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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
NASA NTRS2003

Assessment of Models of Chemically Reacting Granular Flows

A report presents an assessment of a general mathematical model of dense, chemically reacting granular flows like those in fluidized beds used to pyrolize biomass. The model incorporates submodels that have been described in several NASA Tech Briefs articles, including "Generalized Mathematical Model of Pyrolysis of Biomass" (NPO-20068) NASA Tech Briefs, Vol. 22, No. 2 (February 1998), page 60; "Model of Pyrolysis of Biomass in a Fluidized-Bed Reactor" (NPO-20708), NASA Tech Briefs, Vol. 25, No. 6 (June 2001), page 59; and "Model of Fluidized Bed Containing Reacting Solids and Gases" (NPO- 30163), which appears elsewhere in this issue. The model was used to perform computational simulations in a test case of pyrolysis in a reactor containing sand and biomass (i.e., plant material) particles through which passes a flow of hot nitrogen. The boundary conditions and other parameters were selected for the test case to enable assessment of the validity of some assumptions incorporated into submodels of granular stresses, granular thermal conductivity, and heating of particles. The results of the simulation are interpreted as partly affirming the assumptions in some respects and indicating the need for refinements of the assumptions and the affected submodels in other respects.

Bellan, Josette↗
DOE OSTI2020

Operando S/TEM Reactions of Pt/TiO 2 Catalysts for Catalytic Fast Pyrolysis

Conversion of lignocellulosic biomass into the transportation fuel is an attractive concept. Using ex situ Catalytic Fast Pyrolysis (CFP) improves to upgrade bio-oils via catalytic deoxygenation of the biomass pyrolysis vapors. Zeolites are often used in this technique as the catalyst; however, in order to reduce minimum fuel selling price and improve carbon yields, ongoing research emphasizes catalyst optimization. By using bifunctional metal-acid catalysts and utilizing hydrogen, it is possible to improve carbon yields by minimizing the carbon-containing light gasses (since oxygen is removed aswater) and by reducing coke formation. Current research and development activities focuses on Pt/TiO 2 catalysts as the most promising catalyst candidates for the hydrodeoxygenation process. Here, our aim is to determine the structure-function relationships of the Pt/TiO 2 catalyst and the role of Pt dispersions within the catalyst on performance, using operando scanning transmission electron microscopy (S/TEM).

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

Effect of Temperature on the Pilot-Scale Catalytic Pyrolysis of Loblolly Pine

A pilot-scale biomass catalytic pyrolysis unit with a nominal throughput of one tonne of biomass per day (1TPD) has been in operation since 2013 to investigate the process parameters that have the largest influence on biocrude yield, oxygen content, and chemical composition. A parametric study was conducted to investigate the effect of pyrolysis temperature, ranging from 433 to 581 °C, on biocrude yield and quality. A locally sourced loblolly pine feedstock and a commercially available, spray dried, nonzeolitic γ-Al 2 O 3 catalyst were used in individual experiments conducted at each pyrolysis temperature to achieve a minimum of 4 h of steady-state continuous operation. Typically, 600–800 kg of biomass was fed over a 12-h period, with one experiment extended to almost 29 h (1144-kg biomass fed) and one experiment interrupted by a process upset after just 7 h (411-kg biomass fed). Comprehensive analysis of collected gas, liquid, and solid products were used to calculate carbon balances (77% to 107%) for each experiment. The biocrude yield ranged from 12 to 18 wt % C and, in general, decreased with increasing pyrolysis temperature. The average steady-state biocrude yield as a function of temperature translated to a biocrude production rate between 40 and 50 gallons per dry ton. The biocrude oxygen content varied between 21 and 31 wt %, on a dry basis, and as expected, decreased with increasing pyrolysis temperature. The identified components in the semivolatile biocrude products are mostly methoxyphenols and other multiphenolic compounds. The multiphenolic compounds are demethoxylated at pyrolysis temperatures above 500 °C, producing biocrudes with higher concentrations of monophenols and polycyclic aromatic hydrocarbons. The concentration of anhydrosugars, like levoglucosan in the biocrudes, decreased with increasing pyrolysis temperature from ∼15 to ∼1 vol %.

biofuels↗
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 OSTI2022

Chapter 11: Biochar Production

In production of biochar, thermochemical processes that can be used to treat biomass include pyrolysis, gasification, hydrothermal processing, and combustion. Each of these processes is defined by specific operating conditions (e.g., temperature, presence of oxygen) and feedstock requirements for optimal conversion to the product of primary interest. Each process results in varying fractions of gaseous, liquid, and solid products. Though other publications have emphasized the gaseous bio-energy products of such processes (e.g., bio-oil, synthesis gas or "syngas") with biochar as a co-product, in this discussion, we focus primarily on biochar as the In production of biochar, thermochemical processes that can be used to treat biomass include pyrolysis, gasification, hydrothermal processing, and combustion. Each of these processes is defined by specific operating conditions (e.g., temperature, presence of oxygen) and feedstock requirements for optimal conversion to the product of primary interest. Each process results in varying fractions of gaseous, liquid, and solid products. Though other publications have emphasized the gaseous bio-energy products of such processes (e.g., bio-oil, synthesis gas or "syngas") with biochar as a co-product, in this discussion, we focus primarily on biochar as the main product, with heat and electrical energy as co-products of secondary interest. The reasons for this are as follows: when producing biochar, heat is the simplest form of energy to capture and utilize, electrical energy can be generated from heat energy with a wide range of available technologies small and large; rather than immediately combusting the gases released from biomass, there is potential to refine the gases into bio-oil and syngas. However, much larger investments of capital are needed to build facilities for which gaseous fuel production is the primary goal, as compared to those focused on biochar production with heat and electrical energy co-products. While the economic viability of biochar production will be improved by production of high-value co-products (e.g., wood acids for use in pesticides), the simplest production scheme is one in which biochar and heat are the primary products. Here we aim to provide a broader overview of thermochemical processes and technologies most relevant to biochar production in its current state of commercialization. All biochar is a result of pyrolysis (the reaction) but not all biochar is made with a dedicated pyrolysis reactor (the technology type). Further, all biochar is the result of a lack of complete combustion (the reaction), even biochar produced in a combustion or gasification reactor (the technology type). This is an important distinction to acknowledge in the following sections in which we discuss both thermochemical conversion reactions and technology types.

biochar↗
DOE OSTI2020

In-situ measurement of pyrolysis and combustion gases from biomass burning using swept wavelength external cavity quantum cascade lasers

Broadband high-speed absorption spectroscopy using swept-wavelength external cavity quantum cascade lasers (ECQCLs) is applied to measure multiple pyrolysis and combustion gases in biomass burning experiments. Two broadly-tunable swept-ECQCL systems were used, with the first tuned over a range of 2089-2262 cm -1 (4.42 – 4.79 µm) to measure spectra of CO 2 , H 2 O, and CO. The second was tuned over a range of 920-1150 cm -1 (8.70 – 10.9 µm) to measure spectra of ammonia (NH 3 ), ethene (C 2 H 4 ), and methanol (MeOH). Absorption spectra were measured continuously at a 100 Hz rate throughout the burn process, including inhomogeneous flame regions, and analyzed to determine time-resolved gas concentrations and temperature. The results provide in-situ, dynamic information regarding gas-phase species as they are generated, close to the biomass fuel source.

09 BIOMASS FUELS↗
DOE OSTI2025

Impacts of Biomass Feedstock Pre-Processing on Heat and Mass Transfer During Pyrolysis Using X-Ray Computed Tomography and Multiscale Modeling

Knowledge of the transport properties of biomass particles such as porosity, tortuosity, and permeability is paramount for high-fidelity modeling of biomass pyrolysis due to the heat and mass transfer limitations imposed by particle microstructure. X-ray computed tomography (XCT) is a non-destructive imaging method that enables full 3D reconstructions of the biomass particle microstructure with high resolution, permitting direct calculation of porosity, tortuosity, and permeability from real particle geometries. In this study, XCT imaging revealed the 3D microstructures of particles and chars from pyrolytic conversion of cylindrically cut or milled/pelletized loblolly pine samples. The porosity, tortuosity, and permeability were calculated directly from the XCT geometries via open-source microstructural analysis tool MATBOX+TauFactor (https://github.com/NREL/MATBOX_Microstructure_analysis_toolbox) and computational fluid dynamics (CFD) simulations using our solver, Mesoflow (https://github.com/NREL/mesoflow). These properties were used in a reactor scale model developed in COMSOL of the single particle reactor at NREL to investigate the impact of feedstock pre-processing on biomass conversion during pyrolysis with rigorous experimental validation.

biomass↗
DOE OSTI2022

Understanding Biomass and Polymer Feedstock Variability Through Analytical Pyrolysis and Two Dimensional Gas Chromatography and Mass Spectrometry

Moving toward a circular carbon economy requires enabling reuse of carbon-based macromolecules like those in biomass and polymers. Meeting this goal requires increased upcycling of waste products into higher value products. For biomass waste such as corn stover, pine needles, or bark, one approach is using pyrolysis to convert these feedstocks into bio-oil that can be used for liquid fuel or transformed into other hydrocarbon based products, like bio-polymers. Waste plastics can be upcycled or recycled into new products, or alternatively converted into bio-oil by pyrolysis. Macromolecules from biomass and polymers are challenging to convert into liquid fuel or chemical feedstocks, due to large and sometimes heterogeneous networks of polymeric bonds. We work with the Idaho National Laboratory’s Biomass Feedstock National User Facility and Department of Energy’s Feedstock Conversion Interface Consortium to develop a molecular understanding of biomass variability that occurs naturally and as a result of storage or preprocessing techniques applied to feedstocks, to understand chemical reactions occurring during pyrolysis and other biomass or polymer conversion techniques. Using two dimensional gas chromatography mass spectrometry coupled to analytical pyrolysis provides insight into the molecular changes that occur during the pyrolysis event, and these insights can extend to bench or pilot scale pyrolysis conversions. Understanding pyrolysis of biomass and polymers at a molecular level contributes to development of new tools to predict and manipulate the optimum conditions and identify the best storage, preprocessing, and conversion techniques to maximize output of specific high-value chemical species in the conversion to fuels, or to characterize feedstocks for blending before pyrolysis. Identification and understanding of the molecular level changes resulting from novel preprocessing techniques that can be used to control and manipulate the chemical output of bench or pilot scale pyrolysis is another focus of investigation, including the use of gamma irradiation, acid, or enzyme pre-treatments. We also focus on the impacts of storage conditions and techniques, which can affect moisture levels, degradation, and impacts from naturally occurring microbes in the environment.

09 BIOMASS FUELS↗
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 OSTI2020

Air Pollutant Emissions and Regulatory Implications of Co-Processing Raw Bio-Oil in U.S. Petroleum Refineries

Pyrolysis oil, often referred as bio-oil or biocrude, has attracted considerable attention because it has higher energy density and carbon content compared to the raw biomass. Using pyrolysis oil derived from low cost and underutilized biomass to produce renewable hydrocarbon fuels provides a viable link between the agriculture/forestry and (petro-) chemical industry. Co-processing bio-oil with vacuum gas oil (VGO) in petroleum refinery is appealing due to the relatively low capital requirement to retrofit refinery and the compatibility of fuel products with existing infrastructure. In order to implement co-processing, a petroleum refinery would need to consider several process modifications and therefore could be subject to varying levels of air permitting requirements based on bio-oil co-processing ratio, co-processing capacity in existing units, the amount of regulated pollutants expected to be emitted, among other factors. This analysis considers co-processing 5% (by weight) of raw bio-oil with VGO in the fluidized catalytic cracking (FCC) unit(s) in a petroleum refinery. We estimate the potential increase in emissions of regulated air pollutants resulting from the modifications required to implement bio-oil co-processing and evaluate the regulatory and permitting implications for three FCC size categories in the U.S. refineries, which could co-processes raw bio-oil to produce partially renewable transportation fuels. We also assess technically feasible emission control options petroleum refineries could adopt to avoid being subject to major source permitting requirements if the estimated increase in regulated air pollutant emission exceeds the applicable threshold for major modifications. Insights from our analysis can help overcome challenges and risks associated with timely obtaining air permits required to implement bio-oil co-processing in existing refineries. Our analysis also provides needed information for decision makers (e.g., local air quality agencies) to understand the potential air quality implications for retrofitting refineries to co-process bio-oil, particularly in areas with high concentration of petroleum refineries.

09 BIOMASS FUELS↗
DOE OSTI2022

Measurement of Transport Properties of Woody Biomass Feedstock Particles Before and After Pyrolysis by Numerical Analysis of X-Ray Tomographic Reconstructions

Lignocellulosic biomass has a complex, species-specific microstructure that governs heat and mass transport during conversion processes. A quantitative understanding of the evolution of pore size and structure is critical to optimize conversion processes for biofuel and bio-based chemical production. Further, improving our understanding of the microstructure of biochar coproduct will accelerate development of its myriad applications. This work quantitatively compares the microstructural features and the anisotropic permeabilities of two woody feedstocks, red oak and Douglas fir, using X-ray computed tomography (XCT) before and after the feedstocks are subjected to pyrolysis. Quantitative analysis of the three-dimensional (3D) reconstructions allows for direct calculations of void fractions, pore size distributions and tortuosity factors. Next, 3D images are imported into an immersed boundary based finite volume solver to simulate gas flow through the porous structure and to directly calculate the principal permeabilities along longitudinal, radial, and tangential directions. The permeabilities of native biomass are seen to differ by three to four orders of magnitude in the different principal directions, but we find that this anisotropy is substantially reduced in the biochar formed during pyrolysis. The quantitative transport properties reported here enhance the ability of pyrolysis simulations to account for feedstock-specific effects and thereby provide a useful touchstone for the biorefining community.

09 BIOMASS FUELS↗
DOE OSTI2024

Techno-economic and life-cycle analysis of strategies for improving operability and biomass quality in catalytic fast pyrolysis of forest residues

Many of the challenges faced by the first commercial biorefineries were associated with feedstock handling, quality, and cost. Strategies are needed to enable further expansion of biorefineries and meet the growing demand for bio-based fuels and products. Here, we examine 2 key feedstock challenges and mitigation strategies in the context of a catalytic fast pyrolysis (CFP) biorefinery: (1) the operability of the feed system, which may be improved by modifying the minimum particle size fed to the reactor, and (2) the quality of the biomass, which may be improved by employing air classification to remove undesirable material and increase fuel yields. We conduct techno-economic analysis (TEA) and life-cycle analysis for these strategies, employing a discrete event simulation model for biomass preprocessing combined with a series of correlations developed from literature data and a rigorous CFP conversion model. Our results highlight the importance of balancing increased cost and material losses from preprocessing against improved operability and fuel yields. Economics and sustainability were optimized when operating at the lowest minimum particle size, emphasizing the importance of minimizing material losses while maintaining the operability of the process. Economically, additional costs and material losses from air classification could be acceptable due to improved biomass conversion, and an optimum air classification speed was identified; however, the fuel GHG emissions were minimized when air classification was not used. Valorizing material removed during preprocessing as a coproduct could improve economics and sustainability, decreasing the burden of material losses.

09 - BIOMASS FUELS↗
DOE OSTI2024

Microwave-Assisted Gasification of Biochar: Effect of Operational Parameters and Biochar Composition on Syngas Production

The utilization of microwave-assisted gasification for biomass/plastic is a promising route toward clean energy production, contributing to a reduction in carbon footprint. This method facilitates the conversion of biomass into syngas with enhanced hydrogen (H2) yield, surpassing conventional heating approaches. However, the gasification of biochar, a byproduct resulting from the initial rapid pyrolysis of biomass, appears as a rate-determining step in biomass gasification. To ensure high conversion efficiency, particularly in pilot or larger scales, the maintenance of high biochar reactivity is essential, which can be achieved by introducing catalysts to minimize biochar formation. Furthermore, given the susceptibility of biochar to microwave heating, gaining a comprehensive understanding of its behavior in the presence of microwave-active catalysts under microwave conditions is crucial to obtain valuable insights into the underlying mechanisms, thereby improving overall biomass gasification efficiency. In the previous study, magnetite (Fe3O4) was selected for microwave-assisted gasification for biomass/plastic due to its dual role as a catalyst and microwave absorber and demonstrated considerably enhanced hydrogen production. Herein, Fe3O4 is rationally modified with metal promoters and their synergistic effect toward biochar gasification performance is investigated. The data shows that metal promoted Fe3O4 shows a higher syngas yield than that of pristine Fe3O4 in biochar.

Mai, Duy Hien↗
DOE OSTI2020

Insights into Mechanisms of Screw Feeder Plugging by Heated Pine Forestry Residues Using in-situ and Correlative Microscopy

Increasing concerns about global carbon emissions due to fossil fuel use has created interest in renewable fuel alternatives, such as lignocellulosic biomass. With an estimated global biomass production probability ten-fold higher than projected need, functionalizing and scaling biomass conversion processes, like pyrolysis, is a promising component of a diverse sustainable energy program (Kan, Strezov, & Evans, 2016). Pyrolysis reactors employed in biomass conversion often encounter the known problem of screw feeder plugging, halting work and reducing efficiency of biorefineries. Although the screw feeder is not heated directly, conductive heat transfer from the fluidized bed pyrolysis reactor creates a temperature gradient, where particles experience temperatures between 22°C and 500°C from the time they enter the feeder to being emptied into the reactor (Digman, Joo, & Kim, 2009; Nieminen & Folke, 1982). The impact of unintentional heating on this highly variable feedstock may result in particle morphology modification, surface texture transformation, and the evolution of viscous compounds and may contribute to screw feeder plugging (Haas, Nimlos, & Donohoe, 2009; Ingram et al., 2008). We hypothesized that particles of various anatomical fractions (including needles, branches, bark, cambium, and whitewood) will experience dramatic changes during this heating regime, which will be characterized by decreased particle size, increased surface roughness, degradation of key structural macromolecules, and generation of viscous compounds that would result in increased particle friction and cohesion, contributing to screw feeder plugging.

biofuels↗
DOE OSTI2026

Polymers from Levoglucosenone and Other Anhydrosugars (CRADA Final Report)

The goal of this work is to identify promising drop-in or novel polymers that can be produced from levoglucosenone (LGO), CyreneTM, or other anhydrous sugars. LGO is a potentially important feedstock for polymers produced from renewable sources and can be produced in high yields by the company Circa from the pyrolysis of cellulose and biomass. NLR has a long history with anhydrosugars, pyrolysis and biomass-based polymers and has recently developed machine learning (ML) tools for predicting polymer properties. The DOE has recently supported efforts to identify coproducts from pyrolysis of biomass and their use in the production of performance advantaged polymers. DOE is also supporting the development of ML and molecular modeling for predicting and understanding polymer properties. NLR will leverage this expertise and experience to map out the pathways to polymers from LGO, use ML to identify the properties of novel polymers and estimate the market application space. From this effort NLR will deliver a summary report that outlines the most promising pathways based on quantitative and qualitative metrics for producing polymers from LGO.

09 BIOMASS FUELS↗