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At least 361 records · Page 20

Branched Bio-Lubricant Base Oil Production through Aldol Condensation

Currently, lubricant base oils are derived from petroleum, a nonrenewable feedstock that contributes to greenhouse gas emissions. Bioderived, renewable lubricant base oils can mitigate environmental challenges and offer superior cold flow properties by incorporating branches to the base oil's hydrocarbon backbone with an appropriate synthetic strategy. A strategy was developed to synthesize branched alkanes for lubricant base oil in two steps from 12-tricosanone, obtained from bioderived fatty acids, and furfural, obtained from lignocellulosic biomass. The reaction pathway involves carbon–carbon coupling through aldol condensation followed by hydrodeoxygenation (HDO). Various solvents (non-polar, aprotic and polar, protic) and reaction conditions were screened to achieve a maximum yield of 94.3% of aldol condensation products, containing the majority of a C 33 furan (79.5%) followed by a C 28 furan (14.8%). Subsequent HDO of aldol condensation products over an Ir-ReO x /SiO 2 catalyst produced lubricant-ranged branched alkanes (C 28 and C 33 ) with 61.4% yield and small fractions (<11%) of alkanes with carbon numbers between C 15 and C 10 . The viscous properties of the produced bio-lubricant base oil were comparable to commercial petroleum-derived Group III and Group IV base oils. Overall, this approach serves as a potential stepping-stone to replace petroleumderived base oils and, in turn, reduce greenhouse gas emissions associated with current lubricant production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogenolysis of Poly(Ethylene–co–Vinyl Alcohol) and Related Polymer Blends over Ruthenium Heterogeneous Catalysts

The hydrogenolysis of polymers is emerging as a promising approach to deconstruct plastic waste into valuable chemicals. Yet, the complexity of plastic waste, including multilayer packaging, is a significant barrier to handling realistic waste streams. Herein, we reveal fundamental insights into a new chemical route for transforming a previously unaddressed fraction of plastic waste – poly(ethylene–co­­–vinyl alcohol) (EVOH) and related polymer blends – into alkane products. Additionally, we report that Ru/ZrO2 is active for the concurrent hydrogenolysis, hydrogenation, and hydrodeoxygenation of EVOH and its thermal degradation products into alkanes (C1–C35) and water. Detailed reaction data, product analysis, and catalyst characterization reveal that the in–situ thermal degradation of EVOH forms aromatic intermediates that are detrimental to catalytic activity. Increased hydrogen pressure promotes hydrogenation of these aromatics, preventing catalyst deactivation and improving alkane product yields. Calculated apparent rates of C–C scission reveal that the hydrogenolysis of EVOH is slower than low–density polyethylene. We apply these findings to achieve hydrogenolysis of EVOH/polyethylene blends and elucidate the sensitivity of hydrogenolysis catalysts to such blends. Overall, we demonstrate progress towards efficient catalytic processes for the hydroconversion of waste multilayer film plastic packaging into valuable products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reactivity of novel high-performance fuels on commercial three-way catalysts for control of emissions from spark-ignition engines

The Department of Energy “Co-Optimization of Fuels and Engines” initiative aims to simultaneously develop novel high-performance fuels with advanced engine designs to reduce petroleum consumption. To achieve commercialization, advanced engines running on alternative fuels still must meet emissions regulations. Warm three-way catalysts (TWC) are very effective at meeting the stringent emissions regulations on pollutants such as nitrogen oxides (NOx), non-methane organic gases (NMOG) and carbon monoxide (CO) from gasoline-fueled spark-ignition (SI) engines operating under stoichiometric conditions; thus, most SI engine emissions occur during cold-start, when the TWC has not yet achieved light-off. In the current study, the light-off behavior of novel high-performance fuel candidates has been investigated on a hydrothermally-aged commercial TWC using a synthetic engine-exhaust flow reactor system according to industry guidelines. Over 30 potential fuel components were examined in this study, including alkanes, alkenes, alcohols, ketones, esters, aromatic ethers, and non-oxygenated aromatic hydrocarbons. Short-chain acyclic oxygenates, including alcohols, ketones, and esters, tended to light off at relatively low temperatures, while alkenes, aromatics, and cyclic oxygenates tended to light off at relatively high temperatures. The light-off behavior of alkanes and alkenes depended strongly on their size and structure. In terms of the influence on CO light-off on the TWC, the fuels fell into two distinct categories: (i) non-inhibiting species including C 2 -C 3 alcohols, alkanes, acyclic ketones, and esters; and (ii) inhibiting species including alkenes, aromatic hydrocarbons, cyclic oxygenates, and C 4 alcohols.

33 ADVANCED PROPULSION SYSTEMS↗

Air quality impacts from the development of unconventional oil and gas well pads: Air toxics and other volatile organic compounds

Unconventional oil and natural gas development (UOGD) has expanded rapidly across the United States in recent decades and raised concerns about associated air quality impacts. While significant effort has been made to quantify methane emissions, relatively few observations have been made of Volatile Organic Compounds (VOCs), especially during drilling and completion of new wells. Extensive air monitoring during development of several large, multi-well pads in Broomfield, Colorado, in the Denver-Julesburg Basin, provides a novel opportunity to examine changes in local air toxics and other VOC concentrations during well drilling and completions and production. These operations offer an especially useful case to study as several management practices were implemented to reduce emissions (e.g., electrified, grid-powered drill rigs and closed loop fluid handling systems to reduce truck traffic and limit fluid handling on the pad). With simultaneous measurements of methane and 50 VOCs from October 2018 to December 2022 at as many as 19 sites near well pads, in adjacent neighborhoods, and at a more distant reference location, we identify impacts from each phase of well development and production. Use of weekly, time-integrated canisters, a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous photoionization detectors (PID) to trigger canister collection upon detection of VOC-rich plumes, and an instrumented vehicle, provided a powerful suite of measurements to characterize both transient plumes and longer-term changes in air quality. Prior to the start of well development, VOC gradients were small across Broomfield. Once drilling commenced, concentrations of oil and gas (O&G) related VOCs, including alkanes and aromatics, increased around active well pads. Concentration increases were clearly apparent during certain operations, including drilling, coil tubing/millout operations, and production tubing installation. Emissions of C 8 –C 10 n-alkanes during drilling operations highlighted the importance of VOC emissions from synthetic drilling mud chosen to reduce odor impacts. More than 90 samples were collected of transient plumes. Using composition measurements, meteorological data, and information about well pad activities, these plumes were connected with specific UOGD operations including drilling, flowback, and production equipment maintenance. The chemical signatures of these plumes differed by operation type (e.g., C 8 –C 10 n-alkanes constituted a larger fraction of measured VOCs in drilling-related plumes). Concentrations of individual, oil and gas-related VOCs in these plumes were often several orders of magnitude higher than in background air, with maximum ethane and benzene concentrations of 79,600 and 819 ppbv, respectively. Because these plumes typically impact a monitoring site for just several minutes, they are easily missed by slower-responding instruments. Study measurements highlight future emission mitigation opportunities during UOGD operations, including better control of emissions from shakers that separate drill cuttings from drilling mud, production separator maintenance operations, and periodic emptying of sand cans during flowback operations.

54 ENVIRONMENTAL SCIENCES↗

Structural evolutions of small aromatic mixtures under extreme temperature conditions: Insights from ReaxFF molecular dynamics investigations

Conversion mechanisms of carbonaceous materials during controlled pyrolysis under high temperature currently rely on empirical understanding, rather than a detailed atomistic description of the underlying chemical evolution. Here in this work, a series of molecular dynamics simulations, based on reactive force fields, were performed to probe the structural evolutions of small aromatic (number of aromatic rings ≤4) mixtures under extreme conditions (temperature 3000–4000 K). For any temperature studied and independent of the presence of alkane radicals, three major gas-phase byproducts, H 2 , C 2 H 2 , and C 2 H 4 , were found in bulk treated by rapid heating. Temperatures as well as alkane addition can affect the production/consumption rates and fractionation of these gas species. Compared to alkane radicals, temperatures also play important roles in modulating the initial growth pathways of solid carbon clusters. At 3000 K, aromatic carbon cluster formation is mainly initiated through the direct combination of aryl radicals. Conversely, at 4000K, carbon cluster formation is initiated by the assembly of chained radicals, since substantial polyacetylenic chains were produced. Through cross comparison on different simulation models/methods, as well as with experiments, the effect of processing conditions on carbonaceous materials conversion was revealed, and underlying mechanisms responsible for the observed phenomena are proposed.

36 MATERIALS SCIENCE↗

Towards improved conversion of wet waste to jet fuel with atomic layer deposition-coated hydrodeoxygenation catalysts

The conversion of wet waste-derived volatile fatty acids into jet fuel-range hydrocarbons is a promising route for increasing the production of sustainable aviation fuel; however, the cost and moderate alkane selectivity of Pt-based hydrodeoxygenation catalysts present challenges for commercialization. Here, to address this, we used atomic layer deposition to apply TiO 2 overcoats to Pt/Al 2 O 3 catalysts and create new interface sites that exhibited 8 times higher site time yield of the desirable n-alkane product than uncoated catalyst. Through TPR/TPD, XPS, CO DRIFTS, and DFT calculations, we found that the increased selectivity of the ALD-coated catalyst was due to the creation of O vacancies at the Pt-TiO 2 interface under reducing conditions, resulting in new Ti 3+ acid sites near the active metal. Maximum conversion and alkane selectivity during HDO was achieved with an ALD-coated 0.5% wt Pt catalyst, indicating that TiO 2 ALD can be used to maximize the utility of precious-metal catalysts.

09 BIOMASS FUELS↗

Equilibrium carbon isotope fractionation factors of hydrocarbons: Semi-empirical force-field method

Here, we have calculated the reduced partition function ratios for carbon isotopes (β-factor) of 67 hydrocarbons (alkanes, alkenes, alkynes, cycloalkanes, and aromatics), including their 267 single-substituted isotopomers. The calculations were performed using the harmonic oscillator – rigid rotator model and the Urey / Bigeleisen-Mayer approach. Normal frequencies of molecular vibrations of the isotopologues were calculated from the molecular structures data and valence field force constants stored in the Light-handled Elucidation of Vibrations (LEV) database elaborated by Dr. Gribov and his colleagues in Russia. The LEV database is constructed from experimental spectroscopic and structural data by solving inverse problems of molecular vibrations. The LEV is internally consistent and the most comprehensive database available to date. The β-factor were calculated in the temperature range of 200–800 K with a 10 K step. Our calculations predict that the β-factors increase with an increasing number of C atoms within the same groups of hydrocarbons (e.g., alkanes). Our calculations also show a general descending order of 13 C enrichments among the different groups of hydrocarbons: cycloalkanes, aromatics, alkenes (double bonds) and isoalkanes, alkanes, alkynes (triple bonds). Position-specific, intramolecular isotope effects within hydrocarbons are determined by the β-factors of C in the different functional groups in the order: quaternary (C), tertiary (methine, CH), secondary (methylene, CH 2 ), primary (methyl, CH 3 ) and double bond (C=C), saturated bond (C - C), triple bond (HC≡). Our calculations on bulk and position-specific carbon isotope β-factors of the hydrocarbons, which are generally consistent with very limited ab initio calculations in the literature, are internally consistent and the most comprehensive to date for future applications to position-specific isotope geochemistry of hydrocarbons.

58 GEOSCIENCES↗

Solvent-pore interactions in the Eagle Ford shale formation

In this work, the effect of solvent extraction on pore space was examined on a suite of samples from the Eagle Ford Shale Formation with varying lithologies and maturities. Several solvents -toluene, cyclohexane, methanol, dichloromethane, and hydrochloric acid- were contacted with shale samples, extracting the compatible organic matter. The porosity in these extracted shale samples was compared to unmodified samples. The amount and type of organic matter extracted were determined using Gas Chromatography - Mass Spectrometry, and the porosity was determined by (Ultra) Small Angle Neutron Scattering. Mostly alkanes and aromatics were detected in the extracts, but other portions of bitumen may also have been present. Only higher molecular weight alkanes were extracted with hydrochloric acid, suggesting that physical dissolution of carbonate minerals may have liberated this portion of organic matter and the solvent was not able to penetrate the bitumen and kerogen to extract the lower molecular weight alkanes. Lastly, a decrease in porosity with extraction was observed and attributed to a dominant mechanism of kerogen swelling due to kerogen-solvent interaction.

02 PETROLEUM↗

Polypropylene Degradation Catalyzed by Tantalum Hydrides Supported on Sulfated Alumina

Ta–H + sites supported on sulfated aluminum oxide (SAO), [Ta(H) 2 (O–) 2 ][SAO] (1), catalyze the hydrogenolysis of isotactic polypropylene (iPP, M n = 13.3 kDa; D = 2.4; mmmm = 94%) to form low-molecular-weight branched alkanes (C 11 –C 30 ) in good yields (70%). Here, the alkanes formed lose stereochemical information originating from iPP, but residual iPP remains highly isotactic. In the presence of D 2 , similar mixtures of alkanes are formed containing –CH 3–x D x , –CHD, and –CD–. Residual iPP maintains high tacticity and incorporates deuterium primarily into –CH 3 groups of the polymer (–CH 3–x D x /–CHD–/–CD– ~10:1:0). 1 reacts with pinacolborane to form [TaH(κ 2 -H 2 BPin)(O–) 2 ][SAO] (2). At 200 °C in an iPP melt, 2 reacts to form products indicative of C–H bond activation at –CH 3 groups and internal –CH 2 – groups in iPP in a ~1:3 ratio, indicating a slight kinetic preference for C–H bond activation at internal –CH 2 – groups. 1 is more reactive toward iPP than high-density polyethylene in hydrogenolysis reactions

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Monitoring Stray Natural Gas in Groundwater With Dissolved Nitrogen. An Example From Parker County, Texas

Abstract Concern that hydraulic fracturing and natural gas production contaminates groundwater requires techniques to attribute and estimate methane flux. Although dissolved alkane and noble gas chemistry may distinguish thermogenic and microbial methane, low solubility and concentration of methane in atmosphere‐equilibrated groundwater precludes the use of methane to differentiate locations affected by high and low flux of stray methane. We present a method to estimate stray gas infiltration into groundwater using dissolved nitrogen. Due to the high concentration of nitrogen in atmospheric‐recharged groundwater and low concentration in natural gas, dissolved nitrogen in groundwater is much less sensitive to change than dissolved methane and may differentiate groundwater affected high and low flux of stray natural gas. We report alkane and nitrogen chemistry from shallow groundwater wells and eight natural gas production wells in the Barnett Shale footprint to attribute methane and estimate mixing ratios of thermogenic natural gas to groundwater. Most groundwater wells have trace to nondetect concentrations of methane. A cluster of groundwater wells have greater than 10 mg/L dissolved methane concentrations with alkane chemistries similar to natural gas from the Barnett Shale and/or shallower Strawn Group suggesting that localized migration of natural gas occurred. Two‐component mixing models constructed with dissolved nitrogen concentrations and isotope values identify three wells that were likely affected by a large influx of natural gas with gas:water mixing ratios approaching 1:5. Most groundwater wells, even those with greater than 10‐mg/L methane, have dissolved nitrogen chemistry typical of atmosphere‐equilibrated groundwater suggesting natural gas:water mixing ratios smaller than 1:20.

Larson, Toti E.↗

Adsorption in zeolites using mechanically embedded ONIOM clusters

Here, we have explored mechanically embedded three-layer QM/QM/MM ONIOM models for computational studies of binding in Al-substituted zeolites. In all the models considered, the high-level-theory layer consists of the adsorbate molecule and of the framework atoms within the first two coordination spheres of the Al atom and is treated at the M06-2X/6-311G(2df,p) level. For simplicity, flexibility and routine applicability, the outer, low-level-theory layer is treated with the UFF. We have modelled the intermediate-level layer quantum mechanically and investigated the performance of HF theory and of three DFT functionals, B3LYP, M06-2X and ωB97x-D, for different layer sizes and various basis sets, with and without BSSE corrections. We have studied the binding of sixteen probe molecules in H-MFI and compared the computed adsorption enthalpies with published experimental data. We have demonstrated that HF and B3LYP are inadequate for the description of the interactions between the probe molecules and the framework surrounding the metal site of the zeolite on account of their inability to capture dispersion forces. Both M06-2X and ωB97x-D on average converge within ca. 10% of the experimental values. We have further demonstrated transferability of the approach by computing the binding enthalpies of n-alkanes (C1–C8) in H-MFI, H-BEA and H-FAU, with very satisfactory agreement with experiment. The computed entropies of adsorption of n-alkanes in H-MFI are also found to be in good agreement with experimental data. Finally, we compare with published adsorption energies calculated by periodic-DFT for n-C3 to n-C6 alkanes, water and methanol in H-ZSM-5 and find very good agreement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Accessing metal-specific orbital interactions in C–H activation with resonant inelastic X-ray scattering

Photochemically prepared transition-metal complexes are known to be effective at cleaving the strong C–H bonds of organic molecules in room temperature solutions. There is also ample theoretical evidence that the two-way, metal to ligand (MLCT) and ligand to metal (LMCT), charge-transfer between an incoming alkane C–H group and the transition metal is the decisive interaction in the C–H activation reaction. What is missing, however, are experimental methods to directly probe these interactions in order to reveal what determines reactivity of intermediates and the rate of the reaction. Here, using quantum chemical simulations we predict and propose future time-resolved valence-to-core resonant inelastic X-ray scattering (VtC-RIXS) experiments at the transition metal L-edge as a method to provide a full account of the evolution of metal–alkane interactions during transition-metal mediated C–H activation reactions. For the model system cyclopentadienyl rhodium dicarbonyl (CpRh(CO) 2 ), we demonstrate, by simulating the VtC-RIXS signatures of key intermediates in the C–H activation pathway, how the Rh-centered valence-excited states accessible through VtC-RIXS directly reflect changes in donation and back-donation between the alkane C–H group and the transition metal as the reaction proceeds via those intermediates. We benchmark and validate our quantum chemical simulations against experimental steady-state measurements of CpRh(CO) 2 and Rh(acac)(CO)2 (where acac is acetylacetonate). Our study constitutes the first step towards establishing VtC-RIXS as a new experimental observable for probing reactivity of C–H activation reactions. More generally, the study further motivates the use of time-resolved VtC-RIXS to follow the valence electronic structure evolution along photochemical, photoinitiated and photocatalytic reactions with transition metal complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Volatility characterization of nanoparticles from single and dual-fuel low temperature combustion in compression ignition engines

Our work explores the volatility of particles produced from two diesel low temperature combustion (LTC) modes proposed for high-efficiency compression ignition engines. It also explores mechanisms of particulate formation and growth upon dilution in the near-tailpipe environment. Moreover, the number distribution of exhaust particles from low- and mid-load dual-fuel reactivity controlled compression ignition (RCCI) and single-fuel premixed charge compression ignition (PPCI) modes were experimentally studied over a gradient of dilution temperature. Particle volatility of select particle diameters was investigated using volatility tandem differential mobility analysis (V-TDMA). Evaporation rates for exhaust particles were compared with V-TDMA results for candidate pure n-alkanes to identify species with similar volatility characteristics. The results show that LTC particles are mostly comprised of material with volatility similar to engine oil alkanes. V-TDMA results were used as inputs to an aerosol condensation and evaporation model to support the finding that smaller particles in the distribution are comprised of lower volatility material than large particles under primary dilution conditions. Although the results show that saturation levels are high enough to drive condensation of alkanes onto existing particles under the dilution conditions investigated, they are not high We conclude that observed particles from LTC operation must grow from low concentrations of highly non-volatile compounds present in the exhaust.

33 ADVANCED PROPULSION SYSTEMS↗

A 4 U laser heterodyne radiometer for methane (CH 4 ) and carbon dioxide (CO 2 ) measurements from an occultation-viewing CubeSat

An experimental and kinetic modeling study of the autoignition of 3-methylheptane, a compound representative of the high molecular weight lightly branched alkanes found in large quantities in conventional and synthetic aviation kerosene and diesel fuels, is reported. Shock tube and rapid compression machine ignition delay time measurements are reported over a wide range of conditions of relevance to combustion engine applications: temperatures from 678 to 1356 K; pressures of 6.5, 10, 20, and 50 atm; and equivalence ratios of 0.5, 1.0, and 2.0. The wide range of temperatures examined provides observation of autoignition in three reactivity regimes, including the negative temperature coefficient (NTC) regime characteristic of paraffinic fuels. Comparisons made between the current ignition delay measurements for 3-methylheptane and previous results for n-octane and 2-methylheptane quantifies the influence of a single methyl substitution and its location on the reactivity of alkanes. It is found that the three C8 alkane isomers have indistinguishable high-temperature ignition delay but their ignition delay times deviate in the NTC and low-temperature regimes in correlation with their research octane numbers. The experimental results are compared with the predictions of a proposed kinetic model that includes both high- and low-temperature oxidation chemistry. The model mechanistically explains the differences in reactivity for n-octane, 2-methylheptane, and 3-methylheptane in the NTC through the influence of the methyl substitution on the rates of isomerization reactions in the low-temperature chain branching pathway, that ultimately leads to ketohydroperoxide species, and the competition between low-temperature chain branching and the formation of cyclic ethers, in a chain propagating pathway.

3-Methylheptane↗

Novel, active, and uncultured hydrocarbon-degrading microbes in the ocean

ABSTRACT Given the vast quantity of oil and gas input to the marine environment annually, hydrocarbon degradation by marine microorganisms is an essential ecosystem service. Linkages between taxonomy and hydrocarbon degradation capabilities are largely based on cultivation studies, leaving a knowledge gap regarding the intrinsic ability of uncultured marine microbes to degrade hydrocarbons. To address this knowledge gap, metagenomic sequence data from the Deepwater Horizon (DWH) oil spill deep-sea plume was assembled to which metagenomic and metatranscriptomic reads were mapped. Assembly and binning produced new DWH metagenome-assembled genomes that were evaluated along with their close relatives, all of which are from the marine environment (38 total). These analyses revealed globally distributed hydrocarbon-degrading microbes with clade-specific substrate degradation potentials that have not been reported previously. For example, methane oxidation capabilities were identified in all Cycloclasticus . Furthermore, all Bermanella encoded and expressed genes for non-gaseous n -alkane degradation; however, DWH Bermanella encoded alkane hydroxylase, not alkane 1-monooxygenase. All but one previously unrecognized DWH plume member in the SAR324 and UBA11654 have the capacity for aromatic hydrocarbon degradation. In contrast, Colwellia were diverse in the hydrocarbon substrates they could degrade. All clades encoded nutrient acquisition strategies and response to cold temperatures, while sensory and acquisition capabilities were clade specific. These novel insights regarding hydrocarbon degradation by uncultured planktonic microbes provides missing data, allowing for better prediction of the fate of oil and gas when hydrocarbons are input to the ocean, leading to a greater understanding of the ecological consequences to the marine environment. IMPORTANCE Microbial degradation of hydrocarbons is a critically important process promoting ecosystem health, yet much of what is known about this process is based on physiological experiments with a few hydrocarbon substrates and cultured microbes. Thus, the ability to degrade the diversity of hydrocarbons that comprise oil and gas by microbes in the environment, particularly in the ocean, is not well characterized. Therefore, this study aimed to utilize non-cultivation-based ‘omics data to explore novel genomes of uncultured marine microbes involved in degradation of oil and gas. Analyses of newly assembled metagenomic data and previously existing genomes from other marine data sets, with metagenomic and metatranscriptomic read recruitment, revealed globally distributed hydrocarbon-degrading marine microbes with clade-specific substrate degradation potentials that have not been previously reported. This new understanding of oil and gas degradation by uncultured marine microbes suggested that the global ocean harbors a diversity of hydrocarbon-degrading bacteria, which can act as primary agents regulating ecosystem health.

Howe, Kathryn L.↗

Higher Energy-Content Jet Blending Components Derived from Ethanol (CRADA 467)

This project aims to develop a new sustainable aviation fuel (SAF) that comprises favorable properties, such as high energy density, excellent thermal stability, and favorable cold fold properties. Through catalyst development, this work will provide a route to control the cycloalkane/n-alkane/iso alkane content of a next-generation fuel with minimal or no aromatic content. Combining n-alkane and iso-alkane streams (high specific energy, MJ/kg) with cycloalkanes (higher energy density, MJ/L), is expected to enable at least a 4% net increase in combined (specific (MJ/kg) and volumetric (MJ/L)) energy content without impacting ‘drop-in’ fuel requirements, such as seal swelling. PNNL and LanzaTech have already demonstrated a sustainable, non-petroleum, route to isoalkanes. However, economically attractive cycloalkane production from waste and biomass is challenged by large hydrogen requirements, preferential selectivity to aromatic compounds and low yields to jet fuel range components. Many gaps in understanding cycloalkane properties and performance in complex jet fuel mixtures remain. The close tie and integration of Purdue’s fuel property analysis, with PNNL’s process development, can lead to an economically attractive process. The fuel analysis and testing by Purdue will enable a robust understanding of the properties and behavior of the cycloalkanes produced to inform process development. Additionally, seal-swelling analysis will quantify the ability of fuel blends with zero or minimal aromatics content to satisfy the seal swell requirement of O rings. Lastly, Purdue’s system-level analysis will lead to the development of a roadmap for deployment in key regions that considers system pressures such as hydrogen, water, energy efficiency, and ease of infrastructure access.

10 SYNTHETIC FUELS↗

Thermal Scattering Law Data Development for Paraffin Wax

Paraffin wax is often used as a nuclear moderator to slow down the fast neutrons in experimental critical assemblies [1]. It is a colorless and soft solid material that consists primarily of straight-chain alkanes (n-alkanes), which are hydrocarbons with the general formula CnH2n+2 [2-3]. The length of the hydrocarbon chain ranges from C20 to C30 and higher [2]. It is distinguished by its solid state at room temperature and begins to melt above approximately 310 K [4]. Paraffin wax is a commonly employed substance in the manufacture of shielding. One of its noteworthy characteristics is its ability to effectively absorb the neutrons. Also, it possesses a high macroscopic cross section, which enables it to efficiently moderate neutrons. As a result, paraffin wax is extensively utilized in various applications where moderation and shielding of neutrons are needed. For simulations, it is necessary to evaluate its thermal scattering law (TSL) and cross sections. Computationally, classical molecular dynamics (CMD) simulations provide the capability of simulating atomic details. For example, several unary, binary, and few multi component mixtures have been investigated of the paraffin model by using molecular dynamics simulations [5-12]. An assessment of thermal neutron scattering in a heavy paraffinic oil treated both as a solid and a viscous fluid containing 25% linear branched paraffin (C30H62), 35% one ring cycloalkane (C30H60), 15% two rings cycloalkane (C30H58), and 25% aromatic (C30H60) chains has been studied using CMD simulations for producing TSL data [13]. Nevertheless, there is lack of TSL and cross section data for paraffin wax as most of the reported analyses focus on the unary and binary mixture of n-alkanes, which is not consistent with actual paraffin wax [2]. In this work, we applied the equilibrium CMD simulations technique to explore the structure and dynamical properties of wax, which are fundamental input to calculate the TSL. A paraffin wax system was modeled using the CMD code LAMMPS (Large-scale Atomic/Molecular Massively Parallel Simulator) [14-15] with the semi-empirical COMPASS [16] force field. The density of state (DOS) was calculated from the normalized velocity autocorrelation function (VACF), which is the Fourier transform of the normalized VACF. The DOS was used for the calculation of the TSL and thermal scattering cross sections. The paraffin wax atomic system was constructed by using the MedeA material design platform [17], and was benchmarked using available properties (i.e., density, bond lengths, angles, diffusivity, and viscosity).

Nuclear Criticality Safety Program (NCSP)↗

Overview of Diverse Methyl/Alkyl-Coenzyme M Reductases and Considerations for Their Potential Heterologous Expression

Methyl-coenzyme M reductase (MCR) is an archaeal enzyme that catalyzes the final step of methanogenesis and the first step in the anaerobic oxidation of methane, the energy metabolisms of methanogens and anaerobic methanotrophs (ANME), respectively. Variants of MCR, known as alkyl-coenzyme M reductases, are involved in the anaerobic oxidation of short-chain alkanes including ethane, propane, and butane as well as the catabolism of long-chain alkanes from oil reservoirs. MCR is a dimer of heterotrimers (encoded by mcrABG) and requires the nickel-containing tetrapyrrole prosthetic group known as coenzyme F430. MCR houses a series of unusual post-translational modifications within its active site whose identities vary depending on the organism and whose functions remain unclear. Methanogenic MCRs are encoded in a highly conserved mcrBDCGA gene cluster, which encodes two accessory proteins, McrD and McrC, that are believed to be involved in the assembly and activation of MCR, respectively. The requirement of a unique and complex coenzyme, various unusual post-translational modifications, and many remaining questions surrounding assembly and activation of MCR largely limit in vitro experiments to native enzymes with recombinant methods only recently appearing. Production of MCRs in a heterologous host is an important step toward developing optimized biocatalytic systems for methane production as well as for bioconversion of methane and other alkanes into value-added compounds. This review will first summarize MCR catalysis and structure, followed by a discussion of advances and challenges related to the production of diverse MCRs in a heterologous host.

59 BASIC BIOLOGICAL SCIENCES↗