Dynamics of hydrogen loss and structural changes in pyrolyzing biomass utilizing neutron imaging
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09 BIOMASS FUELS↗
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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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Fast estimation of reaction rates in spherical and non-spherical porous catalysts
Here we present a methodology for modeling multi-step reaction rates in porous catalyst particles for use in CFD-DEM and two fluid models. Single-step effectiveness factors based on a Thiele modulus, while useful, cannot accurately capture the cascading reaction systems common in high temperature vapor-phase chemical reactors like fluidized catalytic cracking units and catalytic biomass fast pyrolysis systems. Instead, multi-step effectiveness vectors derived from steady-state solutions to the governing reaction-diffusion equations are needed. Solutions for various catalyst shapes are presented, including spheres, cylinders, and prisms. Computational challenges inherent in repeated evaluation of reaction rates with diffusion limitations are discussed, and an efficient implementation based on pre-computed lookup tables is proposed and demonstrated on a simulation of a fluidized bed reactor. Open-source code is provided for the compilation of reaction rate tables for use in ODE, DEM, and two-fluid models.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Converting polyisoprene rubbers into bio-jet fuels via a cascade hydropyrolysis and vapor-phase hydrogenation process
Producing alternative drop-in bio-jet fuels from biomass provides a promising approach to achieve carbon neutrality. Here, to upcycle biomass-based polyisoprene rubbers into jet-fuel range C 10 cycloalkane, we proposed a cascade hydropyrolysis and vapor-phase hydrogenation process in a flow-through two-stage pressurized fixed-bed reactor. The hydropyrolysis temperature in the first stage is of vital importance for the formation of primary limonene intermediate in the non-catalytic degradation of polyisoprene rubbers, and a reaction temperature of 460 °C maximized limonene yield to 588.6 mg/g for natural rubber and 546.2 mg/g for Eucommia rubber. Over a Pt/C catalyst loaded in the second stage, the limonene intermediate produced from the first-stage reactor can be completely hydrogenated, giving a 642.7 mg/g yield of jet-fuel range C 10 cycloalkane with 83.6% selectivity. The depolymerization mechanism of polyisoprene rubbers was thoroughly studied, and a competitive reaction between limonene hydrogenation and limonene dehydrogenation was observed. This is the first report on producing C 10 cycloalkane from natural rubbers via a cascade hydropyrolysis and hydrogenation process, providing a promising strategy to upcycle polyisoprene rubbers into bio-jet fuels.
30 DIRECT ENERGY CONVERSION↗
The Kinetic Consequences of Water on Catalytic Methane Pyrolysis
Hydrogen production from biomass and natural gas has emerged as a prominent research area in response to the growing demand for energy from alternative sources that minimize CO 2 emissions. In this study, we investigate the impact of water, which is present in and generated from biomass-derived streams, on carbon nanotube (CNT) growth and hydrogen production during methane decomposition using Ni–Mo/MgO as a catalyst. We reveal here that the role of water on CNT growth is highly complex; its effect depends on the stage of growth at which the water is incorporated. When water is introduced at the beginning of methane decomposition ( t = 0 h), methane conversion rates are negatively impacted. We hypothesize that water inhibits the significant phase changes the Ni–Mo/MgO catalyst undergoes during catalyst carburization. In contrast, the incorporation of a small percentage of water after a stabilization period ( t = 3 h) results in methane conversion rate enhancements that scale with the introduced water partial pressure as water selectively reacts with amorphous carbon deposits that lead to catalyst deactivation, thus prolonging the lifetime of some of the most active sites. Moreover, water incorporation after stabilization significantly reduces the apparent activation energy. Density Functional Theory (DFT) calculations reveal that water preferentially interacts with carbon fragments on the catalyst surface to remove carbon deposits with a barrier lower than that required for methane activation, further supporting its role in cleaning active sites on the catalyst surface. Characterization of the resulting carbon nanotubes reveals the formation of more graphitic materials produced in the presence of water, highlighting the impact of water on nanotube properties. These results provide clarity toward the many ways in which water, or cofeeding of biomass-derived materials, may impact catalytic methane pyrolysis rates.
carbon nanotubes↗
Early-Stage Evaluation of Catalyst Manufacturing Cost and Environmental Impact Using CatCost
The costs and environmental impacts of catalyst manufacture are often neglected during early-stage research because of a lack of accessible, standardized tools to assess them. Here we report the key features of CatCost, a free and public estimation tool for the evaluation of catalyst cost. We demonstrate its functionality with a case study of diverse catalysts (ZSM-5, Pt/TiO2 and Mo2C) for the catalytic fast pyrolysis of biomass. We quantified the economic and environmental improvements made by replacing circulating-bed ZSM-5 with more stable, fixed-bed Pt/TiO2 and Mo2C catalysts, while revealing the effects of synthesis methods and production scale on catalyst costs. The manufacture of ZSM-5 had a large processing cost contribution that was strongly scale dependent, whereas the costs of the other catalysts were dominated by raw materials at all scales. Furthermore, while ZSM-5 costs the least per kilogram, the more stable catalysts cost half as much per gallon of fuel.
BIOMASS FUELS,ENERGY PLANNING, POLICY, AND ECONOMY↗
Corrosion Studies of Pine-Derived Bio-Oil and Heavy Fuel Oil Blends
To reduce the amount of greenhouse gas produced from the combustion of petroleum fuels, renewable liquid fuels are needed. Pyrolysis of biomass provides a means to produce liquid fuels to displace current petroleum products. However, common ferrous alloys are susceptible to high corrosion rates when exposed to bio-oil. This study analyzes the effects of blending bio-oil derived from loblolly pine with heavy fuel oil added to reduce corrosion of common structural alloys. Laboratory corrosion studies of six different blends of bio-oil/heavy fuel oil were performed for 1,000 hours at 50°C. Chemical characterization was also performed to determine the total acid content of each blend. Post-exposure characterizations such as changes in weight, X-ray diffraction, dye penetrant testing, and metallography were performed to provide more insight into the corrosion mechanism of bio-oil/heavy fuel oil blends. We hypothesized that the corrosion rates of ferrous alloys would increase with an increase in bio-oil concentration. The results of these characterization and corrosion studies confirmed this hypothesis and will be reported.
09 BIOMASS FUELS↗
NASA Tech Briefs, May 2003
Topics covered include: Using Diffusion Bonding in Making Piezoelectric Actuators; Wireless Temperature-Monitoring System; Analog Binaural Circuits for Detecting and Locating Leaks; Mirrors Containing Biomimetic Shape-Control Actuators; Surface-Micromachined Planar Arrays of Thermopiles; Cascade Back-Propagation Learning in Neural Networks; Perovskite Superlattices as Tunable Microwave Devices; Rollable Thin-Shell Nanolaminate Mirrors; Flight Tests of a Ministick Controller in an F/A-18 Airplane; Piezoelectrically Actuated Shutter for High Vacuum; Bio-Inspired Engineering of Exploration Systems; Microscope Cells Containing Multiple Micromachined Wells; Electrophoretic Deposition for Fabricating Microbatteries; Integrated Arrays of Ion-Sensitive Electrodes; Model of Fluidized Bed Containing Reacting Solids and Gases; Membrane Mirrors With Bimorph Shape Actuators; Using Fractional Clock-Period Delays in Telemetry Arraying; Developing Generic Software for Spacecraft Avionics; Numerical Study of Pyrolysis of Biomass in Fluidized Beds; and Assessment of Models of Chemically Reacting Granular Flows.
Source record↗
Model of Fluidized Bed Containing Reacting Solids and Gases
A mathematical model has been developed for describing the thermofluid dynamics of a dense, chemically reacting mixture of solid particles and gases. As used here, "dense" signifies having a large volume fraction of particles, as for example in a bubbling fluidized bed. The model is intended especially for application to fluidized beds that contain mixtures of carrier gases, biomass undergoing pyrolysis, and sand. So far, the design of fluidized beds and other gas/solid industrial processing equipment has been based on empirical correlations derived from laboratory- and pilot-scale units. The present mathematical model is a product of continuing efforts to develop a computational capability for optimizing the designs of fluidized beds and related equipment on the basis of first principles. Such a capability could eliminate the need for expensive, time-consuming predesign testing.
Bellan, Josette↗
Detailed modeling of hydrogen release and particle shrinkage during pyrolysis of inhomogeneous wood
Hydrogen release during pyrolysis of woody biomass is studied considering anisotropicity and inhomogeneity of wood structure. A new anisotropic shrinkage model is proposed based on the decomposition of main wood constituents, i.e., cellulose, hemicellulose, and lignin. The new shrinkage model can predict the temporal evolution of the wood structure, and the differences between axial and radial shrinkage during pyrolysis. The model agrees very well with several experimental data from the literature. Based on particle temperature during conversion, the pyrolysis is partitioned into four stages, and the hydrogen release and H 2 formation from each stage are investigated. Stage (IV) of pyrolysis, from 1000 to 1273 K, is found to be efficient for H 2 production owing to the production of considerable mass of H with a minimal amount of tar species. Furthermore, the char quality is found to be different at the end of stages (II), (III), and (IV), where around 67.7, 80.5, and 93.4% wt. of solid residue is made of carbon, respectively. The model is also used to explain how the heating rate affects the temperature distribution inside the particle and how it shifts the peak of hydrogen release. Finally, the pyrolysis of two inhomogeneous wood samples — a beech twig with bark and a beech dowel with growth rings — are investigated. The bark can affect the pyrolysis rate, products, and flow pattern inside the particle. The growth rings do not have a considerable effect on the pyrolysis rate and products, but they have a significant impact on the flow pattern. This has an important implication for char conversion studies where the internal surface area and porosity field distribution have a significant effect on the gasification and oxidation rates.
09 BIOMASS FUELS↗
Opportunity Assessment for Sustainable Aviation Fuel Production from Woody Biomass via Ex Situ Catalytic Fast Pyrolysis and Refinery Hydroprocessing
Biofuels have become a promising solution to reduce emissions in hard-to-electrify transportation sectors, such as aviation. However, several biofuel conversion pathways will likely be needed to scale sustainable aviation fuel (SAF) production to meet lower carbon intensity goals when biomass feedstock availability constraints are considered. This study evaluates the future potential of the catalytic fast pyrolysis (CFP) pathway to contribute to U.S. SAF production goals as outlined in the U.S. Department of Energy’s (DOE) SAF Grand Challenge, understanding that the CFP pathway is still under development toward maturity and scaleup. National forestland resource data from the DOE’s 2023 Billion Ton Study are integrated with recent experimental results demonstrating end-to-end woody biomass conversion to SAF via CFP and hydroprocessing in a novel bioeconomy optimization framework. U.S. refinery hydroprocessing capacity is also considered with repurposing and coprocessing strategies. Results indicate that the CFP process can contribute up to 4.6 billion gallons of SAF annually by 2040, meeting 13% of the 2050 SAF Grand Challenge target while reducing the carbon intensity (CI) of the U.S. jet fuel pool by 16%. The study further explores optimal processing strategies, suggesting that colocating CFP operations with existing petroleum refineries and repurposing some U.S. hydrocracking capacity may offer significant cost advantages and enhance the commercial viability of the CFP pathway. These results underscore the CFP pathway’s potential to support the global aviation industry’s lower carbon intensity objectives while producing other renewable fuels and products.
09 BIOMASS FUELS↗
Predicting the Cetane Number, Yield Sooting Index, Kinematic Viscosity, and Cloud Point for Catalytically Upgraded Pyrolysis Oil Using Artificial Neural Networks
Abstract The conversion of biomass using fast pyrolysis has the potential to be significantly less expensive at scale compared to alternative methods such as fermentation and gasification. Selective upgrading of the products of fast pyrolysis through chemical catalysis produces compounds with lower oxygen content and lower acidity; however, identifying the specific catalytic pathways for producing viable fuels and fuel additives often requires a trial-and-error approach. Specifically, key properties of the compounds must be experimentally tested to evaluate the viability of the resultant compounds. The present work proposes predictive models constructed with artificial neural networks (ANNs) for cetane number (CN), yield sooting index (YSI), kinematic viscosity (KV), and cloud point (CP), with blind test set median absolute errors of 5.14 cetane units, 3.36 yield sooting index units, 0.07 millimeters squared per second, and 4.89 degrees Celsius, respectively. Furthermore, the cetane number, yield sooting index, kinematic viscosity, and cloud point were predicted for over three hundred expected products from the catalytic upgrading of pyrolysis oil. It was discovered that 130 of these compounds have predicted cetane numbers greater than 40, with four of these compounds possessing predicted yield sooting index values significantly less than that of diesel fuel and predicted viscosities and cloud points comparable to that of diesel fuel.
09 BIOMASS FUELS↗
Process Feasibility Analysis of Waste Biomass Valorization to Biochar and Bio-Oil via Slow and Fast Pyrolysis
The United States has abundant biomass and waste feedstock to support the nation's energy addition and affordability targets. Pyrolysis, a thermochemical conversion process, decomposes lignocellulosic feedstocks into liquid, solid, and gaseous fuels that can contribute to the domestic production of biofuels, biopower, and bioproducts. Growing private sector interest in this technology is a key motivation for this comprehensive techno-economic process modeling analysis of a respective biorefinery that includes feedstock preprocessing, slow and fast pyrolysis, and product separation to bio-oil, biochar, and syngas hydrocarbons. Results show that biochar from slow pyrolysis could achieve minimum selling prices (MSPs) of $\$$188-$\$$260/t, competitive with reported market values, while bio-oil from fast pyrolysis is estimated to yield MSPs of $\$$6.49-$\$$9.68/GGE, approximately twice conventional fuel benchmarks. Sensitivity analysis identifies feedstock cost, product yield, and scale as primary cost drivers, while scenarios involving biochar carbon credits and high value applications may substantially improve economics. Overall, these results suggest that continued innovation in feedstock logistics, process integration, and market development will be critical to achieving economically viable and scalable bioproducts.
09 BIOMASS FUELS↗
Feedstock and Catalyst Impact on Bio-Oil Production and FCC Co-Processing to Fuels
NREL’s thermochemical biomass conversion research is focused on ex-situ upgrading of biomass fast-pyrolysis (FP) vapors as an efficient and economical route to completely biogenic pyrolysis-based fuel precursors, potential fuels, and value-added chemicals depending on catalyst choice and process conditions. In this approach, biomass vapors are generated via fast pyrolysis with destabilizing vapor components (char, inorganics, tar aerosols) removed by hot gas filtration to produce conditioned vapors more responsive to catalytic upgrading. A Davison Circulating Riser (DCR), a petroleum industry standard for fluidized catalytic cracking (FCC) catalyst evaluation, was coupled with a custom pyrolyzer system designed to produce consistent composition pyrolysis vapors as feed to the DCR. The coupled system is shown below (Figure 1). Pyrolysis vapors, derived from pure hardwood and softwood, were upgraded using commercially available and laboratory modified zeolite-based catalysts. Upgraded oils were analyzed via 31P and 13C NMR spectroscopy, GCxGC-TOF/MS, carbonyl and ultimate analysis (CHNO), and micro distillation to assess both oil chemistry and distillation behavior as they relate to catalyst and feedstock type for producing fungible hydrocarbon product liquids. Measured process parameters identified from technoeconomic process analysis included achieving oil oxygenate contents of 20% or less, carbon-conversion efficiencies of 30% or more, and catalyst coking rates of 10% or less. A proprietary modified zeolite catalyst from Johnson Matthey produced oils that met these requirements. Using the DCR equipped with a proprietary nozzle system, a second approach focused on reducing the carbon intensity of petroleum-derived hydrocarbon fuels by FCC co-processing these CFP oils with petroleum vacuum gas oil (VGO) to produce biogenic carbon containing fuels. The vapor-phase upgrading results demonstrated for the first time the feasibility of producing refinery-compatible hydrocarbon fuel intermediates entirely from biomass-derived fast-pyrolysis vapors using an industry-accepted DCR system for catalytic upgrading. The co-processing results demonstrated the feasibility of using CFP oils with VGO feeds in FCC refinery operations to produce biogenic carbon containing fuels.
bio-oil↗
Catalytic Fast Pyrolysis with Bio-Oil Recycle to Enhance Yield of Aromatics: Cooperative Research and Development (Final Report)
The objective of this project is to pursue enhanced yields of benzene, toluene, and xylene (BTX) from catalytic fast pyrolysis (CFP) of biomass by recycling a portion of the bio-oil back to the pyrolyzer. Additionally, this work evaluated the impact of CFP process variables on the yields of BTX.
09 BIOMASS FUELS↗
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↗
Feedstock and Catalyst Impact on Bio-Oil Production and FCC Co-Processing to Fuels
NREL's thermochemical biomass conversion research is focused on ex-situ upgrading of biomass fast-pyrolysis (FP) vapors as an efficient route to completely biogenic pyrolysis-based fuel precursors, fuels, and value-added chemicals depending on catalyst and process conditions. A near term pathway being developed uses these liquids for co-processing with petroleum feedstocks to assess biogenic carbon incorporation in hydrocarbon fuel feedstocks for potential refinery use. In this work, the impact of feedstock and catalyst on catalytic fast pyrolysis oil (CFPO) composition was determined with the oils then assessed for biogenic fuel production via FCC (fluidized catalytic cracking) co-processing. Biomass vapors were generated via fast pyrolysis with destabilizing vapor components (char, inorganics, tar aerosols) removed by hot gas filtration to produce clean vapors more responsive to catalytic upgrading. A Davison Circulating Riser (DCR), a petroleum industry standard for fluidized catalytic cracking (FCC) catalyst evaluation, was coupled to a custom pyrolyzer system designed to produce consistent-composition pyrolysis vapors as feed to the DCR. Pyrolysis vapors, derived from pure hardwood and softwood, were upgraded using commercially available modified zeolite-based catalysts to produce CFPOs. These upgraded oils were analyzed via 31P and 13C NMR spectroscopy, GCxGC-TOF/MS, carbonyl and ultimate analysis (CHNO), and simulated distillation (SIMDIS) to assess both oil chemistry and distillation behavior as they relate to catalyst and feedstock type for producing fungible hydrocarbon product liquids. These exploratory vapor-phase-upgrading results demonstrated the feasibility of producing refinery-compatible hydrocarbon fuel intermediates entirely from biomass-derived fast-pyrolysis vapors using an industry-accepted DCR system for catalytic upgrading. The FCC co-processing results demonstrated the feasibility of using CFPOs with VGO feeds in FCC refinery operations to produce biogenic carbon containing fuels.
biogenic carbon↗
Pyrolysis_Molecular_Beam_Mass_Spectra_for_Standard_Biomass_Samples_and_Natural_Variants_of_Switchgrass_Grown_Under_Different_Conditions
This data consists of total ion chromatogram (TIC) normalized Pyrolysis-Molecular Beam Mass Spectrometry (py-MBMS) spectra collected to predict lignin content and lignin monomeric ratios for “Variation in Biomass Yield and Cell Wall Composition in Switchgrass Natural Variants Under Two Nitrogen Regimes” (https://doi.org/10.1007/s12155-025-10838-8).
09 BIOMASS FUELS↗
Biomass Recalcitrance in Willow Under Two Biological Conversion Paradigms: Enzymatic Hydrolysis and Anaerobic Digestion
Biomass recalcitrance, the inherent resistance of plants towards deconstruction, negatively affects the viability of biorefineries. This trait is not only dictated by the properties of the biomass but also by the conversion system used and its interactions with specific features of the biomass. Here, biomass recalcitrance to anaerobic digestion (AD) was assessed using a biomethanation potential (BMP) assay. Plant material (n = 94) was selected from a large population of natural Salix viminalis accessions, previously evaluated for biomass recalcitrance using hydrothermal pretreatment-enzymatic hydrolysis. Correlations between yields from the two biological conversion systems were evaluated, as well as the influence of biomass compositional features, analyzed by pyrolysis-molecular beam mass spectrometry (py-MBMS), and other biomass physical properties on conversion performance. BMP values averaged 198.0 Nml CH 4 /g biomass after 94 days, ranging from 28.6 to 245.9. S lignin and carbohydrate-derived spectral features were positively correlated with performance under both systems, whereas G lignin, p-coumaric acid, and ferulic acid-derived ions were negatively correlated with yields and rates. Most spectral features were more strongly correlated with enzymatic hydrolysis yields compared to methane production. For early-stage methane production and rate, recalcitrance factors were similar compared to enzymatic hydrolysis, with weaker correlations observed at later timepoints. The results suggest that although variation in methane potential was considerably lower than enzymatic hydrolysis yields, a reduced recalcitrance under this system will still be of importance to improve early conversion rates. Spectral features of low methane-producing samples indicate the presence of inhibitory substances, warranting further study.
59 BASIC BIOLOGICAL SCIENCES↗