Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “STIRRING”

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 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

An experimental and kinetic modeling study of the pyrolysis of isoprene, a significant biogenic hydrocarbon in naturally occurring vegetation fires

Isoprene dominates the carbon flux emitted by vegetation and constitutes 40% of non-methane biogenic emissions worldwide. Despite pyrolysis experiments at temperatures above 1000 K showing a link between isoprene combustion and aromatic species formation, comprehensive mechanistic research on isoprene is scarce in the literature. Here, in this work, we carry out an experimental and theoretical study to build, for the first time, a chemical kinetic model describing isoprene pyrolysis. The formation of polycyclic aromatic hydrocarbon (PAH) precursor species, often observed in vegetation fire plumes, is partially explained by isoprene pyrolysis experiments and theoretical modeling. Molecular dynamics (MD) simulations unveil reaction pathways from allylic isoprenyl radicals to allene and cyclopentadiene (CPD) intermediates, two relevant species detected in the experiments. Rate constants for these identified pathways are calculated using variational transition state theory to update the kinetic model, which is validated against single-pulse shock tube (SPST), and jet-stirred reactor (JSR) experimental data in the temperature range of 850–1690 K. The kinetic model presents satisfactory agreement with the SPST experimental data, and a reaction pathway analysis shows that association of propargyl radicals results in benzene formation. The JSR pathway analysis also identifies the prominent reactions for CPD, benzene, styrene, and toluene formation. Our model does not reproduce the CPD experimental profiles, indicating that additional studies are necessary. Overall, our findings advance the understanding of isoprene pyrolysis and its related atmospheric pollutants in naturally occurring vegetation fires where smoldering and oxygen-deficient combustion processes are present.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

A comprehensive experimental and kinetic modeling study of di-isobutylene isomers: Part 1

We report di-isobutylene has received significant attention as a promising fuel blendstock, as it can be synthesized via biological routes and is a short-listed molecule from the Co-Optima initiative. Di-isobutylene is also popularly used as an alkene representative in multi-component surrogate models for engine studies of gasoline fuels. However, there is limited experimental data available in the literature for neat di-isobutylene under engine-like conditions. Hence, most existing di-isobutylene models have not been extensively validated, particularly at lower temperatures (< 1000 K). Most gasoline surrogate models include the di-isobutylene sub-mechanism published by Metcalfe et al. with little or no modification. The current study is undertaken to develop a detailed kinetic model for di-isobutylene and validate the model using a wide range of relevant experimental data. Part 1 of this study exclusively focuses on the low- to intermediate temperature kinetics of di-isobutylene. An upcoming part 2 discusses the high-temperature model development and validation of the relevant experimental targets. Ignition delay time measurements for the di-isobutylene isomers were performed at pressures ranging from 15 - 30 bar at equivalence ratios of 0.5, 1.0, and 2.0 diluted in air and in the temperature range 650 - 900 K using two independent rapid compression machine facilities. In addition, measurements of species identified during the oxidation of these isomers were performed in a jet-stirred reactor and in a rapid compression machine. A detailed kinetic model for the di-isobutylene isomers is developed to capture the wide range of new experimental targets. For the first time, a comprehensive low-temperature chemistry submodel is included. The differences in the important reaction pathways for the accurate prediction of the oxidation of the two DIB isomers are compared using reaction path analysis. In conclusion, the most sensitive reactions controlling the ignition delay times of the DIB isomers under the pressure and temperature conditions necessary for autoignition in engines are identified.

09 BIOMASS FUELS↗
DOE OSTI2022

A wide range experimental study and further development of a kinetic model describing propane oxidation

This work presents an experimental and kinetic modeling study of propane oxidation. Ignition delay times of propane were measured in a high-pressure shock tube and in rapid compression machines in the temperature range 689 - 1700 K at equivalence ratios of 0.5, 1.0 and 2.0 in 'air', for a wide range of pressures from 20 to 90 bar. CO and H 2 O mole fraction profiles for propane oxidation were measured in a shock tube behind reflected shock waves in the temperature range 1370-1840 K at equivalence ratios of 0.5, 1.0 and 2.0 and at a pressure of approximately 1.3 atm. Moreover, propane oxidation was studied using a jet-stirred reactor coupled to a synchrotron vacuum ultraviolet photoionization mass spectrometer at low temperatures in the range 565 - 690 K and at a pressure of 1 atm. Further, this wide range of experimental datasets for propane oxidation was used to reoptimize and update our previous kinetic mechanisms, AramcoMech3.0 and NUIGMech1.1. In the current mechanism, NUIGMech1.3, the thermo-chemical parameters of all species relevant to low-temperature propane oxidation chemistry, including propyl-peroxyl, hydroperoxyl-propyl, hydroperoxyl-propyl-peroxyl, and carbonyl-hydroperoxide radicals, are updated based on newly calculated values at the CCSD(T)-F12/TZ-F12//B2PLYPD3/TZ///B2PLYP-D3/TZ level of theory. The improvements made in the thermochemical values and in the kinetic parameters for the low-temperature propane oxidation reactions in NUIGMech1.3 result in better model agreement with the new IDTs and speciation data, including carbon monoxide, formaldehyde, propene, acetaldehyde and various minor products such as ethylene, acetic acid, acrolein as well as various hydroperoxide and cyclic ether species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Methyl formate oxidation kinetics up to 100 atm

Methyl formate (MF, CH3OCHO), the simplest ester, is a representative oxygenated fuel with high oxygen content, and low sooting tendency. However, its oxidation behavior under high-pressure and intermediate-temperature conditions remains insufficiently understood, especially where low-temperature peroxy radical chemistry, methanol chemistry, and pressure-dependent reaction pathways play a critical role. In this study, MF oxidation experiments were conducted in the Princeton supercritical-pressure jet-stirred reactor (SP-JSR) at 20 and 100 atm over the temperature range of 400–950 K under both fuel-lean and fuel-rich conditions. Based on the experimental results, an updated HP-Mech was developed by incorporating previous MF sub-mechanisms, expanded low-temperature peroxy pathways, and evaluated pressure-dependent decomposition kinetics. The newly updated HP-Mech shows greatly improved performance in predicting the onset temperature, the key intermediate species fractions, methanol formation, and the progression of MF oxidation across all the experimental conditions. Path flux analysis indicates that MF consumption at the onset stage is dominated by H-abstraction at the methyl site, forming CH2OCHO radicals that lead to the formation and isomerization of O2CH2OCHO, driving low-temperature chain propagation. Moreover, H-abstraction at the formate site forms CH3OCO radicals that preferentially decompose to CH3, initiating the methanol formation pathway linked to CH3O2 and HO2 chemistry. At the same time, HO2 formation is strongly coupled to MF oxidation through multiple MF-derived radical pathways. HCO originates from MF oxidation and acts as a key coupling species linking fuel consumption to HO2 buildup, especially under high-pressure and intermediate-temperature conditions. In addition to this dominant channel, supplementary HO2 formation pathways involving CH3, CH3O, CH2OH, and CH3O2 reacting with O2 further connect methanol chemistry and oxygenated radical chemistry to the HO2 pool, indicating the central role of HO2 in governing MF oxidation. Sensitivity analysis identifies MF with OH/HO2/CH3O2 reactions and the HO2/H2O2/OH sequence as the key factors controlling reactivity in the high-pressure and intermediate-temperature regime. MF directly reacts with OH/HO2/CH3O2 to consume the fuel and produce reactive radicals like CH2OCHO and CH3OCO that undergo subsequent oxidation pathways. Moreover, HO2 recombination suppresses oxidation at lower temperatures, while thermal decomposition of H2O2 accelerates OH production and promotes fuel consumption as temperature increases. The direct formation of active OH from HO2 radicals further completes the mechanism, improving its prediction especially during the oxidation onset stage.

Low-temperature Chemistry↗
DOE OSTI2021

Mechanisms and kinetics of citrate-promoted dissolution of a uranyl phosphate mineral

The formation of uranyl phosphate precipitates is a remediation strategy to limit the mobility of uranium in contaminated soils. However, exposure to organic ligands, like the plant exudate citrate, can remobilize the uranium. The purpose of this study is to provide a more thorough comprehension of citrate-promoted dissolution of a uranyl phosphate mineral, chernikovite [(H 3 O)(UO 2 )(PO 4 )·3H 2 O], by determining the extent of uranium release from chernikovite at a wide range of citrate concentrations. Here we have quantified the kinetics of dissolution and proposed potential mechanisms of chernikovite dissolution to gain a better understanding of the fate of uranyl phosphate precipitates in the environment. Batch dissolution and continuously stirred tank reactor (CSTR) experiments indicate that increasing citrate concentrations from 0.1 mM to 50 mM increases the concentration of dissolved uranium. However, at citrate concentrations of 10 mM and greater, the effectiveness of the ligand to enhance the dissolution decreases. Density functional theory modeling and Raman spectroscopy indicate a strong interaction between citrate and the uranyl ions at the surface of the uranyl phosphate. The interaction between citrate and uranyl suggests the formation of an alteration layer of uranyl-citrate surface complexes, which could impede uranium release at citrate concentrations of 10 mM or higher. Together, these results indicate that the citrate-promoted dissolution of chernikovite is a fast reaction that is hindered by a combination of surface saturation and a secondary-phase precipitation reaction at higher concentrations of citrate and reaction times greater than or equal to 72 min based on the hydraulic residence time of CSTR experiments. These findings improve our understanding of the stability of uranyl phosphate for use in sequestration of uranium groundwater plumes at contaminated sites.

58 GEOSCIENCES↗
DOE OSTI2019

A multiscale combustion model formulation for NO x predictions in hydrogen enriched jet flames

Here the present paper investigates the role of combustion models and kinetic mechanisms on the prediction of NO x emissions in a turbulent combustion system where conventional and unconventional routes are equally important for NO x formation. To this end, a lab-scale combustion system working in Moderate and Intense Low-oxygen Dilution (MILD) conditions, namely the Adelaide Jet in Hot Co-flow (JHC) burner, is targeted. The Eddy Dissipation Concept (EDC) and the Partially-Stirred Reactor (PaSR) models are used for turbulence-chemistry interactions. The KEE and GRI2.11 chemical mechanisms are employed. The results show that the choice of the combustion model has a higher impact than the selection of the kinetic mechanism for the investigated cases, indicating that biases in the turbulent reactive flow closure are as important, if not more, as the level of the accuracy of the chemical scheme employed. Moreover, the sensitivity of the NO emissions to the uncertain kinetic parameters of the rate-limiting reactions of the NNH pathway is found to be significant when a detailed kinetic mechanism is used. An engineering modification of the PaSR combustion model is proposed to account for the different chemical time scales of fuel oxidation reactions and NO x formation pathways. It shows an equivalent impact on the emissions of NO than the uncertainty in the NNH pathway kinetics. At the cost of introducing a negligible mass imbalance, the adjustment leads to improved predictions of NO. The investigation establishes a possibility for the engineering modeling of NO formation in turbulent flames with a finite-rate chemistry combustion model that can incorporate a detailed mechanism at an affordable computational cost.

08 HYDROGEN↗
DOE OSTI2021

Shear assisted processing and extrusion of enhanced strength aluminum alloy tubing

Hollow extrusions are used in many industries to make strong, lightweight, and affordable structures. Shear Assisted Processing and Extrusion (ShAPE) enables the extrusion of many alloys, often with noteworthy properties. In this investigation, ShAPE was used to extrude 1 and 2 mm wall tubes of aluminum alloy 6063 measuring 12 mm in diameter at extrusion speeds up to 3.8 m/min. This speed is 10 and 15 times faster than has been reported for any alloy using ShAPE and friction stir back extrusion, respectively. Increasing the extrusion speed from 0.7 to 3.8 m/s resulted in using 68% less process energy at steady state. Microstructural analysis and tensile testing were performed on as-extruded tubes and tubes with a direct T5 heat treatment. Grain refinement from 65 µm to below 20 µm was observed. Growth of macroscale Mg 2 Si strengthening precipitates was not observed. ShAPE processing resulted in recrystallization, and extrusion speed was shown to influence final extrudate texture. Here, transmission electron microscopy analysis revealed that the as-extruded microstructure was free of nanoscale ß" strengthening precipitates. Nanoscale ß" was prominent in direct-aged (T5) ShAPE tubes, similar to a slightly over-aged conventional T6 microstructure. As-extruded tubes had ultimate tensile strengths on par with conventional T5 extrusions and approximately double the total elongation. Tubes that underwent a T5 heat treatment had yield and ultimate strengths averaging 198 and 234 MPa, respectively, with an average total elongation of 11%. The tensile test results are comparable to a conventional T6 heat treatment, but without the solutionization heat treatment step. Mechanical properties either remained flat or improved with increased extrusion speed, which suggests that ShAPE can be scaled up to an industrial process to create energy- and economically efficient high-strength extrusions.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Green synthesis and characterization of graphene nanosheets

Highlights: • For the first time, we have synthesized graphene nanosheets in the presence of pomegranate juice. • Here pomegranate juice was used not only as reductant but also as capping agent. • FT-IR, XRD, SEM, EDS and TEM were used to characterize the samples. • According to TEM image, graphene nanosheet is individually exfoliated after stirring for 24 h. • As shown in the TEM image, graphene monolayer is obtained. - Abstract: For the first time, we have successfully synthesized graphene nanosheets in the presence of pomegranate juice. In this approach, pomegranate juice was used not only as reductant but also as capping agent to form graphene nanosheets. At first, the improved Hummer method to oxidize graphite for the synthesis of graphene oxide (GO) was applied, and then the as-produced graphene oxide was reduced by pomegranate juice to form graphene nanosheets. Fourier transformed infrared (FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), high resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM) and raman were used to characterize the samples. The results obtained from the characterization techniques proved high purity of the final products.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Enhanced photocatalytic activities of TiO2-reduced graphene oxide nanocomposites controlled by TiOC interfacial chemical bond

Highlights: • A series TiO{sub 2}-reduced graphene oxide (RG) nanocomposites were prepared by hydrothermal methods at different temperature. • The photocatalytic performance of TiO{sub 2}-RG was illustrated by a TiOC interfacial chemical bond. • The photocatalytic properties were investigated by UV–vis test and degrading Rhodamine B. • The results revealed that the nanocomposites obtained at 120 °C possessed the optimum photocatalytic performance. - Abstract: In this study, a hydrothermal-prepared TiO{sub 2}-RG nanocomposites series exhibited excellent photocatalytic activities, of which the results can be largely influenced by a TiOC interfacial chemical bond between TiO{sub 2} nanoparticles and RG nanosheets. A stirring TiO{sub 2}-RG sample was prepared as contrast analysis using the same wet process except for heating. The characteristics of the composites were tested by X-ray diffraction (XRD), Raman, FT-IR, Differential scanning calorimetry (DSC), Thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) analysis. The photocatalytic properties were verified by UV–vis diffuse reflectance spectra (DRS) testing as well as degrading Rhodamine B (RhB). Our research results show that the better TiOC interfacial chemical bond was formed, the narrower band gap of the nanocomposite was then obtained. The best hydrothermal synthesizing temperature was found out as 120 °C. The TiO{sub 2}-RG nanocomposite, as inexpensive, nontoxic and highly photo-catalytically active, may let it have a potential use in various photocatalytic applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Highly effective methylated Ti MCM-41 catalyst for cyclohexene oxidation

Highlights: • Methylated TiMCM-41 materials are synthesized by direct room temperature stirring in 3 h of time using NH{sub 3} as a base instead of alkali metal hydroxide. • The synthesized materials are tested for the oxidation reaction of cyclohexene in the presence of H{sub 2}O{sub 2} as an oxidant. • Methylation improved the hydrophobicity of the catalytic active sites of TiMCM-41 materials. - Abstract: A series of Ti containing MCM-41 materials were synthesized with different Si/Ti molar ratios and tested for cyclohexene epoxidation reaction. TiMCM-41 with Si/Ti ratio 40 which gave maximum conversion and selectivity to epoxide was methylated with methyltriethoxysilane (MTES) in this reaction. Accordingly, four different methyl loading (5, 10, 15 and 20 mol % of MTES w.r.t. TEOS) TiMCM-41(Si/Ti 40) samples were prepared. The materials were characterized by different physical techniques such as PXRD, FT-IR spectroscopy, UV–vis DRS spectroscopy, N{sub 2} adsorption-desorption isotherm, SEM-EDX, TEM, TGA and ICP-OES. The catalysts were then tested for cyclohexene epoxidation reaction in the presence of H{sub 2}O{sub 2} avoiding TBHP. The conversion and selectivity for cyclohexene obtained with 10MeTiM-1 (Si/Ti 40) were found to be the best not only among the catalysts investigated in the present work, but also among all the catalysts studied so far for the reaction.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Facile synthesis of the nitrogen-doped graphene quantum dots at low temperature for cellular labeling

Highlights: • The N-GQDs are prepared via a facile stirring method on a magnetic stirrer at low temperature. • The N-GQDs exhibit outstanding biocompatibility in the live HeLa cells for biological applications. • The live cells keep a 100% survival rate in the high N-GQDs concentration of 200 μg mL{sup −1} for 48 h. - Abstract: A facile one-step approach is developed for the large-scale synthesis of nitrogen doped graphene quantum dot (N-GQDs) at low temperature by using citric acid (CA) as the precursor. The emission wavelength of the N-GQDs is nearly excitation-dependent, which may mirror the effects from particles of different sizes and distribution of different emissive sites on nanoparticles. Moreover, the products are then tested with live Hela cells for the extraordinary biocompatibility. The cellular viability is remained to be 100% even after a 48 h exposure with the high N-GQDs concentration of 200 μg mL{sup −1} and this survival rate is really much higher than that have been reported previously. The as-prepared N-GQDs with negligible inherent toxicity exhibit excellent biological applications such as bio-imaging and cell tracking.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

AA2024/SiC metal matrix composites simultaneously improve ductility and cracking resistance during elevated temperature deformation

Here this study uses the stir-casting technique to combine a semi-solid AA2024 alloy directly with finely-sized β-SiC p embedded as a powder or with mechanically alloyed granules as a delivery agent. Liquid-state primary fabrication tends to form agglomerates of reinforcement particles, whereas rolling better distributes the composite constituents. Sub-micron reinforcements of low volume fractions do not significantly increase the hardness of the composite materials. Uniaxial tensile testing at elevated temperatures over a wide range of strain rates showed simultaneous increases in the ductility and crack resistance of AA2024 + SiC p granules embedded as a powder when compared to the non-reinforced control material at lower strain rates, with the same toughness as the control material. The maximum engineering strain of 252.7 ± 19.2% was observed in AA2024/SiCp at a strain rate of 10 -4 s -1 . This improvement in properties is attributed to grain refinement in the MMCs, leading to pinning events during the straining and ductility increases. The resultant impediments to grain growth and crack propagation allow the fine-sized reinforcements to control dynamic microstructural changes during fatigue. Cube {001}<100> is a dominant texture component in AA2024, whereas the Goss {011}<100> and S {123}<634> components mainly represent the texture of the discontinuously reinforced aluminum matrix.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Critical mineral substitutions in IN617: A combined computational and experimental approach to performance evaluation and feasibility

Addressing the escalating demand for critical minerals (CMs) driven by global climate change initiatives, this study explores compositional modifications to Inconel 617 (IN617) by substituting cobalt (Co) with manganese (Mn) across various atomic percentages. Here, we conducted a computational feasibility study employing Molecular Dynamics (MD) simulations to provide strategic guidance for experimental validation. The simulations analyzed tensile strength and corrosion resistance for five modified compositions (M1 to M5) to identify optimal properties. Tensile tests on cubic simulation cells were performed to generate stress-strain curves, revealing the impact of Co replacement with Mn on tensile strength—a metric correlated with hardness. Oxygen penetration simulations were conducted to evaluate corrosion resistance, indicating that reduced oxygen penetration depth corresponds to enhanced resistance. Promising compositions underwent phase diagram calculations for assessing phase stability. The optimal composition (M1), characterized by high tensile strength and minimal oxygen penetration, was chosen for experimental validation using induction melting and friction stir consolidation techniques. The materials were further characterized using SEM-EDS, XRD, and Vickers hardness testing. Our findings suggest that Mn substitution in IN617 can yield mechanical performance at par with high-Co alloys in energy-critical applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

The impact of the third O 2 addition reaction network on ignition delay times of neo-pentane

In this work, we studied the oxidation of neo-pentane by combining experiments, theoretical calculations, and mechanistic developments to elucidate the impact of the 3rd O 2 addition reaction network on ignition delay time predictions. The experiments are based on photoionization mass spectrometry in jet-stirred and time-resolved flow reactors allowing for sensitive detection of the keto-hydroperoxide (KHP) and keto-dihydroperoxide (KDHP) intermediates. With neo-pentane exhibiting a unique symmetric molecular structure, which consequently results only in single KHP and KDHP isomers, theoretical calculations of ionization and fragment appearance energies and of absolute photoionization cross sections enabled the unambiguous identification and quantification of the KHP intermediate. Its temperature and time-resolved profiles together with calculated and experimentally observed KHP-to-KDHP signal ratios were compared to simulation results based on a newly developed mechanism that describes the 3rd O 2 addition reaction network. A satisfactory agreement has been observed between the experimental data points and the simulation results, thus adding confidence to the model's overall performance. Finally, this mechanism was used to predict ignition delay times reported previously in shock tube and rapid compression machine experiments (J. Bugler et al., Combust. Flame 163 (2016) 138–156). While the model accurately reproduces the experimental data, simulations with and without the 3rd O 2 addition reaction network included reveal only a negligible effect on the predicted ignition delay times at 10 and 20 atm. According to model calculations, low temperatures and high pressures promote the importance of the 3rd O2 addition reactions.

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

High pressure ammonia/methanol oxidation up to 100 atm

Here, high pressure ammonia/methanol oxidation and NOx formations were investigated using a recently developed supercritical pressure jet-stirred reactor (SP-JSR) at 20 and 100 atm with temperatures between 550 and 950 K and equivalence ratios of 0.138 and 1.15. The experimental results show that NH 3 oxidation at high pressure is significantly accelerated by the active OH radicals produced from CH 3 OH oxidation. Furthermore, the kinetic interactions between NH 3 and CH 3 OH are governed mainly by the reactions CH 3 OH + NH 2 = CH 2 OH + NH 3 , CH 3 OH + NH 2 = CH 3 O + NH 3 , and CH 2 O + NH 2 = HCO + NH 3 . A HP-Mech model for high-pressure NH 3 /CH 3 OH oxidation was developed in this study. It consists of the most recent NH 3 and CH 3 OH models including some new reactions and updated rate constants from the literature as well as NH 3 -CH 3 OH interactions where rate constants of CH 3 OH + NH 2 = CH 2 OH + NH 3 , CH 3 OH + NH 2 = CH 3 O + NH 3 , NH 2 + CH 2 O = NH 3 + HCO, and NH 2 + CH 2 O = NH 2 CHO + H were theoretically calculated in this study. Our model with these updates improves the prediction for the measured N 2 O/NO x temperature dependence at 100 atm. In addition, the reaction pathway and sensitivity analysis show that N 2 O/NO x /HONO interactions with HO 2 are very important, especially for a fuel-lean mixture at 100 atm. The HONO mole fraction for the fuel-lean mixture at 100 atm was then measured by off-axis integrated cavity output spectroscopy (ICOS) at wavenumber of 6638.26 cm -1 . The experimental data show a significant HONO formation at intermediate temperature that is strongly underpredicted by numerical simulation at 100 atm. Therefore, the HONO related reactions with notable uncertainty at high pressure such as NO + OH (+M) = HONO (+M) and H 2 NO + NO 2 = HONO + HNO need deeper exploration in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

ab initio Sub-Mechanism Development for Cyclopentene Oxidation

To accurately predict low-temperature oxidation behavior, chemical kinetics mechanisms must contain complete reaction networks that include detailed consumption reactions of intermediates produced directly from hydroperoxyalkyl radicals, Q̇OOH, which undergo competing unimolecular reactions and bimolecular reactions with O2. Rates of chain-branching are governed by the flux between the two competing pathways, and inherently depend on temperature, pressure, and oxygen concentration. Neglect of consumption pathways for major oxidation intermediates leads to mechanism truncation error that is ameliorated by expanding the level of detail included in sub-mechanisms and employing ab initio methods for computing rates of elementary reactions and thermochemical properties of species involved. In the present work, an ab initio-derived sub-mechanism is developed using AutoMech to model the chemical kinetics of cyclopentene, a major product of cyclopentane oxidation. The ab initio sub-mechanism builds on a detailed mechanism developed using Reaction Mechanism Generator (RMG) for the specific purpose of determining the extent to which replacing cyclopentene-specific reactions and species with quantum chemical computations reduces model inaccuracies resulting from mechanism truncation error. In an effort to minimize interference from other reactions present during the formation of cyclopentene from cyclopentyl + O2, providing a narrower experimental scope, the model is compared against speciation measurements from jet-stirred reactor (JSR) experiments on cyclopentene oxidation. The experiments utilize vacuum ultraviolet-absorption spectroscopy and mass spectrometry for isomer-resolved speciation of intermediates at 835 Torr from 700 – 950 K. [O2]-dependent experiments were also conducted from 0.057 – 2.01 · 1018 molecules cm–3 at 825 K to examine the influence of oxygen on species profiles. Model predictions using the ab initio-revised mechanism yielded significant improvements in species profiles for both the temperature- and [O2]-dependent measurements, owing in part to increased rates of HOȮ and H2O2 production, which underscores the influence of theoretical calculations of reaction rates involving species produced from Ṙ + O2 such as cyclopentene.

AutoMech↗
DOE OSTI2015

Continuous dry fermentation of swine manure for biogas production

Highlights: • Continuous dry fermentation of swine manure for biogas production is feasible. • The feedstock TS concentration exerted a significant impact on biogas production. • Influences of ammonia and digestate liquidity were investigated in this study. • The results showed that the feedstock TS of swine manure should not exceed 30%. - Abstract: A down plug-flow anaerobic reactor (DPAR) was designed for the feasibility study on continuous dry fermentation of swine manure without any additional stirring. Using fresh swine manure as the feedstock with TS concentration (w/w) of 20%, 25%, 30%, and 35%, stable volumetric biogas production rates of 2.40, 1.92, 0.911, and 0.644 L·(L d){sup −1} and biogas yields of 0.665, 0.532, 0.252, and 0.178 L g{sup −1}VS were obtained respectively, and the TS degradation rates were 46.5%, 45.4%, 53.2%, and 55.6%, respectively. With the increase of feedstock TS concentration, the concentration of ammonia nitrogen grew up to the maximum value of 3500 mg L{sup −1}. Biogas production was obviously inhibited when the concentration of ammonia nitrogen was above 3000 mg L{sup −1}. The maximal volumetric biogas production rate of 2.34 L·(L d){sup −1} and biogas yield of 0.649 L g{sup −1}VS were obtained with TS concentration of 25% at 25 °C without inhibition. Liquidity experiments showed that TS concentration of digestate could be less than 15.8%, and the flow rate of digestate more than 0.98 m s{sup −1} when the feedstock TS concentration was less than 35%, which indicated the digestate could be easily discharged from a DPAR. Therefore, it is feasible to conduct a continuous dry fermentation in a DPAR using fresh swine manure as the feedstock with TS concentration less than 35%, whereas the feedstock TS concentration should not exceed 30% to achieve the maximal biogas production rate and biogas yield.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Experimental and Kinetic Modeling Study of 2-Methyl-2-Butene: Allylic Hydrocarbon Kinetics

Two experimental studies have been carried out on the oxidation of 2-methyl-2-butene, one measuring ignition delay times behind reflected shock waves in a stainless steel shock tube, and the other measuring fuel, intermediate, and product species mole fractions in a jet-stirred reactor (JSR). The shock tube ignition experiments were carried out at three different pressures, approximately 1.7, 11.2, and 31 atm, and at each pressure, fuel-lean (Φ = 0.5), stoichiometric (Φ = 1.0), and fuel-rich (Φ = 2.0) mixtures were examined, with each fuel/oxygen mixture diluted in 99% Ar, for initial postshock temperatures between 1330 and 1730 K. The JSR experiments were performed at nearly atmospheric pressure (800 Torr), with stoichiometric fuel/oxygen mixtures with 0.01 mole fraction of 2M2B fuel, a residence time in the reactor of 1.5 s, and mole fractions of 36 different chemical species were measured over a temperature range from 600 to 1150 K. These JSR experiments represent the first such study reporting detailed species measurements for an unsaturated, branched hydrocarbon fuel larger than iso-butene. A detailed chemical kinetic reaction mechanism was developed to study the important reaction pathways in these experiments, with particular attention on the role played by allylic C–H bonds and allylic pentenyl radicals. The results show that, at high temperatures, this olefinic fuel reacts rapidly, similar to related alkane fuels, but the pronounced thermal stability of the allylic pentenyl species inhibits low temperature reactivity, so 2M2B does not produce “cool flames” or negative temperature coefficient behavior. Furthermore, the connections between olefin hydrocarbon fuels, resulting allylic fuel radicals, the resulting lack of low-temperature reactivity, and the gasoline engine concept of octane sensitivity are discussed.

2-methyl-2-butane↗