Adhesion strength of tetrahydrofuran hydrates is dictated by substrate stiffness

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

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

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

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.

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 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.

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.

Geochemical Indications of Possible Gas Hydrates in the Northeastern South China Sea

Gas hydrate, mainly composed of hydrocarbon gas and water, is considered to be a clean energy in the 21st century. Many indicators such as BSRs （Bottom-Simulating Reflections）, which are thought to be related to gas hydrate, are found in the South China Sea （SCS） in recent years. The northeastern part of the SCS is taken as one of the most potentials in the area by many scientists. It is situated in the conjunction of the northern divergent continental margin and the eastern convergent island margin, whose geological settings are much preferable for gas hydrate to occur. Through this study, brightness temperature anomalies recorded by satellite-based thermal infrared remotely sensed images before or within the imminent earthquake, the high content of hydrocarbon gas acid-degassed from subsurface sediment and the high radioactive thermoluminescence value of subsurface sediment were found in the region. Sometimes brightness temperature anomalies alone exist in the surrounding of the Dongsha Islands. The highest content of hydrocarbon gas amounts to 393 μL methane per kilogram sediment and the highest radioactive thermoluminescence value is 31752 unit; their geometric averages are 60.5 μL/kg and 2688.9 unit respectively. What is more inspiring is that there are three sites where the methane contents are up to 243, 268 and 359μL/kg and their radioactive thermoluminescence values are 8430, 9537 and 20826 unit respectively. These three locations are just in the vicinity of one of the highest confident BSRs identified by predecessors. Meanwhile, the anomalies are generally coincident with other results such as headspace gas anomaly in the sediment and chloride anomaly in the interstitial water in the site 1146 of Leg 184. The above-mentioned anomalies are most possibly to indicate the occurrence of gas hydrate in the northeastern SCS.

Dissociation behavior of “dry water” C_3H_8 hydrate below ice point:Effect of phase state of unreacted residual water on a mechanism of gas hydrates dissociation

The results on a dissociation behavior of propane hydrates prepared from ＂dry water＂ and contained unreacted residual water in the form of ice inclusions or supercooled liquid water（water solution of gas） were presented for temperatures below 273 K.The temperature ramping or pressure release method was used for the dissociation of propane hydrate samples.It was found that the mechanism of gas hydrate dissociation at temperatures below 273 K depended on the phase state of unreacted water in the hydrate sample.Gas hydrates dissociated into ice and gas if the ice inclusions were in the hydrate sample.The samples of propane hydrates with inclusions of unreacted supercooled water only（without ice inclusions） dissociated into supercooled water and gas below the pressure of the supercooled water-hydrate-gas metastable equilibrium.

Simulation of the Accumulation Process of Biogenic Gas Hydrates in the Shenhu Area of Northern South China Sea

Previous work has largely discussed the relations between sediment structures and accumulation of gas hydrates in the Shenhu area of South China Sea, but has not documented why the gas hydrates occurred at the seafloor topographic highs. Many gas hydrate exploration examples abroad also indicate that the saturation of gas hydrates was higher at seafloor topographic highs. This work aims to understand why gas hydrates accumulated at topographic highs and why their saturation is higher.

Experimental Verification on Conversion Mechanism of Calcium Aluminate Cement Hydrates

Calcium aluminate cement(CAC)is a commonly used binder for refractory castables.There has been a long-running debate on the transformation mechanisms of calcium aluminate cement hydrates through solid-state reaction or solutionprecipitation.In order to demonstrate the conversion mechanism of CaO Al2O310H2O(CAH10)to 3CaO Al2O36H2O(C3AH6)and Al2O33H2O(AH3),the CAC pastes cured at 10℃to produce CAH10 was further cured at 60℃with and without free water.The hydration of the pastes was halted by freezing-drying,and the phases and microstructure of hydrates were investigated by XRD and SEM,respectively.The results indicate that CAH10 converts into C3AH6 and AH3 in water presence at 60℃,but does not transform into C3AH6 and AH3 without water,demonstrating that conversion of CAH10 into C3AH6 and AH3 does not happen through solid-state reaction,but takes place through preceding dissolution of CAH10 and subsequent precipitation of AH3 and C3AH6 from the solution.

Energy-efficient methods for production methane from natural gas hydrates

Gas hydrates now are expected to be one of the most important future unconventional energy resources. In this paper, researches on gas hydrate exploitation in laboratory and field were reviewed and discussed from the aspects of energy efficiency. Different exploiting methods and different types of hydrate reservoir were selected to study their effects on energy efficiencies. Both laboratory studies and field tests have shown that the improved technologies can help to increase efficiency for gas hydrate exploitation. And it also showed the trend that gas hydrate exploitation started to change from permafrost to marine. Energy efficiency ratio （EER） and energy return on energy invested （EROI） were introduced as an indicator of efficiency for natural gas hydrate exploitation. An energy-efficient hydrate production process, called ＂Hydrate Chain Energy System （HCES）＂, including treatment of flue gas, replacement of CH4 with CO2, separation of CO2 from CH4, and storage and transportation of CH4 in hydrate form, was proposed for future natural gas hydrate exploitation. In the meanwhile, some problems, such as mechanism of C02 replacement, mechanism of CO2 separation, CH4 storage and transportation are also needed to be solved for increasing the energy efficiency of gas hydrate exploitation.

Experimental study on characteristics of pore water conversion during methane hydrates formation in unsaturated sand

Understanding the pore water conversion characteristics during hydrate formation in porous media is important to study the accumulation mechanism of marine gas hydrate.In this study,low-field NMR was used to study the pore water conversion characteristics during methane hydrate formation in unsaturated sand samples.Results show that the signal intensity of T_(2) distribution isn’t affected by sediment type and pore pressure,but is affected by temperature.The increase in the pressure of hydrogen-containing gas can cause the increase in the signal intensity of T_(2) distribution.The heterogeneity of pore structure is aggravated due to the hydrate formation in porous media.The water conversion rate fluctuates during the hydrate formation.The sand size affects the water conversion ratio and rate by affecting the specific surface of sand in unsaturated porous media.For the fine sand sample,the large specific surface causes a large gas-water contact area resulting in a higher water conversion rate,but causes a large water-sand contact area resulting in a low water conversion ratio(C_(w)=96.2%).The clay can reduce the water conversion rate and ratio,especially montmorillonite(C_(w)=95.8%).The crystal layer of montmorillonite affects the pore water conversion characteristics by hindering the conversion of interlayer water.

A three-dimensional environmental monitoring system for the production of marine gas hydrates

1.Objectives As about 99% of the natural gas hydrate (NGH)resources are stored on the seafloor,it is inevitable that in its process of exploration and production,there will be geohazards such as methane leakage,seabed subsidence,ecosystem damage and even landslide.Therefore,a set of integrated systems for environmental monitoring in the process of NGH production has been proposed in the consideration of environmental disasters that may arise in the process of hydrate production.

Geochemical insights into contribution of petroleum hydrocarbons to the formation of hydrates in the Taixinan Basin, the South China Sea

Methane hydrate in the South China Sea (SCS) has extensively been considered to be biogenic on the basis of its δ13C andδD values.Although previous efforts have greatly been made,the contribution of thermogenic oil/gas has still been underestimated.In this study,biomarkers and porewater geochemical parameters in hydrate-free and hydrate-bearing sediments in the Taixinan Basin,the SCS have been measured for evaluating the contribution of petroleum hydrocarbons to the formation of hydrate deposits via a comparative study of their source inputs of organic matters,environmental conditions,and microbial activities.The results reveal the occurrence of C_(14)–C_(16) branched saturated fatty acids (bSFAs) with relatively high concentrations from sulfate-reducing bacteria(SRBs) in hydrate-bearing sediments in comparison with hydrate-free sediments,which is in accord with the positive δ^(13)C values of dissolved inorganic carbon (DIC),increasing methane concentrations,decreasing alkalinity,and concentration fluctuation of ions (Cl^(-),Br^(-),SO_(4)^(2-),Ca^(2+),and Mg^(2+)).These data indicate the relatively active microbial activities in hydrate-bearing sediments and coincident variations of environmental conditions.Carbon isotope compositions of b SFAs (-34.0‰to -21.2‰),n-alkanes (-34.5‰to-29.3‰),and methane(-70.7‰to -69.9‰) jointly demonstrate that SRBs might thrive on a different type of organic carbon rather than methane.Combining with numerous gas/oil reservoirs and hydrocarbon migration channels in the SCS,the occurrence of unresolved complex mixtures (UCMs),odd-even predominance (OEP) values (about 1.0),and biomarker patterns suggest that petroleum hydrocarbons from deep oil/gas reservoirs are the most probable carbon source.Our new results provide significant evidence that the deep oil/gas reservoirs may make a contribution to the formation of methane hydrate deposits in the SCS.

Geochemical Characteristics of C_5–C_7 Light Hydrocarbons in Gas Hydrates from the Permafrost Region of Qilian Mountains

As an important part of gas hydrates, light hydrocarbons （LHs）, especially C5 to C7 hydrocarbons with various monomer compounds, provide a wide variety of geological and geochemical information, which have received much attention from organic geochemists and petroleum geologists.