Supercritical fluids play a crucial role in material transport within Earth's deep interior.Investigating the pressure-dependent atomic structures and transport properties of such fluids is essential for understan...Supercritical fluids play a crucial role in material transport within Earth's deep interior.Investigating the pressure-dependent atomic structures and transport properties of such fluids is essential for understanding their petrological,chemical,and geophysical behaviors.In this study,we employed first-principles molecular dynamics simulations to explore the structures,self-diffusion coefficients(D),and viscosities(η)of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids under conditions of 2000 K and 3-10 GPa,with water contents of 30 wt% and 50 wt%.Our calculations indicate that at a water content of 30 wt%,Q^(2) and Q^(3) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species(n represents the number of bridging oxygens connected to Si/Al)show minimal changes.At a water content of 50 wt%,Q^(2) and Q^(0) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species show minimal changes.At both water contents,Si-O-H and molecular water in the system exhibit negative pressure dependence,suggesting that the migration of supercritical fluids from deep to shallow regions is accompanied by the release of water.The self-diffusion coefficients in the supercritical NaAlSi_(3)O_(8)-H_(2)O fluid follow the order D_(Na)≈D_(H)>D_(O)>D_(Al)≈D_(Si),with an overall weak negative pressure dependence.By comparing the viscosities of anhydrous and hydrous silicate melts from previous studies,we found that the addition of water caused a transition from negative to positive pressure dependence of viscosity,corresponding to a structural change from polymerization to depolymerization.Additionally,we calculated the fluid mobility Δp/η of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids and found that their mobility is several orders of magnitude higher than that of basalt melt and is also significantly greater than that of carbonate melt.As supercritical fluids ascend from deeper to shallower regions,their mobility is further enhanced,significantly contributing to the transport of elements from subducting slabs to the overlying mantle wedge.展开更多
The use of supercritical CO2 for shale gas extraction is a promising new technology.This paper explores current research into this process,looking at analysis of the mechanism of CH4 displacement in nanoporous shale,t...The use of supercritical CO2 for shale gas extraction is a promising new technology.This paper explores current research into this process,looking at analysis of the mechanism of CH4 displacement in nanoporous shale,the positive and negative effects accompanying its use for sequestration as well as organic extraction,the migration of elements and the swelling process,and the macro and micro control mechanisms involved in permeability enhancement in reservoirs.Fruitful directions for future research are also considered through comparison with hydraulic fracturing.The research findings indicate that ScCO2 fluid replacement can be used to increase gas production and seal up greenhouse gases as an effective,clean and safe method of shale gas exploitation.It is particularly effective for promoting the desorption of CH4 in shale reservoirs that have developed fine neck-wide body pores,and the subtle structural changes effected by ScCO2 fluid in sensitive minerals in reservoirs with a high brittle mineral content also have a positive effect on permeability and storage capacity.The adsorption process has been characterized as consisting of three stages:short-term shrinkage,slow swelling,and stability;an expansion equation has been proposed for CO2/CH4 that incorporates competitive adsorption,collision desorption,and impingement re-adsorption.ScCO2 fracturing has been found to be more effective than hydraulic fracturing for dense reservoirs and more effective at linking up pore-micro-fissure-fracture systems.展开更多
Rare earth elements(REEs)are valuable raw materials which are in great demand in modern high technology industries.Developing methods to produce/recover REEs from waste is significant to the national security of any d...Rare earth elements(REEs)are valuable raw materials which are in great demand in modern high technology industries.Developing methods to produce/recover REEs from waste is significant to the national security of any developed country.This study was focused on investigating the use of supercritical CO2(sCO2)to extract REEs from anthracite acid mine drainage(AMD).Four different mine drainage water source locations at Blaschak Coal Corp.in Pennsylvania,USA were selected for sample collection.An extraction process was developed and demonstrated for two of those water sources containing the highest concentration of REEs.A method involving metal ion coagulation,their dissolution from the sludge into a concentrated aqueous HNO3 solution,complexation with organic ligands and sCO2 extraction was developed to recover REEs from AMD.Specifically,sodium aluminate(NaAlO2)was used as the coagulant to concentrate REEs from the AMD into a solid precipitate.Consequently,over 99%of the REEs in AMD is concentrated in the remaining sludge.During the coagulation process,the effects of pH and NaAlO2 concentration on REE precipitation were investigated.Fuming nitric acid(HNO3)was used to digest the pre-concentrated sludge and tributyl phosphate(TBP)was used to form REE/TBP/HNO3,a non-polar complex with selected REEs,specifically,cerium(Ce),lanthanum(La)and neodymium(Nd).HNO3 concentration and organic/aqueous phase ratio were considered as the variables to improve complexation efficiency.Dynamic extraction experiments using sCO2 and REE/TBP/HNO3 solutions were then conducted at optimal conditions of 60℃and 20 MPa.The overall REE extraction efficiencies are found to increase with the atomic number of the REE.As a result,the average overall REE extraction efficiencies of 41.8%,40.1%and 58.2%for Ce,La and Nd,respectively,are obtained.The potential improvements in the overall extraction efficiency are also discussed.展开更多
Integrally skinned asymmetric gas separation membranes of polyethersulfone(PES)/polyurethane(PU) blend were prepared using supercritical CO_2(SC-CO_2) as a nonsolvent for the polymer solution. The membrane consisted o...Integrally skinned asymmetric gas separation membranes of polyethersulfone(PES)/polyurethane(PU) blend were prepared using supercritical CO_2(SC-CO_2) as a nonsolvent for the polymer solution. The membrane consisted of a dense and a porous layer, which were conjoined to separate CO_2 from CH_4. The FTIR, DSC, tensile and SEM tests were performed to study and characterize the membranes. The results revealed that an increase in SC-CO_2 temperature causes an increment in permeance and a decrease in membrane selectivity. Furthermore,by raising the pressure, both permeance and selectivity increased. The modified membrane with SC-CO_2 had much higher selectivity, about 5.5 times superior to the non-modified membrane. This higher selectivity performance compared to previous works was obtained by taking the advantages of both using partial miscible blend polymer due to the strong polar–polar interaction between PU PES and SC-CO_2 to fabricate the membrane. The response surface methodology(RSM) was applied to find the relationships between several explanatory variables and CO_2 and CH_4 permeance and CO_2/CH_4 selectivity as responses. Finally, the results were validated with the experimental data, which the model results were in good agreement with the available experimental data.展开更多
A supercritical CO2 gas turbine cycle can produce power at high efficiency and the gas turbine is compact compared with the steam turbine. Therefore, it is very advantageous power cycle for the medium temperature rang...A supercritical CO2 gas turbine cycle can produce power at high efficiency and the gas turbine is compact compared with the steam turbine. Therefore, it is very advantageous power cycle for the medium temperature range less than 650 ℃. The purpose of this paper is to show how it can be effectively applied not only to the nuclear power but also to the fossil fired power plant. A design of 300 MWe plant has been carried out, where thermal energy of flue gas leaving a CO2 heater is utilized effectively by means of economizer and a high cycle thermal efficiency of 43.4 % has been achieved. Since the temperature and the pressure difference of the CO2 heater are very high, the structural design becomes very difficult. It is revealed that this problem can be effectively solved by introducing a double expansion turbine cycle. The component designs of the CO2 heater, the economizer, supercritical CO2 turbines, compressors and the recuperators are given and it is shown that these components have good performances and compact sizes.展开更多
Oxidation of n-butanol and 2-pentanol using molecular oxygen in supercritical (SC) CO2 with and without co-solvent is investigated. The results showed that the reaction selectivity is high when the reaction is carried...Oxidation of n-butanol and 2-pentanol using molecular oxygen in supercritical (SC) CO2 with and without co-solvent is investigated. The results showed that the reaction selectivity is high when the reaction is carried out in SC CO2. It has been observed that co-solvent affects conversion and selectivity of the reaction considerably.展开更多
Microporous asymmetric polystyrene （PS） membranes were prepared by supercritical CO2-induced phase inversion. The effects of different process parameters, such as temperature, COe pressure and PS concentration in ca...Microporous asymmetric polystyrene （PS） membranes were prepared by supercritical CO2-induced phase inversion. The effects of different process parameters, such as temperature, COe pressure and PS concentration in casting solution, on the membrane morphologies, pore size distribution and especially on the porosity of the membranes were experimentally investigated. The porosity showed a tendency of increasing to a maximum and then decreasing with an increase of temperature, CO2 pressure or PS concentration. The effects of process parameters on the membrane porosity were explained based on the properties of supercritical fluids.展开更多
In the present work, we investigated the effect of Mucuna deeringiana defatted bran on seed germination of soybean （Glycine max L. Merrill）. For this, the defatted bran was obtained from different operational condit...In the present work, we investigated the effect of Mucuna deeringiana defatted bran on seed germination of soybean （Glycine max L. Merrill）. For this, the defatted bran was obtained from different operational conditions using CO2 under pressurized conditions as solvent. Oil extractions were carried out in a laboratorial scale unit at temperatures ranging from 310 to 330 K, pressure from 15 to 25 MPa and solvent flow set in 3 mL min^-1. The experiment was conducted in a germination chamber （25℃, 12：12 h light：dark photoperiod）, and the germination rate and germination speed index （GSI） were evaluated for seven days. The results showed that the oil extraction with supercritical CO2 concentrates the allelochemical L-3,4-dihydroxyphenylalanine （L-DOPA） in bran with levels from 1.86% to 4.65%. Subsequent experiments revealed that the rate of soybean seed germination was not affected by defatted bran whereas the GSI increased significantly after treatment. In brief, we concluded that the extraction process with supercritical CO2 is efficient to obtain L-DOPA of Mucuna, which influences the soybean seed germination.展开更多
The strontium ions extracted from the aqueous phase into 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide(C_2mimNTf2) with dicyclohexyl-18-crown-6(DCH18C6) was stripped effectively by supercritical CO_2(s...The strontium ions extracted from the aqueous phase into 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide(C_2mimNTf2) with dicyclohexyl-18-crown-6(DCH18C6) was stripped effectively by supercritical CO_2(sc-CO_2).Hexafluoroacetylacetone(HFAA)-acetonitrile was found to be an excellent modifier of sc-CO_2 to enhance the stripping efficiency.In the orthogonal array design(OAD),OA_(25)(5~5)matrix was employed to optimize the stripping of Sr(Ⅱ) from the DCH 18C6-C_2mimNTf_2 system.Effects of five experimental factors:temperature,pressure,concentration of HFAA,static and dynamic extraction times as well as each factor at five-levels on the stripping of Sr(Ⅱ) were optimized.The effects of these parameters were treated by the analysis of variance(ANOVA).The results showed that Sr(II) could be nearly 100%extracted from the IL phase at 308 K,30 MPa,40 min of dynamic extraction and 60 mmol·L^(-1) HFAA in acetonitrile,respectively.Finally,the stripping mechanism was studied by ESI-MS.展开更多
Supercritical CO_(2)(SC-CO_(2))fracturing stands out a promising waterless stimulation technique in the development of unconventional resources.While numerous studies have delved into the inducedfracture mechanism of ...Supercritical CO_(2)(SC-CO_(2))fracturing stands out a promising waterless stimulation technique in the development of unconventional resources.While numerous studies have delved into the inducedfracture mechanism of SC-CO_(2),the small scale of rock samples and synthetic materials used in many studies have limited a comprehensive understanding of fracture propagation in unconventional formations.In this study,cubic tight sandstone samples with dimensions of 300 mm were employed to conduct SC-CO_(2)fractu ring experiments under true-triaxial stre ss conditions.The spatial morphology and quantitative attributes of fracture induced by water and SC-CO_(2)fracturing were compared,while the impact of in-situ stress on fracture propagation was also investigated.The results indicate that the SCCO_(2)fracturing takes approximately ten times longer than water fracturing.Furthermore,under identical stress condition,the breakdown pressure(BP)for SC-CO_(2)fracturing is nearly 25%lower than that for water fracturing.A quantitative analysis of fracture morphology reveals that water fracturing typically produces relatively simple fracture pattern,with the primary fracture distribution predominantly controlled by bedding planes.In contrast,SC-CO_(2)fracturing results in a more complex fracture morphology.As the differential of horizontal principal stress increases,the BP for SC-CO_(2)fractured rock exhibits a downward trend,and the induced fracture morphology becomes more simplified.Moreover,the presence of abnormal in-situ stress leads to a further increase in the BP for SC-CO_(2)fracturing,simultaneously enhancing the development of a more conductive fracture network.These findings provide critical insights into the efficiency and behavior of SC-CO_(2)fracturing in comparison to traditional water-based fracturing,offering valuable implication for its potential applications in unconventional reservoirs.展开更多
With the increasing demand for energy,traditional oil resources are facing depletion and insufficient supply.Many countries are rapidly turning to the development of unconventional oil and gas resources.Among them,sha...With the increasing demand for energy,traditional oil resources are facing depletion and insufficient supply.Many countries are rapidly turning to the development of unconventional oil and gas resources.Among them,shale oil and gas reservoirs have become the focus of unconventional oil and gas resources exploration and development.Based on the characteristics of shale oil and gas reservoirs,supercritical CO_(2) fracturing is more conducive to improving oil recovery than other fracturing technologies.In this paper,the mechanism of fracture initiation and propagation of supercritical CO_(2) in shale is analyzed,including viscosity effect,surface tension effect,permeation diffusion effect of supercritical CO_(2),and dissolution-adsorption effect between CO_(2) and shale.The effects of natural factors,such as shale properties,bedding plane and natural fractures,and controllable factors,proppant,temperature,pressure,CO_(2) concentration and injection rate on fracture initiation and propagation are clarified.The methods of supercritical CO_(2) fracturing process,thickener and proppant optimization to improve the efficiency of supercritical CO_(2) fracturing are discussed.In addition,some new technologies of supercritical CO_(2) fracturing are introduced.The challenges and prospects in the current research are also summarized.For example,supercritical CO_(2) is prone to filtration when passing through porous media,and it is difficult to form a stable flow state.Therefore,in order to achieve stable fracturing fluid suspension and effectively support fractu res,it is urge nt to explo re new fracturing fluid additives or improve fracturing fluid formulations combined with the research of new proppants.This paper is of great significance for understanding the behavior mechanism of supercritical CO_(2) in shale and optimizing fracturing technology.展开更多
High-water-cut mature reservoirs typically serve as the“ballast”for ensuring China’s annual crude oil production of 200 million tons.Despite the use of water flooding and chemical methods,over 40%of crude oil remai...High-water-cut mature reservoirs typically serve as the“ballast”for ensuring China’s annual crude oil production of 200 million tons.Despite the use of water flooding and chemical methods,over 40%of crude oil remains unexploited.It is critical to develop efficient revolutionary technologies to further enhance oil recovery(EOR)by a large percentage in high-water-cut mature reservoirs.To address this issue,the potential of vertical remaining oil in Daqing Oilfield is first analyzed from massive monitoring data.Using molecular dynamics simulation to design optimal synthetic routine,a copolymer without flu-orine or silicon is synthesized by modifying vinyl acetate(VAc)with maleic anhydride(MA)and styrene(St),and treated as a supercritical CO_(2)(scCO_(2))thickener.The underlying EOR mechanism of the scCO_(2) thickener is thereafter clarified by high-temperature,high-pressure oil displacement experiments.The EOR effect by thickened scCO_(2) flooding in a typical high-water-cut mature reservoir is predicted,and future technological advancements of the technique are ultimately discussed.Results show that the ver-tical remaining oil enriched in weakly swept zones is a primary target for further EOR in high-water-cut mature reservoirs.The copolymer typically exhibits good solubility,strong dispersion stability,and high thickening effect in scCO_(2).Under an ambient pressure of 10 MPa and a temperature of 50℃,the disso-lution of copolymer at a mass concentration of 0.2%can effectively increase the viscosity of scCO_(2) by 39.4 times.Due to the synergistic effect between expanding vertical swept volume and inhibiting gas channel-ing,crude oil recovery can be further enhanced by 23.1%for a typical high-water-cut mature reservoir when the scCO_(2) viscosity is increased by 50 times.Our understandings demonstrate that the thickened scCO_(2) flooding technology has significant technical advantages in high-water-cut mature reservoirs,with challenges and future development directions in field-scale applications also highlighted.展开更多
Understanding the solubility of supercritical CO_(2)and its mixtures with other fluids at various temperatures and pressures conditions is critical for their applications,such as extraction processes,material design,a...Understanding the solubility of supercritical CO_(2)and its mixtures with other fluids at various temperatures and pressures conditions is critical for their applications,such as extraction processes,material design,and carbon capture.In the present study,the solubility parameters of supercritical CO_(2),H_(2)O,and their mixtures were calculated by molecular dynamics simulations.The results show that the solubility parameters decrease with increasing temperature and increase with increasing pressure and are linearly proportional to the density.Furthermore,the intermolecular interactions,including the hydrogen bonds,significantly affect the solubility parameter of the CO_(2)-H_(2)O system.展开更多
The study of the effects of supercritical CO_(2)(ScCO_(2))under high temperature and high pressure on the mechanical properties and fracturing potential of shale holds significant implications for advancing our unders...The study of the effects of supercritical CO_(2)(ScCO_(2))under high temperature and high pressure on the mechanical properties and fracturing potential of shale holds significant implications for advancing our understanding of enhanced shale gas extraction and reservoir exploration and development.This study examines the influence of three fluids,i.e.ScCO_(2),deionized water(DW),and ScCO_(2)tDW,on the mechanical properties and fracturability of shale at immersion pressures of 15 MPa and 45 MPa,with a constant temperature of 100C.The key findings are as follows:(1)Uniaxial compressive strength(UCS)of shale decreased by 10.72%,11.95%,and 23.67%at 15 MPa,and by 42.40%,46.84%,and 51.65%at 45 MPa after immersion in ScCO_(2),DW,and ScCO_(2)tDW,respectively,with the most pronounced effect observed in ScCO_(2)tDW;(2)Microstructural analysis revealed that while ScCO_(2)and DW do not significantly alter the microstructure,immersion in ScCO_(2)tDW results in a more complex surface morphology;(3)Acoustic emission(AE)analysis indicates a reduction in stress for crack damage,with a decreased fractal dimension of AE signals in different fluids.AE energy is primarily generated during the unstable crack propagation stage;(4)A quantitative method employing a multi-factor approach combined with the brittleness index(BI)effectively characterizes shale fracturability.Evaluation results show that ScCO_(2)tDW has a more significant effect on shale fracturability,with fracturability indices of 0.833%and 1.180%following soaking at 15 MPa and 45 MPa,respectively.Higher immersion pressure correlates positively with increased shale fracturability.展开更多
Although supercritical carbon dioxide(SC-CO_(2))fracturing shows tremendous potential for maximizing injection efficiency and enhancing storage volumes,few investigations have been reported on the SC-CO_(2) fracturing...Although supercritical carbon dioxide(SC-CO_(2))fracturing shows tremendous potential for maximizing injection efficiency and enhancing storage volumes,few investigations have been reported on the SC-CO_(2) fracturing characteristics of tight basalts and the reactions between fractured basalt and SC-CO_(2).In this study,hydraulic fracturing experiments were conducted on cylindrical basalt specimens using water and SC-CO_(2) as fracturing fluids.Geometric parameters were proposed to characterize the fracture morphologies based on the three-dimensional(3D)reconstructions of fracture networks.The rock slices with induced fractures after SC-CO_(2) fracturing were then processed for fluid(deionized water/SC-CO_(2))-basalt reaction tests.The experimental results demonstrate that SC-CO_(2) fracturing can induce complex and tortuous fractures with spatially dispersed morphologies.Other fracturing behaviors accompanying the acoustic emission(AE)signals and pump pressure changes show that the AE activity responds almost simultaneously to variation in the pump pressure.The fractured basalt blocks exposed to both SC-CO_(2) and water exhibit rough and uneven surfaces,along with decreased intensities in the element peaks,indicating that solubility trapping predominantly occurs during the early injection stage.The above findings provide a laboratory research basis for understanding the fracturing and sequestration issues related to effective CO_(2) utilization.展开更多
Alkaline water electrolysis poses significant potential for large-sc ale indus trial hydrogen generation,but is impeded by the absence of an efficient electrocatalyst capable of operating at high current densities whi...Alkaline water electrolysis poses significant potential for large-sc ale indus trial hydrogen generation,but is impeded by the absence of an efficient electrocatalyst capable of operating at high current densities while maintaining with minimal overpotential.Herein,we construct a mechanically stable and highly active RuSe_(2)/MXene heterojunction electrocatalyst.A typical SC-Ti_(3)C_(2)T_(x)MXene substrate was successfully prepared by supercritical CO_(2)(SC-CO_(2))etching,combined by subsequent DMSO intercalation treatment.Further,the RuSe_(2)nanoparticles were uniformly deposited on the surface of SC-Ti_(3)C_(2)T_(x).Theoretical calculations and experimental results demonstrate that fluorine-rich MXene exhibits stable binding with the active 1T phase RuSe_(2).The as-prepared representative RuSe_(2)@SC-Ti_(3)C_(2)T_(x)-3 heterostructure showed exceptional alkaline hydrogen evolution performance,demonstrating an overpotential of 15 mV at 10 mA cm^(-2)and a Tafel slope of 21.84 mV dec^(-1),which presents excellent HER performance and stability at high-current-density conditions.Moreover,the overpotential under the current density of 500 mA cm^(-2)is merely 182 mV,and the HER efficiency remains unaffected even after 5000 cycles and 120 h of continuous testing.展开更多
The corrosion behavior of 304LN austenitic stainless steel in supercritical CO_(2) at 650℃ was investigated.The results show that 304LN follows Wagner’s law kinetics,forming a protective oxide flm consisting of SiO_...The corrosion behavior of 304LN austenitic stainless steel in supercritical CO_(2) at 650℃ was investigated.The results show that 304LN follows Wagner’s law kinetics,forming a protective oxide flm consisting of SiO_(2),(Cr,Mn)3O_(4),and Cr2O_(3) from the inner to outer layers.A shallow carburization depth of approximately 130 nm indicates excellent resistance to carburization.The roles of key elements in 18/8 austenitic stainless steel represented by 304LN,such as Cr,Ni,and Si,were analyzed,highlighting their contributions to anti-carburization performance and corrosion resistance under harsh conditions.展开更多
Deep shale reservoirs are often associated with extreme geological conditions,including high tem-peratures,substantial horizontal stress differences,elevated closure stresses,and high breakdown pressures.These factors...Deep shale reservoirs are often associated with extreme geological conditions,including high tem-peratures,substantial horizontal stress differences,elevated closure stresses,and high breakdown pressures.These factors pose significant challenges to conventional hydraulic fracturing with water-based fluids,which may induce formation damage and fail to generate complex fracture networks.Supercritical carbon dioxide(SC-CO_(2)),with its low viscosity,high diffusivity,low surface tension,and minimal water sensitivity,has attracted growing attention as an alternative fracturing fluid for deep shale stimulation.This study presents a series of true triaxial large-scale physical experiments using shale samples from the Longmaxi Formation in the southern Sichuan Basin to investigate fracture initiation and propagation behavior under different fracturing fluids.The results show that,under identical experimental conditions,SC-CO_(2)fracturing results in a significantly lower breakdown pressure compared to slick water and promotes the formation of more complex fracture geometries.These advantages are attributed to both the favorable flow characteristics of SC-CO_(2)and its potential chemical interactions with shale minerals.The findings not only confirm the effectiveness of SC-CO_(2)as a fracturing fluid in deep shale environments but also provide new insights into its fracture propagation mechanisms.展开更多
基金funded by National Natural Science Foundation of China(42373033,Yicheng Sun)Fundamental Research Funds for the Central Universities(B240201111,Yicheng Sun)。
文摘Supercritical fluids play a crucial role in material transport within Earth's deep interior.Investigating the pressure-dependent atomic structures and transport properties of such fluids is essential for understanding their petrological,chemical,and geophysical behaviors.In this study,we employed first-principles molecular dynamics simulations to explore the structures,self-diffusion coefficients(D),and viscosities(η)of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids under conditions of 2000 K and 3-10 GPa,with water contents of 30 wt% and 50 wt%.Our calculations indicate that at a water content of 30 wt%,Q^(2) and Q^(3) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species(n represents the number of bridging oxygens connected to Si/Al)show minimal changes.At a water content of 50 wt%,Q^(2) and Q^(0) exhibit a certain degree of positive and negative pressure dependence,respectively,while other Q^(n) species show minimal changes.At both water contents,Si-O-H and molecular water in the system exhibit negative pressure dependence,suggesting that the migration of supercritical fluids from deep to shallow regions is accompanied by the release of water.The self-diffusion coefficients in the supercritical NaAlSi_(3)O_(8)-H_(2)O fluid follow the order D_(Na)≈D_(H)>D_(O)>D_(Al)≈D_(Si),with an overall weak negative pressure dependence.By comparing the viscosities of anhydrous and hydrous silicate melts from previous studies,we found that the addition of water caused a transition from negative to positive pressure dependence of viscosity,corresponding to a structural change from polymerization to depolymerization.Additionally,we calculated the fluid mobility Δp/η of supercritical NaAlSi_(3)O_(8)-H_(2)O fluids and found that their mobility is several orders of magnitude higher than that of basalt melt and is also significantly greater than that of carbonate melt.As supercritical fluids ascend from deeper to shallower regions,their mobility is further enhanced,significantly contributing to the transport of elements from subducting slabs to the overlying mantle wedge.
基金the Foundation Research Project of Jiangsu province(Youth Fund Project)of China(No.BK20150179)the Fundamental Research Funds for the Central Universities(No.2015XKZD07)of China,and the Postdoctoral Science Foundation of Jiangsu Province.
文摘The use of supercritical CO2 for shale gas extraction is a promising new technology.This paper explores current research into this process,looking at analysis of the mechanism of CH4 displacement in nanoporous shale,the positive and negative effects accompanying its use for sequestration as well as organic extraction,the migration of elements and the swelling process,and the macro and micro control mechanisms involved in permeability enhancement in reservoirs.Fruitful directions for future research are also considered through comparison with hydraulic fracturing.The research findings indicate that ScCO2 fluid replacement can be used to increase gas production and seal up greenhouse gases as an effective,clean and safe method of shale gas exploitation.It is particularly effective for promoting the desorption of CH4 in shale reservoirs that have developed fine neck-wide body pores,and the subtle structural changes effected by ScCO2 fluid in sensitive minerals in reservoirs with a high brittle mineral content also have a positive effect on permeability and storage capacity.The adsorption process has been characterized as consisting of three stages:short-term shrinkage,slow swelling,and stability;an expansion equation has been proposed for CO2/CH4 that incorporates competitive adsorption,collision desorption,and impingement re-adsorption.ScCO2 fracturing has been found to be more effective than hydraulic fracturing for dense reservoirs and more effective at linking up pore-micro-fissure-fracture systems.
基金Project supported by Ben Franklin Technology Partners(BFTP)and the Pennsylvania Infrastructure Technology Alliance(PITA)(1366.36)。
文摘Rare earth elements(REEs)are valuable raw materials which are in great demand in modern high technology industries.Developing methods to produce/recover REEs from waste is significant to the national security of any developed country.This study was focused on investigating the use of supercritical CO2(sCO2)to extract REEs from anthracite acid mine drainage(AMD).Four different mine drainage water source locations at Blaschak Coal Corp.in Pennsylvania,USA were selected for sample collection.An extraction process was developed and demonstrated for two of those water sources containing the highest concentration of REEs.A method involving metal ion coagulation,their dissolution from the sludge into a concentrated aqueous HNO3 solution,complexation with organic ligands and sCO2 extraction was developed to recover REEs from AMD.Specifically,sodium aluminate(NaAlO2)was used as the coagulant to concentrate REEs from the AMD into a solid precipitate.Consequently,over 99%of the REEs in AMD is concentrated in the remaining sludge.During the coagulation process,the effects of pH and NaAlO2 concentration on REE precipitation were investigated.Fuming nitric acid(HNO3)was used to digest the pre-concentrated sludge and tributyl phosphate(TBP)was used to form REE/TBP/HNO3,a non-polar complex with selected REEs,specifically,cerium(Ce),lanthanum(La)and neodymium(Nd).HNO3 concentration and organic/aqueous phase ratio were considered as the variables to improve complexation efficiency.Dynamic extraction experiments using sCO2 and REE/TBP/HNO3 solutions were then conducted at optimal conditions of 60℃and 20 MPa.The overall REE extraction efficiencies are found to increase with the atomic number of the REE.As a result,the average overall REE extraction efficiencies of 41.8%,40.1%and 58.2%for Ce,La and Nd,respectively,are obtained.The potential improvements in the overall extraction efficiency are also discussed.
文摘Integrally skinned asymmetric gas separation membranes of polyethersulfone(PES)/polyurethane(PU) blend were prepared using supercritical CO_2(SC-CO_2) as a nonsolvent for the polymer solution. The membrane consisted of a dense and a porous layer, which were conjoined to separate CO_2 from CH_4. The FTIR, DSC, tensile and SEM tests were performed to study and characterize the membranes. The results revealed that an increase in SC-CO_2 temperature causes an increment in permeance and a decrease in membrane selectivity. Furthermore,by raising the pressure, both permeance and selectivity increased. The modified membrane with SC-CO_2 had much higher selectivity, about 5.5 times superior to the non-modified membrane. This higher selectivity performance compared to previous works was obtained by taking the advantages of both using partial miscible blend polymer due to the strong polar–polar interaction between PU PES and SC-CO_2 to fabricate the membrane. The response surface methodology(RSM) was applied to find the relationships between several explanatory variables and CO_2 and CH_4 permeance and CO_2/CH_4 selectivity as responses. Finally, the results were validated with the experimental data, which the model results were in good agreement with the available experimental data.
文摘A supercritical CO2 gas turbine cycle can produce power at high efficiency and the gas turbine is compact compared with the steam turbine. Therefore, it is very advantageous power cycle for the medium temperature range less than 650 ℃. The purpose of this paper is to show how it can be effectively applied not only to the nuclear power but also to the fossil fired power plant. A design of 300 MWe plant has been carried out, where thermal energy of flue gas leaving a CO2 heater is utilized effectively by means of economizer and a high cycle thermal efficiency of 43.4 % has been achieved. Since the temperature and the pressure difference of the CO2 heater are very high, the structural design becomes very difficult. It is revealed that this problem can be effectively solved by introducing a double expansion turbine cycle. The component designs of the CO2 heater, the economizer, supercritical CO2 turbines, compressors and the recuperators are given and it is shown that these components have good performances and compact sizes.
基金supported by National Natural Science Foundation of China(20073056).
文摘Oxidation of n-butanol and 2-pentanol using molecular oxygen in supercritical (SC) CO2 with and without co-solvent is investigated. The results showed that the reaction selectivity is high when the reaction is carried out in SC CO2. It has been observed that co-solvent affects conversion and selectivity of the reaction considerably.
文摘Microporous asymmetric polystyrene （PS） membranes were prepared by supercritical CO2-induced phase inversion. The effects of different process parameters, such as temperature, COe pressure and PS concentration in casting solution, on the membrane morphologies, pore size distribution and especially on the porosity of the membranes were experimentally investigated. The porosity showed a tendency of increasing to a maximum and then decreasing with an increase of temperature, CO2 pressure or PS concentration. The effects of process parameters on the membrane porosity were explained based on the properties of supercritical fluids.
文摘In the present work, we investigated the effect of Mucuna deeringiana defatted bran on seed germination of soybean （Glycine max L. Merrill）. For this, the defatted bran was obtained from different operational conditions using CO2 under pressurized conditions as solvent. Oil extractions were carried out in a laboratorial scale unit at temperatures ranging from 310 to 330 K, pressure from 15 to 25 MPa and solvent flow set in 3 mL min^-1. The experiment was conducted in a germination chamber （25℃, 12：12 h light：dark photoperiod）, and the germination rate and germination speed index （GSI） were evaluated for seven days. The results showed that the oil extraction with supercritical CO2 concentrates the allelochemical L-3,4-dihydroxyphenylalanine （L-DOPA） in bran with levels from 1.86% to 4.65%. Subsequent experiments revealed that the rate of soybean seed germination was not affected by defatted bran whereas the GSI increased significantly after treatment. In brief, we concluded that the extraction process with supercritical CO2 is efficient to obtain L-DOPA of Mucuna, which influences the soybean seed germination.
基金Supported by the National Natural Science Foundation of China(91226112)
文摘The strontium ions extracted from the aqueous phase into 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide(C_2mimNTf2) with dicyclohexyl-18-crown-6(DCH18C6) was stripped effectively by supercritical CO_2(sc-CO_2).Hexafluoroacetylacetone(HFAA)-acetonitrile was found to be an excellent modifier of sc-CO_2 to enhance the stripping efficiency.In the orthogonal array design(OAD),OA_(25)(5~5)matrix was employed to optimize the stripping of Sr(Ⅱ) from the DCH 18C6-C_2mimNTf_2 system.Effects of five experimental factors:temperature,pressure,concentration of HFAA,static and dynamic extraction times as well as each factor at five-levels on the stripping of Sr(Ⅱ) were optimized.The effects of these parameters were treated by the analysis of variance(ANOVA).The results showed that Sr(II) could be nearly 100%extracted from the IL phase at 308 K,30 MPa,40 min of dynamic extraction and 60 mmol·L^(-1) HFAA in acetonitrile,respectively.Finally,the stripping mechanism was studied by ESI-MS.
基金funded by the National Natural Scientific Foundation of China(Nos.52304008,52404038,52474043)the China Postdoctoral Science Foundation(No.2023MD734223)+1 种基金the Key Laboratory of Well Stability and Fluid&Rock Mechanics in Oil and Gas Reservoir of Shaanxi Province(No.23JS047)the Youth Talent Lifting Program of Xi'an Science and Technology Association(No.959202413078)。
文摘Supercritical CO_(2)(SC-CO_(2))fracturing stands out a promising waterless stimulation technique in the development of unconventional resources.While numerous studies have delved into the inducedfracture mechanism of SC-CO_(2),the small scale of rock samples and synthetic materials used in many studies have limited a comprehensive understanding of fracture propagation in unconventional formations.In this study,cubic tight sandstone samples with dimensions of 300 mm were employed to conduct SC-CO_(2)fractu ring experiments under true-triaxial stre ss conditions.The spatial morphology and quantitative attributes of fracture induced by water and SC-CO_(2)fracturing were compared,while the impact of in-situ stress on fracture propagation was also investigated.The results indicate that the SCCO_(2)fracturing takes approximately ten times longer than water fracturing.Furthermore,under identical stress condition,the breakdown pressure(BP)for SC-CO_(2)fracturing is nearly 25%lower than that for water fracturing.A quantitative analysis of fracture morphology reveals that water fracturing typically produces relatively simple fracture pattern,with the primary fracture distribution predominantly controlled by bedding planes.In contrast,SC-CO_(2)fracturing results in a more complex fracture morphology.As the differential of horizontal principal stress increases,the BP for SC-CO_(2)fractured rock exhibits a downward trend,and the induced fracture morphology becomes more simplified.Moreover,the presence of abnormal in-situ stress leads to a further increase in the BP for SC-CO_(2)fracturing,simultaneously enhancing the development of a more conductive fracture network.These findings provide critical insights into the efficiency and behavior of SC-CO_(2)fracturing in comparison to traditional water-based fracturing,offering valuable implication for its potential applications in unconventional reservoirs.
文摘With the increasing demand for energy,traditional oil resources are facing depletion and insufficient supply.Many countries are rapidly turning to the development of unconventional oil and gas resources.Among them,shale oil and gas reservoirs have become the focus of unconventional oil and gas resources exploration and development.Based on the characteristics of shale oil and gas reservoirs,supercritical CO_(2) fracturing is more conducive to improving oil recovery than other fracturing technologies.In this paper,the mechanism of fracture initiation and propagation of supercritical CO_(2) in shale is analyzed,including viscosity effect,surface tension effect,permeation diffusion effect of supercritical CO_(2),and dissolution-adsorption effect between CO_(2) and shale.The effects of natural factors,such as shale properties,bedding plane and natural fractures,and controllable factors,proppant,temperature,pressure,CO_(2) concentration and injection rate on fracture initiation and propagation are clarified.The methods of supercritical CO_(2) fracturing process,thickener and proppant optimization to improve the efficiency of supercritical CO_(2) fracturing are discussed.In addition,some new technologies of supercritical CO_(2) fracturing are introduced.The challenges and prospects in the current research are also summarized.For example,supercritical CO_(2) is prone to filtration when passing through porous media,and it is difficult to form a stable flow state.Therefore,in order to achieve stable fracturing fluid suspension and effectively support fractu res,it is urge nt to explo re new fracturing fluid additives or improve fracturing fluid formulations combined with the research of new proppants.This paper is of great significance for understanding the behavior mechanism of supercritical CO_(2) in shale and optimizing fracturing technology.
基金the National Natural Science Foundation of China(U22B6005,52174043,52474035)the Beijing Natural Science Foundation(3242019)the China National Petroleum Corporation(CNPC)Innovation Foundation(2022DQ02-0208 and 2024DQ02-0114).
文摘High-water-cut mature reservoirs typically serve as the“ballast”for ensuring China’s annual crude oil production of 200 million tons.Despite the use of water flooding and chemical methods,over 40%of crude oil remains unexploited.It is critical to develop efficient revolutionary technologies to further enhance oil recovery(EOR)by a large percentage in high-water-cut mature reservoirs.To address this issue,the potential of vertical remaining oil in Daqing Oilfield is first analyzed from massive monitoring data.Using molecular dynamics simulation to design optimal synthetic routine,a copolymer without flu-orine or silicon is synthesized by modifying vinyl acetate(VAc)with maleic anhydride(MA)and styrene(St),and treated as a supercritical CO_(2)(scCO_(2))thickener.The underlying EOR mechanism of the scCO_(2) thickener is thereafter clarified by high-temperature,high-pressure oil displacement experiments.The EOR effect by thickened scCO_(2) flooding in a typical high-water-cut mature reservoir is predicted,and future technological advancements of the technique are ultimately discussed.Results show that the ver-tical remaining oil enriched in weakly swept zones is a primary target for further EOR in high-water-cut mature reservoirs.The copolymer typically exhibits good solubility,strong dispersion stability,and high thickening effect in scCO_(2).Under an ambient pressure of 10 MPa and a temperature of 50℃,the disso-lution of copolymer at a mass concentration of 0.2%can effectively increase the viscosity of scCO_(2) by 39.4 times.Due to the synergistic effect between expanding vertical swept volume and inhibiting gas channel-ing,crude oil recovery can be further enhanced by 23.1%for a typical high-water-cut mature reservoir when the scCO_(2) viscosity is increased by 50 times.Our understandings demonstrate that the thickened scCO_(2) flooding technology has significant technical advantages in high-water-cut mature reservoirs,with challenges and future development directions in field-scale applications also highlighted.
基金supported by the National Key Research and Development Program of China(Grant No.2019YFE0117200)the National Natural Science Foundation of China(Grant No.41977304).
文摘Understanding the solubility of supercritical CO_(2)and its mixtures with other fluids at various temperatures and pressures conditions is critical for their applications,such as extraction processes,material design,and carbon capture.In the present study,the solubility parameters of supercritical CO_(2),H_(2)O,and their mixtures were calculated by molecular dynamics simulations.The results show that the solubility parameters decrease with increasing temperature and increase with increasing pressure and are linearly proportional to the density.Furthermore,the intermolecular interactions,including the hydrogen bonds,significantly affect the solubility parameter of the CO_(2)-H_(2)O system.
基金financial support from the Science and Technology Innovation Program of Hunan Province(Grant No.2023RC1021)the National Natural Science Foundation of China(Grant No.52231012)+1 种基金the Natural Science Foundation of Hainan Province(Grant No.424QN213)the Scientific Research Foundation of Hainan University.
文摘The study of the effects of supercritical CO_(2)(ScCO_(2))under high temperature and high pressure on the mechanical properties and fracturing potential of shale holds significant implications for advancing our understanding of enhanced shale gas extraction and reservoir exploration and development.This study examines the influence of three fluids,i.e.ScCO_(2),deionized water(DW),and ScCO_(2)tDW,on the mechanical properties and fracturability of shale at immersion pressures of 15 MPa and 45 MPa,with a constant temperature of 100C.The key findings are as follows:(1)Uniaxial compressive strength(UCS)of shale decreased by 10.72%,11.95%,and 23.67%at 15 MPa,and by 42.40%,46.84%,and 51.65%at 45 MPa after immersion in ScCO_(2),DW,and ScCO_(2)tDW,respectively,with the most pronounced effect observed in ScCO_(2)tDW;(2)Microstructural analysis revealed that while ScCO_(2)and DW do not significantly alter the microstructure,immersion in ScCO_(2)tDW results in a more complex surface morphology;(3)Acoustic emission(AE)analysis indicates a reduction in stress for crack damage,with a decreased fractal dimension of AE signals in different fluids.AE energy is primarily generated during the unstable crack propagation stage;(4)A quantitative method employing a multi-factor approach combined with the brittleness index(BI)effectively characterizes shale fracturability.Evaluation results show that ScCO_(2)tDW has a more significant effect on shale fracturability,with fracturability indices of 0.833%and 1.180%following soaking at 15 MPa and 45 MPa,respectively.Higher immersion pressure correlates positively with increased shale fracturability.
基金supported by the National Key Research and Development Project(Grant No.2023YFE0110900)the National Natural Science Foundation of China(Grant No.42320104003)the Shanghai Pujiang Programme(Grant No.23PJD105).
文摘Although supercritical carbon dioxide(SC-CO_(2))fracturing shows tremendous potential for maximizing injection efficiency and enhancing storage volumes,few investigations have been reported on the SC-CO_(2) fracturing characteristics of tight basalts and the reactions between fractured basalt and SC-CO_(2).In this study,hydraulic fracturing experiments were conducted on cylindrical basalt specimens using water and SC-CO_(2) as fracturing fluids.Geometric parameters were proposed to characterize the fracture morphologies based on the three-dimensional(3D)reconstructions of fracture networks.The rock slices with induced fractures after SC-CO_(2) fracturing were then processed for fluid(deionized water/SC-CO_(2))-basalt reaction tests.The experimental results demonstrate that SC-CO_(2) fracturing can induce complex and tortuous fractures with spatially dispersed morphologies.Other fracturing behaviors accompanying the acoustic emission(AE)signals and pump pressure changes show that the AE activity responds almost simultaneously to variation in the pump pressure.The fractured basalt blocks exposed to both SC-CO_(2) and water exhibit rough and uneven surfaces,along with decreased intensities in the element peaks,indicating that solubility trapping predominantly occurs during the early injection stage.The above findings provide a laboratory research basis for understanding the fracturing and sequestration issues related to effective CO_(2) utilization.
基金financially supported by the China Postdoctoral Science Foundation(Nos.2021TQ0300 and 2021M702946)Henan Science and Technology Department(Nos.242102231034 and 242301420040)+1 种基金the joint project from Henan Province,the China-National Natural Science Foundation(No.U2004208)the Central Plains Science and Technology Innovation Leading Talent Project(No.234200510008)
文摘Alkaline water electrolysis poses significant potential for large-sc ale indus trial hydrogen generation,but is impeded by the absence of an efficient electrocatalyst capable of operating at high current densities while maintaining with minimal overpotential.Herein,we construct a mechanically stable and highly active RuSe_(2)/MXene heterojunction electrocatalyst.A typical SC-Ti_(3)C_(2)T_(x)MXene substrate was successfully prepared by supercritical CO_(2)(SC-CO_(2))etching,combined by subsequent DMSO intercalation treatment.Further,the RuSe_(2)nanoparticles were uniformly deposited on the surface of SC-Ti_(3)C_(2)T_(x).Theoretical calculations and experimental results demonstrate that fluorine-rich MXene exhibits stable binding with the active 1T phase RuSe_(2).The as-prepared representative RuSe_(2)@SC-Ti_(3)C_(2)T_(x)-3 heterostructure showed exceptional alkaline hydrogen evolution performance,demonstrating an overpotential of 15 mV at 10 mA cm^(-2)and a Tafel slope of 21.84 mV dec^(-1),which presents excellent HER performance and stability at high-current-density conditions.Moreover,the overpotential under the current density of 500 mA cm^(-2)is merely 182 mV,and the HER efficiency remains unaffected even after 5000 cycles and 120 h of continuous testing.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDA0410000)the CAS Project for Young Scientists in Basic Research(No.YSBR-043)+1 种基金the CNNC Science Fund for Talented Young Scholars,the National Funding Program for Postdoctoral Researchers(GZC20232747)the Youth Innovation Promotion Association CAS(2022187).
文摘The corrosion behavior of 304LN austenitic stainless steel in supercritical CO_(2) at 650℃ was investigated.The results show that 304LN follows Wagner’s law kinetics,forming a protective oxide flm consisting of SiO_(2),(Cr,Mn)3O_(4),and Cr2O_(3) from the inner to outer layers.A shallow carburization depth of approximately 130 nm indicates excellent resistance to carburization.The roles of key elements in 18/8 austenitic stainless steel represented by 304LN,such as Cr,Ni,and Si,were analyzed,highlighting their contributions to anti-carburization performance and corrosion resistance under harsh conditions.
文摘Deep shale reservoirs are often associated with extreme geological conditions,including high tem-peratures,substantial horizontal stress differences,elevated closure stresses,and high breakdown pressures.These factors pose significant challenges to conventional hydraulic fracturing with water-based fluids,which may induce formation damage and fail to generate complex fracture networks.Supercritical carbon dioxide(SC-CO_(2)),with its low viscosity,high diffusivity,low surface tension,and minimal water sensitivity,has attracted growing attention as an alternative fracturing fluid for deep shale stimulation.This study presents a series of true triaxial large-scale physical experiments using shale samples from the Longmaxi Formation in the southern Sichuan Basin to investigate fracture initiation and propagation behavior under different fracturing fluids.The results show that,under identical experimental conditions,SC-CO_(2)fracturing results in a significantly lower breakdown pressure compared to slick water and promotes the formation of more complex fracture geometries.These advantages are attributed to both the favorable flow characteristics of SC-CO_(2)and its potential chemical interactions with shale minerals.The findings not only confirm the effectiveness of SC-CO_(2)as a fracturing fluid in deep shale environments but also provide new insights into its fracture propagation mechanisms.
