The connectivity of shale pores and the occurrence of movable oil in shales have long been the focus of research.In this study,samples from wells BX7 and BYY2 in the Eq3^4-10 cyclothem of Qianjiang Formation in the Qi...The connectivity of shale pores and the occurrence of movable oil in shales have long been the focus of research.In this study,samples from wells BX7 and BYY2 in the Eq3^4-10 cyclothem of Qianjiang Formation in the Qianjiang depression,were analyzed.A double mercury injection method was used to distinguish between invalid and effective connected pores.The pore characteristics for occurrence of retained hydrocarbons and movable shale oil were identified by comparing pore changes in low temperature nitrogen adsorption and high pressure mercury injection experiments before and after extraction and the change in the mercury injection amounts in the pores between two separate mercury injections.The results show that less than 50%of the total connected pores in the Eq34-10 cyclothem samples are effective.The development of effective connected pores affects the mobility of shale oil but varies with different lithofacies.The main factor limiting shale oil mobility in Well BX7 is the presence of pores with throat sizes less than 15 nm.In Well BYY2,residual mercury in injection testing of lamellar dolomitic mudstone facies was mainly concentrated in pores with throats of 10-200 nm,and in bulk argillaceous dolomite facies,it was mainly concentrated at 60-300 nm.The throats of hydrocarbon-retaining pores can be 5 nm or even smaller,but pores with movable shale oil in the well were found to have throat sizes greater than 40 nm.Excluding the influence of differences in wettability,the movability of shale oil is mainly affected by differences in lithofacies,the degree of pore deformation caused by diagenesis,the complexity of pore structures,and the connectivity of pore throats.Dissolution and reprecipitation of halite also inhibit the mobility of shale oil.展开更多
A novel negative thermal expansion(NTE) material NdMnO_(3) was synthesized by solid-state method at 1 523 K. The crystal structure, phase transition, pores effect and negative expansion properties of NdMnO_(3) were in...A novel negative thermal expansion(NTE) material NdMnO_(3) was synthesized by solid-state method at 1 523 K. The crystal structure, phase transition, pores effect and negative expansion properties of NdMnO_(3) were investigated by variable temperature X-ray diffraction(XRD), scanning electron microscope(SEM) and variable temperature Raman spectra. The compound exhibits NTE properties in the orderly O' phase crystal structure. When the temperature is from 293 to 759 K, the ceramic NdMnO_(3) shows negative thermal expansion of-4.7×10^(-6)/K. As temperature increases, the ceramic NdMnO_(3) presents NTE property range from 759 to 1 007 K. The average linear expansion coefficient is-18.88×10^(-6)/K. The physical mechanism of NTE is discussed and clarified through experiments.展开更多
The unconnected gas-bearing pores in shale gas reservoirs may be transformed into“potential recoverable pores”after large scale hydraulic fracturing.However,the mainstream pore classification methods of shale gas re...The unconnected gas-bearing pores in shale gas reservoirs may be transformed into“potential recoverable pores”after large scale hydraulic fracturing.However,the mainstream pore classification methods of shale gas reservoirs,do not take the unconnected pores into account,which impacts the evaluation accuracy of reservoir pore effectiveness.To solve this problem,this paper took the shale of Lower Silurian Longmaxi Formation in the southern Sichuan Basin as the research object to carry out experiments on core porosity,centrifugal+gradual drying NMR after saturated with brine and NMR freezeethaw using plunger samples and crushed samples to analyze the volume,main development location and main pore size distribution range of unconnected pores.Then,the pore systems were classified,and the lower limit of effective pore size of connected gas-bearing pores was determined.Finally,the total pore effectiveness of shale gas reservoirs was evaluated,and the influence of unconnected pores on the development of shale gas was discussed.And the following research results were obtained.First,there are a large number of unconnected pores in the shale gas reservoirs of the study area,accounting for 30.23%.Most of them are mainly developed in organic matters and a few are developed in clay minerals.The distribution of pore size ranges from 5 nm to 30 nm.Second,T_(2)cut-off value of clay bound water in the shale gas reservoirs of the study area is 0.26 ms,whose corresponding pore size is 5.35 nm,which is the lower limit of the effective pore size.Third,large-scale hydraulic fracturing can improve the unconnected pores with the size more than 5.35 nm,so effective development of shale gas will be realized.Fourth,after hydraulic fracturing stimulation,the unconnected pores can increase the storage space of fracturing fluid in the matrix,absorb the fracturing fluid in the fractures,replace the shale gas in the pores and promote the automatic alleviation of water lock in shale gas reservoirs,so the single-well shale gas production will be increased.In conclusion,fluid occurrence and pore system in shale pores can be quantitatively divided by means of centrifugal+gradual temperature drying method combined with NMR experiments,mobile water and capillary bound water can be determined by the high speed centrifugal+NMR experiments,and capillary bound water and clay bound water can be determined by the gradual drying t NMR experiments.展开更多
SBA-15 with varied pore size from 4 to 8 nm were synthesized by tuning the temperature of hydrothermal treatment,the supports were then used to load the active phase Cr Oxthrough a conventional impregnation method.The...SBA-15 with varied pore size from 4 to 8 nm were synthesized by tuning the temperature of hydrothermal treatment,the supports were then used to load the active phase Cr Oxthrough a conventional impregnation method.The resulting catalysts were characterized by small/wide angle XRD,N_(2) adsorption/desorption,FT-IR,TEM-EDX,XPS,TPR and CO_(2)-TPD to study the feature of structure,surface chemical state,redox and basicity.It was found from these results that the metal species could be well dispersed on catalysts with larger pore size.Cr^(6+)species could enter into the framework by substituting the Si atoms of SBA-15,and Cr^(3+)mainly exist on extra framework.Pore size had profound effects on reducibility,surface composition and basicity.Cr^(6+)species were necessary to activate the C-H bonds of alkanes,while the basicity played an important role in activating C-O bonds of CO_(2).The best performances were achieved over the sample Cr supported on SBA-15 with a pore diameter of 7 nm in oxidative dehydrogenation of ethane in the presence of CO_(2).展开更多
In this work, the morphologies and pore structures of a series of corncob-derived activated carbons and zeolite templated carbon with ultrahigh surface area were carefully investigated by SEM, HRTEM and N2-sorption ch...In this work, the morphologies and pore structures of a series of corncob-derived activated carbons and zeolite templated carbon with ultrahigh surface area were carefully investigated by SEM, HRTEM and N2-sorption characterization technologies. The high-pressure hydrogen uptake performance was analyzed using standard Pressure-Composition-Temperature apparatus in order to study the pore size effects on hydrogen uptake. These as-obtained porous carbons showed different characteristics of pore size distribution as well as specific surface area. The results indicate that the most effective pores for adsorbing hydrogen depended on the storage pressure. These ultramicropores （0.65-0.85 nm） could be the most effective pores on excess H2 uptake at 1 bar, however, micropores （0.85-2 nm） would play a more important role in excess H2 uptake at higher pressure at 77 K. At room temperature, pore size effects on H2 uptake capacity were very weak. Both specific surface area and total pore volume play more important roles than pore size for H2 uptake at room temperature, which was clearly different from that at 77 K. For applications in future, the corncob-derived activated carbons can be more available than zeolite templated carbons at 77 K. Element doping enhanced hydrogen uptake could be main research direction for improving H2 uptake capacity at room temperature.展开更多
In order to study the permeability and water-resisting ability of the strata on the top of the Ordovician in Longgu Coal Mine, this paper tested the permeability and porosity of the strata, investigated the fracture a...In order to study the permeability and water-resisting ability of the strata on the top of the Ordovician in Longgu Coal Mine, this paper tested the permeability and porosity of the strata, investigated the fracture and pore structure features of the strata, and identified the main channels which govern the permeability and water-resisting ability of the strata. The permeability of the upper, central and lower strata shows as 2.0504 × 10^-3-2.782762× 10^-3, 4.1092 × 10^-3 -7.3387 × 10^-3 and 2.0891 ×10^-3-3.2705 × 10-3 μm^2, respectively, and porosity of that is 0.6786-0.9197%, 0.3109-0.3951% and 0.9829-1.8655%, respectively. The results indicate that： （I） the main channels of the relative water-resisting layer are the pore throats with a diameter more than 6 μm; （2） the major proportion of pore throats in the vertical flow channel and the permeability first increases and then sharply decreases; （3） the fractures occurring from the top to 20 m in depth of the strata were filled and there occurred almost no fracture under the depth of 40 m; and （4） the ratio of turning point of the main flow channel in the strata on top of Ordovician can be used to confirm the thickness of filled water-resisting lavers.展开更多
Coke is an important medium for connecting reaction and regeneration of the methanol to propylene process on the ZSM5 catalyst.Coke grows in the meso and macro pores,it gradually worsens the diffusion inside the catal...Coke is an important medium for connecting reaction and regeneration of the methanol to propylene process on the ZSM5 catalyst.Coke grows in the meso and macro pores,it gradually worsens the diffusion inside the catalyst particle.Furthermore,pore plugging is inevitable which causes the deactivation of ZSM5 catalyst.However,current continuum model cannot reflect the changes in pore structure with clear physical concepts.A discrete model that is verified by the carbon deposition experiments is introduced to indicate the behavior of pore plugging effects.Results show that the pore plugging has a significant effect on the performance of the catalyst.The time varying profile of effectiveness factor is obtained,indicating a regular reduction with the increase of the pore plugging effect.Spatial distributions of pore size that would significantly enhance the plugging effect are also identified.展开更多
Occurrence and mobility of shale oil are prerequisites for evaluating shale oil reserves and prioritizing exploration targets,particularly for heterogeneous lacustrine shales.The Qingshankou Formation in the Gulong Sa...Occurrence and mobility of shale oil are prerequisites for evaluating shale oil reserves and prioritizing exploration targets,particularly for heterogeneous lacustrine shales.The Qingshankou Formation in the Gulong Sag,Songliao Basin is a classic lacustrine pure shale reservoir that contains abundant shale oil resources.The predicted geological reserves of the shale are 1.268×10^(9) t.In this study,field emission scanning electron microscope(FE-SEM),the modular automated processing system(MAPS),pyrolysisgas chromatography(Py-GC),low-pressure nitrogen gas adsorption(LPNA),Soxhlet extraction,pyrolysis,and 2-D nuclear magnetic resonance(NMR)were integrated to describe the shale oil components,microscopic occurrence,mobility,and the effective pore size distribution.Meanwhile,the related controlling factors are discussed.The shale oil in the Qingshankou Fm exists dominantly in the matrix pores of the clay minerals,with small amounts distributed in the intergranular pores of terrigenous clastic grains,intercrystalline pores of pyrite,intragranular pores of ostracod shells,and micro-fractures.Shale oil is distributed in the pore spaces of variable sizes in different lithofacies.The clay mineral-laminated shales are characterized by the broadest range of pore size and largest volume of pore spaces with shale oil distribution,while the ostracod-laminated shales have limited pore spaces retaining oil.Furthermore,the proposed integrated analysis evaluates the shale oil molecules existing in two states:movable,and adsorbed oil,respectively.The result illustrates that movable oil takes up 30.6%e79.4%of the total residual oil.TOC,mineral composition,and pore structures of the shale joint together to control the states and mobility of the shale oil.TOC values are positively correlated with the quantities of shale oil regardless of the state of oil.The mineral components significantly impact the state of shale oil.Noticeable differences in the states of oil were observed following the changing types of minerals,possibly due to their difference in adsorption capacity and wettability.Clay minerals attract more adsorbed oil than movable oil.Felsic minerals generally decrease the occurrence of total and adsorbed oil.Carbonate plays a positive role in hydrocarbon retention of all the shale oil states.As for the pore structure,the average pore size exerts a critical impact on the total,movable,and adsorbed oil content.The total pore volume and specific surface area of shales play a principal role in controlling the total yields and amounts of adsorbed oil.This research improves the understanding of the occurrence characteristics and enrichment mechanisms of shale oil in terrestrial pure shales and provides a reference for locating favorable shale oil exploration areas.展开更多
Tight sandstone gas(hereafter"tight gas")has become a subject of unconventional gas exploration globally.The large-scale development and use of tight gas resources in the USA,in particular,facilitated the ra...Tight sandstone gas(hereafter"tight gas")has become a subject of unconventional gas exploration globally.The large-scale development and use of tight gas resources in the USA,in particular,facilitated the rapid rebound of natural gas production in the USA,in addition to driving the rapid development of tight gas worldwide.In the eastern Ordos Basin,the Upper Paleozoic feature includes multiple layers of gas,a shallow depth,and notable potential for exploration and development.However,the reservoirs in the area are relatively tight,exhibit strong heterogeneity,and possess a complex micropore structure,thus restricting the eff ective economic development of oil and gas.Thus,research on the primary parameters controlling pore throat structure and the seepage capability of low-permeability reservoirs will be beneficial for the effcient exploration and development of natural gas in the eastern Ordos Basin.The parameters of reservoir porosity and percolation ability,as well as permeability,were analyzed using systematic sampling of the of the Upper Paleozoic Benxi,Taiyuan,and Shanxi Formations in the eastern Ordos Basin,constant-rate mercury injection experiments,nuclear magnetic resonance analysis,and gas–water-phase experimental studies.The results indicate that reservoir porosity is controlled by the effective pore volume and number,whereas permeability is controlled by the largest throat radius,rather than the average.The effective pore volume controls the movable fluid saturation,while reservoir percolation capability is controlled by the effective pore volume,irreducible water saturation,and size of the gas–water two-phase seepage zone.展开更多
Based on the finite deformation theory of the continuum and poroelastic theory, the aeoustoelastic theory for fluid-saturated porous media （FSPM） in natural and initial coordi- nates is developed to investigate the ...Based on the finite deformation theory of the continuum and poroelastic theory, the aeoustoelastic theory for fluid-saturated porous media （FSPM） in natural and initial coordi- nates is developed to investigate the influence of effective stresses and fluid pore pressure on wave velocities. Firstly, the assumption of a small dynamic motion superimposed on a largely static pre- deformation of the FSPM yields natural, initial, and final configurations, whose displacements, strains, and stresses of the solid-skeleton and the fluid in an FSPM particle could be described in natural and initial coordinates, respectively. Secondly, the subtraction of initial-state equations of equilibrium from the final-state equations of motion and the introduction of non-linear constitu- rive relations of the FSPM lead to equations of motion for the small dynamic motion. Thirdly, the consideration of homogeneous pre-deformation and the plane harmonic form of the small dynamic motion gives an acoustoelastic equation, which provides analytical formulations for the relation of the fast longitudinal wave, the fast shear wave, the slow shear wave, and the slow longitudinal wave with solid-skeleton stresses and fluid pore-pressure. Lastly, an isotropic FSPM under the close-pore jacketed condition, open-pore jacketed condition, traditional unjacketed condition, and triaxial condition is taken as an example to discuss the velocities of the fast and slow shear waves propagating along the direction of one of the initial principal solid-skeleton strains. The detailed discussion shows that the wave velocities of the FSPM are usually influenced by the effective stresses and the fluid pore pressure. The fluid pore-pressure has little effect on the wave velocities of the FSPM only when the components of the applied initial principal solid-skeleton stresses or strains are equal, which is consistent with the previous experimental results.展开更多
This study developed the equipment for thermo-fluid–solid coupling of methane-containing coal, and investigated the seepage character of loaded coal under different working conditions. Regarding the effective pressur...This study developed the equipment for thermo-fluid–solid coupling of methane-containing coal, and investigated the seepage character of loaded coal under different working conditions. Regarding the effective pressure as a variable, the variation characteristics of the gas permeability of loaded methane-containing coal has been studied under the conditions of different confining pressures and pore pressures. The qualitative and quantitative relationship between effective stress and permeability of loaded methane-containing coal has been established, considering the adsorption of deformation, amount of pore gas compression and temperature variation. The results show that the permeability of coal samples decreases along with the increasing effective stress. Based on the Darcy law, the correlation equation between the effective stress and permeability coefficient of coal seam has been established by combining the permeability coefficient of loaded coal and effective stress. On the basis of experimental data, this equation is used for calculation, and the results are in accordance with the measured gas permeability coefficient of coal seam. In conclusion, this method can be accurate and convenient to determine the gas permeability coefficient of coal seam, and provide evidence for forecasting that of the deep coal seam.展开更多
Inspired by previous resistance models for porous media, a resistance expression of gas migration within coal seams based on the ideal matchstick geometry, combined with the Darcy equation and the modified Poiseuille ...Inspired by previous resistance models for porous media, a resistance expression of gas migration within coal seams based on the ideal matchstick geometry, combined with the Darcy equation and the modified Poiseuille equation is proposed. The resistance to gas migration is generally dynamic because of the variations in adsorption swelling and matrix shrinkage. Due to the limitations of experimental conditions,only a theoretical expression of resistance to gas migration in coal is deduced, and the impacts of tortuosity, effective stress and pore pressure on the resistance are then considered. To validate the proposed expression, previous data from other researchers are adopted for the history matching exercise, and the agreement between the two is good.展开更多
Solid oral controlled release formulations feature numerous clinical advantages for drug candidates with adequate solubility and dissolution rate.However,most new chemical entities exhibit poor water solubility,and he...Solid oral controlled release formulations feature numerous clinical advantages for drug candidates with adequate solubility and dissolution rate.However,most new chemical entities exhibit poor water solubility,and hence are exempt from such benefits.Although combining drug amorphization with controlled release formulation is promising to elevate drug solubility,like other supersaturating systems,the problem of drug recrystallization has yet to be resolved,particularly within the dosage form.Here,we explored the potential of an emerging,non-leachable terpolymer nanoparticle(TPN)pore former as an internal recrystallization inhibitor within controlled release amorphous solid dispersion(CRASD)beads comprising a poorly soluble drug(celecoxib)reservoir and insoluble polymer(ethylcellulose)membrane.Compared to conventional pore former,polyvinylpyrrolidone(PVP),TPN-containing membranes exhibited superior structural integrity,less crystal formation at the CRASD bead surface,and greater extent of celecoxib release.All-atom molecular dynamics analyses revealed that in the presence of TPN,intra-molecular bonding,crystal formation tendency,diffusion coefficient,and molecular flexibility of celecoxib were reduced,while intermolecular H-bonding was increased as compared to PVP.This work suggests that selection of a pore former that promotes prolonged molecular separation within a nanoporous controlled release membrane structure may serve as an effective strategy to enhance amorphicity preservation inside CRASD.展开更多
基金supported by the National Natural Science Foundation of China(No.U19B6003)。
文摘The connectivity of shale pores and the occurrence of movable oil in shales have long been the focus of research.In this study,samples from wells BX7 and BYY2 in the Eq3^4-10 cyclothem of Qianjiang Formation in the Qianjiang depression,were analyzed.A double mercury injection method was used to distinguish between invalid and effective connected pores.The pore characteristics for occurrence of retained hydrocarbons and movable shale oil were identified by comparing pore changes in low temperature nitrogen adsorption and high pressure mercury injection experiments before and after extraction and the change in the mercury injection amounts in the pores between two separate mercury injections.The results show that less than 50%of the total connected pores in the Eq34-10 cyclothem samples are effective.The development of effective connected pores affects the mobility of shale oil but varies with different lithofacies.The main factor limiting shale oil mobility in Well BX7 is the presence of pores with throat sizes less than 15 nm.In Well BYY2,residual mercury in injection testing of lamellar dolomitic mudstone facies was mainly concentrated in pores with throats of 10-200 nm,and in bulk argillaceous dolomite facies,it was mainly concentrated at 60-300 nm.The throats of hydrocarbon-retaining pores can be 5 nm or even smaller,but pores with movable shale oil in the well were found to have throat sizes greater than 40 nm.Excluding the influence of differences in wettability,the movability of shale oil is mainly affected by differences in lithofacies,the degree of pore deformation caused by diagenesis,the complexity of pore structures,and the connectivity of pore throats.Dissolution and reprecipitation of halite also inhibit the mobility of shale oil.
文摘A novel negative thermal expansion(NTE) material NdMnO_(3) was synthesized by solid-state method at 1 523 K. The crystal structure, phase transition, pores effect and negative expansion properties of NdMnO_(3) were investigated by variable temperature X-ray diffraction(XRD), scanning electron microscope(SEM) and variable temperature Raman spectra. The compound exhibits NTE properties in the orderly O' phase crystal structure. When the temperature is from 293 to 759 K, the ceramic NdMnO_(3) shows negative thermal expansion of-4.7×10^(-6)/K. As temperature increases, the ceramic NdMnO_(3) presents NTE property range from 759 to 1 007 K. The average linear expansion coefficient is-18.88×10^(-6)/K. The physical mechanism of NTE is discussed and clarified through experiments.
基金supported by the National Natural Science Foundation of China“Research on nanopore structure characterization and seepage mechanism of shale reservoirs”(No.:51674044)Chongqing Key Industry Common Key Technology Innovation Special Project“Exploration and development key technology and its application of shale gas in Chongqing”(No.:cstc2017zdcyzdyfx0040)+1 种基金Sichuan Applied Basic Research Project“Research on intelligent evaluation system of marine shale gas construction and production core area(provincial key project)”(No.:2019YJ0340)Sichuan Promising Key Project“Study on evaluation of the fracturing effect of shale gas reservoirs based on the law of fracturing fluid flow back”(No.:2019JDRC0095).
文摘The unconnected gas-bearing pores in shale gas reservoirs may be transformed into“potential recoverable pores”after large scale hydraulic fracturing.However,the mainstream pore classification methods of shale gas reservoirs,do not take the unconnected pores into account,which impacts the evaluation accuracy of reservoir pore effectiveness.To solve this problem,this paper took the shale of Lower Silurian Longmaxi Formation in the southern Sichuan Basin as the research object to carry out experiments on core porosity,centrifugal+gradual drying NMR after saturated with brine and NMR freezeethaw using plunger samples and crushed samples to analyze the volume,main development location and main pore size distribution range of unconnected pores.Then,the pore systems were classified,and the lower limit of effective pore size of connected gas-bearing pores was determined.Finally,the total pore effectiveness of shale gas reservoirs was evaluated,and the influence of unconnected pores on the development of shale gas was discussed.And the following research results were obtained.First,there are a large number of unconnected pores in the shale gas reservoirs of the study area,accounting for 30.23%.Most of them are mainly developed in organic matters and a few are developed in clay minerals.The distribution of pore size ranges from 5 nm to 30 nm.Second,T_(2)cut-off value of clay bound water in the shale gas reservoirs of the study area is 0.26 ms,whose corresponding pore size is 5.35 nm,which is the lower limit of the effective pore size.Third,large-scale hydraulic fracturing can improve the unconnected pores with the size more than 5.35 nm,so effective development of shale gas will be realized.Fourth,after hydraulic fracturing stimulation,the unconnected pores can increase the storage space of fracturing fluid in the matrix,absorb the fracturing fluid in the fractures,replace the shale gas in the pores and promote the automatic alleviation of water lock in shale gas reservoirs,so the single-well shale gas production will be increased.In conclusion,fluid occurrence and pore system in shale pores can be quantitatively divided by means of centrifugal+gradual temperature drying method combined with NMR experiments,mobile water and capillary bound water can be determined by the high speed centrifugal+NMR experiments,and capillary bound water and clay bound water can be determined by the gradual drying t NMR experiments.
基金financial supports from National Natural Science Foundation of China(No.21603153)Science and Technology Department of Sichuan Province(No.2016HH0026)the Fundamental Research Funds for the Central Universities(No.YJ201544)。
文摘SBA-15 with varied pore size from 4 to 8 nm were synthesized by tuning the temperature of hydrothermal treatment,the supports were then used to load the active phase Cr Oxthrough a conventional impregnation method.The resulting catalysts were characterized by small/wide angle XRD,N_(2) adsorption/desorption,FT-IR,TEM-EDX,XPS,TPR and CO_(2)-TPD to study the feature of structure,surface chemical state,redox and basicity.It was found from these results that the metal species could be well dispersed on catalysts with larger pore size.Cr^(6+)species could enter into the framework by substituting the Si atoms of SBA-15,and Cr^(3+)mainly exist on extra framework.Pore size had profound effects on reducibility,surface composition and basicity.Cr^(6+)species were necessary to activate the C-H bonds of alkanes,while the basicity played an important role in activating C-O bonds of CO_(2).The best performances were achieved over the sample Cr supported on SBA-15 with a pore diameter of 7 nm in oxidative dehydrogenation of ethane in the presence of CO_(2).
基金supported by the National High Technology Research and Development Program of China(863 Program)(2012AA053305)the International Cooperation Project from Ministry of Science and Technology of China(2010DFA64080)
文摘In this work, the morphologies and pore structures of a series of corncob-derived activated carbons and zeolite templated carbon with ultrahigh surface area were carefully investigated by SEM, HRTEM and N2-sorption characterization technologies. The high-pressure hydrogen uptake performance was analyzed using standard Pressure-Composition-Temperature apparatus in order to study the pore size effects on hydrogen uptake. These as-obtained porous carbons showed different characteristics of pore size distribution as well as specific surface area. The results indicate that the most effective pores for adsorbing hydrogen depended on the storage pressure. These ultramicropores （0.65-0.85 nm） could be the most effective pores on excess H2 uptake at 1 bar, however, micropores （0.85-2 nm） would play a more important role in excess H2 uptake at higher pressure at 77 K. At room temperature, pore size effects on H2 uptake capacity were very weak. Both specific surface area and total pore volume play more important roles than pore size for H2 uptake at room temperature, which was clearly different from that at 77 K. For applications in future, the corncob-derived activated carbons can be more available than zeolite templated carbons at 77 K. Element doping enhanced hydrogen uptake could be main research direction for improving H2 uptake capacity at room temperature.
基金Financial supports for this work provided by the National Basic Research Program of China(2013CB227900)the Innovation of Graduate Student Training Project in Jiangsu Province of China(CXZZ13_0934)
文摘In order to study the permeability and water-resisting ability of the strata on the top of the Ordovician in Longgu Coal Mine, this paper tested the permeability and porosity of the strata, investigated the fracture and pore structure features of the strata, and identified the main channels which govern the permeability and water-resisting ability of the strata. The permeability of the upper, central and lower strata shows as 2.0504 × 10^-3-2.782762× 10^-3, 4.1092 × 10^-3 -7.3387 × 10^-3 and 2.0891 ×10^-3-3.2705 × 10-3 μm^2, respectively, and porosity of that is 0.6786-0.9197%, 0.3109-0.3951% and 0.9829-1.8655%, respectively. The results indicate that： （I） the main channels of the relative water-resisting layer are the pore throats with a diameter more than 6 μm; （2） the major proportion of pore throats in the vertical flow channel and the permeability first increases and then sharply decreases; （3） the fractures occurring from the top to 20 m in depth of the strata were filled and there occurred almost no fracture under the depth of 40 m; and （4） the ratio of turning point of the main flow channel in the strata on top of Ordovician can be used to confirm the thickness of filled water-resisting lavers.
基金the Project of National Natural Science Foundation of China(21822809&21978256)the National Science Fund for Distinguished Young(21525627)+1 种基金the Fundamental Research Funds for the Central Universi-ties(2019XZZX004-03)Ningxia Collaborative Innovation Center for Value Upgrading of Coal-based Synthetic Resin(2017DC57)are gratefully acknowledged.Dr.Zuwei Liao express their dedication to Prof.Xingtian Shu on the occasion of his 80th birthday.
文摘Coke is an important medium for connecting reaction and regeneration of the methanol to propylene process on the ZSM5 catalyst.Coke grows in the meso and macro pores,it gradually worsens the diffusion inside the catalyst particle.Furthermore,pore plugging is inevitable which causes the deactivation of ZSM5 catalyst.However,current continuum model cannot reflect the changes in pore structure with clear physical concepts.A discrete model that is verified by the carbon deposition experiments is introduced to indicate the behavior of pore plugging effects.Results show that the pore plugging has a significant effect on the performance of the catalyst.The time varying profile of effectiveness factor is obtained,indicating a regular reduction with the increase of the pore plugging effect.Spatial distributions of pore size that would significantly enhance the plugging effect are also identified.
基金funded by the National Natural Science Foundation of China(Project 42090025 and 42202152)Heilongjiang Province open competition projects:“Research on the shale oil phase state,seepage mechanism,and integrated geologicalengineering stimulation technology in the Gulong Sag”and“Research on the diagenetic dynamic evolution process and its coupling relationship with pores and fractures”.
文摘Occurrence and mobility of shale oil are prerequisites for evaluating shale oil reserves and prioritizing exploration targets,particularly for heterogeneous lacustrine shales.The Qingshankou Formation in the Gulong Sag,Songliao Basin is a classic lacustrine pure shale reservoir that contains abundant shale oil resources.The predicted geological reserves of the shale are 1.268×10^(9) t.In this study,field emission scanning electron microscope(FE-SEM),the modular automated processing system(MAPS),pyrolysisgas chromatography(Py-GC),low-pressure nitrogen gas adsorption(LPNA),Soxhlet extraction,pyrolysis,and 2-D nuclear magnetic resonance(NMR)were integrated to describe the shale oil components,microscopic occurrence,mobility,and the effective pore size distribution.Meanwhile,the related controlling factors are discussed.The shale oil in the Qingshankou Fm exists dominantly in the matrix pores of the clay minerals,with small amounts distributed in the intergranular pores of terrigenous clastic grains,intercrystalline pores of pyrite,intragranular pores of ostracod shells,and micro-fractures.Shale oil is distributed in the pore spaces of variable sizes in different lithofacies.The clay mineral-laminated shales are characterized by the broadest range of pore size and largest volume of pore spaces with shale oil distribution,while the ostracod-laminated shales have limited pore spaces retaining oil.Furthermore,the proposed integrated analysis evaluates the shale oil molecules existing in two states:movable,and adsorbed oil,respectively.The result illustrates that movable oil takes up 30.6%e79.4%of the total residual oil.TOC,mineral composition,and pore structures of the shale joint together to control the states and mobility of the shale oil.TOC values are positively correlated with the quantities of shale oil regardless of the state of oil.The mineral components significantly impact the state of shale oil.Noticeable differences in the states of oil were observed following the changing types of minerals,possibly due to their difference in adsorption capacity and wettability.Clay minerals attract more adsorbed oil than movable oil.Felsic minerals generally decrease the occurrence of total and adsorbed oil.Carbonate plays a positive role in hydrocarbon retention of all the shale oil states.As for the pore structure,the average pore size exerts a critical impact on the total,movable,and adsorbed oil content.The total pore volume and specific surface area of shales play a principal role in controlling the total yields and amounts of adsorbed oil.This research improves the understanding of the occurrence characteristics and enrichment mechanisms of shale oil in terrestrial pure shales and provides a reference for locating favorable shale oil exploration areas.
基金supported by the National Natural Science Foundation of China(Grants Nos.41390451 and 41172101)the National Key Research Project of China(No.2016YFC0601003)
文摘Tight sandstone gas(hereafter"tight gas")has become a subject of unconventional gas exploration globally.The large-scale development and use of tight gas resources in the USA,in particular,facilitated the rapid rebound of natural gas production in the USA,in addition to driving the rapid development of tight gas worldwide.In the eastern Ordos Basin,the Upper Paleozoic feature includes multiple layers of gas,a shallow depth,and notable potential for exploration and development.However,the reservoirs in the area are relatively tight,exhibit strong heterogeneity,and possess a complex micropore structure,thus restricting the eff ective economic development of oil and gas.Thus,research on the primary parameters controlling pore throat structure and the seepage capability of low-permeability reservoirs will be beneficial for the effcient exploration and development of natural gas in the eastern Ordos Basin.The parameters of reservoir porosity and percolation ability,as well as permeability,were analyzed using systematic sampling of the of the Upper Paleozoic Benxi,Taiyuan,and Shanxi Formations in the eastern Ordos Basin,constant-rate mercury injection experiments,nuclear magnetic resonance analysis,and gas–water-phase experimental studies.The results indicate that reservoir porosity is controlled by the effective pore volume and number,whereas permeability is controlled by the largest throat radius,rather than the average.The effective pore volume controls the movable fluid saturation,while reservoir percolation capability is controlled by the effective pore volume,irreducible water saturation,and size of the gas–water two-phase seepage zone.
基金supported by the National Natural Science Foundation of China(No.11072224)research grantsfrom Institute of Crustal Dynamics(No.ZDJ2012-20) and overseas-returned scholar,Personnel Ministry of China
文摘Based on the finite deformation theory of the continuum and poroelastic theory, the aeoustoelastic theory for fluid-saturated porous media （FSPM） in natural and initial coordi- nates is developed to investigate the influence of effective stresses and fluid pore pressure on wave velocities. Firstly, the assumption of a small dynamic motion superimposed on a largely static pre- deformation of the FSPM yields natural, initial, and final configurations, whose displacements, strains, and stresses of the solid-skeleton and the fluid in an FSPM particle could be described in natural and initial coordinates, respectively. Secondly, the subtraction of initial-state equations of equilibrium from the final-state equations of motion and the introduction of non-linear constitu- rive relations of the FSPM lead to equations of motion for the small dynamic motion. Thirdly, the consideration of homogeneous pre-deformation and the plane harmonic form of the small dynamic motion gives an acoustoelastic equation, which provides analytical formulations for the relation of the fast longitudinal wave, the fast shear wave, the slow shear wave, and the slow longitudinal wave with solid-skeleton stresses and fluid pore-pressure. Lastly, an isotropic FSPM under the close-pore jacketed condition, open-pore jacketed condition, traditional unjacketed condition, and triaxial condition is taken as an example to discuss the velocities of the fast and slow shear waves propagating along the direction of one of the initial principal solid-skeleton strains. The detailed discussion shows that the wave velocities of the FSPM are usually influenced by the effective stresses and the fluid pore pressure. The fluid pore-pressure has little effect on the wave velocities of the FSPM only when the components of the applied initial principal solid-skeleton stresses or strains are equal, which is consistent with the previous experimental results.
基金supported by the National Basic Research Program of China (No. 2012CB723103)the Ministry of Education Innovation Team of China (No. IRT1235)+2 种基金the State Key Laboratory Cultivation Base for Gas Geology and Gas Control of Henan Polytechnic University of China (No. WS2012A01)the Provincial Open Laboratory Fund of Minal Materials Key disciplines of China (No. MEM13-10)China Postdoctoral Science Foundation (No. 2014M552003)
文摘This study developed the equipment for thermo-fluid–solid coupling of methane-containing coal, and investigated the seepage character of loaded coal under different working conditions. Regarding the effective pressure as a variable, the variation characteristics of the gas permeability of loaded methane-containing coal has been studied under the conditions of different confining pressures and pore pressures. The qualitative and quantitative relationship between effective stress and permeability of loaded methane-containing coal has been established, considering the adsorption of deformation, amount of pore gas compression and temperature variation. The results show that the permeability of coal samples decreases along with the increasing effective stress. Based on the Darcy law, the correlation equation between the effective stress and permeability coefficient of coal seam has been established by combining the permeability coefficient of loaded coal and effective stress. On the basis of experimental data, this equation is used for calculation, and the results are in accordance with the measured gas permeability coefficient of coal seam. In conclusion, this method can be accurate and convenient to determine the gas permeability coefficient of coal seam, and provide evidence for forecasting that of the deep coal seam.
基金supported by the State Key Research Development Program of China (Nos. 2016YFC0801402 and 2016YFC0600708)the National Natural Science Foundation of China (No. 51474219)
文摘Inspired by previous resistance models for porous media, a resistance expression of gas migration within coal seams based on the ideal matchstick geometry, combined with the Darcy equation and the modified Poiseuille equation is proposed. The resistance to gas migration is generally dynamic because of the variations in adsorption swelling and matrix shrinkage. Due to the limitations of experimental conditions,only a theoretical expression of resistance to gas migration in coal is deduced, and the impacts of tortuosity, effective stress and pore pressure on the resistance are then considered. To validate the proposed expression, previous data from other researchers are adopted for the history matching exercise, and the agreement between the two is good.
基金supported in part by an Ontario Research Fund-Research Excellence(ORF-RE)grant(Ontario,Canada)in partnership with Patheon by Thermo Fisher Scientific,Natural Sciences and Engineering Research Council(NSERC)of Canada Discovery Grant and Equipment Grants to Xiao Yu Wu,University of Toronto(Canada),Leslie Dan Faculty of Pharmacy Dean's Fund to Jamie Anne Lugtu-Pe,University of Toronto(Canada),Mitacs Accelerate Internship sponsored by Candoo Pharmatech Company Inc.to Xuning Zhang(Canada),NSERC CREATE ContRoL program support to Sako Mirzaie and Hao Han R.Chang(Canada),Ontario Graduate Scholarship(OGS)to Hao Han R.Chang(Canada),and Pharmaceutical Sciences graduate department scholarships to Hao Han R.Chang and Kuan Chen,University of Toronto(Canada).
文摘Solid oral controlled release formulations feature numerous clinical advantages for drug candidates with adequate solubility and dissolution rate.However,most new chemical entities exhibit poor water solubility,and hence are exempt from such benefits.Although combining drug amorphization with controlled release formulation is promising to elevate drug solubility,like other supersaturating systems,the problem of drug recrystallization has yet to be resolved,particularly within the dosage form.Here,we explored the potential of an emerging,non-leachable terpolymer nanoparticle(TPN)pore former as an internal recrystallization inhibitor within controlled release amorphous solid dispersion(CRASD)beads comprising a poorly soluble drug(celecoxib)reservoir and insoluble polymer(ethylcellulose)membrane.Compared to conventional pore former,polyvinylpyrrolidone(PVP),TPN-containing membranes exhibited superior structural integrity,less crystal formation at the CRASD bead surface,and greater extent of celecoxib release.All-atom molecular dynamics analyses revealed that in the presence of TPN,intra-molecular bonding,crystal formation tendency,diffusion coefficient,and molecular flexibility of celecoxib were reduced,while intermolecular H-bonding was increased as compared to PVP.This work suggests that selection of a pore former that promotes prolonged molecular separation within a nanoporous controlled release membrane structure may serve as an effective strategy to enhance amorphicity preservation inside CRASD.
