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.

Microscopic experimental study on the effects of NaCl concentration on the self-preservation effect of methane hydrates under 268.15 K

It is known that salt ions are abundant in the natural environment where natural gas hydrates are located;thus,it is essential to investigate the self-preservation effect of salt ions on methane hydrates.The dissociation behaviors of gas hydrates formed from various NaCl concentration solutions in a quartz sand system at 268.15 K were investigated to reveal the microscopic mechanism of the self-preservation effect under different salt concentrations.Results showed that as the salt concentration rises,the initial rate of hydrate decomposition quickens.Methane hydrate hardly shows self-preservation ability in the 3.35%(mass)NaCl and seawater systems at 268.15 K.Combined the morphology of hydrate observed by the confocal microscope with results obtained from in situ Raman spectroscopy,it was found that during the initial decomposition stage of gas hydrate below the ice point,gas hydrate firstly converts into liquid water and gas molecules,then turns from water to solid ice rather than directly transforming into solid ice and gas molecules.The presence of salt ions interferes with the ability of liquid water to condense into solid ice.The results of this study provide an important guide for the mechanism and application of the self-preservation effect on the storage and transport of gas and the exploitation of natural gas hydrates.

The effect of ethylene-vinyl acetate copolymer on the formation process of wax crystals and hydrates

Ethylene-vinyl acetate copolymer(EVA) as a kind of effective polymeric pour point depressant has been extensively used in the pipeline transportation of crude oil to inhibit wax deposition and improve the low temperature fluidity of crude oil. In this work, molecular dynamics simulations were performed to investigate the effect of EVA on wax-hydrate coexistence system to evaluate the application potentiality of EVA to the flow assurance of deep-sea oil-gas-water multiphase flow system. Our simulation results reveal that wax molecules gradually stretched and stacked from random coiling to a directional and ordered crystalline state during the process of wax solidification. The strong affinity of polar vinyl acetate side chains of EVA to neighboring water molecules made the EVA molecule prefer being in a curly state,which disrupted the ordered crystallization of surrounding wax molecules and delayed the solidification rate of wax cluster. In addition, it is found that EVA cocrystallized with wax molecules to form eutectic when the wax was fully solidified. The simulation results of hydrate nucleation and growth show that the EVA molecule displayed a two-sided effect on gas adsorption of wax crystals, which was the key factor that affected the nucleation and growth of hydrates in the methane-water system. The nonpolar hydrocarbon backbone of EVA increased the diffusion rate of methane and water, allowing more methane to diffuse to the surface of wax crystals, reducing the methane concentration in aqueous solutions and inhibiting the hydrate formation. On the other hand, the nonpolar vinyl acetate chains had a repulsive effect on methane, which reduced the adsorption area of methane on the eutectic surface and decreased the adsorption threshold value of the wax crystal. The excluded methane molecules would continue dissociating in the aqueous phase and participating in the nucleation and growth process of hydrates.Therefore, the probability of hydrate formation would be increased. It was worth noting that the inhibition performance of EVA on hydrate formation mainly played a significant role in the system with small wax crystal, while its hydrate promotion effect played a dominant role in the system with lager wax crystal. In summary, EVA could significantly inhibit both of the wax and hydrate deposition for the waxgas-water multiphase system with low wax content. When the wax content in the system was high, the role of EVA was mainly played in the alleviation of wax crystallization rather than the gas hydrates. The results of the present work can contribute to a better understanding of EVA on wax deposition and hydrate formation, and provide theoretical support of the potential industrial applications of EVA.

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.

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.

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.

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.

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.

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.

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.

1-D Controlled source electromagnetic forward modeling for marine gas hydrates studies

We discuss the feasibility of using controlled-source electromagnetic （CSEM） in the frequency domain for prospecting marine gas hydrates. Based on the Ocean Drilling Program （ODP） Leg 164 log data, we have established several 1-D resistivity models which have different gas hydrate concentrations. Meanwhile, we analyzed the electromagnetic response of marine gas hydrates in the frequency domain based on these models. We also studied the relationship between electrical field magnitude or phase and parameters such as receiver-transmitter distance and frequency. Our numerical modeling results provide us with a quantitative reference for exploration and resource evaluation of marine gas hydrates.

Gas Hydrates in the Qilian Mountain Permafrost, Qinghai, Northwest China

Qilian Mountain permafrost, with area about 10×10^4 km2, locates in the north of Qinghai- Tibet plateau. It equips with perfect conditions and has great prospecting potential for gas hydrate. The Scientific Drilling Project of Gas Hydrate in Qilian Mountain permafrost, which locates in Juhugeng of Muri Coalfield, Tianjun County, Qinghai Province, has been implemented by China Geological Survey in 2008-2009. Four scientific drilling wells have been completed with a total footage of 2059.13 m. Samples of gas hydrate are collected separately from holes DK-1, DK-2 and DK-3. Gas hydrate is hosted under permafrost zone in the 133-396 m interval. The sample is white crystal and easily burning. Anomaly low temperature has been identified by the infrared camera. The gas hydratebearing cores strongly bubble in the water. Gas-bubble and water-drop are emitted from the hydratebearing cores and then characteristic of honeycombed structure is left. The typical spectrum curve of gas hydrate is detected using Raman spectrometry. Furthermore, the logging profile also indicates high electrical resistivity and sonic velocity. Gas hydrate in Qilian Mountain is characterized by a thinner permafrost zone, shallower buried depth, more complex gas component and coal-bed methane origin etc.

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.

Synergistic effect of combination of surfactant and oxide powder on enhancement of gas hydrates nucleation

In the present work we studied the induction periods of hydrate formation of natural gas in pure water, aqueous solutions of surfactants, and in the presence of surfactant together with aluminum oxide nanopowder, the activity of which as hydrate formation inducer was studied previously. Sodium dodecyl sulfate（SDS） or neonol AF-9-12 were used as the surfactants. It was demonstrated that the addition of either surfactants or aluminum oxide powder under our experimental conditions causes a decrease in the induction period of hydrate formation from;05 min for pure water to 30–35 min for water with additives. In the case of the simultaneous presence of surfactants and aluminum oxide powder in the system, induction period decreased to;0 min. So, the synergistic effect of the combination of surfactant and oxide powder on gas hydrate nucleation was demonstrated. Possible reasons of this effect have been discussed.

Gas Sources of Natural Gas Hydrates in the Shenhu Drilling Area, South China Sea: Geochemical Evidence and Geological Analysis

The Shenhu gas hydrate drilling area is located in the central Baiyun sag, Zhu I! depression, Pearl River Mouth basin, northern South China Sea. The gas compositions contained in the hydrate-bearing zones is dominated by methane with content up to 99.89% and 99.91%. The carbon isotope of the methane （δ^13C1） are -56.7%0. and -60.9%0, and its hydrogen isotope （δD） are -199%0 and -180%0, respectively, indicating the methane from the microbial reduction of CO2. Based on the data of measured seafloor temperature and geothermal gradient, the gas formed hydrate reservoirs are from depths 24-1699 m below the seafloor, and main gas-generation zone is present at the depth interval of 416-1165 m. Gas-bearing zones include the Hanjiang Formation, Yuehai Formation, Wanshan Formation and Quaternary sediments. We infer that the microbial gas migrated laterally or vertically along faults （especially interlayer faults）, slump structures, small-scale diapiric structures, regional sand beds and sedimentary boundaries to the hydrate stability zone, and formed natural gas hydrates in the upper Yuehai Formation and lower Wanshan Formation, probably with contribution of a little thermogenic gas from the deep sedments during this process.

SCHEMES OF GAS PRODUCTION FROM NATURAL GAS HYDRATES

Natural gas hydrates are a kind of nonpolluting and high quality energy resources for future, the reserves of which are about twice of the carbon of the current fossil energy (petroleum, natural gas and coal) on the earth. And it will be the most important energy for the 21st century. The energy balance and numerical simulation are applied to study the schemes of the natural gas hydrates production in this paper,and it is considered that both depressurization and thermal stimulation are effective methods for exploiting natural gas hydrates, and that the gas production of the thermal stimulation is higher than that of the depressurization. But thermal stimulation is non-economic because it requires large amounts of energy.Therefore the combination of the two methods is a preferable method for the current development of the natural gas hydrates. The main factors which influence the production of natural gas hydrates are: the temperature of injected water, the injection rate, the initial saturation of the hydrates and the initial temperature of the reservoir which is the most important factor.

Modeling phase equilibria of semiclathrate hydrates of CH_4,CO_2 and N_2 in aqueous solution of tetra-n-butyl ammonium bromide

Semiclathrate hydrates of tetra-n-butyl ammonium bromide （TBAB） offer potential solution for gas storage, transportation, separation of flue gases and CO2 sequestration. Models for phase equilibria for these systems have not yet been developed in open literatures and thus require urgent attention. In this work, the first attempt has been made to model phase equilibria of semiclathrate hydrates of CH4, CO2 and N2 in aqueous solution of TBAB. A thermodynamic model for gas hydrate system as proposed by Chen and Guo has been extended for semiclathrate hydrates of gases in aqueous solution of TBAB. A correlation for the activity of water relating to the system temperature, concentration of TBAB in the system and the nature of guest gas molecule has been proposed. The model results have been validated against available experimental data on phase equilibria of semiclathrate hydrate systems of aqueous TBAB with different gases as guest molecule. The extended Chen and Guo＇s model is found to be suitable to explain the promotion effect of TBAB for the studied gaseous system such as, methane, carbon dioxide and nitrogen as a guest molecule. Additionally, a correlation for the increase in equilibrium formation temperature （hydrate promotion temperature, ATp） of semiclathrate hydrate system with respect to pure gas hydrate system has been developed and applied to semiclathrate hydrate of TBAB with several gases as guest molecules. The developed correlation is found to predict the promotion effect satisfactorily for the system studied.

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.

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.