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At least 865 records · Page 48

The evolution of coal porosity during pyrolysis

Gasification of coal, municipal waste, or other organic materials is a potential hydrogen source that entails complex thermal decomposition and transport processes. This study provides a multiscale analysis of these processes for sub-bituminous (Usibelli, Healy, Alaska) and lignite (Center, North Dakota) coals and provides data useful for process design. The chemistry, mineralogy, and pore structures of pyrolyzed coal and their evolution with thermal decomposition are discussed. Samples pyrolyzed at 200–1000 °C were analyzed by small-angle neutron scattering; ultra-small, small-, and wide-angle X-ray scattering; and other complementary techniques. Scanning electron microscopy showed new pores in the high-temperature-pyrolyzed material. Upon heating, the coals became progressively denser, and the concentration of hydrogen decreased. Changes in pore volume fell into three temperature ranges: an initial, low-temperature range that, for the Usibelli coal, involved an increase in overall porosity; a mid-temperature range associated with pore volume loss; and a high-temperature range associated with significant porosity increase and char formation. This transformation was paralleled by changes in fractal dimension and correlation length. The higher the pyrolysis temperature the greater the small-pore-volume fraction and overall surface area became. Pyrolysis increased the lateral size of coal crystallites, decreased the amorphous fraction, and increased the aromatics fraction and overall coal rank. Comparisons of neutron and X-ray scattering data and subsequent water uptake studies showed that pre-dried coals can re-hydrate relatively rapidly upon exposure to air, which can significantly affect the porosity calculated from small-angle-scattering data. Fits to the cumulative porosity curves provide a method for modeling the physical and chemical transformation of hydrogen-containing feedstock during gasification.

Anovitz, Lawrence {Larry} [ORNL] (ORCID:0000000226↗

The black hole mass and the stellar ring in NGC 3706

We determine the mass of the nuclear black hole (M) in NGC 3706, an early-type galaxy with a central surface brightness minimum arising from an apparent stellar ring, which is misaligned with respect to the galaxy's major axis at larger radii. We fit new HST/STIS and archival data with axisymmetric orbit models to determine M, mass-to-light ratio (Y {sub V}), and dark matter halo profile. The best-fit model parameters with 1σ uncertainties are M=(6.0{sub −0.9}{sup +0.7})×10{sup 8} M{sub ⊙} and Υ{sub V}=6.0±0.2 M{sub ⊙} L{sub ⊙,V}{sup −1} at an assumed distance of 46 Mpc. The models are inconsistent with no black hole at a significance of Δχ{sup 2} = 15.4 and require a dark matter halo to adequately fit the kinematic data, but the fits are consistent with a large range of plausible dark matter halo parameters. The ring is inconsistent with a population of co-rotating stars on circular orbits, which would produce a narrow line-of-sight velocity distribution (LOSVD). Instead, the ring's LOSVD has a small value of |V|/σ, the ratio of mean velocity to velocity dispersion. Based on the observed low |V|/σ, our orbit modeling, and a kinematic decomposition of the ring from the bulge, we conclude that the stellar ring contains stars that orbit in both directions. We consider potential origins for this unique feature, including multiple tidal disruptions of stellar clusters, a change in the gravitational potential from triaxial to axisymmetric, resonant capture and inclining of orbits by a binary black hole, and multiple mergers leading to gas being funneled to the center of the galaxy.

79 ASTRONOMY AND ASTROPHYSICS↗

The effects of arcjet operating condition and constrictor geometry on the plasma plume

Measurements of plasma number density and electron temperature were obtained in the plumes of lab arcjet thrusters using electrostatic probes of both spherical and cylindrical geometry. The two arcjet thrusters used had different constrictor and/or nozzle geometries and operated on mixtures of nitrogen, hydrogen, and ammonia to simulate the decomposition products of hydrazine and ammonia. An increase in the measured electron density was observed for both geometries with increasing arc power at a constant mass flow rate and with increasing mass flow rate at a constant arc current. For a given operating condition, the electron number density decreased exponentially off centerline and followed an inverse distance squared relationship along the thrust axis. Typical measured electron temperatures ranged from 0.1 to 0.2 eV.

Carney, Lynnette M.↗

The effects of arcjet thruster operating condition constrictor geometry on the plasma plume

Measurements of plasma number density and electron temperature were obtained in the plumes of lab arcjet thrusters using electrostatic probes of both spherical and cylindrical geometry. The two arcjet thrusters used had different constrictor and/or nozzle geometries and operated on mixtures of nitrogen, hydrogen, and ammonia to simulate the decomposition products of hydrazine and ammonia. An increase in the measured electron density was observed for both geometries with increasing arc power at a constant mass flow rate and with increasing mass flow rate at a constant arc current. For a given operating condition, the electron number density decreased exponentially off centerline and followed an inverse distance squared relationship along the thrust axis. Typical measured electron temperatures ranged from 0.1 to 0.2 eV.

Carney, Lynnette M.↗

Fuel decomposition and boundary-layer combustion processes of hybrid rocket motors

Using a high-pressure, two-dimensional hybrid motor, an experimental investigation was conducted on fundamental processes involved in hybrid rocket combustion. HTPB (Hydroxyl-terminated Polybutadiene) fuel cross-linked with diisocyanate was burned with GOX under various operating conditions. Large-amplitude pressure oscillations were encountered in earlier test runs. After identifying the source of instability and decoupling the GOX feed-line system and combustion chamber, the pressure oscillations were drastically reduced from +/-20% of the localized mean pressure to an acceptable range of +/-1.5% Embedded fine-wire thermocouples indicated that the surface temperature of the burning fuel was around 1000 K depending upon axial locations and operating conditions. Also, except near the leading-edge region, the subsurface thermal wave profiles in the upstream locations are thicker than those in the downstream locations since the solid-fuel regression rate, in general, increases with distance along the fuel slab. The recovered solid fuel slabs in the laminar portion of the boundary layer exhibited smooth surfaces, indicating the existence of a liquid melt layer on the burning fuel surface in the upstream region. After the transition section, which displayed distinct transverse striations, the surface roughness pattern became quite random and very pronounced in the downstream turbulent boundary-layer region. Both real-time X-ray radiography and ultrasonic pulse-echo techniques were used to determine the instantaneous web thickness burned and instantaneous solid-fuel regression rates over certain portions of the fuel slabs. Globally averaged and axially dependent but time-averaged regression rates were also obtained and presented.

Chiaverini, Martin J.↗

Understanding the morphology and chemical activity of model ZrO x /Au (111) catalysts for CO 2 hydrogenation

In this study, the growth of ZrO x on Au (111) was investigated using scanning tunneling microscopy (STM) and synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS). Nanostructures of ZrO x (x= 1,2) at the sub-monolayer (≤ 0.3 ML) level were prepared by vapor depositing Zr metal onto Au (111) followed by oxidation with O 2 or CO 2 . At low coverages of the admetal (< 0.05 ML), the formed ZrO x nanostructures were dispersed randomly on the terraces and steps of the Au(111) substrate. Strong oxide-metal interactions prevented the formation of islands of zirconia. The ZrO x nanostructures displayed a reactivity towards CO 2 and H 2 not seen for bulk zirconia. C 1 s AP-XPS results indicated that CO 2 molecules adsorbed on Zr/ZrO x /Au(111) surfaces could undergo partial decomposition on Zr (CO 2 , gas → CO gas + O ads ), or react with oxygen sites from ZrO x to yield carbonates (Zr-CO 3, ads ). Further, after exposing ZrO 2 /Au (111) surfaces to 1:3 mixtures of CO 2 :H 2 , the formation of HCOO, CO 3 , and CH 3 O was detected in AP-XP spectra. These chemical species decomposed at temperatures in the range of 400-600 K, making them possible reaction intermediates for methanol synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electric vehicle fast charging infrastructure planning in urban networks considering daily travel and charging behavior

Electric vehicles are a sustainable substitution to conventional vehicles. This work introduces an integrated framework for urban fast charging infrastructure to address the range anxiety issue. A mesoscopic simulation tool is developed to generate trip trajectories, and simulate charging behavior based on various trip attributes. The resulting charging demand is the key input to a mixed-integer nonlinear program that seeks charging station configuration. The model minimizes the total system cost including charging station and charger installation costs, and charging, queuing, and detouring delays. The problem is solved using a decomposition technique incorporating a commercial solver for small networks, and a heuristic algorithm for large-scale networks, in addition to the Golden Section method. The solution quality and significant superiority in the computational efficiency of the decomposition approach are confirmed in comparison with the implicit enumeration approach. Furthermore, the required infrastructure to support urban trips is explored for future market shares and technologies.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Composition-Preserving Extraction and Characterization of Biomass Extrinsic and Intrinsic Inorganic Compounds

The inorganic content of biomass impairs size reduction tool life and the conversion process. Conventional ash extraction relies on furnace combustion that inevitably alters the inorganic compounds due to oxidation and decomposition. This study developed composition-preserving methods for extracting and analyzing extrinsic and intrinsic inorganic compounds. Comprehensive characterization was carried out on selected biomass feedstocks, including corn stover, pine residue, and pine anatomical fractions, to reveal their inorganic species and morphology. The extrinsic inorganic compounds were found to be dominated by quartz, along with other minor minerals, such as albite, microcline, and gehlenite, and have particle sizes ranging from tens to hundreds of micrometers. Among the pine anatomical fractions, the needles contain the highest intrinsic silicon content while the bark trapped the most extrinsic minerals. By correlation of the total ash and extrinsic inorganic contents to the wear behavior, both the extrinsic and intrinsic inorganic compounds were concluded to have made significant contributions to the wear process. Finally, the results here validated a new approach to characterize inorganic compounds in biomass and provided fundamental insights for their potential impact on preprocessing tool wear.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deposit formation in hydrocarbon rocket fuels

An experimental program was conducted to study deposit formation in hydrocarbon fuels under flow conditions that exist in high-pressure, rocket engine cooling systems. A high pressure fuel coking test apparatus was designed and developed and was used to evaluate thermal decomposition (coking) limits and carbon deposition rates in heated copper tubes for two hydrocarbon rocket fuels, RP-1 and commercial-grade propane. Tests were also conducted using JP-7 and chemically-pure propane as being representative of more refined cuts of the baseline fuels. A parametric evaluation of fuel thermal stability was performed at pressures of 136 atm to 340 atm, bulk fuel velocities in the range 6 to 30 m/sec, and tube wall temperatures in the range 422 to 811 K. Results indicated that substantial deposit formation occurs with RP-1 fuel at wall temperatures between 600 and 800 K, with peak deposit formation occurring near 700 K. No improvements were obtained when deoxygenated JP-7 fuel was substituted for RP-1. The carbon deposition rates for the propane fuels were generally higher than those obtained for either of the kerosene fuels at any given wall temperature. There appeared to be little difference between commercial-grade and chemically-pure propane with regard to type and quantity of deposit. Results of tests conducted with RP-1 indicated that the rate of deposit formation increased slightly with pressure over the range 136 atm to 340 atm. Finally, lating the inside wall of the tubes with nickel was found to significantly reduce carbon deposition rates for RP-1 fuel.

Roback, R.↗

Deposit formation in hydrocarbon rocket fuels: Executive summary

An experimental program was conducted to study deposit formation in hydrocarbon fuels under flow conditions that exist in high-pressure, rocket engine cooling systems. A high pressure fuel coking test apparatus was designed and developed and was used to evaluate thermal decomposition (coking) limits and carbon deposition rates in heated copper tubes for two hydrocarbon rocket fuels, RP-1 and commercial-grade propane. Tests were also conducted using JP-7 and chemically-pure propane as being representative of more refined cuts of the baseline fuels. A parametric evaluation of fuel thermal stability was performed at pressures of 136 atm to 340 atm, bulk fuel velocities in the range 6 to 30 m/sec, and tube wall temperatures in the range 422 to 811K. In addition, the effect of the inside wall material on deposit formation was evaluated in selected tests which were conducted using nickel-plated tubes. The results of the tests indicated that substantial deposit formation occurs with RP-1 fuel at wall temperatures between 600 and 800K, with peak deposit formation occurring near 700K. No improvements were obtained when de-oxygenated JP-7 fuel was substituted for RP-1. The carbon deposition rates for the propane fuels were generally higher than those obtained for either of the kerosene fuels at any given wall temperature. There appeared to be little difference between commercial-grade and chemically-pure propane with regard to type and quantity of deposit. The results of tests conducted with RP-1 indicated that the rate of deposit formation increased slightly with pressure over the range 136 atm to 340 atm. Finally, plating the inside wall of the tubes with nickel was found to significantly reduce carbon deposition rates for RP-1 fuel.

Roback, R.↗

A Model of Reduced Kinetics for Alkane Oxidation Using Constituents and Species for N-Heptane

The reduction of elementary or skeletal oxidation kinetics to a subgroup of tractable reactions for inclusion in turbulent combustion codes has been the subject of numerous studies. The skeletal mechanism is obtained from the elementary mechanism by removing from it reactions that are considered negligible for the intent of the specific study considered. As of now, there are many chemical reduction methodologies. A methodology for deriving a reduced kinetic mechanism for alkane oxidation is described and applied to n-heptane. The model is based on partitioning the species of the skeletal kinetic mechanism into lights, defined as those having a carbon number smaller than 3, and heavies, which are the complement of the species ensemble. For modeling purposes, the heavy species are mathematically decomposed into constituents, which are similar but not identical to groups in the group additivity theory. From analysis of the LLNL (Lawrence Livermore National Laboratory) skeletal mechanism in conjunction with CHEMKIN II, it is shown that a similarity variable can be formed such that the appropriately non-dimensionalized global constituent molar density exhibits a self-similar behavior over a very wide range of equivalence ratios, initial pressures and initial temperatures that is of interest for predicting n-heptane oxidation. Furthermore, the oxygen and water molar densities are shown to display a quasi-linear behavior with respect to the similarity variable. The light species ensemble is partitioned into quasi-steady and unsteady species. The reduced model is based on concepts consistent with those of Large Eddy Simulation (LES) in which functional forms are used to replace the small scales eliminated through filtering of the governing equations; in LES, these small scales are unimportant as far as the overwhelming part of dynamic energy is concerned. Here, the scales thought unimportant for recovering the thermodynamic energy are removed. The concept is tested by using tabular information from the LLNL skeletal mechanism in conjunction with CHEMKIN II utilized as surrogate ideal functions replacing the necessary functional forms. The test reveals that the similarity concept is indeed justified and that the combustion temperature is well predicted, but that the ignition time is over-predicted, a fact traced to neglecting a detailed description of the processes leading to the heavies chemical decomposition. To palliate this deficiency, functional modeling is incorporated into this conceptual reduction in addition to the modeling the evolution of the global constituent molar density, the enthalpy evolution of the heavies, the contribution to the reaction rate of the unsteady lights from other light species and from the heavies, the molar density evolution of oxygen and water, and the mole fractions of the quasisteady light species. The model is compact in that there are only nine species-related progress variables. Results are presented showing the performance of the model for predicting the temperature and species evolution. The model reproduces the ignition time over a wide range of equivalence ratios, initial pressure, and initial temperature.

Harstad, Kenneth G.↗

Linear two-pool models are insufficient to infer soil organic matter decomposition temperature sensitivity from incubations

Abstract Terrestrial carbon (C)-climate feedbacks depend strongly on how soil organic matter (SOM) decomposition responds to temperature. This dependency is often represented in land models by the parameter Q 10 , which quantifies the relative increase of microbial soil respiration per 10 °C temperature increase. Many studies have conducted paired laboratory soil incubations and inferred “active” and “slow” pool Q 10 values by fitting linear two-pool models to measured respiration time series. Using a recently published incubation study (Qin et al. in Sci Adv 5(7):eaau1218, 2019) as an example, here we first show that the very high parametric equifinality of the linear two-pool models may render such incubation-based Q 10 estimates unreliable. In particular, we show that, accompanied by the uncertain initial active pool size, the slow pool Q 10 can span a very wide range, including values as high as 100, although all parameter combinations are producing almost equally good model fit with respect to the observations. This result is robust whether or not interactions between the active and slow pools are considered (typically these interactions are not considered when interpreting incubation data, but are part of the predictive soil carbon models). This very large parametric equifinality in the context of interpreting incubation data is consistent with the poor temporal extrapolation capability of linear multi-pool models identified in recent studies. Next, using a microbe-explicit SOM model (RESOM), we show that the inferred two pools and their associated parameters (e.g., Q 10 ) could be artificial constructs and are therefore unreliable concepts for integration into predictive models. We finally discuss uncertainties in applying linear two-pool (or more generally multiple-pool) models to estimate SOM decomposition parameters such as temperature sensitivities from laboratory incubations. We also propose new observations and model structures that could enable better process understanding and more robust predictive capabilities of soil carbon dynamics.

54 ENVIRONMENTAL SCIENCES↗

Photoionization mass spectrometric measurements of initial reaction pathways in low-temperature oxidation of 2,5-dimethylhexane

The product formation from R + O 2 reactions relevant to low-temperature autoignition chemistry was studied for 2,5-dimethylhexane, a symmetrically branched octane isomer, at 550 and 650 K using Cl-atom initiated oxidation and multiplexed photoionization mass spectrometry (MPIMS). The interpretation of time- and photon-energy-resolved mass spectra led to three specific results important to characterizing the initial oxidation steps: (1) quantified isomer-resolved branching ratios for HO 2 + alkene channels; (2) 2,2,5,5-tetramethyltetrahydrofuran is formed in substantial yield from addition of O 2 to tertiary 2,5-dimethylhex-2-yl followed by isomerization of the resulting ROO adduct to tertiary hydroperoxyalkyl (QOOH) and exhibits a positive dependence on temperature over the range covered leading to a higher flux relative to aggregate cyclic ether yield. The higher relative flux is explained by a 1,5-hydrogen atom shift reaction that converts the initial primary alkyl radical (2,5-dimethylhex-1-yl) to the tertiary alkyl radical 2,5-dimethylhex-2-yl, providing an additional source of tertiary alkyl radicals. Furthermore, quantum-chemical and master-equation calculations of the unimolecular decomposition of the primary alkyl radical reveal that isomerization to the tertiary alkyl radical is the most favorable pathway, and is favored over O 2 -addition at 650 K under the conditions herein. The isomerization pathway to tertiary alkyl radicals therefore contributes an additional mechanism to 2,2,5,5-tetramethyltetrahydrofuran formation; (3) carbonyl species (acetone, propanal, and methylpropanal) consistent with β-scission of QOOH radicals were formed in significant yield, indicating unimolecular QOOH decomposition into carbonyl + alkene + OH.

2,2,5,5-tetramethyl-tetrahydrofuran↗

Infrared spectral signatures of interfacial water at TiO 2 –electrolyte interfaces from deep potential molecular dynamics

Vibrational spectroscopy is a powerful tool for probing water at oxide–electrolyte interfaces, but its molecular interpretation can be challenging. Here, we employ deep potential long-range molecular dynamics simulations with layer-resolved spectral analysis to investigate the microscopic origins of the infrared (IR) response of water at the interface with anatase TiO 2 (101), a prototypical oxide surface. The calculated interfacial spectra exhibit characteristic modifications compared to bulk water IR spectra, including enhanced intensities, a red shifted and broadened stretching band, and a higher-frequency shoulder, in qualitative agreement with experiments. Spectral decomposition shows that these signatures originate mainly from the first interfacial water layer, dominated by surface-bound H 2 O at Ti 5C sites, with secondary contributions from the second layer. A moderate salt concentration (0.4 M NaCl) leaves both the interfacial structure and the spectra essentially unchanged, while tuning the pH strongly modulates the spectral intensity. We establish a scaling relation linking the spectral intensity to the surface water dissociation fraction and the dipole moment, both governed by interfacial electric fields. These findings provide a microscopic framework for interpreting IR spectra of oxide–electrolyte interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interdiffusion at Room Temperature in Cu-Ni(Fe) Nanolaminates

The decomposition of a one-dimensional composition wave in Cu-Ni(Fe) nanolaminate structures is quantified using X-ray diffraction to assess kinetics of the interdiffusion process for samples aged at room temperature for 30 years. Definitive evidence for growth to the composition modulation within the chemical spinodal is found through measurement of a negative interdiffusivity for each of sixteen different nanolaminate samples over a composition wavelength range of 2.1–10.6 nm. A diffusivity value D of 1.77 × 10 -24 cm 2 ·s -1 is determined for the Cu-Ni(Fe) alloy system, perhaps the first such measurement at a ratio of melt temperature to test temperature that is greater than 5. The anomalously high diffusivity value with respect to bulk diffusion is attributed to the nanolaminate structure that features paths for short-circuit diffusion through interlayer grain boundaries.

36 MATERIALS SCIENCE↗

Shock-tube study of carbon monoxide dissociation kinetics

Carbon monoxide dissociation-rate data were obtained over the temperature range 5600-12,000 K. The experiments were conducted with undiluted CO to emphasize rate constants applicable to molecular gas systems. Data were obtained as time-resolved pressure measurements on the end wall of a shock tube and, in some cases, as emission histories of the C2 Swan system (0-0 band) behind incident shock waves. Results confirm the presence of C2 as an intermediate species in CO decomposition.

Hanson, R. K.↗

A polyoxometalate flow battery

A redox flow battery utilizing two, three-electron polyoxometalate redox couples (SiV V 3 W VI 9 O 40 7– /SiV IV 3 W VI 9 O 40 10- and SiV IV 3 W VI 9 O 40 10- /SiV IV 3 W V 3 W VI 6 O 40 13- ) was investigated for use in stationary storage in either aqueous or non-aqueous conditions. The aqueous battery had coulombic efficiencies greater than 95% with relatively low capacity fading over 100 cycles. Infrared studies showed there was no decomposition of the compound under these conditions. The non-aqueous analog had a higher operating voltage but at the expense of coulombic efficiency. The spontaneous formation of these clusters by self-assembly facilitates recovery of the battery after being subjected to reversed polarity. Polyoxometalates offer a new approach to stationary storage materials because they are capable of undergoing multi-electron reactions and are stable over a wide range of pH values and temperatures.

25 ENERGY STORAGE↗

A Facile Molecular Precursor Route to Metal Phosphide Nanoparticles and Their Evaluation as Hydrodeoxygenation Catalysts

Metal phosphides have been identified as a promising class of materials for the catalytic upgrading of bio-oils, which are renewable and potentially inexpensive sources for liquid fuels. Herein, we report the facile synthesis of a series of solid, phase-pure metal phosphide nanoparticles (NPs) (Ni 2 P, Rh 2 P, and Pd 3 P) utilizing commercially available, air-stable metal–phosphine complexes in a one-pot reaction. This single-source molecular precursor route provides an alternative method to access metal phosphide NPs with controlled phases and without the formation of metal NP intermediates that can lead to hollow particles. The formation of the Ni 2 P NPs was shown to proceed through an amorphous Ni–P intermediate, leading to the desired NP morphology and metal-rich phase. This low-temperature, rapid route to well-defined metal NPs is expected to have broad applicability to a variety of readily available or easily synthesized metal–phosphine complexes with high decomposition temperatures. Hydrodeoxygenation of acetic acid, an abundant bio-oil component, was performed to investigate H 2 activation and deoxygenation pathways under conditions that are relevant to ex situ catalytic fast pyrolysis (high temperatures, low pressures, and near-stoichiometric H 2 concentrations). The catalytic performance of the silica-supported metal phosphide NPs was compared to the analogous incipient wetness (IW) metal and metal phosphide catalysts over the range 200–500 °C. Decarbonylation was the primary pathway for H 2 incorporation in the presence of all of the catalysts except NP-Pd 3 P, which exhibited minimal productive activity, and IW-Ni, which evolved H 2 . The highly controlled NP-Ni2P and NP-Rh2P catalysts, which were stable under these conditions, behaved comparably to the IW-metal phosphides, with a slight shift to higher product onset temperatures, likely due to the presence of surface ligands. Most importantly, the NP-Ni 2 P catalyst exhibited H 2 activation and incorporation, in contrast to IW-Ni, indicating that the behavior of the metal phosphide is significantly different from that of the parent metal, and more closely resembles that of noble metal catalysts.

09 BIOMASS FUELS↗