Search NASA⌕ Search

SEARCH · Search NASA

Results for “Pyrolysis”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 181 records · Page 10

Molecular Weight Distribution Analysis of Pyrolysis Oils by Gel Permeation Chromatography

Comprehensive analysis of the molecular weight distribution of raw and catalytic fast pyrolysis oils derived from biomass remains a key technical hurdle to understanding oil quality as it relates to downstream use and multiple methods may be necessary to accurately represent all components present. Here, we report the molecular weight distribution metrics of fast pyrolysis (FP) and catalytic fast pyrolysis (CFP) oils as determined by gel permeation chromatography (GPC) combined with UV-diode array (UV), differential refractive index (RI), and multi-angle laser light scattering (MALS) detection. The measured molar mass distributions revealed that FP oil consisted of a higher proportion of larger products relative to the low molecular weight products contained in the CFP oil. GPC/RI and UV methods showed FP oil to have higher weight-average molecular weight (Mw) and number-average molecular weight (Mn) than CFP oil based on elution time. However, GPC/MALS, determined the two oils to have similar overall molecular weight distribution metrics (Mw and Mn) and yielded values significantly higher than those determined by RI and UV detectors relative to external standards. Overall, the use of a multiple detection GPC method could enable a more accurate comparison and determination of true molecular weight metrics of bio-oils.

BIOMASS FUELS↗

Pyrolysis Vapor and Bio-Oil Preconditioning via Ex Situ Hydrodeoxygenation and Alkylation Using a Heteropolyacid Catalyst

Ex situ catalytic preconditioning of biomass pyrolysis vapors (partial deoxygenation) has the potential for both reducing the oxygen content and beneficially influencing the oxygen speciation of condense bio-oils for enhancement of downstream condensed phase upgrading processes. Here, condensed phase upgrading processes may refer to both coprocessing and hydroprocessing with vacuum gas-oil (VGO). Reduction of oxygen content to produce bio-oils with greater hydrophobicity can enhance VGO-solubility while tailoring of oxygen speciation by removal of reactive carbonyls (e.g., acetic acid) can lessen catalytic deactivation via coking reactions. 1,2 Furthermore, enhanced VGO-solubility and reduced coking leads to greater biogenic carbon incorporation in end-products from condensed phase upgrading processes. By leveraging the hydrodeoxygenation and alkylation activity of a titania-supported molybdenum-heteropolyacid (Mo-HPA/TiO2) catalyst, pyrolysis vapors and resulting condensed bio-oils were effectively preconditioned for downstream upgrading. 3 Data regarding the use of Mo-HPA/TiO2 for pyrolysis vapor preconditioning will be presented on, including method of employment, catalyst characterization, and impacts on bio-oil in relation to downstream condensed phase upgrading processes. Our approach is to: Compare Mo-HPA/TiO2 product distribution to HZSM-5; Investigate Mo-HPA/TiO2 regeneration and characterize changes in acid site character; Assess product differences in terms of enhanced VGO-solubility.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Impact of Tree Age and Anatomical Fraction on Forest Residue Pyrolysis and Hydrotreating

Utilization of cost-advantaged biomass and waste resources to produce clean, domestic biofuels will be a key factor in decarbonizing transportation in the United States. This study investigates how the distribution of anatomical fractions (stem wood, bark, needles, branches) from pine forest residues of different ages impacts pyrolysis and hydrotreating processes, including product composition, carbon efficiency, economics, and overall sustainability. Commercially sourced 13- and 23-year-old loblolly pine residues were chosen to represent available resources; whole tree thinnings, and tops and branches from merchantable timber, respectively. Detailed characterization of the residue samples, product distributions, bio-oil, char, and gas characterization data are presented for 13 experiments, including the individual fractions, blends, and air-classified samples to reduce ash content. Pyrolysis mass balances averaged 97 +/- 3%. As expected, bio-oil yields were lower for the bark, needles, and blends with high proportions of these (53-56% dry basis), and highest for the debarked stem wood (67-71% dry basis). Lower yields were attributed to the high ash content of the needles, but also to the high lignin content in the bark (>50%), which is hypothesized to have led to increased char formation during pyrolysis. Higher-oil yield was generally correlated with total volatiles, hydrogen, oxygen, glucan, and mannan; somewhat correlated with xylan and acetyl content; and negatively correlated with total carbon, fixed carbon, nitrogen, sulfur, and extractives. Air classification of the residues was effective in reducing ash content (1.5% to 0.64%), extractives (~7% to 2%), and sulfur (0.04% to 0.02%), resulting in a small increase in yield, a significant increase in the GC-detectable proportion of oil (27% to 34%) and a net economic benefit. These experimental results were used to conduct technoeconomic and life cycle analyses, which are also summarized here.

biofuels↗

Variable Orientation of Biomass/Fast Microwave Pyrolysis Yield

Biomass that is considered “unusable” can be reused through the pyrolysis or extreme heating of mass with no oxygen. Pyrolysis can be an extremely beneficial practice for the fuel industry; however, the physical process of pyrolysis can be difficult to obtain consistent results. The goal to my research is to find a more physically efficient process to obtain an equal or greater amount of biofuel in comparison to the original process that is currently used. This will be obtained by pyrolyzing biomass pellets in different volumes and orientations and observation the results/yields.

09 BIOMASS FUELS↗

Modeling Heat Transfer and Reaction Kinetics of Biomass in Pyrolysis Feeding Systems

Biomass feedstocks can be used to produce low carbon-intensity chemicals and liquid fuels by displacing fossil-fuel sources. Pyrolysis is the thermal decomposition of biomass in the absence of oxygen and can be used to produce crude biofuels. A typical feeding mechanism for pyrolysis reactors is by lock hopper followed by a horizontal auger feeder. Particle agglomeration and plugging of the auger screw are regularly occurring phenomena that is detrimental to the process since it results in the need for periodic inspection and cleaning. The underlying mechanisms leading to agglomeration and plugging are unclear, but a working hypothesis is that heat from the reactor raises the temperature of the biomass in the feeder to the point at which preliminary decomposition reactions occur and produce "sticky" products. Using principles of heat and mass transfer, we derived one-dimensional differential equations for heat flow from the pyrolysis reactor through the auger feeder. Temperature profiles were solved from the system of one-dimensional differential equations using the shooting method. Subsequently, we used the temperature profiles as a one-way coupling to a reaction model for the biomass in the feeder. Kinetic models were adopted from the literature and used to predict the formation of intermediates, products, char, extractives, and metaplastics as well as phase changes along the auger feeder. Species were identified that correlated with softening of the biomass, causing it to become sticky and plug the feeder. We will discuss the details of this work, our findings, and the direction of future work that includes fully coupled transport and reaction-kinetics simulations.

BIOMASS FUELS↗

PAH formation from jet stirred reactor pyrolysis of gasoline surrogates

Soot particles and their precursor polycyclic aromatic hydrocarbon (PAH) species, formed during combustion, are responsible for particulate emissions in gasoline direct injection (GDI) engines. To better understand the effects of fuel composition on formation of soot in GDI engines, the pyrolysis of several gasoline surrogates was studied in a jet-stirred reactor across a broad temperature range at atmospheric pressure and 1 s residence time. Fuel and intermediate species, including aromatics up to naphthalene, were measured using gas chromatography (GC). PAH concentrations from pyrolysis of surrogate fuels were compared to gain insight into the effects of fuel composition on PAH formation. In addition, synergistic effects were observed in pyrolysis experiments of binary blends. A detailed kinetic model, recently developed at Lawrence Livermore National Laboratory (LLNL), successfully captured the effects of blending and the concentration of major PAHs. Major reaction pathways are discussed, as well as the role of important intermediate species, such as acetylene, and resonantly stabilized radicals such as allyl, propargyl, cyclopentadienyl, and benzyl in the formation of PAH.

36 MATERIALS SCIENCE↗

Low temperature upcycling of polyethylene to gasoline range chemicals: Hydrogen transfer and heat compensation to endothermic pyrolysis reaction over zeolites

Selective production of gasoline ranged chemicals were of great interest in the field of plastic upcycling. Here this work reports exothermic hydrogen transfer reaction which was observed when HY zeolite was adopted to catalytic pyrolyze the polyethylene to gasoline ranged chemicals, while it was not observed when H-ZSM5 was used as catalyst. Both zeolite catalysts could significantly bring down the reaction temperature from 500 to 300–350 °C. TG-FITR analysis revealed that products obtained with HY zeolites were dominated with saturated hydrocarbons as compared to H-ZSM5 where the combination of alkanes, alkenes, and aromatics was obtained. In addition to the formation of saturated compounds, the TG-DSC analysis confirmed that, over the HY zeolites, the endothermic hydrogen transfer reaction of olefins occurred along with the pyrolysis of LDPE visibly when the zeolite ratio in the zeolite/polyethylene mixture exceeded 50% by mass. The TG results also indicated that the polyethylene undergone nearly 100% converted with very few residues. Further product analysis from batch pyrolysis by GC-MS confirmed that gasoline ranged iso-alkanes were produced over HY zeolite. This study highlighted that coupling exothermic hydrogen transfer reactions with endothermic pyrolysis could be an energy-efficient way of producing gasoline ranged chemicals. Chemical upcycling of plastics is tunable by using different zeolite combinations for the formation of desired products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical Diversity of Oligomers in Biomass Fast Pyrolysis Oils, Part 2: Heavy Lignin-Derived Molecules and Highly Dehydrated Sugars from Dichloromethane-Insoluble Pyrolytic Lignin

Here, this paper, the second in a series, investigates the water-insoluble, dichloromethane (DCM)-insoluble residue of BTG pyrolysis oil, also known in the literature as high-molecular-weight pyrolytic lignin (HMW-PL). HMW-PL accounts for 9.2 wt % of the original bio-oil, which is known to increase upon aging and contribute to coke formation during bio-oil upgrading. Understanding its composition is crucial for managing pyrolysis oil during the processing. The HMW-PL was fractionated using a silica gel column with solvents of increasing polarity: ethyl acetate (EA), acetone (AC), isopropanol (ISO), and methanol (MeOH), yielding 49.2, 19.9, 8.2, and 8.1 wt %, respectively. Each subfraction was characterized by UV-fluorescence, FTIR, HSQC NMR, and (−)APCI-FT-Orbitrap MS. Analysis revealed that the EA subfraction primarily contained aromatic dimers (C 19 –C 20 ) and trimers (C 17 –C 13 ), while the MeOH subfraction was rich in oxygenated aliphatic monomers (C 8 –C 16 ) likely derived from sugar dehydration products. The resulting fractions were further separated via preparatory HPLC. Fifty-five candidate molecular structures were proposed based on the Orbitrap MS data, supported by UV-fluorescence, FTIR, and NMR results. This fractionation strategy defined four distinct subfractions, enabling the proposal of surrogate molecular structures and advancing the molecular-level understanding of the HMW-PL fraction in the pyrolysis bio-oil.

High-Molecular-Weight PL↗

4D structural changes and pore network model of biomass during pyrolysis

Biochar is an engineered carbon-rich substance used for soil improvement, environmental management, and other diverse applications. To date, the understanding of how biomass affects biochar microstructure has been limited due to the complexity of analysis involved in tracing the changes in the physical structure of biomass as it undergoes thermochemical conversion. In this study, we used synchrotron x-ray micro-tomography to visualize changes in the internal structure of biochar from diverse feedstock (miscanthus straw pellets, wheat straw pellets, oilseed rape straw pellets, and rice husk) during pyrolysis by collecting a sequence of 3D scans at 50 °C intervals during progressive heating from 50 °C to 800 °C. The results show a strong dependence of biochar porosity on feedstock as well as pyrolysis temperature, with observed porosity in the range of 7.41–60.56%. Our results show that the porosity, total surface area, pore volume, and equivalent diameter of the largest pore increases with increasing pyrolysis temperature up to about 550 °C. The most dramatic development of pore structure occurred in the temperature range of 350–450 °C. This understanding is pivotal for optimizing biochar’s properties for specific applications in soil improvement, environmental management, and beyond. By elucidating the nuanced variations in biochar’s physical characteristics across different production temperatures and feedstocks, this research advances the practical application of biochar, offering significant benefits in agricultural, environmental, and engineering contexts.

54 ENVIRONMENTAL SCIENCES↗

Gas-phase pyrolysis of trans 3-pentenenitrile: competition between direct and isomerization-mediated dissociation

The flash pyrolysis of trans 3-pentenenitrile (3-PN, CH 3 –$CH=CH$–CH 2 –CN) was studied by combining the results of VUV photoionization mass spectra with broadband microwave spectra recorded as a function of the temperature of the pyrolysis tube. The two separated functional groups (vinyl and nitrile) open up isomerization as an initial step in competition with unimolecular dissociation. Primary products were detected by keeping the 3-PN concentration low and limiting reaction times to the traversal time of the gas in the pyrolysis tube (~100 μs). The reaction is quenched and products are cooled by expansion into vacuum before interrogation over the 8–18 GHz region using chirped-pulse broadband methods. 118 nm VUV photoionization of the same reaction mixture provides a means of detecting all products with ionization potentials below 10.5 eV with minimal fragmentation. These results are combined with a detailed computational investigation of the C 5 H 7 N and related potential energy surfaces, leading to a consistent picture of the unimolecular decomposition of 3-PN. Loss of two H-atoms to form a 79 amu product is proven from its microwave transitions to contain trans-Z-2,4-pentadienenitrile, while no pyridine is observed. Methyl loss, HCN loss, and breaking the central C(2)–C(3) bond all occur following isomerization of the position of the double bond, thereby opening up low-energy pathways to these decomposition channels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

First principles reaction discovery: from the Schrodinger equation to experimental prediction for methane pyrolysis

Our recent success in exploiting graphical processing units (GPUs) to accelerate quantum chemistry computations led to the development of the ab initio nanoreactor, a computational framework for automatic reaction discovery and kinetic model construction. In this work, we apply the ab initio nanoreactor to methane pyrolysis, from automatic reaction discovery to path refinement and kinetic modeling. Elementary reactions occurring during methane pyrolysis are revealed using GPU-accelerated ab initio molecular dynamics simulations. Subsequently, these reaction paths are refined at a higher level of theory with optimized reactant, product, and transition state geometries. Reaction rate coefficients are calculated by transition state theory based on the optimized reaction paths. The discovered reactions lead to a kinetic model with 53 species and 134 reactions, which is validated against experimental data and simulations using literature kinetic models. We highlight the advantage of leveraging local brute force and Monte Carlo sensitivity analysis approaches for efficient identification of important reactions. Both sensitivity approaches can further improve the accuracy of the methane pyrolysis kinetic model. The results in this work demonstrate the power of the ab initio nanoreactor framework for computationally affordable systematic reaction discovery and accurate kinetic modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Effects of Polyolefin Structure and Source on Pyrolysis-Derived Plastic Oil Composition

Seven types of plastics were pyrolyzed in a fluidized bed reactor: post-consumer recycled (PCR) high-density polyethylene (HDPE), PCR polypropylene (PP), virgin resins of varying molecular weights of HDPE, virgin resins of low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and (PP). Pyrolysis produced non-condensable gases (C1-C3), liquid phase products (C4-C40), and solids (C40+ and chars), with alkane, alkene, alkadiene, aromatic, and multi-cycloaromatics as the predominant compounds. Polymer structure had the greatest impact on product distribution, with minimal influence from molecular weight. Branches in polyethylene (PE) acted as thermal defects initiating degradation. Higher branch density in PE led to increased concentrations of aromatics, branched alkanes, and internal alkenes. PP and PE exhibited distinct degradation mechanisms, with PP requiring less energy for decomposition and yielding more oil. Here, pyrolysis oil from PCR HDPE and PCR PP contained a higher proportion of branched compounds. Additives in PCR plastics may promote isomerization during pyrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Predicting the Cetane Number, Yield Sooting Index, Kinematic Viscosity, and Cloud Point for Catalytically Upgraded Pyrolysis Oil Using Artificial Neural Networks

Abstract The conversion of biomass using fast pyrolysis has the potential to be significantly less expensive at scale compared to alternative methods such as fermentation and gasification. Selective upgrading of the products of fast pyrolysis through chemical catalysis produces compounds with lower oxygen content and lower acidity; however, identifying the specific catalytic pathways for producing viable fuels and fuel additives often requires a trial-and-error approach. Specifically, key properties of the compounds must be experimentally tested to evaluate the viability of the resultant compounds. The present work proposes predictive models constructed with artificial neural networks (ANNs) for cetane number (CN), yield sooting index (YSI), kinematic viscosity (KV), and cloud point (CP), with blind test set median absolute errors of 5.14 cetane units, 3.36 yield sooting index units, 0.07 millimeters squared per second, and 4.89 degrees Celsius, respectively. Furthermore, the cetane number, yield sooting index, kinematic viscosity, and cloud point were predicted for over three hundred expected products from the catalytic upgrading of pyrolysis oil. It was discovered that 130 of these compounds have predicted cetane numbers greater than 40, with four of these compounds possessing predicted yield sooting index values significantly less than that of diesel fuel and predicted viscosities and cloud points comparable to that of diesel fuel.

09 BIOMASS FUELS↗

Hydroformylation of pyrolysis oils to aldehydes and alcohols from polyolefin waste

Waste plastics are an abundant feedstock for the production of renewable chemicals. Pyrolysis of waste plastics produces pyrolysis oils with high concentrations of olefins (>50 weight %). The traditional petrochemical industry uses several energy-intensive steps to produce olefins from fossil feedstocks such as naphtha, natural gas, and crude oil. In this work, we demonstrate that pyrolysis oil can be used to produce aldehydes through hydroformylation, taking advantage of the olefin functionality. These aldehydes can then be reduced to mono- and dialcohols, oxidized to mono- and dicarboxylic acids, or aminated to mono- and diamines by using homogeneous and heterogeneous catalysis. This route produces high-value oxygenated chemicals from low-value postconsumer recycled polyethylene. Here, we project that the chemicals produced by this route could lower greenhouse gas emissions ~60% compared with their production through petroleum feedstocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

End-of-Life Plastics Management: A Review: Mechanical recycling, pyrolysis and hydrocracking methods

End-of-life plastics present a significant challenge to achieving a sustainable economy. It is crucial to develop environmentally friendly technologies to process the waste streams beyond landfilling. This review provides a detailed overview of end-of-life plastics management, covering mechanical recycling, pyrolysis and hydrocracking methods. Mechanical recycling is the predominant technique employed on a large scale in recycling end-of-life plastics, and this review discusses the technoeconomic assessment and life cycle assessment (LCA) of mechanical recycling. This review also summarises key studies concentrating on chemical recycling techniques for handling end-of-life plastics. Among these, pyrolysis and hydrocracking are discussed in depth. Recent advancements and fundamentals of these two techniques are covered, highlighting their significance in tackling the plastic waste challenge. The prospects of scaling up pyrolysis and hydrocracking technologies are interpreted in terms of technical and economic feasibility. The discussion concludes with recommendations for future research to commercialise chemical recycling of end-of-life plastics.

Chemistry↗

Controlled Pyrolysis: A Robust Scalable Composite Recycling Technology

The reinforced composites industry is facing significant challenges in handling the scrap composite material from automobile manufacturing, the wind turbine industry, and others. The fibers in the material, whether they be carbon, glass, or other materials have commercial value if they can be recovered successfully. Successfully means the fibers are clean with no sizing or other binders and have adequate strength and physical properties that would allow them to be economically reprocessed into valuable product. The composites recycling project was an industry-collaborative effort to develop a composite recycling technology using controlled pyrolysis. Through the recycling of scrap and end-of-life (EOL) cured composite materials, this pilot study was intended to create a business case by realizing a cost-effective means for recycling EOL and production scrap composite materials, ultimately reducing the volume of composite materials destined for landfill. The project was led by the Institute for Advanced Composites Manufacturing Innovation (IACMI), the American Composites Manufacturers Association (ACMA), Oak Ridge National Laboratory (ORNL), Continental Structural Plastics (CSP) a Teijin Group Company, CHZ Technologies, and A. Schulman with support from Owens Corning, John Deere, General Electric (GE), Ashland LLC, and Plastics Europe (CEFIC). The team studied and tested CHZ Technologies’ controlled pyrolysis system, known as the Thermolyzer TM , which operates on a scalable basis to convert organic polymer materials into a clean synthesis gas and char containing the recoverable carbon and glass fiber reinforcement. The recoverable energy contained in the input polymers creates the synthesis gas that can be used to provide heat to the Thermolyzer TM primary reactor in a sustainable manner. That is, once the Thermolyzer TM is started with a small amount of external natural gas, the synthesis gas that is created from the polymers will continue to operate the burners so long as feedstock is supplied. The reinforcing fiber materials remaining in the solid phase char were separated and cleaned for re-use in other polymer systems based on the retained properties of the fibers. The study created reports (attached in the appendix) on the Mass and Energy Balances, syngas analytics, VOC assessment, yield analysis and other analytics necessary for a Techno-Economic Analysis (TEA) to quantify the economic impact of the recovery and sustainable re-use of the carbon and glass fibers. The process consisted of 4 steps: Selection of 4 samples of cured composite waste materials from project partners interested in materials recycling and recovering the reinforcing fibers for best case re-use. The materials included glass fiber (GF) polyester/vinyl ester automotive SMC from CSP, GF epoxy balsa/PVC foam wind blades from GE, carbon fiber (CF) epoxy wind blade laminated spar caps from GE, and GF/CF epoxy hybrid assembly from John Deere. Processing the waste composite samples into 1-2” shreds. Packaging the shredded composites into bulk sacks on international shipping pallets for shipment to KUG in Forst (Lausitz), Germany. Pyrolysis of the shredded composites under controlled conditions designed for each polymer system. Collecting samples of the gas and char for analysis. Shipping the char containing the CF/GF back to the US for the next steps of testing the fibers and developing protocols for sustainable re-use of the fibers in composite applications.

36 MATERIALS SCIENCE↗

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↗

Implementation of Detailed Polyethylene Pyrolysis Kinetics into CFD Simulations using Machine Learning

Municipal solid waste (MSW) and waste plastics have received significant attention due to the issues of waste generation and storage, as well as their potential as an energy resource. High-density polyethylene (HDPE) makes up a large portion of plastic waste and has been the subject of several conversion studies. However, the mechanisms associated with converting HDPE through pyrolysis and gasification are extensive and complex making them difficult to implement into high-fidelity computational fluid dynamic (CFD) simulations. For this project, a primary pyrolysis mechanism containing 42 unique species and 737 heterogeneous reactions was used to generate kinetic data over a range of operating conditions. A machine learning (ML) model was developed to replicate the results of the detailed pyrolysis mechanism while significantly increasing the computational efficiency. A deep operator network (DeepONet) architecture was adopted to train the model using time steps relevant to CFD simulations. The ML used physics-based loss functions to ensure mass conservation. The ML model has been deployed in simple MFiX CFD simulations, single particle, and an experimental drop tube reactor, and has shown promising performance compared to the original scheme.

Houston, Ross↗