Methane Hydrate Formation Research Articles

Bubble Evolution and Its Effects on Methane Hydrate Formation in a Restricted Space

Bubble Evolution and Its Effects on Methane Hydrate Formation in a Restricted Space

Biodegradable MAM-based amphiphilic block copolymers: Toward efficient and eco-friendly kinetic inhibitors for methane hydrate formation

The development of low dosage hydrate inhibitors holds significant implications for the oil and gas industry. Some commercially available inhibitors, such as Luvicap EG, are derived from the lactam-containing polymer PVCap, which exhibit limited biodegradability and possess low cloud point (30-40℃), thereby constraining their practical utility. The present study successfully synthesized a series of novel amphiphilic block copolymers based on methacrylamide (MAM) by introducing biodegradable hydrophobic esters (ε-caprolactone (CL), δ-valerolactone (VL), and glycolide (GA)) onto the main chain of poly (methyl acrylamide) (PMAM), serving as KHIs. The synthesized MAM-based polymers maintain water solubility within the range of 0–98 ℃ without thermal responsiveness, effectively preventing deposition issues associated with traditional KHIs. Additionally, all MAM-based polymers demonstrated good biodegradability. The dynamics experiments have shown that PMAM homopolymers did not possess KHI effect, while the MAM-based block copolymers, especially PMAM-b-PVL, exhibited excellent performance in inhibiting hydrate nucleation. At low concentrations, the KHI effect of PMAM-b-PVL was comparable to that of the commercial KHI Luvicap EG. The in-situ Raman spectroscopy experiment further revealed the inhibition mechanism of the amphiphilic polymers, which was achieved by forming effective arrangements at the gas–liquid interface and disrupting the water structure in the interfacial region, thereby impeding the formation of hydrate cages, especially large cages. The findings provided a promising and environmentally friendly solution for the management of hydrates in the oil and gas industry

Comprehensive characterizations of core sediments recovered from Shenhu W17 well in South China sea and its impact on methane hydrate kinetics

Natural Gas Hydrates (NGH) is considered a vast unconventional energy source that holds significant promise in addressing future energy demands. In Shenhu area (located at northern slope of the South China Sea, SCS), there has been conducted a series of further studies of NGH such as exploration, drilling, and twice field production testing. The lithological characteristics of cores from marine sediments and their influence on methane hydrate (MH) formation are relatively unknown and merits further investigation. In this study, we conducted a chain of lithological characterization on the core sediments recovered from Shenhu W17 well, the coring well which located near the 1st NGH field production in SCS. The core sediments are classified as clayey-silt, its median grain size is 6.91 μm, comprising primarily clay minerals, quartz, and calcite. According to X-ray diffraction analysis, the main content of clay minerals is illite-smectite layers, illite, chlorite, and kaolinite, respectively. Porosity of the core sediments is 32.5% and the permeability is 7.8 mD based on mercury intrusion tests. Four types of primary pores are identified based on SEM and QEMSCAN analysis: intergranular pore, intercrystalline pore, intragranular pore, and pores associated with marine fossils. Moreover, the influence of the recovered core sediments (0–40 wt%) on MH formation kinetics were examined with morphology observed to elucidate the MH-core sediments interaction. The induction time was reduced significantly to ∼20 min in the presence of SCS core sediments. A two-stage MH formation behavior is observed with a maximum gas uptake of 134.1 Vg·Vw−1: (a) an initial MH formation at the gas-liquid interface with MH upward growth and fine-grain sediments migration; and (b) a second stage of significant MH growth with layered formation of MH and core sediments. The capillary channels of MH formed facilities the migration of core sediments, which in turn provides additional gas-liquid contact area for MH formation. The study provides valuable insights on the role Shenhu core sediments in MH formation, which is essential for understanding the spatial heterogeneity of NGH in reservoir and for designing suitable production strategy.

Rheological behavior of deep eutectic solvent promoted methane hydrate formation

Natural gas hydrates are recognized as a crucial and sustainable energy resource. The formation, dissociation, and flow properties of CH4 hydrate from deep eutectic solvents (DESs) are investigated using a high-pressure rheometer. In this work, rheological experiments are performed using two DESs namely, tetrabutylammonium bromide + ethylene Glycol (TBAB + EG, DES1) and methyltriphenylphosphonium bromide + ethylene Glycol (MTPB + EG, DES2) at 1 wt% concentration, 274 K temperature and 8 MPa pressure. The hydrate formation starts around 1.7 h for DES1 and around 4 h for DES2. Pressure and viscosity of the slurry are analyzed while methane hydrate forms and dissociates. The pressure drop experienced during hydrate formation is roughly 1.4 MPa for DES1 and 1.7 MPa for DES2. Further, viscosity profiles are analyzed for both DESs with varying shear rate. The viscosity gradually decreases as the shear rate increases. At equilibrium conditions of pure CH4, a spike is observed during dissociation. The rheological data is further analyzed with Cross model to validate the shear-thinning behavior of methane hydrate.

Low-field MRI study of the 1H distribution and migration in porous sediments during natural gas conversion from methane hydrate

Gas hydrates, crystalline compounds formed from water and guest molecules like methane, are gaining attention as a promising clean energy source. While research has extensively focused on the extraction and transport of natural gas hydrates from offshore marine sediments, the dynamic processes in the porous sediments remain under explored. This study employs low-field Magnetic Resonance Imaging (MRI) to investigate the in-situ formation and dissociation of methane hydrate within a partially saturated stack of glass beads. By integrating advanced MRI techniques, including 1D dhk SPRITE, bulk T1 distribution, and 2D spatial T2 imaging, this research provides a comprehensive analysis of fluid distribution and migration during phase transitions in the porous sediments. Three key findings emerged from the study. First, SE-SPI measurements successfully quantified hydrate and residual water saturation, aligning with previous X-ray CT and high-field MRI studies and validating low-field MRI for hydrate research. Secondly, this study introduced a volumetric approach to T1 and T2 measurements, distinguishing between free and bound water, with characteristic relaxation times for each, confirming the technique's capability to differentiate types of residual water. Finally, spatially resolved T2 relaxation time distributions revealed vertical fluid migration within the pore spaces, identifying an equilibrium zone where inflow and outflow rates were balanced. Overall, this study underscores the effectiveness of low-field MRI as a noninvasive tool for analyzing hydrate-bearing sediments. The findings lay the groundwork for further exploration of hydrate in porous sediments, enhancing our understanding of gas production dynamics in hydrate-rich environments.

Effect of Sodium Chloride on the Kinetics of Methane Hydrate Formation in Bulk Soy Lecithin Solutions

Effect of Sodium Chloride on the Kinetics of Methane Hydrate Formation in Bulk Soy Lecithin Solutions

Effect of Allyl and Propargyl Alcohols on the Equilibrium Conditions of Methane Hydrate Formation

Effect of Allyl and Propargyl Alcohols on the Equilibrium Conditions of Methane Hydrate Formation

Beyond gas supersaturation: Dissecting the secondary formation of methane hydrate

Rapid secondary formation of gas hydrate is a critical issue in gas transportation and at the same time has foreseeable potential in future gas storage. Despite the devoted research in the past decade, the intrinsic mechanism of the secondary formation of gas hydrate, is still an on-going subject of debate. Because the secondary formation of gas hydrate is commonly observed under conditions with extraordinarily high content of gas, gas supersaturation is hypothesized as one crucial mechanism. To dissect the gas supersaturation hypothesis, Molecular Dynamics simulations were conducted systematically with hydrate secondary formation in solutions with various gas concentrations covering supersaturation conditions. The effects of key parameters influencing the secondary formation of hydrate, including system temperature and local methane concentration, were explored. The results revealed for the first time a U-shape-like trend in the induction time of hydrate formation with the increase of gas concentration, pinpointing an optimal gas content with the given environmental temperature and pressure. Importantly, the findings highlighted the needed revision of the current gas supersaturation hypothesis in both methane hydrate mitigation and application. This work not only advanced the current understanding of the secondary formation of methane hydrate but also contributed to the fundamental knowledge essential for future gas storage by gas hydrates.

Mineral effects on methane hydrate formation and distribution in sand sediments

Methane hydrate is a promising energy resource widely occurring in the world, but the formation and distribution of methane hydrate in marine sediments with complex minerals remains unclear. Due to the small pore space and fine-grained size of clay minerals, the contact relationship between methane hydrate and clay mineral surface under excess water has not been characterized fully, which is required to investigate the mineral effect on methane hydrate formation. In this study, cryo-SEM was applied to observe the distribution of methane hydrate synthesized in pure quartz sands and the quartz sands mixed with montmorillonite or illite separately. According to the results of the research, methane hydrate dispersedly forms in the pore space away from and on the surface of quartz under a local excess water condition. In addition, methane hydrate occurs away from montmorillonite in pores with excess water and contacts the edge of montmorillonite under a local excess-gas condition. Moreover, methane hydrate was only observed to form away from illite aggregates in the pore with residual water. Montmorillonite and illite influence the preferable distribution of methane hydrate to occur away from mineral surface in excess water condition. In the sediments composed of different minerals, methane hydrate forms stochastically in the pore space and grows up individually. As a result, the findings of this study significantly expand the understanding of the formation and distribution of methane hydrate in marine sediments and the prediction of physical properties of hydrate-bearing sediments, and provide insights into natural gas hydrate exploration and production.

Methane hydrate formation between graphene oxide nanosheets: Insights from molecular dynamics simulations

This work focuses computationally on the role of graphene and graphene oxide nanosheets in improving the formation of methane gas hydrate and their potential as a promising alternative to traditional gas storage and transportation method. To evaluate methane gas mechanism storage between graphene and graphene oxide nanosheets including C8O-flat, C8O-polar, and C8(OH)2 surfaces, radial distribution function, mean squared displacement, number of hydrogen bonding, and coordination number were taken under consideration. Our results showed that methane hydrate is well formed between graphene, C8O-flat, and C8O-polar nanosheets. C8(OH)2 nanosheet has an inhibitory effect on the gas hydrate formation caused by the formation of hydrogen bonds between the hydroxyl functional groups of the sheets and water molecules. To further investigate the degree of hydrate formation, a four-body structural order (F4φ) was obtained. The values of the F4φ parameter for the C8O-flat, graphene, C8O-polar, and C8(OH)2 systems are 0.6, 0.55, 0.51, and −0.02, respectively. These values indicate the presence of an almost complete and regular network of methane hydrate between the first three mentioned sheets. However, the negative value of the F4φ parameter in the last one suggests the absence of significant hydrate formation by ice-like structure of water molecules. The effect of different temperatures on the formation of methane hydrate was also investigated. It is observed that the hydrate structure completely breaks down in the range of 300–400 K in the different structures.

On the Significance of Hydrate Formation/Dissociation during CO2 Injection in Depleted Gas Reservoirs

Summary The study aims to quantitatively assess the risk of hydrate formation within the porous formation and its consequences on injectivity during storage of CO2 in depleted gas reservoirs considering low temperatures caused by the Joule-Thomson (JT) effect and hydrate kinetics. Hydrates formed during CO2 storage operation can occupy porous spaces in the reservoir rock, reducing the rock’s permeability and thus becoming a hindrance to the storage project. The aim was to understand which mechanisms can mitigate or prevent the formation of hydrates. The key mechanisms we studied included water dry-out, heat exchange with surrounding rock formation, and capillary pressure. A semicompositional thermal reservoir simulator is used to model the fluid and heat flow of CO2 through a reservoir initially composed of brine and methane. The simulator can model the formation and dissociation of both methane and CO2 hydrates using kinetic reactions. This approach has the advantage of computing the amount of hydrate deposited and estimating its effects on the porosity and permeability alteration. Sensitivity analyses are also carried out to investigate the impact of different parameters and mechanisms on the deposition of hydrates and the injectivity of CO2. Simulation results for a simplified model were verified with results from the literature. The key results of this work are as follows: (1) The JT effect strongly depends on the reservoir permeability and initial pressure and could lead to the formation of hydrates within the porous media even when the injected CO2 temperature was higher than the hydrate equilibrium temperature; (2) the heat gain from underburden and overburden rock formations could prevent hydrates formed at late time; (3) permeability reduction increased the formation of hydrates due to an increased JT cooling; and (4) water dry-out near the wellbore did not prevent hydrate formation. Finally, the role of capillary pressure was quite complex, as it reduced the formation of hydrates in certain cases and increased in other cases. Simulating this process with heat flow and hydrate reactions was also shown to present severe numerical issues. It was critical to select convergence criteria and linear system tolerances to avoid large material balance and numerical errors.

Study on the formation process of methane hydrates on the surface of wax crystals with pour point depressant

Molecular dynamics simulations were applied to clarify the kinetic pathways and mechanism in the process of methane hydrate formation on the wax crystal surface with ethylene–vinyl acetate copolymer (EVA). The simulation results showed that methane molecules near the surfaces would adsorb on the surfaces of wax-EVA eutectic, while hydrates formed in the bulk of the solution away from the surfaces. The VA side chains on the wax crystal surface inhibit/promote the growth of hydrates by influencing the growth and re-dissolution process of methane nano-bubbles on eutectic surface. When a small amount of VA side chains was introduced on the wax crystal surface, as the simulation proceeded, the generated hydrates would gradually decompose. However, when more VA side chains distribute on the surface of wax crystals, the growth rate of hydrates would increase. In addition, hydrates and wax crystals could connect through a semi-cage structure, in which the VA side chain served as the guest of this semi-cage, making the eutectic and hydrates form a whole and increasing the risk of co-deposition of wax crystals and hydrates.

Kinetics of methane hydrate formation in a 1200 ml unstirred reactor for natural gas storage

Solidified natural gas (SNG) technology via clathrate hydrates, enhanced by promoters such as tetrahydrofuran (THF), promises large-scale natural gas storage due to its high volumetric capacity and mild storage conditions. Despite its potential for industrial scale-up, limited research exists on methane hydrate formation behaviors in large reactors (>1000 cm3), which is crucial for evaluating practical storage performance. In this study, methane hydrate formation kinetics were investigated in a scaled-up unstirred reactor (1200 cm3) at 288.15 K and 283.15 K, and 5.0 MPa. Methane uptake, system pressure, gas and liquid phase temperatures, and hydrate morphologies were analyzed to describe the dynamic hydrate formation process. Results reveal three effects of increased reactor size in contrast to smaller reactors: (i) heterogeneous distribution of THF-rich and methane-rich hydrates; (ii) hydrate bulk show a hollow inner structure with a cavity due to the wall-climbing behavior of hydrate growth; (iii) optimal THF concentration no longer always agrees with stoichiometric 5.56 mol%, which is case-dependent. These effects are attributed to higher diffusion resistances for methane molecules and more intensive heat accumulation. These findings provide some insight into the kinetics of methane hydrate formation in industrial reactors, which is critical for the commercialization of SNG technology.

Insight into the micro-mechanism of hydrate-based methane storage from active ice

Gas hydrate formation in active ice holds significant potential for solidified natural gas storage, while the deep understanding of its micro-mechanism is required for the futural application of such a technology. In this study, the kinetics and micro-properties of methane hydrate formation enhanced by active ice (porous ice containing an unfrozen solution layer of sodium dodecyl sulfate) were investigated via experiments and molecular dynamics (MD) simulations. Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray diffraction (XRD) differential scanning calorimetry (DSC) characterization, and in-situ visual observation confirmed the formation of sI methane hydrate in the active ice system and the occurrence of single-crystal hydrate, and also indicated the occurrence of active water near the surface of porous active ice during the active ice formation. A sensitivity analysis of the hydrate kinetics experiments suggested that temperature is the primary driver of rapid methane hydrate formation in the active ice system. The shortest induction time and t90 for hydrate formation were recorded at 5 s and 5.5 min, respectively. Furthermore, MD simulations indicated that the direct hydrate nucleation and growth in the active water, heat transfer from gas hydrate to ice, and the diffusion of active water (1.24 × 10-9 m2/s) and methane (7.10 × 10-8 m2/s) into the porous ice structure are the primary mechanism that enhances hydrate formation kinetics and methane storage capacity. This work provides an essential microscopic mechanism of the “active ice → active water → gas hydrate” circulation that contributes to the deep understanding and futural application of the efficient hydrate-based solidified methane storage in active ice system.

Synergistic effect of alcohol polyoxyethylene ether sodium sulphate and copper foam on methane hydrate formation

AbstractNatural gas is the cleanest fossil energy source and its consumption is increasing rapidly, so an efficient natural gas way of storing and transporting is urgently needed. Solidified natural gas (SNG) technology is gaining traction because of its higher safety, lower cost, and flexible storage and transportation modes. To improve the methane uptake rate in SNG technology, this work investigated the growth of methane hydrate in fatty alcohol polyoxyethylene ether sodium sulphate (AES) solution with the addition of three different pores per inch (PPI) of copper foam (CF). The results showed that the addition of AES caused the hydrate to grow upwards along the wall, and the methane uptake in the 300 ppm AES solution was increased by 623% compared to pure water. CF not only provided more nucleation sites for hydrate but also transferred the heat generated during hydration. Moreover, there was a synergistic effect between AES and CF and the solution could continuously transport upward along the continuous metal skeleton to increase the gas–liquid contact area. Thus, the formation rate and induction time of methane hydrate improve. Hydrate had the highest methane uptake in the 20 PPI CF system and the lower the pressure, the greater the ability of CF to promote hydrate formation. The methane uptake improved by 27.6% and the induction time was reduced by 59.7% compared to the pure AES system at 6 MPa. This work is aimed at advancing SNG technology (especially at low pressure) and informs the theoretical foundation.

Insights into the dual effect of an amphiphilic additive on hydrate formation from a water structure perspective

Chemical additives play an important role in gas hydrate formation, which involves the transformation of water structure. However, the relationship between the effects of additives on water structure and hydrate formation is inconclusive, especially for amphiphilic molecules. Here, we investigate the changes in water structure caused by rhamnolipid (Rha) biosurfactants and the resulting effect on methane hydrate formation through kinetic experiments, morphological observation, and in situ Raman spectroscopy. The Gaussian peaks of strongly hydrogen-bonded and weakly hydrogen-bonded water are identified, of which the integrated intensity and position are compared. It is found that the dual effect of Rha on hydrate formation kinetics, namely nucleation inhibition and growth promotion, is attributed to the ordered arrangement of water molecules with stronger hydrogen bonding interactions induced by the charged head groups. The strongly hydrogen-bonded water inhibits nucleation but promotes growth. In addition, the adsorption of Rha on montmorillonite (MMT) eliminates the changes in water structure and the dual effect of hydrate formation kinetics, providing further evidence for the above conclusion. These insights pave the way for a deeper understanding of hydrate formation kinetics from a water structure perspective, as well as providing a scientific basis for the commercial application of surfactants.

Phase equilibrium data for semiclathrate hydrates formed with n-propyl, tri-n-butylammonium bromide and tri-n-butyl, n-pentylammonium bromide under methane, carbon dioxide and nitrogen gas pressure

Semiclathrate hydrates are water-based materials formed from aqueous solutions of ionic substances. To enhance the gas capture performance of these materials, it is necessary to direct focus on the cation, which is a key part of construction of the hydrogen-bonding framework. In this paper, we focus on the partly-asymmetric cations, i.e., the n-propyl, tri-n-butylammonium bromide (N3444Br) and tri-n‑butyl, n-pentylammonium bromide (N4445Br), which are yet to be subjected to gas hydrate formation. The three phase equilibrium (gas–hydrate–liquid) conditions for the systems of (N3444Br or N4445Br) + H2O + (CH4, CO2 or N2) in the range of the pressure and mass fractions of the aqueous solutions between 1 and 11 MPa and 0.10–0.40, respectively, are reported. In all the systems, the semiclathrate hydrates were successfully formed under gas pressure. It was demonstrated that both the N3444Br and N4445Br salts promoted hydrate formation under these gases, while in the case with lean aqueous solutions N3444Br acted as an inhibitor of methane hydrate formation in pure water system. The present data are compared with the literature data, and the effect of the side chain length on the phase behavior of the semiclathrate hydrate phase is discussed.

Methane hydrate formation in amino acids / sodium montmorillonite systems

To understand the occurrence of natural gas hydrates in seabed sediments, it is crucial to examine the mechanisms of methane (CH4) hydrate formation in sodium montmorillonite (Na-Mt) systems in the presence of amino acid. Accordingly, this study employed kinetics experiments and molecular dynamics simulations to investigate CH4 hydrate nucleation and growth in an Na-Mt system containing alanine (Ala), leucine (Leu), and phenylalanine (Phe), respectively. Kinetics and Raman experiments showed that, compared with Ala, Leu and Phe enhanced hydrogen bonding between water molecules surrounding Na-Mt. This enhancement was due to the long carbon chain of Leu and the phenyl ring of Phe and facilitated CH4 hydrate formation. Moreover, in the Na-Mt system, Ala reduced CH4 consumption, whereas Leu and Phe increased CH4 consumption. Molecular dynamics simulations revealed that the strength of electrostatic interactions between the negatively charged Na-Mt surface and the functional groups of amino acids affected the distribution of amino acids, thereby altering CH4 aggregation and CH4 hydrate nucleation processes. The strong interaction between Na-Mt and Ala significantly disrupted interfacial interactions between Na-Mt and water molecules. In contrast, the weaker interactions between Na-Mt and Leu and Phe, respectively, meant that these amino acids affected CH4 hydrate nucleation in the bulk-like solution by influencing the arrangement of water molecules. These findings indicate that interfacial interactions between Na-Mt and amino acids play a crucial role in CH4 hydrate formation. Overall, this study generated insights into the formation kinetics and nucleation properties of CH4 hydrates in clay mineral–amino acid complexes that may increase understanding about the occurrence of natural gas hydrates in marine sediments.

Revealing the kinetic behaviors of hydrate formation on bubble surface with different pressure gradients in deep-sea methane seepage areas of the South China Sea

In the deep-sea methane seepage environment, hydrate formation on the methane bubbles is a crucial pathway for methane transformation, and plays an important role in determining whether seepage methane can enter the surface ocean. While how the pressure determines the hydrate formation process in different water depths remains unclear. In this study, we investigated the formation kinetic characteristics and microstructure evolution of methane hydrate on suspended gas bubbles within varied pressure conditions. The pressure range (4–14 MPa) was in the deep-sea methane seepage environment. The results indicated that pressure obviously affected the hydrate film formation characteristics. As pressure increased, the lateral growth rate of the hydrate film accelerated, the hydrate crystal particles became smaller, and the initial hydrate film surface became smoother. Raman spectroscopy results showed that pressure changes did not obviously alter the microporous evolution on the hydrate film surface, that the gas-phase/water-phase Raman peak area ratio exhibited similar trends. The dissolved methane concentration under different pressure conditions was not the primary factor affecting hydrate thickening, rather, it depended mainly on the driving force. This study is of great significance in revealing the characteristics of methane hydrate formation and methane transfer in the oceanic methane seepage environment.

Methane Hydrate Formation and Decomposition Process in Clay-Silt Slurries

Methane Hydrate Formation and Decomposition Process in Clay-Silt Slurries