Clathrate Hydrate-Solid Surface Adhesive Shear Strength Measurements on Carbon Steel Surfaces.

Oil and gas flowlines operating in subsea or cold terrestrial environments face the risk of forming hydrate deposits and plugs. The pressure differential across a hydrate plug can cause the plug to detach from the pipe wall and travel through the pipeline, potentially impacting a bend or inline equipment, causing damage or injury to personnel. Therefore, the hydrate-solid adhesive shear strength is of interest in estimating the maximum allowable differential pressure across a plug during depressurization procedures before the plug is likely to detach from the pipe wall.

The crystal orientation of THF clathrates in nano-confinement by polarized Raman spectroscopy.

Gas hydrates form at high pressure and low temperatures in marine sediments and permafrost regions of the earth. Despite forming in nanoporous structures, gas hydrates have been extensively studied only in bulk. Understanding nucleation and growth of gas hydrates in nonporous confinement can help create ways for storage and utilization as a future energy source.

Microscopic insights on clathrate hydrate growth from non-equilibrium molecular dynamics simulations.

Clathrate hydrates form and grow at interfaces. Understanding the relevant molecular processes is crucial for developing hydrate-based technologies. Many computational studies focus on hydrate growth within the aqueous phase using the 'direct coexistence method', which is limited in its ability to investigate hydrate film growth at hydrocarbon-water interfaces.

Stochastic Cellular Automata Modeling of CO Hydrate Growth and Morphology.

Carbon dioxide (CO) hydrates are important in a diverse range of applications and technologies in the environmental and energy fields. The development of such technologies relies on fundamental understanding, which necessitates not only experimental but also computational studies of the growth behavior of CO hydrates and the factors affecting their crystal morphology. As experimental observations show that the morphology of CO hydrate particles differs depending on growth conditions, a detailed understanding of the relation between the hydrate structure and growth conditions would be helpful.

Wetting Properties of Clathrate Hydrates in the Presence of Polycyclic Aromatic Compounds: Evidence of Ion-Specific Effects.

Polycyclic aromatic hydrocarbons (PAHs) have attracted remarkable multidisciplinary attention due to their intriguing π-π stacking configurations, showing enormous opportunity for their use in a variety of advanced applications. To secure progress, detailed knowledge on PAHs' interfacial properties is required. Employing molecular dynamics, we probe the wetting properties of brine droplets (KCl, NaCl, and CaCl) on sII methane-ethane hydrate surfaces immersed in various oil solvents.

Midstream on a chip: ensuring safe carbon dioxide transportation for carbon capture and storage.

Emerging technologies like enhanced oil recovery and carbon sequestration rely on carbon dioxide water content data to ensure that pipelines remain sub-saturated to avoid corrosion and hydrate flow assurance issues. To improve throughput and confidence in the hydrate phase equilibria data to avoid pipeline blockages, further research into the carbon dioxide water content must be conducted. However, the liquid carbon dioxide regime is experimentally difficult to study and the available data disagree between studies.

Surface morphology effects on clathrate hydrate wettability.

Hypothesis: Clathrate hydrates preferentially form at interfaces; hence, wetting properties play an important role in their formation, growth, and agglomeration. Experimental evidence suggests that the hydrate preparation process can strongly affect contact angle measurements, leading to the different results reported in the literature. These differences hamper technological progress.

Water Wettability Coupled with Film Growth on Realistic Cyclopentane Hydrate Surfaces.

Although the wettability of hydrate surfaces and hydrate film growth are key to understanding hydrate agglomeration and pipeline plugging, a quantitative understanding of the coupled behavior between both phenomena is lacking. measurements of wettability coupled with film growth were performed for cyclopentane hydrate surfaces in cyclopentane at atmospheric pressure and temperatures between 1.5-6.

Correlating Antiagglomerant Performance with Gas Hydrate Cohesion.

Although inhibiting hydrate formation in hydrocarbon-water systems is paramount in preventing pipe blockage in hydrocarbon transport systems, the molecular mechanisms responsible for antiagglomerant (AA) performance are not completely understood. To better understand why macroscopic performance is affected by apparently small changes in the AA molecular structure, we perform molecular dynamics simulations. We quantify the cohesion energy between two gas hydrate nanoparticles dispersed in liquid hydrocarbons in the presence of different AAs, and we achieve excellent agreement against experimental data obtained at high pressure using the micromechanical force apparatus.

Carbon dioxide hydrate in a microfluidic device: Phase boundary and crystallization kinetics measurements with micro-Raman spectroscopy.

Various emerging carbon capture technologies depend on being able to reliably and consistently grow carbon dioxide hydrate, particularly in packed media. However, there are limited kinetic data for carbon dioxide hydrates at this length scale. In this work, carbon dioxide hydrate propagation rates and conversion were evaluated in a high pressure silicon microfluidic device.

Structural Effects of Gas Hydrate Antiagglomerant Molecules on Interfacial Interparticle Force Interactions.

Gas hydrate interparticle cohesive forces are important to determine the hydrate crystal particle agglomeration behavior and subsequent hydrate slurry transport that is critical to preventing potentially catastrophic consequences of subsea oil/gas pipeline blockages. A unique high-pressure micromechanical force apparatus has been employed to investigate the effect of the molecular structure of industrially relevant hydrate antiagglomerant (AA) inhibitors on gas hydrate crystal interparticle interactions. Four AA molecules with known detailed structures [quaternary ammonium salts with two long tails (R1) and one short tail (R2)] in which the R1 has 12 carbon (C12) and 8 carbon (C8) and saturated (C-C) versus unsaturated (C═C) bonding are used in this work to investigate their interfacial activity to suppress hydrate crystal interparticle interactions in the presence of two liquid hydrocarbons (-dodecane and -heptane).

The effect of surfactants on hydrate particle agglomeration in liquid hydrocarbon continuous systems: a molecular dynamics simulation study.

Anti-agglomerants (AAs), both natural and commercial, are currently being considered for gas hydrate risk management of petroleum pipelines in offshore operations. However, the molecular mechanisms of the interaction between the AAs and gas hydrate surfaces and the prevention of hydrate agglomeration remain critical and complex questions that need to be addressed to advance this technology. Here, we use molecular dynamics (MD) simulations to investigate the effect of model surfactant molecules (polynuclear aromatic carboxylic acids) on the agglomeration behaviour of gas hydrate particles and disruption of the capillary liquid bridge between hydrate particles.

Hydrate Growth on Methane Gas Bubbles in the Presence of Salt.

Methane bubble dispersions in a water column can be observed in both vertical subsea piping as well as subsea gas seepages. Hydrate growth has been shown to occur at the gas-water interface under flowing conditions, yet the majority of the current literature is limited to quiescent systems. Gas hydrate risks in subsea piping have been shown to increase in late life production wells with increased water content and with gas-in-water bubble dispersions.

New in Situ Measurements of the Viscosity of Gas Clathrate Hydrate Slurries Formed from Model Water-in-Oil Emulsions.

In situ rheological measurements for clathrate hydrate slurries were performed using a high pressure rheometer to determine the effect of hydrate particles on the viscosity and transportability of these slurries. These measurements were conducted using a well-characterized model water-in-oil emulsion ( Delgado-Linares et al. Model Water in-Oil Emulsions for Gas Hydrate Studies in Oil Continuous Systems .

Interfacial Properties and Mechanisms Dominating Gas Hydrate Cohesion and Adhesion in Liquid and Vapor Hydrocarbon Phases.

The interfacial properties and mechanisms of gas hydrate systems play a major role in controlling their interparticle and surface interactions, which is desirable for nearly all energy applications of clathrate hydrates. In particular, preventing gas hydrate interparticle agglomeration and/or particle-surface deposition is critical to the prevention of gas hydrate blockages during the exploration and transportation of oil and gas subsea flow lines. These agglomeration and deposition processes are dominated by particle-particle cohesive forces and particle-surface adhesive force.

Overview: Nucleation of clathrate hydrates.

Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations.

High pressure micromechanical force measurements of the effects of surface corrosion and salinity on CH/CH hydrate particle-surface interactions.

In order to investigate the mechanism of gas hydrate deposition and agglomeration in gas dominated flowlines, a high-pressure micromechanical force (MMF) apparatus was applied to directly measure CH/CH hydrate adhesion/cohesion forces under low temperature and high pressure conditions. A CH/CH gas mixture was used as the hydrate former. Adhesion forces between hydrate particles and carbon steel (CS) surfaces were measured, and the effects of corrosion on adhesion forces were analyzed.

Self-preservation and structural transition of gas hydrates during dissociation below the ice point: an in situ study using Raman spectroscopy.

The hydrate structure type and dissociation behavior for pure methane and methane-ethane hydrates at temperatures below the ice point and atmospheric pressure were investigated using in situ Raman spectroscopic analysis. The self-preservation effect of sI methane hydrate is significant at lower temperatures (268.15 to 270.

Interfacial phenomena in gas hydrate systems.

Gas hydrates are crystalline inclusion compounds, where molecular cages of water trap lighter species under specific thermodynamic conditions. Hydrates play an essential role in global energy systems, as both a hinderance when formed in traditional fuel production and a substantial resource when formed by nature. In both traditional and unconventional fuel production, hydrates share interfaces with a tremendous diversity of materials, including hydrocarbons, aqueous solutions, and inorganic solids.

Micromechanical measurements of the effect of surfactants on cyclopentane hydrate shell properties.

Investigating the effect of surfactants on clathrate hydrate growth and morphology, especially particle shell strength and cohesion force, is critical to advancing new strategies to mitigate hydrate plug formation. In this study, dodecylbenzenesulfonic acid and polysorbate 80 surfactants were included during the growth of cyclopentane hydrates at several concentrations above and below the critical micelle concentration. A novel micromechanical method was applied to determine the force required to puncture the hydrate shell using a glass cantilever (with and without surfactants), with annealing times ranging from immediately after the hydrate nucleated to 90 minutes after formation.

How Properties of Solid Surfaces Modulate the Nucleation of Gas Hydrate.

Molecular dynamics simulations were performed for CO2 dissolved in water near silica surfaces to investigate how the hydrophilicity and crystallinity of solid surfaces modulate the local structure of adjacent molecules and the nucleation of CO2 hydrates. Our simulations reveal that the hydrophilicity of solid surfaces can change the local structure of water molecules and gas distribution near liquid-solid interfaces, and thus alter the mechanism and dynamics of gas hydrate nucleation. Interestingly, we find that hydrate nucleation tends to occur more easily on relatively less hydrophilic surfaces.

Reaction coordinate of incipient methane clathrate hydrate nucleation.

Nucleation from solution is a ubiquitous phenomenon with relevance to myriad scientific disciplines, including pharmaceuticals, biomineralization, and disease. One prominent example is the nucleation of clathrate hydrates, multicomponent crystalline inclusion compounds relevant to the energy industry where they block pipelines and also constitute a potential vast energy resource. Despite their importance, the molecular mechanism of incipient hydrate formation remains unknown.

Development of a high pressure micromechanical force apparatus.

The formation of gas hydrates and subsequent plugging of pipelines are risks that need to be well understood during the production and transportation of oil and gas in subsea flowlines. These flowlines are typically operating at low temperature and high pressure conditions, which are well within the hydrate formation stability region. One of the key processes for hydrate plugs to develop is the agglomeration of hydrates.

Quantitative measurement and mechanisms for CH4 production from hydrates with the injection of liquid CO2.

The recovery of gas from natural gas hydrates under the permafrost and in oceanic sediments is of particular interest in energy and environmental fields because of the attractive process to release methane gas through the injection of CO2. The sequestration of CO2, a notorious greenhouse gas, in hydrates has the potential to be used in enhanced gas recovery techniques, while simultaneously releasing CH4 locked within the gas bearing hydrates. In this study, we present quantitative experiments to investigate results of possible CH4-CO2 exchange kinetics from injection of liquid CO2 through CH4 hydrates.

Two-component order parameter for quantifying clathrate hydrate nucleation and growth.

Methane clathrate hydrate nucleation and growth is investigated via analysis of molecular dynamics simulations using a new order parameter. This order parameter (OP), named the Mutually Coordinated Guest (MCG) OP, quantifies the appearance and connectivity of molecular clusters composed of guests separated by water clusters. It is the first two-component OP used for quantifying hydrate nucleation and growth.