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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

Cycloheptatrienyl (tropyl) radical, C{sub 7}H{sub 7}, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C{sub 7}H{sub 7} were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C{sub 7}H{sub 7} are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C{sub 7}H{sub 7}) radicals but rather only benzyl (C{sub 6}H{sub 5}CH{sub 2}). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C{sub 6}H{sub 5}CH{sub 2}, C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Perspective on Catalytic Hydrodeoxygenation of Biomass Pyrolysis Oils: Essential Roles of Fe-Based Catalysts

Catalytic fast pyrolysis is the most promising approach for biofuel production due to its simple process and versatility to handle lignocellulosic biomass feedstocks with varying and complex compositions. Here, compared with in situ catalytic fast pyrolysis, ex situ catalytic pyrolysis has the flexibility of optimizing the pyrolysis step and catalytic process individually to improve the quality of pyrolysis oil (stability, oxygen content, acid number, etc.) and to maximize the carbon efficiency in the conversion of biomass to pyrolysis oil. Hydrodeoxygenation is one of the key catalytic functions in ex situ catalytic fast pyrolysis. Recently, Fe-based catalysts have been reported to exhibit superior catalytic properties in the hydrodeoxygenation of model compounds in pyrolysis oil, which potentially makes the ex situ pyrolysis of biomass commercially viable due to the abundance and low cost of Fe. Here, we briefly summarize the recent progress on Fe-based catalysts for the hydrodeoxygenation of biomass, and provide perspectives on how to further improve Fe-based catalysts (activity and stability) for their potential applications in the emerging area of biomass conversion.

09 BIOMASS FUELS↗
DOE OSTI2021

Impacts of Anisotropic Porosity on Heat Transfer and Off-Gassing during Biomass Pyrolysis

The pore structure of biogenic materials imbues the ability to deliver water and nutrients through a plant from root to leaf. This anisotropic pore granularity can also play a significant role in processes such as biomass pyrolysis that are used to convert these materials into useful products like heat, fuel, and chemicals. Evolutions in modeling of biomass pyrolysis as well as imaging of pore structures allow for further insights into the concerted physics of phase change-induced off-gassing, heat transfer, and chemical reactions. In this work, we report a biomass single particle model which incorporates these physics to explore the impact of implementing anisotropic permeability and diffusivity on the conversion time and yields predicted for pyrolysis of oak and pine particles. Simulation results showed that anisotropic permeability impacts predicted conversion time more than 2 times when the Biot number is above 0.1 and pyrolysis numbers (Py 1 , Py 2 ) are less than 20. Pore structure significantly impacts predicted pyrolytic conversion time (>8 times) when the Biot number is above 1 and the pyrolysis number is below 1, i.e., the “conduction controlled” regime. Therefore, these nondimensional numbers reflect that when internal heat conduction limits pyrolysis performance, internal pyrolysis off-gassing further retards effective heat transfer rates as a closely coupled phenomenon. Overall, this study highlights physically meaningful opportunities to improve particle-scale pyrolysis modeling and experimental validation relevant to a variety of feedstock identities and preparations, guiding the future design of pyrolyzers for efficient biomass conversion.

09 BIOMASS FUELS↗
DOE OSTI2016

Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis

Here, biomass pyrolysis offers a promising means to rapidly depolymerize lignocellulosic biomass for subsequent catalytic upgrading to renewable fuels. Substantial efforts are currently ongoing to optimize pyrolysis processes including various fast pyrolysis and catalytic fast pyrolysis schemes. In all cases, complex aqueous streams are generated containing solubilized organic compounds that are not converted to target fuels or chemicals and are often slated for wastewater treatment, in turn creating an economic burden on the biorefinery. Valorization of the species in these aqueous streams, however, offers significant potential for substantially improving the economics and sustainability of thermochemical biorefineries. To that end, here we provide a thorough characterization of the aqueous streams from four pilot-scale pyrolysis processes: namely, from fast pyrolysis, fast pyrolysis with downstream fractionation, in situ catalytic fast pyrolysis, and ex situ catalytic fast pyrolysis. These configurations and processes represent characteristic pyrolysis processes undergoing intense development currently. Using a comprehensive suite of aqueous-compatible analytical techniques, we quantitatively characterize between 12 g kg -1 of organic carbon of a highly aqueous catalytic fast pyrolysis stream and up to 315 g kg -1 of organic carbon present in the fast pyrolysis aqueous streams. In all cases, the analysis ranges between 75 and 100% of mass closure. The composition and stream properties closely match the nature of pyrolysis processes, with high contents of carbohydrate-derived compounds in the fast pyrolysis aqueous phase, high acid content in nearly all streams, and mostly recalcitrant phenolics in the heavily deoxygenated ex situ catalytic fast pyrolysis stream. Overall, this work provides a detailed compositional analysis of aqueous streams from leading thermochemical processes -- analyses that are critical for subsequent development of selective valorization strategies for these waste streams.

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 OSTI2024

The Effect of Air Separations on Fast Pyrolysis Products for Forest Residue Feedstocks

This study investigates the intricate relationship between biomass preprocessing and pyrolysis product yields, employing the air classification technique for the treatment of loblolly pine residues with varying moisture content. A comprehensive exploration of the physicochemical properties of air-classified loblolly pine informs a sophisticated pyrolysis simulation model. Given the complex and multifaceted nature of biomass pyrolysis, operating across diverse temporal and spatial scales, a pyrolysis kinetics-based CFD–DEM simulation method is employed to predict product yields. Results showed that the elevated moisture content amplifies particle adhesiveness, necessitating augmented air velocities for effective separation, thereby influencing the efficiency of the separation process. While carbon and hydrogen contents exhibit relative stability across diverse moisture contents and blower frequencies, the oxygen content undergoes noticeable changes. For example, the oxygen contents were measured as 29.2 and 38.6 wt% in the light fraction of 30% moisture content sample at blower frequencies of 10 and 20 Hz, respectively. An intriguing finding emerges from pyrolysis simulation, indicating that a lower blower frequency in air classification moderately enhances bio-oil yield and significantly improves its quality, particularly in terms of water content. For instance, the water content in the bio-oil was about 1.5% and 10% in the heavy and light fractions, respectively from 10% moisture sample under 15 Hz blower frequency. In summary, a detailed understanding and strategic manipulation of critical material attributes in biomass through efficient fractionation techniques are imperative for advancing fast pyrolysis as a sustainable avenue for renewable energy and chemical production.

09 BIOMASS FUELS↗
DOE OSTI2024

Effect of pyrolysis operating conditions on the catalytic co‐pyrolysis of low‐density polyethylene and polyethylene terephthalate with zeolite catalysts

Abstract In this study, the catalytic (co‐)pyrolysis of low‐density polyethylene (LDPE) and polyethylene terephthalate (PET) with HZSM‐5 and HY zeolite catalysts was conducted in a micro‐pyrolysis reactor coupled to a two‐dimensional gas chromatography system. Pyrolysis operating conditions, such as the pyrolysis temperature, the catalyst to feedstock (CF) ratio, and the LDPE:PET ratio, were varied. It was found that for the co‐pyrolysis of LDPE and PET, HZSM‐5 led to higher yields of C2‐C4 olefins and monoaromatic products. Lower CF ratios increased the yield of C2‐C4 olefins for LDPE pyrolysis, but decreased benzene yield for PET pyrolysis, concomitant with an increased yield in benzoic acid. A lower temperature of 400°C which was sufficient for the pyrolysis of LDPE, led to incomplete conversion of PET. Surface response diagrams were used to visualize the impact of the various pyrolysis operating conditions on the yield of C2‐C4 olefins and BTEX, which serve as target products for the circular economy.

Okonsky, Sean Timothy↗
DOE OSTI2020

Mechanistic Insight into Lignin Slow Pyrolysis by Linking Pyrolysis Chemistry and Carbon Material Properties

As a highly abundant renewable carbon source, lignin can be converted to a variety of advanced carbon materials with tailorable properties through slow pyrolysis. In this study, slow pyrolysis of kraft lignin, for the first time, was investigated with a commercial pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS) system through evolved gas analysis-MS (EGA-MS) and heart-cutting-GC–MS (HC-GC–MS) analyses. These analyses allow recovery and examination of the multiphased gas products generated from thermal decomposition of lignin during slow pyrolysis at a controlled heating rate over a long time course, thus making it possible to link operation conditions, pyrolysis chemistry, and carbon material properties. The overall product distributions, including volatiles and solid products, were quantitatively tracked at different heating rates (2, 20, and 40 °C/min) and different temperature regions (100–200, 200–300, and 300–600 °C). Solid residues were further characterized using a suite of analytical tools, in correlation with the investigation of formation mechanisms of volatiles to reveal the reaction chemistry of lignin during slow pyrolysis and to determine the morphology, pore structure, and interfacial chemical properties. This study provides critical insights into the slow pyrolysis chemistry of lignin and the properties of the resulting carbon material. These results will facilitate a better design and control of the lignin slow pyrolysis process for synthesizing functional carbon materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Microwave-assisted pyrolysis of Mississippi coal: A comparative study with conventional pyrolysis

Pyrolysis conditions greatly affect the structure-reactivity relationship of char during coal gasification. Here, this work investigated the effect of temperature and microwave heating on the structural properties of the chars generated during pyrolysis, as well as gaseous and tar products. Results showed that microwave pyrolysis of Mississippi coal produced more gaseous products and less tars compared to conventional pyrolysis. Higher CO/CO 2 ratio (>1) was observed under microwave pyrolysis compared to conventional pyrolysis (CO/CO2 < 1), which may be explained by a greater extent of gasification between solid carbon and the CO 2 formed during microwave pyrolysis. Additionally, in microwave pyrolysis, the oil tars generated exhibited lower concentrations of polar oxygenates, while the wax tars showed higher concentrations of non-polar alkanes, as observed from the intensity of CH vibrations in FTIR. The product compositions and FTIR analysis of the tars (oils and waxes) suggest that the microwave interacted preferentially with these polar species, which have relatively higher dielectric properties compared to alkanes. The structure–reactivity relationship of the chars produced was also investigated using a variety of characterization tools such as XRD, BET, SEM, EDS, and FTIR. Finally, the char reactivity towards combustion suggested that microwave-produced chars have a higher thermal stability, likely due to lower O/C ratios, and could be utilized in the metallurgical industry.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

Vacuum Pyrolysis of Hybrid Poplar Milled Wood Lignin with Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry Analysis of Feedstock and Products for the Elucidation of Reaction Mechanisms

The pyrolysis of lignocellulosic materials is a promising technique to produce fuels and chemicals. It is well known that the most abundant products of lignin pyrolysis are oligomeric molecules, known as pyrolytic lignin (PL). The chemical composition of PL has been extensively studied; however, there is still an important debate whether these oligomers are produced directly from the lignin or from the recombination of monomeric pyrolytic products. Existing theories are unable to describe the effect of vacuum on the distribution of pyrolysis products. Hybrid poplar milled wood lignin (MWL) was initially isolated and thoroughly characterized by Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS). Chemical formulas were assigned to each oligomeric compound detected. The MWL was also subjected to vacuum pyrolysis in a modified pyroprobe at 250, 750, and 1000 mbar (absolute pressure), and the resulting liquid products were analyzed by FT-ICR MS. A new strategy to assign structural representations to the oligomeric PL products is proposed, based on the plausible pyrolysis reaction mechanisms of depolymerization/fragmentation applied to original MWL oligomer formulas. Our results support the hypothesis that PL is formed from the removal of moieties from primary lignin pyrolysis products with between three and five aromatic rings. This depolymerization/fragmentation allows the oligomers to reduce their molecular weights to the point where they can be removed from the reaction zone by direct vaporization. Furthermore, this phenomenon highlights the importance of pressure on removal mechanisms and their impact on the molecular weight of the resulting products from lignin pyrolysis.

09 BIOMASS FUELS↗
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

Coprocessing Biomass Fast Pyrolysis and Catalytic Fast Pyrolysis Oils with Vacuum Gas Oil in Refinery Hydroprocessing

Fast pyrolysis and catalytic fast pyrolysis (CFP) have been considered to be promising approaches for converting lignocellulosic biomass into liquid bio-oils followed by upgrading to produce fuel-range hydrocarbon products. Co-processing fast pyrolysis and CFP bio-oils with petroleum feedstocks leverages the existing petroleum refining infrastructure, which reduces Capex for the overall conversion technologies for biomass to fuel and enables fast adoption of the technologies and biofuels. Here, we reported the co-processing of different woody fast pyrolysis and CFP bio-oils with petroleum vacuum gas oil (VGO) at 5-25% bio-oil blending levels over a NiMo sulfide catalyst for mild hydrocracking. The catalyst activities over ~300 hours time on stream, the product yield and properties, and the biogenic carbon content in products are provided. Co-processing of the raw fast pyrolysis bio-oil in our configuration was not successful because the instability of the bio-oil resulted in reactor plugging and bio-oil stabilization by hydrogenation enabled their stable co-processing with VGO, whereas the CFP bio-oil can be co-processed without pretreatment. Simultaneous hydrodesulfurization, hydrodeoxygenation, and hydrocracking reactions occurred during co-processing and no obvious decrease in hydrodesulfurization and hydrocracking conversion of VGO was observed, suggesting the minimal impact of co-processed bio-oils on the reaction of VGO and also the simultaneous conversion of bio-oil and VGO to produce fuel products with much-reduced S and O content. Biogenic carbon content in co-processed products calculated by yield mass balance, together with results from isotopic measurements, indicates high biogenic carbon incorporation into liquid hydrocarbon products. In conclusion, higher biogenic carbon incorporation into fuel products was observed when co-processing CFP bio-oils than the fast pyrolysis bio-oils and over 90% of carbon in CFP bio-oil was incorporated into liquid hydrocarbon products.

09 BIOMASS FUELS↗
DOE OSTI2023

Effect of secondary gas-phase reactions (SGR) in pyrolysis of carbon feedstocks for anisotropic carbon materials production – 3: Modifying non-coking coal tar through co-pyrolysis of coal with linear low-density polyethylene and high-impact polystyrene

Herein, this work focuses on co-pyrolysis experiments of Utah Sufco coal with linear low-density polyethylene (LLDPE) and high-impact polystyrene (HIPS). These two plastic types have differing pyrolysis chemistries and have different hydrogen transfer behavior. Similar to earlier work in this series of papers, controlled secondary gas-phase reactions during pyrolysis were used to induce cracking and condensation reactions among the pyrolytic tar species. Co-pyrolysis tests were performed with feed plastic percentages ranging from 10-20 wt% and pyrolysis SGR temperatures ranging from 800-900°C. Analyses of the intermediate tar products showed that oxygen contents and aromaticity were substantially different, depending on the plastic, and resulting pitch softening points and mesophase contents also varied greatly depending on the starting plastic feedstock used. Most of the synergies observed in the co-pyrolysis results were negative, except for the oxygen content. Oxygen contents were higher than expected when LLDPE was used, resulting in reactive pitches with softening points > 350°C. On the other hand, oxygen contents were lower than expected when HIPS was used, resulting in less reactive pitches. Ultimately, only the HIPS/coal samples created at the SGR temperature of 900°C had reasonable softening points at or under 350°C, making them the only samples created in this work potentially suitable for mesophase pitch-based carbon fiber production. The success in creating fusible mesophase pitches from co-pyrolyzing HIPS with Utah Sufco coal is likely attributed to the fact that polystyrene is a stronger hydrogen acceptor rather than donor, which should facilitate more cracking rather than stabilizing tar oxygen functional groups, making the tar species ultimately less reactive during thermal conversion to mesophase pitch.

01 COAL, LIGNITE, AND PEAT↗
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

Machine Learning Reduced Order Model for Cost and Emission Assessment of a Pyrolysis System

Biomass pyrolysis is a promising approach for producing economic and environmentally-friendly fuels and bioproducts. Biomass pyrolysis experiments show that feedstock properties have a significant impact on product yields and composition. Scientists are developing detailed chemical reaction mechanisms to capture the relationships between biomass composition and pyrolysis yields. These mechanisms can be computationally intensive. In this study, we investigate the use of a machine learning reduced order model (ROM) for assessing the costs and emissions of a pyrolysis biorefinery. Here, we developed a Kriging-based ROM to predict pyrolysis yields of 314 feedstock samples based on the results of a detailed chemical kinetic pyrolysis mechanism. The ROM is integrated into a chemical process model for calculating mass and energy yields in a commercial-scale (2000 tonne/day) biorefinery. The ROM estimated biofuel yields of 65 to 130 gallons per ton of dry biomass. This results in biofuel minimum fuel-selling prices of $2.62 to $5.43 per gallon and emissions of -13.62 to 145 kg of CO 2 per MJ. The ROM achieved an average mean square error of 1.8e-20 and a mean absolute error of 0.53%. These results suggest that ROMs can facilitate rapid feedstock screening for biorefinery systems.

09 BIOMASS FUELS↗