The reaction mechanism for alkylation of benzene with propylene over the β zeolite and the MCM-22 zeolite were investigated respectively by in-situ IR spectrometry. Three types of experiments were carried out. （1） ...The reaction mechanism for alkylation of benzene with propylene over the β zeolite and the MCM-22 zeolite were investigated respectively by in-situ IR spectrometry. Three types of experiments were carried out. （1） IR spectra of the gas-phase propylene, benzene and isopropyl benzene were recorded. （2） IR spectra of the above-mentioned substances as adsorbates that have combined with the zeolite wafer were recorded. （3） IR spectra of the reaction modes were recorded. The test results showed that the alkytation reaction over the zeolite β was ascribed to the mechanism of carbonium ions, whereas the alkylation reaction over the zeolite MCM-22 was ascribed to the synchronous reaction mechanism.展开更多
The amphiphilic copolymer poly（hydroxyethyl methacrylate-co-tert-butyl methacrylate） [P（HEMA-co-tBMA）] was synthesized by activators regenerated by electron transfer atom transfer radical polymerization （ARGET A...The amphiphilic copolymer poly（hydroxyethyl methacrylate-co-tert-butyl methacrylate） [P（HEMA-co-tBMA）] was synthesized by activators regenerated by electron transfer atom transfer radical polymerization （ARGET ATRP）, with the synthesis process monitored by in-situ infrared spectroscopy （IR）. The molecular weight, chem- ical structure and characteristics of the copolymer were determined by 1H NMR, gas chromatography and gel permeation chromatography. The influences of various parameters on the living polymerization were explored. The molecular weight of the copolymer with narrow molecular weight distribution （Mw/Mn 〈 1.50） increases ap- proximately linearly with the monomer conversion, indicating a good control of polymerization. In the reaction temperature range from 50 ℃ to 90 ℃, the monomer conversion is higher at 60 ℃. The tBMA conversion rate decreases gradually with the increase of tBMA content, while the HEMA conversion is hardly affected by HEMA content. Weak polar solvent is more favorable to the polymerization compared to polar solvent. The molar ratio of reducing agent to catalyst has significant effect on the polymerization and increasing the amount of reducing agent will accelerate the reaction rate but causes wider molecular weight distribution. It is indicated that in-situ IR monitoring contributes to a more in-depth understanding of the mechanism of methacrylate monomer copolymerization.展开更多
The adsorption of acetonitrile, the co-adsorption of acetonitrile with CO, and hydrogenation of acetonitrile on fresh Mo2C/γ-Al2O3 catalyst were studied by in situ IR spectroscopy. It was found out that CH3CN exhibit...The adsorption of acetonitrile, the co-adsorption of acetonitrile with CO, and hydrogenation of acetonitrile on fresh Mo2C/γ-Al2O3 catalyst were studied by in situ IR spectroscopy. It was found out that CH3CN exhibited strong interaction with the fresh Mo2C/γ-Al2O3 catalyst and was adsorbed mainly on Moδ+ sites of fresh Mo2C/γ-Al2O3 catalyst. Moreover, CH3CN could affect the shifting of IR spectra for CO adsorption towards a lower wave number. The IR spectroscopic study on acetonitrile hydrogenation showed that CH3CN could be easily hydrogenated in the presence of H2 on the Mo2C/γ-Al2O3 catalyst. Furthermore, it was observed that CH3 CN could be selectively hydrogenated to imines on fresh Mo2C/γ-Al2O3 catalyst. Additionally, the active sites of fresh Mo2C/γ-Al2O3 catalyst might be covered with coke during the hydrogenation reaction of acetonitrile. The treatment of catalyst with hydrogen at 673 K could not completely remove coke deposits on the surface of the Mo2C/γ-Al2O3 catalyst.展开更多
Revealing the localized corrosion process of Mg alloy is considered as one of the most significant ways for improving its corrosion resistance.The reliable monitor should be high distinguishability and real-time in li...Revealing the localized corrosion process of Mg alloy is considered as one of the most significant ways for improving its corrosion resistance.The reliable monitor should be high distinguishability and real-time in liquid environment.Herein,Mg-9Al-1Fe and Mg-9Al-1Fe-1Gd alloys were designed to highlight the impact of intermetallic on the corrosion behaviour.In-situ AFM with a special electrolyte circulation system and quasi-in-situ SEM observation were used to monitor the corrosion process of the designed alloys.SEM-EDS and TEM-SAED were applied to identify the intermetallic in the designed alloys,and their volta potentials were measured by SKPFM.According to the real-time and real-space in-situ AFM monitor,the corrosion process consisted of dissolution of anodicα-Mg phase,accumulation of corrosion products around cathodic phase and shedding of some fine cathodic phase.Then,the localized corrosion process of Mg alloy was revealed combined with the results of the monitor of corrosion process and Volta potential difference.展开更多
In-situ conversion presents a promising technique for exploiting continental oil shale formations,characterized by highly fractured organic-rich rock.A 3D in-situ conversion model,which incorporates a discrete fractur...In-situ conversion presents a promising technique for exploiting continental oil shale formations,characterized by highly fractured organic-rich rock.A 3D in-situ conversion model,which incorporates a discrete fracture network,is developed using a self-developed thermal-flow-chemical(TFC)simulator.Analysis of the model elucidates the in-situ conversion process in three stages and defines the transformation of fluids into three distinct outcomes according to their end stages.The findings indicate that kerogen decomposition increases fluid pressure,activating fractures and subsequently enhancing permeability.A comprehensive analysis of activated fracture permeability and heating power reveals four distinct production modes,highlighting that increasing heating power correlates with higher cumulative fluid production.Activated fractures,with heightened permeability,facilitate the mobility of heavy oil toward production wells but hinder its cracking,thereby limiting light hydrocarbon production.Additionally,energy efficiency research demonstrates the feasibility of the in-situ conversion in terms of energy utilization,especially when considering the surplus energy from high-fluctuation energy sources such as wind and solar power to provide heating.展开更多
Deep in-situ rock mechanics considers the influence of the in-situ environment on mechanical properties,differentiating it from traditional rock mechanics.To investigate the effect of in-situ stress,pore pressure pres...Deep in-situ rock mechanics considers the influence of the in-situ environment on mechanical properties,differentiating it from traditional rock mechanics.To investigate the effect of in-situ stress,pore pressure preserved environment on the mechanical difference of sandstone,four tests are numerically modeled by COMSOL:conventional triaxial test,conventional pore pressure test,in-situ stress restoration and reconstruction test,and in-situ pore pressure-preserved test(not yet realized in the laboratory).The in-situ stress restoration parameter is introduced to characterize the recovery effect of in-situ stress on elastic modulus and heterogeneous distribution of sandstone at different depths.A random function and nonuniform pore pressure coefficient are employed to describe the non-uniform distribution of pore pressure in the in-situ environment.Numerical results are compared with existing experimental data to validate the models and calibrate the numerical parameters.By extracting mechanical parameters from numerical cores,the stress-strain curves of the four tests under different depths,in-situ stress and pore pressure are compared.The influence of non-uniform pore pressure coefficient and depth on the peak strength of sandstone is analyzed.The results show a strong linear relationship between the in-situ stress restoration parameter and depth,effectively characterizing the enhanced effect of stress restoration and reconstruction methods on the elastic modulus of conventional cores at different depths.The in-situ pore pressurepreserved test exhibits lower peak stress and peak strain compared to the other three tests,and sandstone subjected to non-uniform pore pressure is more prone to plastic damage and failure.Moreover,the influence of non-uniform pore pressure on peak strength gradually diminished with increasing depth.展开更多
The autothermic pyrolysis in-situ conversion process (ATS) consumes latent heat of residual organic matter after kerogen pyrolysis by oxidation reaction, and it has the advantages of low development cost and exploitat...The autothermic pyrolysis in-situ conversion process (ATS) consumes latent heat of residual organic matter after kerogen pyrolysis by oxidation reaction, and it has the advantages of low development cost and exploitation of deep oil shale resources. However, the heating mechanism and the characteristic of different reaction zones are still unclear. In this study, an ATS numerical simulation model was proposed for the development of oil shale, which considers the pyrolysis of kerogen, high-temperature oxidation, and low-temperature oxidation. Based on the above model, the mechanism of the ATS was analyzed and the effects of preheating temperature, O_(2) content, and injection rate on recovery factor and energy efficiency were studied. The results showed that the ATS in the formation can be divided into five characteristic zones by evolution of the oil and O_(2) distribution, and the solid organic matter, including residue zone, autothermic zone, pyrolysis zone, preheating zone, and original zone. Energy efficiency was much higher for the ATS than for the high-temperature nitrogen injection in-situ conversion process (HNICP). There is a threshold value of the preheating temperature, the oil content, and the injection rate during the ATS, which is 400 °C, 0.18, and 1100 m3/day, respectively, in this study.展开更多
Field-assisted electrocatalytic reactions are demonstrated to be sufficient strategies in enhancing the electrocatalyst activities for oxygen evolution reaction(OER).Here,we report the in-situ magnetic field enhanced ...Field-assisted electrocatalytic reactions are demonstrated to be sufficient strategies in enhancing the electrocatalyst activities for oxygen evolution reaction(OER).Here,we report the in-situ magnetic field enhanced electrocatalytic activity in ferromagnetic FeCo_(2)O_(4)nanofibers.Our results demonstrate that the overpotential of FeCo_(2)O_(4)nanofibers at 10 mA cm^(-2)shows a left-shift of 40 mV for the OER by applying an external magnetic field,and no obvious change has been observed in the non-ferromagnetic-order Co3O4nanofibers.Calculation results indicate that there are more overlaps between the density of states for Co3d and O 2p by applying an external magnetic field.Accordingly,the spin hybridization of 3d-2p and the kinetics of spin charge transfer are optimized in ferromagnetic FeCo_(2)O_(4),which can promote the adsorption of oxygen-intermediates and electron transfer,significantly improving its electrocatalytic efficiency.What’s more,the maximum power density of the FeCo_(2)O_(4)nanofibers based Zn-air battery(ZAB)increases from 97.3 mW cm^(-2)to 108.2 mW cm^(-2)by applying an external magnetic field,providing a new idea for the application of magnetic cathode electrocatalysts in ZABs.展开更多
The complexity of diagenesis and hydrocarbon accumulation in the deep reservoirs in southern Junggar Basin restricts hydrocarbon exploration in the lower reservoir assemblage. The lithofacies and diagenesis of reservo...The complexity of diagenesis and hydrocarbon accumulation in the deep reservoirs in southern Junggar Basin restricts hydrocarbon exploration in the lower reservoir assemblage. The lithofacies and diagenesis of reservoirs in the Cretaceous Qingshuihe Formation in the Gaoquan structure of the Sikeshu Sag, southern Junggar Basin were analyzed. On this basis, the thermal history was calibrated using calcite in-situ U-Pb dating and fluid inclusion analysis to depict the hydrocarbon accumulation process in the Gaoquan structure. The results show that the Qingshuihe reservoir experienced two phases of calcite cementation and three phases of hydrocarbon charging. The calcite cements are dated to be (122.1±6.4) Ma, (14.4±1.0) Ma - (14.2±0.3) Ma. The hydrocarbon charging events occurred at around 14.2-30.0 Ma (low-mature oil), 14.2 Ma (mature oil), and 2 Ma (high-mature gas). The latter two phases of hydrocarbon charging contributed dominantly to the formation of reservoir. Due to the S-N compressive thrust activity during the late Himalayan period since 2 Ma, the traps in the Gaoquan structure were reshaped, especially the effective traps which developed in the main reservoir-forming period were decreased significantly in scale, resulting in weak hydrocarbon shows in the middle-lower part of the structure. This indicates that the effective traps in key reservoir-forming period controlled hydrocarbon enrichment and distribution in the lower reservoir assemblage. Calcite U-Pb dating combined with fluid inclusion analysis can help effectively describe the complex diagenesis and hydrocarbon accumulation process in the central-west part of the basin.展开更多
文摘The reaction mechanism for alkylation of benzene with propylene over the β zeolite and the MCM-22 zeolite were investigated respectively by in-situ IR spectrometry. Three types of experiments were carried out. （1） IR spectra of the gas-phase propylene, benzene and isopropyl benzene were recorded. （2） IR spectra of the above-mentioned substances as adsorbates that have combined with the zeolite wafer were recorded. （3） IR spectra of the reaction modes were recorded. The test results showed that the alkytation reaction over the zeolite β was ascribed to the mechanism of carbonium ions, whereas the alkylation reaction over the zeolite MCM-22 was ascribed to the synchronous reaction mechanism.
基金Supported by the National Natural Science Foundation of China(21176090,21136003)Team Project of Natural Science Foundation of Guangdong Province(S2011030001366)+1 种基金Science and Technology Foundation of Guangdong Province(2012B050600010)Fundamental Research Funds for the Central Universities(2013ZP0010)
文摘The amphiphilic copolymer poly（hydroxyethyl methacrylate-co-tert-butyl methacrylate） [P（HEMA-co-tBMA）] was synthesized by activators regenerated by electron transfer atom transfer radical polymerization （ARGET ATRP）, with the synthesis process monitored by in-situ infrared spectroscopy （IR）. The molecular weight, chem- ical structure and characteristics of the copolymer were determined by 1H NMR, gas chromatography and gel permeation chromatography. The influences of various parameters on the living polymerization were explored. The molecular weight of the copolymer with narrow molecular weight distribution （Mw/Mn 〈 1.50） increases ap- proximately linearly with the monomer conversion, indicating a good control of polymerization. In the reaction temperature range from 50 ℃ to 90 ℃, the monomer conversion is higher at 60 ℃. The tBMA conversion rate decreases gradually with the increase of tBMA content, while the HEMA conversion is hardly affected by HEMA content. Weak polar solvent is more favorable to the polymerization compared to polar solvent. The molar ratio of reducing agent to catalyst has significant effect on the polymerization and increasing the amount of reducing agent will accelerate the reaction rate but causes wider molecular weight distribution. It is indicated that in-situ IR monitoring contributes to a more in-depth understanding of the mechanism of methacrylate monomer copolymerization.
基金financially supported by the National Natural Science Foundation of China (No. 21573101)the Liaoning Provincial Natural Science Foundation (No. 2014020107)+1 种基金the Program for Liaoning Excellent Talents in Universities (No. LJQ2014041)sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry (SRF for ROCS, SEM)
文摘The adsorption of acetonitrile, the co-adsorption of acetonitrile with CO, and hydrogenation of acetonitrile on fresh Mo2C/γ-Al2O3 catalyst were studied by in situ IR spectroscopy. It was found out that CH3CN exhibited strong interaction with the fresh Mo2C/γ-Al2O3 catalyst and was adsorbed mainly on Moδ+ sites of fresh Mo2C/γ-Al2O3 catalyst. Moreover, CH3CN could affect the shifting of IR spectra for CO adsorption towards a lower wave number. The IR spectroscopic study on acetonitrile hydrogenation showed that CH3CN could be easily hydrogenated in the presence of H2 on the Mo2C/γ-Al2O3 catalyst. Furthermore, it was observed that CH3 CN could be selectively hydrogenated to imines on fresh Mo2C/γ-Al2O3 catalyst. Additionally, the active sites of fresh Mo2C/γ-Al2O3 catalyst might be covered with coke during the hydrogenation reaction of acetonitrile. The treatment of catalyst with hydrogen at 673 K could not completely remove coke deposits on the surface of the Mo2C/γ-Al2O3 catalyst.
基金support by the National Natural Science Foundation of China(51961026)the Interdisciplinary Innovation Fund of Nanchang University(Project No.2019-9166-27060003).
文摘Revealing the localized corrosion process of Mg alloy is considered as one of the most significant ways for improving its corrosion resistance.The reliable monitor should be high distinguishability and real-time in liquid environment.Herein,Mg-9Al-1Fe and Mg-9Al-1Fe-1Gd alloys were designed to highlight the impact of intermetallic on the corrosion behaviour.In-situ AFM with a special electrolyte circulation system and quasi-in-situ SEM observation were used to monitor the corrosion process of the designed alloys.SEM-EDS and TEM-SAED were applied to identify the intermetallic in the designed alloys,and their volta potentials were measured by SKPFM.According to the real-time and real-space in-situ AFM monitor,the corrosion process consisted of dissolution of anodicα-Mg phase,accumulation of corrosion products around cathodic phase and shedding of some fine cathodic phase.Then,the localized corrosion process of Mg alloy was revealed combined with the results of the monitor of corrosion process and Volta potential difference.
基金supported by the National Natural Science Foundation of China (Grant No.42090023)the Alliance of International Science Organization (ANSO)Scholarship for Young Talents+3 种基金the Key Deployment Program of Chinese Academy of Sciences (YJKYYQ20190043,ZDBS-LY-DQC003,KFZD-SW-422,ZDRW-ZS-2021-3-1)the Scientific Research and Technology Development Project of China National Petroleum Corpo ration (2022DJ5503)the CAS Key Technology Talent ProgramSupercomputing Laboratory,IGGCAS。
文摘In-situ conversion presents a promising technique for exploiting continental oil shale formations,characterized by highly fractured organic-rich rock.A 3D in-situ conversion model,which incorporates a discrete fracture network,is developed using a self-developed thermal-flow-chemical(TFC)simulator.Analysis of the model elucidates the in-situ conversion process in three stages and defines the transformation of fluids into three distinct outcomes according to their end stages.The findings indicate that kerogen decomposition increases fluid pressure,activating fractures and subsequently enhancing permeability.A comprehensive analysis of activated fracture permeability and heating power reveals four distinct production modes,highlighting that increasing heating power correlates with higher cumulative fluid production.Activated fractures,with heightened permeability,facilitate the mobility of heavy oil toward production wells but hinder its cracking,thereby limiting light hydrocarbon production.Additionally,energy efficiency research demonstrates the feasibility of the in-situ conversion in terms of energy utilization,especially when considering the surplus energy from high-fluctuation energy sources such as wind and solar power to provide heating.
基金supported by the National Natural Science Foundation of China(Nos.51827901 and 52121003)the 111 Project(No.B14006)+1 种基金the Yueqi Outstanding Scholar Program of CUMTB(No.2017A03)the Fundamental Research Funds for the Central Universities(No.2022YJSNY13).
文摘Deep in-situ rock mechanics considers the influence of the in-situ environment on mechanical properties,differentiating it from traditional rock mechanics.To investigate the effect of in-situ stress,pore pressure preserved environment on the mechanical difference of sandstone,four tests are numerically modeled by COMSOL:conventional triaxial test,conventional pore pressure test,in-situ stress restoration and reconstruction test,and in-situ pore pressure-preserved test(not yet realized in the laboratory).The in-situ stress restoration parameter is introduced to characterize the recovery effect of in-situ stress on elastic modulus and heterogeneous distribution of sandstone at different depths.A random function and nonuniform pore pressure coefficient are employed to describe the non-uniform distribution of pore pressure in the in-situ environment.Numerical results are compared with existing experimental data to validate the models and calibrate the numerical parameters.By extracting mechanical parameters from numerical cores,the stress-strain curves of the four tests under different depths,in-situ stress and pore pressure are compared.The influence of non-uniform pore pressure coefficient and depth on the peak strength of sandstone is analyzed.The results show a strong linear relationship between the in-situ stress restoration parameter and depth,effectively characterizing the enhanced effect of stress restoration and reconstruction methods on the elastic modulus of conventional cores at different depths.The in-situ pore pressurepreserved test exhibits lower peak stress and peak strain compared to the other three tests,and sandstone subjected to non-uniform pore pressure is more prone to plastic damage and failure.Moreover,the influence of non-uniform pore pressure on peak strength gradually diminished with increasing depth.
基金financial support offered by the National Key R&D Program of China(Grant No.2019YFA0705502,Grant No.2019YFA0705501)the National Natural Science Fund Project of China(Grant No.4210020395)+1 种基金the China Postdoctoral Science Foundation(Grant No.2021M700053)Technology Development Plan Project of Jilin Province(Grant No.20200201219JC).
文摘The autothermic pyrolysis in-situ conversion process (ATS) consumes latent heat of residual organic matter after kerogen pyrolysis by oxidation reaction, and it has the advantages of low development cost and exploitation of deep oil shale resources. However, the heating mechanism and the characteristic of different reaction zones are still unclear. In this study, an ATS numerical simulation model was proposed for the development of oil shale, which considers the pyrolysis of kerogen, high-temperature oxidation, and low-temperature oxidation. Based on the above model, the mechanism of the ATS was analyzed and the effects of preheating temperature, O_(2) content, and injection rate on recovery factor and energy efficiency were studied. The results showed that the ATS in the formation can be divided into five characteristic zones by evolution of the oil and O_(2) distribution, and the solid organic matter, including residue zone, autothermic zone, pyrolysis zone, preheating zone, and original zone. Energy efficiency was much higher for the ATS than for the high-temperature nitrogen injection in-situ conversion process (HNICP). There is a threshold value of the preheating temperature, the oil content, and the injection rate during the ATS, which is 400 °C, 0.18, and 1100 m3/day, respectively, in this study.
基金financially supported by the Natural Science Foundation(NSF) of China(91963201 and 12174163)the Creation of Science and Technology of Northwest Normal University,China(NWNU-LKQN2020-22)。
文摘Field-assisted electrocatalytic reactions are demonstrated to be sufficient strategies in enhancing the electrocatalyst activities for oxygen evolution reaction(OER).Here,we report the in-situ magnetic field enhanced electrocatalytic activity in ferromagnetic FeCo_(2)O_(4)nanofibers.Our results demonstrate that the overpotential of FeCo_(2)O_(4)nanofibers at 10 mA cm^(-2)shows a left-shift of 40 mV for the OER by applying an external magnetic field,and no obvious change has been observed in the non-ferromagnetic-order Co3O4nanofibers.Calculation results indicate that there are more overlaps between the density of states for Co3d and O 2p by applying an external magnetic field.Accordingly,the spin hybridization of 3d-2p and the kinetics of spin charge transfer are optimized in ferromagnetic FeCo_(2)O_(4),which can promote the adsorption of oxygen-intermediates and electron transfer,significantly improving its electrocatalytic efficiency.What’s more,the maximum power density of the FeCo_(2)O_(4)nanofibers based Zn-air battery(ZAB)increases from 97.3 mW cm^(-2)to 108.2 mW cm^(-2)by applying an external magnetic field,providing a new idea for the application of magnetic cathode electrocatalysts in ZABs.
基金Supported by PetroChina Science and Technology Development Project(2023ZZ0206,2021DJ0303,2021DJ0105,2021DJ0203)National Natural ScienceFoundation of China(U22B6002).
文摘The complexity of diagenesis and hydrocarbon accumulation in the deep reservoirs in southern Junggar Basin restricts hydrocarbon exploration in the lower reservoir assemblage. The lithofacies and diagenesis of reservoirs in the Cretaceous Qingshuihe Formation in the Gaoquan structure of the Sikeshu Sag, southern Junggar Basin were analyzed. On this basis, the thermal history was calibrated using calcite in-situ U-Pb dating and fluid inclusion analysis to depict the hydrocarbon accumulation process in the Gaoquan structure. The results show that the Qingshuihe reservoir experienced two phases of calcite cementation and three phases of hydrocarbon charging. The calcite cements are dated to be (122.1±6.4) Ma, (14.4±1.0) Ma - (14.2±0.3) Ma. The hydrocarbon charging events occurred at around 14.2-30.0 Ma (low-mature oil), 14.2 Ma (mature oil), and 2 Ma (high-mature gas). The latter two phases of hydrocarbon charging contributed dominantly to the formation of reservoir. Due to the S-N compressive thrust activity during the late Himalayan period since 2 Ma, the traps in the Gaoquan structure were reshaped, especially the effective traps which developed in the main reservoir-forming period were decreased significantly in scale, resulting in weak hydrocarbon shows in the middle-lower part of the structure. This indicates that the effective traps in key reservoir-forming period controlled hydrocarbon enrichment and distribution in the lower reservoir assemblage. Calcite U-Pb dating combined with fluid inclusion analysis can help effectively describe the complex diagenesis and hydrocarbon accumulation process in the central-west part of the basin.
