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.

Comparison and application of different empirical correlations for estimating the hydrate safety margin of oil-based drilling fluids containing ethylene glycol

As the oil and gas industries continue to increase their activity in deep water, gas hydrate hazards will become more serious and challenging, both at present and in the future. Accurate predictions of the hydrate-free zone and the suitable addition of salts and/or alcohols in preparing drilling fluids are particularly important both in preventing hydrate problems and decreasing the cost of drilling operations. In this paper, we compared several empirical correlations commonly used to estimate the hydrate inhibition effect of aqueous organic and electrolyte solutions using experiments with ethylene glycol （EG） as a hydrate inhibitor. The results show that the Najibi et al. correlation （for single and mixed thermodynamic inhibitors） and the Ostergaard et al. empirical correlation （for single thermodynamic inhibitors） are suitable for estimating the hydrate safety margin of oil-based drilling fluids （OBDFs） in the presence of thermodynamic hydrate inhibitors. According to the two correlations, the OBDF, composed of 1.6 L vaporizing oil, 2% emulsifying agent, 1% organobentonite, 0.5% SP-1, 1% LP-1, 10% water and 40% EG, can be safely used at a water depth of up to 1900 m. However, for more accurate predictions for drilling fluids, the effects of the solid phase, especially bentonite, on hydrate inhibition need to be considered and included in the application of these two empirical correlations.

Effect of hydrophilic silica nanoparticles on hydrate formation: Insight from the experimental study

Invasion of drilling fluid into natural gas hydrate deposits during drilling might damage the reservoir,induce hydrate dissociation and then cause wellbore instability and distortion of the data from well logging. Adding nanoparticles into drilling fluid is an effective method in reducing the invasion of drilling fluid and enhancing borehole stability. However, the addition of nanoparticles might also introduce hydrate formation risk in borehole because they can act as the "seeds" for hydrate nucleation. This paper presents an experimental study of the effect of hydrophilic silica nanoparticle on gas hydrate formation in a dynamic methane/liquid-water system. In the experiment, the ultrapure water with and without1.0 wt%–6.0 wt% concentrations of silica nanoparticles, grain sizes of 20 and 50 nm, were pressurized by methane gas under varied conditions of temperature and pressure. The induction time, the gas consumption, and the average rate of gas consumption in the system were measured and compared to those in ultrapure water. The results show that a concentration of 4.0 wt% hydrophilic SiO_2 particles with a grain size of 50 nm has a relatively strong inhibition effect on hydrate formation when the initial experimental condition is 5.0 °C and 5.0 MPa. Compared to ultrapure water, the hydrophilic nano-SiO_2 fluid increases the induction time for hydrate formation by 194% and decreases the amount and average rate of hydrate formation by 10% and 17%, respectively. This inhibition effect may be attributed to the hydrophilicity,amount and aggregation of silica nanoparticle according to the results of water activity and zeta potential measurements. Our work also elucidates hydrophilic, instead of hydrophobic, nanoparticles can be added to the drilling fluid to maintain wellbore stability and to protect the hydrate reservoir from drilling mud damage, because they exhibit certain degree of hydrate inhibition which can reduce the risk of hydrate reformation and aggregation during gas hydrate or deep water drilling if their concentration can be controlled properly.

Gas-hydrate formation,agglomeration and inhibition in oil-based drilling fluids for deep-water drilling

One of the main challenges in deep-water drilling is gas-hydrate plugs,which make the drilling unsafe.Some oil-based drilling fluids（OBDF） that would be used for deep-water drilling in the South China Sea were tested to investigate the characteristics of gas-hydrate formation,agglomeration and inhibition by an experimental system under the temperature of 4 ？C and pressure of 20 MPa,which would be similar to the case of 2000 m water depth.The results validate the hydrate shell formation model and show that the water cut can greatly influence hydrate formation and agglomeration behaviors in the OBDF.The oleophobic effect enhanced by hydrate shell formation which weakens or destroys the interfacial films effect and the hydrophilic effect are the dominant agglomeration mechanism of hydrate particles.The formation of gas hydrates in OBDF is easier and quicker than in water-based drilling fluids in deep-water conditions of low temperature and high pressure because the former is a W/O dispersive emulsion which means much more gas-water interfaces and nucleation sites than the later.Higher ethylene glycol concentrations can inhibit the formation of gas hydrates and to some extent also act as an anti-agglomerant to inhibit hydrates agglomeration in the OBDF.

Geothermal energy exploitation from depleted high-temperature gas reservoirs by recycling CO_(2): The superiority and existing problems

CO_(2) can be used as an alternative injectant to exploit geothermal energy from depleted high-temperature gas reservoirs due to its high mobility and unique thermal properties.However,there has been a lack of systematic analysis on the heat mining mechanism and performance of CO_(2),as well as the problems that may occur during geothermal energy exploitation at specific gas reservoir conditions.In this paper,a base numerical simulation model of a typical depleted high-temperature gas reservoir was established to simulate the geothermal energy exploitation processes via recycling CO_(2) and water,with a view to investigate whether and/or at which conditions CO_(2) is more suitable than water for geothermal energy exploitation.The problems that may occur during the CO_(2)-based geothermal energy exploitation were also analyzed along with proposed feasible solutions.The results indicate that,for a depleted low-permeability gas reservoir with dimensions of 1000 m×500 m×50 m and temperature of 150℃ using a single injection-production well group for 40 years of operation,the heat mining rate of CO_(2) can be up to 3.8 MW at a circulation flow rate of 18 kg s^(-1)due to its high mobility along with the flow path in the gas reservoir,while the heat mining rate of water is only about 2 MW due to limitations on the injectivity and mobility.The reservoir physical property and injection-production scheme have some effects on the heat mining rate,but CO_(2)always has better performance than water at most reservoir and operation conditions,even under a high water saturation.The main problems for CO_(2) circulation are wellbore corrosion and salt precipitation that can occur when the reservoir has high water saturation and high salinity,in which serious salt precipitation can reduce formation permeability and result in a decline of CO_(2) heat mining rate (e.g.up to 24%reduction).It is proposed to apply a low-salinity water slug before CO_(2)injection to reduce the damage caused by salt precipitation.For high-permeability gas reservoirs with high water saturation and high salinity,the superiority of CO_(2) as a heat transmission fluid becomes obscure and water injection is recommended.

Hydrate formation and distribution within unconsolidated sediment:Insights from laboratory electrical resistivity tomography

Laboratory visual detection on the hydrate accumulation process provides an effective and low-cost method to uncover hydrate accumulation mechanisms in nature.However,the spatial hydrate distribution and its dynamic evolutionary behaviors are still not fully understood due to the lack of methods and experimental systems.Toward this goal,we built a two-dimensional electrical resistivity tomography(ERT)apparatus capable of measuring spatial and temporal characteristics of hydrate-bearing porous media.Beach sand(0.05–0.85 mm)was used to form artificial methane hydrate-bearing sediment.The experiments were conducted at 1°C under excess water conditions and the ERT data were acquired and analyzed.This study demonstrates the utility of the ERT method for hydrate mapping in laboratory-scale.The results indicate that the average electrical conductivity decreases nonlinearly with the formation of the hydrate.At some special time-intervals,the average conductivity fluctuates within a certain scope.The plane conductivity fields evolve heterogeneously and the local preferential hydrate-forming positions alternate throughout the experimental duration.We speculate that the combination of hydrate formation itself and salt-removal effect plays a dominant role in the spatial and temporal hydrate distribution,as well as geophysical parameters changing behaviors during hydrate accumulation.

Experimental study on sand production and coupling response of silty hydrate reservoir with different contents of fine clay during depressurization

To further understand the characteristics of clay and sand production(hereafter collectively referred to as sand production)and to provide optimization designs of sand control schemes are critical for gas production from clayey silt natural gas hydrate reservoirs in the South China Sea.Thus,gas-water-sand production behavoirs and coupling reservoir subsidence characteristics before,during,and after hydrate dissociation of the clayey silt hydrate reservoirs with different clay contents(5%,10%,15%,20%,25%,and 30%)have been studied through a self-developed experimental system.The results show that with the increase of clay content,the total mass of sand production first increases and then decreases,and it reaches maximum when the clayey content is 20%.The sand production is the lowest before hydrate dissociation and increases significantly during hydrate dissociation,which mainly occurs in the high-speed gas and water production stage at the beginning of hydrate dissociation.After hydrate dissociation,the sand production decreases significantly.During the whole depressurization process,the clay and free sand particles generally move to the sand outlet due to the fluid driving force and overlying stress extrusion.However,for conditions of high clay contents,those particles fail to pass through the sand control screen and gradually accumulate and block the screen by forming a mud cake,which greatly reduce the permeability of the screen and limite sand production as well as gas and water production.Our research lays a foundation for sand production prediction and sand control scheme selection during gas recovery from clayey silty hydrate reservoirs that greatly need to consider a balance between sand control and gas productivity.

Large-Scale Test Model of the Progressive Deformation and Failure of Cracked Soil Slopes

A large-scale test bed(LWH=6 m×3 m×2.8 m)instrumented with various sensors is used to examine the effects of rainfall infiltration and evaporation on the deformation and failure of cracked soil slopes,taking the Anhui area along the Yangtze River as a field example.The results indicate that(1)during rainfall,the soil around the shallow shrinkage fissures attains transient saturation,and the attendant decrease of matric suction is the primary cause of the shallow slope failure;(2)slope deformation continues during post-rainfall evaporation;(3)if a period of evaporation is followed by heavy rainfall,soil creep is concentrated near the deepest cracks,and two zones of steep gradients in pore pressure form at the crest and toe of the slope.Finally,a saturated zone forms near each crack base and gradually enlarges,eventually forming a continuous saturated layer that induces the slope instability or failure.

Effect on the Performance of Drilling Fluids at Downhole Rock Surfaces at Low Temperatures

To maintain gas hydrate stability, low-temperature drilling fluids and high drilling speeds should be used while drilling in gas hydrate-bearing sediments. The effect of the drilling fluid on downhole rock surfaces at low temperatures is very important to increase the drilling rate. This paper analyzed the action mechanism of the drilling fluid on downhole rock surfaces and established a corresponding evaluation method. The softening effect of six simulated drilling fluids with 0.1 wt.% of four common surfactants and two common organic salts on the downhole rock surface strength was evaluated experimentally using the established method at low temperature. The experimental results showed that the surfactants and organic salts used in the drilling fluids aided in the reduction of the strength of the downhole rock surface, and the established evaluation method was able to quantitatively reveal the difference in the softening effect of the different drilling fluids through comparison with water. In particular, the most common surfactant that is used in drilling fluids, sodium dodecyl sulfate（SDS）, had a very good softening effect while drilling under low-temperature conditions, which can be widely applied during drilling in low-temperature formations, such as natural gas hydrate-bearing sediments, the deep seafloor and permafrost.

Effect of hydrophilic silica nanoparticles on hydrate formation during methane gas migration in a simulated wellbore

Natural gas hydrates are mostly formed in low-permeability and fractured muddy sedimentary formations.Adding suitable nanoparticles to the drilling fluid system can improve its filtrate resistance and fracture plugging,and effectively weaken the invasion of drilling fluid into the reservoir.However,it is likely that nanoparticles promote hydrate formation and accumulation in wellbores which will induce accidents.Therefore,this study investigated the effect of hydrophilic silica nanoparticles with particle sizes of 30 nm,60 nm,and 80 nm and concentrations of 0.5e4.0 wt%on hydrate formation during upward migration of methane gas using a dynamic simulation system for hydrate formation in a wellbore.The experimental results show that under the condition of methane gas migration,hydrophilic silica nanoparticles inhibit hydrate formation.The inhibition effect increased with the growth in the particle size under a constant concentration,whereas it first increased and then decreased with increasing nanoparticle concentration under a constant particle size.The strongest inhibition effect was observed at a hydrophilic silica nanoparticle concentration of 2.0 wt%.The influence of hydrophilic silica nanoparticles on hydrate formation may be mainly determined by their hydrophilic properties,heat and mass transfer,and gas migration in the wellbore.Our research indicates that hydrophilic silica nanoparticles can be added to hydrate drilling fluid systems if their concentration can be properly controlled.