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
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
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
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
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
Hydrate-based gas separation offers a promising approach for coalbed methane recovery,reaching energy conservation and emissions reduction.This study innovatively applied high-gravity technology to enhance hydrate for...Hydrate-based gas separation offers a promising approach for coalbed methane recovery,reaching energy conservation and emissions reduction.This study innovatively applied high-gravity technology to enhance hydrate formation in separating 25%CH_(4)/67%N_(2)/8%O_(2) for achieving rapid and efficient methane recovery.Systematic investigations were conducted at 283.2 K and 3.0 MPa with tetrahydrofuran at a molar concentration of 5.56%and L-tryptophan at a mass concentration of 0.5%additives,first evaluating liquid flow rate effects(0–20 mL/min)on mixed hydrate kinetic performance and separation efficiency,followed by rotating speed optimization(0–1200 r·min^(-1))under the optimal liquid flow rate.The high-gravity system amplified the gas–liquid contact area by~1155 times through cascaded liquid supply and secondary shear effects,methane molecules entered the hydrate phase rapidly under the highest driving force with the significantly intensified mass transfer.Optimal conditions(20 mL/min,600 r·min^(-1))yielded an exceptional initial hydrate growth rate of 58.59 mmol/(mol·h)and methane recovery of 50.76%,about 71.33 and 0.58 times higher than the static system,respectively.Gas chromatography and Raman spectrometer analyses revealed superior methane enrichment in hydrate phase at 90%gas uptake completion,with a concurrent 41.17%reduction in process duration.These findings demonstrate the efficacy of high-gravity-enhanced hydrate technology for coalbed methane separation,offering valuable insights for optimizing clean energy utilization.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
Marine gas hydrates are highly sensitive to temperature and pressure fluctuations,and deviations from in-situ conditions may cause irreversible changes in phase state,microstructure,and mechanical properties.However,c...Marine gas hydrates are highly sensitive to temperature and pressure fluctuations,and deviations from in-situ conditions may cause irreversible changes in phase state,microstructure,and mechanical properties.However,conventional samplers often fail to maintain sealing and thermal stability,resulting in low sampling success rates.To address these challenges,an in-situ temperature-and pressure-preserved sampler for marine applications has been developed.The experimental results indicate that the selfdeveloped magnetically controlled pressure-preserved controller reliably achieves autonomous triggering and self-sealing,provides an initial sealing force of 83 N,and is capable of maintaining pressures up to 40 MPa.Additionally,a custom-designed intelligent temperature control chip and high-precision sensors were integrated into the sampler.Through the design of an optimized heat transfer structure,a temperature-preserved system was developed,achieving no more than a 0.3℃ rise in temperature within 2 h.The performance evaluation and sampling operations of the sampler were conducted at the Haima Cold Seep in the South China Sea,resulting in the successful recovery of hydrate maintained under in-situ pressure of 13.8 MPa and a temperature of 6.5℃.This advancement enables the acquisition of high-fidelity hydrate samples,providing critical support for the safe exploitation and scientific analysis of marine gas hydrate resources.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
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 274.1...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.展开更多
The decomposition kinetics for formation of CO2 hydrates in 90 cm 3wet natural silica sands were studied systematically using the depressurization method at the temperatures ranging from 273.2 to 277.2 K and the press...The decomposition kinetics for formation of CO2 hydrates in 90 cm 3wet natural silica sands were studied systematically using the depressurization method at the temperatures ranging from 273.2 to 277.2 K and the pressures from 0.5 to 1.0 MPa.The effects of temperature,pressure,particle diameter,porosity,and salinity of formation water on the decomposition kinetics were investigated.The results show that the dissociation percentage increases as temperature increases or as the initial decomposition pressure decreases.An increase in porosity or a decrease in particle diameter of silica sands accelerates the decomposition.Increasing the salinity of the formation water gives rise to a faster decomposition.However,a combination of the present results with the observations in literature reveals that the effect of the coexisting ionic solute depends on its chemical structure.展开更多
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 escap...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.展开更多
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...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.展开更多
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...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.展开更多
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...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.展开更多
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.
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 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.
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.
基金The financial support from the Nature Scientific Foundation of Heilongjiang Province(No.YQ2022E041)the Postdoctoral Research Start-up Funds in Heilongjiang Province(No.2023BSH14)the Basic scientific research project of Heilongjiang Provincial University(No.2024-KYYWF-1090)。
文摘Hydrate-based gas separation offers a promising approach for coalbed methane recovery,reaching energy conservation and emissions reduction.This study innovatively applied high-gravity technology to enhance hydrate formation in separating 25%CH_(4)/67%N_(2)/8%O_(2) for achieving rapid and efficient methane recovery.Systematic investigations were conducted at 283.2 K and 3.0 MPa with tetrahydrofuran at a molar concentration of 5.56%and L-tryptophan at a mass concentration of 0.5%additives,first evaluating liquid flow rate effects(0–20 mL/min)on mixed hydrate kinetic performance and separation efficiency,followed by rotating speed optimization(0–1200 r·min^(-1))under the optimal liquid flow rate.The high-gravity system amplified the gas–liquid contact area by~1155 times through cascaded liquid supply and secondary shear effects,methane molecules entered the hydrate phase rapidly under the highest driving force with the significantly intensified mass transfer.Optimal conditions(20 mL/min,600 r·min^(-1))yielded an exceptional initial hydrate growth rate of 58.59 mmol/(mol·h)and methane recovery of 50.76%,about 71.33 and 0.58 times higher than the static system,respectively.Gas chromatography and Raman spectrometer analyses revealed superior methane enrichment in hydrate phase at 90%gas uptake completion,with a concurrent 41.17%reduction in process duration.These findings demonstrate the efficacy of high-gravity-enhanced hydrate technology for coalbed methane separation,offering valuable insights for optimizing clean energy utilization.
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financially supported by Shenzhen Science and Technology Program(Nos.JSGG20220831105002005 and KJZD20231025152759002)Support from the National Natural Science Foundation of China(Nos.52374357 and 523B2101)funded by the Shared Voyages Project for Deep-sea and Abyss Scientific Research and Equipment Sea Trials of Hainan Deep-Sea Technology Innovation Center(No.DSTIC-GXHC-2022002)。
文摘Marine gas hydrates are highly sensitive to temperature and pressure fluctuations,and deviations from in-situ conditions may cause irreversible changes in phase state,microstructure,and mechanical properties.However,conventional samplers often fail to maintain sealing and thermal stability,resulting in low sampling success rates.To address these challenges,an in-situ temperature-and pressure-preserved sampler for marine applications has been developed.The experimental results indicate that the selfdeveloped magnetically controlled pressure-preserved controller reliably achieves autonomous triggering and self-sealing,provides an initial sealing force of 83 N,and is capable of maintaining pressures up to 40 MPa.Additionally,a custom-designed intelligent temperature control chip and high-precision sensors were integrated into the sampler.Through the design of an optimized heat transfer structure,a temperature-preserved system was developed,achieving no more than a 0.3℃ rise in temperature within 2 h.The performance evaluation and sampling operations of the sampler were conducted at the Haima Cold Seep in the South China Sea,resulting in the successful recovery of hydrate maintained under in-situ pressure of 13.8 MPa and a temperature of 6.5℃.This advancement enables the acquisition of high-fidelity hydrate samples,providing critical support for the safe exploitation and scientific analysis of marine gas hydrate resources.
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.
基金supported by the National Natural Science Foundation of China(grant numbers 51606125,51802190,21978171,51876130,51674240)the Innovation Program of Shanghai Municipal Education Commission(grant number 13ZZ117)。
文摘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.
基金Supported by the National Natural Science Foundation of China（40673043 20576073） the Program for New Century Excellent Talents in University from Ministry of Education of China（NCET-06-0088）
文摘The decomposition kinetics for formation of CO2 hydrates in 90 cm 3wet natural silica sands were studied systematically using the depressurization method at the temperatures ranging from 273.2 to 277.2 K and the pressures from 0.5 to 1.0 MPa.The effects of temperature,pressure,particle diameter,porosity,and salinity of formation water on the decomposition kinetics were investigated.The results show that the dissociation percentage increases as temperature increases or as the initial decomposition pressure decreases.An increase in porosity or a decrease in particle diameter of silica sands accelerates the decomposition.Increasing the salinity of the formation water gives rise to a faster decomposition.However,a combination of the present results with the observations in literature reveals that the effect of the coexisting ionic solute depends on its chemical structure.
基金supported by the National Natural Science Foundation of China (40673043 and 20576073)the Program for New Century Excellent Talents in University of Ministry of Education of China (NCET-06-0088)
文摘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.
文摘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.
文摘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.
基金the financial support of the National Natural Science Foundation of China(41876051 and 41872136)the China Postdoctoral Science Foundation(2021M701815)the Postdoctoral Innovative Talents Support Program in Shandong Province(SDBX2021015).
文摘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.
