Showing papers by "ExxonMobil published in 2013"

Organic matter–hosted pore system, Marcellus Formation (Devonian), Pennsylvania

Abstract: The Marcellus Formation of Pennsylvania represents an outstanding example of an organic matter (OM)–hosted pore system; most pores detectable by field-emission scanning electron microscopy (FE-SEM) are associated with OM instead of mineral matrix. In the two wells studied here, total organic carbon (TOC) content is a stronger control on OM-hosted porosity than is thermal maturity. The two study wells span a maturity from late wet gas (vitrinite reflectance [Ro], 1.0%) to dry gas (Ro, 2.1%). Samples with a TOC less than 5.5 wt. % display a positive correlation between TOC and porosity, but samples with a TOC greater than 5.5 wt. % display little or no increase in porosity with a further increasing TOC. In a subset of samples (14) across a range of TOC (2.3–13.6 wt. %), the pore volume detectable by FE-SEM is a small fraction of total porosity, ranging from 2 to 32% of the helium porosity. Importantly, the FE-SEM–visible porosity in OM decreases significantly with increasing TOC, diminishing from 30% of OM volume to less than 1% of OM volume across the range of TOC. The morphology and size of OM-hosted pores also vary systematically with TOC. The interpretation of this anticorrelation between OM content and SEM-visible pores remains uncertain. Samples with the lowest OM porosity (higher TOC) may represent gas expulsion (pore collapse) that was more complete as a consequence of greater OM connectivity and framework compaction, whereas samples with higher OM porosity (lower TOC) correspond to rigid mineral frameworks that inhibited compactional expulsion of methane-filled bubbles. Alternatively, higher TOC samples may contain OM (low initial hydrogen index, relatively unreactive) that is less prone to development of FE-SEM–detectable pores. In this interpretation, OM type, controlled by sequence-stratigraphic position, is a factor in determining pore-size distribution.

Life Cycle Greenhouse Gas Emissions and Freshwater Consumption of Marcellus Shale Gas

Abstract: We present results of a life cycle assessment (LCA) of Marcellus shale gas used for power generation. The analysis employs the most extensive data set of any LCA of shale gas to date, encompassing data from actual gas production and power generation operations. Results indicate that a typical Marcellus gas life cycle yields 466 kg CO2eq/MWh (80% confidence interval: 450–567 kg CO2eq/MWh) of greenhouse gas (GHG) emissions and 224 gal/MWh (80% CI: 185–305 gal/MWh) of freshwater consumption. Operations associated with hydraulic fracturing constitute only 1.2% of the life cycle GHG emissions, and 6.2% of the life cycle freshwater consumption. These results are influenced most strongly by the estimated ultimate recovery (EUR) of the well and the power plant efficiency: increase in either quantity will reduce both life cycle freshwater consumption and GHG emissions relative to power generated at the plant. We conclude by comparing the life cycle impacts of Marcellus gas and U.S. coal: The carbon footprint of Ma...

Molecular Dynamics Simulation of Homogeneous Crystal Nucleation in Polyethylene

Abstract: Using a realistic united-atom force field, molecular dynamics simulations were performed to study homogeneous nucleation of the crystal phase at about 30% supercooling from the melts of n-pentacontahectane (C150) and a linear polyethylene (C1000), both of which are long enough to exhibit the chain folding that is characteristic of polymer crystallization. The nucleation rate was calculated and the critical nuclei were identified using a mean first-passage time analysis. The nucleation rate was found to be insensitive to the chain length in this range of molecular weight. The critical nucleus contains about 150 carbons on average and is significantly smaller than the radius of gyration of the chains, at this supercooling. A cylinder model was used to characterize the shape of the crystal nuclei and to calculate the interfacial free energies. A chain segment analysis was performed to characterize the topology of the crystal surface in terms of loops (including folds) and tails. The length distribution of lo...

Hydrocarbon Conversion Process

Abstract: The invention relates to methods and equipment for converting C 3+ olefin to, e.g., one or more of di-C 3+ olefin, oligomers and polymers of C 3+ olefin, branched C 4+ -aldehydes, C 4+ -carboxylic acids, and C 4+ oxygenates. The invention encompasses producing methyl tert-butyl ether and diisobutylene, and converting methyl tert-butyl ether to isobutylene.

The use of biomonitoring data in exposure and human health risk assessment: benzene case study.

Abstract: A framework of “Common Criteria” (i.e. a series of questions) has been developed to inform the use and evaluation of biomonitoring data in the context of human exposure and risk assessment. The data-rich chemical benzene was selected for use in a case study to assess whether refinement of the Common Criteria framework was necessary, and to gain additional perspective on approaches for integrating biomonitoring data into a risk-based context. The available data for benzene satisfied most of the Common Criteria and allowed for a risk-based evaluation of the benzene biomonitoring data. In general, biomarker (blood benzene, urinary benzene and urinary S-phenylmercapturic acid) central tendency (i.e. mean, median and geometric mean) concentrations for non-smokers are at or below the predicted blood or urine concentrations that would correspond to exposure at the US Environmental Protection Agency reference concentration (30 µg/m3), but greater than blood or urine concentrations relating to the air conc...

Tomographically Enhanced Full Wavefield Inversion

Abstract: Method for improving convergence in gradient-based iterative inversion of seismic data ( 101 ), especially advantageous for full wavefield inversion The method comprises decomposing the gradient into two (or more) components ( 103 ), typically the migration component and the tomographic component, then weighting the components to compensate for unequal frequency content in the data ( 104 ), then recombining the weighted components ( 105 ), and using the recombined gradient to update ( 106 ) the physical properties model ( 102 )

Detrital zircon geochronology from the Bighorn Basin, Wyoming, USA: Implications for tectonostratigraphic evolution and paleogeography

Abstract: Tectonostratigraphic assemblages record phases of basin history during which the fundamental controls of tectonic setting, subsidence style, and basin geometry are relatively similar. Because these fundamental controls, in combination with climate and eustasy, influence paleogeography and sediment-dispersal patterns, they should also yield similar patterns, or facies, of detrital zircon age spectra. Such age-distribution patterns should be documented on the craton in order to make meaningful comparisons to sedimentary rocks from suspect terranes along continental margins. The Rocky Mountains of western North America provide excellent outcrops of sedimentary rocks that record >500 m.y. of tectonostratigraphic evolution. One such Phanerozoic section is exposed along the margins of the Bighorn Basin in northwest Wyoming, from which we report over 4000 U/Th/Pb detrital zircon ages from 48 samples that span a stratigraphic interval from the Middle Cambrian Flathead Sandstone through the Eocene Willwood Formation. These data provide one of the most complete records of detrital zircon age patterns from this part of cratonic North America. The stratigraphic record of the Bighorn Basin is subdivided into four tectonostratigraphic assemblages (TSA1–TSA4). These assemblages record an initial passive margin, followed by a transition to a convergent margin, followed by a marine-dominated retroarc foreland basin, followed by a retroarc foreland segmented by local basement uplifts. This tectonostratigraphic architecture is expressed as four, first-order patterns within the detrital zircon age distributions. TSA1 represents a Paleozoic–Triassic proximal continental margin assemblage dominated by Proterozoic zircons with abundant grains in the 1600–1950 Ma range, a Grenville population at ca. 1100 Ma, and a Phanerozoic population at ca. 420 Ma. TSA2 is a transitional assemblage associated with the Jurassic–Early Cretaceous organization of a west-facing convergent margin and Cordilleran orogen. The TSA2 detrital zircon age distribution is characterized by the appearance of Mesozoic grains, age peaks at ca. 420 and 600 Ma, and a dominant population of Grenville (1.0–1.1 Ga) grains with a suite of Proterozoic grains diminishing in abundance as age increases to 1.9 Ga. TSA3 sedimentary rocks were deposited in the Cretaceous Interior Seaway in a retroarc foreland basin and are dominated by zircons for which ages are close to the depositional age of the strata, reflecting input from the active Idaho Batholith and Sierran segments of the Cordilleran magmatic arc. The older zircon fractions from TSA3 sedimentary rocks are characterized by a dominant detrital zircon age peak at 1.7–1.8 Ga, which probably reflects reworking of Belt Supergroup metasedimentary rocks from the northwest into the Cretaceous foreland, based on regional paleogeographic patterns. TSA4 reflects the phase of basin fill associated with Paleogene structural segmentation of the retroarc foreland during the Laramide orogeny. Detrital zircon age spectra from this assemblage record erosion and redeposition of all previous sedimentary rocks from surrounding basement uplifts. Patterns of detrital zircon ages reflect fundamental changes in paleogeography and sediment dispersal at the 10–100 m.y. time scale and are clearly related to major tectonic events or phases. Detrital zircon ages also provide evidence for linkages between convergent margin processes such as arc magmatism and sedimentation in the retroarc foreland. During these times of strong arc-retroarc linkage, detrital zircon geochronology provides a potentially useful tool for high-resolution chronostratigraphy.

Effect of tides on mouth bar morphology and hydrodynamics

Abstract: [1] Mouth bars are morphological units important for deltas, estuaries, or rivers debouching into the sea. Several processes affect the formation of these deposits. This paper focuses on the role of tides on shaping mouth bars, presenting both hydrodynamic and morphodynamic results. The effect of tides is analyzed in two end-member configurations: a river with a small tidal discharge compared to the fluvial discharge (fluvial dominated) and a river with a very large tidal discharge (tidal dominated). Mouth bar formation is analyzed using the coupled hydrodynamic and morphodynamic model Delft3D. The presence of tides influences the hydrodynamics of the jet exiting the river mouth and causes an increase in the averaged jet spreading. At low tide the lower water depth in the basin promotes a drawdown water profile in the river and an accelerated flow near the mouth. The resulting velocity field is characterized by residual currents affecting growth and final shape of the mouth bar. Simulations indicate that mouth deposits are characterized by the presence of two channels for negligible tidal discharge, whereas three principal channels are present in the tidal-dominated case, with a central channel typical of tidal inlets. On the basis of our numerical analyses, we present a robust criterion for the occurrence of mouth deposits with three channels. Trifurcations form when the tidal discharge is large with respect to the fluvial one and the tidal amplitude is small compared to the water depth. Finally, predicted mouth bar morphologies are compared with good agreement to river mouths in the Gulf of Mexico, USA.

Experimental Correlation Between Interfacial Water Structure and Mineral Reactivity.

Abstract: We present an experimental demonstration of the effect of solvent structure on the interfacial reactivity of the silica/water interface using in situ vibrational Sum-frequency Generation (vSFG) spectroscopy. The response of the molecular arrangement of the interfacial solvent to the presence of cations is pH dependent with the highest sensitivity at neutral pH, relevant to geochemical and biological environments. The pH-dependent changes in vSFG spectra are in excellent correlation with the enhancement of quartz dissolution in salt water, which was hypothesized by Dove et al. to be due to changes of the interfacial solvent structure at the silica surface. vSFG provides mechanistic insights into silica dissolution and sheds light on the role of ions in altering interfacial solvent ordering, which has implications in fields ranging from protein-water interactions to oil recovery.

River channel lateral mobility: metrics, time scales, and controls

Abstract: [1] Alluvial river channels are intrinsically mobile. We mapped channel planform extent in a series of experiments to measure instantaneous rates of channel motion, loss of planform overlap with the original positions of the channels, and reworking of the fluvial surface over which the channels moved. These experiments comprise two aggrading deltas, one subsiding delta that underwent cyclical base level changes, and one braided channel system that was seeded with vegetation. We find that the amounts of channel planform overlap and remaining unreworked fluvial surface area both decay exponentially with time, and that these metrics and the instantaneously-measured rates of channel motion scale predictably with one another in spite of the different time scales of the processes they record. Rates of channel planform change increase with increasing sediment flux and bed and planform irregularity, and decrease with the establishment of riparian vegetation. Aggradation does not noticeably affect channel mobility, but induces avulsions that allow the channels to more rapidly rework the fluvial surface. Additional findings include that: (1) sediment flux in the braided experiment equals its rate of bar migration, (2) channel widths are normally distributed with time, and (3) we can use our channel mobility metrics to connect surface processes with the resultant fluvial stratigraphy.

Three-Dimensional Implicit Stratigraphic Model Building From Remote Sensing Data on Tetrahedral Meshes: Theory and Application to a Regional Model of La Popa Basin, NE Mexico

Abstract: Remote sensing data provide significant information to constrain the geometry of geological structures at depth. However, the use of intraformational geomorphologic features such as flatirons and incised valleys often calls for tedious user interaction during 3-D model building. We propose a new method to generate 3-D models of stratigraphic formations, based primarily on remote sensing images and digital elevation models. This method is based on interpretations of the main relief markers and interpolation of a stratigraphic property on a tetahedral mesh covering the domain of study. The tetrahedral mesh provides a convenient way to integrate available data during the interpolation while accounting for discontinuities such as faults. Interpretive expert input may be provided through constrained interactive editing on arbitrary cross-sections, and additional surface or subsurface data may also be integrated in the modeling. We demonstrate this global workflow on a structurally complex basin in the Sierra Madre Oriental, Northeastern Mexico.

First principles derived, transferable force fields for CO2 adsorption in Na-exchanged cationic zeolites

Abstract: The development of accurate force fields is vital for predicting adsorption in porous materials. Previously, we introduced a first principles-based transferable force field for CO2 adsorption in siliceous zeolites (Fang et al., J. Phys. Chem. C, 2012, 116, 10692). In this study, we extend our approach to CO2 adsorption in cationic zeolites which possess more complex structures. Na-exchanged zeolites are chosen for demonstrating the approach. These methods account for several structural complexities including Al distribution, cation positions and cation mobility, all of which are important for predicting adsorption. The simulation results are validated with high-resolution experimental measurements of isotherms and microcalorimetric heats of adsorption on well-characterized materials. The choice of first-principles method has a significant influence on the ability of force fields to accurately describe CO2–zeolite interactions. The PBE-D2 derived force field, which performed well for CO2 adsorption in siliceous zeolites, does not do so for Na-exchanged zeolites; the PBE-D2 method overestimates CO2 adsorption energies on multi-cation sites that are common in cationic zeolites with low Si/Al ratios. In contrast, a force field derived from the DFT/CC method performed well. Agreement was obtained between simulation and experiment not only for LTA-4A on which the force field fitting is based, but for other two common adsorbents, NaX and NaY.

Characterization of Asphaltene Building Blocks by Cracking under Favorable Hydrogenation Conditions

Abstract: The chemical building blocks that comprise petroleum asphaltene molecules were determined by thermal cracking of samples under conditions that minimized alterations to aromatic and cycloalkyl groups. Favorable hydrogenation conditions that used tetralin as a hydrogen-donor solvent and an iron-based catalyst allowed asphaltenes derived from different crude oils to yield approximately 50–60 wt % distillates (<538 °C fraction), with coke yields below 10 wt %, and reach conversions of the vacuum residue fraction between 65 and 75 wt %. Products in a wide range of boiling points, from naphtha to heavy material in the vacuum residue range, were observed by simulated distillation. Quantitative recovery of the cracked products, with mass balances above 96%, and characterization of the distillate fraction by gas chromatography–field ionization–time-of-flight high-resolution mass spectrometry (GC–FI–TOF HR MS) provided information on the abundance of building blocks, including saturates, 1–3-ring aromatics, 4+-ring...

Alternatives to in vivo tests to detect endocrine disrupting chemicals (EDCs) in fish and amphibians--screening for estrogen, androgen and thyroid hormone disruption.

Abstract: Endocrine disruption is considered a highly relevant hazard for environmental risk assessment of chemicals, plant protection products, biocides and pharmaceuticals. Therefore, screening tests with a focus on interference with estrogen, androgen, and thyroid hormone pathways in fish and amphibians have been developed. However, they use a large number of animals and short-term alternatives to animal tests would be advantageous. Therefore, the status of alternative assays for endocrine disruption in fish and frogs was assessed by a detailed literature analysis. The aim was to (i) determine the strengths and limitations of alternative assays and (ii) present conclusions regarding chemical specificity, sensitivity, and correlation with in vivo data. Data from 1995 to present were collected related to the detection/testing of estrogen-, androgen-, and thyroid-active chemicals in the following test systems: cell lines, primary cells, fish/frog embryos, yeast and cell-free systems. The review shows that the majority of alternative assays measure effects directly mediated by receptor binding or resulting from interference with hormone synthesis. Other mechanisms were rarely analysed. A database was established and used for a quantitative and comparative analysis. For example, a high correlation was observed between cell-free ligand binding and cell-based reporter cell assays, between fish and frog estrogenic data and between fish embryo tests and in vivo reproductive effects. It was concluded that there is a need for a more systematic study of the predictive capacity of alternative tests and ways to reduce inter- and intra-assay variability.

System and method of recirculating exhaust gas for use in a plurality of flow paths in a gas turbine engine

Abstract: A method includes generating an exhaust gas from combustion gases with a turbine; recirculating the exhaust gas along an exhaust recirculation flow path; reducing moisture within the exhaust gas along the exhaust recirculation path with an exhaust gas processing system; providing the exhaust gas to a first exhaust gas inlet of an exhaust gas compressor for compression; and providing the exhaust gas from the exhaust recirculation path to a second exhaust gas inlet separate from the first exhaust gas inlet for cooling, preheating, sealing, or any combination thereof.

Connectivity-Based Parallel Replica Dynamics for Chemically Reactive Systems: From Femtoseconds to Microseconds

Abstract: Reactive force field methods such as AIREBO, ReaxFF and COMB, are extremely useful for studying physical and chemical interactions between molecules and materials. However, many chemical reactions have relatively high activation energies, putting them beyond the times-scale of conventional molecular dynamics (MD) at modest temperatures. To capture the low-temperature long-lived radical chemistry in atomistic simulations, we have developed a new transition detection scheme for performing Reactive Parallel Replica Dynamics (RPRD) simulation enabling an extended MD time-scales, essentially up to a microsecond using ReaxFF. In the newly implemented event detection scheme, the transition events are identified whenever there is a change in connectivity of any atom. 1-Heptene pyrolysis is chosen as a model system, and RPRD simulations are performed at temperatures as low as 1350K for up to 1 μs for a system consisting of 40 heptene molecules. The chemical mechanism and the product distribution that were obtained...

A kinematic rupture model generator incorporating spatial interdependency of earthquake source parameters

Abstract: S U M M A R Y Based on the results obtained by analysing a large number of dynamic strike slip and dipping fault ruptures we construct a kinematic rupture model generator that incorporates some of the key source parameters extracted from the dynamic rupture models. In this kinematic rupture model, the slip rate function includes the final slip, the rise time, the local rupture velocity and the peak time (a measure of the impulsive part of the slip rate function). A four-dimensional correlation matrix is used to describe the spatial interdependency between the four source parameters—each of which is modelled as correlated random field. Each source parameter has a different marginal distribution determined from the analysis of the dynamic models. The marginal distributions are allowed to change as a function of distance from the hypocentre. The autocorrelation of each parameter is modelled by a power spectrum that follows a power law. The value of the spectral decay of the power law for the different source parameters is based on the results obtained from the dynamic rupture models. Finally, the values of rise time and peak time are adjusted such that the moment rate function fits a Brune spectrum for a specified corner frequency. We validate the rupture model generator using observed strong motion near field recording for the 1994 Northridge earthquake and the 1989 Loma Prieta earthquake. We perform comparisons with the rupture model generator of Liu et al. We find that only considering the response spectral bias of a best model is not sufficient to validate a rupture model generator. Thus we test the predictive power of the two rupture model generators if multiple ruptures are computed. Overall, the new rupture model generator yields a better prediction, compared to Liu et al., for the two validation events, especially in predicting observed PGV values and pseudospectral velocity at low frequencies (<1Hz).