Gas Hydrate Research Articles

Gas Hydrate Plugging Mechanisms during Transient Shut–In/Restart Operation in Fully Dispersed Systems

Gas hydrate formation poses a significant challenge in offshore oil and gas production, particularly during cold restarts after extended shut–ins, which can lead to pipeline blockages. Although steady–state models have traditionally been used to predict hydrate formation under continuous production conditions, these models are often inadequate for transient operations due to issues like near–zero fluid flow shear affecting the viscosity calculations of hydrate slurries. This study introduces novel conceptual models for dispersed water–in–crude oil systems specifically designed for cold restart scenarios. The models are supported by direct observations and various experimental approaches, including bottle tests, rheometer measurements, micromechanical force apparatus, and rocking cell studies, which elucidate the underlying mechanisms of hydrate formation. Additionally, this work introduces a modeling approach to represent conceptual pictures, incorporating particle settling and yield stress, to determine whether the system will plug or not upon restart. Validation is provided through transient large–scale flowloop tests, confirming the plugging mechanisms outlined. This comprehensive approach offers insights into conditions that may safely prevent or potentially lead to blockages in the fully dispersed system during field restarts, thereby enhancing the understanding and management of gas hydrate risks in offshore oil and gas operations.

Molecular insights into the impact of mineral pore size on methane hydrate formation

Natural gas hydrates are not only substantial energy sources but also have significant applications in the chemical industry and other fields. Although investigating hydrate formation in sediment minerals is crucial for their development and utilization, the underlying hydrate formation mechanism remains unclear. Here, molecular simulations were conducted in systems incorporating hydrophobic and hydrophilic pores of different sizes to investigate methane hydrate formation processes. The findings suggest that, as the hydrophobic slit size increases, there is a larger number of dissolved methane after the system reaches a metastable equilibrium state. The probability of cage formation indicates that hydrate cages readily form on hydrophobic surfaces or in the solution phase near the solution/gas interface. The larger slits are preferred for hydrate nucleation, regardless of whether the surface is hydrophobic, with most initial nuclei located near the liquid/methane interface. However, the interface perturbation can lead to the movement and growth of hydrate nuclei near the solution/methane interface into the bulk solution phase. Additionally, hydrate can nucleate and grow on the hydrophobic surface, facilitated by the adsorbed methane molecules and nonstandard cages. Pores hinder methane storage capacity in the hydrate phase due to the confinement effect and the amorphous nature of the hydrate formed. These molecular-level findings enhance our understanding of hydrate formation in sedimentary environments and porous materials, benefiting the development of natural gas hydrates and the use of porous materials for gas storage and transportation.

Fundamental insights into multistep depressurization of CH4/CO2 hydrates in the presence of N2 or air

Exploitation of natural gas hydrates provides an alternative way to address energy crisis. Dilute CO2 gas (13–30mol%CO2 with remaining N2/Air) injection into CH4 hydrates for hydrate swapping (SW) allows cheaper and more practical CH4 recovery and in-situ CO2 sequestration. However, the roles of N2/Air in dilute CO2 gas during exploitation remain unknown. It is unclear whether depressurization should be coupled after SW and continued below CH4 hydrate stability pressure. This work employed multistep depressurization (MD) to dissociate the mixed hydrates formed after SW from 86.5 to 97.9 bar at 0.7–1.2 °C in bulk-water and sandpack with CH4 hydrate saturation of 4.1–25.3 %. Effects of N2/Air on exploitation were investigated by examining hydrate morphologies and gas compositions. Morphological results in bulk-water indicated higher N2 fraction in 20mol%CO2/N2 triggered more CO2-rich hydrate reformation and CH4-rich hydrate dissociation. Exploitation results in sandpack indicated 13mol%CO2/N2 produced the highest CH4 swapping percent (46.6 %) and CO2 hydrate sequestration percent (29.1 %). Air exerted weaker promoting effects on exploitation compared with equivalent N2. The promotion of N2/Air on exploitation was dominated by dilute CO2 gas injection altering mixed hydrate equilibrium which varied with time-dependent gaseous compositions during MD. l-methionine of 3000 ppm had stronger promoting effects on CO2 sequestration in sandpack than bulk-water depending on mass transfer and water availability. Ceasing points (13.9–31.4 bar) suggested MD could be continued below CH4/above CO2 hydrate stability pressures and before water production. For the first time, this study provided insights into the roles of N2/Air to determine injection gas types and depressurization schemes for efficient and safe hydrate exploitation in gas-rich hydrate-bearing sediment.

Growth Kinetics and Porous Structure of Surfactant-Promoted Gas Hydrate.

Surfactants present in tiny amounts in the aqueous phase are known to be efficient gas hydrate promoters; yet, the promotion mechanisms are still not fully understood. Understanding and directing those mechanisms is key to the implementation of gas-hydrate-based applications such as gas storage and separation, secondary refrigeration or water treatment, and desalination. In this work, the growth at the water/gas interface and the porous structure of surfactant-promoted methane hydrate are observed by optical microscopy and Raman imaging in glass capillaries used as optical cells. Hollow crystals are continuously generated and expelled from the methane/water meniscus into the water or surfactant solution, where they ultimately form the skeleton of a porous medium filled with the solution. Unprecedented information is gathered over a range of scales from the molecular scale (crystal structure and cage filling) to the mesoscale (crystal morphologies, growth habits and pore sizes) and macroscale (rates and amounts of water and gas converted into hydrate and hydrate porosity). Following an early steady-state growth regime, a sudden order-of-magnitude increase of the conversion rate occurs, which is related to gaseous methane microbubbles being directly incorporated across the meniscus in the aqueous solution and later converted to methane hydrate. An assessment and comparison are made of the mechanisms and performance of two common anionic surfactants known to be efficient gas hydrate promoters, SDS (sodium dodecyl sulfate) and AOT (dioctylsulfosuccinate sodium or AerosolOcTyl). AOT provides a quicker but more limited conversion into hydrate than SDS, suggesting that it is more appropriate for continuous flow processes while SDS is better suited for gas storage applications. Raman spectra reveal that cage filling by methane of structure I methane hydrate is not affected by surfactants.

Current Status and Development Trend of Research on Polymer-Based Kinetic Inhibitors for Natural Gas Hydrates.

As the understanding of natural gas hydrates as a vast potential resource deepens, their importance as a future clean energy source becomes increasingly evident. However, natural gas hydrates trend towards secondary generation during extraction and transportation, leading to safety issues such as pipeline blockages. Consequently, developing new and efficient natural gas hydrate inhibitors has become a focal point in hydrate research. Kinetic hydrate inhibitors (KHIs) offer an effective solution by disrupting the nucleation and growth processes of hydrates without altering their thermodynamic equilibrium conditions. This paper systematically reviews the latest research progress and development trends in KHIs for natural gas hydrates, covering their development history, classification, and inhibition mechanisms. It particularly focuses on the chemical properties, inhibition effects, and mechanisms of polymer inhibitors such as polyvinylpyrrolidone (PVP) and polyvinylcaprolactam (PVCap). Studies indicate that these polymer inhibitors provide an economical and efficient solution due to their low dosage and environmental friendliness. Additionally, this paper explores the environmental impact and biodegradability of these inhibitors, offering guidance for future research, including the development, optimization, and environmental assessment of new inhibitors. Through a comprehensive analysis of existing research, this work aims to provide a theoretical foundation and technical reference for the commercial development of natural gas hydrates, promoting their safe and efficient use as a clean energy resource.

Process-controlled gas hydrate formation in coffee solutions for the application of cold concentration

CO2 gas hydrates occur in aqueous systems at elevated pressure and low temperature. They offer prospect to energy efficiency and gentle concentration of liquid foods. In current research, the formation of CO2 gas hydrates in a batch autoclave system for pure water and pure coffee (13–40 wt%) was investigated. Hydrate formation was highly reproducible. When reducing the temperature from 4 to 1 °C, induction times in 13 wt% coffee solutions approached zero, regardless of the applied target pressure (36 vs. 41 bar). Over the used range of temperature, pressure and concentration, different gas hydrate morphologies could be observed, ranging from dispersed gas hydrate crystals in coffee slurry to ordered, large-scale structures. The formation of large continuous hydrate structures bears application potential for efficient removal of gas hydrates from the concentrated liquid.

Implementation of a Numerically Stable Algorithm for Capillary Hysteresis in Gas Hydrate Deposits.

We develop a numerically stable algorithm of intrinsic capillary hysteresis for numerical simulation of gas hydrate deposits where cyclic drainage and imbibition processes occur. The algorithm is motivated by the elastoplastic return mapping, and it is an extension of the recently developed algorithm of two-phase immiscible flow, which provides numerical stability with the fully implicit method. We consider the effective gas and aqueous saturations normalized by total fluid phase saturation implicitly affected by the dynamic formation and dissociation of hydrates. Specifically, gas saturation is additively decomposed into the reversible and irreversible parts, and the algorithm computes the reversible and irreversible parts dynamically during the evolution of gas saturation. We perform numerical tests, including a field-scale case, by implementing the code of the capillary hysteresis in a gas hydrate flow simulator. We find that the developed algorithm is stable and robust for repeated drainage and imbibition processes in gas hydrate systems. Since cyclic depressurization is one of the promising production scenarios for gas production from marine gas hydrate deposits, the developed algorithm and code will provide robust and high-fidelity simulation in the forward simulation of multiphase flow.

Effect of Surfactants on the Synthesis and Dissociation of Gas Hydrates

The synthesis and dissociation of methane hydrate and carbon dioxide hydrate were studied. Nonflammable gas hydrates can be used to extinguish flames in confined spaces. To increase the extinguishing efficiency, it is necessary to increase the dissociation rate (gas release rate) by using surfactant. The work investigates gas hydrates synthesized using sodium dodecyl sulfate (SDS). Experimental studies were carried out in wide ranges of surfactant concentration, the number of the stirrer revolutions and the initial water volume. To achieve the maximum rate of synthesis and dissociation, optimization of the specified parameters was performed. The influence of the key parameters on the dissociation rate was investigated experimentally and theoretically. The novelty of the work lies in solving a complex of interrelated tasks on the synthesis and dissociation of gas hydrate. It is shown that in order to achieve the maximum dissociation rate of carbon dioxide hydrate, it is necessary to optimize the following parameters: the diameter of the particles and their porosity, the porosity of the layer and the external heat flux.

Monitoring the developmental trend and competitive landscape of natural gas hydrate through patent analysis.

Natural gas hydrate (NGH) is a significant alternative energy resource in achieving carbon neutrality. The developmental trend and competitive landscape of NGH exploitation and production are crucial for policymakers in government, managers of enterprises, and researchers. This study introduces a novel framework for conducting an in-depth analysis of NGH, integrating patentometrics, technology evolution, and correlation relationships to monitor developmental trends and competitive landscape through patent analysis. The results indicate that China, the USA, and Japan have distinct technology advantages. Current technological developments in the NGH field focus primarily on extraction technologies, equipment, and processing systems. The co-opetition analysis among countries reveals that the most extensive international cooperation network is primarily in Europe and the USA, with national partnerships in Asia concentrated in China and Japan. Institutional cooperation remains limited, primarily within universities in China, while both the USA and Japan foster collaboration between enterprises. The competitive landscapes of key NGH-related technologies among countries and institutions are also examined. This study contributes not only to monitoring the developmental trend and competitive landscape in NGH but also to providing policy recommendations for government and enterprises regarding strategic management and collaborative innovation.

The geomechanical response of the Gulf of Mexico Green Canyon 955 reservoir to gas hydrate dissociation: A model based on sediment properties with and without gas hydrate

Gas hydrate is commonly found concentrated in sand- and silt-rich reservoirs and these are thought to have great potential as an energy resource. To evaluate this potential, it is critical to understand their in-situ stress state and their behavior during production. We explore the geomechanical behavior of sandy silt sediments from a hydrate reservoir at Green Canyon GC 955, deep-water Gulf of Mexico without hydrate and compare these results to previous work on the same sandy silty sediments with hydrate present. Previous results from hydrate-bearing sediments at GC 955 using intact specimens show that the ratio of lateral to axial effective stress under uniaxial strain (K0) is strongly time-dependent and over long timescales approaches 1 (isostatic stress state). New results from sediments without hydrate using reconstituted specimens reveal that K0 is 0.51 and independent of time and stress. The reservoir without hydrate is approximately three times more compressible than with hydrate. In addition, we find that hydrate-free sediments have a normalized creep rate of Cα/Cc of about 0.028 at all stress levels, whereas hydrate bearing sediments exhibit a decrease in Cα/Cc with stress. We use these observations to present a new geomechanical model that describes how stress and porosity evolve during production of the hydrate reservoir. The key insight in our proposed model is that the sediment skeleton and gas hydrate phases share any applied external load in proportion to their relative stiffnesses. The model results predict that hydrate-bearing sediments are stiffer than gas hydrate-free sediments and that K0 reduces dramatically after gas hydrate dissociation, as is observed. At GC 955, a 5 MPa depressurization is needed to cause gas hydrate dissociation. This change in pore pressure increases the vertical and horizontal effective stresses from 3.8 to 8.8 MPa and 3.8–4.4 MPa, respectively. The dramatic vertical effective stress increase will cause significant compaction (7%) and perturb stresses near the wellbore. These experimental observations and the load-sharing model presented have the potential to underpin a new generation of hydrate reservoir simulation models, which may drive more effective production approaches.

Effects of methanol and ethylene glycol on the interactions between methane hydrate particles and water droplets

Hydrate particle agglomeration is one of the main causes of hydrate blockage in pipelines. Although methanol (MeOH) and ethylene glycol (MeG) are the most used thermodynamic hydrate inhibitors, their effects on the micromechanics behavior of natural gas hydrate particle agglomeration are not clear. In this study, the effects of MeOH and MeG on the interaction force between methane hydrate particles and droplets were investigated using a self-built high-pressure hydrate microforce measuring device. The results suggest that, with the concentration increase from 1% to 7%, for the system with MeOH, the adhesion force reduced by 11% to 33%, while for MeG, the adhesion force reduced by 15% to 43%. On the one hand, the addition of inhibitors reduces the phase equilibrium temperature, which decreases the solidification rate of water in liquid bridge, and on the other hand, they reduce the interfacial tension. both reductions lead to lower adhesion force. Furthermore, in comparison with MeG, the MeOH solutions present a lower contact angle, resulting in a larger hydrate particle-droplet contact area and thus relatively higher adhesion force. The measurement and observation in the present work provide new insight into the mechanism of methanol and ethylene glycol on inhibiting hydrate agglomeration, which is important in advancing the management of hydrate formation in pipelines.

An improved analytical model of effective thermal conductivity for hydrate-bearing sediments during elastic-plastic deformation and local thermal stimulation

As one of the crucial thermal properties controlling the dissociation of natural gas hydrate (NGH), effective thermal conductivity (ETC) should be precisely determined to improve the efficiency of NGH exploitation. But so far, most existing analytical ETC models of hydrate-bearing sediments could not accurately characterize the evolution of ETC. In this paper, an improved analytical model is derived for quantitatively revealing physical relations between ETC and various influencing factors during elastic-plastic deformation and local thermal stimulation processes, including hydrate saturation change, complex pore structures evolution, and hydrate occurrence patterns transition. The effectiveness of the proposed model is validated against available experimental data and compared with other existing models, then effects of various critical parameters on ETC are investigated. Results show that the porosity of hydrate-bearing sediments is accurately predicted during both loading and unloading processes, and the calculated ETC values under various conditions (effective stress, hydrate saturation, and temperature) are satisfactory with the test data. Contributions of elastic deformation and plastic deformation to ETC increments are quantitatively obtained. It is noteworthy that this proposed model is significant to reveal the evolution mechanisms of ETC, helping to accurately predict gas production and offer better plans for efficient NGH exploitations.

Study on the hydrate growth characteristics and rheology of silica-containing sand water-in-oil emulsion system

Understanding the transportability of silica-sand-containing hydrate slurries is crucial for production safety of non-consolidated natural gas hydrate reservoirs, especially when solid-state fluidization technology is utilized. Despite some research on silica sand and marine sediments’ influence on hydrate formation kinetics, rheological studies are scarce for systems with silica sands. The formation process of cyclopentane hydrates under the coexistence of hydrophilic silica particles and surfactants were observed. The effects of the concentration and particle size of silica sands as well as the water cut and surfactant concentration of emulsion on the rheological properties of hydrate slurries were investigated using a rheometer. The results indicated: (1) Hydrophilic sand aggregates were entrapped in water droplets, indirectly affecting the oil–water contact area due to the increase in water droplet volume, which was conducive to the combination of alkanes and water molecules to form a hydrate shell; silica particles provided nucleation sites at the oil–water interface to promote the adsorption and aggregation of cyclopentane molecules. (2) The synergistic effect of silica sand and surfactants significantly shortened the induction time of hydrates and increased the viscosity of the slurry. As the concentration of silica sand (1 wt%, 5 wt%, 10 wt%) increased, the induction time of hydrate formation decreased by 44.8 min. Within the concentration range below 5 wt%, the viscosity of the slurry increased as the concentration increased, with an amplitude of 13830.7 mPa·s. The induction time of hydrate formation decreased with increasing silica sand particle size (2 μm, 6.5 μm, 12 μm), but the size of silica sand particles had no significant effect on the viscosity of the slurry. (3) Hydrate slurries in all systems exhibited shear-thinning behavior. There was no obvious relationship between the yield stress of slurry under different silica sand concentrations. However, the yield stress of the slurry was inversely proportional to the size of silica sand particles. The yield stress decreased by 141.13 Pa when the size of silica sand particles increased from 2 μm to 12 μm. Overall, this study highlighted the influence of silica sand presence on flow safety assurance in solid-state fluidization technology.

The effect of various crystalline forms of HFC 134a hydrate on the growth rate and desalination efficiency

Experimental studies on the synthesis of HFC 134a hydrate in the liquid HFC 134a – water system were performed. Despite today's lack of research on the use of HFC 134a hydrate for desalination of seawater and separation of harmful impurities by HFC 134a hydrate synthesis, this method has prospects for development: HFC 134a hydrate is synthesized at relatively high temperature and low pressure; it is poorly soluble in water, which simplifies gas hydrate separation from water–salt solution; it has high volumetric storage density and relatively high thermal conductivity. In spite of its low solubility in water, HFC hydrate exhibits relatively high growth rates. The growth of various crystalline forms and the peculiarities of their occurrence in pure water, aqueous salt solution, as well as with the addition of surfactant are considered. The use of SDS increases the HFC hydrate growth rate. For the first time, it was shown that the intensive growth of HFC 134a hydrate in the form of needles throughout the entire volume of the liquid allows increasing the efficiency of desalination. It is important to consider the desalination process comprehensively, taking into account the crystal forms, crystal growth rate, crystal defects, as well as taking into account the degree of salt removal. Simultaneously with the bubble growth, a thin gas hydrate film is shown to grow on the bubble surface. A detailed consideration of the stages of such hydrate growth is provided to explain the high-speed synthesis of porous HFC hydrate due to boiling of liquid HFC and vaporization.

Phase equilibria and crystallographic structure of clathrate hydrate formed with carbon dioxide and cyclohexanone

This paper reports the phase equilibrium and crystallographic data of the hydrate formed in the CO2 + cyclohexanone + water system. We measured the phase equilibrium condition and conducted the powder X-ray diffraction measurements. The formation of the structure II hydrate in the system of CO2 + cyclohexanone + water was observed at the temperature from 270.0 K to 275.6 K, under the pressure from 0.62 MPa to 1.70 MPa.At 270.0 K – 275.6 K and 0.62 MPa – 1.70 MPa, the structure II hydrate formed, and the phase equilibrium condition alleviated in the system of CO2 + cyclohexanone + water, while the hydrate formed at 276.5 K - 280.7 K and 2.02 MPa – 3.33 MPa, displayed structure I and cyclohexanone acted as an inhibitor. Equilibrium conditions were measured using the isochoric method, revealing different p-T slopes at high and low temperatures. The high-temperature slope closely resembled that of structure I CO2 hydrate reported previously. We continuously monitored temperature and pressure during the structural phase transition, resulting in a slope change. To directly determine the hydrate structure, PXRD measurements were conducted on two samples: one from the high-temperature side and the other from the low-temperature side. The sample from the high-temperature side exhibited structure I with a lattice constant of 11.8749 (9) Å at 153 K, while the low-temperature sample displayed structure II with a lattice constant of 17.443(1) Å at 153 K.

Exploring C3F8 as a gaseous structure H hydrate former: Implications for hydrate-based greenhouse gas separation and recovery

Octafluoropropane (C3F8) is a fluorinated gas (F-gas) known for its high global warming potential. In this study, the role of C3F8 as a novel gaseous structure H (sH) hydrate former was investigated. By employing a comprehensive methodology involving thermodynamic, crystallographic, and spectroscopic analyses, the successful encapsulation of C3F8 into the large cages of sH hydrates was unveiled for the first time. The incorporation of C3F8 into sH hydrates was inferred from a shift in the thermodynamic hydrate phase equilibria, and unequivocal evidence of successful C3F8 encapsulation was obtained using powder X-ray diffraction, 13C nuclear magnetic resonance, and Raman spectroscopy. The findings showed that C3F8 overcame the conventional limitations associated with sH hydrate formers, which are predominantly liquid and solid substances, thereby significantly expanding the scope of potential gaseous sH hydrate formers. This advancement not only enhances the fundamental understanding of gas hydrate formers but also opens up new avenues for hydrate-based technologies, particularly in the separation and recovery of large-size F-gases, which have substantial environmental implications.

Multiphysics Measurements for Detection of Gas Hydrate Formation in Undersaturated Oil Coreflooding Experiments with Seawater Injection

Multiphysics Measurements for Detection of Gas Hydrate Formation in Undersaturated Oil Coreflooding Experiments with Seawater Injection

Dependence of the formation kinetics of carbon dioxide hydrate on clay aging for solid carbon dioxide storage

Clay-based marine sediments have great potential for safe and effective carbon dioxide (CO2) encapsulation by storing enormous amounts of CO2 in solid gas hydrate form. However, the aging of clay with time changes the surface properties of clay and complicates the CO2 hydrate formation behaviors in sediments. Due to the long clay aging period, it is difficult to identify the role of clay aging in the formation of CO2 hydrate in marine sediments. Here, we used ultrasonication and plasma treatment to simulate the breakage and oxidation of clay nanoflakes in aging and investigated the influence of clay aging on CO2 hydrate formation kinetics. We found that the breakage and oxidation of clay nanoflakes would disrupt the siloxane rings and graft hydroxyl on the clay nanoflakes. This decreased the negative charge density of clay nanoflakes and weakened the interfacial interaction of clay nanoflakes with the surrounding water. Therefore, the small clay nanoflakes enriched in hydroxyl would disrupt the surrounding tetrahedral water structure analogous to the CO2 hydrate, resulting in the prolongation of CO2 hydrate nucleation. These results revealed the influence of the structure-function relationship of clay nanoflakes with CO2 hydrate formation and are favorable for the development of hydrate-based CO2 storage.

Numerical study on the stimulation effect of boundary sealing and hot water injection in marine challenging gas hydrate extraction

This study proposed a novel development mode combining boundary sealing and hot water injection to address the challenges of gas leakage, limited reservoir sensible heat, boundary water intrusion, and low productivity faced by challenging hydrate extraction, and the stimulation effect was numerically investigated with Shenhu hydrates as the geological background. The results showed that lower boundary permeability facilitated pressure propagation and achieved volumetric dissociation of hydrates, whereas insufficient formation energy resulted in substantial gas retention. Hot water injection was effective for stimulation, but open boundaries could not maintain the high injection pressure, leading to massive hot water losses and gas escapes. However, their combination achieved a synergistic stimulation like “1 + 1 > 2” because a piston water drive similar to secondary recovery in oil and gas development was formed. Relative to three-spot well patterns, the five-spot shortened the extraction cycle by 680 days and enhanced the gas-to-water ratio by 17%. Increasing injection pressure enhanced water yield more significantly while the improvement of gas yield was more significant by increasing hot water temperature. Overall, high-pressure and high-temperature injection was suggested for gas enhancement and water control. These findings provide important guidance for advancing the commercial development of challenging hydrates.

Influence of Varying Underinhibition on Methanol in Gas Hydrate Agglomeration

Influence of Varying Underinhibition on Methanol in Gas Hydrate Agglomeration