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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Coupling particle scale model and SuperDEM–CFD for multiscale simulation of biomass pyrolysis in a packed bed pyrolyzer

An efficient biomass pyrolysis process requires a comprehensive understanding of the chemical and physical phenomena that occur at multi-length and time scales. In this study, a multiscale computational approach was developed and validated for biomass pyrolysis in a packed-bed reactor by integrating pyrolysis kinetics, a particle scale model, and SuperDEM-CFD in open-source code MFiX. A one-dimensional particle-scale model that discretizes the characteristic length of biomass particle into layers was developed to predict the intraparticle phenomena inside a single particle. The 1D model was validated by comparing it with a single biomass particle pyrolysis experiment. Here, a recently developed SuperDEM-CFD model was employed to simulate the non-spherical particle-particle contact and fluid-particle interaction. The coupled model was applied to simulate the pyrolysis of cubic biomass particles in a packed bed and validated by comparing with experimental data. Simulation with and without particle-scale model was compared, and the effect of the gas-solid heat transfer models was also investigated.

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 OSTI2021

Flame stability analysis of flame spray pyrolysis by artificial intelligence

Flame spray pyrolysis (FSP) is a process used to synthesize nanoparticles through the combustion of an atomized precursor solution; this process has applications in catalysts, battery materials, and pigments. Current limitations revolve around understanding how to consistently achieve a stable flame and the reliable production of nanoparticles. Machine learning and artificial intelligence algorithms that detect unstable flame conditions in real time may be a means of streamlining the synthesis process and improving FSP efficiency. In this study, the FSP flame stability is first quantified by analyzing the brightness of the flame's anchor point. This analysis is then used to label data for both unsupervised and supervised machine learning approaches. The unsupervised learning approach allows for autonomous labeling and classification of new data by representing data in a reduced dimensional space and identifying combinations of features that most effectively cluster it. The supervised learning approach, on the other hand, requires human labeling of training and test data but is able to classify multiple objects of interest (such as the burner and pilot flames) within the video feed. The accuracy of each of these techniques is compared against the evaluations of human experts. Both the unsupervised and supervised approaches can track and classify FSP flame conditions in real time to alert users of unstable flame conditions. This research has the potential to autonomously track and manage flame spray pyrolysis as well as other flame technologies by monitoring and classifying the flame stability.

42 ENGINEERING↗
DOE OSTI2020

Investigating biomass composition and size effects on fast pyrolysis using global sensitivity analysis and CFD simulations

It is notoriously difficult to build an accurate universal model for biomass pyrolysis due to its sensitivity to a wide number of critical material attributes such as chemical species and physical sizes. In this work, a biomass pyrolysis kinetics with 32 heterogeneous reactions and 59 species was implemented in an open-source multiphase computational fluid dynamics (CFD) software MFiX and validated against two different experimental pyrolysis data sets that provided detailed data describing chemical component yields. The reaction scheme was then used to build a surrogate model and assess the sensitivity of pyrolysis yields to feedstock compositions. The sensitivity analysis determined that the yield of bio-char showed a strong positive sensitivity to the carbon-rich lignin and tannin pseudo-species in the reaction scheme while the bio-oil and bio-gas were correlated to oxygen-rich lignin pseudo-species. The reaction scheme was then integrated into a coarse-grained discrete element model to simulate fast pyrolysis in a bubbling fluidized bed over a range of feedstock particle sizes. The reactor simulations showed further sensitivity to particle size and hydrodynamics. Notably, particles under 0.5 mm have small heat transfer limitations but left the reactor before completely converting and thus reduced the bio-oil yield. Results from this study can be used to guide future development of highly accurate models for fast pyrolysis reactors with a variety of feedstock properties and operating conditions.

09 BIOMASS FUELS↗
DOE OSTI2022

Using Chemical Reactor Models to Predict Fluidized Bed Pyrolysis Yields of Biomass Feedstocks

A detailed biomass pyrolysis kinetics scheme is implemented in reduced-order reactor models to predict chemical species yields from a fluidized bed reactor. The biomass composition in terms of cellulose, hemicellulose, lignins, and extractives are determined for several biomass feedstocks. Model results are compared to yields measured from a two-inch diameter bench-scale fluidized bed reactor operating at fast pyrolysis conditions. The reduced-order chemical reactor models compare favorably with the experimental measurements and capture trends in product yields due to biomass compositional effects such as high ash content. This work offers a computationally inexpensive approach to predict the quality of biomass pyrolysis products in a timely manner. Source code for the reactor models along with a biomass composition web tool are made available online for future scientific research efforts.

09 BIOMASS FUELS↗
DOE OSTI2022

Cracking during pyrolysis of preceramic polymers within glass microtubes

Abstract Cracking of preceramic polymers during pyrolysis under highly‐constrained conditions is examined by X‐ray computed tomography of fine glass microtubes containing the pyrolyzing material. The microtubes represent model geometries that mimic the long channels between fibers during production of ceramic composites by precursor impregnation and pyrolysis. Complementary fracture mechanics analyses of interface cracking and crack kinking are used to glean insights into the conditions under which periodic alternating cracks form. A key finding is that alternating cracks are an inherent feature of constrained pyrolysis . This feature is attributable in large part to the high energy release rates for interface cracks to kink into the pyrolyzing material under the hydrostatic tension developed during pyrolysis. It also requires interfaces with toughness comparable to that of the pyrolyzing material, to prevent large‐scale interface separation. The results further indicate the need for small uniform spaces for pyrolysis within fiber preforms in order to produce networks of fine periodic pyrolysis cracks; these networks in turn facilitate impregnation and pyrolysis in subsequent processing cycles.

Larson, Natalie M.↗
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 OSTI2022

The Signature C=C=O Stretch of Propenylketenes and Ketene Clusters [Book Chapter]

A combined experimental and theoretical approach has been used to examine the signature antisymmetric C=C=O stretch of prop-1-enylketene and prop-2-enylketene, as well as a series of ketene multimers and hydrates. Optimization and frequency calculations executed at the B3LYP/6-311G++(d,p) level of theory reveal four conformers of prop-1-enylketene and three conformers of prop-2-enylketene. These ketenes were generated via the pyrolysis of 3-pentenoic anhydride and 4-pentenoic anhydride, respectively, and isolated in low-temperature argon matrices prior to FTIR analysis. The resultant spectra display several bands consistent with B3LYP predictions. A similar computational and experimental survey of ketene multimers and hydrates, generated by the pyrolysis of acetic anhydride, has generated a list of frequencies for the antisymmetric C=C=O stretching mode. Furthermore, the results provide useful benchmarks for identification of propenylketenes in future experiments as well as insight for assigning other substituted ketenes in infrared spectra.

02 PETROLEUM↗
DOE OSTI2023

Correlating viscosity and die swell in 3D printing of polyphenylsulfone: A thermo-mechanical optimization modus operandi

Additive manufacturing (AM) of polyphenylsulfone (PPSU), an amorphous high-performance polymer (HPP), has shown promise in exhibiting structural integrity for many applications. With thermoplastic material extrusion 3D printing, parts consisting of layered melts exhibited voids, where the adhesion quality and void size depend on the processing parameters implemented during printing. However, the structure-process-property (SPP) relationships between the thermal properties and rheological and mechanical behavior of AM PPSU are poorly understood. Here, in this study, a comprehensive analysis of the thermal, thermo-mechanical, and layer-by-layer build-up of PPSU is investigated and correlated with viscosity and extrudate die swell behavior with void fraction volume as confirmed by high-resolution x-ray computed tomography (XCT). Gas chromatography–mass spectrometry (GC–MS) pyrolysis confirmed PPSU composition and degradation at 480 °C, consistent with thermo-gravimetric analysis TGA. A 141% difference in viscosity was observed when processing temperatures increased from 350 °C to 400 °C. Likewise, extrudate die swell decreased with increasing temperatures, resulting in a 17% difference. Tensile and compressive properties confirmed that higher extruding temperatures resulted in lower porosity and higher mechanical strength. In general, higher extruding temperatures lower the viscosity to allow for stronger cohesion between layers; however, increasing the temperature too high results in a below unity extrudate die swell, reducing mechanical properties. Therefore, to optimize the mechanical integrity of 3D printed amorphous PPSU parts, an increase in the viscosity, near unity of the extrudate die swell, and tempered extrusion temperature are needed.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Rapid Construction of Validated Chemistry Models for Advanced Biofuels (Co-Optima Final Report)

Computer methods were developed and demonstrated that make it possible to predict the combustion and pyrolysis chemistry of proposed biofuels, even before the biofuels are ever manufactured or experimentally tested. The methods are based on first-principles calculations of reaction rates and equilibria. A large number of complicated calculations are required, so we developed a computer workflow that automates many of the steps. With the chemical structure of the biofuel and the system conditions (temperature, pressure, compositions, etc.) as the input, the computer methods can construct a detailed kinetic model with refined parameters without intense human intervention. The automation of model construction makes it practical for a single engineer to make the predictions in a reasonable time period. The accuracy of the computer predictions was tested by measuring the time-profiles of various reaction intermediates (carbon monoxide, carbon dioxide, water, formaldehyde, methane, and ethylene) formed as the biofuels pyrolyze or ignite using sophisticated laser shock tube methods. Several biofuels, including methyl propyl ether, cyclopentanone, butyl acetate isomers, etc., were carefully studied to demonstrate the validity of the proposed computational and experimental methodology. This research project opens up the possibility for assessing some proposed biofuels on the computer without expensive experimental campaigns. The new computer methods are open source and well-documented, allowing a knowledgeable modeler to easily access the developed methods and implement them in their work routine. Moreover, they are also convenient and powerful, promising for developing the fuel chemistry models needed for use in engine simulators, facilitating co-optimization of new engine designs with new fuels.

09 BIOMASS FUELS↗
DOE OSTI2024

Decomposition characteristics of C4F7N-based SF6-alternative gas mixtures

C4F7N [2,3,3,3-tetrafluoro-2-(trifluoromethyl)propanenitrile]/CO2 gas mixtures are being developed as an eco-friendly electrical insulator to replace SF6, the most potent greenhouse industrial gaseous dielectric. However, recent studies have reported complicated and often conflicting decomposition pathways for C4F7N/CO2 gas mixtures, which has raised concerns. In this work, the decomposition characteristics of C4F7N/CO2 gas mixtures were studied comprehensively by both designed computations and experiments. Computations were performed starting from fundamental propositions of C4F7N/CO2 decompositions, which were further experimentally verified by pyrolysis, long-term thermal aging with/without catalytic materials (industrial-grade molecular sieves 4A), and electrical decomposition by spark discharge. The results of both computations and experiments suggest that in an ideal thermal decomposition, C4F7N is likely to decompose into C2F6 and small fluoronitriles first at high temperatures. The generation of C3F6 and C2N2 from C4F7N thermal decomposition at lower temperatures appears because of the catalytic effect of incompatible materials, for example, the industrial-grade molecular sieves 4A that we tested. The electron impact dissociation of C4F7N plays an important role in C4F7N electrical decomposition, leading to additional formation of distinctive small molecules of CF4 and C2N2 of low concentrations. It was pointed out based on a real arcing test in a load disconnector that the decomposition of C4F7N gas mixtures in real applications will be at a much moderate and manageable rate than what was obtained from the highly accelerated laboratory tests presented in this work. The signatures of decomposition products extracted in this study provide invaluable guidance for developing decomposition-based diagnosis and fixation of decomposition byproducts toward SF6-free power grids.

Physics↗
DOE OSTI2021

BETO 2021 Peer Review - FCIC Task 6: High Temperature Conversion

The impacts of feedstock variability on pyrolysis processes are significant but poorly defined. Current engineering designs are based on empirical guidelines, useful only over a narrow range of feedstock properties. The objectives of this project are to (1) Develop science-based knowledge of how feedstock attributes and operational parameters impact pyrolysis process reliability and product quality; and (2) Build an experimental and computational toolset that predicts these outcomes, enabling processes to optimize reliability and product quality. Biomass is a complex feedstock. Controlling for and testing the effects of individual attributes is very challenging. This project couples multiscale experimentation and modeling to accurately capture the fundamental physics and chemistry of biomass flow and conversion behavior in feeding and pyrolysis reactor operations. Our focus is on pine residue attributes – anatomical fraction (bark, needles, wood), particle morphology (size/shape distribution, density, porosity), and chemical composition (extractives, biopolymers, alkali metals) – that impact product quality for downstream catalytic upgrading. Because detailed pyrolysis product characterization is limited, cutting-edge analytical techniques are being developed to reveal impactful product attributes. The tools and knowledge developed here will enable integrated pyrolysis-based processes that are more robust, flexible, and market-responsive with respect to feedstock variability.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2022

Catalysts by pyrolysis: Direct observation of transformations during re-pyrolysis of transition metal-nitrogen-carbon materials leading to state-of-the-art platinum group metal-free electrocatalyst

Transition metal-nitrogen-carbon (M-N-C) materials have been the focus of scientists’ efforts to address the rising need for earth-abundant materials solutions for energy technology and decarbonization of the economy. They are viewed as one of the most promising candidates to replace platinum group metal (PGM) catalysts in the fuel cell and energy conversion fields, including the application of oxygen reduction reaction, carbon dioxide reduction reaction, and nitrogen reduction reaction. In the effort to improve M-N-C materials properties and achieve atomic dispersity of the transition metal in the carbonaceous matrix, a re-pyrolysis process has been proposed. This secondary heat treatment process of already obtained primary pyrolysis-derived M-N-C materials has been widely reported to substantially improve the electrochemical performance and operational stability of the catalysts. Here, we report a systematic investigation of this process used on samples of templated M-N-C catalysts to obtain state-of-the-art catalysts via in situ heating X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDS), electron energy loss spectroscopy (EELS), X-ray diffraction (XRD), and X-ray computed tomography (CT) characterization methods. It is found that the re-pyrolysis of M-N-C materials could result in the partial amorphization of the carbonaceous substrate. It causes the rearrangement and transformation of multitudinous N moieties, leading to optimization of their morphological display and association with atomically dispersed transition metal dopants. Ultimately, the re-pyrolysis results in an increase in uniformity of the active Fe-Nx sites distribution without the formation of nano-crystalline phases (metallic or carbide) and with overall preservation of the morphology of the carbonaceous framework achieved during the first formative pyrolysis step of the templated synthesis. Finally, these observations provide confirmation that empirically established re-pyrolysis is recommended to be used on all M-N-C materials despite the different synthesis routes to obtain a practical advanced catalytic material.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Open source implementation of glued sphere discrete element method and nonspherical biomass fast pyrolysis simulation

Here, in this research, a glued-sphere Discrete Element Method (DEM) method was implemented in the open-source, Computational Fluid Dynamics (CFD) software MFiX. The implementation was verified using a cylinder-wall collision and then validated by simulating the packing and fluidization of non-spherical particles. The validated code was applied to simulate fast pyrolysis of non-spherical biomass particles in a bubbling fluidized bed. The glued sphere occupancy ratio was proposed to quantify the quality of shape resolution using glued sphere. Shape resolution showed significant influence on the packing height in the simulation of particle packing and an occupancy ratio of 80 % was recommended. Its influence is minor in fully fluidized bed but can be 8 times higher in fixed fluidized bed. Three tested heat transfer models predicted similar yields of elongated biomass fast pyrolysis. The solver developed in this research can be used to simulate other multiphase reacting flows involving non-spherical particles.

42 ENGINEERING↗
DOE OSTI2022

Mechanistic insights into metal, nitrogen doped carbon catalysts for oxygen reduction: progress in computational modeling

We report metal and nitrogen doped carbon materials (denoted as M–N–C) synthesized through high-temperature pyrolysis have been found to exhibit activity for oxygen reduction reaction (ORR) approaching that of Pt and electrochemical stability higher than previous MN 4 -containing macrocyclic molecular catalysts. Tremendous efforts have thus been devoted to the advancement of M–N–C catalysts as an economical alternative to Pt-based catalysts for proton exchange membrane fuel cell cathodes with a focus on simultaneously improving activity and stability. To this end, novel computational modeling techniques have been developed and applied to acquire knowledge crucial for accelerating the pace of M–N–C catalyst development. In this review, recent progress in computational method development, as well as the predictions of chemical structure of active sites, reaction pathways, ORR kinetics, and catalyst stability in electrochemical environments, are critically surveyed. Moreover, the crucial role of computational modeling to elucidate the functional mechanism of M–N–C catalysts for ORR in acid media and enable rational design of M–N–C catalysts is discussed with a visionary outlook for the field.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Experimental and Theoretical Study of Oxolan-3-one Thermal Decomposition

The thermal decomposition of oxolan-3-one, a common component of the bio-oil formed during biomass pyrolysis, has been studied using ab initio calculations and experiments employing pulsed gas-phase pyrolysis with matrix isolation FTIR product detection. Four pathways for unimolecular decomposition were predicted using computational methods. The dominant reaction channel led to carbon monoxide, formaldehyde, and ethylene, all of which were observed experimentally. Here, the other channels led to an assortment of products including ketene, water, propyne, and acetylene, which were all confirmed in the matrix-isolation FTIR spectra. There is also evidence for the production of substituted ketenes in pyrolysis, most likely hydroxyketene and methylketene.

09 BIOMASS FUELS↗