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.

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.

Particle Size Optimization of Thermochemical Salt Hydrates for High Energy Density Thermal Storage

Thermal energy storage(TES)solutions offer opportunities to reduce energy consumption,greenhouse gas emissions,and cost.Specifically,they can help reduce the peak load and address the intermittency of renewable energy sources by time shifting the load,which are critical toward zero energy buildings.Thermochemical materials(TCMs)as a class of TES undergo a solid-gas reversible chemical reaction with water vapor to store and release energy with high storage capacities(600 kWh m^(-3))and negligible self-discharge that makes them uniquely suited as compact,stand-alone units for daily or seasonal storage.However,TCMs suffer from instabilities at the material(salt particles)and reactor level(packed beds of salt),resulting in poor multi-cycle efficiency and high-levelized cost of storage.In this study,a model is developed to predict the pulverization limit or Rcrit of various salt hydrates during thermal cycling.This is critical as it provides design rules to make mechanically stable TCM composites as well as enables the use of more energy-efficient manufacturing process(solid-state mixing)to make the composites.The model is experimentally validated on multiple TCM salt hydrates with different water content,and effect of Rcrit on hydration and dehydration kinetics is also investigated.

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.

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.

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.

Using 4C OBS to reveal the distribution and velocity attributes of gas hydrates at the northern continental slope of South China Sea

To investigate the distribution and velocity attributes of gas hydrates in the northern continental slope of South China Sea, Guangzhou Marine Geological Survey conducted four-component （4C） ocean-bottom seismometer （OBS） surveys. A case study is presented to show the results of acquiring and processing OBS data for detecting gas hydrates. Key processing steps such as repositioning, reorientation, PZ summation, and mirror imaging are discussed. Repositioning and reorientation find the correct location and direction of nodes. PZ summation matches P- and Z-components and sums them to separate upgoing and downgoing waves. Upgoing waves are used in conventional imaging, whereas downgoing waves are used in mirror imaging. Mirror imaging uses the energy of the receiver ghost reflection to improve the illumination of shallow structures, where gas hydrates and the associated bottom-simulating reflections （BSRs） are located. We developed a new method of velocity analysis using mirror imaging. The proposed method is based on velocity scanning and iterative prestack time migration. The final imaging results are promising. When combined with the derived velocity field, we can characterize the BSR and shallow structures; hence, we conclude that using 4C OBS can reveal the distribution and velocity attributes of gas hydrates.

Multicomponent seismic forward modeling of gas hydrates beneath the seafloor

We investigated the effect of microscopic distribution modes of hydrates in porous sediments, and the saturation of hydrates and free gas on the elastic properties of saturated sediments. We simulated the propagation of seismic waves in gas hydrate-bearing sediments beneath the seafloor, and obtained the common receiver gathers of compressional waves（P-waves） and shear waves（S-waves）. The numerical results suggest that the interface between sediments containing gas hydrates and free gas produces a large-amplitude bottomsimulating reflector. The analysis of multicomponent common receiver data suggests that ocean-bottom seismometers receive the converted waves of upgoing P- and S-waves, which increases the complexity of the wavefield record.

Applications of seismic techniques to gas hydrates prediction

Based on the sensitivity of geophysical response to gas hydrates contained in sediments, we studied the prediction of gas hydrates with seismic techniques, including seismic attributes analysis, AVO, inverted velocity field construction for dipping formations, and pseudo-well constrained impedance inversion. We used an optimal integration of geophysical techniques results in a set of reliable and effective workflows to predict gas hydrates. The results show that the integrated analysis of the combination of reflectivity amplitude, instantaneous phase, interval velocity, relative impedance, absolute impedance, and AVO intercept is a valid combination of techniques for identifying the BSR （Bottom Simulated Reflector） from the lower boundary of the gas hydrates. Integration of seismic sections, relative and absolute impedance sections, and interval velocity sections can improve the validity of gas hydrates determination. The combination of instantaneous frequency, energy half attenuation time, interval velocity, AVO intercept, AVO product, and AVO fluid factor accurately locates the escaped gas beneath the BSR. With these conclusions, the combined techniques have been used to successfully predict the gas hydrates in the Dongsha Sea area.

Raman Spectroscopy of Nitrogen Clathrate Hydrates

Nitrogen hydrate samples were synthesized using liquid nitrogen and powder ice at 16 MPa and 253 K. Confocal laser Raman spectroscopy was used to investigate the characteristics of nitrogen clathrate hydrates. The results show that the Raman peaks of N-N and O-H stretching vibration in nitrogen hydrates are observed at 2322.4 and 3092.1 cm^-1, respectively, which are very similar to those in natural air clathrate hydrates. For comparison, we measured the Raman peaks of N-N stretching vibration both in liquid nitrogen and nitrogen molecules saturated water, which appear at 2326.6 and 2325.0 cm^-1, respectively. The Raman spectroscopic observations on the dissociation process suggest that nitrogen molecules occupy both the large and small cages in nitrogen clathrate hydrates. However, only one Raman peak is observed for N N stretching vibration because the difference of the environment of nitrogen molecules between large and small cages is too small to be differentiated by Raman spectroscopy.

Migration and accumulation characteristics of natural gas hydrates in the uplifts and their slope zones in the Qiongdongnan Basin,China

Various factors controlling the accumulation of natural gas hydrates(NGHs)form various enrichment and accumulation modes through organic combination.This study mainly analyzes the geological and geophysical characteristics of the NGHs occurrence in the uplifts and their slope zones within the deep-water area in the Qiongdongnan(QDN)Basin(also referred to as the study area).Furthermore,it investigates the dominant governing factors and models of NGHs migration and accumulation in the study area.The results are as follows.(1)The uplifts and their slope zones in the study area lie in the dominant pressure-relief direction of fluids in central hydrocarbon-rich sags in the area,which provide sufficient gas sources for the NGHs accumulation and enrichment through pathways such as gas chimneys and faults.(2)The top and flanks of gas chimneys below the bottom simulating reflectors(BSRs)show high-amplitude seismic reflections and pronounced transverse charging of free gas,indicating the occurrence of a large amount of gas accumulation at the heights of the uplifts.(3)Chimneys,faults,and high-porosity and high-permeability strata,which connect the gas hydrate temperature-pressure stability zones(GHSZs)with thermogenic gas and biogenic gas,form the main hydrate migration system.(4)The reservoir system in the study area comprises sedimentary interlayers consisting of mass transport deposits(MTDs)and turbidites.In addition,the reservoir system has developed fissure-and pore-filling types of hydrates in the pathways.The above well-matched controlling factors of hydrate accumulation enable the uplifts and their slope zones in the study area to become the favorable targets of NGHs exploration.

Methane hydrates:A future clean energy resource

Natural gas has been considered as the best transition fuel into the future carbon constraint world.The ever-increasing demand for natural gas has prompted expanding research and development activities worldwide for exploring methane hydrates as a future energy resource.With its vast global resource volume(~3000 trillion cubic meter CH4)and high energy storage capacity(170 CH4 v/v methane hydrate),recovering energy from naturally-occurring methane hydrate has attracted both academic and industry interests to demonstrate the technical feasibility and economic viability.In this review paper,we highlight the recent advances in fundamental researches,seminal discoveries and implications from ongoing drilling programs and field production tests,the impending knowledge gaps and the future perspectives of recovering energy from methane hydrates.We further emphasize the current scientific,technological and economic challenges in realizing long-term commercial gas production from methane hydrate reservoir.The continuous growth of the corresponding experimental studies in China should target these specific challenges to narrow the knowledge gaps between laboratory-scale investigations and reservoir-scale applications.Furthermore,we briefly discuss both the environmental and geomechanical issues related to exploiting methane hydrate as the future energy resource and believe that they should be of paramount importance in the future development of novel gas production technologies.

Effects of Temperature on the Preparation of Magnesium Carbonate Hydrates by Reaction of MgCI2 with Na2CO3

Homogeneous(unseeded)precipitation of magnesium carbonate hydrates by the reaction of MgCl2 with Na2CO3 in supersaturated solutions between 273 and 363K was investigated.The compositions,morphologies and filtration characteristics of the precipitates were studied in detail.The magnesium carbonate hydrates obtained at 313K and in the range of 343-363K showed good morphologies and filtration characteristics.Magnesium oxides(MgO)with high purity(97.6%-99.4%)were obtained by calcining magnesium carbonate hydrates at 1073K.

Effects of Curing Systems on Properties of High Volume Fine Mineral Powder RPC and Appearance of Hydrates

The effects of different curing systems on the properties of high volume fine mineral powder RPC （reactive powder concrete） and the appearances of hydrates were studied. The experimental results show that dry-heating curing promotes the development of pozzolanic reactivity of fine mineral powder; due to low cement content, 0.20 water-bind ratio and high reactive fine mineral powder content, the strength of RPC increases by around 200% after steam curing and subsequent dry-heating curing. Scanning electron microscopy and energy spectrum diagram showed that： after the high volume fine mineral powder RPC with 0.16 water-bind ratio underwent steam curing and dry-heating curing, there was no significant change in the appearance of hydrates; after the RPC with 0.20 water-bind ratio, the cement content of 150 kg/m3 and more steel slag powder underwent dry-heating curing, there was a certain change in the appearance of C-S-H, the structure of gel was more compact and was uniformly distributed, and the Ca/Si of C-S-H gel decreased from 1.41 to around 1.20.

Decomposition Kinetics for Formation of CO_2 Hydrates in Natural Silica Sands

The decomposition kinetics for formation of CO2 hydrates in 90 cm 3wet natural silica sands were studied systematically using the depressurization method at the temperatures ranging from 273.2 to 277.2 K and the pressures from 0.5 to 1.0 MPa.The effects of temperature,pressure,particle diameter,porosity,and salinity of formation water on the decomposition kinetics were investigated.The results show that the dissociation percentage increases as temperature increases or as the initial decomposition pressure decreases.An increase in porosity or a decrease in particle diameter of silica sands accelerates the decomposition.Increasing the salinity of the formation water gives rise to a faster decomposition.However,a combination of the present results with the observations in literature reveals that the effect of the coexisting ionic solute depends on its chemical structure.

Separation of ionic liquids from dilute aqueous solutions using the method based on CO_2 hydrates

Ionic liquids （ILs） have been regarded as the potential novel solvents for improved analytical- and process-scale separation methods.The development of methods for the recovery of ILs from aqueous solutions to escape contamination and recycle samples will ultimately govern the viability of ILs in the future industrial applications. Therefore, in this paper a new method for separation of ILs from their dilute aqueous solutions and simultaneously purification of water was proposed on the basis of the CO2 hydrate formation. For illustration, the dilute aqueous solutions with concentrations of ILs ranging from 2× 10^-3 mol% to 2×10^-1 mol% were concentrated. The results show that the separation efficiency is very impressive and that the new method is applicable to aqueous solutions of both hydrophobic and hydrophilic ILs. Compared to the literature separation method based on the supercritical CO2, the new method is applicable to lower concentrations, and more importantly, its operation condition is mild.

China Has Successfully Conducted its First Pilot Production of Natural Gas Hydrates

Natural gas methane and hydrates are a chemical compound of water molecules formed under low temperature and high pressure. The decomposition of 1 m^3 of natural gas hydrates can release about 0.8 m^3 of water and 164 m3 of natural gas. Thus, natural gas hydrates are characterized by their high-energy density and huge resource potential. It is estimated that the world＇s total natural gas hydrates resource amount is equivalent to twice the total carbon amount of the global proven conventional fuels and can meet the human energy requirement in the future for 1000 years. They are thus the first choice to replace conventional energy of petroleum and coal.

Accelerated methane storage in clathrate hydrates using surfactantstabilized suspension with graphite nanoparticles

In this study,enhanced kinetics of methane hydrate formation in the sodium dodecyl sulfate(SDS)solution with different concentrations of suspended graphite nanoparticles(GNPs)were investigated at 6.1-9.0 MPa and 274.15 K.The GNPs with rough surfaces and excellent thermal conductivity not only provided a considerable number of microsites for hydrate nucleation but also facilitated the fast hydrate heat transfer in the suspension system.At a relatively low pressure of 6.1 MPa,the suspension with 0.4 wt%of GNPs exhibited the minimum induction time of 22 min and maximum methane uptake of 126.1 cm3·cm-3.However,the methane storage performances of the suspensions with higher and lower concentrations of GNPs were not satisfactory.At the applied pressure,the temperature increase arising from the hydrate heat in the suspension system with the optimized concentration(0.4 wt%)of GNPs was more significant than that in the traditional SDS solution.Furthermore,compared with those of the system without GNPs,enhanced hydration rate and storage capacity were achieved in the suspensions with GNPs,and the storage capacities were increased by 3.9%-17.0%.The promotion effect of GNPs on gas hydrate formation at low pressure is much more obvious than that at high pressure.