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Elucidating the temperature and density dependence of silver chloride hydration numbers in high-temperature water vapor: A first-principles molecular simulation study

Hydration numbers of metal complexes in low-density aqueous solutions are required for developing geochemical models for ore-forming metals and for designing supercritical desalination processes. In this study, we investigate the temperature and density dependence of the hydration numbers of silver chloride at 623 K, 673 K, and 713 K and densities of 10–100 kg/m 3 . Experimental estimates of the hydration number in the literature for AgCl at these conditions are inconclusive and possibly contradictory as to the temperature and density dependence. First-principles molecular simulation presents an attractive alternative to experimental measurements. Specifically, recent work shows that machine-learning-accelerated nested Monte Carlo simulations provide reliable estimates for the hydration numbers of CuCl at 623 K from 10 to 100 kg/m 3 . Using the same technique, we find a monotonic temperature dependence, with the hydration number decreasing slightly with increasing temperature. In addition, the simulation-predicted hydration numbers steadily increase with increasing density. These temperature and density trends are in agreement with certain experimental data sets. Therefore, this work demonstrates how first-principles Monte Carlo simulations assist in resolving discrepancies between experimental data sets. Our simulation results also correctly predict that the hydration number, and thus also the solubility, of AgCl is lower than that of CuCl under the same conditions. Furthermore, the bond length and angle formed between the water complex and AgCl differ from those for CuCl, consistent with the lower solubility of AgCl.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of Hydration on Supported V 2 O 5 /TiO 2 Catalysts as Explored by Magnetic Resonance Spectroscopy

Supported vanadium oxide catalysts are important industrial materials for a wide array of chemical transformations. The condition of surface hydration is of particular interest as a reflection of the state of a freshly manufactured catalysts prior to its activation in catalytic reactors or under conditions of photocatalysis where surface vandia are exposed to moisture. Under such conditions, the surface vanadia species undergo structural changes as evidenced by 51 V MAS NMR in this study. For low surface vanadia densities on titania, a modest trend towards the formation of dimeric and oligomeric vanadia species was observed under hydrated conditions when compared to the corresponding dehydrated catalyst, which contains a large abundance of monomeric vanadia species. The incorporation of tungsten oxide to the V 2 O 5 /TiO 2 catalyst with low surface vanadia density, however, is found to better stabilize the surface vanadia species on the titania support upon hydration than its tungsta-free counterpart. This stabilization is not an intrinsic property of more extensively oligomerized surface vanadia species in the presence of tungsten oxide, evidenced by conditions of high concentrations of surface vanadia oligomers on titania that exhibit dramatic structural changes upon hydration. At high surface vanadia coverage under hydrated environments, the simultaneous observation of crystalline V 2 O 5 nanoparticles and a mobile phase of surface vanadia species is apparent, where vanadia species are dissolved in the thin hydration layer on the titania support. These new findings have broad implications on the behavior of other metal oxide species on high surface oxide supports under hydrated conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laboratory Electrical Conductivity of Marine Gas Hydrate

Methane hydrate was synthesized from pure water ice and flash frozen seawater, with varying amounts of sand or silt added. Electrical conductivity was determined by impedance spectroscopy, using equivalent circuit modeling to separate the effects of electrodes and to gain insight into conduction mechanisms. Silt and sand increase the conductivity of pure hydrate; we infer by contaminant NaCl contributing to conduction in hydrate, to values in agreement with resistivities observed in well logs through hydrate–saturated sediment. The addition of silt and sand lowers the conductivity of hydrate synthesized from seawater by an amount consistent with Archie's law. Here, all samples were characterized using cryogenic scanning electron microscopy and energy dispersive spectroscopy, which show good connectivity of salt and brine phases. Electrical conductivity measurements of pure hydrate and hydrate mixed with silt during pressure–induced dissociation support previous conclusions that sediment increases dissociation rate.

58 GEOSCIENCES↗

In-Situ Applied Coatings for Mitigating Gas Hydrate Deposition in Deepwater Operations (Final Scientific/Technical Report)

The Project objectives of this work were focused on the need to develop, investigate, and validate for field and commercial deployment robust pipeline surface treatments to prevent / minimize hydrate and other flow assurance solids deposition in subsea oil flowlines. A robust pipeline treatment that can prevent hydrate and wax/asphaltene adhesion/deposition will be a major fundamental breakthrough in hydrate and flow assurance science and engineering, and to critical Deepwater field operations. The project addressed the current major outstanding issue of mitigating gas hydrate and other solids deposition in different pipeline conditions, a major outstanding issue that has not been solved to-date, despite previous attempts/studies. The major goal of this project was to develop and investigate for deployment robust pipeline coatings to mitigate gas hydrate deposition in Deepwater oil flowlines, which will be critical in offshore leak and spill prevention. As oil and gas production wells mature, the water content and oil composition can change and increase the risk of gas hydrate, wax, and asphaltene deposition and blockages in flowlines, with the cost of complete inhibition becoming prohibitive. The ability to mitigate flow assurance risks in maturing flowlines can extend the life of the field, significantly reduce operational costs from inhibitor injection and prevent potential safety hazards to personnel and equipment and can prevent potential environmental hazards leading to catastrophic hydrocarbon emissions. This research allows for a novel, cost-effective method of mitigating gas hydrate and other pipeline solids deposition/blockages in flowlines, extending the life of the field while being minimally disruptive to normal flowline operation. The omniphobic surface treatment developed in this work can significantly improve the economics of energy transport by providing flow assurance and limiting catastrophic blowouts.

02 PETROLEUM↗

A pseudo-kinetic model to simulate phase changes in gas hydrate bearing sediments

Herein, modeling of the phase transitions anticipated in gas hydrate bearing sediments (GHBS) is critical for a proper understanding of time-dependent changes in states and volumes (e.g. the production of methane from this type of soils). We propose a new pseudo-kinetic approach to simulate the typical phase changes anticipated in GHBS, using published experimental results involving gas hydrate dissociation that are the basis of a widely used kinetic model. The proposed pseudo-kinetic model is formulated in the pressure-temperature (P-T) plane and assumes a rate of gas hydrate dissociation (or formation) proportional to the distance between the current state and the phase boundary. The model consists of only one parameter and is simple to implement in numerical simulators. A similar concept is used to model ice formation/thawing phenomena, but based on the ice/liquid-water phase boundary. We implemented the pseudo-kinetic model in a fully coupled thermo-hydro-chemo-mechanical (THCM) finite element code and validated it against experimental results performed on the dissociation of synthetic gas hydrate. We also evaluated the pseudo-kinetic model using synthetic cases covering several scenarios associated with gas hydrate formation/dissociation and ice formation/thawing. The model successfully reproduced the gas production test from a natural GHBS core from Korea (scaled gas venting experiment over 14 h), and also the formation of gas hydrate and ice in permafrost in Alaska (over 2 × 10 6 years). -The analyses show the versatility of the proposed pseudo-kinetic approach by applying it to model the different types of phase transitions typically encounter in GHBS. The simple formulation, easy implementation in numerical simulator, and reduced number of parameters (only one per phase change) make this model an attractive option for simulating phase transformations in problems involving GHBS.

58 GEOSCIENCES↗

Hydration Mimicry by Membrane Ion Channels

Ions transiting biomembranes might pass readily from water through ion-specific membrane proteins if these protein channels provide environments similar to the aqueous solution hydration environment. In fact, bulk aqueous solution is an important reference condition for the ion permeation process. Assessment of this hydration mimicry concept depends on understanding the hydration structure and free energies of metal ions in water in order to provide a comparison for the membrane channel environment. To refine these considerations, we review local hydration structures of ions in bulk water and the molecular quasi-chemical theory that provides hydration free energies. In doing so, we note some current views of ion binding to membrane channels and suggest new physical chemical calculations and experiments that might further clarify the hydration mimicry concept.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gas hydrate quantification in Walker Ridge block 313, Gulf of Mexico, from full-waveform inversion of ocean-bottom seismic data

The Gulf of Mexico (GOM) Joint Industry Project Leg 2 logging-while-drilling data in Walker Ridge lease block 313 (WR313) in the GOM detected gas hydrate in coarse- and fine-grained sediments at sites WR313-G and WR313-H. The coarse-grained units are thin ([Formula: see text]) and highly saturated, whereas the fine-grained unit is thick (approximately 200 m) with low saturation and fracture-filling gas hydrate. Unlike its coarse-grained counterpart, the seismic character of the fine-grained unit does not clearly indicate the presence of gas hydrate, which would likely have remained undiscovered in the absence of drilling. In this paper, through frequency-domain acoustic full-waveform inversion (FWI) of ocean-bottom seismometer data along a 2D multichannel seismic transect near sites WR313-G and WR313-H, we detect and quantify gas hydrate in the fine-grained unit. Key results are as follows: First, the base of the gas hydrate stability zone, which is not obvious in the reflection profile, can be discerned in the FWI results. Second, the gas hydrate in the fine-grained unit is mainly confined to the area between two sets of opposite-dipping normal faults implying that the fault architecture may be partially responsible for this gas hydrate accumulation and distribution.

Geochemistry & Geophysics↗

Numerical simulation of gas production from natural gas hydrate deposits with multi-branch wells: Influence of reservoir properties

Vast amounts of natural gas hydrate are buried in subseafloor sediments without impermeable boundaries, which is recognized as an essential energy source for the future. Previously, the multi-branch well was proposed to enhance the recovery efficiency of natural gas hydrate, and the gas production rate has been dramatically improved comparing with the vertical well. However, the multi-branch well shows a terrible performance in gas production duration. Here, as a continuation of the previous study, numerical simulations were conducted to investigate the influence of hydrate reservoir properties on the gas production potential. Results indicate that it is hard to extract hydrate commercially for hydrate accumulations without impermeable boundaries. A high initial hydrate saturation leads to a long gas production duration but a low gas production rate. An increase in the intrinsic permeability of isotropic reservoirs would shorten the gas production duration and result in a low gas recovery ratio. Permeability anisotropy shows a noticeable effect on enhancing the gas recovery ratio and the gas production duration due to the improved pressure propagation pattern. Therefore, in the upcoming field tests, reservoir reconstructions that enhance permeability anisotropy are strongly suggested to obtain better outcomes.

03 NATURAL GAS↗

Dynamic in situ imaging of methane hydrate formation in coal media

Fast 3D X-ray imaging has proved to provide crucial insights into multi-phase dynamic processes in various geomaterials. In particular, many in situ imaging experiments have been made to study gas-hydrate formation in porous sandy samples. Such imaging is challenging for the methane gas-hydrate formation in coal samples because of the coal micro-porosity structure and lower X-ray contrast. Here we present results of the first dynamic in situ micro-computed tomography experiment of methane-hydrate formation in coal samples. Synchrotron phase-contrast tomography techniques allowed to achieve necessary contrast levels to separate all the materials of interest (gas, water, coal, and gas hydrate) in reconstructed images with high spatial and temporal resolution. The imaging results are compared to the ones from a similar tomographic experiment with sand samples. Methane-hydrate formation is accompanied by the water movements caused by cryogenic water suction that happens in sequences of short fast movements with longer equilibrium states in between. Only one type of the hydrate formation was observed in coal (growth as shells on grain boundaries) as opposed to three types in sand (shells, growth into gas pockets, and inside water volumes). In particular, this leads to a slower hydrateformation speed in coal. For the coal sample, we also observed water extraction from grains, and interpreted it as competitive sorption of methane. Lastly, we visualized the dynamic behavior of this water extraction via microchannels inside the coal grains, and performed nano-tomography imaging of these channels for a better understanding of this phenomenon.

58 GEOSCIENCES↗

Validation of strongly coupled geomechanics and gas hydrate reservoir simulation with multiscale laboratory tests

In this work, we validate a coupled flow-geomechanics simulator for gas hydrate deposits, named T+M AM , performing two meter-scale laboratory experiments of gas hydrates for production by depressurization, replicating the gas hydrate deposit in the Ulleung Basin, East Sea, South Korea. The first experiment with a sand-only specimen is a 1D 1 m-scale depressurization test based on the excess gas method, which represents the grain coating hydrate growth. On the other hand, the second is a 3D 1.5 m-scale test with the excess water method for a sand-mud alternating layer system, representing the pore filling hydrate growth. We measure production and displacement at the top with different depressurization levels. In particular, the 3D test exhibits high coupling strength of substantial deformation induced by incompressibility of water and high deformability of the specimen. For validation, we match pressure, flow rate, and displacement between the experimental data and numerical results. Thus, we identify that T+M AM is a reliable simulator, which can be applied to fields in both permafrost and deep oceanic hydrate deposits of strongly coupled flow and geomechanics systems. This validation also implies that other coupled simulators based on the same coupling formulation as T+M AM can be validated when individual flow and geomechanics simulators are stable and reliable.

02 PETROLEUM↗

Local stress within a granular molecular solvent matrix, a mechanism for individual ion hydration

The activity of water is important in many natural systems and directed processes. To better understand water activity, the hydration of individual ions is approximated for a recently developed speciation-based solution model. Here a matrix of values for hydration of complete salts (anion and cation) was used as source data to calculate individual ion hydration values. Some electrolytes were excluded from calculations of individual ion hydration due to the prevalence of ion pairing and resulting liberation of water upon ion pairing. Evaluation of the periodic trends emerging from individual ion hydration values suggests that ionic volume, relative to the volume of molecular water, dictates both modeled hydration requirements (related to vapor-liquid-equilibrium-derived activity) as well as properties historically described by hydrodynamic radius (ion diffusion and solution viscosity). When water is conceptualized as a granular three-dimensional matrix, solutes may function as substitutional defects (dilation or constriction) inducing local compressive or tensile stress. These results have implications on the mechanism of the Hofmeister series and series reversals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of layer bending on montmorillonite hydration and structure from molecular simulation

Conceptual models of smectite hydration include planar (flat) clay layers that undergo stepwise expansion as successive monolayers of water molecules fill the interlayer regions. However, X-ray diffraction (XRD) studies indicate the presence of interstratified hydration states, suggesting non-uniform interlayer hydration in smectites. Additionally, recent theoretical studies have shown that clay layers can adopt bent configurations over nanometer-scale lateral dimensions with minimal effect on mechanical properties. Therefore, in this study we used molecular simulations to evaluate structural properties and water adsorption isotherms for montmorillonite models composed of bent clay layers in mixed hydration states. Results are compared with models consisting of planar clay layers with interstratified hydration states (e.g. 1W–2W). The small degree of bending in these models (up to 1.5 Å of vertical displacement over a 1.3 nm lateral dimension) had little or no effect on bond lengths and angle distributions within the clay layers. Except for models that included dry states, porosities and simulated water adsorption isotherms were nearly identical for bent or flat clay layers with the same averaged layer spacing. Similar agreement was seen with Na- and Ca-exchanged clays. In conclusion, while the small bent models did not retain their configurations during unconstrained molecular dynamics simulation with flexible clay layers, we show that bent structures are stable at much larger length scales by simulating a 41.6×7.1 nm 2 system that included dehydrated and hydrated regions in the same interlayer.

58 GEOSCIENCES↗

Tuning Perovskites’ Hydration-Induced Chemical Expansion with Octahedral Tilt Angles

Hydration-induced strains in proton-conducting oxides compromise chemo-mechanical stability when these materials are applied in protonic ceramic electrochemical cells. Here, to develop design principles for zero-strain materials, we systematically studied the hydration coefficients of chemical expansion (CCEs) in perovskite (Sr, Ba)(Ce, Zr, Y)O 3–x solid solutions with in situ dilatometry and thermogravimetric analysis in the range of 430–630 °C. By including and decoupling a wide range of tolerance factors and lattice parameters, we were able to identify a minimum in hydration CCEs (0–0.02) at intermediate tolerance factor values (t ≈ 0.95). Conversely, despite expectations of lower CCEs in larger unit cells, no general trend in CCE versus lattice parameter was found, and opposite trends could be seen for Sr(Ce, Zr, Y)O 3–x versus Ba(Ce, Zr, Y)O 3–x separately. In situ neutron diffraction (ND) enabled atomistic insight. Upon decreasing t, chemical strain anisotropy increased, but this trend did not match the U-shaped dependence of macroscopic CCEs on t. Instead, perovskites with intermediate t, hosting intermediate octahedral tilt angles in the nominally dry state, underwent the largest change in the B–O–B angles during hydration. Accommodating hydration through decreasing B–O–B angles is beneficial because it does not result in large lattice parameter changes. We propose an intermediate tolerance factor as a simple structural descriptor to enable near-zero hydration strains in proton-conducting perovskites.

36 MATERIALS SCIENCE↗

Hydration Free Energies of Polypeptides from Popular Implicit Solvent Models versus All-Atom Simulation Results Based on Molecular Quasichemical Theory

Calculating the hydration free energy of a macromolecule in all-atom simulations has long remained a challenge, necessitating the use of models wherein the effect of the solvent is captured without explicit account of solvent degrees of freedom. This situation has changed with developments in the molecular quasi-chemical theory (QCT)-an approach that enables calculation of the hydration free energy of macromolecules within all-atom simulations at the same resolution as is possible for small molecular solutes. The theory also provides a rigorous and physically transparent framework to conceptualize and model interactions in molecular solutions and thus provides a convenient framework to investigate the assumptions in implicit solvent models. In this study, we compare the results using molecular QCT versus predictions from EEF1, ABSINTH, and GB/SA implicit solvent models for polyglycine and polyalanine solutes covering a range of chain lengths and conformations. The hydration free energies or the differences in hydration free energies between conformers obtained from the implicit solvent models do not agree with explicit solvent results, with the deviations being largest for the group additive EEF1 and ABSINTH models. GB/SA does better in capturing the qualitative trends seen in explicit solvent results. Finally, analysis founded on QCT reveals the critical importance of the cooperativity of hydration that is inherent in the hydrophilic and hydrophobic contributions to hydration-physics that is not well captured in additive models but somewhat better accounted for by means of a dielectric in the GB/SA approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrophilic and Apolar Hydration in Densely Grafted Cationic Brushes and Counterions with Large Mobilities

We employ all-atom molecular dynamics (MD) simulation framework to unravel water microstructure and ion properties for cationic [Poly(2-(methacryloyloxy)ethyl trimethylammonium chloride] (PMETAC) brushes with chloride ions as counterions. First, we identify locally separate water domains (or first hydration shells) each around the {N(CH 3 ) 3 } + and the C=O functional groups of the PMETAC chain and one around the Cl - ion. These first hydration shells around the respective moieties overlap and the extent of the overlap depends on the nature of the species triggering it. Second, despite the overlap, the water molecules in these domains demonstrate disparate properties dictated by the properties of the atoms/groups around which they are located. For example, the presence of the methyl groups make the {N(CH 3 ) 3 } + group trigger apolar hydration as evidenced by the corresponding orientation of the dipole of the water molecules around the {N(CH 3 ) 3 } + moiety. These water molecules around the N(CH 3 ) 3 } + group also have enhanced tetrahedrality as compared to the water molecules constituting the hydration layer around the C=O group and the Cl - counterion. Our simulations also identify that there is an intervening water layer between the Cl - ion and {N(CH 3 ) 3 } + group: this layer prevents the Cl - ion from coming very close to the {N(CH 3 ) 3 } + group. As a consequence, there is a significantly large mobility of the Cl - ions inside the PMETAC brush layer. Furthermore, the C=O group of the PE chain, due to the partial negative charge on the oxygen atom and the specific structure of the PMETAC brush system, demonstrates strongly hydrophilic behavior and enforces a specific dipole response of water molecules analogous to that experienced by water around anionic species of high charge density. As a result, our findings confirm that PMETAC brushes undergo hydrophilic hydration at one site, apolar hydration at another site, and ensures large mobility of the supported Cl- counterions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Charge Dependence of Local Hydration Dynamics in Poly(Acrylic Acid) Solutions

Localized measurements of hydration dynamics surrounding poly(acrylic acid) (pAA) chains are executed using Overhauser dynamic nuclear polarization relaxometry to determine the role of polymer protonation state on the polymer solvation environment. Alterations in polymer concentration and solution pH uncovered three different regimes of local water dynamics ranging from bulk-water-like to subdued water diffusivity. These experiments, combined with molecular dynamics simulations, reveal that the presence of deprotonated carboxylic acid groups promotes a hydrophilic local environment and extended polymer chain configurations that together incentivize the incorporation of bulk-like water near the polymer. This results in a stretched polymer conformation that leads to faster observed hydration dynamics in the local hydration environment. Meanwhile, protonated carboxylic acid groups are expected to engage in intrapolymer hydrogen bonding between monomer groups, resulting in a more collapsed conformation and slower observed hydration dynamics. The importance of the carboxylic acid groups on mediating hydration behavior is further illustrated by their role in dictating the solvation environment around poly(acrylic acid-stat-(poly(ethylene glycol) methyl ether acrylate) (p(AA-stat-PEGMEA)) copolymers with varying monomer ratios. Furthermore, these local hydration measurements establish a connection between local water dynamics and polymer chain conformation and may provide additional molecular perspective into poly(acrylic acid)’s classification as a superabsorbent polymer.

Conformation↗

Salt Hydrate Eutectic Thermal Energy Storage for Building Thermal Regulation (Final Technical Report)

Thermal energy storage is anticipated to play an important role in developing the power grid of the future - a power grid that meets increasing demands of users, is resistant to disruptions, but also allows for greater penetration of renewable resources. Specifically, thermal energy storage materials can be integrated into HVAC systems and building envelopes, where they can be used to shift power demands for building climate control from periods of peak demand to periods of low demand. Phase change materials (PCMs) are compelling as low-cost, high energy density thermal energy storage materials for building thermal management. However, there is a lack of high performance low-cost PCMs within the specific temperature ranges which would most effectively allow for power load shifting. Inorganic salt hydrates represent a promising class of PCMs, but their inherent limitations cause them to be currently unavailable for reliable building applications. The overarching goals of this research effort are to: 1) Discover low-cost, high volumetric density salt hydrate eutectic PCMs to store low-quality heat (10 to 40 °C); 2) Introduce a high thermal conductivity matrix to reduce the time constant for energy storage to ~0.1 to 1 hr, incorporate nucleation catalysts to decrease undercooling, and utilize microencapsulation and shape stabilization approaches, minimizing moisture loss/gain, mitigating phase separation, and maintaining stable melting behavior over the lifetime of the compounds; 3) Evaluate the impact these systems have on peak load shifting, and the potential for overall energy savings under different climatic scenarios and building configurations. These goals will be achieved by an integrated research program consisting of six cohesive research subtasks: 1) Materials discovery of eutectic salt hydrate PCMs by using computationally predicted thermodynamic equilibria, coupled with high-throughput experimental validation, 2) Rapid experimental screening of nucleation catalysts identified through robust computational databases, 3) Embedding salt hydrate PCM into a low cost and scalable high conductivity matrix, 4) Microencapsulation of salt hydrate microspheres using hybrid inorganic-polymer microencapsulation approach, 5) Shape stabilization by thermoreversible salt hydrate salogels, and 6) Analysis of end-use using thermal simulations, and characterization of mock-up energy storage finished components.

25 ENERGY STORAGE↗

Surface Treatment Strategies for Mitigating Gas Hydrate & Asphaltene Formation, Growth, and Deposition in Flowloops

Abstract Numerous solids including gas hydrates, waxes, and asphaltenes have the potential to form in the production lines of gas and oil fields. This creates a highly non-ideal scenario as the accumulation of said species leads to flow assurance issues, especially with long-term processes like deposition. Since an ever-increasing amount of material is deposited in place at the pipe surface, production stoppage or active mitigation efforts become inevitable. The latter production issues result in increased safety risks and operational expenditures. Therefore, a cost-effective, passive deposition mitigation technology, such as a pipeline coating or surface treatment is especially appealing. The ability to address multiple pipeline flow assurance issues simultaneously without actively disrupting production would represent a dramatic step forward in this area. This study is part of a long-term ongoing effort that evaluates the performance and application of an omniphobic surface treatment for solids deposition prevention in industrially relevant systems. In particular, this specific work concentrates on the efficacy and robustness of the treatment under fully flowing conditions. The apparatuses utilized for this include two flowloops: a lab-scale, high-pressure flowloop for gas hydrate and surface treatment durability studies, and a bench-scale, atmospheric pressure loop for crude oil and asphaltene experiments. Film growth in high-pressure flowloop tests corroborated previous reports of delayed gas hydrate nucleation observed in rocking cells. Without the aid of the memory effect, treated oil-dominated experiments never experienced hydrate formation, spending upwards of a week in the hydrate stability zone (at the subcooled/fluid test conditions). Subsequent tests which utilized the memory effect then revealed that the hydrate formation rate reduced in the presence of the surface treatment compared to a bare stainless-steel surface. This testing was part of a larger set of trials conducted in the flowloop, which lasted about one year. The surface treatment durability under flowing conditions was evaluated during this time. Even after experiencing ∼4000 operating hours and 2 full pressure cycles, no evidence of delamination or damage was detected. Finally, as part of an extension to previous work, corroded surface asphaltene deposition experiments were performed in a bench-top flowloop. Treated experiments displayed an order of magnitude reduction in both total oil (all fractions of crude oil) and asphaltene fraction deposited.

03 NATURAL GAS↗