch its kinetics from HER-dominated to NO 3 RR-dominated pathways. At 3.8 wt % Ru doping of Mo 2 C, a 75% single pass conversion of nitrate (0.1 M) to ammonium in a 16 cm 2 flow electrolyzer was achieved, corresponding to an ammonium yield rate of 9.07 mmol h –1 at a full cell voltage of 2 V. As confirmed by DFT calculations and kinetic isotope experiments, ruthenium dopants in the matrix serve as the sink point for adsorbed hydrogen during NO 3 RR to promote the cooperative deoxygenation of *NO 3 and *NO 2 on the Ru–Mo cocatalytic site. Our study suggests that optimizing hydrogen acquisition and deoxygenation reactions in cocatalytic systems is an effective strategy for electrochemical synthesis.

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

DOE Energy Frontier Research Centers Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio)

New capabilities to predict, design and control the chemistries of carbon could answer a global imperative to transition from fossil-based to sustainable transportation fuels. While the use of inexpensive hydrocarbons has been an unparalleled achievement and enabler of economic prosperity for many nations, singular dependence upon crude oil has given rise to systemic vulnerabilities in climate, energy, economic, and national security. Lignocellulosic biomass, a renewable and carbon-neutral resource, has the potential to displace an estimated annual equivalent of three billion barrels of oil in the U.S. alone (National Research Council 2009, U. S. Department of Energy, 2011). However, biomass has only one-third the energy density of crude oil (Agrawal and Singh 2009, Richard 2010) and lacks petroleum’s versatility as a feedstock for fuels and chemicals. These limitations keep biomass conversion below the efficiency level needed for strategic impact while the scientific challenge of routing carbon from one molecular context to another remains unmet. In 2009, the Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio) recognized the potential of chemical catalysis and fast pyrolysis to overcome such limitations by transforming the main components of biomass (cellulose, xylan, and lignin) from grasses and trees directly to liquid hydrocarbons and aromatic co-products. Enabled by the EFRC high-risk, high-reward approach to grand challenge science, C3Bio researchers have been key national players in disrupting the conventional paradigm of the cellulosic biorefinery into a new future of “no carbon left behind”—the full utilization of carbon from plant cell walls in energy-dense fuels (Fig. 1). We identified catalytic and fast-pyrolytic pathways that utilize cellulose, xylan and, most significantly, lignin. We developed catalytic processes that deoxygenate and transform monomers and isolated polymers into useful products and tested their use with intact biomass. We gained control of lignin synthesis within plants and initiated tailoring biomass to its end-use through the tools of plant molecular biology and genetic engineering. C3Bio breakthroughs have increased the energy density of biomass-derived substrates via catalytic and pyrolytic conversions into products such as benzoquinones, furfural and hydroxymethylfurfural, levoglucosan and levulinic acid, methoxypropylphenols and propylbenzene. Such advances in biomass conversion would not have been possible without simultaneous advances in analytical instrumentation and methodologies, and imaging technologies and applications. The legacy science developed by C3Bio enables design and control strategies for achieving a targeted product portfolio of fuel and chemical feedstocks from a diverse range of native and tailored biomass. Our research provides the knowledge base required for a bio-economy with product streams as diverse in functionality as those of the petrochemical industry. Coupling targeted computational modeling with experimentation, we achieved: (1) fundamental understanding of biopolymers and cell wall architecture assembly, (2) discovery of new chemistries that allow the development of highly selective pathways to fuels and desirable chemicals, and (3) an integrated systems-level understanding to control catalytic and pyrolytic pathways.

09 BIOMASS FUELS↗
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 OSTI2025

Cleavage of C-O and C-C Bonds in Lignin-Derived Compounds to Produce Aromatics Using Molybdenum-Containing MFI Zeolites

Lignin, the most abundant source of renewable arenes, is a viable feedstock for the production of aromatic compounds. However, the prevalence of resilient C-C bonded oligomeric fragments in lignin-derived streams can compromise monomer yields during reductive catalytic fractionation (RCF). To address this issue, we developed a bifunctional molybdenum-containing MFI (Mo/H-MFI) zeolite catalyst capable of cleaving both C-O and C-C bonds in lignin-derived molecules to produce aromatic monomers. Using propylguaiacol as a model compound, we demonstrated the importance of proximity between metallic molybdenum carbide sites and the Bronsted acid sites in the zeolite in achieving high carbon yields (~80%) of benzene, toluene, propylbenzene, and phenol while maintaining catalyst stability (>98% stable conversion for 20 h). A reaction network involving both C-O and C-C bond cleavage pathways was proposed based on kinetic studies using key intermediates as feeds. Finally, we successfully depolymerized partially deoxygenated lignin oil obtained from the RCF of poplar using a continuous, two-pass catalytic process. This work highlights the potential of the bifunctional Mo/H-MFI catalyst in upgrading complex lignin feedstocks and provides a methodological approach for converting lignin-derived compounds into platform aromatic chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

110th Anniversary: Microkinetic Modeling of the Vapor Phase Upgrading of Biomass-Derived Oxygenates

Bio-oil produced from fast pyrolysis of biomass is a complex mixture of more than 200 compounds, including oxygenates and acids. As these species are highly undesirable in fuels, catalytic upgrading of biomass pyrolysis product vapors, also known as catalytic fast pyrolysis, is performed to upgrade the vapors to valuable fuels and chemicals. This work presents a detailed microkinetic model, composed of elementary steps, of the catalytic upgrading of acetic acid and acetone, two common oxygenates present in bio-oil. An automated network generator was utilized to construct a reaction network composed of 580 unique species and 2160 unique reactions. The kinetic parameters for each reaction in the network were estimated using transition state theory, the Evans-Polanyi relationship, and thermodynamic data. The resulting mechanistic model is able to describe experimental data presented in the literature for the transformation of acetic acid and acetone on HZSM-5 in a fixed-bed reactor, which is modeled as a plug-flow reactor. Additionally, the model solutions reveal vital information regarding the mechanism by which acetic acid and acetone are upgraded to valuable fuels and chemicals. In the first phase of the mechanism, acetic acid is converted to acetone via acylium ion addition to acetic acid; this is followed by decarboxylation of acetoacetic acid. The second phase is dominated by the self-aldol condensation of acetone, which is shown to occur predominantly through the keto form of acetone rather than the enol form, and subsequent deoxygenation reactions leading to olefins and aromatics. Finally, net rate analysis shows that aromatics are primarily formed via a pathway including aldol condensation of mesityl oxide, whereas olefins are produced from the addition of isobutene and subsequent cracking.

09 BIOMASS FUELS↗
DOE OSTI2020

Role of the metal-support interface in the hydrodeoxygenation reaction of phenol

In this paper, the effect of interfacial sites between Pd particles and Nb 2 O 5 species is investigated by testing a series of Pd-Nb 2 O 5 /SiO 2 catalysts with different niobium loadings for the HDO reaction of phenol in the gas phase. Important differences in the selectivity to deoxygenated product were observed depending on the presence of niobium oxide close to Pd particles, which reveals the key role of the type of active phase in the control of reaction steps. It was found that Pd/SiO 2 catalyst promotes hydrogenation pathways, producing cyclohexanone as the major product. For Pd-Nb 2 O 5 /SiO 2 catalyst containing a Nb/Pd molar ratio of 0.5, a sharp increase in the selectivity to benzene is observed (7.5-fold). Increasing the Nb/Pd molar ratio, the formation of benzene is enhanced. The results showed that the Pd-Nb 2 O 5 interface, composed by an oxophilic oxide in the perimeter of the metal particle, is responsible for the activation of the Csingle bondO bond, promoting the deoxygenation reaction.

09 BIOMASS FUELS↗
DOE OSTI2023

Significance of pH and iron-sulfur chemistry for molybdenum sequestration under sulfidic conditions

Molybdenum (Mo), a redox-sensitive trace metal, plays an important role in recording ancient oxygenation and deoxygenation events as a paleoredox proxy. The mobility and reactivity of Mo in aqueous conditions are closely tied to the chemistry of reduced sulfur and iron species. However, our current knowledge on the formation, structure, stability, and condensation pathways of FeMoS clusters in aqueous settings remains limited, which has driven the current study. In this study, we conducted systematic experiments investigating the interactions between dissolved Mo (initially introduced as molybdate, MoO 4 2– , or tetrathiomolybdate, MoS 4 2– ), ferrous iron (Fe 2+ ), and sulfide (ΣH 2 S aq ) in variously defined abiotic sulfidic systems to determine the external conditions (i.e., pH, and reactant concentrations and ratios) necessary for the formation of solid-phase Fe-Mo sulfides. Solution samples of each system were monitored using ultraviolet-visible spectroscopy (UV–vis) to track the degree of thiolation of dissolved Mo species. Precipitates were analyzed using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) to determine their elemental compositions and valences, and structure (i.e., crystalline or amorphous), respectively. All FeMoS precipitates were amorphous and contained 76–90% Mo(IV) and 10–24% Mo(V) with a trend toward lower Mo(IV):Mo(V) ratios with increasing pH. The degree of Mo thiolation, which was strongly dependent on solution pH and Fe 2+ concentrations, greatly affected the amount of Mo sequestered (i.e., an increased degree of Mo thiolation in solution led to an increased amount of Mo in the final FeMoS precipitate). Furthermore, these findings suggest that changes in pH and Fe 2+ concentrations may be responsible for the sulfide-independent variations in Mo behavior observed in euxinic basins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Surface acetone reactions on ZnxZryOz: A DRIFTS-MS study

We report a systematic DRIFTS-MS study of surface acetone aldolization and self-deoxygenation reactions on ZrO2 and Zn1Zr10Oz, using temperature programmed surface reactions of both acetone reactant and possible intermediate compounds including diacetone alcohol, mesityl oxide, phorone, and isophorone. DRIFTS was used to monitor the evolution of surface species while MS was used to track corresponding gas phase products, in an attempt to identify the distinct reaction pathways observed on the two catalysts as well as the role zinc plays in the corresponding reaction pathways. It is found that aldol condensation (or aldolization) of acetone occurs readily at low temperature (298?K), forming mainly acetone dimers (i.e., diacetone alcohol, DAA/mesityl oxide, MSO) on both ZrO2 and Zn1Zr10Oz with the latter being more active. At elevated temperatures, secondary MSO reactions are diverted, mainly caused by the different Lewis basicity on the two catalysts. Over ZrO2, MSO reacts with activated acetone (acetone enolate) to form a surface 4,4-dimethyl-2,6-heptadione (phorone-C), which is further converted into a stable isophorone intermediate. At temperatures above 473?K, polymerization/oligomerization of isophorone along with basic hydroxyl promoted decomposition reactions occur, leading to the formation of heavier carbonaceous surface species and gas-phase side products (methane and CO2). The addition of zinc balances the surface acid-base properties on ZnxZryOz (i.e., Zn1Zr10Oz) via not only enhancing the surface Lewis basicity but passivating the strong acidity. This balance, especially the enhanced surface Lewis basicity largely promotes the a-H abstraction of MSO to form MSO enolate on the Zn1Zr10Oz, which thus favors the aldolization of MSO enolate and acetone, a reaction tends to form 2,6-dimethyl-2,5-heptadien-4-one (phorone-A). Phorone-A then readily decomposes to produce isobutene as a major product at temperature as low as 373?K. Note that, despite the facile formation of isobutene at low temperatures, a high temperature (673?K) is still necessary to release the strongly adsorbed formate/carbonate/acetate species via CO2 formation.

Li, Houqian↗
DOE OSTI2019

Investigation of solvent effects in the hydrodeoxygenation of levulinic acid to γ-valerolactone over Ru catalysts

Liquid phase, reductive deoxygenation of biomass derived platform chemicals over transition metal surfaces constitutes an efficient scheme for upgrading lignocellulosic biomass. The solvation effects on the reaction kinetics of the hydrodeoxygenation (HDO) of levulinic acid (LA) towards the formation of γ-valerolactone (GVL) over Ru(0001) has been studied in three condensed phase media, i.e., liquid water, methanol, and 1,4-dioxane. Detailed microkinetic models have been developed incorporating various catalytic pathways including formation of 4-hydroxypentanoic acid (HPA) and α-angelicalactone (AGL) to simulate the catalytic activity of Ru(0001) under various reaction conditions of solvent, temperature, and partial pressures. Our microkinetic models suggest that direct catalytic conversion with alkoxy formation is the preferred reaction mechanism in all reaction environments. Here, we find that water facilitates the reaction kinetics significantly and that the solvent effect is strongest at lower temperatures (T<373 K). Here, rate increases due to liquid water solvation effects of 2-4 orders of magnitude are observed. All solvents increase the rate of reaction relative to the gas phase; however, solvation effects decrease with decrease in polarity. 1,4-dioxane increases the rate only minimally due to competitive adsorption of the solvent molecules despite facilitating the partially rate controlling step of the LA hydrogenation to an alkoxy intermediate.

1,4-Dioxane↗
DOE OSTI2022

Assessing the Role of the Support in Acetic Acid Hydrodeoxygenation Selectivity on Pt/TiO2

To produce drop-in quality biofuels following the thermochemical conversion of biomass via catalytic fast pyrolysis (CFP), hydrodeoxygenation (HDO) reactions can be performed to remove excess oxygen and create a more stable bio-oil product. HDO reactions involve co-feeding the CFP vapor-phase product and H2 gas over bi-functional catalysts, such as noble-metal catalysts supported on reducible metal oxides (e.g., Pt/TiO2). Recent model-compound studies, focusing on important classes of species in the CFP vapor mixture, have sought to determine the role of the various Pt/TiO2 actives sites (i.e., Pt-metal, TiO2-support, Pt-TiO2-interfacial sites) in producing the observed desired deoxygenation and undesired decarboxylation/decarbonylation products. One important class of compounds in the CFP vapor-phase product is carboxylic acids (e.g., acetic acid). Prior experimental work on acetic acid HDO (AA-HDO) found that Pt/C and Pt/TiO2 catalysts favored the formation of undesired C-C and desired C-O bond-dissociation products; however, the fundamental surface chemistry driving this shift in selectivity has not been established. This presentation employs atomic-scale modeling to determine, through comparisons of adsorption and reaction energetics, how Pt-metal, Pt-TiO2-interface, and interfacial-vacancy sites catalyze the competing reaction pathways for AA-HDO. Our analysis indicates that hydroxyl vacancies at the Pt-TiO2 interface are critical for lowering barriers for C-O bond-cleavage steps, such that they become favorable/competitive with respect to C-C bond-dissociation steps.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗
DOE OSTI2022

Experimental-based mechanistic study and optimization of hydrothermal liquefaction of anaerobic digestates

Valorization of agricultural and food waste digestates is crucial for sustainable waste management to reduce environmental impacts and improve the economics of commercial farms. Hydrothermal liquefaction (HTL) of anaerobic digestates was evaluated to recover resources by converting them into carbon-dense biocrude oil and a nutrient-rich HTL aqueous phase (HTL-AP) coproduct. The effects of HTL temperature (280–360 °C), reaction time (10–50 min), feedstock pH (2.5–8.5), digestate salt content (1–5 wt%), and digestate cellulose-to-lignin ratio (0.2–1.8) on energy and nutrient recovery were systematically investigated in a set of well-designed experiments following a half-fractional central composite protocol. Response surface analysis combined with HTL product characterization and comparative literature study produced a comprehensive reaction pathway for HTL of anaerobic digestates. Moreover, this analysis revealed the importance of acidic feedstocks (pH 3.00–5.53), high reaction temperatures (337–360 °C), and reaction times <45 or 45–50 min for digestates with Cel/Lig >1 or <1, for maximizing the energy recovered in biocrude (high carbon yield and low heteroatom content) and the amounts of P, NH 3 –N, and Mg distributed in the HTL-AP. Acidic conditions catalyzed biocrude production, inhibited the Maillard reaction (lowering the nitrogen content in biocrude), and partitioned nutrients into the HTL-AP. Higher reaction temperatures coupled with longer reaction times activated hydro-denitrogenation and deoxygenation reactions to improve biocrude quality. Finally, this work provides not only validated methods to achieve targeted resource recovery for specific feedstock compositions using HTL, but also a comprehensive mechanistic understanding of the HTL of biomass waste for controlling target product characteristics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2024

Eddy-Mediated Turbulent Mixing of Oxygen in the Equatorial Pacific

In the tropical Pacific, weak ventilation and intense microbial respiration at depth give rise to a low dissolved oxygen (O 2 ) environment that is thought to be ventilated primarily by the equatorial current system (ECS). The role of mesoscale eddies and vertical mixing as potential pathways of O 2 supply in this region, however, remains poorly known due to sparse observations and coarse model resolution. Using an eddy resolving simulation of ocean circulation and biogeochemistry, we assess the contribution of these processes to the O 2 budget balance and find that vertical mixing of O 2 , which is modulated by the surface wind speed and the vertical shear of the eddying currents, contributes substantially to the replenishment of O 2 in the upper equatorial Pacific thermocline, complementing the advective supply of O 2 by the ECS and meridional circulation at depth. These transport processes vary seasonally in conjunction with the wind: mixing of O 2 into the upper thermocline is strongest during boreal summer and fall when the vertical shear and eddy kinetic energy are intensified. The relationship between eddy activity and the downward mixing of O 2 arises from the modulation of equatorial turbulence by Tropical Instability Waves via their impacts on the vertical shear. This interaction of processes across scales sustains a local pathway of O 2 delivery into the equatorial Pacific interior and highlights the need for adequate observations and models of turbulent mixing and mesoscale processes for understanding and predicting the fate of the tropical Pacific O 2 content in a warmer and more stratified ocean.

Eddy-Mediated↗
DOE OSTI2025

Renewable diesel and bio-aromatics production from waste cooking oil using ethanol as a hydrogen donor in deoxygenation reaction

Biofuels offer a promising solution in the fight against climate change. With a global increase in waste cooking oil, this research investigated the production of bio-hydrogenated diesel (BHD) from waste cooking oil, using ethanol as a hydrogen donor in the deoxygenation process. A hydrolyzed waste cooking oil model compound served as the feedstock, and the deoxygenation was performed at 300–400 °C. The catalysts used in the experiments were 2.6 wt% Ni and 7.8 wt% Mo (2.6Ni-7.8Mo) and 10 wt% Ni and 5 wt% Mo (10Ni-5Mo) on γ-Al 2 O 3 . The results showed that ethanol is an effective hydrogen donor for biofuel production without the need for external hydrogen at an elevated pressure. The increasing temperature enhanced the free fatty acid (FFA) conversion and n-alkane selectivity in the oil product, with the highest FFA conversion and alkane selectivity of 100 % and 46 %, respectively, observed at 400 °C for the sulfided 10Ni-5Mo catalyst. On the other hand, 2.6Ni-7.8Mo offers 100 % FFA conversion with a lower n-alkane selectivity of 35 % at identical temperatures. The total acid number (TAN) of the oil products decreased from 174.03 mg KOH/g of feedstock to 9.43 and 8.67 mg KOH/g with the sulfided 2.6Ni-7.8Mo and 10Ni-5Mo catalysts, respectively. Both the catalysts achieved similar heating values (~43 MJ/kg) at 400 °C. This is a significant improvement to the HHV of the feedstock, which was 36.02 MJ/kg. Additionally, aromatic compounds, mainly BTXE (benzene, toluene, xylene, and ethylbenzene), were also produced. Compared to glycerol as a hydrogen donor, ethanol more effectively increased n-alkane selectivity due to its higher effective hydrogen-to-carbon ratio (H/C eff ). Conversely, glycerol was more advantageous for achieving greater selectivity towards BTXE compounds due to its lower H/C eff , which potentially leads to coke formation. Since aromatic compounds are intermediates in coke production, glycerol provides higher aromatic selectivity than ethanol. Finally, this study presents an alternative pathway for producing diesel fuel from waste cooking oil using ethanol as a hydrogen donor.

36 MATERIALS SCIENCE↗