Showing papers by "ExxonMobil published in 2017"

A critical review on hemicellulose pyrolysis

Abstract: Fast pyrolysis is a promising thermochemical technology that breaks down renewable and abundant lignocellulosic biomass into a primary liquid product (bio-oil) in seconds. The bio-oil can then be potentially catalytically upgraded into transportation fuels and multiple commodity chemicals. Hemicellulose is one of the three major components of lignocellulosic biomass and is characterized as a group of cell wall polysaccharides that are neither cellulose nor pectin. The composition and structural features of hemicellulose (mixture of different heterogeneous polysaccharides) and different specific hemicellulose polysaccharides are reviewed. Particular focus is then given to reviewing the status of hemicellulose pyrolysis in terms of experimental investigations, reaction mechanisms, and kinetic modeling. For each aspect, recent results, challenges, and future prospects are addressed.

Control of zeolite framework flexibility and pore topology for separation of ethane and ethylene.

Abstract: The discovery of new materials for separating ethylene from ethane by adsorption, instead of using cryogenic distillation, is a key milestone for molecular separations because of the multiple and widely extended uses of these molecules in industry. This technique has the potential to provide tremendous energy savings when compared with the currently used cryogenic distillation process for ethylene produced through steam cracking. Here we describe the synthesis and structural determination of a flexible pure silica zeolite (ITQ-55). This material can kinetically separate ethylene from ethane with an unprecedented selectivity of ~100, owing to its distinctive pore topology with large heart-shaped cages and framework flexibility. Control of such properties extends the boundaries for applicability of zeolites to challenging separations.

Heavy Oil Based Mixtures of Different Origins and Treatments Studied by Atomic Force Microscopy

Abstract: Heavy oil molecular mixtures were investigated on the basis of single molecules resolved by atomic force microscopy. The eight different samples analyzed include asphaltenes and other heavy oil fractions of different geographic/geologic origin and processing steps applied. The collected AFM data of individual molecules provide information about the molecular geometry, aromaticity, the content of nonhexagonal rings, typical types and locations of heterocycles, occurrence, length and connectivity of alkyl side chains, and ratio of archipelago- vs island-type architectures. Common and distinguishing structural motifs for the different samples could be identified. The measured size distributions and the degree of unsaturation by scanning probe microscopy is consistent with mass spectrometry data presented herein. The results obtained reveal the complexity, properties and specifics of heavy oil fractions with implications for upstream oil production and downstream oil processing. Moreover, the identified molec...

Learning to Run Heuristics in Tree Search.

Abstract: “Primal heuristics” are a key contributor to the improved performance of exact branch-and-bound solvers for combinatorial optimization and integer programming. Perhaps the most crucial question concerning primal heuristics is that of at which nodes they should run, to which the typical answer is via hard-coded rules or fixed solver parameters tuned, offline, by trial-and-error. Alternatively, a heuristic should be run when it is most likely to succeed, based on the problem instance’s characteristics, the state of the search, etc. In this work, we study the problem of deciding at which node a heuristic should be run, such that the overall (primal) performance of the solver is optimized. To our knowledge, this is the first attempt at formalizing and systematically addressing this problem. Central to our approach is the use of Machine Learning (ML) for predicting whether a heuristic will succeed at a given node. We give a theoretical framework for analyzing this decision-making process in a simplified setting, propose a ML approach for modeling heuristic success likelihood, and design practical rules that leverage the ML models to dynamically decide whether to run a heuristic at each node of the search tree. Experimentally, our approach improves the primal performance of a stateof-the-art Mixed Integer Programming solver by up to 6% on a set of benchmark instances, and by up to 60% on a family of hard Independent Set instances.

Characterizing aliphatic moieties in hydrocarbons with atomic force microscopy

Abstract: We designed and studied hydrocarbon model compounds by high-resolution noncontact atomic force microscopy. In addition to planar polycyclic aromatic moieties, these novel model compounds feature linear alkyl and cycloaliphatic motifs that exist in most hydrocarbon resources - particularly in petroleum asphaltenes and other petroleum fractions - or in lipids in biological samples. We demonstrate successful intact deposition by sublimation of the alkyl-aromatics, and differentiate aliphatic moieties from their aromatic counterparts which were generated from the former by atomic manipulation. The characterization by AFM in combination with atomic manipulation provides clear fingerprints of the aromatic and aliphatic moieties that will facilitate their assignment in a priori unknown samples.

Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

Abstract: The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates. Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT). Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydr)oxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur. Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron monosulfide phases meters below the SMT demonstrates that in sulfide-limited systems metastable sulfur constituents are not readily converted to pyrite but can be buried to deeper sediment depths. Our data show that in non-steady state systems, redox zones do not occur in sequence but can reappear or proceed in inverse sequence throughout the sediment column, causing similar mineral alteration processes to occur at the same time at different sediment depths.

Nature of Catalytically Active Sites in the Supported WO3/ZrO2 Solid Acid System: A Current Perspective

Abstract: Tungstated zirconia (WO3/ZrO2) is one of the most well-studied solid acid catalyst systems and continues to attract the attention of both academia and industry. Understanding and controlling the properties of WO3/ZrO2 catalysts has been a topic of considerable interest over almost the past three decades, with a particular focus on discovering the relationship between catalytic activity and the molecular structure of the surface acid site. Amorphous tungsten oxide (WOx) species on ZrO2 surfaces were previously proposed to be very active for different acidic reactions such as alcohol dehydration and alkane isomerization. Recent developments in electron optical characterization and in situ spectroscopy techniques have allowed researchers to isolate the size, structure, and composition of the most active catalytic species, which are shown to be three-dimensional distorted Zr-WOx clusters (0.8–1.0 nm). Complementary theoretical calculations of the Bronsted acidity of these Zr-WOx clusters have confirmed that t...

The Rate of Crude Oil Biodegradation in the Sea

Abstract: Various groups have studied the rate of oil biodegradation in the sea over many years, but with no consensus on results. This can be attributed to many factors, but we show here that the principal confounding influence is the concentration of oil used in different experiments. Because of dilution, measured concentrations of dispersed oil in the sea are sub-parts-per-million within a day of dispersal, and at such concentrations the rate of biodegradation of detectable oil hydrocarbons has an apparent half-life of 7–14 days. This can be contrasted with the rate of degradation at the higher concentrations found in oil slicks or when stranded on a shoreline; there the apparent half-life varies from many months to many years.

Relaxations and discretizations for the pooling problem

Abstract: The pooling problem is a folklore NP-hard global optimization problem that finds applications in industries such as petrochemical refining, wastewater treatment and mining. This paper assimilates the vast literature on this problem that is dispersed over different areas and gives new insights on prevalent techniques. We also present new ideas for computing dual bounds on the global optimum by solving high-dimensional linear programs. Finally, we propose discretization methods for inner approximating the feasible region and obtaining good primal bounds. Valid inequalities are derived for the discretized models, which are formulated as mixed integer linear programs. The strength of our relaxations and usefulness of our discretizations is empirically validated on random test instances. We report best known primal bounds on some of the large-scale instances.

How to make a 350-m-thick lowstand systems tract in 17,000 years: The Late Pleistocene Po River (Italy) lowstand wedge

Abstract: The 350-m-thick succession of the Po River lowstand wedge (Italy) associated with the Last Glacial Maximum (deposited over ∼17 k.y) contains stratal architecture at a physical scale commonly attributed to much longer time scales, with complex, systematically varying internal clinothem characteristics. This study investigated clinothem stacking patterns and controls through the integration of seismic reflection data with sediment attributes, micropaleontology, regional climate, eustacy, and high-resolution age control possible only in Quaternary sequences. Three clinothem types are differentiated based on topset geometry, shelf-edge and onlap-point trajectory, internal seismic facies, and interpreted bottomset deposits: type A has moderate topset aggradation, ascending shelf-edge trajectory, and mass-transport bottomset deposits; type B has eroded topset, descending shelf-edge trajectory, and bottomset distributary channel-lobe complexes; and type C has maximal topset aggradation, ascending shelf-edge trajectory, and concordant bottomsets. Type A and C clinothems exhibit reduced sediment bypass and delivery to the basin, whereas type B clinothems are associated with short intervals of increased sediment export from the shelf to deeper water. Clinothems individually span a range of 0.4–4.7 k.y., contemporaneous with significant eustatic and climate changes, but their stacking patterns resemble those found in ancient successions and ascribed to significantly longer durations, indicating that (1) the response time of ancient continental margin–scale systems to high-frequency variations in accommodation and sediment supply could be as short as centuries, (2) even millennial- to centennial-scale stratal units can record substantial influence of allogenic controls, and (3) sandy deposits can be compartmentalized even in a short-duration lowstand systems tract.

Avoidance of Density Anomalies as a Structural Principle for Semicrystalline Polymers: The Importance of Chain Ends and Chain Tilt

Abstract: On the basis of sufficiently realistic chain models and simulations, it is concluded that the commonly used models of the lamellar structure of melt-crystallized semicrystalline polymers unintentionally but inevitably contain layers with a higher density than in the crystallites (density anomalies). The density excess would be particularly pronounced in polymers with planar zigzag conformations in the crystallites, such as polyethylene (PE). To avoid density anomalies, the structural models must be modified, with chain ends at the crystal surface and/or chain tilt in the crystallites. NMR and X-ray evidence for these structural features in PE is presented. Termination of chains at the crystal surface keeps dangling chain ends out of the crowded interfacial layer, reducing the density at the interface by about 17% for Mn = 15 kg/mol, a common value in commercial high-density polyethylenes. NMR of PEs shows that most CH3 end groups are indeed in all-trans chains in a nearly solid-like environment. When the ...

Paleosols and associated channel-belt sand bodies from a continuously subsiding late Quaternary system (Po Basin, Italy): New insights into continental sequence stratigraphy

Abstract: Previous sequence-stratigraphic work has emphasized the key role of paleosols and associated sand-dominated fluvial bodies as key features for interpreting alluvial architecture. The temporal resolution of the ancient record is, however, insufficient to fully explain the complex relationship between soil formation and the evolution of fluvial systems under changing sea-level and climate conditions. In this paper, we present a detailed record of paleosol−channel belt relationships reconstructed from the subsurface of a rapidly subsiding region (Po Plain, Italy) that spans almost all of the last glacial-interglacial cycle (∼120 k.y.). The studied succession preserves a systematic bipartite zonation into a thick paleosol-bearing segment close to the basin margin and a sand-dominated interval, with vertically amalgamated channel belts, in an axial position. Individual paleosols are weakly developed and represent key stratigraphic markers that can be traced basinwide into adjacent, essentially contemporaneous, unconfined channel-belt deposits. Unlike conventional models of late Quaternary alluvial−coastal plain systems, no persistent incised valley was established in the Po system during the last glacial-interglacial cycle. Continuous accommodation was the key depositional control on alluvial stratigraphy during the prolonged (∼90 k.y.) phase of late Pleistocene sea-level fall, which led to the deposition of a thick, dominantly aggradational alluvial succession. The development of shallowly incised, short-lived valley systems took place only at the transition to glacial stages associated with substantial sea-level drop (marine oxygen isotope stage [MIS] 3-2 transition, and possibly MIS 5-4 transition). This study shows that in rapidly subsiding settings with high rates of sedimentation, incised valley systems may be replaced by aggradationally stacked, essentially nonincised fluvial bodies. In these cases, overbank packages bounded by immature paleosols represent the most likely alternative to the highly weathered interfluve paleosol predicted by classic sequence-stratigraphic models. Fourth-order sequence boundaries and lower-rank erosional surfaces may be easily confused at the ∼100 k.y. scale, and transgressive surfaces, defining the onset of retrogradation, may become the most readily identifiable sequence-stratigraphic surfaces.

Role of the Freight Sector in Future Climate Change Mitigation Scenarios.

Abstract: The freight sector’s role is examined using the Global Change Assessment Model (GCAM) for a range of climate change mitigation scenarios and future freight demand assumptions. Energy usage and CO2 emissions from freight have historically grown with a correlation to GDP, and there is limited evidence of near-term global decoupling of freight demand from GDP. Over the 21st century, greenhouse gas (GHG) emissions from freight are projected to grow faster than passenger transportation or other major end-use sectors, with the magnitude of growth dependent on the assumed extent of long-term decoupling. In climate change mitigation scenarios that apply a price to GHG emissions, mitigation of freight emissions (including the effects of demand elasticity, mode and technology shifting, and fuel substitution) is more limited than for other demand sectors. In such scenarios, shifting to less-emitting transportation modes and technologies is projected to play a relatively small role in reducing freight emissions in GC...

Influence of the architecture of magma-poor hyperextended rifted margins on orogens produced by the closure of narrow versus wide oceans

Abstract: Orogens resulting from the closure of narrow oceans, such as the Alps or the Pyrenees, usually lack voluminous synsubduction and synorogenic magmatism. Such orogenies are essentially controlled by mechanical processes in which the initial architecture of the original rifted margins strongly controls the architecture of the orogen. In this paper we first provide a synthesis of the structure, dimensions, and lithology of hyperextended rift systems and oceans, based on recent seismic and petrologic data. We then investigate how rift-related inheritance influences crustal characteristics and mantle geochemistry of orogens related to the closure of narrow oceans, and compare them to orogens resulting from the closure of wide and/or mature oceans. Our results show that narrow oceans usually lack a mature spreading system forming Penrose-type oceanic crust (i.e., 6–7-km-thick basaltic oceanic crust typical of steady-state spreading systems; see Anonymous, 1972), in contrast to wide oceans. However, there is statistically no difference in the structural and lithological architecture of their passive continental margins. Thus, the main difference between narrow and wide oceans is whether the margins are separated by a significant amount of oceanic crust and underlying depleted mantle. In addition, due to the lack of significant magmatism during the closure of narrow oceans, the mantle wedge is likely to remain relatively fertile compared to the wedge above long-lasting subduction of wide oceans. This difference in mantle composition may dictate the magmatic budget of subsequent orogenic collapse or rifting events.

Determination of Isosteric Heat of Adsorption by Quenched Solid Density Functional Theory.

Abstract: The heat of adsorption is one of the most important parameters characterizing energetic heterogeneity of the adsorbent surface. Heats of adsorption are either determined directly by calorimetry or calculated from adsorption isotherms measured at different temperatures using the thermodynamic Clausius–Clapeyron equation. Here, we present a method for calculating the isosteric heat of adsorption that requires as input only a single adsorption isotherm measured at one temperature. The proposed method is implemented with either nonlocal (NLDFT) or quenched solid (QSDFT) density functional theory models of adsorption that are currently widely used for calculating pore size distributions in various micro- and mesoporous solids. The pore size distribution determined from the same experimental isotherm is used for predicting the isosteric heat. The QSDFT method has advantages of taking into account two factors contributing to the structural heterogeneity of adsorbents: the molecular level roughness of the surface...

A framework for cumulative risk assessment in the 21st century.

Abstract: The ILSI Health and Environmental Sciences Institute (HESI) has developed a framework to support a transition in the way in which information for chemical risk assessment is obtained and used (RISK21). The approach is based on detailed problem formulation, where exposure drives the data acquisition process in order to enable informed decision-making on human health safety as soon as sufficient evidence is available. Information is evaluated in a transparent and consistent way with the aim of optimizing available resources. In the context of risk assessment, cumulative risk assessment (CRA) poses additional problems and questions that can be addressed using the RISK21 approach. The focus in CRA to date has generally been on chemicals that have common mechanisms of action. Recently, concern has also been expressed about chemicals acting on multiple pathways that lead to a common health outcome, and non-chemical other conditions (non-chemical stressors) that can lead to or modify a common outcome. Acknowledging that CRAs, as described above, are more conceptually, methodologically and computationally complex than traditional single-stressor risk assessments, RISK21 further developed the framework for implementation of workable processes and procedures for conducting assessments of combined effects from exposure to multiple chemicals and non-chemical stressors. As part of the problem formulation process, this evidence-based framework allows the identification of the circumstances in which it is appropriate to conduct a CRA for a group of compounds. A tiered approach is then proposed, where additional chemical stressors and/or non-chemical modulating factors (ModFs) are considered sequentially. Criteria are provided to facilitate the decision on whether or not to include ModFs in the formal quantitative assessment, with the intention to help focus the use of available resources to have the greatest potential to protect public health.

Benchmarking of manganese oxide materials with CO oxidation as catalysts for low temperature selective oxidation

Abstract: CO oxidation behavior of different manganese oxide materials was studied as a model probe reaction to benchmark catalytic activities that could be useful for other aerobic oxidations. K-OMS-2, which showed intermediate activity [Ea = 3.0 and 6.3 kcal/mol for K-OMS-2 (made in solvent free procedure or SF) and K-OMS-2 (made via hydrothermal route or REF) respectively], were chosen for metal dopant studies using microwave assisted hydrothermal synthesis. These were further characterized using X-ray diffraction (XRD), N2 sorption, Raman spectroscopy, scanning electron microscopy (SEM), and carbon monoxide temperature programmed reduction (CO-TPR). Additional characterization was carried out for Ni-K-OMS-2 materials using atomic absorption spectroscopy (AAS) and thermogravimetric analysis-mass spectroscopy (TGA-MS). Doping K-OMS-2 with Ni resulted in a large increase in oxygen mobility and re-adsorption, and the moderate activation energy for CO oxidation (13. kcal/mol) by Ni-K-OMS-2(SF) suggests that Ni-doped materials are good candidates for low temperature selective oxidation.

Developing a framework for dynamic risk assessment using Bayesian networks and reliability data

Abstract: Process Safety in the oil and gas industry is managed through a robust Process Safety Management (PSM) system that involves the assessment of the risks associated with a facility in all steps of its life cycle. Risk levels tend to fluctuate throughout the life cycle of many processes due to several time varying risk factors (performances of the safety barriers, equipment conditions, staff competence, incidents history, etc.). While current practices for quantitative risk assessments (e.g. Bow-tie analysis (BT), Layer of protection analysis (LOPA) etc.) have brought significant improvements in the management of major hazards, they are static in nature and do not fully take into account the dynamic nature of risk and how it improves risk-based decision making. In an attempt to continually enhance the risk management in process facilities, the oil and gas industry has put in very significant efforts over the last decade toward the development of process safety key performance indicators (KPI or parameters to be observed) to continuously measure or gauge the efficiency of safety management systems and reduce the risks of major incidents. This has increased the sources of information that are used to assess risks in real-time. The use of such KPIs has proved to be a major step forward in the improvement of process safety in major hazards facilities. Looking toward the future, there appears to be an opportunity to use the multiple KPIs measured at a process plant to assess the quantitative measure of risk levels at the facility on a time-variant basis. ExxonMobil Research Qatar (EMRQ) has partnered with the Mary Kay O'Connor Process Safety Center – Qatar (MKOPSC-Q) to develop a tool that monitors, in real time, the potential increases in risk levels as a result of pre-identified risk factors and process safety related data, using Bayesian Belief Networks (BN). The development of the tool involved two phases: 1) Development of a methodology that establishes the framework for the tool and 2) Development of the tool itself with the use of JAVA programming language. The overall tool is to be called PULSE, which stands for Process Unit Life Safety Evaluation. In this context, the paper presents a case study of the quantitative risk assessment of a process unit using BN. The different steps of the development of the BN are detailed, including: translation of a Bowtie into a skeletal BN, modification of the skeletal BN to incorporate reliability data, and insertion of equipment failure evidence into the BN for dynamic modeling. In addition, an overview of PULSE is presented. The outcomes of the dynamic modeling of the BN with real time insertion of evidence are discussed and recommendation for the framework for a dynamic risk assessment tool are made.

Impact of high-resolution FWI in the Western Black Sea: Revealing overburden and reservoir complexity

Abstract: The Western Black Sea (WBS) is now an area of active petroleum exploration, and several seismic surveys have been acquired to support the ongoing activity. Seismic imaging in the WBS is challenging due to the presence of complex overburden, such as canyons, shallow gas channels, and complex shallow stratigraphy. Such overburden complexities create amplitude dimming and wipeouts in the images and cause structural distortions of the reservoir units. Conventional velocity model building and seismic migration methods are not optimal for addressing such challenges. Full-wavefield inversion (FWI) technology was applied to overcome the complex seismic-imaging challenges in the WBS and to support the exploration and development program. To date, a suite of FWI products has been used to identify shallow hazards, derisk prospects, optimize well placement, perform accurate resource estimation, and support development planning. Unlike traditional seismic migration, generated FWI products are not simply depictions of ...