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At least 145 records · Page 8

Predicting CO 2 Plume Migration in Heterogeneous Formations Using Conditional Deep Convolutional Generative Adversarial Network

Numerical simulation of flow and transport in heterogeneous formations has long been studied, especially for uncertainty quantification and risk assessment. The high computational cost associated with running large-scale numerical simulations in a Monte Carlo sense has motivated the development of surrogate models, which aim to capture the important input-output relations of physics-based models but require only a fraction of the cost of full model runs. In this work, we formulate a conditional deep convolutional generative adversarial network (cDC-GAN) surrogate model to learn the dynamic functional mappings in multiphase models. The cDC-GAN belongs to a class of semisupervised learning methods that can be used to learn the data generation processes. Like the original GAN, a main strength of the cDC-GAN is that it includes a self-training scheme for improving the quality of generative modeling in a game theoretic framework, without requiring extensive statistical knowledge and assumptions on input data distributions. In particular, our cDC-GAN model is designed to learn cross-domain mappings between high-dimensional input (e.g., permeability) and output (e.g., phase saturations) pairs, with the ability to incorporate conditioning information (e.g., prediction time). As a use case, we demonstrate the performance of cDC-GAN for predicting the migration of carbon dioxide (CO 2 ) plume in heterogeneous carbon storage reservoirs, which has both numerical and practical significance because of the safe storage requirements now mandated in many countries. Results show that cDC-GAN achieves high accuracy in predicting the spatial and temporal evolution patterns of the injected CO 2 plume, as compared to the original results obtained using a compositional reservoir simulator. The performance of cDC-GAN models, trained using the same number of training samples, stays relatively robust when the level of spatial heterogeneity is increased. Our cDC-GAN is pattern based and is not limited by the underlying physics. Thus, it provides a general framework for developing surrogate models, and for conducting uncertainty analyses for a wide range of physics-based models used in both groundwater and subsurface energy exploration applications.

54 ENVIRONMENTAL SCIENCES↗

Linking basin-scale and pore-scale gas hydrate distribution patterns in diffusion-dominated marine hydrate systems: DIFFUSION-DRIVEN HYDRATE GROWTH IN SANDS

The goal of this study is to computationally determine the potential distribution patterns of diffusion-driven methane hydrate accumulations in coarse-grained marine sediments. Diffusion of dissolved methane in marine gas hydrate systems has been proposed as a potential transport mechanism through which large concentrations of hydrate can preferentially accumulate in coarse-grained sediments over geologic time. Using one-dimensional compositional reservoir simulations, we examine hydrate distribution patterns at the scale of individual sand layers (1 to 20 m thick) that are deposited between microbially active fine-grained material buried through the gas hydrate stability zone (GHSZ). We then extrapolate to two- dimensional and basin-scale three-dimensional simulations, where we model dipping sands and multilayered systems. We find that properties of a sand layer including pore size distribution, layer thickness, dip, and proximity to other layers in multilayered systems all exert control on diffusive methane fluxes toward and within a sand, which in turn impact the distribution of hydrate throughout a sand unit. In all of these simulations, we incorporate data on physical properties and sand layer geometries from the Terrebonne Basin gas hydrate system in the Gulf of Mexico. We demonstrate that diffusion can generate high hydrate saturations (upward of 90%) at the edges of thin sands at shallow depths within the GHSZ, but that it is ineffective at producing high hydrate saturations throughout thick (greater than 10 m) sands buried deep within the GHSZ. As a result, we find that hydrate in fine-grained material can preserve high hydrate saturations in nearby thin sands with burial.

03 NATURAL GAS↗

Response surface modeling of CO 2 dynamic storage efficiency factor in high permeability thick sandstones

In order to utilize as much of the pore space for CO 2 storage in high permeability thick saline aquifers, it is vital to investigate the interactions of injected CO 2 with formation brine and rock. In order to quantify the displacement process, we investigate the dynamic storage efficiency factor (DSEF) for saline aquifers where pressure increase is minimal during the injection phase. Dimensionless numbers are derived from basic governing equations, constitutive equations, initial and boundary conditions using the inspection analysis. Then using the Hammersley sequence sampling, 178 numerical experiments are designed, and a compositional reservoir simulator is used to perform these simulations. In the next step, response surface regression analysis is used to establish a relationship between DSEF obtained from the numerical simulations and the corresponding dimensionless numbers. The simulation results show that for the studied conditions the underground dynamics is mostly influenced by the gravity number, followed by effective aspect ratio and dip numbers. The results from the response surface regression analysis are used to develop a correlation, which can be used to estimate the dynamic CO 2 storage capacity of relevant zones. This study provides quantitative measures for the different competing mechanisms involved in underground displacement of fluids in CO 2 geological storage, which can serve as a useful tool during planning phase of storage projects.

02 PETROLEUM↗

High-Temperature Corrosion of Chromia-Forming Ni-Based Alloys in CO 2 Containing Impurities

Future technologies require structural materials resistant to environmental degradation in high-temperature CO 2 -rich environments. In this work, we exposed several commercially available Ni-based alloys (230, 263, 282, 617, 625, and 740H) to atmospheric pressure gases intended to simulate the compositions expected in future direct-fired supercritical CO 2 power cycles. The alloys were exposed to 95% CO 2 + 4% H 2 O + 1% O 2 and the same gas containing 0.1% SO 2 at temperatures of 600, 650, 700, 750, and 800 °C for 2500 h. With minor exceptions, chromia scales formed on all alloys at all temperatures in the SO 2 -free gas, yielding parabolic growth rates that followed an Arrhenius temperature dependence. Behavior in the SO 2 -containing gas was more complex. Generally, the alloys performed well at temperatures of 650, 750, and 800 °C. While some alloys further performed relatively well across the whole temperature range, several of the alloys experienced chromia failure resulting in non-protective duplex oxide scales and high oxidation rates, at temperatures of 600 and 700 °C. Deviation from protective behavior was associated with internal sulfide formation and, additionally for the case of 600 °C, external sulfate formation. Extensive carburization accompanied growth of the non-protective duplex oxide scales, which made it more difficult for the alloy to recover after initiation of the sulfur-induced accelerated corrosion process. The thermodynamic and kinetic factors influencing the accelerated corrosion in the presence of sulfur are discussed. The results suggest that caution is required when assessing compatibility of Ni-based alloys for CO 2 -based systems when sulfur-based impurities are expected.

36 MATERIALS SCIENCE↗

Integrated modeling of second phase precipitation in cold-worked 316 stainless steels under irradiation

The current work combines the Cluster Dynamics (CD) technique and CALPHAD-based precipitation modeling to address the second phase precipitation in cold-worked (CW) 316 stainless steels (SS) under irradiation at 300–400 °C. CD provides the radiation enhanced diffusion and dislocation evolution as inputs for the precipitation model. The CALPHAD-based precipitation model treats the nucleation, growth and coarsening of precipitation processes based on classical nucleation theory and evolution equations, and simulates the composition, size and size distribution of precipitate phases. We benchmark the model against available experimental data at fast reactor conditions (9.4 × 10 –7 dpa/s and 390 °C) and then use the model to predict the phase instability of CW 316 SS under light water reactor (LWR) extended life conditions (7 × 10 –8 dpa/s and 275 °C). The model accurately predicts the γ' (Ni 3 Si) precipitation evolution under fast reactor conditions and that the formation of this phase is dominated by radiation enhanced segregation. The model also predicts a carbide volume fraction that agrees well with available experimental data from a PWR reactor but is much higher than the volume fraction observed in fast reactors. We propose that radiation enhanced dissolution and/or carbon depletion at sinks that occurs at high flux could be the main sources of this inconsistency. The integrated model predicts ~1.2% volume fraction for carbide and ~3.0% volume fraction for γ' for typical CW 316 SS (with 0.054 wt% carbon) under LWR extended life conditions. Finally, this work provides valuable insights into the magnitudes and mechanisms of precipitation in irradiated CW 316 SS for nuclear applications.

36 MATERIALS SCIENCE↗

A multi-phase-field model of topological pattern formation during electrochemical dealloying of binary alloys

Porous metal structures produced by electrochemical dealloying have been extensively studied for use in various applications that require high surface areas. A new comprehensive multi-phase-field (MPF) model is proposed to study topological porous patterns formed by spontaneously etching a bulk binary alloy that involves electrochemical reactions, bulk and surface diffusion, ion transport, applied electrode potential, and charge conservation. The governing equations for the alloy-porous cluster-electrolyte system account for a generalized Butler-Volmer electrochemical reaction and are in accordance with the classical nucleation theory. Based on a quantitative examination of the effects of electrode potential and precursor composition, the simulation results reproduce typical phenomena including passive surface dealloying, active porosity evolution, critical potential, and characteristic length scale in two-dimension (2-D) and three-dimension (3-D). To consider more complicated dealloying systems, the evolutions of a bimodal porous metal structure, nanocomposite, and nested porous network with a structured hierarchy are investigated. Finally, the proposed model can be a useful tool for understanding and predicting the morphology evolution of diverse porous structures during electrochemical dealloying.

Hierarchical porous structure↗

Facile and Efficient Decontamination of Thorium from Rare Earths Based on Selective Selenite Crystallization

The coexistence of radioactive contaminants (e.g., thorium, uranium, and their daughters) in rare earth minerals introduces significant environmental, economic, and technological hurdles in modern rare earth production. Capable, low cost, and green decontamination strategies are therefore desired to ameliorate this problem. In this work, we report a single-step and quantitative decontamination strategy of thorium from rare earths based on a unique periodic trend in the formation of crystalline selenite compounds across the lanthanide series, where Ce(III) is fully oxidized in situ to Ce(IV). This gives rise to a crystallization system that is highly selective to trap tetravalent f-blocks while all other trivalent lanthanides completely remain in solution when coexist. These findings are bolstered by first-principles calculations of lattice energies and an examination of bonding in these compounds. This system is contrasted with typical natural and synthetic systems, where trivalent and tetravalent f-block elements often cocrystallize. The separation factors after one round of crystallization were determined from binary systems of Th(IV)/La(III), Th(IV)/Eu(III), and Th(IV)/Yb(III) to reach 2.1 × 10 5 , 1.2 × 10 5 , and 9 × 10 4 , respectively. Selective crystallization of thorium from a simulated monazite composite yields a separation factor of 1.9 × 10 3 with nearly quantitative removal of thorium.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Identifying High Ionic Conductivity Compositions of Ionic Liquid Electrolytes Using Features of the Solvation Environment

Binary mixtures of ionic liquids with molecular solvents are gaining interest in electrochemical applications due to the improvement in their performance over neat ionic liquids. Dilution with suitable molecular solvents can reduce the viscosity and facilitate faster diffusion of ions, thereby yielding substantially higher ionic conductivity than that for a pure ionic liquid. Although viscosity and diffusion coefficients typically behave as monotonic functions of concentration, ionic conductivity often passes through a peak value at an optimum molar ratio of the molecular solvent to the ionic liquid. The ionic conductivity maximum is generally explained in terms of a balance between the ease of charge transport and the concentration of the charge carriers. In this work, fluctuation in the local environment surrounding an ion is invoked as a plausible explanation for the ionic conductivity mechanism with a binary mixture of 1-ethyl-3-methylimidazolium tetrafluoroborate and ethylene glycol as an example. The magnitude of the dynamism in the local environment is captured by measuring the spatial and temporal features of the solvation environment. Standard deviation in the number of ions in the solvation environment serves as a spatial feature, while the cage correlation lifetimes for oppositely charged ions within the first solvation shell serve as a temporal feature. Large standard deviations in the cluster ion population and short cage correlation lifetimes are indicators of highly dynamic ionic environment at the molecular level and consequently yield high ionic conductivity. Such compositions were found to be in good agreement with the optimum ionic liquid mole fractions obtained through experimental measurement. Short cage correlation lifetimes enable the identification of optimum mixture compositions using simulation trajectories significantly shorter than those required to implement the Nernst–Einstein or Einstein formalisms for calculating ionic conductivity. We validated the applicability of this approach across force fields and in six ionic liquid-molecular solvent electrolytes formed with combination of cations, anions, and solvents. We offer a computationally efficient approach of screening ionic liquid-molecular solvent binary mixture electrolytes to identify molar ratios that yield high ionic conductivity.

25 ENERGY STORAGE↗

Ion-Exchange Interdiffusion Model with Potential Application to Long-Term Nuclear Waste Glass Performance

Ion exchange is an integral mechanism influencing the corrosion of glasses. Due to the formation of alteration layers in aqueous conditions, it is difficult to conclusively deconvolute the process of ion exchange from other processes, principally dissolution of the glass matrix. Therefore, we have developed a method to isolate alkali diffusion that involves contacting glass coupons with a solution of 6 LiCl dissolved in functionally inert dimethyl sulfoxide. Here, we employ the method at temperatures ranging from 25 to 150 °C with various glass formulations. Glass compositions include simulant nuclear waste glasses, such as SON68 and the international simple glass (ISG), glasses in which the nature of the alkali element was varied, and glasses that contained more than one alkali element. An interdiffusion model based on Fick’s second law was developed and applied to all experiments to extract diffusion coefficients. The model expands established models of interdiffusion to the case where multiple types of alkali sites are present in the glass. Activation energies for alkali ion exchange were calculated and the results are in agreement with those obtained in glass strengthening experiments but are nearly five times higher than values reported for diffusion-controlled processes in nuclear waste glass corrosion experiments. A discussion of the root causes for this apparent discrepancy is provided. The interdiffusion model derived from laboratory experiments is expected to be useful for modeling glass corrosion in a geological repository when the silicon concentration is high.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sulfurized Polyacrylonitrile for High-Performance Lithium–Sulfur Batteries: In-Depth Computational Approach Revealing Multiple Sulfur’s Reduction Pathways and Hidden Li + Storage Mechanisms for Extra Discharge Capacity

Like no other sulfur host material, polyacrylonitrile-derived sulfurized carbon (SPAN) promises improved electrochemical performance for lithium–sulfur batteries, based on its compatibility with carbonate solvents and ability to prevent self-discharge and shuttle effect. However, a complete understanding of the SPAN’s lithiation mechanism is still missing because its structural features vary widely with synthesis conditions, and its electrochemical performance deviates from elemental sulfur. This study continues our research on the elucidation of the SPAN’s structural characteristics and lithiation mechanisms via computational approaches. Here, our models reproduce most experimental data regarding carbon’s graphitization level and conjugated ordering, sulfur–carbon covalent bonding, sulfur loading, and elemental composition. Our simulations emulate the discharge voltage observed in experiments for the first discharge, which reveals that sulfur follows multiple reduction pathways based on its interaction with the carbon backbone. Sulfur reduction takes place above 1.0 V vs Li/Li + mostly in the SPAN-like material, with no long-chain lithium polysulfide formation. Below 1.0 V vs Li/Li + , the backbone’s electrochemical activity occurs via multiple C–Li and N–Li interactions, mostly with edge carbon atoms and pyridinic nitrogen. Moreover, we identify Li + binding sites throughout the graphitized backbone that might lead to prohibited energy costs for Li + deintercalation, which may explain the irreversible capacity loss between the first and second discharges. This work improves understanding of lithiation mechanisms in sulfurized carbon, which is useful for rationally designing SPAN synthesis pathways tailored to increase sulfur loading and enhanced electrochemical performance.

25 ENERGY STORAGE↗

Modelling the local atomic structure of molybdenum in nuclear waste glasses with ab initio molecular dynamics simulations

The nature of chemical bonding of molybdenum in high level nuclear waste glasses has been elucidated by ab initio molecular dynamics simulations. Two compositions, (SiO2)57.5 – (B2O3)10 – (Na2O)15 – (CaO)15 – (MoO3)2.5 and (SiO2)57.3 – (B2O3)20 – (Na2O)6.8 – (Li2O)13.4 – (MoO3)2.5 , were considered in order to investigate the effect of ionic and covalent components on the glass structure and the formation of the crystallisation precursors (Na2MoO4 and CaMoO4). The coordination environments of Mo cations and the corresponding bond lengths calculated from our model are in excellent agreement with experimental observations. The analysis of the first coordination shell reveals two different types of molybdenum host matrix bonds in the lithium sodium borosilicate glass. Based on the structural data and the bond valence model, we demonstrate that the Mo cation can be found in a redox state and the molybdate tetrahedron can be connected with the borosilicate network in a way that inhibits the formation of crystalline molybdates. These results significantly extend our understanding of bonding in Mo-containing nuclear waste glasses and demonstrate that tailoring the glass composition to specific heavy metal constituents can facilitate incorporation of heavy metals at high concentrations. K.K. was supported through the Impact Studentship scheme at UCL co-funded by the IHI Corporation and UCL. P.V.S. thanks the Royal Society, which supported preliminary work on this project, and the Laboratory Directed Research and Development program at PNNL, a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy. Via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), this work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Blends of Methylated-Poly(ethylenimine) and Amorphous Porous Organic Cages for SO 2 Adsorption

Porous organic cages (POCs) are emerging porous materials that exhibit intriguing properties in the areas of self-assembly, host-guest interaction, and solution processability. Here in this work, we explore the applicability of POCs as molecular porous supports for polymeric amines. We find that primary amines in poly(ethylenimine) (PEI) can undergo metathesis with the imine bonds present in POCs, resulting in non-porous products. This problem can be overcome by transforming the primary amines in PEI to tertiary amines via methylation. The methylated PEI (mPEI) forms homogeneous composites with amorphous scrambled porous organic cages (ASPOCs) without undesired reactions or phase separation. The microscopic structure of the composites is studied using molecular dynamics simulations. Finally, these composite materials are evaluated as adsorbents for low concentration SO2 (200 ppm) adsorption and show good thermal and cyclic stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Water alternative gas (WAG) optimization for a heterogeneous Brazilian pre-salt carbonate reservoir

Water alternating gas (WAG) is a cyclical process that involves alternating water and gas injections with the primary goal to improve sweep efficiency by maintaining initial high pressure, slowing water and gas breakthrough, and lowering oil viscosity. The objective of this work is to apply and optimize a WAG strategy on a carbonate field with light oil, compare it to the initially planned water-flooding strategy, and investigate the capability of WAG to improve field production. In this research, a compositional reservoir simulator was used to model a WAG process by injecting produced gas into the reservoir, using the same well structure as an optimized water-flooding strategy. Subsequently, a WAG strategy was created, optimizing the number and locations of wells, to facilitate a comparative analysis of the two recovery methods. The WAG optimization involved a detailed assessment of variables such as bottom hole pressure (BHP), WAG cycle duration, maximum gas oil ratio (GOR), and well positioning, to achieve a high net present value (NPV). The study focuses on the application of WAG optimization modeling in unconventional reservoirs, specifically pre-salt carbonate reservoirs, and investigates its implications on production strategy and forecast, emphasizing its potential for maximizing NPV and oil recovery in a recently producing field. The results showed that WAG improved reservoir performance when compared to water injection and produced a greater amount of oil. This solution showed potential to be tested under uncertainties (reservoir heterogeneity, faults, fractures, karsts, vugs, etc.) as future steps.

54 ENVIRONMENTAL SCIENCES↗

Subtropical Jet Regulates Arabian Winter Precipitation: A Viable Mechanism

The present study explores the mechanism governing wintertime (November–April) precipitation over the Arabian Peninsula (AP) using a 17-yr-long (2002–18) high-resolution WRF simulation. The composite analysis of strong precipitation events suggests that the equatorward extension of the upper-level jet together with the embedded upper-level trough creates a positive (cyclonic) midlevel vorticity and subsequently generates an anomalous lower-level convergence through Ekman pumping. This leads to the development of an anomalous surface low, which is further enhanced in the presence of the existing Red Sea trough over the AP. This surface low weakens the persistent anticyclone over the AP, shifting it further eastward to the Arabian Sea. The eastward shift in the lower-level anticyclone contributes to the transport of warm, moist air from the Arabian Sea and the Red Sea toward the AP. This warm, moist air converges with the cold and dry air advected by the midlatitude jet and creates a moisture convergence zone, leading to the initiation of convection. We test the proposed mechanism through numerical experiments with modified upper-level wind and demonstrate that a strong, southward intrusion of the jet can indeed lead to precipitation over the AP. The above mechanism also explains the interannual variability of precipitation over the AP. During wet years, we notice approximately 3 m s -1 stronger jet core magnitude and about a 2° equatorward shift of the jet compared to dry years. While the equatorward extension of the jet explains about 21% of the interannual variability, the jet magnitude explains around 7% of the variability during wet years.

54 ENVIRONMENTAL SCIENCES↗

The initial dissolution rates of simulated UK Magnox–ThORP blend nuclear waste glass as a function of pH, temperature and waste loading

The first comprehensive assessment of the dissolution kinetics of simulant Magnox–THORP blended UK high-level waste glass, obtained by performing a range of single-pass flow-through experiments, is reported here. Inherent forward rates of glass dissolution were determined over a temperature range of 23 to 70°C and an alkaline pH range of 8.0 to 12.0. Linear regression techniques were applied to the TST kinetic rate law to obtain fundamental parameters necessary to model the dissolution kinetics of UK high-level waste glass (the activation energy (Ea), pH power law coefficient (η) and the intrinsic rate constant (k0)), which is of importance to the post-closure safety case for the geological disposal of vitreous products. The activation energies based on B release ranged from 55 ± 3 to 83 ± 9 kJ mol–1, indicating that Magnox–THORP blend glass dissolution has a surface-controlled mechanism, similar to that of other high- level waste simulant glass compositions such as the French SON68 and LAW in the US. Forward dissolution rates, based on Si, B and Na release, suggested that the dissolution mechanism under dilute conditions, and pH and temperature ranges of this study, was not sensitive to composition as defined by HLW-incorporation rate.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗