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.

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.

Auto-Detection Method Using Convolution Neural Network for Bottom-Simulating Reflectors

In studies on gas hydrate,bottom-simulating reflectors(BSR)are used to determine the potential hydrate-bearing sedimentary layers.Usually,BSR detection is performed manually by experienced interpreters.Therefore,a method for implementing an auto-matic BSR detection process should be established.In this study,we develop a novel architecture for BSR characterization using the convolutional neural network(CNN)technique.We propose the use of Stokes’transform(ST)to obtain a time-frequency spectrum for the input of CNN.ST fully uses the frequency content of the seismic data,and a part of the 3D seismic data collected from the Blake Ridge is utilized to train the CNN.Synthetic seismic records with variable signal-to-noise ratios(SNR),as well as Blake Ridge seismic data,were used to validate the detection effect of the CNN.Results show that the CNN trained by this method exhibits excellent performance in noise-resistant testing and achieves an accuracy of more than 89% in field seismic data detection.

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.

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.

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.

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.

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 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.

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.

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.

Optimization of Gas Production from Hydrate-Bearing Sediments with Fluctuation Characteristics

As an important source of low-carbon,clean fossil energy,natural gas hydrate plays an important role in improving the global energy consumption structure.Developing the hydrate industry in the South China Sea is important to achieving‘carbon peak and carbon neutrality’goals as soon as possible.Deep-water areas subjected to the action of long-term stress and tectonic movement have developed complex and volatile terrains,and as such,the morphologies of hydrate-bearing sediments(HBSs)fluctuate correspondingly.The key to numerically simulating HBS morphologies is the establishment of the conceptual model,which represents the objective and real description of the actual geological body.However,current numerical simulation models have characterized HBSs into horizontal strata without considering the fluctuation characteristics.Simply representing the HBS as a horizontal element reduces simulation accuracy.Therefore,the commonly used horizontal HBS model and a model considering the HBS’s fluctuation characteristics with the data of the SH2 site in the Shenhu Sea area were first constructed in this paper.Then,their production behaviors were compared,and the huge impact of the fluctuation characteristics on HBS production was determined.On this basis,the key parameters affecting the depressurization production of the fluctuating HBSs were studied and optimized.The research results show that the fluctuation characteristics have an obvious influence on the hydrate production of HBSs by affecting their temperatures and pressure distributions,as well as the transmission of the pressure drop and methane gas discharge.Furthermore,the results show that the gas productivity of fluctuating HBSs was about 5%less than that of horizontal HBSs.By optimizing the depressurization amplitude,well length,and layout location of vertical wells,the productivity of fluctuating HBSs increased by about 56.6%.

Enhanced gas production and CO_(2) storage in hydrate-bearing sediments via pre-depressurization and rapid CO_(2) injection

Carbon emission reduction and clean energy development are urgent demands for mankind in the coming decades.Exploring an efficient CO_(2) storage method can significantly reduce CO_(2) emissions in the short term.In this study,we attempted to construct sediment samples with different residual CH_(4) hydrate amounts and reservoir conditions,and then investigate the potentials of both CO_(2) storage and enhanced CH_(4) recovery in depleted gas hydrate deposits in the permafrost and ocean zones,respectively.The results demonstrate that CO_(2) hydrate formation rate can be significantly improved due to the presence of residual hydrate seeds;However,excessive residual hydrates in turn lead to the decrease in CO_(2) storage efficiency.Affected by the T-P conditions of the reservoir,the storage amount of liquid CO_(2) can reach 8 times that of gaseous CO_(2),and CO_(2) stored in hydrate form reaches 2-4 times.Additionally,we noticed two other advantages of this method.One is that CO_(2) injection can enhance CH_(4) recovery rate and increases CH_(4) recovery by 10%-20%.The second is that hydrate saturation in the reservoir can be restored to 20%-40%,which means that the solid volume of the reservoir avoids serious shrinkage.Obviously,this is crucial for protecting the goaf stability.In summary,this approach is greatly promising for high-efficient CO_(2) storage and safe exploitation of gas hydrate.

Correlation between hydration properties and electrochemical performances on Ln cation size effect in layered perovskite for protonic ceramic fuel cells

PrBa_(0.5)Sr_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(PrBSCF) has attracted much research interest as a potential triple ionic and electronic conductor(TIEC) electrode for protonic ceramic fuel cells(PCFCs). The chemical formula for Pr BSCF is AA'B_(2)O_(5+δ), with Pr(A-site) and Ba/Sr(A'-site) alternately stacked along the c-axis. Due to these structural features, the bulk oxygen ion diffusivity is significantly enhanced through the disorder-free channels in the PrO layer;thus, the A site cations(lanthanide ions) play a pivotal role in determining the overall electrochemical properties of layered perovskites. Consequently, previous research has predominantly focused on the electrical properties and oxygen bulk/surface kinetics of Ln cation effects,whereas the hydration properties for PCFC systems remain unidentified. Here, we thoroughly examined the proton uptake behavior and thermodynamic parameters for the hydration reaction to conclusively determine the changes in the electrochemical performances depending on LnBa_(0.5)Sr_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(LnBSCF,Ln=Pr, Nd, and Gd) cathodes. At 500 ℃, the quantitative proton concentration of PrBSCF was 2.04 mol% and progressively decreased as the Ln cation size decreased. Similarly, the Gibbs free energy indicated that less energy was required for the formation of protonic defects in the order of Pr BSCF < Nd BSCF < Gd BSCF. To elucidate the close relationship between hydration properties and electrochemical performances in LnBSCF cathodes, PCFC single cell measurements and analysis of the distribution of relaxation time were further investigated.

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.

A New Heat Transfer Model for Multi-Gradient Drilling with Hollow Sphere Injection

Multi-gradient drilling is a new offshore drilling method.The accurate calculation of the related wellbore temperature is of great significance for the prediction of the gas hydrate formation area and the precise control of the wellbore pressure.In this study,a new heat transfer model is proposed by which the variable mass flow is properly taken into account.Using this model,the effects of the main factors influencing the wellbore temperature are analyzed.The results indicate that at the position where the separation injection device is installed,the temperature increase of the fluid in the drill pipe is mitigated due to the inflow/outflow of hollow spheres,and the temperature drop of the fluid in the annulus also decreases.In addition,a lower separation efficiency of the device,a shallower installation depth and a smaller circulating displacement tend to increase the temperature near the bottom of the annulus,thereby helping to reduce the hydrate generation area and playing a positive role in the prevention and control of hydrates in deepwater drilling.

On the Preparation of Low-Temperature-Rise and Low-Shrinkage Concrete Based on Phosphorus Slag

The effects of different contents of a MgO expansive agent and phosphorus slag on the mechanical properties,shrinkage behavior,and the heat of hydration of concrete were studied.The slump flow,setting time,dry shrinkage,and hydration heat were used as sensitive parameters to assess the response of the considered specimens.As shown by the results,in general,with an increase in the phosphorus slag content,the hydration heat of concrete decreases for all ages,but the early strength displays a downward trend and the dry shrinkage rate increases.The 90-d strength and dry shrinkage of concrete could be improved with a phosphorus residue content between 0%-20%,with the best performances in terms of mechanical properties and shrinkage characteristics being achieved for a content of 20 kg/m^(3).On the basis of these results,it can be concluded that appropriate amounts of phosphorus slag and MgO expansive agent can be used to improve the compressive strength of concrete in the later stage by reducing the hydration heat and dry shrinkage rate,respectively.

Evaluation of the Shallow Gas Hydrate Production Based on the Radial Drilling-Heat Injection-Back Fill Method

It has been evidenced that shallow gas hydrate resources are abundant in deep oceans worldwide.Their geological back-ground,occurrence,and other characteristics differ significantly from deep-seated hydrates.Because of the high risk of well construction and low production efficiency,they are difficult to be recovered by using conventional oil production methods.As a result,this paper proposes an alternative design based on a combination of radial drilling,heat injection,and backfilling methods.Multi-branch holes are used to penetrate shallow gas hydrate reservoirs to expand the depressurization area,and heat injection is utilized as a supplement to improve gas production.Geotechnical information collected from an investigation site close to the offshore production well in the South China Sea is used to assess the essential components of this plan,including well construction stability and gas production behavior.It demonstrates that the hydraulic fracturing of the 60mbsf overburden layer can be prevented by regulating the drilling fluid densities.However,the traditional well structure is unstable,and the suction anchor is advised for better mechanical performance.The gas produc-tion rate can be significantly increased by combining hot water injection and depressurization methods.Additionally,the suitable produc-tion equipment already in use is discussed.

Deep-large faults controlling on the distribution of the venting gas hydrate system in the middle of the Qiongdongnan Basin, South China Sea

Many locations with concentrated hydrates at vents have confirmed the presence of abundant thermogenic gas in the middle of the Qiongdongnan Basin(QDNB).However,the impact of deep structures on gasbearing fluids migration and gas hydrates distribution in tectonically inactive regions is still unclear.In this study,the authors apply high-resolution 3D seismic and logging while drilling(LWD)data from the middle of the QDNB to investigate the influence of deep-large faults on gas chimneys and preferred gasescape pipes.The findings reveal the following:(1)Two significant deep-large faults,F1 and F2,developed on the edge of the Songnan Low Uplift,control the dominant migration of thermogenic hydrocarbons and determine the initial locations of gas chimneys.(2)The formation of gas chimneys is likely related to fault activation and reactivation.Gas chimney 1 is primarily arises from convergent fluid migration resulting from the intersection of the two faults,while the gas chimney 2 benefits from a steeper fault plane and shorter migration distance of fault F2.(3)Most gas-escape pipes are situated near the apex of the two faults.Their reactivations facilitate free gas flow into the GHSZ and contribute to the formation of fracture‐filling hydrates.

Research Progress of Additives to Improve Hydration Resistance of Magnesia-calcium Materials

Magnesia-calcium materials have stable hot performance,good resistance to the erosion and corrosion of liquid steel and steel slag,and a special role in purifying liquid steel,so they are widely used in iron and steel industry.However,hydration of magnesia-calcium materials seriously restricts their use,so researches have been done to improve their hydration resistance,obtaining a series of achievements.In this paper,the improvements on the hydration resistance of magnesia-calcium materials by additives in recent 20 years were presented,and their mechanisms were summarized.