Gas Hydrate Research Articles

Role of Amphiphilicity in Low-Dosage Biodegradable Inhibitors for Clathrate Hydrate: A Kinetic Study of Inhibition by Highly Branched Poly(l-lysine)s

Role of Amphiphilicity in Low-Dosage Biodegradable Inhibitors for Clathrate Hydrate: A Kinetic Study of Inhibition by Highly Branched Poly(<scp>l</scp>-lysine)s

Gas–Water–Sand Inflow Patterns and Completion Optimization in Hydrate Wells with Different Sand Control Completions

Sand production poses a significant problem for marine natural gas hydrate efficient production. However, the bottom hole gas–water–sand inflow pattern remains unclear, hindering the design of standalone screen and gravel packing sand control completions. Therefore, gas–water–sand inflow patterns were studied in horizontal and vertical wells with the two completions. The experimental results showed that gas–water stratification occurred in horizontal and vertical standalone screen wells. The gas–water interface changed dynamically, leading to an uneven screen plugging, with severe plugging at the bottom and high permeability at the top. The high sand production rate and low well deviation angle exacerbated screen plugging, resulting in a faster rising rate of the gas–water interface. The screen plugging degree initially decreased and then increased as the gas–water ratio increased, resulting in the corresponding variation in the gas–water interface rising rate. Conversely, gas–water stratification did not occur in the gravel packing well because of the pore throat formed between the packing gravels. However, the impact of gas and water led to gravel rearrangement and the formation of erosion holes, causing sand control failure. A higher gas–water ratio and lower packing degree could result in more severe destabilization. Therefore, for the standalone screen completion, sand control accuracy should be designed at different levels according to the uneven plugging degree of the screen. For the gravel packing completion, increase the gravel density without destabilizing the hydrate reservoir, and use the coated gravel with a cementing effect to improve the gravel layer stability. In addition, the screen sand control accuracy inside the gravel packing layer should be designed according to the sand size to keep long-term stable hydrate production.

Semi-automated analysis of faults with meter-scale displacements and networks of planar features using high-resolution 3D seismic to investigate gas leakage at the Vestnesa Ridge, eastern Fram Strait

We develop a semiautomated method for extracting faults and other planar features from two high-resolution (HR) seismic volumes in the eastern Fram Strait. We assess seismic data quality and resolution prior to structural interpretation to determine the appropriate processing workflow. This workflow, designed for HR data sets, identifies meter-scale (&gt;3–4 m) faults and other planar features, picked up by subtle changes in the curvature and discontinuities of seismic reflections, to investigate their relationship with fluid migration in the shallow subsurface. Although evidence exists for Holocene (approximately &lt;8 ka) fault-associated gas seepage, structures in both volumes are presently sealing. We assess structures based on those that have measurable throw (faults) and those that do not (planar features). Structures lacking measurable throw are significant because they appear to represent fluid flow pathways. This technique enhances the analysis of the geometries of the mapped structures, facilitating the interpretation of meter-scale fault throws and the orientations of planar features. We provide insights into the evolution of structures previously linked to episodes of fluid migration and gas leakage at the Vestnesa Ridge. We infer zones of dilation (i.e., opening) at locations where faults or networks of planar features interact and investigate how these structures influence localized uplift and shallowing of the interface between free gas and gas hydrate (i.e., the bottom-simulating reflection).

RATIONALE FOR THE USE OF A HYDRATE FORMATION INHIBITOR IN PRODUCTION WELLS IN WESTERN SIBERIA

Operation of the gas transmission system under hydrate conditions leads to the risk of deposits, changes in operating modes and plugging of pipelines and gas transmission equipment. Inhibitors such as methanol and glycols are mainly used to prevent hydrate formation. Less commonly, small amounts of polymer compounds (kinetic inhibitors) are used, which instead of inhibiting formation work thermodynamically, slowing the rate of formation of gas hydrates. However, the problems associated with excessive methanol consumption and the production of products that do not meet the standards for the content of dissolved methanol remain unresolved. These problems can be solved by improving the technological scheme of gas collection and treatment. The article focuses on the use of methanol as a hydrate inhibitor, which effectively prevents this process. It has been shown that in order to optimize the flow rate of methanol, it is necessary to take into account the salinity of formation water. The urgency of the problem is due to the high risks for the normal operation of wells, since gas hydrates can lead to clogging of equipment and pipelines, which in turn can cause emergencies and shutdown of the entire production. The article describes the current status of field development in Western Siberia, including an analysis of reserves and an assessment of production potential. Seven pay zones have been identified in the field, two of which are associated with the Upper Cretaceous deposits, four with the Upper Jurassic and one with the Middle Jurassic. The authors proposed a method for calculating the optimal amount of methanol required to prevent the formation of gas hydrates. The calculations are based on data on the composition of Cenomanian gas, temperature and other conditions in the field under consideration. The study identified critical points where gas hydrates are most likely to form. This made it possible to accurately calculate the required amount of methanol to maintain the hydrate-free state of the wells. The results of testing in the field of Western Siberia showed that the dosing of methanol is an effective means to prevent hydrate formation.

Production Simulation of Stimulated Reservoir Volume in Gas Hydrate Formation with Three-Dimensional Embedded Discrete Fracture Model

Natural gas hydrates (NGHs) in the Shenhu area of the South China Sea are deposited in low-permeability clayey silt sediments. As a renewable energy source with such a low carbon emission, the exploitation and recovery rate of NGH make it difficult to meet industrial requirements using existing development strategies. Research into an economically rewarding method of gas hydrate development is important for sustainable energy development. Hydraulic fracturing is an effective stimulation technique to improve the fluid conductivity. In this paper, an efficient three-dimensional embedded discrete fracture model is developed to investigate the production simulation of hydraulically fractured gas hydrate reservoirs considering the stimulated reservoir volume (SRV). The proposed model is applied to a hydraulically fractured production evaluation of vertical wells, horizontal wells, and complex structural wells. To verify the feasibility of the method, three test cases are established for different well types as well as different fractures. The effects of fracture position, fracture conductivity, fracture half-length, and stimulated reservoir volume size on gas production are presented. The results show that the production enhancement in multi-stage fractured horizontal wells is obvious compared to that of vertical wells, while spiral multilateral wells are less sensitive to fractures due to the distribution of wellbore branches and perforation points. Appropriate stimulated reservoir volume size can obtain high gas production and production efficiency.

Experimental Study on Mechanical Properties of Artificial Cores Saturated With Ice: An Analogical Simulation to Natural Gas Hydrate Bearing Sediments

ABSTRACTThis work takes the natural gas hydrate (NGH) reservoir in the Shenhu area at the South China Sea as the target. Using the quartz sand, calcite grains, and illite powder as the main mineral composites, and Portland cement as the bonding material, the host skeleton with similar porosity and mechanical properties to the target reservoir were prepared. Ice was used to simulate natural gas hydrates for their high similarity in mechanical properties and distributions within porous host. The ice saturation in the host skeleton is quantitatively controlled by the quality method. As an analogical simulation, artificial samples with different ice saturations were tested by uniaxial compression measurements and the Brazilian tensile tests, aiming to reveal the mechanical behavior of NGH sediments. The results indicated that the plasticity of the artificial sample increases and its damage form transitions from brittleness to ductility as the ice saturation increases. The effects of free water and ice on the strength of saturated samples are quite different. The free water tends to reduce the strength of the sample due to illite hydration and change of internal friction. The bonding effect of ice tends to increase the strength of the sample, while the ice could also reduce the internal friction. When the ice saturation is larger than 30%, the compressive and tensile strengths of the sample increase with ice saturation, which could be regressed as yc = 2.2628S + 0.8322, and yt = 0.411S + 0.0273, respectively. The constitutive model was developed based on the equivalent medium theory and the D‐P criterion, which could describe the experiment data well with deviations less than 10%.

Saturation model for pore-type gas hydrate based on additional muddy conductive digital core

Abstract Original natural gas hydrate rock samples readily decompose under environmental changes during extraction, presenting challenges to conventional rock electrical analysis. This results in difficulty obtaining the cementation factor m and saturation exponent n of hydrate samples, thereby complicating the evaluation of hydrate saturation. Therefore, a method for revising the rock electrical parameters by digital core technology is proposed. Utilizing X-ray CT images of artificial gas hydrate samples, digital core models of natural gas hydrates were established. An erosion algorithm was employed to simulate the variation in mud content within the digital core, followed by the calculation of resistivity using the finite element method after meshing. Through analyzing the primary micro-pore structure parameters that influence the rock electrical parameters, the saturation model was subsequently refined. The results showed that the resistivity of hydrate digital core magnifies with increasing saturation of hydrate, tortuosity, and pore-throat ratio, but decreases with increasing coordination number and mud content. The rock electrical parameters were changed with the alteration of micro-pore structure. Based on the relationship between m, n, and micro-pore structure parameters, established a correction equation for them, further improved the Indonesian equation. The saturation of hydrate reservoir in Shenhu Sea area was evaluated using the modified Indonesian equation. The modified equation reduced the relative error from 34.8% to 15.6%, significantly enhanced the calculation accuracy.

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.

High Resolution X-ray Diffraction Studies of the Natural Minerals of Gas Hydrates and Occurrence of Mixed Phases

The types and concentrations of gas hydrates collected from four different geological sites were analyzed using high-resolution angular dispersive X-ray powder diffraction, with synchrotron radiation as the source. Measurements were taken across a temperature range of 80 to 300 K and a pressure range of 0.1 to 80 MPa. All four gas hydrate samples showed the presence of three mixed crystal structures: structures I, II, and H. Additionally, the ice Ih structure was inherently present in all the natural gas hydrate minerals. The variation in the types and concentrations of gas hydrates can be attributed to the diversity of natural gases at different geographic locations.

Energy Efficiency Analysis of Hydrate and Ionic Liquid-Based Binary Gas Separation Processes

Energy Efficiency Analysis of Hydrate and Ionic Liquid-Based Binary Gas Separation Processes

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.

Magnetically recoverable nanoparticle organic hybrid materials as kinetic hydrate inhibitors

Gas hydrates pose significant risks in the oil and gas industry because of their tendency to form blockages in transportation pipelines under low-temperature and high-pressure conditions. Conventional thermodynamic hydrate inhibitors require high dosages, with associated substantial costs and environmental concerns. Kinetic hydrate inhibitors (KHIs), which operate at much lower dosages, offer a more sustainable solution but are often limited by environmental compatibility and recovery problems. In this study, we introduce a novel class of magnetically recoverable KHIs utilizing nanoparticle organic hybrid materials (NOHMs), named NOHM-I-PNIPAM, featuring a tunable Fe3O4 core-SiO2 shell structure with poly(N-isopropylacrylamide) (PNIPAM) as the organic component. The chemical properties of NOHM-I-PNIPAM were characterized using TEM, FT-IR, and XPS. The hydrate kinetic inhibition performance was evaluated with a CH4 (90 %) + C2H6 (7 %) + C3H8 (3 %). Various grafting densities of PNIPAM on NOHMs and weight fractions of NOHM-I-PNIPAM were used to explore NOHM-I-PNIPAM’s role in the formation kinetics of natural gas hydrates under different cooling rates. Notably, the NOHM-I-PNIPAM (1.0), when utilized at a 2 wt% dosage, exhibited the most effective inhibition performance in terms of the onset temperature of CH4 (90 %) + C2H6 (7 %) + C3H8 (3 %) hydrate. Considering the effective concentration of PNIPAM in NOHM-I-PNIPAM, the inhibition performance was found to be comparable to that of conventional PNIPAM. Results showed that NOHM-I-PNIPAM is a promising KHI due to its combined properties of magnetic separation and comparable kinetic inhibition performance. Experimentally, NOHM-I-PNIPAM demonstrated stability over long-term cycles and was effectively magnetically separated. Hence, we believe that this work can provide valuable insights into the potential of NOHMs as recoverable and reusable KHIs for industrial applications for flow assurance.

Study on growth characteristics of TBAB clathrate hydrate from flowing TBAB solution in a rectangular channel

Study on growth characteristics of TBAB clathrate hydrate from flowing TBAB solution in a rectangular channel

The role of mobile muds in basin form and fill in the tectonic and sedimentologically complex region of the Southeastern Margin of the Caribbean Plate, Trinidad and Tobago, West Indies

The southern portions of the Barbados Accretionary Prism and the eastern deepwater region of Trinidad and Tobago are a seafloor terrain marked by scattered mud volcanoes, mud walls, and mud canopies that rise several hundred meters above the modern seafloor. We use 3D seismic and recently drilled wells to examine this area, dividing it into three tectonomorphic provinces based on the nature of the mud architecture, the structuration, basin types developed, and sedimentary systems occupying the basins. Mud architectures become more massive as one moves northward toward the active tectonic prism. The mud wall in the far northern Mud Wall Province is classified as a mud canopy system, similar to those documented by workers in the North Sabah Pagasa Wedge, Borneo. The Trinidad mud canopy exhibits sutures in the mud mass margins (akin to salt sutures) that separate submasses likely composed of different materials and exhibiting different pressures and properties. These submasses and associated sutures are imageable using the sweetness attributes on the near-stack seismic volume. Anticlines in the isolated mud and distributive provinces, similar to those that are the dominant hydrocarbon-producing structures onshore and offshore Trinidad, show mobile mud cores and are associated with extensional and compressional faulting that provide pathways for hydrocarbon migration into the surrounding lutokinetic stratigraphy. A bottom simulating reflector associated with the base of the gas hydrate zone, extensive across the study area, may be a good indicator of fluid flux activity and subsurface pressure states in mud masses. It is important to use all the seismic data volumes (full, near, mid, and far seismic data stacks) to assess different aspects of these mud diapiric systems.

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.

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

Natural gas hydrates are non-stoichiometric crystalline compounds composed of natural gas and water, typically found in the pore spaces constructed by minerals. Mineral crystals exhibit significant variations in surface properties among different crystal facets. Despite the importance of these mineral crystal facets, previous studies have not reported their influence on natural gas hydrates. To address this gap, we focused on quartz, a vital component of hydrate reservoirs, and studied the process of natural gas hydrates formation and dissociation on its distinct crystal facets. In our investigation, we simplified pores as narrow gap spaces between two parallel quartz substrates, and captured the entire process with a microscope. The results indicate that the formation and dissociation of natural gas hydrates are notably influenced by the distinct crystal facets of quartz. The influences of quartz crystal facet on the hydrate formation are primarily attributed to two factors, wettability and hydroxyl concentration of quartz crystal facet. We have also revealed the mechanism of how quartz crystal facet influences the hydrate dissociation. This research provides a fundamental understanding of how mineral crystal facets influence the hydrate formation and dissociation, offering a novel perspective for the design of processes for extracting hydrate.

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.

Quantifying the relative provenance contributions to submarine channel systems in the Qiongdongnan Basin since the Miocene: Implications for tectonic responses and channel migration

AbstractThe submarine Miocene Central Canyon and Pleistocene channel systems in the Qiongdongnan Basin constitute valuable sedimentary records that provide insight into the depositional processes and sediment routing from the hinterland to the deep sea. However, the primary source of sediment for the Pleistocene channel systems and the variation in relative sediment contributions since the Miocene from potential source terranes remain unknown. We have integrated new and published detrital zircon U–Pb ages and rare earth elements (REEs) from Pleistocene channel sands and late Miocene Central Canyon sands in the Qiongdongnan Basin to analyse the sediment routing system of these channel systems since the Miocene. Qualitative analyses of REEs, comparisons of detrital zircon age spectra, and multidimensional scaling plots suggest that the Red River is a significant source of sediment supply. The quantitative analysis of sediment mixing models indicates that the Pleistocene channel sands were mainly sourced from the Red River (62.8%–85.7%), followed by Central Vietnam rivers (4.8%–27.1%), with a minor amount derived from rivers in Hainan Island, Northern Vietnam and Southern Vietnam. Sand sediments, mainly from the Red River system, were deposited in the Yinggehai Basin, then transported and deposited again in the Qiongdongnan Basin. The relatively stable and major sediment supply from the Red River since the Miocene may have been driven by the uplift of the Tibetan Plateau. This study quantifies the relative provenance contributions to submarine channel systems in the Qiongdongnan Basin since the Miocene. It provides crucial geological implications for tectonic responses to channel migrations and the prediction of gas hydrates in sandy reservoirs.

Numerical simulation of hydrate particle behavior in vertical pipeline gas-liquid flow

During the extraction of deep terrestrial and deep-sea natural gas reservoirs, changes in temperature and pressure in the production well can lead to the formation of natural gas hydrates in the wellbore, blocking the flow channel and posing significant challenges to gas well production and management. To address this, we have established a mathematical model to describe the flow characteristics of hydrate multiphase flow systems in vertical pipelines. We employ Computational Fluid Dynamics simulations coupled with a Population Balance Model to predict the formation and breakage of hydrate particles, taking into account mechanisms such as particle collision, aggregation, and breakage. We have analyzed the impact of gas flow rate, slurry flow rate, and hydrate volume fraction on hydrate particle size in the pipeline. The results indicate that hydrate particles tend to aggregate at the bottom of the pipeline. The larger the hydrate slurry flow rate, the faster the hydrate particle size increases. As the gas phase flow rate increases, the increase in particle size slows down. High gas phase flow rates help form turbulence to suppress particle aggregation, velocity fluctuations contribute to particle aggregation growth, and stable velocities facilitate particle decomposition. The increase in hydrate volume fraction significantly increases the diameter of hydrates in the center of the pipeline. The research results can provide suggestions for wellbore blockage caused by hydrate particle aggregation on the wall and a decline in gas well production during actual natural gas well production.