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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Performance of Structural Alloys in Bio-oil Production, Upgrading, and Storage Systems

Selection of corrosion-resistant, cost-effective structural materials for the process and containment vessels required for the production, upgrading, and storage of biomass-derived oils has been the subject of study in our laboratory for many years. The wide variety of biomass resources and the many liquefaction techniques and processing conditions result in products with a broad range of properties and compositions. Here, this paper will address the materials issues in three distinct areas. In production, materials are exposed to temperatures that range from 350 to 550 °C depending upon the process. Generally, austenitic stainless steels have performed reasonably well, although thicker oxide scales and intergranular attack have sometimes been observed. For storage and transport of the bio-oil products, temperatures experienced by the containment materials are not expected to exceed 50 °C. Our studies have shown that most raw bio-oils contain significant concentrations of organic acids, and low-molecular-weight organic acids were quite corrosive to carbon and low alloy steels. For some applications, subsequent processing is required, which includes hydrotreating or co-processing with a petroleum-derived liquid. These processes utilize a catalyst that requires periodic retreatment with a sulfidizing gas, and the exposure to this gas at elevated temperatures can cause appreciable corrosion to the more common austenitic stainless steels. The materials considered most cost-effective and sufficiently corrosion-resistant for each of these environments were identified.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Nonthermal hydrogen plasma-enabled ambient, fast lignin hydrogenolysis to valuable chemicals and bio-oils

The reduction of fossil fuel resources and the ongoing surge in global energy demand have captured the interest of researchers worldwide, prompting a focus on developing renewable energy sources. For this reason, biomass conversion has emerged as a crucial pathway for renewable fuel production. Lignin, constituting 10–35% of woody biomass, represents a significant and largely untapped sustainable feedstock. Despite the potential of lignin, a substantial portion of this lignocellulosic residue remains unused, with approximately 60% considered waste. This study addresses the challenge of underutilized lignin by introducing an innovative approach to its hydrogenolysis. Despite their potential, existing hydrogenolysis methods face obstacles such as complexity, high cost, and the need for high temperatures or pressures. Herein we report a noncatalytic nonthermal hydrogen plasma method for lignin hydrogenolysis, conducted under ambient temperature and pressure conditions. Our method proves to be highly effective in breaking lignin bonds, achieving complete conversion, and generating valuable gaseous and bio-oil products including methane and aromatic dimers and monomers obtained from guaiacyl and syringyl units within the lignin structure. Our results showed an increase in gaseous products, especially methane, and aromatic monomer yields, as well as a reduction in total bio-oil and biochar yields and lignin functional groups by increasing reaction time, input power, and H2 partial pressure. This research confirms the considerable promise of utilizing noncatalytic nonthermal hydrogen plasma-assisted hydrogenolysis as an effective technique for producing gaseous and liquid fuels from lignin.

Pishva, Parsa↗
DOE OSTI2021

Process for selectively recovering a phenolic compound from feedstock comprising bio-crude and/or bio-oil

A process for selectively recovering a phenolic compound from feedstock comprising bio-crude and/or bio-oil is described. The recovery efficiency of the selected phenolic compound is greater than 70 wt % and the purity of the recovered selected phenolic compound is higher than 80 wt %. The process comprises distilling the feedstock to isolate the selected phenolic compound in a first distillate fraction comprising the selected phenolic compound, concentrating the selected phenolic compound from the first distillate fraction in a concentrated mixture, and purifying the concentrated mixture to recover the selected phenolic compound.

Mante, Ofei D.↗
DOE OSTI2022

Determination of Phenolic Groups in Bio-Oils Using Revised Folin-Ciocalteu Methods: Single Cuvette and Plate Reader. Laboratory Analytical Procedure (LAP), Issue Date: May 12, 2022

Phenol components are ubiquitous in wood-derived bio-oils and biocrudes. Their reaction with other functional groups (e.g., aldehydes) may contribute to the formation of carbonaceous species and the expected thermal instability of pyrolysis oils. During hydrotreating, phenols can be recalcitrant species, requiring higher reaction temperatures than other oxygen-containing functional groups. Phenols are also present in upgraded products and have been shown to lead to catalyst deactivation during hydrotreating. They also are the first oxygenated functional group to re-appear in the upgraded product, signaling catalyst deactivation. This procedure covers the determination of phenolic compounds in fast pyrolysis oils. This Laboratory Analytical Procedure (LAP) includes two methods, the first allowing for shorter analysis time at increased reaction temperature, while the second employs a longer analysis time but at room temperature. Additionally, the use of both a single cuvette and of a plate reader are also presented.

09 BIOMASS FUELS↗
DOE OSTI2024

Co-Processing Fast Pyrolysis Bio-Oils and Hydrothermal Liquefaction Biocrudes in Fluid Catalytic Cracking and Hydroprocessing in Refineries

Co-processing of biogenic feedstocks within the existing petroleum infrastructure represents an opportunity to incorporate large volumes of bio-carbon into transportation fuels. However, upgrading intermediate liquids from biomass and waste to final products efficiently and economically, while minimizing impacts to existing refinery infrastructure, remains a notable barrier to commercialization. The co-processing project, Bio-oil Co-processing with Refinery Streams, aimed to generate foundational knowledge for processing renewable intermediates in petroleum refineries and offer co-processing strategies, as well as develop new methods for biogenic carbon tracking and measurement.

bio-oil↗
DOE OSTI2022

Valorization of bio-oils

Methods are disclosed to make coke, graphite, graphene and other materials from biomass derived bio-oil.

Baldwin, Robert Milton↗
DOE OSTI2023

Design and Operation of a Multi-Bed Catalytic Micro-Reactor for the Study of Co-Processing of Bio-Oils with VGO

An industry wide shift from fossil-based fuel to renewable fuel sources including biomass, municipal waste, and plastics will require new process monitoring methods to minimize transitional risks including off specification product formation and catalyst deactivation. This project aims to provide a machine learning based process monitoring tool composed of online, slipstream mass spectra for use in biomass refineries and co-processing in existing refineries allowing operators to monitor product qualities and adjust process conditions accordingly. In order to maximize the robustness of the tool, large volumes of data must be collected to fine tune model parameters which consists of both micro and pilot scale mass spectral data. Micro-scale data is collected with a multi-tube micro-reactor housing up to six catalysts in horizontal beds, coupled with a molecular beam mass spectrometer. A pyrolizer equipped with an auto-sampler streamlines the micro-scale data collection process. This type of pyrolizer/micro-reactor configuration does not exist on the market, and therefore had to be created for the purposes of this project. The design and commissioning of this reactor will be presented in detail. This reactor set-up is highly flexible and increases throughput of analysis. For catalyst testing, each bed can be individually selected simply by turning valves. For catalyst reduction and regeneration, simultaneous flow through all six beds is used. The reproducibility of the system was first assessed with whole biomass pyrolysis along with pyrolysis of calibration standards. Initial work on this system evaluated two FCC catalysts, equilibrium catalyst (E-cat), and a proprietary catalyst from Johnson Matthey specifically design for co-processing of bio-oil with vacuum gas oil (VGO). This work used model compounds and VGO which illuminated differences in products produced by the catalysts.

biomass↗
DOE OSTI2023

Bio-Oil Co-Processing with Refinery Streams

The project seeks to accelerate the adoption of co-processing biomass-derived feedstocks with petroleum streams in operating petroleum refineries to produce biogenic-carbon-containing fuels.

bio-crude↗
DOE OSTI2021

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↗
DOE OSTI2020

Accelerated Aging of Fast Pyrolysis Bio-Oils

Carbonyl content is a better metric for tracking aging than viscosity. Existing aging test (24 hours @ 80 °C) is too severe, and correlates to more room temperature aging than would realistically occur. New aging test proposed: 2 hours @ 80 °C correlates to 1-3 months of room temperature storage. Aging is slowed in cold storage, but still occurs.

aging↗
DOE OSTI2020

Performance of Base and Noble Metals for Electrocatalytic Hydrogenation of Bio-Oil-Derived Oxygenated Compounds

Electrocatalytic hydrogenation is a particularly attractive approach for converting the most unstable compounds in biogenic feedstocks at ambient conditions without external hydrogen. Here, we synthesized a variety of carbon-supported transition metal catalysts and characterized their activity for the electrocatalytic hydrogenation of a series of model compounds and pyrolysis oil. Carbonyl compounds, especially aromatic aldehydes, such as furfural and benzaldehyde, are particularly inclined to hydrogenation driven by an applied current. This was verified with pure solutions of the model compounds and with pyrolysis oil, where we achieved stable and steady continuous operation on Pd. By choosing the optimal catalyst composition, the conversion of benzaldehyde shifted from alcohol production (e.g., on Pd and Cu) to dimerization (e.g., on Co, Ni, and Zn). Pd and Cu were shown to offer the best compromise between reaction rates and efficiency although, in general, base metals offer similar conversions but better efficiencies that noble metals. Thus, the present work offers foundational results and guidelines for choosing the optimal metal catalyst and the applied potential for processing organic feedstocks as a function of its composition.

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

Improved Hydrogen Utilization and Carbon Recovery for Higher Efficiency Thermochemical Bio-oil Pathways

The goal of this project was to develop a novel integrated direct biomass liquefaction process with improved hydrogen utilization and better carbon efficiency compared to other thermochemical conversion technologies for advanced biofuels production. Reactive catalytic fast pyrolysis, or RCFP, combines a robust hydrodeoxygenation catalyst for in situ pyrolysis in an excess of hydrogen at atmospheric (low) pressure. RCFP was developed to leverage advantages from catalytic fast pyrolysis (process simplicity and improved bio-crude quality) and biomass hydropyrolysis (enhanced hydrodeoxygenation) to produce a thermally-stable, low oxygen containing bio-crude intermediate that can be upgraded in a single conventional hydroprocessing step to produce gasoline- and diesel-range hydrocarbons. In parallel, carbon lost to the aqueous phase was recovered as renewable methane from anaerobic digestion to offset fossil carbon required to meet the hydrogen demand of the integrated process.

09 BIOMASS FUELS↗
DOE OSTI2022

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↗