Essential oil was extracted from Artemisia lavandulaefolia DC.by steam distillation（SD） and supercritical-CO2 fluid extraction（SFE）,respectively.The constituents of the essentil oils extracted with those two metho...Essential oil was extracted from Artemisia lavandulaefolia DC.by steam distillation（SD） and supercritical-CO2 fluid extraction（SFE）,respectively.The constituents of the essentil oils extracted with those two methods were analyzed by gas chromatography-mass spectrometry（GC-MS） and insecticidal activities of the essential oils were evaluated,then the results were compared to assess their biological activity.Thirty-one compounds were identified in the essential oil extracted by SD,and its main components were eucalyptol,α,α,4-trimethyl-3-cyclohexene-1-methanol and so on.Twenty-two compounds were identified for the essential oil extracted by SFE,and its main components were cyclodecene,n-hexadecanoic acid and so on.Six chemical compositions were all contained in the essential oils extracted by the two methods,i.e.,eucalyptol,α,α,4-trimethyl-3-cyclohexene-1-methanol,caryophyllene,[3aS-（3aα,3bβ,4β,7α,7aS）]-octahydro-7-methyl-3-methylene-4-（1-methylethyl）-1H-cyclopenta[1,3]cyclopropa-[1,2]benzene,nerolidol and（-）-Spathulenol.The fumigation toxicity of the essential oil obtained by means of SD to the adults of Sitophilus zeamais is significantly higher than that of the essential oil by means of SFE.The contact toxicity of the essential oil obtained by means of SFE to the adults of S.zeamais is higher than that of the essential oil obtained by means of SD,but the difference is not significant.展开更多
A smart response fluid was designed and developed to overcome the challenges of gas channeling during CO_(2)flooding in low-permeability,tight oil reservoirs.The fluid is based on Gemini surfactant with self-assembly ...A smart response fluid was designed and developed to overcome the challenges of gas channeling during CO_(2)flooding in low-permeability,tight oil reservoirs.The fluid is based on Gemini surfactant with self-assembly capabilities,and the tertiary amine group serves as the response component.The responsive characteristics and corresponding mechanism of the smart fluid during the interaction with CO_(2)/oil were studied,followed by the shear characteristics of the thickened aggregates obtained by the smart fluid responding to CO_(2).The temperature and salt resistance of the smart fluid and the aggregates were evaluated,and their feasibility and effectiveness in sweep-controlling during the CO_(2)flooding were confirmed.This research reveals:(1)Thickened aggregates could be assembled since the smart fluid interacted with CO_(2).When the mass fraction of the smart fluid ranged from 0.05%to 2.50%,the thickening ratio changed from 9 to 246,with viscosity reaching 13 to 3100 mPas.As a result,the sweep efficiency in low-permeability core models could be increased in our experiments.(2)When the smart fluid(0.5%to 1.0%)was exposed to simulated oil,the oil/fluid interfacial tension decreased to the level of 1×10^(-2)mN/m.Furthermore,the vesicle-like micelles in the smart fluid completely transformed into spherical micelles when the fluid was exposed to simulated oil with the saturation greater than 10%.As a result,the smart fluid could maintain low oil/fluid interfacial tension,and would not be thickened after oil exposure.(3)When the smart fluid interacted with CO_(2),the aggregates showed self-healing properties in terms of shear-thinning,static-thickening,and structural integrity after several shear-static cycles.Therefore,this fluid is safe to be placed in deep reservoirs.(4)The long-term temperature and salt resistance of the smart fluid and thickened aggregates have been confirmed.展开更多
Slickwater-based fracturing fluid has recently garnered significant attention as the major fluid for volumetric fracturing;however,lots of challenges and limitations such as low viscosity,poor salt tolerance,and possi...Slickwater-based fracturing fluid has recently garnered significant attention as the major fluid for volumetric fracturing;however,lots of challenges and limitations such as low viscosity,poor salt tolerance,and possible formation damage hinder the application of the conventional simple slickwater-based fracturing fluid.In addition,nanomaterials have proven to be potential solutions or improvements to a number of challenges associated with the slickwater.In this paper,molybdenum disulfide(MoS_(2))nanosheets were chemically synthesized by hydrothermal method and applied to improve the performance of conventional slickwater-based fracturing fluid.Firstly,the microstructure characteristics and crystal type of the MoS_(2)nanosheets were analyzed by SEM,EDS,TEM,XPS,and Raman spectroscopy techniques.Then,a series of evaluation experiments were carried out to compare the performance of MoS_(2)nanosheet-modified slickwater with the conventional slickwater,including rheology,drag reduction,and sand suspension.Finally,the enhanced imbibition capacity and potential mechanism of the nanosheet-modified slickwater were systematically investigated.The results showed that the self-synthesized MoS_(2)nanosheets displayed a distinct ultrathin flake-like morphology and a lateral size in the range of tens of nanometers.In the nano-composites,each MoS_(2)nanosheet plays the role of cross-linking point,so as to make the spatial structure of the entire system more compact.Moreover,nanosheet-modified slickwater demonstrates more excellent properties in rheology,drag reduction,and sand suspension.The nanosheet-modified slickwater has a higher apparent viscosity after shearing 120 min under 90℃ and 170 s^(−1).The maximum drag reduction rate achieved 76.3%at 20℃,and the sand settling time of proppants with different mesh in the nano-composites was prolonged.Spontaneous imbibition experiments showed that the gel-breaking fluid of nanosheet-modified slickwater exhibited excellent capability of oil-detaching,and increase the oil recovery to∼35.43%.By observing and analyzing the interfacial behavior of MoS_(2)nanosheets under stimulated reservoir conditions,it was found that the presence of an interfacial tension gradient and the formation of a climbing film may play an essential role in the spontaneous imbibition mechanism.This work innovatively uses two-dimensional MoS_(2)nanosheets to modify regular slickwater and confirms the feasibility of flake-like nanomaterials to improve the performance of slickwater.The study also reveals the underlying mechanism of enhanced imbibition efficiency of the nano-composites.展开更多
Based on the petrology,isotope geochemistry and fluid inclusions analysis,we established the evolutionary mode of the diagenetic fluid of dawsonite-bearing sandstone in the Jiyang Depression.Dawsonite-bearing sandston...Based on the petrology,isotope geochemistry and fluid inclusions analysis,we established the evolutionary mode of the diagenetic fluid of dawsonite-bearing sandstone in the Jiyang Depression.Dawsonite-bearing sandstone is characterized by double injection of CO_(2)and oil-gas in the Jiyang Depression that have experienced a relatively complex diagenetic fluid evolution process.The diagenetic sequence of secondary minerals involves secondary enlargement of quartz,kaolinite,first-stage calcite,dawsonite,second-stage calcite,ferrocalcite,dolomite and ankerite.Hydrocarbon charging in the dawsonite-bearing sandstone occurred at around 2.6–0 Myr.The CO_(2)charging event occurred during Dongying tectonism,forming the Pingfangwang CO_(2)gas reservoir,which provided an abundant carbon source for dawsonite precipitation.Carbon and oxygen isotopic compositions of dawsonite demonstrate that CO_(2)forming the dawsonite was of an inorganic origin derived from the mantle,and that water mediating the proc-ess during dawsonite precipitation was sequestered brine with a fluid temperature of 82℃.The evolutionary sequence of the diagenetic fluid in the dawsonite-bearing sandstone was:alkaline syngenetic fluids,weak alkaline fluids during organic acid forma-tion,acidic fluids in the early stage of CO_(2)injection,alkaline fluids in the late stage of CO_(2)injection,and weak alkaline fluids during oil and gas charging.The mode indicates an increase in-HCO_(3)because of the CO_(2)injection,and the loss of Ca^(2+)and Mg^(2+)due to the precipitation of carbonate minerals.Therefore,the evolutionary mode of diagenetic fluids is in good agreement with high HCO_(3)^(-),low Ca^(2+)and low Mg^(2+)composition of the present formation water in the dawsonite-bearing sandstone.展开更多
A series of TiO 2-MoO 3 nano-composite photocatalysts were prepared by supercritical fluid dry method(SCFD) and an impregnation technique with TiCl 4 and (NH 4) 6Mo 7O 24 ·4H 2O as the starting materia...A series of TiO 2-MoO 3 nano-composite photocatalysts were prepared by supercritical fluid dry method(SCFD) and an impregnation technique with TiCl 4 and (NH 4) 6Mo 7O 24 ·4H 2O as the starting materials. The catalysts were characterized by the means of XRD, TEM and UV-Vis. Methyl orange was used as model compound for the evaluation of their catalytic activities. The results indicated that the photo-catalyst prepared by SCFD had the advantages of small size(12.84 nm), narrow distribution and good dispersivity. The presence of small amount of Mo in composite catalyst gives rise to the red shift of its absorbance wavelength, decrease of its energy gap and increase of the utility of visible light. Furthermore, higher surface acidity of the photo-catalyst was obtained as the result of the addition of MoO 3. Compared with pure TiO 2, the catalytic activity of the TiO 2-MoO 3 nano-composite photo-catalyst was improved significantly. As the doping concentration of the composite catalysts was controlled at 0.6%(molar percentage), 100% degradation of methyl orange was achieved with in 1.2 h irradiation time.展开更多
We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,ind...We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,indicating that Raman quantification of CH4/CO2 molar ratio can be applied to those fluid inclusions(FIs)with high internal pressure(i.e.,>15 MPa).Secondly,the v1(CH4)peak position shifts to lower wavenumber with increasing pressure at constant temperature,confirming that the v1(CH4)peak position can be used to calculate the fluid pressure.However,this method should be carefully calibrated before applying to FI analyses because large discrepancies exist among the reported v1(CH4)-P curves,especially in the highpressure range.These calibrations are applied to CH4-rich FIs in quartz veins of the Silurian Longmaxi black shales in southern Sichuan Basin.The vapor phases of these FIs are mainly composed of CH4 and minor CO2,with CO2 molar fractions from4.4%to 7.4%.The pressure of single-phase gas FI ranges from 103.65 to 128.35 MPa at room temperature,which is higher than previously reported.Thermodynamic calculations supported the presence of extremely high-pressure CH4-saturated fluid(218.03–256.82 MPa at 200°C),which may be responsible for the expulsion of CH4 to adjacent reservoirs.展开更多
Raman peaks of various hydrates in the H20-NaCl-CaCl2 system have been previously identified, but a quantitative relationship between the Raman peaks and XNaCl （i.e.,NaCl/ （NaCl＋CaCl2）） has not been established, ...Raman peaks of various hydrates in the H20-NaCl-CaCl2 system have been previously identified, but a quantitative relationship between the Raman peaks and XNaCl （i.e.,NaCl/ （NaCl＋CaCl2）） has not been established, mainly due to the difficulty to freeze the solutions. This problem was solved by adding alumina powder to the solutions to facilitate nucleation of crystals. Cryogenic （-185℃） Raman spectroscopic studies of alumina-spiced solutions indicate that XNaCl is linearly correlated with the total peak area fraction of hydrohalite. Capsules of solutions made from silica capillary were prepared to simulate fluid inclusions. Most of these artificial fluid inclusions could not be totally frozen even at temperatures as low as -185℃, and the total peak area fraction of hydrohalite is not correlated linearly with XNaCI. However, the degree of deviation （△XNaCl） from the linear correlation established earlier is related to the amount of residual solution, which is reflected by the ratio （r） of the baseline ＂bump＂ area, resulting from the interstitial unfrozen brine near 3435 cm^-1, and the total hydrate peak area between 3350 and 3600 cm^-1. A linear correlation between △XNaCl and r is established to estimate XNaCl from cryogenic Raman spectroscopic analysis for fluid inclusions.展开更多
基金Supported by the Technology Development Project of Jilin Province,China(Nos.20090571 and 20090262)the Development and Reform Project of Jilin Province,China(No.20071033)+2 种基金the State Administration of Quality Supervision Project,China(No.2008IK253)the Jingyue Development Zone Project of Changchun City,China(No.2007C010)the Scientific Research Fund of Jilin Agricultural University,China(No.2007040)
文摘Essential oil was extracted from Artemisia lavandulaefolia DC.by steam distillation（SD） and supercritical-CO2 fluid extraction（SFE）,respectively.The constituents of the essentil oils extracted with those two methods were analyzed by gas chromatography-mass spectrometry（GC-MS） and insecticidal activities of the essential oils were evaluated,then the results were compared to assess their biological activity.Thirty-one compounds were identified in the essential oil extracted by SD,and its main components were eucalyptol,α,α,4-trimethyl-3-cyclohexene-1-methanol and so on.Twenty-two compounds were identified for the essential oil extracted by SFE,and its main components were cyclodecene,n-hexadecanoic acid and so on.Six chemical compositions were all contained in the essential oils extracted by the two methods,i.e.,eucalyptol,α,α,4-trimethyl-3-cyclohexene-1-methanol,caryophyllene,[3aS-（3aα,3bβ,4β,7α,7aS）]-octahydro-7-methyl-3-methylene-4-（1-methylethyl）-1H-cyclopenta[1,3]cyclopropa-[1,2]benzene,nerolidol and（-）-Spathulenol.The fumigation toxicity of the essential oil obtained by means of SD to the adults of Sitophilus zeamais is significantly higher than that of the essential oil by means of SFE.The contact toxicity of the essential oil obtained by means of SFE to the adults of S.zeamais is higher than that of the essential oil obtained by means of SD,but the difference is not significant.
基金Supported by the PetroChina Science and Technology Major Project(2019-E2607)PetroChina Exploration and Production Company Science and Technology Project(KS2020-01-09).
文摘A smart response fluid was designed and developed to overcome the challenges of gas channeling during CO_(2)flooding in low-permeability,tight oil reservoirs.The fluid is based on Gemini surfactant with self-assembly capabilities,and the tertiary amine group serves as the response component.The responsive characteristics and corresponding mechanism of the smart fluid during the interaction with CO_(2)/oil were studied,followed by the shear characteristics of the thickened aggregates obtained by the smart fluid responding to CO_(2).The temperature and salt resistance of the smart fluid and the aggregates were evaluated,and their feasibility and effectiveness in sweep-controlling during the CO_(2)flooding were confirmed.This research reveals:(1)Thickened aggregates could be assembled since the smart fluid interacted with CO_(2).When the mass fraction of the smart fluid ranged from 0.05%to 2.50%,the thickening ratio changed from 9 to 246,with viscosity reaching 13 to 3100 mPas.As a result,the sweep efficiency in low-permeability core models could be increased in our experiments.(2)When the smart fluid(0.5%to 1.0%)was exposed to simulated oil,the oil/fluid interfacial tension decreased to the level of 1×10^(-2)mN/m.Furthermore,the vesicle-like micelles in the smart fluid completely transformed into spherical micelles when the fluid was exposed to simulated oil with the saturation greater than 10%.As a result,the smart fluid could maintain low oil/fluid interfacial tension,and would not be thickened after oil exposure.(3)When the smart fluid interacted with CO_(2),the aggregates showed self-healing properties in terms of shear-thinning,static-thickening,and structural integrity after several shear-static cycles.Therefore,this fluid is safe to be placed in deep reservoirs.(4)The long-term temperature and salt resistance of the smart fluid and thickened aggregates have been confirmed.
基金This research was financially supported by the National Natural Science Foundation of China(Grant Nos.52004306 and 52174045)the Strategic Cooperation Technology Projects of CNPC and CUPB(Grant Nos.ZLZX2020-01 and ZLZX2020-02)the National Sciencea and Technology Major Projects of China(Grant Nos.2016ZX05030005and 2016ZX05051003).
文摘Slickwater-based fracturing fluid has recently garnered significant attention as the major fluid for volumetric fracturing;however,lots of challenges and limitations such as low viscosity,poor salt tolerance,and possible formation damage hinder the application of the conventional simple slickwater-based fracturing fluid.In addition,nanomaterials have proven to be potential solutions or improvements to a number of challenges associated with the slickwater.In this paper,molybdenum disulfide(MoS_(2))nanosheets were chemically synthesized by hydrothermal method and applied to improve the performance of conventional slickwater-based fracturing fluid.Firstly,the microstructure characteristics and crystal type of the MoS_(2)nanosheets were analyzed by SEM,EDS,TEM,XPS,and Raman spectroscopy techniques.Then,a series of evaluation experiments were carried out to compare the performance of MoS_(2)nanosheet-modified slickwater with the conventional slickwater,including rheology,drag reduction,and sand suspension.Finally,the enhanced imbibition capacity and potential mechanism of the nanosheet-modified slickwater were systematically investigated.The results showed that the self-synthesized MoS_(2)nanosheets displayed a distinct ultrathin flake-like morphology and a lateral size in the range of tens of nanometers.In the nano-composites,each MoS_(2)nanosheet plays the role of cross-linking point,so as to make the spatial structure of the entire system more compact.Moreover,nanosheet-modified slickwater demonstrates more excellent properties in rheology,drag reduction,and sand suspension.The nanosheet-modified slickwater has a higher apparent viscosity after shearing 120 min under 90℃ and 170 s^(−1).The maximum drag reduction rate achieved 76.3%at 20℃,and the sand settling time of proppants with different mesh in the nano-composites was prolonged.Spontaneous imbibition experiments showed that the gel-breaking fluid of nanosheet-modified slickwater exhibited excellent capability of oil-detaching,and increase the oil recovery to∼35.43%.By observing and analyzing the interfacial behavior of MoS_(2)nanosheets under stimulated reservoir conditions,it was found that the presence of an interfacial tension gradient and the formation of a climbing film may play an essential role in the spontaneous imbibition mechanism.This work innovatively uses two-dimensional MoS_(2)nanosheets to modify regular slickwater and confirms the feasibility of flake-like nanomaterials to improve the performance of slickwater.The study also reveals the underlying mechanism of enhanced imbibition efficiency of the nano-composites.
基金supported by the National Natural Science Foundation of China(Nos.42072130,41872152).
文摘Based on the petrology,isotope geochemistry and fluid inclusions analysis,we established the evolutionary mode of the diagenetic fluid of dawsonite-bearing sandstone in the Jiyang Depression.Dawsonite-bearing sandstone is characterized by double injection of CO_(2)and oil-gas in the Jiyang Depression that have experienced a relatively complex diagenetic fluid evolution process.The diagenetic sequence of secondary minerals involves secondary enlargement of quartz,kaolinite,first-stage calcite,dawsonite,second-stage calcite,ferrocalcite,dolomite and ankerite.Hydrocarbon charging in the dawsonite-bearing sandstone occurred at around 2.6–0 Myr.The CO_(2)charging event occurred during Dongying tectonism,forming the Pingfangwang CO_(2)gas reservoir,which provided an abundant carbon source for dawsonite precipitation.Carbon and oxygen isotopic compositions of dawsonite demonstrate that CO_(2)forming the dawsonite was of an inorganic origin derived from the mantle,and that water mediating the proc-ess during dawsonite precipitation was sequestered brine with a fluid temperature of 82℃.The evolutionary sequence of the diagenetic fluid in the dawsonite-bearing sandstone was:alkaline syngenetic fluids,weak alkaline fluids during organic acid forma-tion,acidic fluids in the early stage of CO_(2)injection,alkaline fluids in the late stage of CO_(2)injection,and weak alkaline fluids during oil and gas charging.The mode indicates an increase in-HCO_(3)because of the CO_(2)injection,and the loss of Ca^(2+)and Mg^(2+)due to the precipitation of carbonate minerals.Therefore,the evolutionary mode of diagenetic fluids is in good agreement with high HCO_(3)^(-),low Ca^(2+)and low Mg^(2+)composition of the present formation water in the dawsonite-bearing sandstone.
文摘A series of TiO 2-MoO 3 nano-composite photocatalysts were prepared by supercritical fluid dry method(SCFD) and an impregnation technique with TiCl 4 and (NH 4) 6Mo 7O 24 ·4H 2O as the starting materials. The catalysts were characterized by the means of XRD, TEM and UV-Vis. Methyl orange was used as model compound for the evaluation of their catalytic activities. The results indicated that the photo-catalyst prepared by SCFD had the advantages of small size(12.84 nm), narrow distribution and good dispersivity. The presence of small amount of Mo in composite catalyst gives rise to the red shift of its absorbance wavelength, decrease of its energy gap and increase of the utility of visible light. Furthermore, higher surface acidity of the photo-catalyst was obtained as the result of the addition of MoO 3. Compared with pure TiO 2, the catalytic activity of the TiO 2-MoO 3 nano-composite photo-catalyst was improved significantly. As the doping concentration of the composite catalysts was controlled at 0.6%(molar percentage), 100% degradation of methyl orange was achieved with in 1.2 h irradiation time.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.41922023 and 41830425)the Fundamental Research Funds for the Central Universities(Grant Nos.020614380056 and 020614380078).
文摘We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,indicating that Raman quantification of CH4/CO2 molar ratio can be applied to those fluid inclusions(FIs)with high internal pressure(i.e.,>15 MPa).Secondly,the v1(CH4)peak position shifts to lower wavenumber with increasing pressure at constant temperature,confirming that the v1(CH4)peak position can be used to calculate the fluid pressure.However,this method should be carefully calibrated before applying to FI analyses because large discrepancies exist among the reported v1(CH4)-P curves,especially in the highpressure range.These calibrations are applied to CH4-rich FIs in quartz veins of the Silurian Longmaxi black shales in southern Sichuan Basin.The vapor phases of these FIs are mainly composed of CH4 and minor CO2,with CO2 molar fractions from4.4%to 7.4%.The pressure of single-phase gas FI ranges from 103.65 to 128.35 MPa at room temperature,which is higher than previously reported.Thermodynamic calculations supported the presence of extremely high-pressure CH4-saturated fluid(218.03–256.82 MPa at 200°C),which may be responsible for the expulsion of CH4 to adjacent reservoirs.
基金supported by an NSERC-Discovery grant(to Chi)in part by the Knowledge Innovation Program of Chinese Academy of Sciences(SIDSSE201302)
文摘Raman peaks of various hydrates in the H20-NaCl-CaCl2 system have been previously identified, but a quantitative relationship between the Raman peaks and XNaCl （i.e.,NaCl/ （NaCl＋CaCl2）） has not been established, mainly due to the difficulty to freeze the solutions. This problem was solved by adding alumina powder to the solutions to facilitate nucleation of crystals. Cryogenic （-185℃） Raman spectroscopic studies of alumina-spiced solutions indicate that XNaCl is linearly correlated with the total peak area fraction of hydrohalite. Capsules of solutions made from silica capillary were prepared to simulate fluid inclusions. Most of these artificial fluid inclusions could not be totally frozen even at temperatures as low as -185℃, and the total peak area fraction of hydrohalite is not correlated linearly with XNaCI. However, the degree of deviation （△XNaCl） from the linear correlation established earlier is related to the amount of residual solution, which is reflected by the ratio （r） of the baseline ＂bump＂ area, resulting from the interstitial unfrozen brine near 3435 cm^-1, and the total hydrate peak area between 3350 and 3600 cm^-1. A linear correlation between △XNaCl and r is established to estimate XNaCl from cryogenic Raman spectroscopic analysis for fluid inclusions.
