As a kind of novel environmental-friendly surfactant,Gemini surfactant has attracted extensive research interests in its effects on gas hydrate formation.We investigated the effects of dioctyl sodium sulfosuccinate(AO...As a kind of novel environmental-friendly surfactant,Gemini surfactant has attracted extensive research interests in its effects on gas hydrate formation.We investigated the effects of dioctyl sodium sulfosuccinate(AOT)on the formation thermodynamics/kinetics of CH_(4)and CO_(2)hydrates.Experimental results indicate that while AOT does not exhibit significant thermodynamic promotion for hydrate formation,it demonstrates favorable kinetic promotion effects.Its promotion effect surpasses that of the traditional kinetic promoter SDS and can enhance the gas storage capacity of hydrates.Utilizing the Chen-Guo hydrate model and adsorption kinetic model,we established a kinetic model for AOT with a predictive deviation of 7.17%and fitted key parameters accordingly.展开更多
This study proposes and systematically evaluates an optimized integration of warm surface seawater injection with depressurization for the long-term exploitation of marine natural gas hydrates.By employing comprehensi...This study proposes and systematically evaluates an optimized integration of warm surface seawater injection with depressurization for the long-term exploitation of marine natural gas hydrates.By employing comprehensive multiphysics simulations guided by field data from hydrate production tests in the South China Sea,we pinpoint key operational parameters—such as injection rates,depths,and timings—that notably enhance production efficiency.The results indicate that a 3-phase hydrate reservoir transitions from a free-gas-dominated production stage to a hydrate-decomposition-dominated stage.Moderate warm seawater injection supplies additional heat during the hydrate decomposition phase,thereby enhancing stable production;however,excessively high injection rates can impede the depressurization process.Only injection at an appropriate depth simultaneously balances thermal supplementation and the pressure gradient,leading to higher overall productivity.A“depressurization-driven sensible-heat supply window”is introduced,highlighting that timely seawater injection following initial depressurization prolongs reservoir dissociation dynamics.In this study area,commencing seawater injection at 170 d of depressurization proved optimal.This optimized integration leverages clean and renewable thermal energy,providing essential insights into thermal supplementation strategies with significant implications for sustainable,economically feasible,and efficient commercial-scale hydrate production.展开更多
An efficient acetic acid mediated metal-free oxidative C—H cross coupling of imidazo[1,2-a]pyridines with glyoxal hydrates has been developed under air atmosphere.The present protocol exhibits broad substrate scope,g...An efficient acetic acid mediated metal-free oxidative C—H cross coupling of imidazo[1,2-a]pyridines with glyoxal hydrates has been developed under air atmosphere.The present protocol exhibits broad substrate scope,good functional group tolerance,and enables the construction of a series of 1,2-dicarbonyl imidazo[1,2-a]pyridines in good yields.The reaction mechanism studies suggest that the reactions proceed through the electrophilic substitution and subsequent oxidation pathway.展开更多
Weak cementation between natural gas hydrates and mud–sand seriously affects the solid-fluidized mining of natural gas hydrates. In this study, we analyze the debonding of natural gas hydrate sediment (NGHS) particle...Weak cementation between natural gas hydrates and mud–sand seriously affects the solid-fluidized mining of natural gas hydrates. In this study, we analyze the debonding of natural gas hydrate sediment (NGHS) particles by applying the principle of spiral-cyclone coupling separation. To achieve this, weakly cemented NGHS particle and mechanical models were established. In the flow field of the spiral-cyclone flow-coupling separator, the motion characteristics of the weakly cemented NGHS particles and the destruction process of the cementation bond were analyzed. The destruction of the bonds mainly occurred in the spiral channel, and the destruction efficiency of the bonds was mainly affected by the rotational speed. Collision analysis of the particles and walls showed that when the velocity is 10–16 m·s^(−1), the cementation bond can be broken. The greater the speed, the better the effect of the bond fracture. The breaking rate of the cementation bonds was 85.7%. This study is significant for improving the degumming efficiency in natural gas hydrate exploitation, improving the recovery efficiency of hydrates, and promoting the commercialization of hydrate solid fluidization exploitation.展开更多
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 ...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.展开更多
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 ...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.展开更多
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 co...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.展开更多
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 dissociat...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.展开更多
Free water available in calcium aluminate cement(CAC)-bonded castables is crucial for the hydration of CAC and the conversion of hydration products in the curing and drying processes,as both the hydration and conversi...Free water available in calcium aluminate cement(CAC)-bonded castables is crucial for the hydration of CAC and the conversion of hydration products in the curing and drying processes,as both the hydration and conversion reactions are dissolution–precipitation reactions.To elucidate the effect of different levels of free water loss upon the hydration of CAC,the conversion of hydration products and the mechanical strength of the CAC-bonded castables,the CAC-bonded castables were subjected to sealed and unsealed curing conditions at 50℃ and drying at 110℃.The results demonstrate that the fast removal of free water during unsealed curing would hinder the conversion from 2CaO·Al_(2)O_(3)·8H_(2)O to 3CaO·Al_(2)O_(3)·6H_(2)O and consequently prevent the deterioration of strength.As a comparison,although sealed-cured samples have less water loss and high degree of hydration of CAC,they still show lower strength than the unsealed samples after curing.The following drying process further accelerates the hydration of residual calcium aluminate clinkers for both the sealed and unsealed samples,but still does not favor the conversion from 2CaO·Al_(2)O_(3)·8H_(2)O to 3CaO·Al_(2)O_(3)·6H_(2)O in the unsealed-cured samples.展开更多
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 temperat...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.展开更多
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...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.展开更多
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 ...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.展开更多
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...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.展开更多
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 ...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.展开更多
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...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.展开更多
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 res...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.展开更多
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 characteri...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.展开更多
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 e...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.展开更多
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 ch...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.展开更多
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-heatin...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.展开更多
基金supported by National Natural Science Foundation of China(22278424,22127812,22008257).
文摘As a kind of novel environmental-friendly surfactant,Gemini surfactant has attracted extensive research interests in its effects on gas hydrate formation.We investigated the effects of dioctyl sodium sulfosuccinate(AOT)on the formation thermodynamics/kinetics of CH_(4)and CO_(2)hydrates.Experimental results indicate that while AOT does not exhibit significant thermodynamic promotion for hydrate formation,it demonstrates favorable kinetic promotion effects.Its promotion effect surpasses that of the traditional kinetic promoter SDS and can enhance the gas storage capacity of hydrates.Utilizing the Chen-Guo hydrate model and adsorption kinetic model,we established a kinetic model for AOT with a predictive deviation of 7.17%and fitted key parameters accordingly.
基金supported by the National Key R&D Program of China(No.2024YFB4206700)the Joint Geological Funds of the National Natural Science Foundation of China(No.U2244223)+5 种基金the China Scholarship Council Program(No.202404910533)the Guangdong Major Project of Basic and Applied Basic Research(No.2020B0301030003)the China Geological Survey Project(No.DD20211350)the Key Deployment Program of Chinese Academy of Sciences(Nos.YJKYYQ20190043,ZDBS-LY-DQC003,KFZD-SW-422,and ZDRW-ZS-2021-3-1)the Scientific Research and Technology Development Project of China National Petroleum Corporation(No.2022DJ5503)the Supercomputing Laboratory,IGGCAS.
文摘This study proposes and systematically evaluates an optimized integration of warm surface seawater injection with depressurization for the long-term exploitation of marine natural gas hydrates.By employing comprehensive multiphysics simulations guided by field data from hydrate production tests in the South China Sea,we pinpoint key operational parameters—such as injection rates,depths,and timings—that notably enhance production efficiency.The results indicate that a 3-phase hydrate reservoir transitions from a free-gas-dominated production stage to a hydrate-decomposition-dominated stage.Moderate warm seawater injection supplies additional heat during the hydrate decomposition phase,thereby enhancing stable production;however,excessively high injection rates can impede the depressurization process.Only injection at an appropriate depth simultaneously balances thermal supplementation and the pressure gradient,leading to higher overall productivity.A“depressurization-driven sensible-heat supply window”is introduced,highlighting that timely seawater injection following initial depressurization prolongs reservoir dissociation dynamics.In this study area,commencing seawater injection at 170 d of depressurization proved optimal.This optimized integration leverages clean and renewable thermal energy,providing essential insights into thermal supplementation strategies with significant implications for sustainable,economically feasible,and efficient commercial-scale hydrate production.
文摘An efficient acetic acid mediated metal-free oxidative C—H cross coupling of imidazo[1,2-a]pyridines with glyoxal hydrates has been developed under air atmosphere.The present protocol exhibits broad substrate scope,good functional group tolerance,and enables the construction of a series of 1,2-dicarbonyl imidazo[1,2-a]pyridines in good yields.The reaction mechanism studies suggest that the reactions proceed through the electrophilic substitution and subsequent oxidation pathway.
基金funded by the State Key Laboratory of Natural Gas Hydrate of China(2022-KFJJ-SHW)the National Key Research and Development Program of China(2021YFC2800903)+2 种基金the National Natural Science Foundation of China(52004235)the National Natural Science Foundation General Program of China(52374011)the Miaozi Engineering Cultivation Project of Sichuan Science and Technology Department of China(MZG20230127).
文摘Weak cementation between natural gas hydrates and mud–sand seriously affects the solid-fluidized mining of natural gas hydrates. In this study, we analyze the debonding of natural gas hydrate sediment (NGHS) particles by applying the principle of spiral-cyclone coupling separation. To achieve this, weakly cemented NGHS particle and mechanical models were established. In the flow field of the spiral-cyclone flow-coupling separator, the motion characteristics of the weakly cemented NGHS particles and the destruction process of the cementation bond were analyzed. The destruction of the bonds mainly occurred in the spiral channel, and the destruction efficiency of the bonds was mainly affected by the rotational speed. Collision analysis of the particles and walls showed that when the velocity is 10–16 m·s^(−1), the cementation bond can be broken. The greater the speed, the better the effect of the bond fracture. The breaking rate of the cementation bonds was 85.7%. This study is significant for improving the degumming efficiency in natural gas hydrate exploitation, improving the recovery efficiency of hydrates, and promoting the commercialization of hydrate solid fluidization exploitation.
基金jointly supported by the National Natural Science Foundation of China(42376222,U22A20581,and 42076069)Key Research and Development Program of Hainan Province(ZDYF2024GXJS002)China Geological Survey(DD20230402)。
文摘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.
基金supported by the National Natural Science Foundation of China(52104069,U20B6005)Beijing Municipal Natural Science Foundation(3232030)Science Foundation of China University of Petroleum,Beijing(2462023BJRC018,2462020YXZZ045).
文摘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.
基金This work is financially supported by the Key Laboratory of Icing and Anti/De-icing of CARDC(Grant No.IADL20210402)the National Natural Science Foundation of China(Grant Nos.12002350,12172314,11772278 and 11904300)+1 种基金the Jiangxi Provincial Outstanding Young Talents Program(Grant No.20192BCBL23029)the Fundamental Research Funds for the Central Universities(Xiamen University:Grant No.20720210025).
文摘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.
基金financial support received from the Basic Research Program of Qinghai Province(2023-ZJ-703)the National Natural Science Foundation of China(22178379,42206223)the National Key Research and Development Programof China(2021YFC2800902)is gratefully acknowledged.
文摘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.
基金the National Natural Science Foundation of China(52172030)for the financial support.
文摘Free water available in calcium aluminate cement(CAC)-bonded castables is crucial for the hydration of CAC and the conversion of hydration products in the curing and drying processes,as both the hydration and conversion reactions are dissolution–precipitation reactions.To elucidate the effect of different levels of free water loss upon the hydration of CAC,the conversion of hydration products and the mechanical strength of the CAC-bonded castables,the CAC-bonded castables were subjected to sealed and unsealed curing conditions at 50℃ and drying at 110℃.The results demonstrate that the fast removal of free water during unsealed curing would hinder the conversion from 2CaO·Al_(2)O_(3)·8H_(2)O to 3CaO·Al_(2)O_(3)·6H_(2)O and consequently prevent the deterioration of strength.As a comparison,although sealed-cured samples have less water loss and high degree of hydration of CAC,they still show lower strength than the unsealed samples after curing.The following drying process further accelerates the hydration of residual calcium aluminate clinkers for both the sealed and unsealed samples,but still does not favor the conversion from 2CaO·Al_(2)O_(3)·8H_(2)O to 3CaO·Al_(2)O_(3)·6H_(2)O in the unsealed-cured samples.
基金financial support received from National Natural Science Foundation of China(22178378 and 22127812)"Tianchi Talent"Recruitment Program,Xinjiang Tianshan Innovation Team(2022TSYCTD0002)Xinjiang Uygur Region"One Case,One Policy"Strategic Talent Introduction Project(XQZX20240054)are gratefully acknowledged.
文摘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.
基金supported by the Energy Efficiency and Renewable Energy,Building Technologies Program,of the US Department of Energy,under contract no.DE-AC02-05CH11231the support on the DSC/TGA 3+supported by the Office of Science,Office of Basic Energy Sciences,of the U.S.Department of Energy under Contract No.DE-AC02-05CH11231
文摘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.
基金the National Natural Science Foundation of China(NSFC 21676145)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD,China).
文摘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.
基金supported by the National Hi-tech Research and Development Program of China(863 Program)(Grant No.2013AA092501)the China Geological Survey Projects(Grant Nos.GZH201100303 and GZH201100305)
文摘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.
基金supported by the National Natural Science Foundation of China(No.41174087,41204089)the National Oil and Gas Major Project(No.2011ZX05005-005)
文摘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.
基金National Gas Hydrates Integral Appraisal Project (GZH200200203-05).
文摘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.
文摘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.
基金funded by the projects initiated by the China Geological Survey(DD20190217 and DD20190230)the key special project for introduced talent team of Southern Marine Science and Engineering Guangdong Laboratory(Guangzhou)(GML2019ZD0102)Guangdong Major project of Basic and Applied Basic Research(2020B0301030003).
文摘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.
基金The financial support from the National University of Singapore (R-279-000-542-114)the EDB and LRS for the industrial postgraduate programme (IPP) scholarship
文摘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.
基金Supported by the National Natural Science Foundation of China （20876161） and the National Basic Research Program of China （2007CB613501, 2009CB219904）.
文摘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.
基金Funded by the Science and Technology Foundation of Beijing Municipal Education Commission (KM200410016004)
文摘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.
