Rheological study of methane gas hydrates in the presence of micron-sized sand particles

Natural gas hydrates,intricate crystalline structures formed by water molecules and small gas molecules,have emerged as a significant and globally impactful clean energy resource.However,their commercial exploitation faces challenges,particularly operational disruptions caused by sand-related blockages.Understanding the rheological properties of hydrate slurry,especially in the presence of micron-sized sand particles,is imperative for ensuring the flow assurance of subsea hydrate exploitation.This study extensively investigates the rheological properties of sand-containing hydrate slurries.The findings reveal that these slurries exhibit non-Newtonian fluid characteristics,including yield stress,thixotropy,and shear-thinning behavior.Solid-like elastic features are observed in sand-containing hydrate slurries before yielding,transitioning to viscous behavior after yielding.Even with a minimal amount of sand,both static yield stress and yield strain experience substantial changes,correlating with the increase in sand concentration.The research conclusively establishes the thixotropic nature of sand-hydrate slurries,where the viscosity decay rate is directly influenced by the shear rate.These insights aim to contribute comprehensively to the development of effective flow assurance strategies,ensuring the safe and stable operation of subsea hydrate exploitation.

Adhesion strength of tetrahydrofuran hydrates is dictated by substrate stiffness

Understanding the hydrate adhesion is important to tackling hydrate accretion in petro-pipelines.Herein,the relationship between the Tetrahydrofuran(THF)hydrate adhesion strength(AS)and surface stiffness on elastic coatings is systemically examined by experimental shear force measurements and theoretical methods.The mechanical factor-elastic modulus of the coatings greatly dictates the hydrate AS,which is explained by the adhesion mechanics theory,beyond the usual factors such as wettability and structural roughness.Moreover,the hydrate AS increases with reducing the thickness of the elastic coatings,resulted from the decrease of the apparent surface elastic modulus.The effect of critical thickness for the elastic materials with variable elastic modulus on the hydrate AS is also revealed.This study provides deep perspectives on the regulation of the hydrate AS by the elastic modulus of elastic materials,which is of significance to design anti-hydrate surfaces for mitigation of hydrate accretion in petro-pipelines.

Formation Characteristics of CO_(2) Hydrates in the Presence of Porous Media and NaCl

Hydrate-based CO_(2) sequestration is an effective method for reducing the greenhouse effect,and the presence of porous media and NaCl can impact the formation characteristics of hydrates.This study uses the constant volume temperature search method to investigate the effects of quartz sand particle size(0.006‒0.03 mm),water saturation(30%–90%),and NaCl concentration(1%‒9%)on the phase equilibrium and kinetics of CO_(2) hydrates within a temperature range of 273‒285 K and pressure range of 1.0‒3.5 MPa.The results indicate that a decrease in quartz sand particle size or an increase in NaCl concentration shifts the hydrate phase equilibrium curve towards lower temperatures and higher pressures,making hydrate generation conditions more demanding.In different particle size systems,there are no significant changes in the rate of CO_(2) hydrate formation or conversion rate.The highest hydrate conversion rate of 71.1%is observed in a 0.015 mm particle size system.With increasing water saturation,both the generation rate and conversion rate of CO_(2) hydrates show a trend of first increasing and then decreasing.Meanwhile,low concentrations of NaCl(1%–3%)are found to enhance the formation and conversion rates of CO_(2) hydrates.However,as NaCl concentration increases,the rate of CO_(2) hydrate formation and conversion rate decrease.

Geological reservoir and resource potential(10^(13)m^(3))of gas hydrates in the South China Sea

A detailed understanding of the distribution and potential of natural gas hydrate(NGHs)resources is crucial to fostering the industrialization of those resources in the South China Sea,where NGHs are abundant.In this study,this study analyzed the applicability of resource evaluation methods,including the volumetric,genesis,and analogy methods,and estimated NGHs resource potential in the South China Sea by using scientific resource evaluation methods based on the factors controlling the geological accumulation and the reservoir characteristics of NGHs.Furthermore,this study compared the evaluation results of NGHs resource evaluations in representative worldwise sea areas via rational analysis.The results of this study are as follows:(1)The gas hydrate accumulation in the South China Sea is characterized by multiple sources of gas supply,multi-channel migration,and extensive accumulation,which are significantly different from those of oil and gas and other unconventional resources.(2)The evaluation of gas hydrate resources in the South China Sea is a highly targeted,stratified,and multidisciplinary evaluation of geological resources under the framework of a multi-type gas hydrate resource evaluation system and focuses on the comprehensive utilization of multi-source heterogeneous data.(3)Global NGHs resources is n×10^(15)m^(3),while the NGHs resources in the South China Sea are estimated to be 10^(13)m^(3),which is comparable to the abundance of typical marine NGHs deposits in other parts of the world.In the South China Sea,the NGHs resources have a broad prospect and provide a substantial resource base for production tests and industrialization of NGHs.

Mechanical Modeling and Analysis of Stability Deterioration of Production Well During Marine Hydrate Depressurization Production

Different from oil and gas production,hydrate reservoirs are shallow and unconsolidated,whose mechanical properties deteriorate with hydrate decomposition.Therefore,the formations will undergo significant subsidence during depressurization,which will destroy the original force state of the production well.However,existing research on the stability of oil and gas production wells assumes the formation to be stable,and lacks consideration of the force exerted on the hydrate production well by formation subsidence caused by hydrate decomposition during production.To fill this gap,this paper proposes an analytical method for the dynamic evolution of the stability of hydrate production well considering the effects of hydrate decomposition.Based on the mechanical model of the production well,the basis for stability analysis has been proposed.A multi-field coupling model of the force state of the production well considering the effect of hydrate decomposition and formation subsidence is established,and a solver is developed.The analytical approach is verified by its good agreement with the results from the numerical method.A case study found that the decomposition of hydrate will increase the pulling-down force and reduce the supporting force,which is the main reason for the stability deterioration.The higher the initial hydrate saturation,the larger the reservoir thickness,and the lower the production pressure,the worse the stability or even instability.This work can provide a theoretical reference for the stability maintaining of the production well.

Structure, Formation, Properties, and Application of Calcium and Magnesium Silicate Hydrates System—A Review

In order to expand the advantages of strong durability and high compressive strength of calcium silicate hydrates(C-S-H),at the same time to make up for the poor early mechanical strength of magnesium silicate hydrates (M-S-H),we present the features and advantages of C-S-H and M-S-H and a comprehensive review of the progress on CaO-MgO-SiO_(2)-H_(2)O.Moreover,we systematically describe natural calcium and magnesium silicate minerals and thermodynamic properties of CaO-MgO-SiO_(2)-H_(2)O.The effect of magnesium on C-S-H and calcium on M-S-H is summarized deeply;the formation and structural feature of CaO-MgO-SiO_(2)-H_(2)O is also explained in detail.Finally,the development of calcium and magnesium silicate hydrates in the future is pointed out,and the further research is discussed and estimated.

Application of the monitoring and early warning system for internal solitary waves:Take the second natural gas hydrates production test in the South China Sea as an example

Internal solitary waves(ISWs) contain great energy and have the characteristics of emergency and concealment. To avoid their damage to offshore engineering, a new generation of monitoring and early warning system for ISWs was developed using technologies of double buoys monitoring, intelligent realtime data transmission, and automatic software identification. The system was applied to the second natural gas hydrates(NGHs) production test in the Shenhu Area, South China Sea(SCS) and successfully provided the early warning of ISWs for 173 days(from October 2019 to April 2020). The abrupt changes in the thrust force of the drilling platform under the attack of ISWs were consistent with the early warning information, proving the reliability of this system. A total of 93 ISWs were detected around the drilling platform. Most of them occurred during the spring tides in October–December 2019 and April 2020, while few of them occurred in winter. As suggested by the theoretical model, the full-depth structure of ISWs was a typical current profile of mode-1, and the velocities of wave-induced currents can reach 80 cm/s and30 cm/s, respectively, in the upper ocean and near the seabed. The ISWs may be primarily generated from the interactions between the topography and semidiurnal tides in the Luzon Strait, and then propagate westward to the drilling platform. This study could serve as an important reference for the early warning of ISWs for offshore engineering construction in the future.

TBAB hydrate formation and growth in a microdevice under static and dynamic conditions

The natural gas hydrate has become one of the most promising future green energy sources on the earth.The natural gas hydrates mostly exist in the sediments with porous structure, so a solid understanding of the hydrate formation and growth processes in the porous medium is of significance for the exploitation of natural gas hydrate. The micro-packed bed device is one of the efficient microfluidic devices in the engineering field, but it has been rarely used for the hydrate-based research. In this study, a transparent micro-packed bed device filled with glass beads was developed to mimic the porous condition of sediments, and used to in-situ visualize the hydrate formation and growth habits in the pore spaces under both static and dynamic conditions. For the static experiment, two types of hydrate growth patterns in porous medium were observed and identified in the micro-packed bed device, which were the graincoating growth and pore-filling growth. For the dynamic condition, the hydrate formation, growth,distribution habits and hydrate blockage phenomena in the pore spaces were in-situ visually captured.The impacts of flowrate and subcooling on the pressure variation of the micro-packed bed and the duration of the hydrate growth under dynamic flow condition in pores were in-situ monitored and analyzed. The higher flowrate could result in the faster hydrate growth and more severe blockage in pores, but the effect of subcooling condition might be less significant at the high flowrate.

Saturation Estimation with Complex Electrical Conductivity for Hydrate-Bearing Clayey Sediments:An Experimental Study

Clays have considerable influence on the electrical properties of hydrate-bearing sediments.It is desirable to understand the electrical properties of hydrate-bearing clayey sediments and to build hydrate saturation(S_(h))models for reservoir evaluation and monitoring.The electrical properties of tetrahydrofuran-hydrate-bearing sediments with montmorillonite are characterized by complex conductivity at frequencies from 0.01 Hz to 1 kHz.The effects of clay and Sh on the complex conductivity were analyzed.A decrease and increase in electrical conductance result from the clay-swelling-induced blockage and ion migration in the electrical double layer(EDL),respectively.The quadrature conductivity increases with the clay content up to 10%because of the increased surface site density of counterions in EDL.Both the in-phase conductivity and quadrature conductivity decrease consistently with increasing Sh from 0.50 to 0.90.Three sets of models for Sh evaluation were developed.The model based on the Simandoux equation outperforms Archie’s formula,with a root-mean-square error(E_(RMS))of 1.8%and 3.9%,respectively,highlighting the clay effects on the in-phase conductivity.The fre-quency effect correlations based on in-phase and quadrature conductivities exhibit inferior performance(E_(RMS)=11.6%and 13.2%,re-spectively)due to the challenge of choosing an appropriate pair of frequencies and intrinsic uncertainties from two measurements.The second-order Cole-Cole formula can be used to fit the complex-conductivity spectra.One pair of inverted Cole-Cole parameters,i.e.,characteristic time and chargeability,is employed to predict S_(h) with an E_(RMS) of 5.05%and 9.05%,respectively.

Passability test and simulation of sand control string with natural gas hydrates completion in large curvature hole

To meet the requirements of marine natural gas hydrate exploitation,it is necessary to improve the penetration of completion sand control string in the large curvature borehole.In this study,large curvature test wells were selected to carry out the running test of sand control string with pre-packed screen.Meanwhile,the running simulation was performed by using the Landmark software.The results show that the sand control packer and screen can be run smoothly in the wellbore with a dogleg angle of more than 20°/30 m and keep the structure stable.Additionally,the comprehensive friction coefficient is 0.4,under which and the simulation shows that the sand control string for hydrate exploitation can be run smoothly.These findings have important guiding significance for running the completion sand control string in natural gas hydrate exploitation.

Rate-limiting factors in hydrate decomposition through depressurization across various scales:A mini-review

Natural gas hydrate is an energy resource for methane that has a carbon quantity twice more than all traditional fossil fuels combined.However,their practical application in the field has been limited due to the challenges of long-term preparation,high costs and associated risks.Experimental studies,on the other hand,offer a safe and cost-effective means of exploring the mechanisms of hydrate dissociation and optimizing exploitation conditions.Gas hydrate decomposition is a complicated process along with intrinsic kinetics,mass transfer and heat transfer,which are the influencing factors for hydrate decomposition rate.The identification of the rate-limiting factor for hydrate dissociation during depressurization varies with the scale of the reservoir,making it challenging to extrapolate findings from laboratory experiments to the actual exploitation.This review aims to summarize current knowledge of investigations on hydrate decomposition on the subject of the research scale(core scale,middle scale,large scale and field tests)and to analyze determining factors for decomposition rate,considering the various research scales and their associated influencing factors.

New insights into the deposition of natural gas hydrate on pipeline surfaces:A molecular dynamics simulation study

Natural gas hydrate(NGH)can cause pipeline blockages during the transportation of oil and gas under high pressures and low temperatures.Reducing hydrate adhesion on pipelines is viewed as an efficient way to prevent NGH blockages.Previous studies suggested the water film can greatly increase hydrate adhesion in gas-dominant system.Herein,by performing the molecular dynamics simulations,we find in water-dominant system,the water film plays different roles in hydrate deposition on Fe and its corrosion surfaces.Specifically,due to the strong affinity of water on Fe surface,the deposited hydrate cannot convert the adsorbed water into hydrate,thus,a water film exists.As water affinities decrease(Fe>Fe_(2)O_(3)>FeO>Fe_(3)O_(4)),adsorbed water would convert to amorphous hydrate on Fe_(2)O_(3)and form the ordered hydrate on FeO and Fe_(3)O_(4)after hydrate deposition.While absorbed water film converts to amorphous or to hydrate,the adhesion strength of hydrate continuously increases(Fe<Fe_(2)O_(3)<FeO<Fe_(3)O_(4)).This is because the detachment of deposited hydrate prefers to occur at soft region of liquid layer,the process of which becomes harder as liquid layer vanishes.As a result,contrary to gas-dominant system,the water film plays the weakening roles on hydrate adhesion in water-dominant system.Overall,our results can help to better understand the hydrate deposition mechanisms on Fe and its corrosion surfaces and suggest hydrate deposition can be adjusted by changing water affinities on pipeline surfaces.

Molecular simulation study on the evolution process of hydrate residual structures into hydrate

The clathrate hydrate memory effect is a fascinating phenomenon with potential applications in carbon capture,utilization and storage(CCUS),gas separation,and gas storage as it can accelerate the secondary formation of clathrate hydrate.However,the underlying mechanism of this effect remains unclear.To gain a better understanding of the mechanism,we conducted molecular dynamic simulations to simulate the initial formation and reformation processes of methane hydrate.In this work,we showed the evolution process of hydrate residual structures into hydrate cages.The simulation results indicate that the residual structures are closely related to the existence of hydrate memory effect,and the higher the contribution of hydrate dissociated water to the hydrate nucleation process,the faster the hydrate nucleation.After hydrate dissociation,the locally ordered structures still exist after hydrate dissociation and can promote the formation of cluster structures,thus accelerating hydrate nucleation.Additionally,the nucleation process of hydrate and the formation process of clusters are inseparable.The size of clusters composed of cup-cage structures is critical for hydrate nucleation.The residence time at high temperature after hydrate decomposition will affect the strength of the hydrate memory effect.Our simulation results provide microscopic insights into the occurrence of the hydrate memory effect and shed light on the hydrate reformation process at the molecular scale.

Effects of the Water-Cement Ratio and the Molding Temperature on the Hydration Heat of Cement

The effects of the water-cement ratio and the molding temperature on the hydration heat of cement were investigated with semi-adiabatic calorimetry.The specimens were prepared with water-cement ratios of 0.31,0.38,and 0.45,and the molding temperature was specified at 10 and 20℃.The experimental results show that,as the water-binder ratio increases,the value of the second temperature peak on the temperature curve of the cement paste decreases,and the age at which the peak appears is delayed.The higher the water-cement ratio,the higher the hydration heat release in the early period of cement hydration,but this trend reverses in the late period.There are intersection points of the total hydration heat curve of the cement pastes under the influence of the water-cement ratio,and this law can be observed at both molding temperatures.With the increase in the molding temperature,the age of the second temperature peak on the temperature curve of the cement paste will advance,but the temperature peak will decrease.The higher the molding temperature,the earlier the acceleration period of the cement hydration began,and the larger the hydration heat of the cement in the early stage,but the smaller the total heat in the late period.A subsection function calculation model of the hydration heat,which was based on the existing models,was proposed in order to predict the heat of the hydration of the concrete.

Hydration Behavior and Cementitious Properties of Calcium Carbonate-aluminate Minerals Composite

The purpose of this research is to investigate the hydration behavior and cementitious properties of the mixture of calcium carbonate and aluminate, and to explore whether it can be adopted as a new low-carbon cementitious material. The composite system of calcium carbonate and aluminate minerals is studied by measuring the component of hydration products, the hydration heat, setting time and compressive strength.The results prove that the composite system has certain cementitious properties and is feasible to prepare new low-carbon cement.

Wetting sub-nanochannels via ionic hydration effect for improving charging dynamics

The ionic transport in sub-nanochannels plays a key role in energy storage,yet suffers from a high energy barrier.Wetting sub-nanochannels is crucial to accelerate ionic transport,but the introduction of water is challenging because of the hydrophobic extreme confinement.We propose wetting the channels by the exothermic hydration process of pre-intercalated ions,the effect of which varies distinctly with different ionic hydration structures and energies.Compared to the failed pre-intercalation of SO_(4)^(2-),HSO_(4)^(-) with weak hydration energy results in a marginal effect on the HOMO(Highest Occupied Molecular Orbital)level of water to avoid water splitting during the electrochemical intercalation.Meanwhile,the ability of water introduction is reserved by the initial incomplete dissociation state of HSO_(4)^(-),so the consequent exothermic reionization and hydration processes of the intercalated HSO_(4)^(-) promote the water introduction into sub-nanochannels,finally forming the stable confined water through hydrogen bonding with functional groups.The wetted channels exhibit a significantly enhanced ionic diffusion coef-ficient by~9.4 times.

Numerical Simulation on Production Trials by Using Depressurization for Typical Marine Hydrate Reservoirs:Well Type and Formation Dip

Natural gas hydrate has huge reserves and is widely distributed in marine environment.Its commercial development is of great significance for alleviating the contradiction between energy supply and demand.As an efficient research method,numerical simulation can provide valuable insights for the design and optimization of hydrate development.However,most of the current production models simplify the reservoir as a two-dimensional(2D)horizontal layered model,often ignoring the impact of formation dip angle.To improve the accuracy of production prediction and provide theoretical support for the optimization of production well design,two three-dimensional(3D)geological models with different dip angles based on the geological data from two typical sites are constructed.The vertical well,horizontal well and multilateral wells are deployed in these reservoirs with different permeabilities to perform production trial,and the sensitivity analysis of dip angles is also carried out.The short-term production behaviors in high and low permeability reservoirs with different dip angles are exhibited.The simulation results show that 1)the gas and water production behaviors for different well types in the two typical reservoirs show obviously different variation laws when the short-term depressurization is conducted in the inclined formation;2)the inclined formation will reduce the gas production and increase the water extraction,and the phenomena becomes pronounced as the dip angle increases,particularly in the low-permeability reservoirs;3)and the impact of formation dip on hydrate recovery does not change significantly with the variation of well type.

Deformation Characteristics of Hydrate-Bearing Sediments

The safe and efficient development of natural gas hydrate requires a deep understanding of the deformation behaviors of reservoirs.In this study,a series of triaxial shearing tests are carried out to investigate the deformation properties of hydrate-bearing sediments.Variations of volumetric and lateral strains versus hydrate saturation are analyzed comprehensively.Results indicate that the sediments with high hydrate saturation show dilative behaviors,which lead to strain-softening characteristics during shearing.The volumetric strain curves have a tendency to transform gradually from dilatation to compression with the increase in effective confining pressure.An easy prediction model is proposed to describe the relationship between volumetric and axial strains.The model coefficientβis the key dominating factor for the shape of volumetric strain curves and can be determined by the hydrate saturation and stress state.Moreover,a modified model is established for the calculation of lateral strain.The corresponding determination method is provided for the easy estimation of model coefficients for medium sand sediments containing hydrate.This study provides a theoretical and experimental reference for deformation estimation in natural gas hydrate development.

Numerical Investigation of Combined Production of Natural Gas Hydrate and Conventional Gas

Natural gas hydrate(NGH)is generally produced and accumulated together with the underlying conventional gas.Therefore,optimizing the production technology of these two gases should be seen as a relevant way to effectively reduce the exploitation cost of the gas hydrate.In this study,three types of models accounting for the coexistence of these gases are considered.Type A considers the upper hydrate-bearing layer(HBL)adjacent to the lower conventional gas layer(CGL);with the Type B a permeable interlayer exists between the upper HBL and the lower CGL;with the type C there is an impermeable interlayer between the upper HBL and the lower CGL.The production performances associated with the above three models are calculated under different conditions,including only a depressurized HBL(only HBL DP);only a depressurized CGL(only CGL DP);and both the HBL and the CGL being depressurized(HBL+CGL DP).The results show that for Type A and Type B coexistence accumulation models,when only HBL or CGL is depressurized,the gas from the other layer will flow into the production layer due to the pressure difference between the two layers.In the coexistence accumulation model of type C,the cumulative gas production is much lower than that of Type A and Type B,regardless of whether only HBL DP,only CGL DP,or HBL+CGL DP are considered.This indicates that the impermeable interlayer restricts the cross-flow of gas between HBL and CGL.For three different coexistence accumulation models,CGL DP has the largest gas-to-water ratio.

Effect of Skeleton Grain Size on the Saturation of Gas Hydrate in Natural Sediments

Natural gas hydrate is prospected as a new and promising,highly clean energy resource that mainly occurs in perma-frost or at continental margins.Its formation is subject to many soil conditions,such as grain size,matrix materials,pore morphology,and permeability.In this study,we propose that grain size is the most decisive parameter that affects the saturation of gas hydrate in sediments based on data from Ocean Drilling Program Leg 164 and Mallik 5L-38,which represent marine sediments and terrestrial sediments,respectively.Our study reveals that high gas hydrate saturation generally occurs in coarse-grained sand,regardless of whether sediment formation is homogeneous or inhomogeneous,and the sorting of sediments may affect the hydrate saturation to a certain degree.Using grain size and sorting of sediments may be the most intuitive proxy method for a rough estimation of hydrate saturation.Further study is necessary to fully understand the relationship between hydrate morphology and sediment grain size,even though massive hydrates are typically found in fine clayey-rich sediments.