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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Converting polycarbonate and polystyrene plastic wastes intoaromatic hydrocarbons via catalytic fast co-pyrolysis

Thermochemical conversion of plastic wastes is a promising approach to produce alternative energy-based fuels. Herein, we conducted catalytic fast co-pyrolysis of polycarbonate (PC) and polystyrene (PS) to generate aromatic hydrocarbons using HZSM-5 (Zeolite Socony Mobil-5, hydrogen, Aluminosilicate) as a catalyst. The results indicated that employing HZSM-5 in the catalytic conversion of PC facilitated the synthesis of aromatic hydrocarbons in comparison to the non-catalytic run. A competitive reaction between aromatic hydrocarbons and aromatic oxygenates was observed within the studied temperature region, and catalytic degradation temperature of 700 °C maximized the competing reaction towards the formation of targeted aromatic hydrocarbons at the expense of phenolic products. Catalyst type also played a vital role in the catalytic decomposition of PC wastes, and HZSM-5 with different Si/Al molar ratios produced more aromatic hydrocarbons than HY (Zeolite Y, hydrogen, Faujasite). Regarding the effect of Si/Al molar ration in HZSM-5 on the distribution of monocyclic aromatic hydrocarbons (MAHs), a Si/Al molar ratio of 38 maximized benzene formation with an advanced factor of 5.1. Catalytic fast co-pyrolysis of PC with hydrogen-rich plastic wastes including polypropylene (PP), polyethylene (PE), and polystyrene (PS) favored the production of MAHs, and PS was the most effective hydrogen donor with a ~2.5-fold increase. The additive effect of MAHs increased at first and then decreased when the PC percentage was elevated from 30 % to 90 %, achieving the maximum value of 32.4 % at 70 % PC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Hexamethyldisiloxane pyrolysis: probing H-atom initiation by femtosecond two-photon LIF

Previous experiments have led to the hypothesis that pyrolysis of silica nanoparticle precursors carried in an inert central gas jet surrounded by a laminar flame is initiated not by thermal decomposition (the measured jet temperatures are too low for pyrolysis), but by reactions with H-atoms diffusing from the surrounding flame into the jet. The current work tests this hypothesis using femtosecond two-photon laser-induced fluorescence (fs-TPLIF) to image H-atom concentrations in the same flame configuration as the previous experiments. Methane flames (ϕ = 0.83, 1.01 and 1.13) were generated using a multi-element diffusion (Hencken) burner equipped with a central tube through which the N2 jet was introduced. The fs-TPLIF line imaging showed significant concentrations of H-atoms in the nitrogen jets at heights above the burner (HAB) close to the methane flame front. The measurements indicate radial diffusion of the H atoms from the flame to the jet is significant. The H-atom concentrations in the jet increased with increasing stoichiometry of the methane flame. Additional experiments were performed with hexamethyldisiloxane entrained in the central jet flow. In each case, a diffusion flame producing silica nanoparticles was established at the boundaries between the central jet and the methane flames. The 2D H-atom images showed a transition from over-ventilated diffusion flames to under-ventilated diffusion flames with increasing equivalence ratio. Furthermore, the fs-TPLIF profiles show a significant production of H-atoms within the jet when the surrounding flame is lean. This knowledge contributes to a deeper understanding of the underlying mechanisms governing these synthesis flame systems and opens avenues for advancing silica nanoparticle synthesis techniques.

Kim, Keunsoo↗
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 OSTI2020

Dynamic Life-Cycle Analysis of Fast Pyrolysis Biorefineries: Impacts of Feedstock Moisture Content and Particle Size

The commercialization of biorefineries has been met with significant obstacles due to the technical difficulties of handling solid biomass feedstocks, which are highly variable in physical properties and chemical compositions. An understanding of the principles of unit operations along the supply chain is key to the success of the biofuel industry. This study applies a dynamic life-cycle analysis (DLCA) methodology by developing quantitative relationships between the inputs and outputs for each unit operation based on scientific understanding of the causal effects. Using the DLCA, we assessed system sustainability of drop-in fuel production from fast pyrolysis of pine residues followed by hydro-processing. Life-cycle greenhouse gas (GHG) emissions were calculated for 4641 runs involving two key feedstock parameters: moisture content after field drying and particle size of the feed to pyrolyzer. Moisture contents varied between 25% and 35%, while particle sizes varied between 0.5 and 5 mm in these runs. The life-cycle GHG emissions of these cases vary from 22 to 40 g/MJ. Close examination of each unit operation's contribution to the total GHG emissions reveals that low moisture content after field drying produces savings in energy consumption during feedstock transportation and on-site drying. However, although small particle size leads to overall higher fuel yield, it also requires a significant amount of energy for feedstock size reduction and fuel production. The energy penalty outweighs the benefit of increased fuel yields, especially when fine particles (<1 mm) are used for pyrolysis; thus, small particle size leads to increased GHG emissions overall. The results highlight the trade-offs between the energy demand for preprocessing and the conversion yields, which can be addressed with DLCA.

09 BIOMASS FUELS↗
DOE OSTI2020

Synthesis of high-entropy alloy nanoparticles on supports by the fast moving bed pyrolysis

High-entropy alloy nanoparticles (HEA-NPs) are important class of materials with significant technological potential. However, the strategies for synthesizing uniformly dispersed HEA-NPs on granular supports such as carbon materials, γ-Al 2 O 3 , and zeolite, which is vital to their practical applications, are largely unexplored. Herein, we present a fast moving bed pyrolysis strategy to immobilize HEA-NPs on granular supports with a narrow size distribution of 2 nm up to denary (MnCoNiCuRhPdSnIrPtAu) HEA-NPs at 923 K. Fast moving bed pyrolysis strategy ensures the mixed metal precursors rapidly and simultaneously pyrolyzed at high temperatures, resulting in nuclei with a small size. The representative quinary (FeCoPdIrPt) HEA-NPs exhibit high stability (150 h) toward hydrogen evolution reaction with high mass activity, which is 26 times higher than the commercial Pt/C at an overpotential of 100 mV. Our strategy provides an improved methodology for synthesizing HEA-NPs on various supports.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Introducing bioderived solvents for safer and more sustainable 19 F benchtop NMR analysis of pyrolysis oils

The development of increasingly sustainable analytical chemistry techniques is a growing area of research. Detailed knowledge of bio-oil composition is crucial for the wider use of this alternative, sustainable fuel product, whether by guiding and optimising the pyrolysis processes or for indicating appropriate upgrading methods. The oxygen-containing species in the oil are most important to analyse as they are key to the long-term stability and further processing of the oil. A common analytical method is derivatisation, inserting 19 F nuclei only into specific compounds in the sample, so that a sparser NMR spectrum of a subset of the compounds present can be acquired with even a benchtop NMR spectrometer. However, the derivatisation reactions themselves are not benign, with the most commonly used method relying on DMF throughout. While DMF is highly effective in facilitating the derivatisation reaction, it is not only harmful but increasingly restricted in use. By substituting DMF with ethyl lactate, the reaction is rendered safer and more sustainable. The change in solvent does not affect the NMR results, with estimates of total carbonyl content comparable with those produced by titration. The spectra acquired are detailed enough to also allow the quantification of the different carbonyl functional groups present. By switching to ethyl lactate, it is possible to increase the amount of water in the solvent mixture, further reducing the environmental impact, user risks and cost of the analytical method. By replacing harmful solvents with greener alternatives, benchtop NMR analyses of pyrolysis oils are increasingly safer to run, increasingly cheaper to run, and increasingly more accessible to a wide range of different users.

Tang, Bridget [Aston University, Birmingham (Unite↗
DOE OSTI2019

Ex Situ and In Situ Catalytic Fast Pyrolysis Models (ASPEN PLUS MODELS) [SWR-16-12]

These models are based on the 2015 Design Report of Dutta et al. found here: https://www.nrel.gov/docs/fy15osti/62455.pdf The models are distributed under the GNU General Public License. You will need a separate license to use the Aspen Plus and Microsoft Excel software packages in order to run the models. These models relate to an Aspen Plus process model for in situ and ex situ upgrading of fast pyrolysis vapors for the conversion of biomass to hydrocarbon fuels. It is based on conceptual designs that allow projections of future commercial implementations of the technologies based on a combination of research and existing commercial technologies. Results from the model are documented in a detailed design report NREL/TP-5100-62455 (available at http://www.nrel.gov/docs/fy15osti/62455.pdf). The model consists of the following key operations: (a) fast pyrolysis and vapor upgrading, (b) vapor condensation and recovery of an organic liquid and an aqueous phase, (c) hydroprocessing of the liquid organic phase to produce a fuel blendstock, (d) hydrogen production from off gases, (e) electricity production from excess heat, (f) other utilities such as cooling water, (g) wastewater utilization and treatment.

Dutta, Abhijit↗
DOE OSTI2026

Kinetics of Hydrogen Generation from In-Situ Methane Pyrolysis: Enhanced by Electromagnetic Heating and Natural Catalysts of Reservoir Rocks

Catalytic pyrolysis of methane (CH4) is a promising approach to generate hydrogen (H2). The apparent activation energy of this process has a significant influence on the efficiency and required temperature for H2 generation. Preliminary experiments indicate that minerals present in shales have catalytic effects during in-situ H2 generation from shale reservoirs under electromagnetic (EM) heating. However, the quantitative role of such natural catalysts on apparent activation energy is not explored yet. This research evaluated the role of reservoir rock (shale) in EM heating and on the apparent activation energy of methane pyrolysis (MP) for in-situ H2 generation. Experiments are conducted in a customized EM reactor with frequency 2.45 GHz, and reaction temperature and generated gases are measured by a real-time IR pyrometer and gas analyzer, respectively. It is found that shale samples experienced thermal runway (TR) at 420 ºC under 0.15 kW EM power without any artificial heating promoter. In the presence of spent shale, CH4 conversion started approximately at 600 ºC with negligible amount of carbon dioxide (CO2) generated during this process. We further calculated apparent reaction order and apparent activation energy for MP process in the presence of shale under EM heating, which are 0.4357 and 98.12 kJ/mol, respectively. This research paves a way for leveraging the role of minerals as natural catalysts for enhancing H2 generation under EM heating in petroleum reservoirs.

02 PETROLEUM↗
DOE OSTI2019

Wood-to-Fuel for California's Transportation Sector using Autothermal Pyrolysis (FRD-17-002 Progress Report)

In the month of December, we planned to have the Site License Agreement with SPI from them for final signatures, make further progress on the market assessment for the Wood-to-Bio-oil Market Report, and continue moving towards getting the subcontracts in place with Iowa State University and Frontline BioEnergy, LLC. The hope was to be able to get the finalized Site License Agreement back from SPI/Gary Blanc this month. Unfortunately, since we were in the immediate aftermath of fire season in California, and Gary was still unavailable as a result, we did not. Thankfully, it does not appear that there will be any major difficulties with getting the agreement finalized and signed, once Gary is available again, as SPI is constant in their support and eagerness for this effort to go forward, so we are not concerned that this is a risk to the project at this time. During the month of December, further research was completed on understand and evaluating the availability and potential availability of fire clearing, and other, forestry residue in California. Further investigations into the negative emissions of biomass pyrolysis products and their upgrading for use in other products (such as fuels) by incorporating carbon capture, drying and compression, and sequestration systems were conducted. The cost to achieve the maximum amount of negative emissions from these biomass-pyrolysis products with carbon capture and sequestration techniques was calculated. Sensitivity analysis was employed to understand how feedstock collection cost and product selling price affects this cost. We continued with the process towards subcontracting with Iowa State University and Frontline BioEnergy. Increased emphasis was placed on getting an updated budget from Frontline BioEnergy, LLC., so it can be submitted for approval of replacing a subcontractor, as we understand this is of utmost importance to the CAM. Frontline reported being very close to an updated budget, waiting on contracted labor costs remaining.

09 BIOMASS FUELS↗
DOE OSTI2020

Wood-to-Fuel for California's Transportation Sector using Autothermal Pyrolysis (FRD-17-002 Progress Report)

During the month of January, further research was carried out on understanding and evaluating the availability and potential availability of fire clearing, and other, forestry residue in California. Further investigations into the negative emissions of biomass pyrolysis products and their upgrading for use in other products (such as fuels) by incorporating carbon capture, drying and compression, and sequestration systems were executed. The cost to achieve the maximum amount of negative emissions from these biomass-pyrolysis products with carbon capture and sequestration techniques was calculated. Sensitivity analysis was employed to understand how feedstock collection cost and product selling price affects this cost.

09 BIOMASS FUELS↗
DOE OSTI2021

Wood-to-Fuel Demonstration Project for California's Transportation Sector using Autothermal Pyrolysis (Non-Proprietary Summary Process Hazard Assessment)

Frontline has prioritized personnel safety, equipment preservation, and environmental protection throughout the design process of the autothermal pyrolysis unit. To facilitate a safe design, Frontline completed an informal hazards and operability (HAZOP) study and a formal HAZOP study, and employ management of change procedures. The result of these safety procedures is a plant that will function in a safe manner with a limited and acceptable amount of risk. Frontline took an approach it used in previous projects to execute a preliminary, internally facilitated hazards and operability (HAZOP) study. While this HAZOP study was performed without any subsequent change tracking, it enables a group of well-trained engineers to consider the safety implications of each part of the plant in a thorough and methodical manner. Frontline chose to bring in a pyrolysis consultant (Daren Daugaard of Burning Oak Energy) to participate in the review. Following the preliminary HAZOP and once the detailed design work was nearing completion, Frontline performed a formal HAZOP with a third-party facilitator, Jason Stittleburg of Novetus Engineering. Although the plant is not subject to process safety management (PSM) requirements, this formal HAZOP was performed in accordance with OSHA regulations deemed reasonable for PSM. Finally, after the formal HAZOP was conducted, Frontline maintained a safe system by implementing and following management of change procedures on each substantial change to the process. Frontline has kept a record of each subsequent change made to the formal HAZOP P&IDs. The process hazard assessment process allowed Frontline to find and correct several unacceptable configurations within the plant.

09 BIOMASS FUELS↗
DOE OSTI2020

Bespoke, High-Purity Coal Tar with Microwave Plasma Pyrolysis

This presentation discusses H Quest Vanguard's method for generating bespoke, high-purity coal tar using microwave plasma pyrolysis. Demand for coal and coal-derived products is discussed. Mechanisms, properties and advantages of microwave plasma flash pyrolysis and its products are discussed.

Viswanathan, Vignesh↗
DOE OSTI2021

Microwave Plasma Flash Pyrolysis for Coal-to-Product Applications

Since 2010, the US coal industry has experienced a precipitous decline, with coal production volumes dropping by as much as 35% according to EIA. This decline is hardly surprising given that 90% of domestic coal use is allocated to electricity production: While coal generation supplied about 45% of the nation's power in 2010, its share is projected to fall to only 22% in 2020. Fortunately, alternative uses for coal as a feedstock rather than as energy source are available. Coal tar is an established feedstock for chemicals and high-value carbon products including carbon fiber and battery-grade graphites. At present, growth of these uses is constrained by the low availability, purity, and yields of currently available coal liquids, and high energy- and CO2-intensity of current methods of production (i.e. coking). Previously reported work conducted in a partnership with Pacific Northwest National Laboratory demonstrated technical and economic viability of flash pyrolysis of coal in a microwave plasma environment at bench scales targeting production of fuel feedstocks (synthetic oil). H Quest’s work since then indicated promise of microwave-derived coal liquids to be uniquely suited for the lower-cost production of carbon materials, including synthetic graphite, carbon fiber, and composites. Low bulk process temperatures, subsecond residence times, and ambient pressure operation enable small-scale deployment, reduce capital and operating costs, and suppress formation of impurities, including QI material, typical in conventional coal tars. With no inherent production of CO2 or water consumption, microwave plasma flash pyrolysis presents a viable route to the sustainable production of both platform chemicals and carbon-based materials. Most recently, H Quest developed a novel, ruggedized microwave plasma reactor, which departs from the proof-of-concept approach and addresses the problems typically encountered in scaling laboratory microwave plasma apparata (e.g. eliminating fragile quartz enclosures prone to coking and fouling). This reactor has been integrated with a 15kW microwave power supply, a pulverized coal injection system, and a product recovery system. A series of screening tests across a range of coals (including hv-, lv-bituminous and subbituminous PRB), entrainment gas flows and compositions and microwave energy inputs are performed to evaluate conversion rates within the novel, scaled-up system, confirm yields of liquid products, and to perform compositional (GC/MS and elemental) analyses of the products. Results of these tests will be presented and discussed.

Skoptsov, George↗
DOE OSTI2022

Nanostructured Powders Made from Flame Spray Pyrolysis for Li-Ion Cathode

Flame processes are the most economic ones to produce fine powders and have been used to produce pigment titanium oxide and fused silica in large volumes. In this work a flame spray pyrolysis (FSP) process is used to make positive electrode materials for Li-ion battery, which is made of complex metal oxide powders, such as Li(Ni1/3Mn1/3Co1/3)O2. In particular, the work was focused on making the NMC materials with stoichiometric compositions and desired morphologies. During the pyrolysis process different morphologies can be formed, involving often powders with primary nanoparticles. Such nanostructures were found to have affected the battery performance. Detailed results of the synthesis, characterization, and battery testing of the NMC powder materials will be presented.

25 ENERGY STORAGE↗
DOE OSTI2022

Life-cycle Analysis of Conversion of Post-Use Plastic via Pyrolysis with the GREET Model

In this report, we present an updated LCA of the PTF pathway developed at Argonne. Benavides et al. (2017) analyzed the environmental impact of producing ultra-low sulfur (ULS) diesel fuel from PUP via pyrolysis (the most common PTF technology). We used the Greenhouse gases, Regulated Emissions, and Energy use in Technologies (GREET®) model and collected data from eight PTF companies to assess the potential energy and environmental benefits associated with this technology (Argonne, 2020). We conducted a survey and aggregated the dataset based on the different responses, which included plant capacity, process yields, feedstock composition, material and energy inputs, and outputs, and other parameters. We calculated the energy, greenhouse gas (GHG) emissions, and water consumption of its intermediate product pyrolysis oil and final product PUP-derived ULS diesel and compared the results to those metrics for their conventional counterparts (crude naphtha and petroleum ULS diesel fuel).

10 SYNTHETIC FUELS↗
DOE OSTI2021

An Experimental Kinetics Study of Isopropanol Pyrolysis and Oxidation behind Reflected Shock Waves

Isopropanol has potential as a future bio-derived fuel and is a promising substitute for ethanol in gasoline blends. Even so, little has been done in terms of high-temperature chemical kinetic speciation studies of this molecule. To this end, experiments were conducted in a shock tube using simultaneous CO and H2O laser absorption measurements. Water and CO formation during isopropanol pyrolysis was also examined at temperatures between 1127 and 2162 K at an average pressure of 1.42 atm. Species profiles were collected at temperatures between 1332 and 1728 K and at an average pressure of 1.26 atm for equivalence ratios of 0.5, 1.0, and 2.0 in highly diluted mixtures of 20% helium and 79.5% argon. Species profiles were also compared to four modern C3 alcohol mechanisms, including the impact of recent rate constant measurements. The Li et al. (2019) and Saggese et al. (2021) models both best predict CO and water production under pyrolysis conditions, while the AramcoMech 3.0 and Capriolo and Konnov models better predict the oxidation experimental profiles. Additionally, previous studies have collected ignition delay time (τign) data for isopropanol but are limited to low pressures in highly dilute mixtures. Therefore, real fuel–air experiments were conducted in a heated shock tube with isopropanol for stoichiometric and lean conditions at 10 and 25 atm between 942 and 1428 K. Comparisons to previous experimental results highlight the need for real fuel–air experiments and proper interpretation of shock-tube data. The AramcoMech 3.0 model over predicts τign values, while the Li et al. model severely under predicts τign. The models by Capriolo and Konnov and Saggese et al. show good agreement with experimental τign values. A sensitivity analysis using these two models highlights the underlying chemistry for isopropanol combustion at 25 atm. Additionally, modifying the Li et al. model with a recently measured reaction rate shows improvement in the model’s ability to predict CO and water profiles during dilute oxidation. Finally, a regression analysis was performed to quantify τign results from this study.

09 BIOMASS FUELS↗
DOE OSTI2019

Gas-phase pyrolysis products emitted by prescribed fires in pine forests with a shrub understory in the southeastern United States

Here we confirm pyrolysis gases from prescribed burns conducted inpine forests with a shrub understory captured using a manual extraction device. The device selectively sampled emissions ahead of the flame front,minimizing the collection of oxidized gases, with the captured gases analyzed in the laboratory using infrared (IR) absorption spectroscopy. Results show that emission ratios (ERs) relative to CO for ethene and acetylene were significantly greater than in previous fire studies, suggesting that the sample device was able to collect gases predominantly generated prior to ignition. Additional evidence that ignition had not begun was corroborated by novel IR detections of several species, in particular naphthalene. With regards to oxygenated species, several aldehydes (acrolein, furaldehyde, acetaldehyde,formaldehyde) and carboxylic acids (formic, acetic) were all observed;results show that ERs for acetaldehyde were noticeably greater, while ERs for formaldehyde and acetic acid were lower compared to other studies. The acetylene-to-furan ratio also suggests that high-temperature pyrolysis was the dominant process generating the collected gases.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1965

Nitrogen dioxide produced by self-sustained pyrolysis of nitrous oxide

Apparatus is developed for achieving continuous self-sustaining pyrolysis reaction in the production of nitrogen dioxide from nitrous oxide. The process becomes self-sustaining because of the exothermic reaction and the regenerative heating of the gases in the pyrolysis chamber.

Sabol, A. P.↗