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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Impact of Tree Age and Anatomical Fraction on Forest Residue Pyrolysis and Hydrotreating

Utilization of cost-advantaged biomass and waste resources to produce clean, domestic biofuels will be a key factor in decarbonizing transportation in the United States. This study investigates how the distribution of anatomical fractions (stem wood, bark, needles, branches) from pine forest residues of different ages impacts pyrolysis and hydrotreating processes, including product composition, carbon efficiency, economics, and overall sustainability. Commercially sourced 13- and 23-year-old loblolly pine residues were chosen to represent available resources; whole tree thinnings, and tops and branches from merchantable timber, respectively. Detailed characterization of the residue samples, product distributions, bio-oil, char, and gas characterization data are presented for 13 experiments, including the individual fractions, blends, and air-classified samples to reduce ash content. Pyrolysis mass balances averaged 97 +/- 3%. As expected, bio-oil yields were lower for the bark, needles, and blends with high proportions of these (53-56% dry basis), and highest for the debarked stem wood (67-71% dry basis). Lower yields were attributed to the high ash content of the needles, but also to the high lignin content in the bark (>50%), which is hypothesized to have led to increased char formation during pyrolysis. Higher-oil yield was generally correlated with total volatiles, hydrogen, oxygen, glucan, and mannan; somewhat correlated with xylan and acetyl content; and negatively correlated with total carbon, fixed carbon, nitrogen, sulfur, and extractives. Air classification of the residues was effective in reducing ash content (1.5% to 0.64%), extractives (~7% to 2%), and sulfur (0.04% to 0.02%), resulting in a small increase in yield, a significant increase in the GC-detectable proportion of oil (27% to 34%) and a net economic benefit. These experimental results were used to conduct technoeconomic and life cycle analyses, which are also summarized here.

biofuels↗
DOE OSTI2020

Environmental and Economic Assessments and Uncertainties of Multiple Lignocellulosic Biomass Utilization for Bioenergy Products: Case Studies

Life-cycle assessment (LCA) and techno-economic analysis (TEA) were applied to assess the economic feasibility and environmental benefits of utilizing multiple biomass feedstocks for bioenergy products under three different technological pathways with consideration of uncertainties. Three cases were studied for the production of pellets, biomass-based electricity, and pyrolysis bio-oil. A Monte Carlo simulation was used to examine the uncertainties of fossil energy consumption, bioenergy conversion efficiency, stochastic production rate, etc. The cradle-to-gate LCA results showed that pellet production had the lowest greenhouse gas (GHG) emissions, water and fossil fuels consumption (8.29 kg CO2 eq (equivalent), 0.46 kg, and 105.42 MJ, respectively). The conversion process presented a greater environmental impact for all three bioenergy products. When producing 46,929 Mg of pellets, 223,380 MWh of electricity, and 78,000 barrels of pyrolysis oil, the net present values (NPV) indicated that only pellet and electricity production were profitable with NPVs of $1.20 million for pellets, and $5.59 million for biopower. Uncertainty analysis indicated that pellet production showed the highest uncertainty in GHG emission, and bio-oil production had the least uncertainty in GHG emission but had risks producing greater-than-normal amounts of GHG. Biopower production had the highest probability to be a profitable investment with 85.23%.

09 BIOMASS FUELS↗
DOE OSTI2022

Sustainable conversion of biomass to rationally designed lithium-ion battery graphite

The carbon net negative conversion of bio-char, the low value byproduct of pyrolysis bio-oil production from biomass, to high value, very high purity, highly crystalline flake graphite agglomerates with rationally designed shape and size tailored for lithium-ion battery energy storage material is reported. The process is highly efficient, 0.41 g/Wh; the energy content of its co-product of the process, bio-oil, exceeds that needed to power the process. It is shown that the shape of the starting material is retained during the transformation, allowing the ultimate morphology of the graphite agglomerates to be engineered from relatively malleable biomass. In contrast to commercial graphite production, the process can be performed at small scale with low equipment costs, enabling individual research laboratories to produce Li-ion grade graphite with customizable shape, size and porosity for Si/graphite composite and other graphite involved anodes. The mechanism of the graphitization of bio-char, a “non-graphitizable” carbon, is explored, suggesting the molten metal catalyst is absorbed into the pore structure, transported through and transforming the largely immobile biochar. Finally, the transformation of biomass to rationally designed graphite morphologies with Li-ion anode performance that closely mimic commercial shaped graphite is demonstrated.

09 BIOMASS FUELS↗
DOE OSTI2022

CFD-DEM Modeling of Autothermal Pyrolysis of Corn Stover with a Coupled Particle- and Reactor-Scale Framework

Autothermal operation of fast pyrolysis is an efficient process-intensification technique wherein exothermic oxidation reactions are used to overcome the heat-transfer bottleneck of conventional pyrolysis. The development of accurate, reliable modeling toolsets is imperative to generating a deeper understanding of biomass autothermal pyrolysis systems to support scale-up and industrial deployment. This modeling effort describes the development of single-particle and reactor models which incorporate detailed reaction schemes and simultaneous exothermic oxidation reactions. The particle-scale model was parameterized for corn stover feedstock with particle morphology, density, ash content, and biopolymer composition, all of which impact the emergent conversion characteristics during pyrolysis. Results were then used to parameterize a reactor-scale autothermal pyrolysis model, which was developed using a coarse-grained computational fluid dynamic-discrete element method. The simulation results compared well with experimental results, with the predicted bio-oil, light gas, and biochar yield within 3.0 wt% of the experimental yields. Further analyses were performed to test the influence of equivalence ratio, biomass injection position, and particle size distribution on autothermal pyrolysis. The analysis of the physio-chemical properties of the fluid and solid phase inside the reactor and at the reactor outlet help reveal important process interactions of autothermal pyrolysis.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗
DOE OSTI2020

Corrosion Susceptibility of Cr–Mo Steels and Ferritic Stainless Steels in Biomass-Derived Pyrolysis Oil Constituents

In this work, to better understand and evaluate the corrosion performance of candidate structural steels and ferritic stainless steels for production, transport, and storage of biomass pyrolysis oils, corrosion studies were conducted in selected organic constituents of bio-oils, including catechol, formic acid, and their mixtures as well as lactobionic acid, using electrochemical impedance spectroscopy. R 2 , the resistance against corrosion reaction, was obtained by fitting measured impedance spectra into an equivalent circuit. The values of R 2 were then used to assess corrosion resistance of the steels in each organic constituent and mixture. Type 410 and 430 stainless steels were resistant to corrosion in all tested organic constituents, while 2.25Cr-1Mo steel was not. 9Cr-1Mo steel was corrosion resistant in catechol but not in the other mixtures that contained organic acids. On the basis of the results of this work, it is suggested that the corrosion resistance against organic acids is attributed to formation of a Cr-rich passive film that requires stainless steels with critical Cr levels in excess of approximately 11 wt %. In catechol-only solution, lower levels of Cr intermediate between that of 2.25Cr-1Mo steel and 9Cr-1Mo steel appeared sufficient.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Developing a High Value Chemical Coproduct: Bio-Base Insecticides from Catalytic Fast Pyrolysis

Coproduction of biochemicals from the thermochemical conversion of biomass is a strategy to reduce biofuel costs and improve bio-oil quality in an integrated biorefinery. (Challenge) Cost effective separations of coproducts from thermochemical conversion streams remains a challenge largely due to the heterogenous nature and stability of thermochemical conversion streams. (Solution) Bio-based insecticides isolated from catalytic fast pyrolysis (CFP) oils are a viable coproduct that can overcome the oil is more stable, they are a high value product, and they can remain a mixture of components. (Approach) This work focuses on the development of a bio-based insecticide coproduct that is distilled from a catalytic fast pyrolysis bio-oil produced using a platinum on titanium dioxide (Pt/TiO2) catalyst to upgrade pyrolysis vapors.

BIOMASS FUELS↗
DOE OSTI2021

Overview and technology opportunities for thermochemically-produced bio-blendstocks

Global demand for transportation fuels is projected to increase 40% by 2040, and biomass-derived fuels (biofuels) play a crucial role in substituting fossil fuels and mitigating greenhouse gas emissions. Currently, biofuels are mainly consumed as blendstocks combined with petroleum-based fuels, and effective conversion technologies can address the quality challenges for offering standalone biofuels. Thermochemical conversion process is one of the most promising pathways among existing technologies for biofuel production. However, the major barriers are unwanted characteristics (e.g., thermal instability) of intermediate products, such as bio-oil, and required upgrading treatments for producing compatible fuels. Here, this study highlights the merits and critical challenges of thermochemical conversion and physicochemical upgrading technologies for bio-blendstock production from lignocellulosic biomass. The novelty of this study lies in potential directions for future research through both critical and systematic literature reviews, and the proposed intensified process for lignocellulosic-based fuel blendstocks production. It is concluded that recovery and fractionation strategies (e.g., quenching and stripping) can maximize process yields and add values in the efficient conversion pathways. Effective quenching can stop secondary free radical reactions and improve liquid yields over gas and solid yields. Stripping process can improve process yield, catalyst lifespan, and thermal stability. It is further concluded that physicochemical treatments are not as effective as thermochemical treatments, but have advantages of mild operating conditions and potential for integrated solutions in conjunction with other treatments.

09 BIOMASS FUELS↗
DOE OSTI2022

Effects of Surface Hydrophobicity on Catalytic Transfer Hydrogenation of Styrene with Formic Acid in a Biphasic Mixture

Transfer hydrogenation (TH) of unsaturated hydrocarbons with formic acid (FA) is an attractive processing pathway for the reduction of lignocellulosic pyrolysis oils. The low solubility of hydrophobic bio-oil species in water and FA in oil necessitates the use of a biphasic system as the reaction environment. Here, we report the effects of Pd/silica catalyst surface wettability on the TH reaction rate. Modification of the surface with short chain (C1–C4) alkyl silanes resulted in an increase in the reaction rate as compared to the unmodified catalyst. In contrast, modification of the surface with sulfonate (hydrophilic) and C18 alkyl silanes (hydrophobic) resulted in a decrease in the reaction rate as compared to the unmodified catalyst. Here, the results are discussed in terms of the catalyst interfacial activity and relative affinity of the reagents to the Pd active sites. An observed change in the apparent reaction order in styrene for a hydrophilic catalyst suggests that changing catalyst surface wettability from hydrophilic to hydrophobic resulted in a switch from a transport-limited to a kinetic-limited reaction regime.

09 BIOMASS FUELS↗
DOE OSTI2024

Engineered $\mathrm{Ru}$ on $\mathrm{HY}$ zeolite catalyst for continuous and selective hydrodeoxygenation of lignin phenolics to cycloalkanes under moderate conditions

Here we report a continuous selective hydrodeoxygenation (HDO) process of guaiacol conversion to cycloalkanes under 180 °C/1 MPa, which results in improved HDO chemistry for lignin-based jet fuel production. The incipient wetness impregnation method was modified to prepare an HY zeolite-supported Ru catalyst with better metal dispersion and acid site uniformity, which overcomes the low conversion and selectivity of previous literature. The modified catalyst (Ru-HY-60-MI) was tested in a continuous fixed bed reactor, resulting in increased HDO conversion of guaiacol to cycloalkanes compared to the unmodified catalyst. Pressure, temperature, and weight hourly space velocity-dependent tests validate guaiacol HDO over Ru-HY-60-MI catalyzed ring hydrogenation of guaiacol to 2-methoxycyclohexanol, acid-catalyzed demethoxylation and dehydration to cyclohexene, and further hydrogenation of cyclohexene to cyclohexane. These experiments enable exploring a continuous HDO process, demonstrate effectiveness for other ß-ß and a-O-4 lignin representatives and real lignin bio-oil, and pave the way towards commercialization of lignin-based jet fuel

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

Oxidation of phenolic compounds during autothermal pyrolysis of lignocellulose

Fast pyrolysis is traditionally defined as the rapid decomposition of organic material in the absence of oxygen to produce primarily a liquid product known as bio-oil. However, the introduction of small amounts of oxygen to the process holds prospects of internally generating the energy needed for pyrolysis. The present study investigates the partial oxidation of lignin-derived compounds during pyrolysis, which generates both carbon oxides and aromatic carbonyl compounds. Analysis of lignin derived phenolic compounds was performed to determine if the composition had changed under oxidative conditions. NMR analyses indicates aromatic carbonyls increased under oxidative conditions, with a corresponding decrease in phenolic hydroxyl groups. Finally, model phenolic compounds were pyrolyzed to help understand the role of partial oxidation during autothermal pyrolysis of lignocellulosic biomass.

09 BIOMASS FUELS↗
DOE OSTI2019

Strategies to Valorize the Hydrothermal Liquefaction-Derived Aqueous Phase into Fuels and Chemicals

Valorization options for the aqueous fraction produced by the hydrothermal liquefaction of terrestrial feedstocks were developed. The processes focused on carboxylic acids, which are abundant in the aqueous fraction. A clean up process for the aqueous phase based on activated carbon absorption followed by liquid-liquid extraction was demonstrated that significantly reduces color bodies and inorganic contaminants while simultaneously concentrating desirable organic constituents. Conversion of the cleaned aqueous phase was then demonstrated for both a ketonization reaction and steam reforming. Condensed phase ketonization over LaxZryOz catalyst was found to exhibit both excellent hydrothermal stability and ketonization activity. Necessity for feedstock cleanup was established and stable condensed phase ketonization operation was demonstrated for ~100 hours with HTL-process derived material. Steam reforming was also demonstrated by employing a dual-bed catalyst configuration whereby carboxylic acids first undergo ketonization over CeO2 in the vapor phase followed by steam reforming of the ketone intermediates over Co/CeO2. The dual-bed approach reduced coke deposition and thus catalyst stability improved. Techno-economic analysis was used to assess economic viability for producing fuel from the bio-oil fraction and either propene (formed via hydrogenation and dehydration of acetone, the primary ketonization product) or hydrogen from the aqueous stream. The ketonization and steam reforming cases were separately modeled and benchmarked to a process utilizing anaerobic digestion. Resulting minimum fuel selling prices of $3.7, $4.2, and $4.3/GGE were obtained for the production of olefins via ketonization, reduction and dehydration; steam reforming; and anaerobic digestion processes, respectively. Both the steam reforming and anaerobic digestion processes benefited by avoiding the need for natural gas by producing the hydrogen on-site required for biocrude hydrotreatment. However, the condensed ketonization process had the lowest minimum fuel selling price because of the co-product olefins generated for sale.

Biomass, hydrothermal liquefaction, techno economi↗
DOE OSTI2024

Pilot-Scale Algal Oil Production

The main objective of the project is complete: development of a preliminary planning and design for a pilot-scale algal oil cultivation and processing facility, FEL-3 design with -5% / +15% cost estimate accuracy, and conversion of the algal oil to biofuel in an off-site existing bio-oil refinery. The design basis includes 10 tons per day of dried algae cultivated with CO 2 supplied by direct air capture, electricity supplied solar power, well water supply, zero liquid discharge, off-site extraction, and off-site conversion of oil to biofuel. The design and permitting package is an important milestone in the path to commercialization of algal biofuels and bioproducts as it provides the preliminary design, permitting path, long-term land lease, planning documents, and team needed for success in future engineering, construction, start-up and operations of a pilot-scale farm at a site in Paso Robles, CA. Outcomes of the business assessment include (i) identification of a product spectrum for economical algal biofuels using co-products with markets that are commensurate with production of 6-7 billion gallons per year of sustainable aviation fuel (SAF), renewable diesel, and renewable gasoline, (ii) a path toward near-term contribution of algae oil to SAF, and (iii) an approach for long-term operation of a pilot-scale farm.

09 BIOMASS FUELS↗
DOE OSTI2025

Introducing bioderived solvents for safer and more sustainable 19 F benchtop NMR analysis of pyrolysis oils

The development of increasingly sustainable analytical chemistry techniques is a growing area of research. Detailed knowledge of bio-oil composition is crucial for the wider use of this alternative, sustainable fuel product, whether by guiding and optimising the pyrolysis processes or for indicating appropriate upgrading methods. The oxygen-containing species in the oil are most important to analyse as they are key to the long-term stability and further processing of the oil. A common analytical method is derivatisation, inserting 19 F nuclei only into specific compounds in the sample, so that a sparser NMR spectrum of a subset of the compounds present can be acquired with even a benchtop NMR spectrometer. However, the derivatisation reactions themselves are not benign, with the most commonly used method relying on DMF throughout. While DMF is highly effective in facilitating the derivatisation reaction, it is not only harmful but increasingly restricted in use. By substituting DMF with ethyl lactate, the reaction is rendered safer and more sustainable. The change in solvent does not affect the NMR results, with estimates of total carbonyl content comparable with those produced by titration. The spectra acquired are detailed enough to also allow the quantification of the different carbonyl functional groups present. By switching to ethyl lactate, it is possible to increase the amount of water in the solvent mixture, further reducing the environmental impact, user risks and cost of the analytical method. By replacing harmful solvents with greener alternatives, benchtop NMR analyses of pyrolysis oils are increasingly safer to run, increasingly cheaper to run, and increasingly more accessible to a wide range of different users.

Tang, Bridget [Aston University, Birmingham (Unite↗
DOE OSTI2022

Co-Hydrotreating of Catalytic Fast Pyrolysis Oils with Straight-Run Diesel

Catalytic Fast Pyrolysis (CFP) of biomass provides an opportunity for producing stabilized bio-oils (CFP oils) that can be further processed into hydrocarbon transportation fuels via hydroprocessing. Standalone hydrotreating of CFP oils has been pursued and has been shown to be able to produce hydrocarbon products with low oxygen contents of <1wt%, but the process is costly due to the high requirements of hydrogen and high capital costs. The costs can be reduced by co-processing in refineries, which takes advantage of the existing refinery infrastructure and the economies of the larger scale of petroleum processing operations. In this contribution, we evaluated co-hydrotreating of CFP oil with straight-run diesel in a laboratory continuous hydrotreating reactor. The CFP oil had been produced over a bi-functional metal-acid catalyst (Pt/TiO2) and contained 17 wt% oxygen on dry basis, and it was fed to the reactor together with straight-run diesel in the proportion of 20 vol%:80 vol%. The co-hydrotreated diesel products had acceptable cetane numbers (>40), and the calculated carbon efficiencies were high (~95%) for the CFP portion of the feed mixtures. Biogenic carbon incorporation in the product was confirmed by C-14 analysis. Sulfided NiMo catalyst gave better performance with respect to the diesel product quality than CoMo did due to the higher hydrogenation activity of NiMo. A comparison of standalone hydrotreating of the CFP oil and the straight-run diesel to co-hydrotreating showed good correspondence. Major challenges and risks associated with co-hydrotreating are discussed in this presentation.

biomass↗
DOE OSTI2024

Cycloalkane-rich sustainable aviation fuel production via hydrotreating lignocellulosic biomass-derived catalytic fast pyrolysis oils

Sustainable aviation fuel (SAF) produced from lignocellulosic biomass is emerging as an ideal alternative to conventional jet fuel for aviation sector decarbonization. Catalytic fast pyrolysis (CFP) can convert lignocellulosic biomass into relatively stable bio-oil that can be selectively transformed to various transportation fuels through hydroprocessing under conditions of different severities. In this contribution, two CFP oils produced from pine-based feedstocks over different types of catalysts (i.e., ZSM-5 and Pt/TiO 2 catalysts) were hydrotreated at 125 bar in a non-isothermal process with a maximum temperature of 385 °C over a sulfided NiMo/Al 2 O 3 catalyst to produce SAF with high cycloalkane concentrations of 89–92 wt%. Cycloalkanes are an important component of jet fuel with advantageous fuel properties, such as high energy density, low sooting, and potential for replacing aromatic hydrocarbons to provide good seal swelling properties. The hydrotreating process successfully converted 91–92% of the biogenic carbon in the CFP oil intermediates to liquid-phase hydrotreated products. Through distillation, 39–40 wt% of the hydrotreated oils were collected in the jet-fuel range as SAF fractions. The rest of the hydrotreated product could be valorized as fuels (e.g., diesel) or chemicals. The SAF fractions with oxygen contents below the detection limit (<0.01 wt%) met ASTM D7566 finished fuel blend and D4054 Tier 1 specifications with respect to density, lower heating value (LHV), volatility, flash point, and freeze point. These results indicate hydrotreating lignocellulosic biomass-derived CFP oil as a promising pathway to produce high-quality SAF rich in cycloalkanes. Continued research is required to increase the SAF yield by process improvements, such as increased CFP oil yields, and an enhanced production of SAF-range molecules via e.g., cracking of high-molecular weight compounds either during CFP or hydrotreating, as well as evaluation of a broader range of jet fuel properties and performance requirements.

09 BIOMASS FUELS↗
DOE OSTI2020

Molecular Weight Distribution Analysis of Pyrolysis Oils by Gel Permeation Chromatography

Comprehensive analysis of the molecular weight distribution of raw and catalytic fast pyrolysis oils derived from biomass remains a key technical hurdle to understanding oil quality as it relates to downstream use and multiple methods may be necessary to accurately represent all components present. Here, we report the molecular weight distribution metrics of fast pyrolysis (FP) and catalytic fast pyrolysis (CFP) oils as determined by gel permeation chromatography (GPC) combined with UV-diode array (UV), differential refractive index (RI), and multi-angle laser light scattering (MALS) detection. The measured molar mass distributions revealed that FP oil consisted of a higher proportion of larger products relative to the low molecular weight products contained in the CFP oil. GPC/RI and UV methods showed FP oil to have higher weight-average molecular weight (Mw) and number-average molecular weight (Mn) than CFP oil based on elution time. However, GPC/MALS, determined the two oils to have similar overall molecular weight distribution metrics (Mw and Mn) and yielded values significantly higher than those determined by RI and UV detectors relative to external standards. Overall, the use of a multiple detection GPC method could enable a more accurate comparison and determination of true molecular weight metrics of bio-oils.

BIOMASS FUELS↗