Showing papers by "ExxonMobil published in 2001"

Granular flow down an inclined plane: Bagnold scaling and rheology

Abstract: We have performed a systematic, large-scale simulation study of granular media in two and three dimensions, investigating the rheology of cohesionless granular particles in inclined plane geometries, i.e., chute flows. We find that over a wide range of parameter space of interaction coefficients and inclination angles, a steady-state flow regime exists in which the energy input from gravity balances that dissipated from friction and inelastic collisions. In this regime, the bulk packing fraction (away from the top free surface and the bottom plate boundary) remains constant as a function of depth z, of the pile. The velocity profile in the direction of flow vx(z) scales with height of the pile H, according to vx(z) proportional to H(alpha), with alpha=1.52+/-0.05. However, the behavior of the normal stresses indicates that existing simple theories of granular flow do not capture all of the features evidenced in the simulations.

Kendrick mass defect spectrum: a compact visual analysis for ultrahigh-resolution broadband mass spectra.

Abstract: At currently achievable Fourier transform ion cyclotron resonance broadband mass spectrometry resolving power (m/Δm50% > 350 000 for 200 < m/z < 1000), it would be necessary to spread out a conventional mass spectrum over ∼200 m in order to provide visual resolution of the most closely resolved peaks. Fortunately, there are natural gaps in a typical mass spectrum, spaced 1 Da apart, because virtually no commonly encountered elemental compositions yield masses at those values. Thus, it is possible to break a broadband mass spectrum into 1-Da segments, rotate each segment by 90°, scale each segment according to its mass defect (i.e., difference between exact and nominal mass), and then compress the spacing between the segments to yield a compact display. For hydrocarbon systems, conversion from IUPAC mass to “Kendrick” mass (i.e., multiplying each mass by 14.00000/14.01565) further simplifies the display by rectilinearizing the peak patterns. The resulting display preserves not only the “coarse” spacings (e...

Providing clarity and a common language to the "fuzzy front end"

Abstract: OVERVIEW:Eight companies that were Process Effectiveness Network members of the Industrial Research Institute attempted to collectively determine the best practices of the Fuzzy Front End (FFE) of innovation. Comparing one company's processes to those of another proved insurmountable because there was neither a common language nor clear and consistent definition of the key elements of the front end. As a result, the group developed a theoretical construct, defined as the New Concept Development (NCD) model, in order to provide a common language and insights on the front end activities. The model consists of three key parts: five front end elements, the engine that powers the elements, and external influencing factors. Proficiency of the FFE was evaluated at 19 companies by using the NCD model. Highly innovative companies were found to be more proficient in the FFE and in several elements of the NCD model.

Use of multiattribute transforms to predict log properties from seismic data

Abstract: We describe a new method for predicting well‐log properties from seismic data. The analysis data consist of a series of target logs from wells which tie a 3-D seismic volume. The target logs theoretically may be of any type; however, the greatest success to date has been in predicting porosity logs. From the 3-D seismic volume a series of sample‐based attributes is calculated. The objective is to derive a multiattribute transform, which is a linear or nonlinear transform between a subset of the attributes and the target log values. The selected subset is determined by a process of forward stepwise regression, which derives increasingly larger subsets of attributes. An extension of conventional crossplotting involves the use of a convolutional operator to resolve frequency differences between the target logs and the seismic data. In the linear mode, the transform consists of a series of weights derived by least‐squares minimization. In the nonlinear mode, a neural network is trained, using the selected att...

Palladium-catalyzed Reppe carbonylation.

Abstract: PdX2L2/L/HA (A = weakly coordinating anion, L = phosphine) complexes are active catalysts in the hydroesterification of alkenes, alkynes, and conjugated dienes. Shell, the only major corporate player in the field, recently developed two very active catalyst systems tailored to the hydroesterification of either alkenes or alkynes. The hydroesterification of propyne with their Pd(OAc)2/PN/HA (PN = (2-pyridyl)diphenylphosphine, HA = strong acid with weakly coordinating anion, like methanesulfonic acid) catalyst has been declared commercially ready. However, despite the significant progress in the activity of Pd-hydroesterification catalysts, further improvements are warranted. Thus, for example, activity maintenance still seems to be an issue. Homogeneous Pd catalysts are prone to a number of deactivation reactions. Activity and stability promoters are often corrosive and add to the complexity of the system, making it less attractive. Nonetheless, the versatility of the process and its tolerance toward the functional groups of substrates should appeal especially to the makers of specialty products. Although hydroesterification yields esters from alkenes, alkynes, and dienes in fewer steps than hydroformylation does, the latter has some advantages at the current state of the art. (1) Hydroformylation catalysts, particularly some recently published phosphine-modified Rh systems, can achieve very high regioselectivity for the linear product that hydroesterification catalysts cannot match yet. By analogy with hydroformylation, bulkier ligands ought to be tested in hydroesterification to increase normal-ester selectivity. (2) Hydroformylation is proven, commercial. Hydroesterification can only replace it if it can provide significant economic incentives. Similar or just marginally better performance could not justify the cost of development of a new technology. (3) Hydroesterification requires pure CO while hydroformylation uses syngas, a mixture of CO and H2. The latter is typically more available and less expensive (for industrial applications CO is most often separated from syngas). (4) The acid component of the hydroesterification catalyst makes the process corrosive. It would be desirable to develop new hydroesterification catalysts that do not require acid stabilizer/activity booster. Clearly, any new hydroesterification technology will directly compete with the hydroformylation route. This is especially true for olefin feeds, since both processes add one CO to the olefin, yielding oxygenates that can be converted into identical products. For some niche applications, like the production of MMA from propyne, hydroesterification seems to have an advantage as compared to hydroformylation due to the high activity and selectivity of the Pd(OAc)2/(2-pyridyl)diphenylphosphine catalyst. Since hydroesterification is an emerging technology, it is reasonable to assume that the potential for improvement is greater than in the mature hydroformylation. It is therefore possible that hydroesterification will become competitive in the future; thus, continued effort in the field is warranted.

Polymer‐Based Photonic Crystals

Abstract: In this report, we highlight the development of polymers as 1D photonic crystals and subsequently place special emphasis on the activities in self-assembled block copolymers as a promising platform material for new photonic crystals. We review recent progress, including the use of plasticizer and homopolymer blends of diblock copolymers to increase periodicity and the role of self-assembly in producing 2D and 3D photonic crystals. The employment of inorganic nanoparticles to increase the dielectric contrast and the application of a biasing field during self-assembly to control the long-range domain order and orientation are examined, as well as in-situ tunable materials via a mechanochromic materials system. Finally, the inherent optical anisotropy of extruded polymer films and side-chain liquid-crystalline polymers is shown to provide greater degrees of freedom for further novel optical designs.

Reading chemical fine print: Resolution and identification of 3000 nitrogen-containing aromatic compounds from a single electrospray ionization Fourier transform ion cyclotron resonance mass spectrum of heavy petroleum crude oil

Abstract: Extra heavy petroleum crude oil (50% of the mixture boils at >566 °C) has been analyzed directly, without prior fractionation, by a high-field (9.4 T) Fourier transform ion cyclotron resonance mass spectrometer coupled to an external micro-electrospray ion source. At an average mass resolving power, (m/Δm50% ≈ 50 000), a single wideband (250−1250 Da) mass spectrum exhibited ∼5000 resolved peaks with an average mass of 617 Da (e.g., up to 7−10 resolved peaks at each nominal mass). Their elemental compositions were positively identified by accurate mass measurement with an average deviation of less than 1 mDa from each assigned elemental composition. The number of elemental compositions at each nominal mass, the number of sulfur/oxygen atoms in a molecule, and aromaticity each increase with increasing mass. On the basis of elemental composition alone, we resolve more than 3000 distinct chemical formulas (excluding 13C isotopic species). Of the 3000 unique elemental compositions, we identify 12 major heteroa...

Method for production of hydrocarbons from organic-rich rock

Abstract: A method for accelerating the conversion of kerogen to hydrocarbons in a subterranean formation containing organic-rich rock that is located in the vicinity of reservoir-quality strata. Sufficient heat is generated in the reservoir-quality strata such that it heats the organic-rich rock in the subterranean formation and accelerates the conversion of kerogen to hydrocarbons in the formation.

Lake-type controls on petroleum source rock potential in nonmarine basins

Abstract: Based on numerous empirical observations of lacustrine basin strata, we propose a three-fold classification of lacustrine facies associations that accounts for the most important features of lacustrine petroleum source rocks and provides a predictive framework for exploration in nonmarine basins where lacustrine facies are incompletely delineated. (1) The fluvial-lacustrine facies association is characterized by freshwater lacustrine mudstones interbedded with fluvial-deltaic deposits, commonly including coal. Shoreline progradation dominates basin fill, resulting in the stacking of indistinctly expressed cycles up to 10 m thick. In map view, the deposits may be regionally widespread but laterally discontinuous and contain strong facies contrasts. Transported terrestrial organic matter contributes to mixed type I-III kerogens that generate waxy oil (type I kerogen is hydrogen rich and oil prone; type III kerogen is hydrogen poor and mainly gas prone). The Luman Tongue of the Green River Formation (Wyoming) and the Honyanchi Formation (Junggar basin, China) provide examples of this facies association, which is also present in the Songliao basin of northeastern China, the Central Sumatra basin, and the Cretaceous Doba/Doseo basins in west-central Africa. (2) The fluctuating profundal facies association represents a combination of progradational and aggradational basin fill and includes some of the world's richest source rocks. Deposits are regionally extensive in map view, having relatively homogenous source facies containing oil-prone, type I kerogen. Examples include the Laney Member of the Green River Formation (Wyoming), the Lucaogou Formation (Junggar basin, China), the Bucomazi Formation (offshore west Africa), and the Lagoa Feia Formation (Campos basin, Brazil). (3) The evaporative facies association represents dominantly aggradational fill related to desiccation cycles in saline to hypersaline lakes and may include evaporite and eolianite deposits. Sublittoral organic-rich mudstone facies are relatively thin but may be (Begin page 1034) quite rich and widespread. The highest organic enrichment coincides with the deepest lake stages. Low input of land plant organic matter results in minimal lateral contrasts in organic content. In some cases a distinctive type I-S (sulfur-rich) kerogen may generate oil at thermal maturities as low as 0.45% vitrinite reflectance equivalent. Examples include the Wilkins Peak Member of the Green River Formation (Wyoming), the Jingjingzigou Formation (Junggar basin, China), the Jianghan and Qaidam basins (China), and the Blanca Lila Formation (Argentina).

Alkylation of aromatics with ethylene and propylene: recent developments in commercial processes

Abstract: This paper provides an overview of current industrial alkylation processes for the production of ethylbenzene and cumene. In recent years, zeolite catalysts have begun to displace the conventional aluminum chloride and solid phosphoric acid (SPA) Friedel–Crafts catalysts used in both ethylbenzene and cumene processes. This transformation has been particularly rapid in the case of cumene technology, where more than 50% of the worldwide cumene capacity has converted to zeolite catalysts in the last 5 years.

The dating of shallow faults in the Earth's crust

Abstract: Direct dating of ductile shear zones and calculation of uplift/exhumation rates can be done using various radiometric dating techniques. But radiometric dating of shallow crustal faulting, which occurs in the crust's brittle regime, has remained difficult1,2,3,4 because the low temperatures typical of shallow crusted faults prevent the complete syntectonic mineral recrystallization that occurs in deeper faults. Both old (detrital) and newly grown (authigenic) fine-grained phyllosilicates are thus preserved in shallow fault zones and therefore their radiometric ages reflect a mixture of both mineral populations. Also, the loss of 39Ar during neutron irradiation in dating of clay minerals can produce erroneously old ages. Here we present a method of characterizing the clay populations in fault gouge, using X-ray modelling, combined with sample encapsulation, and show how it can be used to date near-surface fault activity reliably. We examine fault gouge from the Lewis thrust of the southern Canadian Rockies, which we determine to be ∼52 Myr old. This result requires the western North America stress regime to have changed from contraction to extension in only a few million years during the Eocene. We also estimate the uplift/exhumation age and sedimentary source of these rocks to be ∼172 Myr.

Toward Separation and Purification of Olefins Using Dithiolene Complexes: An Electrochemical Approach

Abstract: The complex Ni[S2C2(CF3)2]2reacts with light olefins, including ethylene and propylene, selectively and reversibly. The reaction is not poisoned by hydrogen gas, carbon monoxide, acetylene, or hydrogen sulfide, which are commonly present in olefin streams, presumably because olefin binding occurs through the sulfur ligand rather than the metal center. The reversible reaction of olefins with Ni[S2C2(CN)2]2 n ( n = 0, −1, −2) can be controlled electrochemically, where the oxidation state–dependent binding and release of olefins are fast on the electrochemical time scale. The observed tolerance to poisons and controllable electrochemical reactivity present an alternative approach to the separation of olefins from complex streams.

Slurry hydroprocessing for heavy oil upgrading using supported slurry catalysts

Abstract: A slurry hydroprocessing process (SHP) where a hydrocarbon feedstock is treated at slurry hydrotreating conditions, in the presence of a hydrogen containing treat gas and in the presence of a supported metallic catalyst which is a supported sulfide of a metal selected from the group of non-noble Group VIII metals, Group VIB metals and mixtures thereof where the support is an inorganic oxide and where the catalyst has an average diameter of about 0.5 to about 100 microns to obtain a first product stream comprising the catalyst and a hydroprocessed feedstream; separating the first product into a catalyst-free product stream and a catalyst-containing stream and recycling at least a portion of the catalyst-containing stream back to the hydroprocessing step.

Maturity trends in Raman spectra from kerogen and coal

Abstract: The present work explores the potential of Raman spectroscopy to provide maturity information about catagenesis stage kerogens and coals. The first-order Raman spectra of coals and kerogens show a broad amorphous A band between 1310 and 1360 cm-1 and a graphite-like G band near 1580−1600 cm-1. As vitrinite reflectance (R0) increases, the Raman A band becomes narrower and shifts to lower frequencies while the absorption strength of the A band relative to the G band decreases. The area ratio of the A band to G band (R = fA/fG) decreases from 3.2 to 2.4 in going from the least mature sample up to R0 = 2.0%. Similar trends were observed for maturation suites of Type II and other Type III kerogens. Laboratory thermolysis produced a range of samples with well-defined laboratory R0. The changes in the Raman A and G bands from the laboratory matured samples directionally paralled the natural samples. These results demonstrate that the Raman spectra of catagenesis stage samples vary in regular ways with sample mat...

Propylene impact copolymers

Abstract: This invention relates to propylene impact copolymer compositions. In particular, these unique and improved compositions can be produced using conventional, commercial-scale processes.

Early Oligocene initiation of North Atlantic Deep Water formation

Abstract: Dating the onset of deep-water flow between the Arctic and North Atlantic oceans is critical for modelling climate change in the Northern Hemisphere1, 2 and for explaining changes in global ocean circulation throughout the Cenozoic era3 (from about 65 million years ago to the present). In the early Cenozoic era, exchange between these two ocean basins was inhibited by the Greenland–Scotland ridge3, 4, but a gateway through the Faeroe–Shetland basin has been hypothesized3, 5. Previous estimates of the date marking the onset of deep-water circulation through this basin—on the basis of circumstantial evidence from neighbouring basins—have been contradictory5, 6, 7, 8, 9, ranging from about 35 to 15 million years ago. Here we describe the newly discovered Southeast Faeroes drift, which extends for 120 km parallel to the basin axis. The onset of deposition in this drift has been dated to the early Oligocene epoch (~35 million years ago) from a petroleum exploration borehole. We show that the drift was deposited under a southerly flow regime, and conclude that the initiation of deep-water circulation from the Norwegian Sea into the North Atlantic Ocean took place much earlier than is currently assumed in most numerical models of ancient ocean circulation.

Structure and dynamics of carbon black-filled elastomers

Abstract: The linear and nonlinear melt viscoelastic properties for a series of carbon black-filled polymer composites were studied. Complementary tapping-mode atomic force microscopy (AFM) studies were used to examine the dispersion and structural correlations of the filler particles in these composites. The low-frequency dependence of the linear viscoelastic moduli gradually changes from liquidlike behavior for the unfilled polymer to pseudosolid character for composites with more than 9 vol % carbon black filler. The plateau modulus, inferred from the linear viscoelastic response, exhibits a somewhat discontinuous change at about 9 vol % filler. On the basis of the linear viscoelastic response, we postulate that the carbon black filler forms a continuous percolated network structure beyond 9 vol % filler, considerably lower than that expected from theoretical calculations for overlapping spheres and ellipsoids. We suggest that the lower threshold for percolation is due to the polymer mediation of the filler structure, resulting from the low functionality of the polymer and, consequently, few strong polymer–filler interactions, allowing for long loops and tails that can either bridge filler particles or entangle with one another. Furthermore, the strain amplitude for the transition from linear behavior to nonlinear behavior of the modulus for the composites with greater than 9 vol % filler is independent of frequency, and this critical strain amplitude decreases with increasing filler concentration. Complementary AFM measurements suggest a well-dispersed carbon black structure with the nearest neighbor distance showing a discontinuous decrease at about 9 vol % filler, again consistent with the formation of a filler network structure beyond 9 vol % carbon black. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 256–275, 2001

Graft-modified polymers based on novel propylene ethylene copolymers

Abstract: Propylene ethylene copolymers with an ethylene content between 8 and 32 mole % have been grafted with maleic anhydride and a peroxide. The functionality level is higher than what is reported with polypropylene.

Integrated lubricant upgrading process

Abstract: A process for upgrading oil feedstock wherein the feedstock is hydrotreated, hydrocracked, and flashed and/or distilled. The bottoms are then vacuum distilled to adjust viscosity and volatility. The refined feed is then extracted, dewaxed, and cascaded to a hydrofinishing step, where it is contacted with a catalyst having a metal hydrogenation function in order to produce lubricant products.

Process for stimulating microbial activity in a hydrocarbon-bearing, subterranean formation

Abstract: A process is disclosed for stimulating the activity of microbial consortia in a subterranean formation to convert hydrocarbons to methane, which can be produced. Fluid and rock of the formation are analyzed. The presence of microbial consortia is determined and a characterization made (preferably genetic) of at least one microorganism of the consortia, at least one being a methanogenic microorganism. The characterization is compared with at least one known characterization derived from a known microorganism having one or more known physiological and ecological characteristics. This information, together with the information obtained from the analysis of the fluid and rock, is used to determine an ecological environment that promotes in situ microbial degradation of formation hydrocarbons and promotes microbial generation of methane by at least one methanogenic microorganism of the consortia. This information is then used as the basis for modifying the formation environment to produce methane.

Stability of atmospheric CO2 levels across the Triassic/Jurassic boundary.

Abstract: The Triassic/Jurassic boundary, 208 million years ago, is associated with widespread extinctions in both the marine and terrestrial biota. The cause of these extinctions has been widely attributed to the eruption of flood basalts of the Central Atlantic Magmatic Province. This volcanic event is thought to have released significant amounts of CO2 into the atmosphere, which could have led to catastrophic greenhouse warming, but the evidence for CO2-induced extinction remains equivocal. Here we present the carbon isotope compositions of pedogenic calcite from palaeosol formations, spanning a 20-Myr period across the Triassic/Jurassic boundary. Using a standard diffusion model, we interpret these isotopic data to represent a rise in atmospheric CO2 concentrations of about 250 p.p.m. across the boundary, as compared with previous estimates of a 2,000-4,000 p.p.m. increase. The relative stability of atmospheric CO2 across this boundary suggests that environmental degradation and extinctions during the Early Jurassic were not caused by volcanic outgassing of CO2. Other volcanic effects-such as the release of atmospheric aerosols or tectonically driven sea-level change-may have been responsible for this event.

Membrane separation in solvent lube dewaxing

Abstract: Exxon Mobil Corporation and W.R. Grace have developed an enhanced process for recovering solvents used in the refining of lubricants. The membrane-based process provides higher yields of lube oil, while simultaneously consuming less energy, decreasing cooling water use, and potentially reducing the level of volatile organic emissions from the dewaxing operation. The yield increase equates to a process savings, for a typical commercial plant, of about 2 million barrels of crude oil per year. By recovering and recycling the dewaxing solvent while bypassing the energy intensive parts of the plant, a single facility could reduce fuel oil consumption by 36,000 barrels/year, and greenhouse gas emissions by about 20,000 tons/year for each plant. The same plant would reduce cooling water use by nearly 4 million gallons/day, and, the release of dewaxing solvents, which are volatile organic materials, could be decreased by 50–200 tons/year per plant depending on the mechanical condition of its equipment. This technology was first implemented commercially at Exxon Mobil's Beaumont, Texas, Refinery. It can be easily retrofitted into existing plants or incorporated into new plant designs, and is currently available for license as the trademarked process MAX-DEWAX®.

Fuel supply apparatus for an internal combustion engine

Abstract: A gasoline in a material fuel tank is separated into a high-RON fuel having a higher octane value than the material fuel and a low-RON fuel having a lower octane value than the material fuel, by a separator device equipped with a separation membrane. Using a fuel switching mechanism, one or both of the high-RON fuel and the low-RON fuel are supplied to the engine in accordance with the state of operation of the engine. As the octane value of a fuel can be changed in accordance with the engine operation state, the state of combustion in the engine improves, so that both an increase in engine output and an improvement in an exhaust property can be achieved.