In response to the problems of unclear distribution of deep-water pre-salt carbonate reservoirs and formation conditions of large oil fields in the Santos passive continental margin basin,based on comprehensive utiliz...In response to the problems of unclear distribution of deep-water pre-salt carbonate reservoirs and formation conditions of large oil fields in the Santos passive continental margin basin,based on comprehensive utilization of geological,seismic,and core data,and reconstruction of Early Cretaceous prototype basin and lithofacies paleogeography,it is proposed for the first time that the construction of pre-salt carbonate build-ups was controlled by two types of isolated platforms:inter-depression fault-uplift and intra-depression fault-high.The inter-depression fault-uplift isolated platforms are distributed on the present-day pre-salt uplifted zones between depressions,and are built on half-and fault-horst blocks that were inherited and developed in the early intra-continental and inter-continental rift stages.The late intra-continental rift coquinas of the ITP Formation and the early inter-continental rift microbial limestones of the BVE Formation are continuously constructed;intra-depression fault-high isolated platforms are distributed in the current pre-salt depression zones,built on the uplifted zones formed by volcanic rock build-ups in the early prototype stage of intra-continental rifts,and only the BVE microbial limestones are developed.Both types of limestones formed into mound-shoal bodies,that have the characteristics of large reservoir thickness and good physical properties.Based on the dissection of large pre-salt oil fields discovered in the Santos Basin,it has been found that both types of platforms could form large-scale combined structural-stratigraphic traps,surrounded by high-quality lacustrine and lagoon source rocks at the periphery,and efficiently sealed by thick high-quality evaporite rocks above,forming the optimal combination of source,reservoir and cap in the form of“lower generation,middle storage,and upper cap”,with a high degree of oil and gas enrichment.It has been found that the large oil fields are all bottom water massive oil fields with a unified pressure system,and they are all filled to the spill-point.The future exploration is recommended to focus on the inter-depression fault-uplift isolated platforms in the western uplift zone and the southern section of eastern uplift zones,as well as intra-depression fault-high isolated platforms in the central depression zone.The result not only provides an important basis for the advanced selection of potential play fairways,bidding of new blocks,and deployment of awarded exploration blocks in the Santos Basin,but also provides a reference for the global selection of deep-water exploration blocks in passive continental margin basins.展开更多
Ethylene carbonate(EC)is widely used in lithium-ion batteries due to its optimal overall performance with satisfactory conductivity,relatively stable solid electrolyte interphase(SEI),and wide electrochemical window.E...Ethylene carbonate(EC)is widely used in lithium-ion batteries due to its optimal overall performance with satisfactory conductivity,relatively stable solid electrolyte interphase(SEI),and wide electrochemical window.EC is also the most widely used electrolyte solvent in sodium ion batteries.However,compared to lithium metal,sodium metal(Na)shows higher activity and reacts violently with EC-based electrolyte(NaPF_(6)as solute),which leads to the failure of sodium metal batteries(SMBs).Herein,we reveal the electrochemical instability mechanism of EC on sodium metal battery,and find that the com-bination of EC and NaPF_(6) is electrically reduced in sodium metal anode during charging,resulting in the reduction of the first coulombic efficiency,and the continuous consumption of electrolyte leads to the cell failure.To address the above issues,an additive modified linear carbonate-based electrolyte is provided as a substitute for EC based electrolytes.Specifically,ethyl methyl carbonate(EMC)and dimethyl carbon-ate(DMC)as solvents and fluoroethylene carbonate(FEC)as SEI-forming additive have been identified as the optimal solvent for NaFP_(6)based electrolyte and used in Na_(4)Fe_(3)(PO_(4))_(2)(P_(2)O_(7))/Na batteries.The batter-ies exhibit excellent capacity retention rate of about 80%over 1000 cycles at a cut-off voltage of 4.3 V.展开更多
Enzyme-induced carbonate precipitation(EICP)is an emanating,eco-friendly and potentially sound technique that has presented promise in various geotechnical applications.However,the durability and microscopic character...Enzyme-induced carbonate precipitation(EICP)is an emanating,eco-friendly and potentially sound technique that has presented promise in various geotechnical applications.However,the durability and microscopic characteristics of EICP-treated specimens against the impact of drying-wetting(D-W)cycles is under-explored yet.This study investigates the evolution of mechanical behavior and pore charac-teristics of EICP-treated sea sand subjected to D-W cycles.The uniaxial compressive strength(UCS)tests,synchrotron radiation micro-computed tomography(micro-CT),and three-dimensional(3D)recon-struction of CT images were performed to study the multiscale evolution characteristics of EICP-reinforced sea sand under the effect of D-W cycles.The potential correlations between microstructure characteristics and macro-mechanical property deterioration were investigated using gray relational analysis(GRA).Results showed that the UCS of EICP-treated specimens decreases by 63.7% after 15 D-W cycles.The proportion of mesopores gradually decreases whereas the proportion of macropores in-creases due to the exfoliated calcium carbonate with increasing number of D-W cycles.The micro-structure in EICP-reinforced sea sand was gradually disintegrated,resulting in increasing pore size and development of pore shape from ellipsoidal to columnar and branched.The gray relational degree suggested that the weight loss rate and UCS deterioration were attributed to the development of branched pores with a size of 100-1000 m m under the action of D-W cycles.Overall,the results in this study provide a useful guidancee for the long-term stability and evolution characteristics of EICP-reinforced sea sand under D-W weathering conditions.展开更多
To gain insight into the flow mechanisms and stress sensitivity for fractured-vuggy reservoirs,several core models with different structural characteristics were designed and fabricated to investigate the impact of ef...To gain insight into the flow mechanisms and stress sensitivity for fractured-vuggy reservoirs,several core models with different structural characteristics were designed and fabricated to investigate the impact of effective stress on permeability for carbonate fractured-vuggy rocks(CFVR).It shows that the permeability performance curves under different pore and confining pressures(i.e.altered stress conditions)for the fractured core models and the vuggy core models have similar change patterns.The ranges of permeability variation are significantly wider at high pore pressures,indicating that permeability reduction is the most significant during the early stage of development for fractured-vuggy reservoirs.Since each obtained effective stress coefficient for permeability(ESCP)varies with the changes in confining pressure and pore pressure,the effective stresses for permeability of four representative CFVR show obvious nonlinear characteristics,and the variation ranges of ESCP are all between 0 and 1.Meanwhile,a comprehensive ESCP mathematical model considering triple media,including matrix pores,fractures,and dissolved vugs,was proposed.It is proved theoretically that the ESCP of CFVR generally varies between 0 and 1.Additionally,the regression results showed that the power model ranked highest among the four empirical models mainly applied in stress sensitivity characterization,followed by the logarithmic model,exponential model,and binomial model.The concept of“permeability decline rate”was introduced to better evaluate the stress sensitivity performance for CFVR,in which the one-fracture rock is the strongest,followed by the fracture-vug rock and two-horizontalfracture rock;the through-hole rock is the weakest.In general,this study provides a theoretical basis to guide the design of development and adjustment programs for carbonate fractured-vuggy reservoirs.展开更多
The deterioration of unstable rock mass raised interest in evaluating rock mass quality.However,the traditional evaluation method for the geological strength index(GSI)primarily emphasizes the rock structure and chara...The deterioration of unstable rock mass raised interest in evaluating rock mass quality.However,the traditional evaluation method for the geological strength index(GSI)primarily emphasizes the rock structure and characteristics of discontinuities.It ignores the influence of mineral composition and shows a deficiency in assessing the integrity coefficient.In this context,hyperspectral imaging and digital panoramic borehole camera technologies are applied to analyze the mineral content and integrity of rock mass.Based on the carbonate mineral content and fissure area ratio,the strength reduction factor and integrity coefficient are calculated to improve the GSI evaluation method.According to the results of mineral classification and fissure identification,the strength reduction factor and integrity coefficient increase with the depth of rock mass.The rock mass GSI calculated by the improved method is mainly concentrated between 40 and 60,which is close to the calculation results of the traditional method.The GSI error rates obtained by the two methods are mostly less than 10%,indicating the rationality of the hyperspectral-digital borehole image coupled evaluation method.Moreover,the sensitivity of the fissure area ratio(Sr)to GSI is greater than that of the strength reduction factor(a),which means the proposed GSI is suitable for rocks with significant fissure development.The improved method reduces the influence of subjective factors and provides a reliable index for the deterioration evaluation of rock mass.展开更多
Based on the situation and progress of marine oil/gas exploration in the Sichuan Basin,SW China,the whole petroleum system is divided for marine carbonate rocks of the basin according to the combinations of hydrocarbo...Based on the situation and progress of marine oil/gas exploration in the Sichuan Basin,SW China,the whole petroleum system is divided for marine carbonate rocks of the basin according to the combinations of hydrocarbon accumulation elements,especially the source rock.The hydrocarbon accumulation characteristics of each whole petroleum system are analyzed,the patterns of integrated conventional and unconventional hydrocarbon accumulation are summarized,and the favorable exploration targets are proposed.Under the control of multiple extensional-convergent tectonic cycles,the marine carbonate rocks of the Sichuan Basin contain three sets of regional source rocks and three sets of regional cap rocks,and can be divided into the Cambrian,Silurian and Permian whole petroleum systems.These whole petroleum systems present mainly independent hydrocarbon accumulation,containing natural gas of affinity individually.Locally,large fault zones run through multiple whole petroleum systems,forming a fault-controlled complex whole petroleum system.The hydrocarbon accumulation sequence of continental shelf facies shale gas accumulation,marginal platform facies-controlled gas reservoirs,and intra-platform fault-and facies-controlled gas reservoirs is common in the whole petroleum system,with a stereoscopic accumulation and orderly distribution pattern.High-quality source rock is fundamental to the formation of large gas fields,and natural gas in a whole petroleum system is generally enriched near and within the source rocks.The development and maintenance of large-scale reservoirs are essential for natural gas enrichment,multiple sources,oil and gas transformation,and dynamic adjustment are the characteristics of marine petroleum accumulation,and good preservation conditions are critical to natural gas accumulation.Large-scale marginal-platform reef-bank facies zones,deep shale gas,and large-scale lithological complexes related to source-connected faults are future marine hydrocarbon exploration targets in the Sichuan Basin.展开更多
Different from rivers in humid areas,the variability of riverine CO_(2) system in arid areas is heavily impacted by anthropogenic disturbance with the increasing urbanization and water withdrawals.In this study,the wa...Different from rivers in humid areas,the variability of riverine CO_(2) system in arid areas is heavily impacted by anthropogenic disturbance with the increasing urbanization and water withdrawals.In this study,the water chemistry and the controls of carbonate system in an urbanized river(the Fenhe River)on the semi-arid Loess Plateau were analyzed.The water chemistry of the river water showed that the high dissolved inorganic carbon(DIC)concentration(about 37 mg L^(-1))in the upstream with a karst land type was mainly sourced from carbonate weathering involved by H_(2)CO_(3) and H_(2)SO_(4),resulting in an oversaturated partial pressure of CO_(2)(pCO_(2))(about 800μatm).In comparison,damming resulted in the widespread appearance of non-free flowing river segments,and aquatic photosynthesis dominated the DIC and pCO_(2) spatiality demonstrated by the enriched stable isotope of DIC(δ^(13)CDIC).Especially in the mid-downstream flowing through major cities in warm and low-runoff August,some river segments even acted as an atmospheric CO_(2) sink.The noteworthy is wastewater input leading to a sudden increase in DIC(>55 mg L^(-1))and pCO_(2)(>4500μatm)in the downstream of Taiyuan City,and in cold November the increased DIC even extended to the outlet of the river.Our results highlight the effects of aquatic production induced by damming and urban sewage input on riverine CO_(2) system in semi-arid areas,and reducing sewage discharge may mitigate CO_(2) emission from the rivers.展开更多
Glycerol carbonate,an important glycerol value-added product,has been widely used as an active intermediate and inert solvent in the synthesis of cosmetics,detergents,chemical intermediates,polymers,and so on.The dire...Glycerol carbonate,an important glycerol value-added product,has been widely used as an active intermediate and inert solvent in the synthesis of cosmetics,detergents,chemical intermediates,polymers,and so on.The direct carbonylation from glycerol with CO_(2)is considered a promising route,but still tough work due to the thermodynamic stability and the kinetic inertness of CO_(2).In this work,highlyselective direct carbonylation of glycerol and CO_(2)into glycerol carbonate has been achieved over highly dispersed MgInCe-mixed metal oxides(MgInCe-MMO),which were prepared through the topological transformation derived from the MgInCe-layered double hydroxides(MgInCe-LDHs).By precisely modulating the surface basic-acidic properties and the oxygen vacancies,an efficient carbonylation of glycerol with CO_(2)has been achieved with a selectivity of up to>99%to glycerol carbonate.Deep investigation into the synergistic catalysis of base-acid sites and oxygen vacancies has been clarified.展开更多
Carbonate electrolytes are one of the most desirable electrolytes for high-energy lithium-sulfur batteries(LSBs)because of their successful implementation in commercial Li-ion batteries.The low-polysulfide-solubility ...Carbonate electrolytes are one of the most desirable electrolytes for high-energy lithium-sulfur batteries(LSBs)because of their successful implementation in commercial Li-ion batteries.The low-polysulfide-solubility feature of some carbonate solvents also makes them very promising for overcoming the shuttle effects of LSBs.However,regular sulfur electrodes experience undesired electrochemical mechanisms in carbonate electrolytes due to side reactions.In this study,we report a catalytic redox mechanism of sulfur in propylene carbonate(PC)electrolyte based on a compari-son study.The catalytic mechanism is characterized by the interactions between polysulfides and dual N/O functional groups on the host carbon,which largely prevents side reactions between polysulfides and the carbonate electrolyte.Such a mechanism coupled with the low-polysulfide-solubility feature leads to stable cycling of LSBs in PC electrolyte.Favorable dual N/O functional groups are identified via a density functional theory study.This work provides an alternative route for enabling LSBs in carbonate electrolytes.展开更多
Urea generation through electrochemical CO_(2) and NO_(3)~-co-reduction reaction(CO_(2)NO_(3)RR)is still limited by either the low selectivity or yield rate of urea.Herein,we report copper carbonate hydroxide(Cu_2(OH)...Urea generation through electrochemical CO_(2) and NO_(3)~-co-reduction reaction(CO_(2)NO_(3)RR)is still limited by either the low selectivity or yield rate of urea.Herein,we report copper carbonate hydroxide(Cu_2(OH)_2CO_(3))as an efficient CO_(2)NO_(3)RR electrocatalyst with an impressive urea Faradaic efficiency of45.2%±2.1%and a high yield rate of 1564.5±145.2μg h~(-1)mg_(cat)~(-1).More importantly,H_(2) evolution is fully inhibited on this electrocatalyst over a wide potential range between-0.3 and-0.8 V versus reversible hydrogen electrode.Our thermodynamic simulation reveals that the first C-N coupling follows a unique pathway on Cu_2(OH)_2CO_(3) by combining the two intermediates,~*COOH and~*NHO.This work demonstrates that high selectivity and yield rate of urea can be simultaneously achieved on simple Cu-based electrocatalysts in CO_(2)NO_(3)RR,and provide guidance for rational design of more advanced catalysts.展开更多
Molten carbonate is an excellent electrolyte for the electrochemical reduction of CO_(2)to carbonaceous materials.However,the electrolyte–electrode-reaction relationship has not been well understood.Herein,we propose...Molten carbonate is an excellent electrolyte for the electrochemical reduction of CO_(2)to carbonaceous materials.However,the electrolyte–electrode-reaction relationship has not been well understood.Herein,we propose a general descriptor,the CO_(2)activity,to reveal the electrolyte–electrode-reaction relationship by thermodynamic calculations and experimental studies.Experimental studies agree well with theoretical predictions that both cations(Li^(+),Ca^(2+),Sr^(2+)and Ba^(2+))and anions(BO_(2)^(-),Ti_(5)O_(14)^(8-),SiO_(3)^(2-))can modulate the CO_(2)activity to control both cathode and anode reactions in a typical molten carbonate electrolyzer in terms of tuning reaction products and overpotentials.In this regard,the reduction of CO_(3)^(2-)can be interpreted as the direct reduction of CO_(2)generated from the dissociated CO_(3)^(2-),and the CO_(2)activity can be used as a general descriptor to predict the electrode reaction in molten carbonate.Overall,the CO_(2)activity descriptor unlocks the electrolyte–electrode-reaction relationship,thereby providing fundamental insights into guiding molten carbonate CO_(2)electrolysis.展开更多
In intracratnoic basins, the effect of strike-slip faults on sedimentary microfacies is generally underestimated due to their small scale. Based on the integration of core, well logs, and three-dimensional seismic dat...In intracratnoic basins, the effect of strike-slip faults on sedimentary microfacies is generally underestimated due to their small scale. Based on the integration of core, well logs, and three-dimensional seismic data, this study presents a comprehensive analysis of the Permian carbonate platform and strike-slip faults in the southwestern Kaijiang-Liangping trough of the Sichuan Basin. The relationship between strike-slip faults and Permian carbonate microfacies is investigated. The results reveals the existence of a NW-trending strike-slip fault zone along the platform margin, exhibiting clear segmentation. The western side of the study area exhibits a rimmed platform margin characterized by type I reefs, which corresponds to the presence of a large-scale strike-slip fault zone. In contrast, the eastern side is characterized by a norimmed and weak rimmed platform margin, accompanied by type II reefs, which align with smaller strike-slip fault zones. It was found that the strike-slip fault had some effects on the platform and reef-shoal complex of the Permain Changxing Formation. First, the platform was divided by strike-slip fault into three segments to show rimmed, week rimmed and norimmed platform. Second, reef-shoal complex devolped along the faulted high position in the strike-slip fault zone, and separated by faulted depression. Third, strike-slip faults can offset or migrated the reef-shoal complex and platform margin. Additionally, the thickness of the platform margin varies across strike-slip fault zone, which is related to the activity of strike-slip faults. The strike-slip faults affect the microfacies by controlling the pre-depositional paleotopography. This case suggests that the strike-slip faults play a crucial role in the diversity and distribution of carbonate microfacies in the intracratonic basin.展开更多
The in-situ generated oxyanions at electrochemically reconstructed catalysts from metal-based nonoxide compounds have been proven to significantly accelerate oxygen evolution reaction(OER)kinetics.However,it remains a...The in-situ generated oxyanions at electrochemically reconstructed catalysts from metal-based nonoxide compounds have been proven to significantly accelerate oxygen evolution reaction(OER)kinetics.However,it remains a challenge to retain these self-released oxyanions at reconstructed catalysts,hindering its utilization as a tool to develop efficient OER catalysts.Here,we demonstrate a versatile selftransformed carbonate regulation strategy to efficiently retain the self-released chalcogenate at Co oxyhydroxides reconstructed from carbon-incorporated Co selenides under OER conditions.These selftransformed CO_(3)^(2-)can induce electron accumulation and narrow d bond at Co sites to facilitate the Co3d-O 2p orbital hybridization between Co sites and SeO_(x)^(2-)for enhanced SeO_(x)^(2-)retention,which can accelerate the rate-limiting step for^(*)OOH formation during OER.Relative to CoOOH-SeO_(x)^(2-)with limited SeO_(x)^(2-)residues,CoOOH-CO_(3)^(2-)/SeO_(x)^(2-)with elevated SeO_(x)^(2-)retention by CO_(3)^(2-)regulation exhibited a 5.6-fold increase in current density and a remarkable lower Tafel slope towards OER.This strategy paves a rational avenue to design efficient catalysts for electrooxidation reactions through finely regulating self-released oxyanions at reconstructed structures.展开更多
For engineering structures with saline soil as a filling material,such as channel slope,road subgrade,etc.,the rich soluble salt in the soil is an important potential factor affecting their safety performance.This stu...For engineering structures with saline soil as a filling material,such as channel slope,road subgrade,etc.,the rich soluble salt in the soil is an important potential factor affecting their safety performance.This study examines the Atterberg limits,shear strength,and compressibility of carbonate saline soil samples with different NaHCO3 contents in Northeast China.The mechanism underlying the influence of salt content on soil macroscopic properties was investigated based on a volumetric flask test,a mercury intrusion porosimetry(MIP)test,and a scanning electron microscopic(SEM)test.The results demonstrated that when NaHCO3 contents were lower than the threshold value of 1.5%,the bound water film adsorbed on the surface of clay particles thickened continuously,and correspondingly,the Atterberg limits and plasticity index increased rapidly as the increase of sodium ion content.Meanwhile,the bonding force between particles was weakened,the dispersion of large aggregates was enhanced,and the soil structure became looser.Macroscopically,the compressibility increased and the shear strength(mainly cohesion)decreased by 28.64%.However,when the NaHCO3 content exceeded the threshold value of 1.5%,the salt gradually approached solubility and filled the pores between particles in the form of crystals,resulting in a decrease in soil porosity.The cementation effect generated by salt crystals increased the bonding force between soil particles,leading to a decrease in plasticity index and an improvement in soil mechanical properties.Moreover,this work provides valuable suggestions and theoretical guidance for the scientific utilization of carbonate saline soil in backfill engineering projects.展开更多
Flotation separation of calcite from fluorite is a challenge on low-grade fluorite flotation that limits the recovery and purity of fluorite concentrate.A new acid leaching–flotation process for fluorite is proposed ...Flotation separation of calcite from fluorite is a challenge on low-grade fluorite flotation that limits the recovery and purity of fluorite concentrate.A new acid leaching–flotation process for fluorite is proposed in this work.This innovative process raised the fluor-ite’s grade to 97.26wt%while producing nanoscale calcium carbonate from its leachate,which contained plenty of calcium ions.On the production of nanoscale calcium carbonate,the impacts of concentration,temperature,and titration rate were examined.By modifying the process conditions and utilizing crystal conditioning agents,calcite-type and amorphous calcium carbonates with corresponding particle sizes of 1.823 and 1.511μm were produced.The influence of the impurity ions Mn^(2+),Mg^(2+),and Fe^(3+)was demonstrated to reduce the particle size of nanoscale calcium carbonate and make crystal shape easier to manage in the fluorite leach solution system compared with the calcium chloride solution.The combination of the acid leaching–flotation process and the nanoscale calcium carbonate preparation method improved the grade of fluorite while recovering calcite resources,thus presenting a novel idea for the effective and clean usage of low-quality fluorite resources with embedded microfine particles.展开更多
Dimethyl carbonate(DMC)is a crucial chemical raw material widely used in organic synthesis,lithiumion battery electrolytes,and various other fields.The current primary industrial process employs a conventional sodium ...Dimethyl carbonate(DMC)is a crucial chemical raw material widely used in organic synthesis,lithiumion battery electrolytes,and various other fields.The current primary industrial process employs a conventional sodium methoxide basic catalyst to produce DMC through the transesterification reaction between vinyl carbonate and methanol.However,the utilization of this catalyst presents several challenges during the process,including equipment corrosion,the generation of solid waste,susceptibility to deactivation,and complexities in separation and recovery.To address these limitations,a series of alkaline poly(ionic liquid)s,i.e.[DVBPIL][PHO],[DVCPIL][PHO],and[TBVPIL][PHO],with different crosslinking degrees and structures,were synthesized through the construction of cross-linked polymeric monomers and functionalization.These poly(ionic liquid)s exhibit cross-linked structures and controllable cationic and anionic characteristics.Research was conducted to investigate the effect of the cross-linking degree and structure on the catalytic performance of transesterification in synthesizing DMC.It was discovered that the appropriate cross-linking degree and structure of the[DVCPIL][PHO]catalyst resulted in a DMC yield of up to 80.6%.Furthermore,this catalyst material exhibited good stability,maintaining its catalytic activity after repeated use five times without significant changes.The results of this study demonstrate the potential for using alkaline poly(ionic liquid)s as a highly efficient and sustainable alternative to traditional catalysts for the transesterification synthesis of DMC.展开更多
The direct synthesis of dimethyl carbonate(DMC)from CO_(2)and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes.Herein,a series of cerium oxide catalysts ...The direct synthesis of dimethyl carbonate(DMC)from CO_(2)and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes.Herein,a series of cerium oxide catalysts with various textural features and surface properties were prepared by the one-pot synthesis method for the direct DMC synthesis from CO_(2)and methanol,and the structure-performance relationship was investigated in detail.Characterization results revealed that both of surface acid-base properties and the oxygen vacancies contents decreased with the rising crystallinity at increasingly higher calcination temperature accompanied by an unexpectedly volcano-shaped trend of DMC yield observed on the catalysts.In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)studies indicated that the adsorption rate of methanol is slower than that of CO_(2)and the methanol activation state largely influences the formation of key intermediate.Although the enhanced surface acidity-basicity and oxygen vacancies brought by low-temperature calcination could facilitate the activation of CO_(2),the presence of excess strongly basic sites on low-crystallinity sample was detrimental to DMC synthesis due to the preferred formation of unreactive mono/polydentate carbonates as well as the further impediment of methanol activation.Moreover,with the use of 2-cyanopyridine as a dehydration reagent,the DMC synthesis was found to be both influenced by the promotion from the rapid in situ removal of water and the inhibition from the competitive adsorption of hydration products on the same active sites.展开更多
Low salinity water containing sulfate ions can significantly alter the surface wettability of carbonate rocks.Nevertheless,the impact of sulfate concentration on the desorption of oil film on the surface of carbonate ...Low salinity water containing sulfate ions can significantly alter the surface wettability of carbonate rocks.Nevertheless,the impact of sulfate concentration on the desorption of oil film on the surface of carbonate rock is still unknown.This study examines the variations in the wettability of the surface of carbonate rocks in solutions containing varying amounts of sodium sulfate and pure water.The problem is addressed in the framework of molecular dynamics simulation(Material Studio software)and experiments.The experiment’s findings demonstrate that sodium sulfate can increase the rate at which oil moisture is turned into water moisture.The final contact angle is smaller than that of pure water.The results of the simulations show that many water molecules travel down the water channel under the influence of several powerful forces,including the electrostatic force,the van der Waals force and hydrogen bond,crowding out the oil molecules on the calcite’s surface and causing the oil film to separate.The relative concentration curve of water and oil molecules indicates that the separation rate of the oil film on the surface of calcite increases with the number of sulfate ions.展开更多
Flow-slip damage commonly destabilizes coastal slopes.Finding a slope stabilization method for calcareous sands in the South China Sea is crucial.Microbially induced calcite precipitation is a promising,eco-friendly m...Flow-slip damage commonly destabilizes coastal slopes.Finding a slope stabilization method for calcareous sands in the South China Sea is crucial.Microbially induced calcite precipitation is a promising,eco-friendly method for soil stabilization.This study investigates the effect of microbial treatments,initial relative density,initial cell pressure,and initial stress ratio on the flow-slip stability of calcareous sand specimens by using constant shear drained tests.These tests lay the foundation to study the mechanical instability of sand slopes.Results show that the microbial-treated specimens maintain stable stresses longer,take longer to reach the instability,and withstand larger volumetric strains.Microbial treatment effectively enhances sand stability under constant shear drainage,with improvements amplified by higher initial relative density and initial cell pressure.In addition,a smaller initial stress ratio reduces shear effects on the specimen and increases resistance to flow slides.Microanalysis reveals that the flow-slip stability of calcareous sand slopes is enhanced by contact cementation,particle coating,void filling,and mutual embedment of calcium carbonate crystals.展开更多
Based on the waterflooding development in carbonate reservoirs in the Middle East,in order to solve the problem of the poor development effects caused by commingled injection and production,taking the thick bioclastic...Based on the waterflooding development in carbonate reservoirs in the Middle East,in order to solve the problem of the poor development effects caused by commingled injection and production,taking the thick bioclastic limestone reservoirs of Cretaceous in Iran-Iraq as an example,this paper proposes a balanced waterflooding development technology for thick and complex carbonate reservoirs.This technology includes the fine division of development units by concealed baffles and barriers,the combination of multi well type and multi well pattern,and the construction of balanced water injection and recovery system.Thick carbonate reservoirs in Iran-Iraq are characterized by extremely vertical heterogeneity,development of multi-genesis ultra-high permeability zones,and highly concealed baffles and barriers.Based on the technologies of identification,characterization,and sealing evaluation for concealed baffles and barriers,the balanced waterflooding development technology is proposed,and three types of balanced waterflooding development modes/techniques are formed,namely,conventional stratigraphic framework,fine stratigraphic framework,and deepened stratigraphic framework.Numerical simulations show that this technology is able to realize a fine and efficient waterflooding development to recover,in a balanced manner,the reserves of thick and complex carbonate reservoirs in Iran and Iraq.The proposed technology provides a reference for the development optimization of similar reservoirs.展开更多
基金Supported by the National Science and Technology Major Project(2016ZX05029001)CNPC Science and Technology Project(2019D-4310)。
文摘In response to the problems of unclear distribution of deep-water pre-salt carbonate reservoirs and formation conditions of large oil fields in the Santos passive continental margin basin,based on comprehensive utilization of geological,seismic,and core data,and reconstruction of Early Cretaceous prototype basin and lithofacies paleogeography,it is proposed for the first time that the construction of pre-salt carbonate build-ups was controlled by two types of isolated platforms:inter-depression fault-uplift and intra-depression fault-high.The inter-depression fault-uplift isolated platforms are distributed on the present-day pre-salt uplifted zones between depressions,and are built on half-and fault-horst blocks that were inherited and developed in the early intra-continental and inter-continental rift stages.The late intra-continental rift coquinas of the ITP Formation and the early inter-continental rift microbial limestones of the BVE Formation are continuously constructed;intra-depression fault-high isolated platforms are distributed in the current pre-salt depression zones,built on the uplifted zones formed by volcanic rock build-ups in the early prototype stage of intra-continental rifts,and only the BVE microbial limestones are developed.Both types of limestones formed into mound-shoal bodies,that have the characteristics of large reservoir thickness and good physical properties.Based on the dissection of large pre-salt oil fields discovered in the Santos Basin,it has been found that both types of platforms could form large-scale combined structural-stratigraphic traps,surrounded by high-quality lacustrine and lagoon source rocks at the periphery,and efficiently sealed by thick high-quality evaporite rocks above,forming the optimal combination of source,reservoir and cap in the form of“lower generation,middle storage,and upper cap”,with a high degree of oil and gas enrichment.It has been found that the large oil fields are all bottom water massive oil fields with a unified pressure system,and they are all filled to the spill-point.The future exploration is recommended to focus on the inter-depression fault-uplift isolated platforms in the western uplift zone and the southern section of eastern uplift zones,as well as intra-depression fault-high isolated platforms in the central depression zone.The result not only provides an important basis for the advanced selection of potential play fairways,bidding of new blocks,and deployment of awarded exploration blocks in the Santos Basin,but also provides a reference for the global selection of deep-water exploration blocks in passive continental margin basins.
基金supported by the National Natural Science Foundation of China(52172201,51732005,51902118,and 52102249)the China Postdoctoral Science Foundation(2019M662609and 2020T130217)for financial support。
文摘Ethylene carbonate(EC)is widely used in lithium-ion batteries due to its optimal overall performance with satisfactory conductivity,relatively stable solid electrolyte interphase(SEI),and wide electrochemical window.EC is also the most widely used electrolyte solvent in sodium ion batteries.However,compared to lithium metal,sodium metal(Na)shows higher activity and reacts violently with EC-based electrolyte(NaPF_(6)as solute),which leads to the failure of sodium metal batteries(SMBs).Herein,we reveal the electrochemical instability mechanism of EC on sodium metal battery,and find that the com-bination of EC and NaPF_(6) is electrically reduced in sodium metal anode during charging,resulting in the reduction of the first coulombic efficiency,and the continuous consumption of electrolyte leads to the cell failure.To address the above issues,an additive modified linear carbonate-based electrolyte is provided as a substitute for EC based electrolytes.Specifically,ethyl methyl carbonate(EMC)and dimethyl carbon-ate(DMC)as solvents and fluoroethylene carbonate(FEC)as SEI-forming additive have been identified as the optimal solvent for NaFP_(6)based electrolyte and used in Na_(4)Fe_(3)(PO_(4))_(2)(P_(2)O_(7))/Na batteries.The batter-ies exhibit excellent capacity retention rate of about 80%over 1000 cycles at a cut-off voltage of 4.3 V.
基金The authors gratefully acknowledge the financial support of National NaturalScience Foundation of China(Grant No.41972276)Natural Science Foundation of Fujian Province,China(Grant No.2020J06013)"Foal Eagle Program"Youth Top-notch Talent Project of Fujian Province,China(Grant No.00387088).
文摘Enzyme-induced carbonate precipitation(EICP)is an emanating,eco-friendly and potentially sound technique that has presented promise in various geotechnical applications.However,the durability and microscopic characteristics of EICP-treated specimens against the impact of drying-wetting(D-W)cycles is under-explored yet.This study investigates the evolution of mechanical behavior and pore charac-teristics of EICP-treated sea sand subjected to D-W cycles.The uniaxial compressive strength(UCS)tests,synchrotron radiation micro-computed tomography(micro-CT),and three-dimensional(3D)recon-struction of CT images were performed to study the multiscale evolution characteristics of EICP-reinforced sea sand under the effect of D-W cycles.The potential correlations between microstructure characteristics and macro-mechanical property deterioration were investigated using gray relational analysis(GRA).Results showed that the UCS of EICP-treated specimens decreases by 63.7% after 15 D-W cycles.The proportion of mesopores gradually decreases whereas the proportion of macropores in-creases due to the exfoliated calcium carbonate with increasing number of D-W cycles.The micro-structure in EICP-reinforced sea sand was gradually disintegrated,resulting in increasing pore size and development of pore shape from ellipsoidal to columnar and branched.The gray relational degree suggested that the weight loss rate and UCS deterioration were attributed to the development of branched pores with a size of 100-1000 m m under the action of D-W cycles.Overall,the results in this study provide a useful guidancee for the long-term stability and evolution characteristics of EICP-reinforced sea sand under D-W weathering conditions.
基金This work was supported by the Joint Fund of NSFC for Enterprise Innovation and Development(Grant No.U19B6003-02-06)the National Natural Science Foundation of China(Grant No.51974331)+1 种基金the Natural Science Foundation of Jiangsu Province(Grant No.BK20200525)The authors would like to sincerely acknowledge these funding programs for their financial support.Particularly,the support provided by the China Scholarship Council(CSC)during a visit of Ke Sun(File No.202106440065)to the University of Alberta is also sincerely acknowledged.
文摘To gain insight into the flow mechanisms and stress sensitivity for fractured-vuggy reservoirs,several core models with different structural characteristics were designed and fabricated to investigate the impact of effective stress on permeability for carbonate fractured-vuggy rocks(CFVR).It shows that the permeability performance curves under different pore and confining pressures(i.e.altered stress conditions)for the fractured core models and the vuggy core models have similar change patterns.The ranges of permeability variation are significantly wider at high pore pressures,indicating that permeability reduction is the most significant during the early stage of development for fractured-vuggy reservoirs.Since each obtained effective stress coefficient for permeability(ESCP)varies with the changes in confining pressure and pore pressure,the effective stresses for permeability of four representative CFVR show obvious nonlinear characteristics,and the variation ranges of ESCP are all between 0 and 1.Meanwhile,a comprehensive ESCP mathematical model considering triple media,including matrix pores,fractures,and dissolved vugs,was proposed.It is proved theoretically that the ESCP of CFVR generally varies between 0 and 1.Additionally,the regression results showed that the power model ranked highest among the four empirical models mainly applied in stress sensitivity characterization,followed by the logarithmic model,exponential model,and binomial model.The concept of“permeability decline rate”was introduced to better evaluate the stress sensitivity performance for CFVR,in which the one-fracture rock is the strongest,followed by the fracture-vug rock and two-horizontalfracture rock;the through-hole rock is the weakest.In general,this study provides a theoretical basis to guide the design of development and adjustment programs for carbonate fractured-vuggy reservoirs.
基金supported by the National Key R&D Program of China(Grant Nos.2021YFB3901403 and 2023YFC3007203).
文摘The deterioration of unstable rock mass raised interest in evaluating rock mass quality.However,the traditional evaluation method for the geological strength index(GSI)primarily emphasizes the rock structure and characteristics of discontinuities.It ignores the influence of mineral composition and shows a deficiency in assessing the integrity coefficient.In this context,hyperspectral imaging and digital panoramic borehole camera technologies are applied to analyze the mineral content and integrity of rock mass.Based on the carbonate mineral content and fissure area ratio,the strength reduction factor and integrity coefficient are calculated to improve the GSI evaluation method.According to the results of mineral classification and fissure identification,the strength reduction factor and integrity coefficient increase with the depth of rock mass.The rock mass GSI calculated by the improved method is mainly concentrated between 40 and 60,which is close to the calculation results of the traditional method.The GSI error rates obtained by the two methods are mostly less than 10%,indicating the rationality of the hyperspectral-digital borehole image coupled evaluation method.Moreover,the sensitivity of the fissure area ratio(Sr)to GSI is greater than that of the strength reduction factor(a),which means the proposed GSI is suitable for rocks with significant fissure development.The improved method reduces the influence of subjective factors and provides a reliable index for the deterioration evaluation of rock mass.
基金Supported by the National Natural Science Foundation of China(42090022)。
文摘Based on the situation and progress of marine oil/gas exploration in the Sichuan Basin,SW China,the whole petroleum system is divided for marine carbonate rocks of the basin according to the combinations of hydrocarbon accumulation elements,especially the source rock.The hydrocarbon accumulation characteristics of each whole petroleum system are analyzed,the patterns of integrated conventional and unconventional hydrocarbon accumulation are summarized,and the favorable exploration targets are proposed.Under the control of multiple extensional-convergent tectonic cycles,the marine carbonate rocks of the Sichuan Basin contain three sets of regional source rocks and three sets of regional cap rocks,and can be divided into the Cambrian,Silurian and Permian whole petroleum systems.These whole petroleum systems present mainly independent hydrocarbon accumulation,containing natural gas of affinity individually.Locally,large fault zones run through multiple whole petroleum systems,forming a fault-controlled complex whole petroleum system.The hydrocarbon accumulation sequence of continental shelf facies shale gas accumulation,marginal platform facies-controlled gas reservoirs,and intra-platform fault-and facies-controlled gas reservoirs is common in the whole petroleum system,with a stereoscopic accumulation and orderly distribution pattern.High-quality source rock is fundamental to the formation of large gas fields,and natural gas in a whole petroleum system is generally enriched near and within the source rocks.The development and maintenance of large-scale reservoirs are essential for natural gas enrichment,multiple sources,oil and gas transformation,and dynamic adjustment are the characteristics of marine petroleum accumulation,and good preservation conditions are critical to natural gas accumulation.Large-scale marginal-platform reef-bank facies zones,deep shale gas,and large-scale lithological complexes related to source-connected faults are future marine hydrocarbon exploration targets in the Sichuan Basin.
基金supported by the National Natural Science Foundation of China (NSFC) (No.41376123)the Youth Project of Shanxi Basic Research (Nos.20210302124317,201901D211383)+1 种基金the Research and Promotion Project of Water Conservancy Science and Technology in Shanxi Province (No.2023GM41)the Science and Technology Innovation Fund of Shanxi Agricultural University (No.2018YJ21)。
文摘Different from rivers in humid areas,the variability of riverine CO_(2) system in arid areas is heavily impacted by anthropogenic disturbance with the increasing urbanization and water withdrawals.In this study,the water chemistry and the controls of carbonate system in an urbanized river(the Fenhe River)on the semi-arid Loess Plateau were analyzed.The water chemistry of the river water showed that the high dissolved inorganic carbon(DIC)concentration(about 37 mg L^(-1))in the upstream with a karst land type was mainly sourced from carbonate weathering involved by H_(2)CO_(3) and H_(2)SO_(4),resulting in an oversaturated partial pressure of CO_(2)(pCO_(2))(about 800μatm).In comparison,damming resulted in the widespread appearance of non-free flowing river segments,and aquatic photosynthesis dominated the DIC and pCO_(2) spatiality demonstrated by the enriched stable isotope of DIC(δ^(13)CDIC).Especially in the mid-downstream flowing through major cities in warm and low-runoff August,some river segments even acted as an atmospheric CO_(2) sink.The noteworthy is wastewater input leading to a sudden increase in DIC(>55 mg L^(-1))and pCO_(2)(>4500μatm)in the downstream of Taiyuan City,and in cold November the increased DIC even extended to the outlet of the river.Our results highlight the effects of aquatic production induced by damming and urban sewage input on riverine CO_(2) system in semi-arid areas,and reducing sewage discharge may mitigate CO_(2) emission from the rivers.
基金Financial support from the National Key Research and Development Program of China(2022YFB3805602)the National Natural Science Foundation of China(22138001,22288102)the Fundamental Research Funds for the Central Universities。
文摘Glycerol carbonate,an important glycerol value-added product,has been widely used as an active intermediate and inert solvent in the synthesis of cosmetics,detergents,chemical intermediates,polymers,and so on.The direct carbonylation from glycerol with CO_(2)is considered a promising route,but still tough work due to the thermodynamic stability and the kinetic inertness of CO_(2).In this work,highlyselective direct carbonylation of glycerol and CO_(2)into glycerol carbonate has been achieved over highly dispersed MgInCe-mixed metal oxides(MgInCe-MMO),which were prepared through the topological transformation derived from the MgInCe-layered double hydroxides(MgInCe-LDHs).By precisely modulating the surface basic-acidic properties and the oxygen vacancies,an efficient carbonylation of glycerol with CO_(2)has been achieved with a selectivity of up to>99%to glycerol carbonate.Deep investigation into the synergistic catalysis of base-acid sites and oxygen vacancies has been clarified.
文摘Carbonate electrolytes are one of the most desirable electrolytes for high-energy lithium-sulfur batteries(LSBs)because of their successful implementation in commercial Li-ion batteries.The low-polysulfide-solubility feature of some carbonate solvents also makes them very promising for overcoming the shuttle effects of LSBs.However,regular sulfur electrodes experience undesired electrochemical mechanisms in carbonate electrolytes due to side reactions.In this study,we report a catalytic redox mechanism of sulfur in propylene carbonate(PC)electrolyte based on a compari-son study.The catalytic mechanism is characterized by the interactions between polysulfides and dual N/O functional groups on the host carbon,which largely prevents side reactions between polysulfides and the carbonate electrolyte.Such a mechanism coupled with the low-polysulfide-solubility feature leads to stable cycling of LSBs in PC electrolyte.Favorable dual N/O functional groups are identified via a density functional theory study.This work provides an alternative route for enabling LSBs in carbonate electrolytes.
基金supported by the Research Grants Council(26206115,16304821 and 16309418)the Southern Marine Science and Engineering Guangdong Laboratory(Guangzhou)(SMSEGL20SC01)+2 种基金the Innovation and Technology Commission(grant no.ITC-CNERC14EG03)of the Hong Kong Special Administrative Regionthe Hong Kong Postdoctoral Fellowship Scheme(HKUST PDFS2021-4S12 and HKUST PDFS2021-6S08)the support from the Shenzhen fundamental research funding(JCYJ20210324115809026,20200925154115001,JCYJ20200109141216566)。
文摘Urea generation through electrochemical CO_(2) and NO_(3)~-co-reduction reaction(CO_(2)NO_(3)RR)is still limited by either the low selectivity or yield rate of urea.Herein,we report copper carbonate hydroxide(Cu_2(OH)_2CO_(3))as an efficient CO_(2)NO_(3)RR electrocatalyst with an impressive urea Faradaic efficiency of45.2%±2.1%and a high yield rate of 1564.5±145.2μg h~(-1)mg_(cat)~(-1).More importantly,H_(2) evolution is fully inhibited on this electrocatalyst over a wide potential range between-0.3 and-0.8 V versus reversible hydrogen electrode.Our thermodynamic simulation reveals that the first C-N coupling follows a unique pathway on Cu_2(OH)_2CO_(3) by combining the two intermediates,~*COOH and~*NHO.This work demonstrates that high selectivity and yield rate of urea can be simultaneously achieved on simple Cu-based electrocatalysts in CO_(2)NO_(3)RR,and provide guidance for rational design of more advanced catalysts.
基金funded by National Natural Science Foun-dation of China(No.52031008,21673162).
文摘Molten carbonate is an excellent electrolyte for the electrochemical reduction of CO_(2)to carbonaceous materials.However,the electrolyte–electrode-reaction relationship has not been well understood.Herein,we propose a general descriptor,the CO_(2)activity,to reveal the electrolyte–electrode-reaction relationship by thermodynamic calculations and experimental studies.Experimental studies agree well with theoretical predictions that both cations(Li^(+),Ca^(2+),Sr^(2+)and Ba^(2+))and anions(BO_(2)^(-),Ti_(5)O_(14)^(8-),SiO_(3)^(2-))can modulate the CO_(2)activity to control both cathode and anode reactions in a typical molten carbonate electrolyzer in terms of tuning reaction products and overpotentials.In this regard,the reduction of CO_(3)^(2-)can be interpreted as the direct reduction of CO_(2)generated from the dissociated CO_(3)^(2-),and the CO_(2)activity can be used as a general descriptor to predict the electrode reaction in molten carbonate.Overall,the CO_(2)activity descriptor unlocks the electrolyte–electrode-reaction relationship,thereby providing fundamental insights into guiding molten carbonate CO_(2)electrolysis.
基金partly supported by the National Natural Science Foundation of China (Grant No. 4224100017)Science and Technology Cooperation Project of the CNPC-SWPU Innovation Alliance (Grant No.2020CX010300)。
文摘In intracratnoic basins, the effect of strike-slip faults on sedimentary microfacies is generally underestimated due to their small scale. Based on the integration of core, well logs, and three-dimensional seismic data, this study presents a comprehensive analysis of the Permian carbonate platform and strike-slip faults in the southwestern Kaijiang-Liangping trough of the Sichuan Basin. The relationship between strike-slip faults and Permian carbonate microfacies is investigated. The results reveals the existence of a NW-trending strike-slip fault zone along the platform margin, exhibiting clear segmentation. The western side of the study area exhibits a rimmed platform margin characterized by type I reefs, which corresponds to the presence of a large-scale strike-slip fault zone. In contrast, the eastern side is characterized by a norimmed and weak rimmed platform margin, accompanied by type II reefs, which align with smaller strike-slip fault zones. It was found that the strike-slip fault had some effects on the platform and reef-shoal complex of the Permain Changxing Formation. First, the platform was divided by strike-slip fault into three segments to show rimmed, week rimmed and norimmed platform. Second, reef-shoal complex devolped along the faulted high position in the strike-slip fault zone, and separated by faulted depression. Third, strike-slip faults can offset or migrated the reef-shoal complex and platform margin. Additionally, the thickness of the platform margin varies across strike-slip fault zone, which is related to the activity of strike-slip faults. The strike-slip faults affect the microfacies by controlling the pre-depositional paleotopography. This case suggests that the strike-slip faults play a crucial role in the diversity and distribution of carbonate microfacies in the intracratonic basin.
基金supported by the National Natural Science Foundation of China (22002046 and 22379119)the Qin Chuangyuan High-level Innovative and Entrepreneurial Talent Program of Shaanxi Province (QCYRCXM-2023-045)+1 种基金the Youth Talent Support Program of Xi’an Association for Science and Technology (959202313070)the Young Top-notch Talent Program of Xi’an Jiaotong University (HG6J028)。
文摘The in-situ generated oxyanions at electrochemically reconstructed catalysts from metal-based nonoxide compounds have been proven to significantly accelerate oxygen evolution reaction(OER)kinetics.However,it remains a challenge to retain these self-released oxyanions at reconstructed catalysts,hindering its utilization as a tool to develop efficient OER catalysts.Here,we demonstrate a versatile selftransformed carbonate regulation strategy to efficiently retain the self-released chalcogenate at Co oxyhydroxides reconstructed from carbon-incorporated Co selenides under OER conditions.These selftransformed CO_(3)^(2-)can induce electron accumulation and narrow d bond at Co sites to facilitate the Co3d-O 2p orbital hybridization between Co sites and SeO_(x)^(2-)for enhanced SeO_(x)^(2-)retention,which can accelerate the rate-limiting step for^(*)OOH formation during OER.Relative to CoOOH-SeO_(x)^(2-)with limited SeO_(x)^(2-)residues,CoOOH-CO_(3)^(2-)/SeO_(x)^(2-)with elevated SeO_(x)^(2-)retention by CO_(3)^(2-)regulation exhibited a 5.6-fold increase in current density and a remarkable lower Tafel slope towards OER.This strategy paves a rational avenue to design efficient catalysts for electrooxidation reactions through finely regulating self-released oxyanions at reconstructed structures.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.42330708 and 41820104001)。
文摘For engineering structures with saline soil as a filling material,such as channel slope,road subgrade,etc.,the rich soluble salt in the soil is an important potential factor affecting their safety performance.This study examines the Atterberg limits,shear strength,and compressibility of carbonate saline soil samples with different NaHCO3 contents in Northeast China.The mechanism underlying the influence of salt content on soil macroscopic properties was investigated based on a volumetric flask test,a mercury intrusion porosimetry(MIP)test,and a scanning electron microscopic(SEM)test.The results demonstrated that when NaHCO3 contents were lower than the threshold value of 1.5%,the bound water film adsorbed on the surface of clay particles thickened continuously,and correspondingly,the Atterberg limits and plasticity index increased rapidly as the increase of sodium ion content.Meanwhile,the bonding force between particles was weakened,the dispersion of large aggregates was enhanced,and the soil structure became looser.Macroscopically,the compressibility increased and the shear strength(mainly cohesion)decreased by 28.64%.However,when the NaHCO3 content exceeded the threshold value of 1.5%,the salt gradually approached solubility and filled the pores between particles in the form of crystals,resulting in a decrease in soil porosity.The cementation effect generated by salt crystals increased the bonding force between soil particles,leading to a decrease in plasticity index and an improvement in soil mechanical properties.Moreover,this work provides valuable suggestions and theoretical guidance for the scientific utilization of carbonate saline soil in backfill engineering projects.
基金supported by the National Key Research Center and Development Program of the 14th Five-Year Plan,China(No.2022YFC2905105)National Natural Science Foundation of China(Nos.52122406 and 52004337)+2 种基金Hunan High-tech Industry Technology Innovation Leading Plan,China(No.2022GK4056)Hunan Innovative Province Construction Special Project,China(No.2020RC3001)Hunan Postgraduate Research and Innovation Project,China(No.CX20220200).
文摘Flotation separation of calcite from fluorite is a challenge on low-grade fluorite flotation that limits the recovery and purity of fluorite concentrate.A new acid leaching–flotation process for fluorite is proposed in this work.This innovative process raised the fluor-ite’s grade to 97.26wt%while producing nanoscale calcium carbonate from its leachate,which contained plenty of calcium ions.On the production of nanoscale calcium carbonate,the impacts of concentration,temperature,and titration rate were examined.By modifying the process conditions and utilizing crystal conditioning agents,calcite-type and amorphous calcium carbonates with corresponding particle sizes of 1.823 and 1.511μm were produced.The influence of the impurity ions Mn^(2+),Mg^(2+),and Fe^(3+)was demonstrated to reduce the particle size of nanoscale calcium carbonate and make crystal shape easier to manage in the fluorite leach solution system compared with the calcium chloride solution.The combination of the acid leaching–flotation process and the nanoscale calcium carbonate preparation method improved the grade of fluorite while recovering calcite resources,thus presenting a novel idea for the effective and clean usage of low-quality fluorite resources with embedded microfine particles.
基金supported by the National Key Research and Development Program of China(2022YFB4101800)National Natural Science Foundation of China(22278077,22108040)+2 种基金Key Program of Qingyuan Innovation Laboratory(00221004)Research Program of Qingyuan Innovation Laboratory(00523006)Natural Science Foundation of Fujian Province(2022J02019)。
文摘Dimethyl carbonate(DMC)is a crucial chemical raw material widely used in organic synthesis,lithiumion battery electrolytes,and various other fields.The current primary industrial process employs a conventional sodium methoxide basic catalyst to produce DMC through the transesterification reaction between vinyl carbonate and methanol.However,the utilization of this catalyst presents several challenges during the process,including equipment corrosion,the generation of solid waste,susceptibility to deactivation,and complexities in separation and recovery.To address these limitations,a series of alkaline poly(ionic liquid)s,i.e.[DVBPIL][PHO],[DVCPIL][PHO],and[TBVPIL][PHO],with different crosslinking degrees and structures,were synthesized through the construction of cross-linked polymeric monomers and functionalization.These poly(ionic liquid)s exhibit cross-linked structures and controllable cationic and anionic characteristics.Research was conducted to investigate the effect of the cross-linking degree and structure on the catalytic performance of transesterification in synthesizing DMC.It was discovered that the appropriate cross-linking degree and structure of the[DVCPIL][PHO]catalyst resulted in a DMC yield of up to 80.6%.Furthermore,this catalyst material exhibited good stability,maintaining its catalytic activity after repeated use five times without significant changes.The results of this study demonstrate the potential for using alkaline poly(ionic liquid)s as a highly efficient and sustainable alternative to traditional catalysts for the transesterification synthesis of DMC.
文摘The direct synthesis of dimethyl carbonate(DMC)from CO_(2)and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes.Herein,a series of cerium oxide catalysts with various textural features and surface properties were prepared by the one-pot synthesis method for the direct DMC synthesis from CO_(2)and methanol,and the structure-performance relationship was investigated in detail.Characterization results revealed that both of surface acid-base properties and the oxygen vacancies contents decreased with the rising crystallinity at increasingly higher calcination temperature accompanied by an unexpectedly volcano-shaped trend of DMC yield observed on the catalysts.In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)studies indicated that the adsorption rate of methanol is slower than that of CO_(2)and the methanol activation state largely influences the formation of key intermediate.Although the enhanced surface acidity-basicity and oxygen vacancies brought by low-temperature calcination could facilitate the activation of CO_(2),the presence of excess strongly basic sites on low-crystallinity sample was detrimental to DMC synthesis due to the preferred formation of unreactive mono/polydentate carbonates as well as the further impediment of methanol activation.Moreover,with the use of 2-cyanopyridine as a dehydration reagent,the DMC synthesis was found to be both influenced by the promotion from the rapid in situ removal of water and the inhibition from the competitive adsorption of hydration products on the same active sites.
基金supported by CNPC-CZU Innovation Alliancethe Research Start-Up Fund of Changzhou University.
文摘Low salinity water containing sulfate ions can significantly alter the surface wettability of carbonate rocks.Nevertheless,the impact of sulfate concentration on the desorption of oil film on the surface of carbonate rock is still unknown.This study examines the variations in the wettability of the surface of carbonate rocks in solutions containing varying amounts of sodium sulfate and pure water.The problem is addressed in the framework of molecular dynamics simulation(Material Studio software)and experiments.The experiment’s findings demonstrate that sodium sulfate can increase the rate at which oil moisture is turned into water moisture.The final contact angle is smaller than that of pure water.The results of the simulations show that many water molecules travel down the water channel under the influence of several powerful forces,including the electrostatic force,the van der Waals force and hydrogen bond,crowding out the oil molecules on the calcite’s surface and causing the oil film to separate.The relative concentration curve of water and oil molecules indicates that the separation rate of the oil film on the surface of calcite increases with the number of sulfate ions.
基金supported by the Taishan Scholars Program of Shandong Province,China(No.tsqn202306098)supported by the National Natural Science Foundations of China(No.52171282)the Shandong Provincial Key Research and Development Plan,China(No.2021ZLGX04).
文摘Flow-slip damage commonly destabilizes coastal slopes.Finding a slope stabilization method for calcareous sands in the South China Sea is crucial.Microbially induced calcite precipitation is a promising,eco-friendly method for soil stabilization.This study investigates the effect of microbial treatments,initial relative density,initial cell pressure,and initial stress ratio on the flow-slip stability of calcareous sand specimens by using constant shear drained tests.These tests lay the foundation to study the mechanical instability of sand slopes.Results show that the microbial-treated specimens maintain stable stresses longer,take longer to reach the instability,and withstand larger volumetric strains.Microbial treatment effectively enhances sand stability under constant shear drainage,with improvements amplified by higher initial relative density and initial cell pressure.In addition,a smaller initial stress ratio reduces shear effects on the specimen and increases resistance to flow slides.Microanalysis reveals that the flow-slip stability of calcareous sand slopes is enhanced by contact cementation,particle coating,void filling,and mutual embedment of calcium carbonate crystals.
基金Supported by the Major Science and Technology Project of CNPC(2023ZZ19-01).
文摘Based on the waterflooding development in carbonate reservoirs in the Middle East,in order to solve the problem of the poor development effects caused by commingled injection and production,taking the thick bioclastic limestone reservoirs of Cretaceous in Iran-Iraq as an example,this paper proposes a balanced waterflooding development technology for thick and complex carbonate reservoirs.This technology includes the fine division of development units by concealed baffles and barriers,the combination of multi well type and multi well pattern,and the construction of balanced water injection and recovery system.Thick carbonate reservoirs in Iran-Iraq are characterized by extremely vertical heterogeneity,development of multi-genesis ultra-high permeability zones,and highly concealed baffles and barriers.Based on the technologies of identification,characterization,and sealing evaluation for concealed baffles and barriers,the balanced waterflooding development technology is proposed,and three types of balanced waterflooding development modes/techniques are formed,namely,conventional stratigraphic framework,fine stratigraphic framework,and deepened stratigraphic framework.Numerical simulations show that this technology is able to realize a fine and efficient waterflooding development to recover,in a balanced manner,the reserves of thick and complex carbonate reservoirs in Iran and Iraq.The proposed technology provides a reference for the development optimization of similar reservoirs.