Methane Hydrate Research Articles

Reparameterization of the mW model to accurately predict the experimental phase diagram of methane hydrate.

Due to their high computational efficiency, the coarse-grained water models are of particular importance for practical molecular simulations of gas hydrates. In these models, the mW model is successfully used to study many thermodynamics and dynamics of methane hydrate. Yet, despite several decades of intense research, the mW model is still found to overestimate the melting temperature of methane hydrate. We here employ the minimum mean squared error estimation to revisit the key parameter of the mW model, which determines the strength of the tetrahedral angle of the water system. Relying on the free energy calculations, we first estimate the chemical potentials of water in the liquid phase for temperatures at which methane hydrate forms. We then turn to the mean squared error to describe the chemical potential deviation between the mW model and the TIP4P/ice model (the latter could reproduce the experimental phase diagram of methane hydrate). By minimizing the mean squared error, we finally have an optimized parameter for the mW model. In this part, we also discuss the pressure effect on such reparameterization procedure. Moreover, relying on the direct coexistence method, the melting temperature determined using the reparameterized mW model is found to be consistent with the experimental data. This strategy provides a means to improve the coarse-grained model to match the experimental observations for temperatures in the range of interest.

Synthesis of long-chain polyester polymers and their properties as crude oil pour point depressant.

Using acrylic acid advanced ester and styrene as raw materials, the long-chain polyester polymer, polyacrylic acid advanced ester-styrene pour point depressant (P-PPD), was synthesized by molecular design, and its structure was characterized by infrared spectroscopy and nuclear magnetic resonance. In addition, this study experimentally investigated the effect of P-PPD on the phase equilibrium and induction time of natural gas hydrate inhibitors in deionized water (DW) and crude oil/water (O/W) systems, respectively. Polyvinylpyrrolidone (PVP) and mono ethylene glycol (EG) were selected as representatives of kinetic hydrate inhibitor (KHIs) and thermodynamic hydrate inhibitor (THIs), respectively. The results exhibit that P-PPD played a sight role in the phase equilibrium of hydrate, while the addition of P-PPD significantly prolonged the induction time of methane hydrate both in O/W + PVP, OW + EG and O/W + PVP + EG system, indicating that the addition of as-synthesized PPD has a synergistic inhibition effect on the nucleation ability of methane hydrate and can prevent hydrate from formatting during oil and gas transport process, and thus guarantee the flow assurance. The findings of this work will provide a data reference for the hybrid use of hydrate inhibitors and pour point depressants in oil and gas transport.

Pressure-regulated rotational guests in nano-confined spaces suppress heat transport in methane hydrates

Materials with low lattice thermal conductivity are essential for various heat-related applications like thermoelectrics, and usual approaches for achieving this rely on specific crystalline structures. Here, we report a strategy for thermal conductivity reduction and regulation via guest rotational dynamics and their couplings with lattice vibrations. By applying pressure to manipulate rotational states, we find the intensified rotor-lattice couplings of compressed methane hydrate MH-III can trigger strong phonon scatterings and phonon localizations, enabling an almost three-fold suppression of thermal conductivity. Besides, the disorder in methane rotational dynamics results in anharmonic interactions and nonlinear pressure-dependent heat transport. The overall guest rotational dynamics and heat conduction changes can be flexibly regulated by the rotor-lattice coupling strength. We further underscore that this reduction mechanism can be extended to a wide range of systems with different structures. The results demonstrate a potentially universal method for reducing or controlling heat transport by developing a hybrid system with tailored molecular rotors.

Load-bearing characteristics of surface conductor in deepwater gas hydrate formations

The surface conductor is the first structural casing in deepwater natural gas hydrate (NGH) development, bearing the top load while suspending the casings of various layers. NGH decomposition leads to formation settlement, changing the mechanical properties of the formation and reducing the bearing capacity of the surface conductor, threatening the safety and stability of the wellhead. Understanding the bearing characteristics of the surface conductor in the hydrate formation can guide the safe drilling operation in the field. By introducing the negative skin friction theory of pile foundations and based on conventional bearing capacity models, a method for calculating the bearing capacity of surface conductors in NGH formations was developed. Using an NGH drilling simulation apparatus, the accuracy of the bearing capacity theoretical model was verified, empirical coefficients under different conditions were obtained, and the influence of soil parameters, hydrate saturation, and decomposition temperature on the bearing capacity of surface conductors was quantified. The results indicated that compared to clay, sandy soils have higher porosity and significantly weakened strength after the decomposition of NGH; when the hydrate saturation in the formation is 20%, the reduction in bearing capacity of the surface conductor in sand exceeds 30%, and in clay soils, it decreases by 25% after complete decomposition of NGH; as the hydrate saturation increases, the reduction in the bearing capacity of surface conductors after decomposition becomes more significant. Verified through Experimentation, the error of the hydrate-bearing strata-bearing capacity model is around 10%. For short-term test production operations of NGH in water, the design depth for surface conductors is around 100 meters. These research results can provide a scientific theoretical basis for the design of conductor depth below the mud， and reduce operational risks.

A Nonaxial-Type Swirling Cavitating Nozzle for Exploiting Natural Gas Hydrate

Summary Natural gas hydrates (NGHs) have garnered widespread attention in the new energy sector, owing to their efficient and clean combustion properties. NGHs are ice-like substances formed by methane and water under high-pressure and low-temperature conditions, abundantly deposited in seabeds and frozen soil of highlands on Earth. However, the rock shelves of NGH reservoirs are mostly fragile and sparsely colloidal. Traditional mechanical mining methods can easily cause rock-shelf collapses, leading to mining accidents. Long-term indoor experiments and pilot mining projects have shown that cavitating nozzles can provide a feasible solution to the problem of efficient mining of NGHs. To further improve the efficiency of cavitating nozzle mining for NGHs, we have optimized and designed a nonaxial-type swirling cavitating nozzle (NASCN) based on traditional swirling cavitating nozzles (SCNs). Both numerical simulations and indoor experiments have verified the higher mining performance of this nozzle. In the numerical simulation experiments, we analyzed the cavitation performance, erosion performance, and energy consumption characteristics of different cavitating nozzles using the mixture multiphase flow model and the renormalization group (RNG) k-ε turbulence model. In the indoor experiments, we utilized a jet erosion experimental device for NGHs to analyze the erosion effects of different cavitating nozzles on hydrate samples. The results of these experiments indicate that the NASCN reduces energy consumption by 12% compared with traditional nozzles when there is little difference in cavitation performance and erosion performance. Moreover, under similar energy consumption, the NASCN improves erosion efficiency by 35.2% compared with traditional nozzles. These results demonstrate that the NASCN has good application value in the mining engineering of NGHs.

Effect of cement slurry filtrate on methane hydrate stability during deepwater cementing operations

Whether the hydrate layer is stabilized during deepwater cementing operations has a direct impact on the safety of the cementing process and the quality of the cementing. When the cement slurry enters the annular space and waits for solidification, it will be extruded to produce filtrate under the action of formation temperature and pressure. Moreover, the inorganic ions and organic matter contained in the filtrate may penetrate into the formation. However, whether these processes have an effect on the stability of the hydrate layer is not clear at present.In this paper, we initially developed a methane hydrate generation system, termed the water-quartz sand-methane system. This system efficiently produces methane hydrate within a short time and ensures a uniform distribution of the gas-solid phase, which is highly suitable for further research into methane hydrate stability. Subsequently, the primary constituents of the cement slurry filtrate and the principal functional groups of the cement additive were identified. Furthermore, enhancements were made to the existing formula for quantifying methane gas alteration. Additionally, a hydrate testing experimental system was employed to circulate a solution comprising the primary constituents of the cement slurry filtrate over the methane hydrate surface. Ultimately, utilizing the amount of change in the volume of methane gas in the cyclic process as a criterion to evaluate the impact of various components of the cement slurry filtrate on methane hydrate stability, an investigation into the effect of the cement slurry filtrate on methane hydrate stability was conducted. It was confirmed that Ca2+, Na+, Cl- ions within the cement slurry filtrate, along with the pH value, minimally influence methane hydrate stability. Conversely, the cement additive exhibits a discernible disruptive effect on methane hydrate stability, with the retarder demonstrating the most pronounced impact when mass fractions are equated.This study suggests that the adverse effects of amide and carboxyl groups on hydrate stability must be considered in the selection of additives for deepwater cementing slurries. The findings offer guidance for the research and development of additives for deepwater cementing slurries and establish a theoretical foundation for studying cementing slurry systems in hydrate formations.

Effects of Crystal Facets of Quartz on the Formation and Dissociation of Natural Gas Hydrates

Effects of Crystal Facets of Quartz on the Formation and Dissociation of Natural Gas Hydrates

Temperature and Pore Pressure Dependencies of the Mechanical Behavior of Methane Hydrate–Bearing Fine-Grained Sediment

Temperature and Pore Pressure Dependencies of the Mechanical Behavior of Methane Hydrate–Bearing Fine-Grained Sediment

Dissociation temperature of gas hydrates through isenthalpic-isobaric molecular dynamics simulations.

Molecular simulations are a powerful tool to understand phenomena and obtain properties of gas hydrate systems. The direct coexistence method (DCM) in the NVT or NPT ensembles, the most commonly used method to determine hydrate dissociation temperatures, can be computationally expensive due to the need for several long simulations. Through an extensive set of simulations, we report here the details of the DCM within the NPH (isobaric-isenthalpic) ensemble, which require fewer and shorter trajectories. The dissociation pressure of methane hydrates is obtained for pressures of 4, 8, 15, 30, and 50 MPa. The values are in agreement with other literature simulations and experimental data. The results are further validated with the calculation of the enthalpy of dissociation, with a value of 50kJ/mol of methane, also in agreement with the literature. The complexity of a multiphase and multicomponent system presents challenges lacking in simpler water/ice systems. These are found to be dependent on energy conservation. The optimal set of parameters to achieve it is also reported, including a smaller time step and the use of double precision, along with an analysis of some factors that could affect the convergence of the method. Although these parameters require more computational cost, the NPH ensemble is successful in providing the dissociation temperature of gas hydrates in fewer simulations than other ensembles and with productions lasting only 500ns.

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

Characterization of Natural Gas Hydrate Constrained by Well and Seismic Data in Qiongdongnan Basin

This study investigates the natural gas hydrates within the Qiongdongnan Basin by integrating well-log and seismic data. Through pre-stack inversion and rock physics analysis, key parameters such as P-wave and S-wave impedances were utilized to distinguish hydrate-bearing formations from other geological bodies. A low-frequency model was constructed using the Inverse Distance Weighting (IDW) algorithm to improve the precision of parameter inversion. This study employs a multi-constraint inversion strategy, incorporating hard constraints from multiple wells and soft constraints from geological frameworks, ensuring reliable inversion results. Findings indicate that hydrate reservoirs are characterized by increased wave velocity and density due to hydrate accumulation, providing insights into the spatial distribution and characteristics of hydrates. This research enhances the understanding of hydrate reservoirs and offers valuable data for exploration in the Qiongdongnan Basin.

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.

Numerical modelling of CO2-in-water emulsion injection into a water-saturated core

Depressurization method shows promise for methane hydrate (MH) reservoir production, but the reformation of hydrates due to a lack of geothermal heat presents a significant challenge for commercial production. This study proposes a novel approach for MH gas recovery by injecting a CO2-in-water (C/W) emulsion into an MH reservoir aquifer. The exothermic nature of CO2 hydrate formation and liquid CO2 dissolution in water in this method provides heat to the MH layer, effectively preventing hydrate reformation. Subsequently, 1-D numerical models were developed and implemented using the MATLAB Reservoir Simulation Toolbox (MRST). These models were rigorously validated against experimental data under homogeneous conditions and varying injection schemes. The investigation indicated that the average volume fraction of CO2 hydrate within the hydrate particles was found to be 55% of the volume of liquid CO2 droplets. The alternating C/W emulsion injection increased the driving force for CO2 dissolution in water, thereby promoting subsequent hydrate particle decomposition and CO2 hydrate dissolution in water, which effectively mitigated blockage within the porous medium. In conclusion, water alternating C/W emulsion injection, along with the continuous injection of a low volume fraction of liquid CO2 within the C/W emulsion, exhibits promising potential for sustained injection and provides adequate heat to the MH layer, preventing hydrate reformation. Furthermore, the developed numerical model reasonably predicts the behavior of various injection schemes. This developed model can be used for devising long term sub-seabed carbon capture and storage development plan.

Dry Flow Technology as Flow Assurance in Methane Hydrate Development

Dry Flow Technology as Flow Assurance in Methane Hydrate Development

Optimizing Carbon Dioxide Injection for Methane Hydrate Development and Carbon Sequestration: A Long-Term Numerical Simulation Study

Optimizing Carbon Dioxide Injection for Methane Hydrate Development and Carbon Sequestration: A Long-Term Numerical Simulation Study

Effect of Isotropic and Anisotropic Permeability on Gas Production Behavior of Site NGHP-01-10D in Krishna-Godavari Basin

This study reports an investigation into both isotropic and anisotropic permeability effects on gas production behavior during depressurization-induced natural gas hydrate dissociation at site NGHP-01-10D in the Krishna-Godavari basin. Numerical simulations were performed on a reservoir-scale model incorporating a single vertical well, examining different scenarios of permeability ratios (rrz). The investigation assessed gas and water production rates, cumulative production volumes, the gas-to-water ratio, and the spatial distribution of reservoir parameters throughout a production duration of 3 years. The findings indicate that permeability anisotropy has a substantial impact on hydrate dissociation and gas recovery. For rrz > 1, horizontal pressure propagation was promoted and gas production increased. For example, at t = 1100 days, the total gas production improved from 7.88 × 105 ST m3 for rrz = 1 to 55.9 × 105 ST m3 for rrz = 10. For rrz < 1, vertical pressure propagation resulted in higher water production with concomitantly lower rates of gas production rates. Spatial distribution analysis revealed that higher rrz values led to more extensive radial propagation of pressure drop, temperature decrease, gas saturation increase, and hydrate dissociation. The study concludes that higher horizontal permeability enhances depressurization effects, resulting in higher gas production rates and more favorable gas-to-water ratios.

Numerical simulation for subsidence control in CO2 storage and methane hydrate extraction

Gas hydrates are increasingly viewed as a promising alternative to traditional fossil fuels. However, their extraction process poses risks to structural integrity, potentially causing significant subsidence. In this study, we developed a Thermo-Hydro-Mechanical-Chemical (THMC) model to analyze the impact of gas hydrate extraction on seabed subsidence. Our investigation focused on the influence of bottom hole flowing pressure, initial hydrate concentration, gas saturation, permeability, porosity, and rock thermal conductivity on subsidence during gas hydrate extraction via depressurization.The results show that seabed subsidence is affected by various factors such as bottom hole flowing pressure, initial hydrate concentration, gas saturation, permeability, porosity, and rock thermal conductivity. It was noted that significant subsidence is associated with low initial hydrate concentration, high permeability, porosity, low gas saturation, low rock thermal conductivity, and a notable pressure drop of 79.31%.To address this issue, we propose a seabed subsidence mitigation strategy involving CO2 injection. This approach not only safeguards offshore infrastructure and coastal communities but also helps reduce CO2 emissions, aligning with global climate change mitigation efforts. In our model, CO2 injection occurs in the subsurface reservoir at the interface between the free water zone and hydrate-bearing formations. The CO2 hydrates formation process releases heat, which dissociates methane hydrates, allowing the methane to be replaced by CO2 molecules and move towards the production well.Our analysis reveals that increasing injection temperature and rate significantly reduces subsidence. Additionally, the range of investigated injection pressures, which included pressures equal to and more than double the initial reservoir pressure, showed inconsequential impacts on seabed subsidence.The effectiveness of subsidence reduction is significantly enhanced by injecting a CO2/N2 mixture compared to pure CO2 injection. The most substantial reduction in subsidence occurred when a mixture of CO2 and N2 in a 50/50 vol/vol ratio was injected at a high rate.These findings offer crucial insights for optimizing the efficiency and control of gas hydrate extraction methods. They emphasize the importance of employing balanced injection strategies to minimize environmental risks and ensure sustainable energy extraction.

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.

Geochemical and Physical Methods for Estimating the Saturation of Natural Gas Hydrates in Sediments: A Review

The saturation of natural gas hydrates is a key parameter for characterizing hydrate reservoirs, estimating hydrate reserves, and developing hydrate as an energy resource. Several methods have been proposed to estimate hydrate saturation, although most of these studies rely on logging and seismic data. However, the methods for estimating hydrate saturation from recovered core sediments have not been thoroughly reviewed, which hinders a deeper understanding, proper application, and the use of these experimental data to integrate geophysical and numerical model results with the actual geological conditions. In this paper, the methods widely used for estimating natural gas hydrate saturation from core sediments, including those based on pore water chemistry (Cl− concentration, δD, and δ18O values), gas volumetric analysis, and temperature anomaly, have been summarized in terms of the principle, estimation strategy, and issues to be considered of each method. The applicability, advantages and disadvantages, and scope of application of each method are also compared and discussed. All methods for estimating gas hydrate saturation have certain limitations. A comprehensive application of results from multiple methods could lead to a better understanding of the amount of gas hydrate in sediments, although the chlorinity of pore water is the most commonly used method of estimation.

How shallow CO2 hydrate cap affects depressurization production in deeper natural gas hydrate reservoirs: An example at Site W17, South China Sea

The logging results from the Shenhu Sea show that the P-T conditions of NGH deposits are below the CO2 hydrate phase equilibrium curve. The burial depth difference between the CO2 hydrate stable zone and NGH deposits is usually above 100 m, which differs from the laboratory scale. Thus, whether CO2 hydrate caps can provide pore sealing and reinforcement of natural gas hydrate (NGH) overburden at the engineering scale is unknown. Based on this, we aimed to perfect research on the CO2 hydrate cap, including its formation process, effects on NGH exploitation, geomechanical response, and comprehensive benefit evaluation, by establishing a THMC model based on Site W17. Results indicate that (i) CO2 can form hydrates in the overburden layer with a conversion rate of about 28%, preventing the upward escape of residual liquid CO2 due to density difference. (ii) CO2 injection and CO2 hydrate cap formation can increase the decomposition driving force during depressurization to enhance production, but it fails to inhibit water invasion from the upper part of the NGH deposit due to the excessive depth difference. (iii) The CO2 hydrate cap causes strata uplift, thereby mitigating strata subsidence during depressurization production, especially for the cases of horizontal wells, where the subsidence is reduced by about 103.4%. (iv) Injecting too much CO2 may not benefit gas production, where part of the free gas will convert into NGH due to pressure rise. The optimal injection rate in this study is 40,000 m3/d. (v) Indicators like CO2 hydrate conversion rate, gas-water ratio, and maximum strata displacement show that horizontal well systems with CO2 hydrate caps are more beneficial than vertical well systems, and multi-branched well systems are more beneficial than single-direction well systems. These key findings may differ from the laboratory scale, which can provide a reference for applying CO2 hydrate caps in actual NGH exploitation.